CN101024700B

CN101024700B - Acrylic resin filmy material, and product with the same

Info

Publication number: CN101024700B
Application number: CN2007100861299A
Authority: CN
Inventors: 北池幸雄; 安部善纪; 阿部纯一; 北岛浩一郎; 冈崎正吾; 藤井秀幸
Original assignee: Mitsubishi Rayon Co Ltd
Current assignee: Mitsubishi Chemical Corp
Priority date: 2003-01-10
Filing date: 2003-12-26
Publication date: 2011-07-20
Anticipated expiration: 2023-12-26
Also published as: CN1732192A; CN101024700A; CN100424106C

Abstract

An acrylic resin film material comprising at least a multilayer structure polymer with a particular structure prevents a molded item from being whitened during insert- or in-mold molding and meets the requirement for surface hardness, heat resistance, and transparency or matting performance for vehicle applications. It is also possible to use an acrylic resin film material exhibiting a difference of 30% or less between haze values as determined in accordance with the testing method of JIS K7136 (haze measurement method) after and before a tensile test where a test piece with a width of 20 mm is pulled under the conditions of an initial inter-chuck distance of 25 mm, a rate of 50 mm/min and a temperature of 23 DEG C until an end-point inter-chuck distance becomes 33 mm as well as having a pencil hardness of 2B or higher as determined in accordance with JIS K5400.

Description

Membranaceous thing of acrylic resin and goods with the membranaceous thing of this acrylic resin

The application is to be on December 26th, 2003 applying date of original application, application number is 200380108060.5, and denomination of invention is divided an application for the Chinese patent application of " the membranaceous thing of multi-ply construction polymkeric substance and resin combination and acrylic resin, acrylic resin stack membrane, light solidified acrylic resin film and sheet, stack membrane and sheet and the lamination molding that is laminated with these ".

Technical field

The lamination molding that the invention relates to the membranaceous thing of multi-ply construction polymkeric substance and resin combination and acrylic resin, acrylic resin stack membrane, light solidified acrylic resin film and sheet, stack membrane and sheet and be laminated with these.

Background technology

As the method for giving the molding design pattern with low cost, inserts moulding method (insertmolding) or mould internal shaping method (inmold molding) are arranged.The inserts moulding method is to wait the film of the vibrin that bands, polycarbonate resin, acrylic resin etc. or sheet by the preliminary vacuum shaping etc. with having applied printing, form 3D shape, after removing film not or sheet part, in the immigration ejection shaping mould,, substrate resin obtains incorporate molding by being carried out injection molding.On the other hand, mould internal shaping method is that the film or the sheet of the vibrin that bands that will apply printing etc., polycarbonate resin, acrylic resin etc. places in the ejection shaping mould, after applying vacuum forming, in same mould,, substrate resin obtains incorporate molding by being carried out injection molding.

Acrylic resin mould shape thing as the surface hardness that can be used for inserts moulding method or mould internal shaping method, excellent heat resistance, known have with the specified proportion blended contain the polymkeric substance of rubber of specific composition and the thermoplastic polymer that constitutes by specific composition and acrylic resin mould shape thing (for example, with reference to reference 1～4).Such acrylic resin mould shape thing is not only given banding property of molding, but also has the function as the equivalent material of Clear coating.

In addition, disclose with specified proportion and contained the polymkeric substance of rubber of specific composition and the acrylic resin mould shape thing of the thermoplastic polymer that constitutes by specific composition, or contain polymkeric substance and the thermoplastic polymer that constitutes by specific composition and the acrylic resin mould shape thing (for example, with reference to reference 5,6) of matting agent of the rubber of specific composition with specified proportion.Such acrylic resin mould shape thing is not only given banding property of molding, but also has the function as the equivalent material of delustring coating.

In addition, in order to obtain can be used for the surface hardness in mould internal shaping or the inserts shaping, the acrylic resin film of scuff resistance energy excellence, the scheme that proposed the acrylic resin stack membrane of the folded acrylate resin layer that does not in fact contain rubber particles on the upper strata of one side at least of the acrylate resin layer that contains rubber particles is (for example, with reference to reference 14,15.)。

Have again, contain rubber particles after, problems such as weathering resistance and resistance to chemical reagents reduction can take place equally.Therefore, proposed on the one side at least of the acrylate resin layer that contains rubber particles, the scheme of the stack membrane of vinylidene based polymer that lamination acrylic resin and adaptation are good or the like fluorine resin is (for example, with reference to reference 16.)。

In addition, a kind of light solidified membrane or sheet are also disclosed, the light-cured resin that its surface has has following character: applicable to the manufacturing of the good molding of the outward appearance of using mould internal shaping or inserts to be shaped, wear resistant, weathering resistance and resistance to chemical reagents are good, and non-adhesiveness, processibility and storage stability good (with reference to reference 17,18).Such light solidified membrane or sheet are not only given banding property of molding, but also have the function as the equivalent material of delustring coating.

And then, disclose and be applicable to mould internal shaping method or inserts moulding method, with acrylic resin film and the stacked stack membrane that forms of sheet or sheet as acrylate resin layer (for example, with reference to reference 19～22.)。

In addition, also disclose and can be used for the membranaceous thing of the sufficient acrylic resin of processibility, flexibility mould internal shaping method, that constitute by the multi-ply construction polymkeric substance that contains rubber constituent (for example, referring to reference 7.)。

Have again, the membranoid substance that constitutes by the acrylic resin that contains rubber constituent, utilize the good characteristic of its transparency, weathering resistance, flexibility, processibility aspect, can be layered in various resin forming products, carpenter work and on the surface of metal formed article, as the building materials purposes of adorning in dress, the furniture door material window frame core print bathroom inside and outside the vehicle etc. or the like surface layer material, label film, high briliancy reflection material lining film.

In the past, as the membranaceous thing raw material of the acrylic resin that is used for such use, proposed various resin combinations and dropped into practical application.Wherein, as give particularly weathering resistance, the transparency is good and the good membranaceous thing of acrylic resin of proof stress albefaction such as anti-crooked albefaction, known have with alkyl acrylate, alkyl methacrylate and the graft crosslinking agent multi-ply construction polymkeric substance (for example referring to reference 8,9) as the particular configuration of the constituent of polymkeric substance.In addition, also be disclosed (for example referring to reference 10～12) as the membranaceous thing of the acrylic resin with same characteristic with the multi-ply construction polymkeric substance of raw material.Have again, disclose thermoplastic resin composition's (for example referring to reference 13) that the straight chain polymer with hydroxyl that multi-ply construction polymkeric substance and specific composition with particular configuration constitute constitutes as the thermoplastic resin composition of the good membranaceous raw material of acrylic resin of extinction.

In recent years, the portion's material that has the membranaceous thing layer of acrylic resin on the top layer by inserts moulding method or mould internal shaping method are shaped is used to automobile-used parts (for example referring to reference 1).Use contains average particle diameter and has obtained transparent good coating with the membranaceous thing of acrylic resin (for example referring to reference 3) less than 0.2 micron rubber polymer.The polymkeric substance that use contains the rubber of particular configuration is not damaging the coating replacement membranaceous thing of acrylic resin (for example referring to reference 4) that has obtained taking into account plasticizer-resistant albefaction and plasticity under the surface hardness thermotolerance.Use contains the membranaceous thing of acrylic resin of polymkeric substance of rubber that Tg is about 105 ℃ hard core construct and is suggested, and has obtained the good membranaceous thing of acrylic resin (for example referring to reference 2) of surface hardness.Contain matting agent and contain the polymkeric substance of the rubber of specific median size with specified quantitative, the membranaceous thing of acrylic resin (for example referring to reference 5) that obtained extinction, surface hardness, thermotolerance, has excellent moldability.Though the membranaceous thing of acrylic resin (for example referring to reference 6) that obtained having the good extinction of the printing of specific film surface gloss, surface hardness, thermotolerance, has excellent moldability, but, the membranaceous thing of these acrylic resins is existed worried in anti-shaping albefaction.

Particularly, (1) to be shaped be in order to remove membranaceous thing of acrylic resin or the stacked lamination sheet of the membranaceous thing of acrylic resin after vacuum forming to inserts, and the mould internal shaping is the stamping-out (punching) that carries out processing in order to remove the membranaceous thing of acrylic resin that overflows from substrate resin, because the end of molding produces albefaction, thereby damaged the outward appearance of molding, (2) albefaction that when inciting somebody to action the taking-up from mould of (undercutting design undercut design), takes place, (3) for the molding of the convex-concave style that obtains having literal etc. and use when having concavo-convex mould, in vacuum or after pressing empty the shaping, the membranaceous thing of acrylic resin can be filled not exclusively at the jog of mould, and when the temperature of the membranaceous thing of acrylic resin when Tg is following, must be with the substrate resin injection molding, can produce fracture sometimes because resin pressure extends film and albefaction takes place.

Because the anti-plasticity albefaction problem of the above-mentioned membranaceous thing of acrylic resin, when replacing stamping-out (punching) processing to remove the film that overflows by hand, must the part of the albefaction that constitutes the style restriction be heated once again to remove the operation of the part of turning white (white flavor), therefore, industrial utilization is worth low.

In addition, for example obtained the good membranaceous thing of acrylic resin of weathering resistance, solvent resistance, proof stress albefaction, resistance to water-whitening and the transparency and extinction (for example referring to reference 8～12,13).But this communique does not have about the inserts shaping of the membranaceous thing of acrylic resin that obtains or the record of mould internal shaping, not about surface hardness, stable on heating record yet.Though relevant for processibility, flexibility is good and the record of the membranaceous thing mould of this acrylic resin internal shaping (for example referring to reference 7), the membranaceous thing surface hardness of above-mentioned acrylic resin, thermotolerance do not reach automobile-used necessary level equally.

In addition, folded alkyl methacrylate with alkyl with carbonatoms 1～4 is that the Rockwell hardness of principal constituent is the resin layer more than 90 in the M scale range on the upper strata of one side at least of the acrylate resin layer that contains rubber particles, obtains the good acrylic resin stack membrane of scuff resistance (for example referring to reference 14).

Yet the acrylate resin layer that contains rubber particles of this communique record is because its surface hardness is low, and the surface hardness (scuff resistance) of the acrylic resin stack membrane that finally obtains awaits to improve being used for vehicular applications.In addition, the acrylic resin stack membrane of putting down in writing among the embodiment obtains the processing conditions harshness of good molding, often because of the be full of cracks of processing conditions generation acrylate resin layer, disrumpent feelings, laminate portion is peeled off etc.Be that the processing temperature of acrylic resin stack membrane, the issuing velocity of substrate resin etc. are restricted, industrial utilization is worth low.

In addition, by the hard layer that by acrylic resin constitute of the folded crooked elastic rate in the upper strata of one side at least that contains the soft layer that rubber particles, crooked elastic rate constitute at the acrylic resin below the 1500MPa more than 1600MPa, can obtain being applicable to comprising the acrylic resin stack membrane (for example referring to reference 15) that bending or stretch forming add the surface hardness with appropriateness in man-hour and flexibility, molding that the shaping albefaction is few.

This communique has relevant record to anti-shaping albefaction, and wherein used evaluation method is, carries out tension test according to JISK7113-1995 (stretching test methods of plastics), measures the turbidity (haze) of the breaking portion before and after it.In the evaluation of this tension test to anti-shaping albefaction, the turbidity after the test is along with the test conditions of chuck spacing of draw speed, temperature condition, chuck spacing, terminal point etc. and change.But, these test conditionss are not provided relevant record in this communique, indeterminate to the evaluation of anti-shaping albefaction.

In addition, also indeterminate to the composition explanation of putting down in writing among the embodiment as the acrylic rubber of the double-layer structural of acrylic resin stack membrane.

Therefore, with the acrylic rubber of known 2 layers of structure (for example, referring to reference 3) be modulated into and used after median size when mixing with acrylic resin is about 75nm, make the acrylic resin stack membrane of putting down in writing among the embodiment, when carrying out inserts shaping or mould internal shaping, the acrylic resin that use contains rubber particles as the acrylic resin stack membrane of the embodiment 1 of hard layer do not chap, disrumpent feelings, laminate portion is peeled off etc., has observed the shaping albefaction.

In addition, use the acrylic resin do not contain rubber particles as the acrylic resin stack membrane of the embodiment 2～4 of hard layer produced because of processing conditions is uncomfortable be full of cracks, disrumpent feelings, laminate portion is peeled off etc.That is, the processing temperature of acrylic resin stack membrane, the issuing velocity of substrate resin etc. are had strict restriction, its industrial utilization is worth low.

Point out in this communique, make the hard layer that by acrylic resin constitute of crooked elastic rate more than 1600MPa not contain rubber particles substantially, can show the good effect of anti-shaping albefaction.Yet, shaping albinism when stating inserts shaping or mould internal shaping on the implementation takes place at the most soft layer that is accounting for the acrylic resin stack membrane, shaping albefaction part relatively also confirms have albefaction to take place on the printed patterns with unconspicuous wood grain style, therefore, its industrial utilization is worth low.

This be because, at the rubber particles that is used for the acrylic resin film, (for example have if use as the good rubber particles of the proof stress albefaction of specific taper (Taper) structure, grafting structure, referring to reference 5,6), do not reach in the practical application level to the requirement of anti-shaping albefaction.

Yet, if use the now known good unconspicuous good molding of the available anti-shaping albefaction of rubber particles of proof stress albefaction that has as specific taper configurations, grafting structure, as mentioned above, but be difficult to obtain can be used for automobile-used molding with surface hardness.

The acrylic resin film of this communique embodiment 5, its surface hardness (scuff resistance), thermotolerance all do not reach automobile-used necessary level.

In addition, with weathering resistance, solvent resistance good, carry out stacked with the acrylate resin layer of the good vinylidene fluoride polymer layer of the adaptation of acrylate resin layer and the polymkeric substance formation of specific multi-ply construction, the transparency, proof stress albefaction, stack membrane (for example, referring to reference 16) that resistance to water-whitening adaptation good, each interlayer is good have been obtained.Yet inserts is not shaped this communique or the relevant record of mould internal shaping about the stack membrane that obtains is carried out.And, also not about surface hardness (scuff resistance), stable on heating relevant record.

In addition, its surface hardness of the stack membrane of putting down in writing among the embodiment (scuff resistance), thermotolerance are being used for the automobile-used room for improvement that all has.

Have again, also obtained having wear resistant, weathering resistance and resistance to chemical reagents good and the light solidified membrane light-cured resin that non-adhesiveness, processibility and storage stability are good or sheet (reference 17,18) on the surface.

For example, in order to obtain light solidified membrane or sheet, the acrylic resin film that use surface hardness, thermotolerance, has excellent moldability (for example, with reference to reference 1) during as base material film or sheet, because these acrylic resin films have problem in anti-shaping albefaction, so in anti-shaping albefaction, also exist worried equally to light solidified membrane or the sheet that obtains.

And, use the good acrylic resin film of weathering resistance, solvent resistance, proof stress albefaction, resistance to water-whitening and the transparency as base material film or sheet (for example, with reference to reference 8,9) time, because the poor heat resistance of these acrylic resin films, in the drying process that desolventizes that after being coated on Photocurable resin composition on the film, carries out, Photocurable resin composition and acrylic resin film expansion exist the scuff resistance after solidifying, the problem that surface hardness reduces.In addition, when using these acrylic resin films, though can the expansion of acrylic resin film be suppressed to minimum degree by optimizing the optimum drying condition, the device of drying process must maximize, thereby production efficiency is low, and industrial utilization is worth low.In addition,, just can not reduce the amount of residual organic solvent in the light-cured resin layer as described later, occur the variety of issue that causes because of residual solvent easily owing to can not improve drying temperature.In addition, surface hardness for light solidified membrane behind the photocuring or sheet, owing to be subjected to the very big influence as the surface hardness of the film of base material or sheet, the light solidified membrane behind the photocuring of the situation that these acrylic resin films use as base material or the surface hardness of sheet only reach soft.

In addition, inserts moulding method or mould internal shaping method, the stack membrane or the sheet that form as acrylic resin lamination layer with membranaceous thing of acrylic resin or sheet have been obtained being applicable to.(for example, with reference to reference 19～22).Yet, stack membrane or the sheet with these acrylate resin layers only do not launched narration to the importance and the resolution policy of anti-shaping albefaction.

Have again; as the peristome sash of window etc., entry sliding gate, gateway door etc. outer build stack membrane that the surface decoration of building portion's material uses or sheet (below; be called " building materials with stack membrane or sheet "); its main product is on the surface of the substrate that the thermoplastic resin by polyvinyl chloride (PVC) RESINS etc. constitutes, and the sealer that is made of the good acrylic resin of weathering resistance is set forms.These building materials have the character that is difficult for taking place because of deteriorations such as oxidation that ultraviolet ray causes, decomposition with the acrylic resin of the sealer of stack membrane or sheet; and it is because good with consistency such as the UV light absorber of benzotriazole system, benzophenone series etc.; so make that be arranged on substrate sheets and its lip-deep patterned layer usually is not subjected to the ultraviolet injury that contains in the sunlight; promptly be used in outer dress purposes, also can obtain extraordinary weathering resistance.

With known laminating method carry out lamination, at the sealer superimposed layer building materials of lamination of acrylic resin film or sheet with stack membrane or sheet with revealed (for example, with reference to reference 23～25).

Stack membrane or sheet to such use have the requirement of following function.

(1) anti-light echo

The problem that surperficial gloss changes takes place with stack membrane or sheet in building materials easily in manufacturing, manufacturing procedure and under the user mode.That is, in general, building materials are the glossy condition that reaches the appropriateness of expected value with the surface of stack membrane or sheet, by means such as pull and stretch processing and interpolation gloss conditioning agent, formation gloss regulating courses it are adjusted to the regulation glossy condition.But, under the situation of building materials with stack membrane or sheet, even building materials with stack membrane or sheet manufacturing process in its surface adjust to the appropriateness glossy condition, when waiting by surperficial circumvolution (wrapping) processing in the manufacturing procedure of the various substrate surfaces that it are attached to aluminum sash base material or Steel Plate Door base material etc., various materials of processing like this are used for actual use behind the architecture construction such as dwelling house, the state that the gloss that occurs the surface sometimes easily rises, テカリ and color and luster spot etc. diminish outward appearance.These macroscopic irregularitys are when above-mentioned manufacturing procedure and under the state as the material use of building materials usefulness portion, because heat etc., the surface temperature of stack membrane or sheet is in the condition of high temperature, and high temperature will cause the thermoplastic resin of sealer softening thus.That is, the anti-light echo requirement to stack membrane or sheet is relevant with the thermotolerance of the thermoplastic resin of sealer.

(2) secondary processing adaptability

Building materials generally are that being attached at wooden as hard board and veneer sheet, medium density fibre board (MDF) (MDF) etc. is that the synthetic resins of inanimate matter base materials such as base material, calcium silicate board and slabstone, water-setting flake board, fiber-reinforced plastic (FRP) etc. is to use on the surface of various base materials of base material etc. with stack membrane or sheet.But be not only be attached on the flat base material, and sometimes on the surface of base material bending machining or that have concaveconvex shape that has carried out V-arrangement cutting processing etc., carry out solid forming by polishing or vacuum forming method etc. and attach use.Particularly in recent years,, the needs of the ornamental portion material of various special three-dimensional shapes are also increased, thereby just more require the secondary processing adaptability of building materials with the bendability of stack membrane or sheet and solid forming etc. along with the variation of consumer demand.

(3) scuff resistance

In the operation that obtains the lamination molding, to not causing that outward appearance is not good and considering aspect the purposes expansion that is used for easy especially abrasive positions such as peristome sash, entry sliding gate, gateway door such as window, be starved of the good building materials of scuff resistance with stack membrane or sheet because of scratch.As the index of scuff resistance, the pencil hardness of acrylic resin of position, top layer that requires the lamination molding is more than or equal to 2B.Under the situation of pencil hardness more than or equal to the acrylic resin of 2B, the lamination molding that uses these building materials to obtain with stack membrane or sheet has practical scuff resistance, and in the operation that finally becomes the lamination molding, the not good problem of the outward appearance that is caused by scratch is few, can be used for various outer building such as peristome sash, entry sliding gate, gateway door such as above-mentioned window builds portion's material.

The building materials that acrylic resin film is arranged on sealer of record do not launch narration to importance and the resolution policy that has scuff resistance, anti-light echo and anti-shaping albefaction simultaneously with stack membrane or sheet in the reference 23～25.For example, reference 23 and 24 has related to the anti-albefaction that is shaped, but anti-light echo is put down in writing.

In addition, reference 25 has related to anti-light echo, but scuff resistance and anti-shaping albefaction are put down in writing.

Particularly; in the reference 25 by using second-order transition temperature on the sealer at 90 ℃ or acrylic resin film more than it; to be exposed to surface temperature be under the above high temperature of 60 ℃ or its even obtained stack membrane or sheet, also is not easy to take place the chatoyant stack membrane or the sheet of light echo etc.Yet, do not offer some clarification on the composition of this acrylic resin film or the measuring method of second-order transition temperature etc. in this communique.And, in also clearly record of basis for " surface temperature of stack membrane or sheet be 60 ℃ or more than it " that obtain thinking in the practical use after buildings is used it in each manufacturing procedure of lamination molding or supposition.And, not detailed to the record of the processing that how to obtain the lamination molding yet.

In the use field of the building materials that contain stack membrane or sheet with the lamination molding; for example; require the highest position to use stack membrane or the sheet that on sealer, has acrylic resin film in thermotolerances such as the outer wall of wallboard etc., fence, roof, roof sun bath plate, balconies, wish under 90 ℃ environment, to keep still not having in 24 hours gloss variations such as light echo in the surface temperature of stack membrane or sheet.

But, stack membrane or sheet that the acrylic resin film that use is put down in writing in the embodiment of this communique (HBS006 of Mitsubishi Rayon Co., Ltd and HBS027 (trade(brand)name)) obtains, the vibrin that in radius-of-curvature is 0.5 shape is on the base material of 3D shape, be under 80 ℃ the condition in stack membrane or sheet temperature, carry out 3-D stacks, make lamination molding with 3D shape.Use stack membrane or the sheet of HBS006 a little albefaction to occur, use stack membrane or the sheet of HBS027 albefaction to occur.Therefore, restricted to shaping processing temperature, processing conditions etc.

By above explanation as can be known, in the reference 25 building materials that on sealer, have acrylic resin film of record with stack membrane or sheet in the leeway that improvement is still arranged aspect anti-shaping albefaction and the anti-light echo.

In addition, also had document illustration by using specific resin combination to improve the flexibility of acrylic resin film, even use in the little bending machining of radius-of-curvature, high speed bending machining that Deformation velocity is big etc., processing characteristics is good acrylic resin film also.(for example, reference 26).Also disclosed by using specific resin combination, the acrylic resin film that low-temperature processability is good (for example, reference 27,28).Yet, the acrylic resin film of record is not put down in writing its anti-light echo in the reference 26～28, the acrylic resin film of using as raw material with resin combination of record in an embodiment, the anti-light echo of its anticipation does not reach the level of any building materials purposes, is not suitable for building materials with stack membrane or sheet.

On the other hand, () occasion for example, reference 1～4, its anti-light echo is good, but because anti-shaping albefaction is poor, therefore, is not suitable for as building materials with stack membrane or sheet to use the acrylic resin film of excellent heat resistance.

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Summary of the invention

The purpose of this invention is to provide when implementing the shaping of mould internal shaping or inserts, molding does not have albefaction and can be used for the membranaceous thing of the acrylic resin with surface hardness, thermotolerance and the transparency or extinction or the acrylic resin stack membrane of vehicular applications.Another object of the present invention provides when implementing the shaping of mould internal shaping or inserts, and molding does not have albefaction and can be used for the membranaceous thing of light solidified acrylic resin or the acrylic resin stack membrane or the sheet with thermotolerance, scuff resistance, surface hardness of vehicular applications.A further object of the present invention provides under cold conditions, and when implementing manufacturing procedure such as V-type cutting processing and polishing processing, the building materials that molding does not have albefaction and satisfies scuff resistance, anti-light echo are with stack membrane or sheet.And then, the purpose of this invention is to provide these films or sheet are stacked in lamination molding on the base material.

In addition, the purpose of this invention is to provide is multi-ply construction laminate that obtains aforesaid propylene acid resin membranoid substance and the resin combination that contains this multi-ply construction laminate.

Above-mentioned purpose of the present invention can be resolved by following the present invention.

(1) multi-ply construction polymkeric substance (I), its by have (1) innermost layer polymkeric substance (I-A), (2) second-order transition temperature that following monomer component constitutes be 25～100 ℃, with above-mentioned innermost layer polymkeric substance (I-A) form different intermediate layer polymer (I-B) and (3) outermost layer polymkeric substance (I-C) in turn lamination form, wherein

The monomer component that constitutes (1) innermost layer polymkeric substance (I-A) is:

(I-A1) alkyl acrylate 50～99.9 quality %

(I-A2) alkyl methacrylate 0～49.9 quality %

(I-A3) but have other monomer 0～20 quality % of the two keys of copolymerization

(I-A4) multi-functional monomer 0～10 quality %

(I-A5) grafting intersection agent 0.1～10 quality %

The monomer component that constitutes (2) intermediate layer polymer (I-B) is:

(I-B1) alkyl acrylate 9.9～90 quality %

(I-B2) alkyl methacrylate 9.9～90 quality %

(I-B3) but have other monomer 0～20 quality % of the two keys of copolymerization

(I-B4) multi-functional monomer 0～10 quality %

(I-B5) grafting intersection agent 0.1～10 quality %

The monomer component that constitutes (3) outermost layer polymkeric substance (I-C) is:

(I-C1) alkyl methacrylate 80～100 quality %

(I-C2) alkyl acrylate 0～20 quality %

(I-C3) but have other monomer 0～20 quality % of the two keys of copolymerization

(2) resin combination (III), it contains the multi-ply construction polymkeric substance (I) of above-mentioned (1) record and is the thermoplastic polymer (II) of principal constituent with the alkyl methacrylate.

(3) resin combination (IV), it contains multi-ply construction polymkeric substance (I) or the resin combination (III) of above-mentioned (2) record and the matting agent of 0.1～40 mass parts of above-mentioned (1) record of 100 mass parts.

(4) the membranaceous thing of acrylic resin (A), at least a formation in the group that resin combination (III) of the multi-ply construction polymkeric substance (I) of its above-mentioned by being selected from (1) record, above-mentioned (2) record and the resin combination (IV) of above-mentioned (3) record are formed.

(5) the membranaceous thing of acrylic resin (A), it is under the condition of in the early stage 23 ℃ of chuck spacing 25mm, speed 50mm/min, temperature, after making the chuck spacing of terminal point be the tension test of 33mm to the test film of wide 20mm, according to the value of this test film of determination of test method of JIS K7136 (measuring method of turbidity) and difference according to the value of test film before the determination of test method test of JIS K7136 (measuring method of turbidity) be smaller or equal to 30% and pencil hardness (measuring) based on JIS K5400 be more than or equal to 2B.

(6) the membranaceous thing of acrylic resin (A) of above-mentioned (4) or (5) record, its 60 ° of surface glosses at least simultaneously are smaller or equal to 100%.

(7) the membranaceous thing of acrylic resin (A) of any record in above-mentioned (4)～(6), its heat-drawn wire (measuring based on ASTM D648) is more than or equal to 80 ℃.

(8) the membranaceous thing of acrylic resin (A) of any record in above-mentioned (4)～(7), it further has the layer of banding at least on one side.

(9) acrylic resin stack membrane, it is the acrylic resin stack membrane with membranaceous thing of acrylic resin (A) of any record in above-mentioned (4)～(7), and it further has other membranaceous thing of acrylic resin (A ') or the membranaceous thing of fluoro-resin (A ").

(10) the acrylic resin stack membrane of above-mentioned (9) record, it is in that an enterprising step of one side has a layer of banding at least.

(11) light solidified acrylic resin film or sheet, it has the olefin(e) acid resin laminated film of the membranaceous thing of acrylic resin (A) of any record in above-mentioned (4)～(7) or above-mentioned (9) record and contains the thermoplastic resin (z-1) that has free-radical polymerised unsaturated group on side chain and the Photocurable resin composition (Z) of Photoepolymerizationinitiater initiater (z-2) layer.

(12) the light solidified acrylic resin film or the sheet of above-mentioned (11) record, it further has the layer of banding at least on one side.

(13) stack membrane or sheet, it has the acrylic resin stack membrane of the membranaceous thing of acrylic resin (A) that is selected from any record in above-mentioned (4)～(7), above-mentioned (9) record, and one of in the group formed of the light solidified acrylic resin film of above-mentioned (11) record or sheet and thermoplastic resin (C).

(14) stack membrane or the sheet of above-mentioned (13) record, it also has the layer of banding.

(15) building materials that are made of the stack membrane or the sheet of above-mentioned (13) or (14) record are with stack membrane or sheet.

(16) lamination molding, it is one of to be selected from the group that the building materials of the stack membrane of the light solidified acrylic resin film of acrylic resin stack membrane, above-mentioned (11) or (12) record of the membranaceous thing of acrylic resin (A) of any record in above-mentioned (4)～(8), above-mentioned (9) or (10) record or sheet, above-mentioned (13) or (14) record or sheet and above-mentioned (15) record form with stack membrane or sheet at base material (E) superimposed layer to form.

(17) the lamination molding of above-mentioned (16) record, it is the membranaceous thing of acrylic resin (A) by any record in above-mentioned to being selected from (4)～(8), the acrylic resin stack membrane of above-mentioned (9) or (10) record, the light solidified acrylic resin film or the sheet of above-mentioned (11) or (12) record, carry out vacuum forming or press empty the shaping in ejection shaping mould one of in the group that the building materials of stack membrane of above-mentioned (13) or (14) record or sheet and above-mentioned (15) record are formed with stack membrane or sheet, the resin that will constitute above-mentioned base material (E) then in this ejection shaping mould carries out injection molding and integrated and obtain.

(18) the lamination molding of above-mentioned (16) record, it is the membranaceous thing of acrylic resin (A) of any record in above-mentioned to being selected from (4)～(8), the acrylic resin stack membrane of above-mentioned (9) or (10) record, the light solidified acrylic resin film or the sheet of above-mentioned (11) or (12) record, carry out vacuum forming or press empty the shaping one of in the group that the building materials of stack membrane of above-mentioned (13) or (14) record or sheet and above-mentioned (15) record are formed with stack membrane or sheet, insert then in the ejection shaping mould, the resin that will constitute above-mentioned base material (F) in this ejection shaping mould carries out injection molding and obtains.

Use is selected from multi-ply construction polymkeric substance of the present invention (I), the membranaceous thing of acrylic resin (A) one of in the group that resin combination (III) and resin combination (IV) are formed, perhaps use test film chuck spacing 25mm in the early stage to wide 20mm, speed 50mm/min, carry out tension test under 23 ℃ of the temperature, make that the chuck spacing of terminal point is 33mm, the difference of the value of this test film being measured according to the test method of JIS K7136 (measuring method of turbidity) and the value of the test film before testing being measured according to the test method of JIS K7136 (measuring method of turbidity) is 30% or below it then, and pencil hardness (measuring based on JIS K5400) is more than or equal to the membranaceous thing of the acrylic resin of 2B (A), can be provided at when implementing mould internal shaping or inserts shaping, molding does not have albefaction, and the surface hardness that has that can be used for vehicular applications, membranaceous thing of the acrylic resin of the thermotolerance and the transparency or extinction (A) and acrylic resin stack membrane.In addition, can be provided at when implementing mould internal shaping or inserts shaping, molding does not have albefaction and can be used for the membranaceous thing of the acrylic resin with surface hardness, thermotolerance and the transparency or extinction or the acrylic resin stack membrane of vehicular applications.Have, also can be provided under the cold conditions, when implementing manufacturing procedure such as V-type cutting processing and polishing processing, the building materials that molding does not have albefaction and satisfies scuff resistance, anti-light echo are with stack membrane or sheet.And then, can provide these films or sheet are stacked in lamination molding on the base material.

Especially, by one of using in the group that anti-albefaction when implementing mould internal shaping or inserts and the be shaped good membranaceous thing of acrylic resin of the present invention (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet and stack membrane or sheet form, just do not need to carry out the part that when replacing stamping-out (punching) processing to remove the film that overflows by hand style is constituted the albefaction of restriction is heated once again to remove the operation of the part of turning white (distinguishing the flavor of in vain).The membranaceous thing of acrylic resin of the present invention (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet and stack membrane or sheet have high industrial utilization and are worth, and can surmount use in the past greatly.

Embodiment

(multi-ply construction polymkeric substance (I))

Multi-ply construction polymkeric substance (I), it is that following monomer component constitutes by having, innermost layer polymkeric substance (I-A), form with each polymer layer that innermost layer polymkeric substance (I-A) is formed different intermediate layer polymer (I-B) and outermost layer polymkeric substance (I-C).

The monomer component that constitutes innermost layer polymkeric substance (I-A) is:

(I-A1) alkyl acrylate 50～99.9 quality %

(I-A2) alkyl methacrylate 0～49.9 quality %

(I-A3) but have two keys of copolymerization remove (I-A1), 0～20 quality %

(I-A2) monomer in addition

(I-A4) multi-functional monomer 0～10 quality %

(I-A5) grafting intersection agent 0.1～10 quality %

The monomer component that constitutes intermediate layer polymer (I-B) is:

(I-B1) alkyl acrylate 9.9～90 quality %

(I-B2) alkyl methacrylate 9.9～90 quality %

(I-B3) but have two keys of copolymerization remove (I-B1), 0～20 quality %

(I-B2) monomer in addition

(I-B4) multi-functional monomer 0～10 quality %

(I-B5) grafting intersection agent 0.1～10 quality %

The monomer component that constitutes outermost layer polymkeric substance (I-C) is:

(I-C1) alkyl methacrylate 80～100 quality %

(I-C2) alkyl acrylate 0～20 quality %

(I-C3) but have two keys of copolymerization remove (I-C1), 0～20 quality %

(I-C2) monomer in addition

Herein the kind and/or the content difference that are meant " forming different " at least a composition of the monomer component that constitutes each polymkeric substance.

As above constituent, the independent Tg of intermediate layer polymer (I-B) is 25～100 ℃.

Constituting the alkyl acrylate of the composition (I-A1) that contains in the monomer component of innermost layer polymkeric substance (I-A), can be the ester of straight or branched.Specifically can list methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, 2-EHA, vinylformic acid n-octyl etc.These can use separately, or two or more is mixed use.Wherein, preferred n-butyl acrylate.

Constituting the alkyl methacrylate of the composition (I-A2) that contains as required in the monomer component of innermost layer polymkeric substance (I-A), can be the ester of straight or branched.Specifically can list methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA etc.These can use separately, or two or more is mixed use.Wherein, preferable methyl methyl acrylate.

Constitute the composition (I-A3) that contains as required in the monomer component of innermost layer polymkeric substance (I-A) but the monomer except that (I-A1), (I-A2) with the two keys of copolymerization, can list the vinylbenzene, vinyl cyanide, methacrylonitrile of acrylic acid monomer, vinylbenzene, the alkyl replacement of lower alkoxy acrylate, cyano ethyl acrylate, acrylic acid amides, vinylformic acid, methacrylic acid etc. etc.These can use separately, or two or more is mixed use.

Constitute the multi-functional monomer of the composition (I-A4) that contains as required in the monomer component of innermost layer polymkeric substance (I-A), be defined in the monomer of two keys that an intramolecularly contains the copolymerization of two or more same degree.Particularly, preferably use ethylene glycol dimethacrylate, 1,3 butylene glycol dimethacrylate, 1, the alkylene support glycol dimethacrylate of 4-butylene glycol dimethacrylate, propylene glycol dimethacrylate etc.In addition, also can use many vinyl benzenes of Vinylstyrene, trivinylbenzene etc.These can use separately, or two or more is mixed use.Wherein, serve as preferred with the 1,3 butylene glycol dimethacrylate.Even under the complete inoperative situation of multi-functional monomer (I-A4),, just can provide the multi-ply construction polymkeric substance (I) of quite stable as long as there is grafting intersection agent (I-A5) to exist.For example, in the occasion that hot strength etc. is had strict demand, can arbitrarily carry out according to its adding purpose.

Constitute the grafting intersection agent of the composition (I-A5) that contains in the monomer component of innermost layer polymkeric substance (I-A), be defined in an intramolecularly and contain two or more monomers with two keys of closing property of different copolymer.Its object lesson is as the α of copolymerization, the allyl ester of beta-unsaturated carboxylic acid or dicarboxylic acid, methyl allyl ester or butene esters etc.Particularly the allyl ester with vinylformic acid, methacrylic acid, toxilic acid or fumaric acid serves as preferred.Wherein, allyl methacrylate(AMA) is excellent preferred because of effect.In addition, triallyl cyanurate, cyamelide triallyl etc. are effective too.These can use separately, or two or more is mixed use.The agent (I-A5) of grafting intersection mainly is that the covalency unsaturated link(age) on its ester by allyl group, methacrylic or butenyl long-range rapid reaction takes place, and generates chemical bond.Wherein, allyl group, methacrylic or butenyl in fact quite a few in the polymerization of sublevel polymkeric substance effectively, produce the grafting key that connects two interlayers.

And, also can be in polymerization in the presence of the chain-transfer agent.

In the monomer component that constitutes innermost layer polymkeric substance (I-A), the content of alkyl acrylate (I-A1) is 50～99.9 quality %.Consider from the viewpoint of the anti-shaping albefaction of the membranaceous thing of the acrylic resin that obtains (A), be preferably greater than and equal 55 quality %, more preferably greater than equaling 60 quality %.In addition, consider,, be more preferably less than and equal 69.9 quality % preferably smaller or equal to 79.9 quality % from the viewpoint of the surface hardness of the membranaceous thing of the acrylic resin that obtains (A), thermotolerance (light echo when being used for the building materials purposes).

In the monomer component that constitutes innermost layer polymkeric substance (I-A), the content of alkyl methacrylate (I-A2) is 0～49.9 quality %.Be preferably greater than and equal 20 quality %, more preferably greater than equaling 30 quality %.In addition, preferably smaller or equal to 44.9 quality %, be more preferably less than and equal 39.9 quality %.

In the monomer component that constitutes innermost layer polymkeric substance (I-A), the content of the copolymerizable monomer (I-A3) except that (I-A1), (I-A2) with two keys is 0～20 quality %.Preferably smaller or equal to 15 quality %.

In the monomer component that constitutes innermost layer polymkeric substance (I-A), the content of multi-functional monomer (I-A4) is 0～10 quality %.Consider from the viewpoint of the anti-shaping albefaction of the membranaceous thing of the acrylic resin that obtains (A), be preferably greater than and equal 0.1 quality %, more preferably greater than equaling 3 quality %.Consider from giving sufficient flexibility and obdurability,, be more preferably less than and equal 5 quality % preferably smaller or equal to 6 quality %.

In the monomer component that constitutes innermost layer polymkeric substance (I-A), the content of grafting intersection agent (I-A5) is 0.1～10 quality %.When content more than or equal to 0.1 quality %, optics rerum naturas such as the anti-shaping albefaction of the membranaceous thing of the acrylic resin that obtains (A) is good, the back transparency that is shaped can not reduce.Preferred value is more than or equal to 0.5 quality %.In addition, during smaller or equal to 10 quality %, can give the membranaceous thing of the acrylic resin that obtains (A) flexibility, obdurability fully.Preferred value is smaller or equal to 5 quality %, is more preferably smaller or equal to 2 quality %.

Though have no particular limits, the independent Tg of innermost layer polymkeric substance (I-A) is preferably smaller or equal to 10 ℃, is more preferably smaller or equal to 0 ℃.Tg smaller or equal to 10 ℃ under, find that the shock-resistance of the multi-ply construction polymkeric substance (I) obtain is good.Tg can adopt the value of record in the polymer handbook (Polymer HandBook (J.Brandrup, Interscience, 1989) (non-patent literature 1)), calculates with the FOX formula.

The content of the innermost layer polymkeric substance (I-A) in the multi-ply construction polymkeric substance (I) is preferably at 15～50 quality %.Content can give the membranaceous thing of the acrylic resin that obtains (A) anti-shaping albefaction more than or equal under 15% the situation, and, the system of can getting both film and inserts be shaped and the mould internal shaping all can toughness.In addition, content is smaller or equal under 50% the situation, and can get both is used for the film of the necessary surface hardness of vehicle (the anti-light echo when being used for building materials), thereby preferred.More preferably smaller or equal to 35% situation.

Innermost layer polymkeric substance (I-A) can be an individual layer, can be multilayer also, is preferably two-layer.Though be not particularly limited, the two-layer monomer constituent ratio that constitutes innermost layer polymkeric substance (I-A) is preferably different.

Innermost layer polymkeric substance (I-A) by two-layer situation about constituting under, consider preferred la m (I-A from the viewpoint of anti-shaping albefaction, shock-resistance, thermotolerance (the anti-light echo when being used for building materials) and the surface hardness of the membranaceous thing of the acrylic resin that obtains (A) ₁) Tg than outside layer (I-A ₂) Tg low.Particularly, la m (I-A ₁) Tg, consider from the viewpoint of anti-shaping albefaction and shock-resistance, preferably be lower than-30 ℃, outside layer (I-A ₂) Tg, consider preferred-15 ℃～10 ℃ from the viewpoint of surface hardness and thermotolerance (the anti-light echo when being used for building materials).In addition, consider the la m (I-A in the innermost layer polymkeric substance (I-A) from viewpoint from surface hardness and thermotolerance (the anti-light echo when being used for building materials) ₁) content be preferably 1～20 quality %, outside layer (I-A ₂) content be preferably 80～99 quality %.

Constituting the alkyl acrylate of the composition (I-B1) that contains in the monomer component of intermediate layer polymer (I-B), can be the ester of straight or branched.Specifically can list methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, 2-EHA, vinylformic acid n-octyl etc.These can use separately, or two or more is mixed use.Wherein, preferred methyl acrylate, n-butyl acrylate.

Constituting the alkyl methacrylate of the composition (I-B2) that contains in the monomer component of intermediate layer polymer (I-B), can be the ester of straight or branched.Specifically can list methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA etc.These can use separately, or two or more is mixed use.Wherein, preferable methyl methyl acrylate.

Constitute the copolymerizable monomer except that (I-B1), (I-B2) of the composition (I-B3) that contains as required in the monomer component of intermediate layer polymer (I-B), can list the vinylbenzene, vinyl cyanide, methacrylonitrile of acrylic acid monomer, vinylbenzene, the alkyl replacement of lower alkoxy acrylate, cyano ethyl acrylate, acrylic acid amides, vinylformic acid, methacrylic acid etc. etc. with two keys.These can use separately, or two or more is mixed use.

Constitute the multi-functional monomer of the composition (I-B4) that contains as required in the monomer component of intermediate layer polymer (I-B), the preferred ethylene glycol dimethacrylate, 1 that uses, 3-butylene glycol dimethacrylate, 1, the alkylene support glycol dimethacrylate of 4-butylene glycol dimethacrylate, propylene glycol dimethacrylate etc.In addition, also can use many vinyl benzenes of Vinylstyrene, trivinylbenzene etc.Wherein, serve as preferred with the 1,3 butylene glycol dimethacrylate.These can use separately, or two or more is mixed use.Even under the complete inoperative situation of multi-functional monomer (I-B4),, just can provide the multi-ply construction polymkeric substance (I) of quite stable as long as there is grafting intersection agent (I-B5) to exist.For example, in the occasion that hot strength etc. is had strict demand, can arbitrarily carry out according to its adding purpose.

The grafting that constitutes the composition (I-B5) that contains in the monomer component of intermediate layer polymer (I-B) intersects agent, and its object lesson is as the α of copolymerization, the allyl ester of beta-unsaturated carboxylic acid or dicarboxylic acid, methyl allyl ester or butene esters etc.Particularly the allyl ester with vinylformic acid, methacrylic acid, toxilic acid or fumaric acid serves as preferred.Wherein, allyl methacrylate(AMA) is excellent preferred because of effect.In addition, triallyl cyanurate, cyamelide triallyl etc. are effective too.These can use separately, or two or more is mixed use.The agent (I-B5) of grafting intersection mainly is that the covalency unsaturated link(age) on its ester by allyl group, methacrylic or butenyl long-range rapid reaction takes place, and generates chemical bond.Wherein, allyl group, methacrylic or butenyl in fact quite a few in the polymerization of sublevel polymkeric substance effectively, produce the grafting key that connects two interlayers.

And, also can in the presence of chain-transfer agent, carry out polymerization.

In the monomer component that constitutes intermediate layer polymer (I-B), the content of alkyl acrylate (I-B1) is 9.9～90 quality %.Consider from the viewpoint of anti-shaping albefaction, surface hardness and the thermotolerance (light echo when being used for the building materials purposes) of the membranaceous thing of the acrylic resin that obtains (A), be preferably greater than and equal 19.9 quality %, more preferably greater than equaling 29.9 quality %.In addition, preferably smaller or equal to 60 quality %, be more preferably less than and equal 50 quality %.

In the monomer component that constitutes intermediate layer polymer (I-B), the content of alkyl methacrylate (I-B2) is 9.9～90 quality %.Consider from the viewpoint of anti-shaping albefaction, surface hardness and the thermotolerance (light echo when being used for the building materials purposes) of the membranaceous thing of the acrylic resin that obtains (A), be preferably greater than and equal 39.9 quality %, more preferably greater than equaling 49.9 quality %.In addition, preferably smaller or equal to 80 quality %, be more preferably less than and equal 70 quality %.

In the monomer component that constitutes intermediate layer polymer (I-B), the content of the copolymerizable monomer (I-B3) except that (I-B1), (I-B2) with two keys is 0～20 quality %.Preferably smaller or equal to 15 quality %.

In the monomer component that constitutes intermediate layer polymer (I-B), the content of multi-functional monomer (I-B4) is 0～10 quality %.Be endowed sufficient flexibility and obdurability from the membranaceous thing of the acrylic resin that obtains (A) and consider,, be more preferably less than and equal 3 quality % preferably smaller or equal to 6 quality %.

In the monomer component that constitutes intermediate layer polymer (I-B), the content of grafting intersection agent (I-B5) is 0.1～10 quality %.When content more than or equal to 0.1 quality %, optics rerum naturas such as the anti-shaping albefaction of the membranaceous thing of the acrylic resin that obtains (A) is good, the back transparency that is shaped can not reduce.Preferred value is more than or equal to 0.5 quality %.In addition, during smaller or equal to 10 quality %, can give the membranaceous thing of the acrylic resin that obtains (A) flexibility, obdurability fully.Preferred value is smaller or equal to 5 quality %, is more preferably smaller or equal to 2 quality %.

The independent Tg of intermediate layer polymer (I-B) need be 25～100 ℃ scope.Tg is during more than or equal to 25 ℃, the surface hardness of the membranaceous thing of the acrylic resin that obtains (A) and thermotolerance (light echo when being used for the building materials purposes) can arrive vehicle with and the necessary level of building materials.Tg is preferably greater than and equals 40 ℃, more preferably greater than equaling 50 ℃.In addition, as Tg during, obtain anti-shaping albefaction and the good membranaceous thing of acrylic resin (A) of system film smaller or equal to 100 ℃.Tg is preferably smaller or equal to 80 ℃, is more preferably less than to equal 70 ℃.

As mentioned above, by setting the intermediate layer polymer (I-B) of specific composition and Tg, obtained at the present membranaceous thing of acrylic resin (A) that also be difficult to realize, that have anti-shaping albefaction and surface hardness and thermotolerance (light echo when being used for the building materials purposes) concurrently.

Though have no particular limits, the content of the intermediate layer polymer (I-B) in the multi-ply construction polymkeric substance (I) is preferably at 5～35 quality %.If in this scope, in the time of the function of the important intermediate layer polymer (I-B) of anti-shaping albefaction of then stating in realization and surface hardness and thermotolerance (light echo when being used for the building materials purposes) spacing, also can give the membranaceous thing of the acrylic resin that obtains (A) other rerum natura, for example, system film and inserts is shaped and the mould internal shaping all can toughness.More preferably smaller or equal to 20% situation.

Intermediate layer polymer (I-B) is individual layer normally, but also can be two-layer or two-layer more than.

Constituting the alkyl methacrylate of the composition (I-C1) that contains in the monomer component of outermost layer polymkeric substance (I-C), can be the ester of straight or branched.Specifically can list methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA etc.These can use separately, or two or more is mixed use.Wherein, preferable methyl methyl acrylate.

Constituting the alkyl acrylate of the composition (I-C2) that contains as required in the monomer component of outermost layer polymkeric substance (I-C), can be the ester of straight or branched.Specifically can list methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, 2-EHA, vinylformic acid n-octyl etc.These can use separately, or two or more is mixed use.Wherein, preferred methyl acrylate, n-butyl acrylate.

Constitute the copolymerizable monomer except that (I-C1), (I-C2) of the composition (I-C3) that contains as required in the monomer component of outermost layer polymkeric substance (I-C), can list the unsaturated carboxylic acid anhydrides, N-phenyl maleinamide, N-cyclohexyl maleinamide of the vinylbenzene, vinyl cyanide, methacrylonitrile, MALEIC ANHYDRIDE, itaconic anhydride etc. of acrylic acid monomer, vinylbenzene, the alkyl replacement of lower alkoxy acrylate, cyano ethyl acrylate, acrylic acid amides, vinylformic acid, methacrylic acid etc. etc. with two keys.These can use separately, or two or more is mixed use.

In the monomer component that constitutes outermost layer polymkeric substance (I-C), the content of alkyl methacrylate (I-C1) is 80～100 quality %.Consider from the viewpoint of the surface hardness of the membranaceous thing of the acrylic resin that obtains (A) and thermotolerance (light echo when being used for the building materials purposes), be preferably greater than and equal 90 quality %, more preferably greater than equaling 93 quality %.In addition, preferably smaller or equal to 99 quality %.

In the monomer component that constitutes outermost layer polymkeric substance (I-C), the content of alkyl acrylate (I-C2) is 0～20 quality %.Be preferably more than and equal 1 quality %.In addition, preferably smaller or equal to 10 quality %, be more preferably less than and equal 7 quality %.

In the monomer component that constitutes outermost layer polymkeric substance (I-C), the content of the copolymerizable monomer (I-C3) except that (I-C1), (I-C2) with two keys is 0～20 quality, preferably smaller or equal to 15 quality %.

Though be not particularly limited, can when outermost layer polymkeric substance (I-C) polymerization, use chain-transfer agent to adjust the molecular weight of outermost layer polymkeric substance (I-C).The chain-transfer agent that this chain-transfer agent preferably uses in common radical polymerization, particularly, can select carbonatoms is 2～20 alkyl sulfhydryl, sulfydryl acids, thiophenol, tetracol phenixin etc., and these can use separately also can mix two or more use.The content of chain-transfer agent is preferably 0.01～5 mass parts for the monomer (I-C1)～(I-C3) of the polymkeric substance (I-C) of 100 mass parts.More preferably, most preferably be more than or equal to 0.4 mass parts more than or equal to 0.2 mass parts.

Though have no particular limits, the independent Tg of outermost layer polymkeric substance (I-C) is preferably more than and equals 60 ℃.Tg more than or equal to 60 ℃ under owing to can obtain having the surface hardness that is applicable to vehicular applications and the membranaceous thing of acrylic resin (A) of thermotolerance (the anti-light echo when being used for building materials), thereby preferred.More preferred Tg is more than or equal to 80 ℃, preferably more than or equal to 90 ℃.

Though have no particular limits, the content of the outermost layer polymkeric substance (I-C) in the multi-ply construction polymkeric substance (I) is preferably 15～80 quality %.Content considered it is preferred more than or equal to 15% o'clock from surface hardness and thermotolerance (the anti-light echo when being used for building materials).More preferably more than or equal to 45 quality %.In addition, content is during smaller or equal to 80 quality %, because the film that obtains has been endowed anti-shaping albefaction, can be used for that inserts is shaped or the toughness of mould internal shaping, thereby preferred.

Outermost layer polymkeric substance (I-C) is generally individual layer, but also can be two-layer or two-layer more than.

Being applicable to the multi-ply construction polymkeric substance (I) of the membranaceous thing of acrylic resin of the present invention (A), is the polymer layer formation by above-mentioned innermost layer polymkeric substance (I-A), intermediate layer polymer (I-B) and intermediate layer polymer (I-B).

The gel containing ratio of multi-ply construction polymkeric substance (I) equals 50% from obtaining better anti-shaping albefaction viewpoint consideration, being preferably more than, more preferably more than or equal to 60%.The gel containing ratio of this moment is to extract processing under the multi-ply construction polymkeric substance (I) with specified amount (extract before quality) refluxes in acetone solvent, with this treatment solution centrifugation, to measuring (extracting the back quality) after the acetone insoluble components drying, the value that calculates by the following method then:

Quality (g) * 100 before gel containing ratio (%)=extraction back quality (g)/extraction

From anti-shaping albefaction consideration, the gel containing ratio is favourable greatly, but considers from easy plasticity, owing to must have a certain amount of above free crowd thing to exist, so the gel containing ratio is preferably smaller or equal to 80%.

The weight average particle diameter of multi-ply construction polymkeric substance (I) is preferably in the scope of 0.03 μ m～0.3 μ m.Consider from the mechanical characteristics of the membranaceous thing of the acrylic resin that obtains (A), be preferably greater than and equal 0.7 μ m, more preferably greater than equaling 0.9 μ m.In addition, consider from the anti-shaping albefaction and the transparency, preferably smaller or equal to 0.15 μ m, preferably smaller or equal to 0.13 μ m.Weight average particle diameter can Yong Da mound Electricity (strain) the light-scattering photometer DLS-700 (trade(brand)name) of system, use dynamic light scattering determination.

Manufacture method as multi-ply construction polymkeric substance (I), though the method for multistep polymerization one by one by emulsion polymerization method is the polymerization process that is fit to the most, but also be not particularly limited, for example, behind emulsion polymerization, can be by adopting the outstanding turbid polymerization that when outermost layer polymkeric substance (I-C) polymerization, is conversion to outstanding turbid polymerization.

In addition, though have no particular limits, but in the occasion of making multi-ply construction polymkeric substance (I) with emulsion polymerization, preferred polymerization process is: after the emulsion supply response device that the monomer component and the water of the innermost layer polymkeric substance (I-A) in the multi-ply construction polymkeric substance (I) is become with the tensio-active agent hybrid modulation carries out polymerization, successively with the monomer of intermediate layer polymer (I-B) and outermost layer polymkeric substance (I-C) or monomer component respectively the supply response device carry out polymerization.

Carry out polymerization by monomer component with the emulsion supply response device that water becomes with the tensio-active agent hybrid modulation with the innermost layer polymkeric substance (I-A) in the multi-ply construction polymkeric substance (I), when particularly making it be dispersed in the acetone, can easily obtain diameter in this dispersion liquid and be 0～50 multi-ply construction polymkeric substance (I) in the multi-ply construction polymkeric substance (I) of every 100g more than or equal to the number of the particle of 55 μ m.In raw material, use the membranaceous thing of acrylic resin (A) of the multi-ply construction polymkeric substance (I) that obtains like this, has the few characteristic of white point number in the film, even particularly when having implemented printing and omitted the intaglio printing of contact print of the wood grain style of the light light color of incident coining, metal style, pitch-dark style etc., the printing of high level is omitted also less and is had in printing, so this is preferred.

The tensio-active agent that uses during as the modulation emulsion, spendable have, the tensio-active agent of negatively charged ion system, positively charged ion system and nonionic system, but the tensio-active agent that with negatively charged ion is especially serves as preferred.Tensio-active agent as negatively charged ion system for example can exemplify out: rosined soap, calcium oleate, sodium stearate, Sodium tetradecanoate, lauroyl are for the phosphate ester salt of the sulfonate of the sulfuric acid of the carboxylate salt of sodium sarcosinate, alkenyl succinic dicalcium etc., Sodium Lauryl Sulphate BP/USP etc., dioctyl sodium sulphosuccinate, Sodium dodecylbenzene sulfonate, alkyl diphenyl base ether sodium disulfonate system etc., Voranol EP 2001 sodium phosphate system etc. etc.Wherein, the phosphate ester salt with Voranol EP 2001 sodium phosphate system etc. is best.As the concrete particle of above-mentioned tensio-active agent, can enumerate as: Sanyo changes into NC-718, Off ォス Off ァノ one Le LS-529, the Off ォス Off ァノ one Le RS-610NA of chemical industry society of eastern nation system, Off ォス Off ァノ one Le RS-620NA, Off ォス Off ァノ one Le RS-650NA, Off ォス Off ァノ one Le RS-660NA, ラテ system Le P-0404, the ラテ system Le P-0405 of Hua Wangshe system, ラテ system Le P-0406, the ラテ system Le P-0407 (above all is trade(brand)names) of industrial society system.

In addition, as the monomer component of modulation innermost layer polymkeric substance (I-A) and the mixing device of the emulsion of water and tensio-active agent hybrid modulation, just like the various forced emulsification devices of the stirrer that possesses stirring rake and homogenizer, homogeneous agitator etc., film emulsifier unit etc.

In addition, as synthetic emulsion, the oil droplet that can use water droplet to be scattered in w/o type among the monomer component, monomer component is scattered in any dispersed texture in the O/W type among the water.But the oil droplet of monomer component is scattered in the O/W type among the water and since the oil droplet of disperse phase directly smaller or equal to 100 μ m, thereby preferred.

On the other hand, the polymerization starter of use can use known initiator when the innermost layer polymkeric substance (I-A), intermediate layer polymer (I-B) and the outermost layer polymkeric substance (I-C) that form to constitute multi-ply construction polymkeric substance (I), its addition means can use be added to water, monomer in mutually the either party or the addition means among two sides.The redox series initiators that particularly preferred initiator has superoxide, azo series initiators or made up by the oxygenant reductive agent.With the redox series initiators serves as preferred, particularly the sulfoxylate series initiators of being made up of ferrous sulfate disodium edta rongalite hydrogen peroxide.

The addition means of polymerization starter can adopt to water, monomer in mutually the either party or two sides among the method for adding.

The addition of polymerization starter is according to decisions such as polymerizing conditions.

As the method that obtains multi-ply construction polymkeric substance (I), particularly preferred method is: will join the ferrous sulfate that contains in the reactor, after the aqueous solution of disodium EDTA and rongalite is warmed up to polymerization temperature, to contain the monomer component of innermost layer polymkeric substance (I-A) of polymerization starter of superoxide etc. and the emulsion supply response device polymerization of water and tensio-active agent hybrid modulation, then, to contain the monomer component supply response device polymerization of intermediate layer polymer (I-B) of the polymerization starter of superoxide etc., then, will contain the monomer component supply response device polymerization of outermost layer polymkeric substance (I-C) of the polymerization starter of superoxide etc.

Temperature of reaction is with the kind of the polymerization starter that uses and consumption and different.Usually be preferably greater than and equal 40 ℃,, in addition,, be more preferably less than and equal 95 ℃ preferably smaller or equal to 120 ℃ more preferably greater than equaling 60 ℃.

The polymer emulsion that contains ideal multi-ply construction polymkeric substance (I) that is obtained by aforesaid method can should adopt the filtration unit that has been equipped with filtering material to handle as required.This filtration treatment be remove in a large amount of emulsion that from polymerization, produces or polymer raw in or the impurity of in polymerization, sneaking into by the outside, this is for obtaining the more preferably method of multi-ply construction polymkeric substance (I).

Filtration unit as the outfit filter material that uses this moment, preferably used the GAF filtering system and the medial surface in the round tube type filtration chamber of ISP Off ィ Le タ one ズピ one テ one ィ one リミテッ De society of the strainer filter of bag shape to be equipped with the round tube type filter material, in filter material, be equipped with the centrifugal separating type filtration unit of agitating wing, or filter material is at the relative oscillating mode filtration unit of doing horizontal circumferential motion and vertical amplitude motion with the filter material face.

Multi-ply construction polymkeric substance (I) can be made by reclaim multi-ply construction polymkeric substance (I) from the polymer emulsion made from aforesaid method.Be not particularly limited for the method that from polymer emulsion, reclaims multi-ply construction polymkeric substance (I), just like the method for saltouing or acid out solidifies or spraying drying, lyophilize etc. are reclaimed with powdery.

Wherein, in the processing of saltouing with metal-salt, preferably the residual metals content in the multi-ply construction polymkeric substance (I) that finally obtains is smaller or equal to 800ppm.Especially, when using the strong metal-salt of magnesium, sodium etc. and the affinity of water as salting-out agent, this remaining metal content can not be reduced to very low, when flooding in ebullient water as the membranaceous thing of the acrylic resin of raw material (A) to show the multi-ply construction polymkeric substance (I) that finally obtains, albinism takes place, and bigger problem is arranged in practicality.And solidify with calcium system, sulfuric acid system, though show tendency preferably, howsoever, in order to give its good resistance to water-whitening, remaining amount of metal all must be smaller or equal to 800ppm, with trace for well.

Among the present invention, can use multi-ply construction polymkeric substance (I) separately, also can use and use the resin combination (III) of following thermoplastic polymer (II).

(thermoplastic polymer (II))

Thermoplastic polymer (II) is a principal constituent with alkyl methacrylate (II-A) unit preferably.Concrete, with contain carbonatoms be 1～4 alkyl methacrylate (II-A) 50～100 quality %, as required alkyl acrylate (II-B) 0～50 quality % and the monomer component of at least a 0～50 quality % of as required copolymerizable (II-A) with two keys, (II-B) monomer (II-C) in addition obtain through polymerization, reducing viscosity (polymkeric substance 1.0g is dissolved in the 100mL chloroform, 25 ℃ of mensuration) is preferred smaller or equal to the polymkeric substance of 0.15L/g.By also improving surface hardness, thermotolerance (light echo when being used for the building materials purposes) with this thermoplastic polymer (II).Therefore, second-order transition temperature is preferably greater than and equals 80 ℃, smaller or equal to 90 ℃.

As the alkyl methacrylate (II-A) that in the monomer component that constitutes thermoplastic polymer (II), contains, just like methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA etc., but be preferred with the methyl methacrylate.These can use separately or two or more is mixed use.

As the alkyl acrylate (II-B) that in the monomer component that constitutes thermoplastic polymer (II), contains as required,, but be preferred with the methyl acrylate just like methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate etc.These can use separately or two or more is mixed use.

Copolymerizable (II-A) with two keys, (II-B) monomer (II-C) in addition as containing as required in the monomer component that constitutes thermoplastic polymer (II) can use known monomer as required.For example, the unsaturated dicarboxylic acid acid anhydride of the vinyl cyanide base system monomer of the aromatic ethenyl compound of vinylbenzene etc., vinyl cyanide etc., MALEIC ANHYDRIDE, itaconic anhydride etc., N-phenyl maleinamide, N-cyclohexyl maleinamide etc.These can use separately, or two or more is mixed use.

The content of the alkyl methacrylate (II-A) that in the monomer component that constitutes thermoplastic polymer (II), contains, consider from the surface hardness and the thermotolerance (light echo when being used for the building materials purposes) of the membranaceous thing of the acrylic resin that obtains (A), be preferably 50～100 quality %, more preferably greater than equaling 80 quality %, smaller or equal to 99.9 quality %.

The content of the alkyl acrylate (II-B) that in the monomer component that constitutes thermoplastic polymer (II), contains as required, from the system film of the membranaceous thing of the acrylic resin that obtains (A), inserts be shaped and the mould internal shaping all can toughness consider, be preferably 0～50 quality %, more preferably greater than equaling 0.1 quality %, smaller or equal to 20 quality %.

Copolymerizable (II-A) with two keys that contains as required in the monomer component that constitutes thermoplastic polymer (II), the content of (II-B) monomer (II-C) in addition are preferably 0～50 quality %.

(polymkeric substance 1.0g is dissolved in the 100mL chloroform to the reducing viscosity of thermoplastic polymer (II), 25 ℃ of mensuration), from the inserts of the membranaceous thing of the acrylic resin that obtains (A) be shaped and the mould internal shaping all can toughness, the consideration of system film, be preferably greater than and equal 0.01L/g, more preferably greater than equaling 0.03L/g.

There is no particular limitation for the manufacture method of thermoplastic polymer (II), can adopt methods such as common outstanding turbid polymerization, emulsion polymerization, block polymerization.

(resin combination (III))

The resin combination (III) that is suitable for the membranaceous thing of acrylic resin of the present invention (A) use contains multi-ply construction polymkeric substance (I) and thermoplastic polymer (II).Preferably form by multi-ply construction polymkeric substance (I) 1～99 quality % and thermoplastic polymer (II) 1～99 quality %.From the anti-shaping albefaction consideration of the membranaceous thing of the acrylic resin that obtains (A), the content of the multi-ply construction polymkeric substance (I) in the resin combination (III) more preferably is more than or equal to 50 quality %, preferably more than or equal to 70 quality %.And the content of the thermoplastic polymer (II) in the resin combination (III) more preferably is smaller or equal to 50 quality %, is preferably less than to equal 30 quality %.

The gel containing ratio of resin combination (III) is from anti-shaping albefaction and system film consideration, preferably in 10～80% scope, better more than or equal to 20%, more preferably greater than equaling 40%.In addition, better smaller or equal to 75%, preferably smaller or equal to 70%.

(resin combination (IV))

Among the present invention, the membranaceous thing of acrylic resin (A) with extinction can be obtained by above-mentioned multi-ply construction polymkeric substance (I) or resin combination (III), but the resin combination (IV) that preferably contains the matting agent of 0.1～40 mass parts by the resin combination (III) with respect to 100 mass parts obtains.By using matting agent, can further alleviate post forming and add the light echo of man-hour because of the membranaceous thing of thermogenetic acrylic resin (A).

As matting agent, can mix and use known various matting agents in organic system, the inorganic system.Matting agent can use separately, also can two or more mix use.Consider that from the transparency preferably the weight average particle diameter that constitutes as the cross-linked resin of principal constituent with PMMA is for example globular micropartical about 2～15 μ m.In addition, consider, be preferably as follows the described polymkeric substance (VI) that contains the polymkeric substance (V) of hydroxyl and/or contain hydroxyl from the transparency, extinction, system film and plasticity.

The polymkeric substance (VI) that use contains the polymkeric substance (V) of hydroxyl and/or contains hydroxyl can not reduce the physical propertys such as extensibility of the membranaceous thing of acrylic resin (A) basically as matting agent.With the polymkeric substance (V) that contains hydroxyl and/or the polymkeric substance (VI) that contains hydroxyl as the membranaceous thing of the acrylic resin of matting agent (A), even if in mould internal shaping of vacuum forming that needs film in advance etc. etc., the fracture of film also can not take place, thereby can use better.

(polymkeric substance (V) that contains hydroxyl)

The polymkeric substance (V) that contains hydroxyl by total amount be 100 mass parts be alkyl methacrylate 10～99 mass parts of 1～13 alkyl and to have carbonatoms be that the monomer component that alkyl acrylate 0～79 mass parts of 1～8 alkyl is formed obtains through copolymerization by having (methyl) vinylformic acid hydroxyalkyl acrylate 1～80 mass parts that carbonatoms is 1～8 alkyl, having carbonatoms.

It as carbonatoms (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl, just like 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, methacrylic acid 2,3-dihydroxyl propyl ester, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 4-hydroxyl butyl ester etc.These can use or mix two or more use separately.In having (methyl) vinylformic acid hydroxyalkyl acrylate that carbonatoms is 1～8 alkyl, be preferred with the 2-hydroxyethyl methacrylate.

The carbonatoms that has in the monomer component that contains the polymkeric substance of hydroxyl (V) is that the content of (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl is in the scope of 1～80 quality %.When having carbonatoms is the content of (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl during more than or equal to 1 quality %, and extinction effect more improves.In addition, be the content of (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl during when having carbonatoms smaller or equal to 80 quality %, the system film of dispersion of particles, film all becomes better.Consider that from extinction the carbonatoms that has in the monomer component that contains the polymkeric substance of hydroxyl (V) is that the content of (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl is preferably greater than and equals 5 quality %, more preferably greater than equaling 20 quality %.In addition, from system film consideration, the carbonatoms that has in the monomer component that contains the polymkeric substance of hydroxyl (V) is that the content of (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl is preferably smaller or equal to 50 quality %.

On the other hand, dress purposes in being used for vehicle is because might residually have perfume compound, hair cosmetic agent etc., so the general requirement built-in material has resistance to chemical reagents on inside components.The membranaceous thing of acrylic resin is considered the viewpoint of the tolerance of these medicines from (A) demonstrated fully, the carbonatoms that has that contains in the monomer component of polymkeric substance (V) of hydroxyl is that the content of (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl is preferably greater than and equals 5 quality %, and preferably smaller or equal to 25 quality %.Take into account and consider extinction and resistance to chemical reagents, the carbonatoms that has that then contains in the monomer component of polymkeric substance (V) of hydroxyl is that the content of (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl is preferably greater than and equals 10 quality %, is more preferably less than to equal 20 quality %.

As having the alkyl methacrylate that carbonatoms is 1～13 alkyl, the rudimentary alkyl methacrylate of methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate etc. is preferably arranged, wherein, the preferable methyl methyl acrylate.These can use separately, or two or more is mixed use.

The carbonatoms that has that contains in the monomer component of polymkeric substance (V) of hydroxyl is that the content range of alkyl methacrylate of 1～13 alkyl is at 10～99 quality %.The carbonatoms that has that contains in the monomer component of polymkeric substance (V) of hydroxyl is that the content of the alkyl methacrylate of 1～13 alkyl is preferably greater than and equals 30 quality %.In addition, the carbonatoms that has that contains in the monomer component of polymkeric substance (V) of hydroxyl is that the content of alkyl methacrylate of 1～13 alkyl is preferably smaller or equal to 90 quality %.

As having the alkyl acrylate that carbonatoms is 1～8 alkyl, the rudimentary alkyl acrylate of methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA etc. is arranged preferably.These can use separately, or two or more is mixed use.

The carbonatoms that has that contains in the monomer component of polymkeric substance (V) of hydroxyl is that the content range of alkyl acrylate of 1～8 alkyl is at 0～79 quality %.The carbonatoms that has that contains in the monomer component of polymkeric substance (V) of hydroxyl is that the content of the alkyl acrylate of 1～8 alkyl is preferably greater than and equals 0.5 quality %, more preferably more than or equal to 5 quality %.In addition, the carbonatoms that has that contains in the monomer component of polymkeric substance (V) of hydroxyl is that the content of alkyl acrylate of 1～8 alkyl is preferably smaller or equal to 40 quality %, more preferably smaller or equal to 25 quality %.

On the other hand, contain the second-order transition temperature of the polymkeric substance (V) of hydroxyl, consider, be preferably greater than and equal 80 ℃, more preferably greater than equaling 90 ℃ from resistance to chemical reagents.At this moment, contain the content that carbonatoms is the alkyl acrylate of 1～8 alkyl that has in the monomer component of polymkeric substance (V) of hydroxyl, be preferably more than 0 quality %, smaller or equal to 5 quality %, more preferably greater than 0 quality %, smaller or equal to 2 quality %.

The intrinsic viscosity that contains the polymkeric substance (V) of hydroxyl is considered from delustring expression power and aesthetic property, preferably in the scope of 0.05～0.3L/g.The intrinsic viscosity of polymkeric substance (V) that contains hydroxyl is more preferably greater than equaling 0.06L/g.In addition, the intrinsic viscosity that contains the polymkeric substance (V) of hydroxyl is more preferably less than and equals 0.15L/g.

In addition, in order to regulate molecular weight to above-mentioned scope, preferably use the polymerization regulator of mercaptan etc.As mercaptan, if any n-octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan etc., there is no particular limitation at this, can use known various mercaptan.

(polymkeric substance (VI) that contains hydroxyl)

The polymkeric substance (VI) that contains hydroxyl by total amount be 100 mass parts by having (methyl) vinylformic acid hydroxyalkyl acrylate 5～80 mass parts that carbonatoms is 1～8 alkyl, having alkyl methacrylate 10～94 mass parts that carbonatoms is 1～13 alkyl and the monomer component that aromatic vinyl monomer 1～80 mass parts is formed obtains through copolymerization.

As having (methyl) vinylformic acid hydroxyalkyl acrylate that carbonatoms is 1～8 alkyl, can enumerate with the polymkeric substance that contains hydroxyl (V) in identical material, its preferred range is also identical.(methyl) vinylformic acid hydroxyalkyl acrylate that has carbonatoms and be 1～8 alkyl can use separately, or two or more is mixed use.

The carbonatoms that has that contains in the monomer component of polymkeric substance (VI) of hydroxyl is that the content range of (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl is at 5～80 quality %.When having carbonatoms is the content of (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl during more than or equal to 5 quality %, and extinction effect is further enhanced.In addition, be the content of (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl during when having carbonatoms smaller or equal to 80 quality %, dispersion of particles becomes better, and the system film of film is also better.Contain the content that carbonatoms is (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl that has in the monomer component of polymkeric substance (VI) of hydroxyl, consider, be preferably greater than and equal 5 quality %, more preferably greater than equaling 10 quality % from extinction.In addition, contain the content that carbonatoms is (methyl) vinylformic acid hydroxyalkyl acrylate of 1～8 alkyl that has in the monomer component of polymkeric substance (VI) of hydroxyl, consider from system film, resistance to chemical reagents,, be more preferably less than and equal 20 quality % preferably smaller or equal to 50 quality %.

As having the alkyl methacrylate that carbonatoms is 1～13 alkyl, can enumerate with the polymkeric substance that contains hydroxyl (V) in identical material, its preferred range is also identical.The alkyl methacrylate that has carbonatoms and be 1～13 alkyl can use separately, or two or more is mixed use.

The carbonatoms that has that contains in the monomer component of polymkeric substance (VI) of hydroxyl is that the content range of alkyl methacrylate of 1～13 alkyl is at 10～94 quality %.The carbonatoms that has that contains in the monomer component of polymkeric substance (VI) of hydroxyl is that the content of the alkyl methacrylate of 1～13 alkyl is preferably greater than and equals 50 quality %.In addition, the carbonatoms that has that contains in the monomer component of polymkeric substance (VI) of hydroxyl is that the content of alkyl methacrylate of 1～13 alkyl is preferably smaller or equal to 90 quality %.

As aromatic vinyl monomer, can use known any.Its object lesson is as vinylbenzene, alpha-methyl styrene etc.These can use separately, or two or more is mixed use.In aromatic vinyl monomer, be preferred with vinylbenzene.By using aromatic vinyl monomer, can further improve the resistance to chemical reagents of membranoid substance.

The content range that contains the aromatic vinyl monomer in the monomer component of polymkeric substance (VI) of hydroxyl is at 1～80 quality %.The content that contains the aromatic vinyl monomer in the monomer component of polymkeric substance (VI) of hydroxyl is preferably greater than and equals 5 quality %.In addition, the content that contains the aromatic vinyl monomer in the monomer component of polymkeric substance (VI) of hydroxyl is preferably smaller or equal to 40 quality %, is more preferably less than to equal 20 quality %.

The second-order transition temperature that contains the polymkeric substance (VI) of hydroxyl considers from resistance to chemical reagents, is preferably greater than to equal 80 ℃, more preferably greater than equaling 90 ℃.

The intrinsic viscosity that contains the polymkeric substance (VI) of hydroxyl is considered from delustring expression power and aesthetic property, preferably in the scope of 0.05～0.3L/g.The intrinsic viscosity of polymkeric substance (VI) that contains hydroxyl is more preferably greater than equaling 0.06L/g.In addition, the intrinsic viscosity that contains the polymkeric substance (VI) of hydroxyl is more preferably less than and equals 0.15L/g.

As the polymkeric substance that contains hydroxyl (V) with contain the manufacture method of the polymkeric substance (VI) of hydroxyl, there is no particular limitation, but preferred outstanding turbid polymerization, the emulsion polymerization etc. of using.

As outstanding turbid polymeric initiator, can use known various initiator.Its object lesson just like, organo-peroxide, azo-compound etc.These can use separately, or two or more is mixed use.

The addition of initiator is according to polymerizing condition etc. and suitably decision.

As outstanding turbid stablizer, can use known various stablizer.Its object lesson just like, organic colloid polymer substance, mineral colloid polymer substance, inorganic fine particles, and the combination of they and tensio-active agent etc.These can use separately, or two or more is mixed use.

The addition of outstanding turbid stablizer is according to polymerizing condition etc. and suitably decision.

Outstanding turbid polymerization is together carried out the outstanding turbid polymerization of water-based of monomer class with polymerization starter normally in the presence of outstanding turbid stablizer.In addition, also can be dissolved in the monomer and using, hang turbid polymerization dissolving in polymer of monomers.

In the resin combination (IV), with respect to the multi-ply construction polymkeric substance (I) or the resin combination (III) of 100 mass parts, the preferably above-mentioned content of matting agent that contains the polymkeric substance (V) of hydroxyl or contain the polymkeric substance (VI) etc. of hydroxyl is 0.1～40 mass parts.

The content of the matting agent in resin combination (IV) for the multi-ply construction polymkeric substance (I) or resin combination (III) of 100 mass parts, when 0.1 mass parts or its are above, shows better extinction effect.The content of the matting agent in the resin combination (IV) is considered from obtaining good extinction, for the multi-ply construction polymkeric substance (I) or resin combination (III) of 100 mass parts, more preferably more than or equal to 2 mass parts, more preferably greater than equaling 5 mass parts.Preferably smaller or equal to 40 mass parts, more preferably smaller or equal to 20 mass parts, preferably smaller or equal to 15 mass parts.

The gel containing ratio of resin combination of the present invention (IV) is from anti-shaping albefaction and film consideration, preferably 10～80%.More preferably greater than equaling 20%, most preferably more than or equal to 40%.In addition, be more preferably less than and equal 75%, most preferably smaller or equal to 70%.

Of the present inventionly satisfy anti-shaping albefaction and surface hardness, the membranaceous thing of the acrylic resin of the thermotolerance and the transparency or extinction (A) is by above-mentioned multi-ply construction polymkeric substance (I) or multi-ply construction polymkeric substance (I) and the resin combination (III) that is thermoplastic polymer (II) formation of main component with the alkyl methacrylate, perhaps the resin combination (IV) that contains the matting agent of 0.1～40 mass parts with respect to the multi-ply construction polymkeric substance (I) or the resin combination (III) of 100 mass parts obtains.

Among the present invention, above-mentioned thermoplastic polymer (II) can also use reducing viscosity (polymkeric substance 1.0g is dissolved in the 100mL chloroform, 25 ℃ of mensuration) to surpass the thermoplastic polymer (VII) of 0.15L/g.As thermoplastic polymer (VII), concrete have by methyl methacrylate 50～100 quality % and can obtain with other monomer 0～50 quality % polymerization with two keys of its copolymerization.Can with other monomer of its copolymerization with two keys can monomer or mix and use two or more.Thermoplastic polymer (VII) be film the system film, use and to contain the polymkeric substance (V) of hydroxyl or to contain the composition of further optimizing extinction under the occasion of polymkeric substance (VI) of hydroxyl.

The resin combination multi-ply construction polymkeric substance (I) that divides with respect to 100 quality or (III), thermoplastic polymer (VII) preferably surpassing 0 mass parts, uses in the scope smaller or equal to 20 mass parts.From the system film consideration of film, more preferably in the scope of 1～10 mass parts.

The membranaceous thing of acrylic resin of the present invention (A), as required, also can contain general Synergist S-421 95, for example, stablizer, lubrication prescription, processing aid, softening agent, shock-resistant dose, whipping agent, weighting agent, antiseptic-germicide, anti-Fungicide, remover, static inhibitor, tinting material, UV light absorber, photostabilizer etc.

Consider the protection of base material, preferably add UV light absorber to give its weathering resistance.As UV light absorber, can use knownly, also can use the copolymerization type.The molecular weight of the UV light absorber of using is preferably greater than and equals 300, more preferably greater than equaling 400.Use molecular weight more than or equal to 300 UV light absorber, the mold fouling that causes because of the volatilization of UV light absorber in the time of can preventing in ejection shaping mould, to carry out vacuum forming or press empty shaping the etc.In addition, generally speaking, the UV light absorber that molecular weight is high, secular the oozing out after being processed into membrane stage is difficult for taking place, and the time that the UV absorbing properties of also low than molecular weight UV light absorber keeps is long.And, the molecular weight of UV light absorber more than or equal to 300 situation under, the membranaceous thing of acrylic resin (A) is from being expressed into by the T mould in cooling roller cooling period, UV light absorber evaporable amount is few.Like this, the amount because of residual UV light absorber enough can embody good performance.In addition, the evaporable UV light absorber is recrystallize and growth on the exhaust hood that the suspention T template strand that is positioned at T mould top and exhaust are used, and can drop on the film very soon, and it is also few to produce the such problem of apparent defective.

The kind of UV light absorber is not particularly limited, but especially preferably uses molecular weight more than or equal to 400 benzotriazole system or the molecular weight UV light absorber more than or equal to 400 triazine system.The former object lesson has: the trade(brand)name that チバスペシャリティケミカ Le ズ society produces: the trade(brand)name that チヌ PVC Application 234, Xu Dianhuagongyeshe produce: ァデカスタ Block LA-31.The trade(brand)name that the latter's object lesson has チバスペシャリティケミカ Le ズ society to produce: チヌ PVC Application 1577 etc.

When the membranaceous thing of acrylic resin of the present invention (A) when being used for vehicular applications, must have the anti-hair cosmetic agent of various automakers' vehicle specification and the characteristic of anti-perfume compound.Consider these characteristics, preferably use fusing point smaller or equal to 180 ℃ UV light absorber.Such UV light absorber is when when the membranaceous thing of acrylic resin (A) is gone up coating hair cosmetic agent and perfume compound, UV light absorber is difficult to crystallization, particularly preferably is the trade(brand)name that チバスペシャリティケミカ Le ズ society produces: チヌ PVC Application 234, チヌ PVC Application 329, チヌ PVC Application 1577.By using such UV light absorber, when additional hair cosmetic agent and perfume compound, can cause appearance change hardly, therefore, industrial utilization is worth very high.

The addition of UV light absorber is preferably in the scope of 0.1～10 mass parts.Consider that from the viewpoint of weathering resistance improvement addition is 0.5 mass parts more preferably, most preferably is 1 mass parts.Roller pollution, resistance to chemical reagents, the transparency consider that addition is preferably smaller or equal to 5 mass parts, most preferably is smaller or equal to 3 mass parts during from the system film.

In addition, as photostabilizer, can use known product, but in order not only to improve the photostabilization of the membranaceous thing of acrylic resin (A), also further improve its resistance to chemical reagents, then preferably using hindered amine is the free radical scavenger of photostabilizer etc.For example, the appearance change in the time of can significantly improving hair cosmetic agent and adhere to and have very high industrial utilization and be worth.

Hindered amine is that the addition of photostabilizer is preferably in the scope of 0.01～5 mass parts.Consider that from the viewpoint of photostabilization, resistance to chemical reagents improvement addition is preferably 0.1 mass parts, more preferably greater than equaling 0.2 mass parts.Roller pollutes when considering the system film, and addition is preferably smaller or equal to 2 mass parts, preferably smaller or equal to 1 mass parts.

By being photostabilizer also, can obtain being particularly suitable for the membranaceous thing of acrylic resin (A) of vehicular applications with these specific UV light absorber and hindered amine.

Especially, in resin combination (IV), use contains the polymkeric substance (V) of hydroxyl and/or contains the occasion of the polymkeric substance (VI) of hydroxyl as matting agent, with respect to the resin combination (IV) of 100 mass parts, preferably contains the phosphorus series compound of 0.01～3 mass parts.When 0.01 mass parts or its were above, extinction was better with respect to the resin combination (IV) of 100 mass parts for the content of phosphorus series compound.In addition, when 3 mass parts or its were following, the roller during from the system film polluted the content of phosphorus series compound, economic viewpoint considers it is preferred with respect to the resin combination (IV) of 100 mass parts.The content of phosphorus series compound is better when 0.1 mass parts or its are above with respect to the resin combination (IV) of 100 mass parts.In addition, the content of phosphorus series compound is better when 1 mass parts or its are following with respect to the resin combination (IV) of 100 mass parts.

As phosphorus series compound, just like the phosphorous acid ester based compound of trialkyl phosphite, phosphorous acid alkyl aryl ester, aryl phosphite, phosphorous acid nonyl phenylester, phosphorous acid alkyl nonyl phenylester etc.; The phosphoric acid ester based compound of trialkylphosphate, three polyoxy vinyl alkyl ether phosphates, dialkyl phosphate and metal-salt, two polyoxy vinyl alkyl ether phosphates and metal-salt, alkyl phosphate and metal-salt thereof, Voranol EP 2001 phosphoric acid ester and metal-salt thereof etc.; The phosphnate based compound of dialkyl group alkyl phosphnate, alkyl-alkyl phosphnate and metal-salt thereof etc. etc.As phosphorus series compound, consider preferred phosphorous acid based compound from the viewpoint of performance extinction.And, in the phosphorous acid based compound, consider from the viewpoint of performance extinction, be more preferably at the phosphorous acid primitive period and enclose no big substituent material.In addition, consider preferred trialkyl phosphite from the viewpoint of hydrolytic resistance (roller during the system film pollutes).

Addition means as above-mentioned Synergist S-421 95, there is the composition that will contain multi-ply construction polymkeric substance (I) or resin combination (III) or resin combination (IV) together to supply with the method for the forcing machine that is used to form the membranaceous thing of acrylic resin (A), and will have added the mixture of ingredients mixing blended method in various mixing rolls that contains multi-ply construction polymkeric substance (I) or resin combination (III) or resin combination (IV) of Synergist S-421 95 in advance.Mixing roll as using in one method of back has single shaft mixing roll, twin shaft mixing roll, Banbury, roll-type mixing roll etc. usually.

The membranaceous thing of＜acrylic resin (A) 〉

The membranaceous thing of acrylic resin of the present invention (A) is under the condition of in the early stage 23 ℃ of chuck spacing 25mm, speed 50mm/min, temperature, after making the chuck spacing of terminal point be the tension test of 33mm to the test film of wide 20mm, be smaller or equal to 30% with difference according to the value of test film before the determination of test method test of JIS K7136 (measuring method of turbidity) according to the value of this test film of determination of test method of JIS K7136 (measuring method of turbidity).This is poor preferably smaller or equal to 10%, is more preferably less than to equal 5%.The membranaceous thing of acrylic resin (A) and contain its acrylic resin stack membrane, light solidified acrylic resin film or sheet and stack membrane or sheet caused in the shaping albefaction of carrying out that inserts is shaped or take place during the mould internal shaping above-mentioned poor.In addition, in the occasion of using as building materials, cold district carry out V-arrangement cutting processing and circumvolution add the shaping albefaction that produces man-hour also caused above-mentioned poor.

Use the occasion of above-mentioned difference smaller or equal to the membranaceous thing of 30% acrylic resin (A), the shaping albefaction that takes place during owing to inserts shaping or mould internal shaping is not obvious, thereby can obtain the laminated product that printed patterns does not disappear and can not influence outward appearance.In addition, when containing the stack membrane of the membranaceous thing of acrylic resin (A) or sheet and being used for building materials, to add the shaping albefaction that produces man-hour not obvious owing to carry out V-arrangement cutting processing and circumvolution at cold district, thereby can obtain the laminated product that printed patterns does not disappear and can not influence outward appearance.

In addition, under the condition that preferred chuck spacing 25mm, speed 50mm/min, temperature in the early stage is 23 ℃, after making the chuck spacing of terminal point be the tension test of 33mm to the test film of wide 20mm, before the tension test with test after test film according to the determination of test method test of JIS K7136 (measuring method of turbidity) before the difference of value of test film be preferably smaller or equal to 10%.Difference under this condition was smaller or equal to 10% o'clock, owing to compare with common wood grain metal pattern, the part of albefaction is in the printed patterns of tangible pitch-dark style, and the shaping albefaction is also not obvious, so industrial utilization is worth high.Under this condition, more preferably smaller or equal to 5%, be preferably smaller or equal to 1% with the difference of the value of above-mentioned determination of test method.

Have, the pencil hardness of the membranaceous thing of acrylic resin of the present invention (A) (measuring based on JIS K5400) is more than or equal to 2B again.More preferably, most preferably be more than or equal to F more than or equal to HB.

Use pencil hardness more than or equal to the membranaceous thing of the acrylic resin of 2B (A), in the process of carrying out inserts shaping or mould internal shaping, the membranaceous thing of acrylic resin (A) and acrylic resin stack membrane, light solidified acrylic resin film or the sheet and stack membrane or the sheet that contain it are felt bad damage, and the crocking resistance of molding is also good.

Be used for the occasion of vehicular applications, the pencil hardness of the membranaceous thing of acrylic resin of the present invention (A) is preferably more than and equals HB.Use pencil hardness to can be used for a protected decoration, frontend panels, various automobile-used materials such as window conversion panel, air cell covering automatically more than or equal to membranaceous thing of the acrylic resin of HB (A) and acrylic resin stack membrane, light solidified acrylic resin film or the sheet and the laminated product of stack membrane or sheet that contain it.This from extended use industrial be very useful.

Have again, when pencil hardness during more than or equal to F, promptly use shaggy cloth scratch such as gauze also not have tangible scar, owing to have the scuff resistance energy in the practicality that is equal to the molding that uses pencil hardness more than or equal to the membranaceous thing of the acrylic resin of 2H (A), so its industrial utilization is worth very high.

Use pencil hardness of the present invention more than or equal to the membranaceous thing of the acrylic resin of 2B (A), can form the acrylic resin stack membrane.Acrylic resin stack membrane of the present invention like this, as described later, be positioned at when the membranaceous thing of acrylic resin (A) the acrylic resin stack membrane top layer situation from needless to say, even have the acrylate resin layer of pencil hardness more than or equal to 2H (A '-the top layer that a) is positioned at the acrylic resin stack membrane (promptly, the upper strata of the membranaceous thing of acrylic resin (A)), also difficulty reduces its surface hardness.Use this acrylic resin stack membrane, be difficult in and carry out damaging in inserts shaping or the mould internal shaping engineering, and the scuff resistance of molding is also good.HB or more than it preferably, more preferably F or more than it.

Use pencil hardness of the present invention more than or equal to the membranaceous thing of the acrylic resin of 2B (A), can form light solidified acrylic resin film or sheet.Like this light solidified acrylic resin film of the present invention or sheet as described later, are difficult in and carry out damaging in inserts shaping or the mould internal shaping engineering.In addition, because that the light solidified acrylic resin film behind the photocuring or the pencil hardness of sheet are subjected to the influence of pencil hardness of the membranaceous thing of base material acrylic resin (A) is very big, so the hardness of the membranaceous thing of acrylic resin (A) must be more than or equal to 2B.HB or more than it preferably, more preferably F or more than it.

Use pencil hardness of the present invention more than or equal to the membranaceous thing of the acrylic resin of 2B (A), can form as building materials with stack membrane or sheet.Building materials are felt bad damage with stack membrane or sheet in V-arrangement cutting processing and circumvolution processing, and the scuff resistance of molding is also good.

When being used for the building materials purposes, the pencil hardness of the membranaceous thing of acrylic resin of the present invention (A) is HB or more than it preferably.When the pencil hardness of the membranaceous thing of acrylic resin (A) is HB or its when above, use have the membranaceous thing of acrylic resin (A) building materials with the molding of stack membrane or sheet applicable to various building materials portion's materials such as the peristome sash of window etc., entry sliding gate, gateway doors.This viewpoint from extended use is considered, industrial very useful.

When using the membranaceous thing of acrylic resin of the present invention (A) to use, be preferably in 2% or below it according to the turbidity of the membranaceous thing of acrylic resin (A) of the determination of test method of JIS K7136 as the substitute of Clear coating.The membranaceous thing of such acrylic resin (A) is even at the drawing style layer of the blackout of pitch-dark tone etc., and the membranaceous thing of acrylic resin (A) also can not be affected, drawing style layer distinctness, true performance, thereby be preferred.The membranaceous thing of such acrylic resin (A) demonstrates the outward appearance identical with Clear coating.Its turbidity is more preferably 1% or below it, more preferably 0.5% or below it, is preferably in 0.4% or below it.

In addition, the membranaceous thing of acrylic resin of the present invention (A) with the drawing style layer combination of metal style etc. the time, preferably its at least 60 ° of surface glosses of one side smaller or equal to 100%.This surface gloss is more preferably smaller or equal to 50%, preferably smaller or equal to 20%.At least Yi Mian 60 ° of surface glosses have good aesthetic property and extinction smaller or equal to the membranaceous thing of 100% acrylic resin (A).

The heat-drawn wire of the membranaceous thing of acrylic resin of the present invention (A) (measuring based on ASTM D648) is more preferably greater than equaling 80 ℃.Heat-drawn wire is during more than or equal to 80 ℃, and when at high temperature exposing for a long time, the membranaceous thing of acrylic resin (A) surface is because no albefaction, the muddy appearance, so industrial utilization is worth height.In addition, be used for vehicular applications, when the heat-drawn wire of the membranaceous thing of acrylic resin (A) during more than or equal to 80 ℃, use the membranaceous thing of acrylic resin (A) and contain its acrylic resin stack membrane, light solidified acrylic resin film or sheet and the lamination molding of stack membrane or sheet can be used for before control panel be subjected to sunlight point-blank part in waiting for bus.This viewpoint from extended use considers that heat-drawn wire is more preferably greater than equaling 90 ℃.The mensuration of above-mentioned heat-drawn wire be with the raw material granule of the membranaceous thing of acrylic resin (A) behind injection molding, carry out carrying out on the annealed heat-drawn wire determination test sheet in 4 hours at 60 ℃, the heat-drawn wire of mensuration is identical with the heat-drawn wire of the membranaceous thing of acrylic resin (A) usually.

Smaller or equal to the occasion of the membranaceous thing of 100% acrylic resin (A), if heat-drawn wire is more than or equal to 80 ℃, when then at high temperature exposing for a long time, the extinction on the membranaceous thing of acrylic resin (A) surface changes little in 60 ° of surface glosses of one side at least.Therefore, heat-drawn wire is more than or equal to its industrial utility value height of the membranaceous thing of 80 ℃ acrylic resin (A).If heat-drawn wire more than or equal to 90 ℃, is subjected to sunlight point-blank part in then waiting for bus applicable to preceding control panel.This viewpoint from extended use considers that heat-drawn wire is more preferably greater than equaling 90 ℃.

In addition, in the occasion as light solidified acrylic resin film or sheet, the heat-drawn wire of the membranaceous thing of acrylic resin of the present invention (A) (measuring based on ASTM D648) is more preferably greater than equaling 80 ℃.Heat-drawn wire is during more than or equal to 80 ℃, after Photocurable resin composition being coated on the film, remove in the drying process that desolvates, Photocurable resin composition and acrylic resin film stretch and become difficult, scuff resistance after solidifying, the reduction of surface hardness can be suppressed to minimum, owing to can improve drying temperature, so can carry out effective dry with the drying plant of minimum.And, owing to can improve drying temperature, can be reduced in remaining organic solvent amount in light-cured resin described later (Z) layer, therefore be difficult to the variety of issue that generation is caused by remaining solvent.The heat-drawn wire of the membranaceous thing of acrylic resin (A) most preferably is more than or equal to 90 ℃ more preferably more than or equal to 85 ℃.

In addition, use to have the stack membrane of the membranaceous thing of acrylic resin (A) or the occasion that sheet is used as building materials, the heat-drawn wire of the membranaceous thing of acrylic resin (A) (measuring based on ASTM D648) is more preferably greater than equaling 80 ℃.Heat-drawn wire is during more than or equal to 80 ℃, pasting by circumvolution processing etc. on the surface of various base materials and to add man-hour, or when finished various materials being used for for a long time buildings after the construction of dwelling house etc., can obtain difficult stack membrane or the sheet that color and luster such as light echo changes, therefore the utility value height of industry of taking place.In addition, in the building materials purposes, the situation that practical use often has the surface temperature of stack membrane particularly or sheet to uprise.Consider that from expansions such as the outer dress of door material, window frame material, outer wall material, fence, roof, roof sun bath plate, balcony, external door etc., accurate outer dress purposes heat-drawn wire more than or equal to 90 ℃ better.

As the manufacture method of the membranaceous thing of acrylic resin (A) that uses in the present invention, just like the melting extrusion molding of melting casting method, T modulus method, plavini etc., prolong known method such as platen press.

When using the T modulus method to carry out the shaping of the membranaceous thing of acrylic resin (A), if seize the system film on both sides by the arms with several rollers or the band that are selected from metallic roll, nonmetal roller and metal strip, the surface smoothing raising of the membranaceous thing of the acrylic resin that then obtains (A), the printing that can be suppressed at when making printing treatment on the membranaceous thing of acrylic resin (A) is omitted.As metallic roll, metal minute surface touch roll is for example arranged; In No. 2808251 communique of Japanese Patent (reference 29) or the WO97/28950 communique (reference 30) metallic sheath (metal made membrane pipe) of record and be shaped with roller constitute to overlap roller that the mode that contacts uses etc.In addition, as nonmetal roller, touch roll of silicone rubber etc. etc. can be arranged.Have again,, metal continuous band etc. can be arranged as metal strip.Also metallic roll, nonmetal roller and metal strip can be used in combination.

As mentioned above, several rollers that are selected from metallic roll, nonmetal roller and metal strip or with on seize on both sides by the arms the system film method in, preferably, the composition (hereinafter referred to as " acrylic acid resin composition ") that contains multi-ply construction polymkeric substance (I) or resin combination (III) or resin combination (IV) after melting is extruded is seized on both sides by the arms with the state that does not in fact have dumping tower tray (pitch), does not substantially roll and carries out the system film that face duplicates down.Under the situation that does not form dumping tower tray (pitch) system film, owing to carrying out face under not rolling, duplicates the acrylic acid resin composition in process of cooling, and therefore the percent thermal shrinkage of the membranaceous thing of acrylic resin obtained by this method (A) also can reduce.

Carrying out the occasion that melting is extruded with T modulus method etc., while preferably make the acrylic resin of melting state filter 200 orders or the filter mesh more than it is extruded.

In addition, possess the occasion of extinction at the membranaceous thing of acrylic resin (A), after acrylic acid resin composition forms the film shape with the melting extrusion molding of T modulus method etc., preferred immediately with mirror roller and rubber rollers or be with the roller of fold to seize the system film on both sides by the arms.Especially, seize the method for system film with mirror roller and rubber rollers on both sides by the arms and compare, owing to the relatively film of thin thickness that can obtain about 50 μ m, so more preferred with the method for seizing the system film with the roller of mirror roller and band fold on both sides by the arms.

In addition, in prolonging platen press, a side of seizing two mirror rollers of film to the end on both sides by the arms can replace the system film with the roller of rubber rollers or band fold.Perhaps, also can in a single day form the film shape, and then the membranaceous thing of acrylic resin (A) is heated to more than the second-order transition temperature, seize the system film on both sides by the arms with the roller of mirror roller and rubber rollers or band fold with known method.

As mirror roller, can use known various mirror roller.Wherein, the roller of the surface roughness of chromium plating processing smaller or equal to 0.5S carried out in preferred use.

When making film, if the temperature height of mirror roller, then the following of the roller of rubber rollers or band fold is better, show better extinction with the face that joins of roller of rubber rollers or band fold, equally, mirror roller is better to the minute surface replicability of the membranaceous thing of acrylic resin (A), and the smoothness of the face that joins with mirror roller increases, printing is omitted and is tending towards more alleviating.But if the temperature of mirror roller is too high, then the minute surface separability of the membranaceous thing of acrylic resin (A) reduces, and curling round the roll takes place the membranaceous thing of acrylic resin (A).In addition, if the temperature of mirror roller is low excessively, then mirror roller reduces to the minute surface replicability of the membranaceous thing of acrylic resin (A), is difficult to obtain printing the effect that omission fully alleviates, and film is wrinkling easily.Though the temperature of cooling roller is relevant with the second-order transition temperature of acrylic resin, preferably be adjusted to 20～140 ℃ scope, more preferably greater than equaling 50 ℃, be preferably greater than especially to equal 60 ℃.In addition, the temperature of cooling roller is more preferably less than and equals 120 ℃, especially preferably smaller or equal to 100 ℃.

As rubber rollers, can use known various mirror roller.Wherein, consider, preferably use silicone rubber from thermotolerance.In addition, consider preferred salic silicone rubber from obtaining good extinction.The membranaceous thing of acrylic resin (A) is owing to the purposes difference, and the delustring aesthetic property of its expectation is also different, determines with purposes is different so add the granularity of the aluminum oxide in the silicone rubber to.Concrete, can use and add the silicon system silicone rubber etc. that mean particle size is the aluminum oxide 50 quality % of 40 μ m.

In addition, also can replace the silicone rubber roller with the roller of band fold.As the roller of band fold, can use the roller of known various band folds.

In addition, carrying out the occasion that melting is extruded, on one side acrylic resin is used more than or equal to 200 purpose strainer filterings, the way that extrude on one side, it is preferred that the FE (white point) from reduce film considers.

The value of poor (absolute value of (with 60 ° of surface glosses of the face of mirror roller side contacts)-60 ° of surface glosses of the face of mirror roller side contacts (not with)) of the surface gloss of the membranaceous thing of acrylic resin (A) that obtains with aforesaid method can be passed through the kind of nonspecular surface roller of roller etc. of film forming condition, rubber rollers and band fold and controlled.This surface gloss poor, from printing omit property, extinction is considered, preferably 5% or more than it.And surface gloss poor is more preferably 10% or more than it, particularly preferably in 15% or more than it.

Owing to duplicate, can significantly reduce the protrusion of surface that causes because of the foreign matter that prints the omission generation at face with the mirror roller side contacts.Therefore, when the face with the mirror roller side contacts duplicates, can significantly reduce its printing and omit.

On the other hand, or not do not consider from the outward appearance of aesthetic property, delustring with 60 ° of surface glosses of the face of mirror roller side contacts, preferably smaller or equal to 100%, and, be not more preferably less than and equal 50% with 60 ° of surface glosses of the face of mirror roller side contacts.

In addition, relatively have in the film with the surface luster of degree, the heat-drawn wire height of the membranaceous thing of acrylic resin (A), then inserts is shaped or the light echo during the mould internal shaping alleviates.Therefore, the light echo consideration during from inserts shaping or mould internal shaping, the heat-drawn wire height of the membranaceous thing of acrylic resin (A) is preferred.From the following of the roller of aforesaid separability, rubber rollers and band fold, light echo consideration when being shaped by minute surface, the heat-drawn wire of the membranaceous thing of acrylic resin (A) is preferably in 85 ℃～105 ℃ scope, more preferably greater than equaling 90 ℃, and smaller or equal to 100 ℃.

The thickness of the membranaceous thing of acrylic resin of the present invention (A) is preferably 10～500 μ m.When the thickness of the membranaceous thing of acrylic resin (A) during, can obtain being fit to that inserts is shaped or the rigidity of mould internal shaping, and more stably make film smaller or equal to 500 μ m.In addition,, not only can give the protectiveness of base material, and can give the molding that obtains with sufficient depth perception when the thickness of the membranaceous thing of acrylic resin (A) during more than or equal to 10 μ m.The more thickness of the membranaceous thing of acrylic resin (A) is preferably greater than and equals 30 μ m, most preferably more than or equal to 50 μ m.And the thickness of the membranaceous thing of acrylic resin (A) is more preferably less than and equals 300 μ m, most preferably smaller or equal to 200 μ m.

For on molding, forming enough the filming of thickness by coating, must be through the coating that repeats of ten several.At this moment, the cost of cost is higher and productivity is not high.For this reason, lamination molding of the present invention can easily form very thick filming because the membranaceous thing of acrylic resin (A) self formation is filmed, so industrial utilization is worth height.

＜acrylic resin stack membrane 〉

Acrylic resin stack membrane of the present invention is the stack membrane with membranaceous thing of acrylic resin of the present invention (A), can also be the stack membrane that further has the membranaceous thing of other acrylic resin (A ') or the membranaceous thing of fluoro-resin (A ").

As acrylic resin stack membrane of the present invention, when on base material, using the membranaceous thing of acrylic resin (A), when on the top layer, using the membranaceous thing of acrylic resin (A '), the preferred acrylic resin membranaceous thing higher (A ') that use than the surface hardness of the membranaceous thing of acrylic resin (A).Particularly, preferably use pencil hardness (measuring) based on JIS K5400 for 2H or the membranaceous thing of acrylic resin more than it (A '-a).The membranaceous thing of the acrylic resin of the application of the invention (A) is as base material, use pencil hardness as 2H or the membranaceous thing of the acrylic resin more than it (A '-a) as the top layer, owing to compare with existing oneself known acrylic resin stack membrane, can obtain the acrylic resin stack membrane that anti-shaping albefaction, surface hardness (scuff resistance), thermotolerance take into account, be preferred therefore.

In addition, the membranaceous thing of acrylic resin of this moment (A '-a) also can be to be the thermoplastic resin formation of principal constituent with the alkyl methacrylate, in addition, also can be that the resin combination that gets forms by mix the polymkeric substance that contains rubber in this thermoplastic resin, this is not particularly limited.When the acrylic resin stack membrane being carried out inserts shaping or mould internal shaping, the membranaceous thing of acrylic resin (A '-a) stress is slowly insufficient, from avoid chapping, disrumpent feelings, laminate portion glass etc., preferably form by in the thermoplastic resin that with the alkyl methacrylate is principal constituent, mixing the resin combination that the polymkeric substance that contains rubber on a small quantity gets.

In addition, if pencil hardness is more than or equal to 2H, then use the different membranaceous thing of acrylic resin (A) of the content of multi-ply construction polymkeric substance (I) as the membranaceous thing of acrylic resin (A '-a) for good.

In addition, as preferred resin combination, can exemplify out and contain following (i) and (ii).

(i) with the alkyl methacrylate be the thermoplastic resin of principal constituent;

By alkyl methacrylate 50～100 quality %, alkyl acrylate 0～50 quality %, the thermoplastic resin that can constitute with other vinyl monomer 0～49 quality % of their copolymerizations.

The polymkeric substance that (ii) contains rubber.

(ii-a) alkyl acrylate be elastomeric polymer in the presence of, be that monomer carries out graft polymerization and forms rigid polymer with alkyl methacrylate, the median size with 2 layers of structure of Gou Chenging is less than the polymkeric substance that contains rubber of 0.2 μ m thus.

(ii-b) by Tg more than or equal to 0 ℃, the polymkeric substance that contains rubber of 0.2～0.4 μ m of the median size with 3 layers of structure that the outermost layer polymkeric substance that the middle layer elastomeric polymer that the innermost layer polymkeric substance that forms less than the monomer polymerization of 25 ℃ alkyl methacrylates and alkyl acrylate, Tg form less than the monomer polymerization of 0 ℃ alkyl acrylate, the monomer of alkyl methacrylate form constitutes.

More specifically, can enumerate following resin combination.

Zero spy opens the acrylic resin film resin combination of 2002-80678 communique record:

Contain thermoplastic resin (i) 20～94.5 mass parts and contain polymkeric substance (ii-a) 5.5～80 mass parts of rubber, the amount that contains alkyl acrylate in the polymkeric substance (ii-a) of rubber and be elastomeric polymer is the resin combination that 5～72 mass parts (composition (i) and composition (ii) add up to 100 quality powder) constitute.

Zero spy opens the acrylic resin film resin combination of 2002-80679 communique record:

Contain thermoplastic resin (i) 75～94.5 mass parts and contain polymkeric substance (ii-b) 5.5～25 mass parts of rubber, the amount that contains the elastomeric polymer that is made of innermost layer polymkeric substance and middle layer elastomeric polymer in the polymkeric substance (ii-b) of rubber is the resin combination that 5～18 mass parts (composition (i) and composition (ii) add up to 100 quality powder) constitute.

The membranaceous thing of the acrylic resin that uses among the present invention (A '-a), as required, can contain general Synergist S-421 95, for example, stablizer, lubrication prescription, processing aid, softening agent, shock-resistant dose, whipping agent, weighting agent, antiseptic-germicide, anti-Fungicide, remover, static inhibitor, tinting material, matting agent, UV light absorber, photostabilizer etc.

Especially, consider the protection of the color style, tinting material etc. of base material, printing etc., preferably add UV light absorber to give its weathering resistance.The molecular weight of the UV light absorber of using is preferably greater than and equals 300, more preferably greater than equaling 400.Use molecular weight more than or equal to 300 UV light absorber, the mold fouling that causes because of the volatilization of UV light absorber in the time of can preventing in ejection shaping mould, to carry out vacuum forming or press empty shaping the etc.In addition, generally speaking, the UV light absorber that molecular weight is high, secular the oozing out after being processed into membrane stage is difficult for taking place, and the time that the UV absorbing properties of also low than molecular weight UV light absorber keeps is long.

Addition means as above-mentioned Synergist S-421 95, have with form the membranaceous thing of acrylic resin of the present invention (A '-a) the membranaceous thing of acrylic resin (A '-a) together supplies with the method for forcing machine with raw material, and with the membranaceous thing of the acrylic resin that has added Synergist S-421 95 in advance (A '-a) mixture mixing blended method in various mixing rolls of raw material.Mixing roll as using in one method of back has single shaft mixing roll, twin shaft mixing roll, Banbury, roll-type mixing roll etc. usually.

And, in case of necessity, can adopt known method reduce the membranaceous thing of acrylic resin of the present invention (A '-a) gloss.The concrete method that adopts mixing inorganic filler or bridging property polymer particle, the monomer methods that copolymerization contains epoxy group(ing), use the straight chain polymer with hydroxyl method, carry out relief method for processing etc.In addition, also can use to the membranaceous thing of acrylic resin of the present invention (A '-a) carry out painted method for processing.

At this moment, the thickness of the membranaceous thing of acrylic resin (A) in the acrylic resin stack membrane of the present invention is preferably 10～500 μ m, more preferably more than or equal to 30 μ m, smaller or equal to 200 μ m.When thickness during smaller or equal to 500 μ m, the acrylic resin stack membrane that finally obtains has that suitable inserts is shaped or the rigidity of mould internal shaping, and is configured as at the membranaceous thing of acrylic resin (A) and can more stably makes film when membranaceous, is preferred therefore.When thickness during more than or equal to 10 μ m, not only can give the protectiveness of base material, and can give the molding that obtains with sufficient depth perception, be preferred therefore.

In addition, the membranaceous thing of acrylic resin in the acrylic resin stack membrane of the present invention (A '-a) thickness is preferably 1～30 μ m, more preferably greater than equaling 3 μ m, smaller or equal to 20 μ m.When thickness during smaller or equal to 30 μ m, acrylic resin stack membrane of the present invention is surface hardness (scuff resistance) and thermotolerance raising not only, and when stack membrane being carried out inserts shaping or mould internal shaping, can obtain the membranaceous thing of acrylic resin (A '-a) not obvious, the lamination molding that do not influence outward appearance of the peeling off of be full of cracks, disrumpent feelings, laminate portion, albefaction etc. of part, be preferred therefore.In addition, when thickness during more than or equal to 1 μ m, the effect that surface hardness of acrylic resin stack membrane of the present invention (scuff resistance) and thermotolerance are improved is held, and can obtain homogeneous film thickness the membranaceous thing of acrylic resin (A '-a), be preferred therefore.In addition, on molding, forming enough the filming of thickness by coating, must be through the coating that repeats of ten several.Therefore, the higher and productivity of the cost of cost extremely worsens.To this, because lamination molding of the present invention can easily form very thick filming because acrylic resin stack membrane self formation is filmed, industrial utilization is worth height.

Consider from surface hardness (scuff resistance), thermotolerance, with the membranaceous thing of acrylic resin of the present invention (A) be as base material, with pencil hardness 2H or the membranaceous thing of the acrylic resin more than it (A '-a) be used on the top layer side of acrylic resin stack membrane on top layer or the inside side more further the lamination pencil hardness be 2H or the membranaceous thing of the acrylic resin more than it (A '-a) also be fine.In addition, consider weathering resistance, solvent resistance, also can the membranaceous thing of stacked fluoro-resin (A ").

In addition, consider from giving processibility, also can the base material side of acrylic resin stack membrane again the lamination pencil hardness smaller or equal to the membranaceous thing of the acrylic resin of F (A '-b).Like this, not only be shaped by inserts or the vacuum forming of mould internal shaping etc., can also adopt other working method, for example circumvolution processing etc. obtains the molding of 3D shape, and therefore, industrial utilization is worth high.

In addition, as acrylic resin stack membrane of the present invention, when use the membranaceous thing of acrylic resin (A ') on the base material, when on the top layer, using the membranaceous thing of acrylic resin (A), preferred use the acrylic resin membranaceous thing lower than the surface hardness of the membranaceous thing of acrylic resin (A) (A '-b).Particularly, preferably use pencil hardness (measuring) based on JIS K5400 for F or the membranaceous thing of acrylic resin below it (A '-b).HB or below it more preferably, further preferably 3B or below it.

By use pencil hardness as F or the membranaceous thing of the acrylic resin below it (A '-b) as base material, use the membranaceous thing of acrylic resin of the present invention (A) as the top layer, owing to compare with existing known acrylic resin stack membrane, can obtain anti-shaping albefaction very good, have surface of good hardness (scuff resistance), a stable on heating acrylic resin stack membrane, be preferred therefore.

At this moment, the membranaceous thing of acrylic resin (A '-b) preferably form separately or by forming according to the necessary resin combination that mixes with the thermoplastic resin that with the alkyl methacrylate is principal constituent by multi-ply construction polymkeric substance with particular configuration.

Concrete, exemplify out and contain following (i) and resin combination (ii).

It (iii) is the thermoplastic resin of principal constituent with the alkyl methacrylate.

(iii-a) has general formula CH ₂=CHX or CH ₂The independent polymkeric substance of the vinyl monomer of=CXY or vinylidene monomer or these monomeric two or more constitute thermoplastic resin.In the above-mentioned general formula, X, Y can be identical or different, represents H, Cl, F, Br, CH separately ₃, COOH, COOCH ₃, CN, OCOCH ₃, C ₆H ₅, O-low alkyl group, COCH ₃, SO ₃H.

(iii-b) by alkyl methacrylate 50～100 quality %, alkyl acrylate 0～50 quality % of carbonatoms 1～4, but and at least a 0～50 quality % of other vinyl monomer of copolymerization second-order transition temperature that form, polymkeric substance be 100,000～300,000 thermoplastic resin less than 70 ℃, weight-average molecular weight.

The multi-ply construction polymkeric substance (polymkeric substance that contains rubber) that (iv) has particular configuration.

(iv-a) by innermost layer polymkeric substance (iv-aa), cross-linking elasticity polymkeric substance (iv-ab), outermost layer polymkeric substance (iv-ac) as the essential structure unit, be positioned at the multi-ply construction polymkeric substance that the middle layer (iv-ad) of polymkeric substance (iv-ab) and polymkeric substance (iv-ac) interlayer is formed.Wherein, innermost layer polymkeric substance (iv-aa) by having of the alkyl methacrylate (iv-aa1) of the alkyl acrylate of the carbonatoms 1～8 of 80～100 quality % and/or carbonatoms 1～4,0～20 quality % can be with the multi-functional monomer (iv-aa3) of the monomer (iv-aa2) of other pair key of (iv-aa1) copolymerization, 0～10 quality %, intersect agent with respect to the grafting of 0.1～5 quality powder of total amount 100 mass parts of (iv-aa1)～(iv-aa3) and form; Cross-linking elasticity polymkeric substance (iv-ab) by having of the alkyl methacrylate (iv-ab1) of the alkyl acrylate of the carbonatoms 1～8 of 80～100 quality % and/or carbonatoms 1～4,0～20 quality % can be with the multi-functional monomer (iv-ab3) of the monomer (iv-ab2) of other pair key of (iv-ab1) copolymerization, 0～10 quality %, intersect agent with respect to the grafting of 0.1～5 quality powder of total amount 100 mass parts of (iv-ab1)～(iv-ab3) and form; Outermost layer polymkeric substance (iv-ac) by the alkyl methacrylate (iv-ac1) of the carbonatoms 1～4 of 51～100 quality %, but the monomer (iv-ac2) with the two keys of copolymerization of 0～49 quality % forms, second-order transition temperature is at least 60 ℃; Middle layer (iv-ad) is the alkyl acrylate (iv-ad1) by the carbonatoms 1～8 of 10～90 quality %, the alkyl methacrylate (iv-ad2) of the carbonatoms 1～4 of 90～10 quality %, having of 0～20 quality % can reach (iv-ad2) monomer (iv-ad3) of other pair key of copolymerization with (iv-ad1), the multi-functional monomer (iv-ad3) of 0～10 quality %, intersecting agent with respect to the grafting of 0.1～5 quality powder of total amount 100 mass parts of (iv-ad1)～(iv-ad4) forms.

(iv-b) but but in the presence of elastocopolymer 100 mass parts that cross-linkable monomer 0.1～10 quality % by alkyl acrylate 50～99.9 quality %, other vinyl monomer 0～49.9 quality % of copolymerization and copolymerization forms, the multi-ply construction polymkeric substance that alkyl methacrylate 40～100 quality % and the monomer that can form with vinyl monomer 0～60 quality % of its copolymerization or its mixture 10～40 mass parts are got together and obtained.

Example more specifically is just like following resin combination.

The acrylic resin film resin combination of zero special public clear 63-8983 communique record:

By thermoplastic resin (iii-a) 1～99 mass parts and contain the resin combination that polymkeric substance (iv-a) 1～99 mass parts of rubber is formed.

Zero spy opens the acrylic resin film resin combination of flat 11-80487 communique record:

By thermoplastic resin (iii-b) 5～30 mass parts and contain the resin combination that polymkeric substance (iv-b) 75～95 mass parts of rubber are formed.

The membranaceous thing of the acrylic resin that uses among the present invention (A '-b), as required, can contain general Synergist S-421 95, for example, stablizer, lubrication prescription, processing aid, softening agent, shock-resistant dose, whipping agent, weighting agent, antiseptic-germicide, anti-Fungicide, remover, static inhibitor, tinting material, matting agent, UV light absorber, photostabilizer etc.

Addition means as above-mentioned Synergist S-421 95, have with form the membranaceous thing of acrylic resin of the present invention (A '-b) the membranaceous thing of acrylic resin (A '-a) together supplies with the method for forcing machine with raw material, and with the membranaceous thing of the acrylic resin that has added Synergist S-421 95 in advance (A '-b) mixture mixing blended method in various mixing rolls of raw material.Mixing roll as using in one method of back has single shaft mixing roll, twin shaft mixing roll, Banbury, roll-type mixing roll etc. usually.

And, in case of necessity, can adopt known method reduce the membranaceous thing of acrylic resin of the present invention (A '-b) gloss.The concrete method that adopts mixing inorganic filler or bridging property polymer particle, the monomer methods that copolymerization contains epoxy group(ing), use the straight chain polymer with hydroxyl method, carry out relief method for processing etc.In addition, also can use to the membranaceous thing of acrylic resin of the present invention (A '-b) carry out painted method for processing.

At this moment, the membranaceous thing of acrylic resin in the acrylic resin stack membrane of the present invention (A '-b) thickness is preferably 10～500 μ m, more preferably more than or equal to 30 μ m, smaller or equal to 200 μ m.When thickness during smaller or equal to 500 μ m, the acrylic resin stack membrane that finally obtains has that suitable inserts is shaped or the rigidity of mould internal shaping, and is pre-formed at the membranaceous thing of acrylic resin (A) and can more stably makes film when membranaceous, is preferred therefore.When thickness during more than or equal to 10 μ m, not only can give the protectiveness of base material, and can give the molding that obtains with sufficient depth perception, be preferred therefore.

In addition, the membranaceous thing of acrylic resin in the acrylic resin stack membrane of the present invention (A '-a) thickness is preferably 1～30 μ m, more preferably greater than equaling 3 μ m, smaller or equal to 20 μ m.When thickness during smaller or equal to 30 μ m, acrylic resin stack membrane of the present invention is surface hardness (scuff resistance) and thermotolerance raising not only, and when stack membrane being carried out inserts shaping or mould internal shaping, can obtain not having the molding that the shaping albefaction takes place, be preferred therefore.In addition, when thickness during more than or equal to 1 μ m, the effect that surface hardness of acrylic resin stack membrane of the present invention (scuff resistance) and thermotolerance are improved is held, and can obtain the membranaceous thing of acrylic resin (A) of homogeneous film thickness, is preferred therefore.In addition, on molding, forming enough the filming of thickness by coating, must be through the coating that repeats of ten several.Therefore, the higher and productivity of the cost of cost extremely worsens.To this, because lamination molding of the present invention can easily form very thick filming because acrylic resin stack membrane self formation is filmed, industrial utilization is worth height.

Consider from surface hardness (scuff resistance), thermotolerance, with the membranaceous thing of acrylic resin (A '-b) as base material, use on the top layer the membranaceous thing of acrylic resin of the present invention (A) the acrylic resin stack membrane the top layer side more further the lamination pencil hardness as 2H or the membranaceous thing of the acrylic resin more than it (A '-a) also be fine.In addition, consider weathering resistance, solvent resistance, also can the membranaceous thing of stacked fluoro-resin (A ").

In addition, as acrylic resin stack membrane of the present invention, the membranaceous thing of also available acrylic resin (A) as base material, with the membranaceous thing of fluoro-resin (A ") as surface layer material.

Kind for the fluorine resin that constitutes the membranaceous thing of fluoro-resin (A ") is not particularly limited, and can use known fluorine resin.Concrete is the resin combination of principal constituent just like, the multipolymer of the fluorine cpd of partial fluorine ethylene polymer, vinylidene and ethylene fluoride, zellon etc. or the acrylic monomer of alkyl acrylate, alkyl methacrylate etc. or with the partial fluorine ethylene polymer.

At this moment, there is no particular limitation for the position that the membranaceous thing of fluoro-resin (A ") is set; but consider from the weathering resistance and the solvent resistance of acrylic resin stack membrane; the upper strata (that is, the membranaceous thing of fluoro-resin (A ") that the membranaceous thing of fluoro-resin (A ") is preferably disposed on the membranaceous thing of acrylic resin (A) is top layer).

The membranaceous thing of fluoro-resin that the present invention uses (A "); as required; can contain general Synergist S-421 95; for example, stablizer, lubrication prescription, processing aid, softening agent, shock-resistant dose, whipping agent, weighting agent, antiseptic-germicide, anti-Fungicide, remover, static inhibitor, tinting material, matting agent, UV light absorber, photostabilizer etc.

And, the molecular weight of UV light absorber more than or equal to 300 situation under, the membranaceous thing of fluoro-resin (A ") is when film forming, when extruding membranoid substance from the T mould in cooling roller cooling period, UV light absorber evaporable amount is few.Like this, the amount because of residual UV light absorber enough can embody good performance.In addition, the evaporable UV light absorber is recrystallize and growth on the exhaust hood that the suspention T template strand that is positioned at T mould top and exhaust are used, and can drop on the film very soon, and it is also few to produce the such problem of apparent defective.

Addition means as above-mentioned Synergist S-421 95, there is the membranaceous thing of fluoro-resin that will form the membranaceous thing of fluoro-resin of the present invention (A ") (A ") together to supply with the method for forcing machine with raw material, and with mixture mixing blended method in various mixing rolls of the membranaceous thing of the fluoro-resin that has added Synergist S-421 95 in advance (A ") raw material.Mixing roll as using in one method of back has single shaft mixing roll, twin shaft mixing roll, Banbury, roll-type mixing roll etc. usually.

And, in case of necessity, can adopt known method to reduce the gloss of the membranaceous thing of fluoro-resin of the present invention (A ").The concrete method that adopts mixing inorganic filler or bridging property polymer particle, the monomer methods that copolymerization contains epoxy group(ing), use the straight chain polymer with hydroxyl method, carry out relief method for processing etc.In addition, also can use the membranaceous thing of fluoro-resin of the present invention (A ") is carried out painted method for processing.

In addition, the thickness of the membranaceous thing of fluoro-resin in the acrylic resin stack membrane of the present invention (A ") is preferably 1～30 μ m, more preferably greater than equaling 3 μ m, smaller or equal to 20 μ m.When thickness during smaller or equal to 30 μ m, when making acrylic resin stack membrane of the present invention, can significantly not increase cost, and the surface hardness and the scuff resistance of the acrylic resin stack membrane that obtains do not reduce, also can give its weathering resistance and solvent resistance, be preferred therefore.In addition, when thickness during more than or equal to 1 μ m, the effect that the weathering resistance of acrylic resin stack membrane of the present invention and solvent resistance are improved is held, and can obtain the membranaceous thing of fluoro-resin (A ") of homogeneous film thickness, is preferred therefore.In addition, on molding, forming enough the filming of thickness by coating, must be through the coating that repeats of ten several.Therefore, the higher and productivity of the cost of cost extremely worsens.To this, because lamination molding of the present invention can easily form very thick filming because acrylic resin stack membrane self formation is filmed, industrial utilization is worth height.

General, the surface hardness of the membranaceous thing of fluoro-resin (A ") and the membranaceous thing of acrylic resin (A) are equal to or are lower.But because sliding is good, the scuff resistance of acrylic resin stack membrane that therefore has the membranaceous thing of fluoro-resin (A ") on the surface is relatively good.

Formation method as acrylic resin stack membrane of the present invention, carry out the method for lamination after with the membranaceous thing of acrylic resin (A) and other acrylic resin film shape thing (A ') or the membranaceous thing of fluoro-resin (A ") preliminary shaping just like (1); (2) on the molding that in advance the membranaceous thing of other acrylic resin (A ') or the membranaceous thing of fluoro-resin (A ") is shaped, when extruding the membranaceous thing of acrylic resin (A), melting carries out the method for lamination, (3) on the molding that membranaceous thing (A) is shaped with acrylic resin in advance, when extruding the membranaceous thing of other acrylic resin (A ') or the membranaceous thing of fluoro-resin (A "), melting carries out the method for lamination; (4) the membranaceous thing of acrylic resin (A) and other acrylic resin film shape thing (A ') or the membranaceous thing of fluoro-resin (A ") are carried out the method for lamination etc. when melting is extruded.

As the membranaceous thing of acrylic resin (A) and other acrylic resin film shape thing (A ') or the membranaceous thing of fluoro-resin (A ") are pre-formed into membranaceous manufacture method, just like the melting extrusion molding of melting casting method, T modulus method, plavini etc., prolong known method such as platen press.Under the situation that becomes membranization, from economic considerations, preferred T modulus method.

Carry out the method for lamination after with the membranaceous thing of acrylic resin (A) and other acrylic resin film shape thing (A ') or the membranaceous thing of fluoro-resin (A ") preliminary shaping as aforesaid (1), just like laminating methods such as dried laminating, wet laminating, hot melt layer platen presses.If can carry out hot melt, then also can carry out lamination with pressure sintering.

When membranaceous thing (A) and other acrylic resin film shape thing (A ') or the membranaceous thing of fluoro-resin (A ") preliminary shaping, preferably seize the system film on both sides by the arms with a plurality of rollers or the band that are selected from metallic roll, nonmetal roller and the metal strip with acrylic resin.

As aforementioned (2) on the molding that in advance the membranaceous thing of other acrylic resin (A ') or the membranaceous thing of fluoro-resin (A ") is shaped; carry out the method for lamination when the membranaceous thing of acrylic resin (A) is extruded in melting, just like go up at the membranaceous thing of preformed acrylic resin (A ') or the membranaceous thing of fluoro-resin (A ") carry out lamination when extruding the membranaceous thing of acrylic resin (A) by meltings such as T modulus methods extrude lamination etc.

When with the membranaceous thing of other acrylic resin (A ') or the membranaceous thing of fluoro-resin (A ") preliminary shaping, preferably seize the system film on both sides by the arms with a plurality of rollers or the band that are selected from metallic roll, nonmetal roller and the metal strip.

As aforementioned (3) on the molding that membranaceous thing (A) is shaped with acrylic resin in advance, carry out the method for lamination when the membranaceous thing of other acrylic resin (A ') or the membranaceous thing of fluoro-resin (A ") are extruded in melting, just like go up at the membranaceous thing of preformed acrylic resin (A) extrude by meltings such as T modulus methods carry out lamination in the membranaceous thing of acrylic resin (A ') or the membranaceous thing of fluoro-resin (A ") extrude lamination etc.

When membranaceous thing (A) preliminary shaping, preferably seize the system film on both sides by the arms with a plurality of rollers or the band that are selected from metallic roll, nonmetal roller and the metal strip with acrylic resin.

As the method for the membranaceous thing of acrylic resin (A) and other acrylic resin film shape thing (A ') or the membranaceous thing of fluoro-resin (A ") being carried out lamination when melting is extruded of aforementioned (4), just like with before the mould of feed head (feedblock) method etc. then method, expect in the mould of road (multimanifold) method etc. the then laminating method that is shaped of the coextrusion of method etc. outward such as the then mould of method and many groovings (multislot) method etc. more.

In these methods, though have no particular limits, but consider from the manufacturing processed that can reduce the acrylic resin stack membrane, preferably adopt the method for the membranaceous thing of acrylic resin (A) and other acrylic resin film shape thing (A ') or the membranaceous thing of fluoro-resin (A ") being carried out lamination when melting is extruded of aforementioned (4).

When adopting T modulus method lamination acrylic resin stack membrane, if seize the system film on both sides by the arms with a plurality of rollers or the band that are selected from metallic roll, nonmetal roller and the metal strip, printing when the surface smoothing raising of the acrylic resin stack membrane that then obtains, may command are carried out printing treatment to the olefin(e) acid resin laminated film is omitted.

As metallic roll, metal minute surface touch roll is for example arranged; The metallic sheath of putting down in writing in No. 2808251 communique of Japanese Patent or the WO97/28950 communique (metal made membrane pipe) and moulding contact roller that mode uses etc. with what roller constituted with cover.In addition, as nonmetal roller, touch roll of silicone rubber etc. etc. can be arranged.Have again,, metal continuous band etc. can be arranged as metal strip.Also metallic roll, nonmetal roller and metal strip can be used in combination.

As mentioned above, several rollers that are selected from metallic roll, nonmetal roller and metal strip or with on seize on both sides by the arms the system film method in, preferably, acrylic acid resin composition after melting is extruded is seized on both sides by the arms with the state that does not in fact have dumping tower tray (pitch), does not substantially roll and carries out the system film that face duplicates down.Under the situation that does not form dumping tower tray (pitch) system film, owing to carrying out face under not rolling, duplicates the acrylic acid resin composition in process of cooling, and therefore the percent thermal shrinkage of the membranaceous thing of acrylic resin obtained by this method (A) also can reduce.

＜light solidified acrylic resin film or sheet 〉

Light solidified acrylic resin film of the present invention or sheet have membranaceous thing of acrylic resin of the present invention (A) or acrylic resin stack membrane of the present invention and contain the thermoplastic resin (z-1) that has free-radical polymerised unsaturated group on side chain and the Photocurable resin composition (Z) of Photoepolymerizationinitiater initiater (z-2) layer.

Above-mentioned Photocurable resin composition (Z) layer preferably contains the thermoplastic resin (z-1) and the Photoepolymerizationinitiater initiater (z-2) that have free-radical polymerised unsaturated group on side chain, does not contain thermoplastic resin (z-1) cross-linked compound in addition in fact.Among the present invention, by with this Photocurable resin composition (Z) lamination layer on membranaceous thing of acrylic resin (A) or acrylic resin stack membrane, can obtain light solidified acrylic resin film or sheet.Photocurable resin composition among the present invention (Z), owing to have the structure of free-radical polymerised unsaturated group by importing at polymer lateral chain, can carry out crosslinking reaction at the polymer side interchain, therefore can obtain significantly good wear resistant and scuff resistance, and, owing to needn't contain lower molecular weight cross-linked compound, therefore have and to obtain surperficial non-adhesiveness, good light solidified acrylic resin film or the such advantage of sheet of storage stability with reaction-ity ethylene base.

As the thermoplastic resin that has free-radical polymerised unsaturated group on side chain (z-1), it is the polymkeric substance that has free-radical polymerised unsaturated group in 25～175 ℃, preferred 30～150 ℃ polymkeric substance that second-order transition temperature is for example arranged.Concrete, as polymkeric substance, can use following compound (1)～(7) polymerization or copolymerization, polymerization or copolymerization product are imported the polymkeric substance that free-radical polymerised unsaturated group obtains by aftermentioned method ()～(six).Wherein, " (methyl) acrylate " expression acrylate or methacrylic ester, the acid of " (methyl) vinylformic acid " expression acrylic or methacrylic, " (methyl) acrylamide " expression acrylamide or Methacrylamide, " (methyl) acryloyl-oxy " expression acryloyl-oxy or methacryloxypropyl.

(1) has the monomer of hydroxyl: N hydroxymethyl acrylamide, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate, 2-hydroxyl-3-phenoxy group (methyl) acrylate etc.

(2) has the monomer of carboxyl: (methyl) vinylformic acid, acrylyl oxy-ethyl monosuccinic acid ester etc.

(3) has the monomer of epoxy group(ing): epoxypropyl (methyl) acrylate, 3,4-epoxycyclohexyl methyl (methyl) acrylate etc.

(4) has the basic monomer of aziridinyl (aziridinyl): 2-aziridinyl ethyl (methyl) acrylate, 2-aziridinyl propionic acid allyl group etc.

(5) has amino monomer: (methyl) acrylamide, diacetone acrylamide, dimethyl aminoethyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate etc.

(6) has the monomer of sulfuryl: 2-acrylamide-2-methyl propane sulfonic acid etc.

(7) have the monomer of isocyanate group: as 2,4 toluene diisocyanate and 2-hydroxyethylmethacry,ate etc. the vulcabond and affixture, 2-isocyanic ester ethyl (methyl) acrylate of mole affixture with free radical polymerization monomer of active hydrogen

And,, also above-claimed cpd and copolymerisable monomer can be carried out copolymerization for the second-order transition temperature of the polymkeric substance of regulating above-claimed cpd or multipolymer, the rerum natura of light solidified membrane or sheet of being in harmonious proportion.As such copolymerisable monomer, (methyl) esters of acrylic acid, the N-phenyl maleic anhydride of (methyl) methyl acrylate, (methyl) vinylformic acid three ring esters in the last of the ten Heavenly stems, (methyl) isobutyl acrylate etc. imines, cyclohexyl maleic anhydride the contract aromatic ethenyl compound etc. of vinyl monomers such as imide derivative, divinyl, vinylbenzene, alpha-methyl styrene etc. such as imines of imines, N-butyl maleic anhydride that contracts that contracts is for example arranged.

By following method ()～(six), can in above-mentioned polymkeric substance or multipolymer, import free-radical polymerised unsaturated group.

(1) in the polymkeric substance with monomer of hydroxyl (1) or the occasion of multipolymer, monomer with carboxyl (2) that makes (methyl) vinylformic acid etc. etc. carries out condensation reaction.

(2) having the monomer of carboxyl (2), having the polymkeric substance of monomer (6) of sulfuryl or the occasion of multipolymer, make above-mentioned monomer (1) etc. carry out condensation reaction with hydroxyl.

(3) having the monomer of epoxy group(ing) (3), have the monomer (7) of isocyanate group or having the polymkeric substance of monomer (4) of aziridinyl base or the occasion of multipolymer, make above-mentioned monomer (2) that has the monomer (1) of hydroxyl or have carboxyl etc. carry out addition reaction.

(4) in the occasion of polymer of monomers with hydroxyl or carboxyl or multipolymer, make monomer (3) with epoxy group(ing) or monomer (4) with aziridinyl base, perhaps have the monomer (7) or the isocyanate compound of isocyanate group and contain hydroxyl acrylate monomer etc. mole affixture etc. carry out addition reaction.

(5), make above-mentioned monomer (2) etc. carry out condensation reaction with carboxyl in occasion with amino monomer (5).

(6) have amino monomer (5) polymkeric substance or the occasion of multipolymer, making the above-mentioned monomer that has the monomer (3) of epoxy group(ing) or have an acetoacetoxy groups carry out addition reaction.

The inhibitor of polymerization that above-mentioned reaction preferably adds the quinhydrones etc. of trace reacts while send into dry air.

The amount of free-radical polymerised unsaturated group of side chain that on side chain, has the thermoplastic resin (z-1) of free-radical polymerised unsaturated group, consider that from scuff resistance, wear resistant the calculated value that is obtained by preset value when two key equivalents (molecular-weight average of the free-radical polymerised unsaturated group of each side chain) is at average 3000g/mol or be preferably below it.Better two normal scopes of key are at 1200g/mol or below it, preferably at 800g/mol or below it.

Like this, by in thermoplastic resin, importing a plurality of and crosslinked relevant free-radical polymerised unsaturated group, needn't use low-molecular-weight cross-linked compound, even when long-time preservation described later and heating shaping, do not have surface tackiness yet, can effectively improve the curing rerum natura.

The number-average molecular weight of thermoplastic resin (z-1) that has free-radical polymerised unsaturated group on side chain is preferably 5,000～2,500,000 scope, and more preferably 10,000～1,000,000 scope.To used contain light solidified acrylic resin film that the Photocurable resin composition (Z) of the thermoplastic resin that has free-radical polymerised unsaturated group on the side chain (z-1) forms or sheet carry out that inserts is shaped or the mould internal shaping when, from good mould separability with the inserts after increasing photocuring is shaped or the surface hardness consideration of mould internal shaping product, preferred number average molecular weight is more than or equal to 5,000.On the other hand, from synthetic easily and outward appearance consider, and adaptation consideration from showing with the membranaceous thing of acrylic resin (A), preferred number average molecular weight is smaller or equal to 2,500,000.

In addition, the second-order transition temperature that preferably will have the thermoplastic resin (z-1) of free-radical polymerised unsaturated group on side chain is adjusted to 25～175 ℃, more preferably is adjusted to 30～150 ℃.Inserts behind light solidified acrylic resin film during from inserts shaping or mould internal shaping or the good mould separability of sheet and the increase photocuring is shaped or the surface hardness of mould internal shaping product considers that second-order transition temperature is preferably greater than and equals 25 ℃.On the other hand, consider that from the processibility of light solidified acrylic resin film or sheet second-order transition temperature is preferably smaller or equal to 175 ℃.

In addition, consider the second-order transition temperature of the thermoplastic resin that has free-radical polymerised unsaturated group on side chain (z-1) that obtains, then preferably using the ethene with high second-order transition temperature is that polymerizable monomer forms homopolymer.And, consider that raising has the weathering resistance of the thermoplastic resin of free-radical polymerised unsaturated group (z-1) on side chain, be polymerizable monomer then as ethene, preferably use with the acrylic resin of (methyl) esters of acrylic acid as principal constituent.In addition, as described later, in Photocurable resin composition of the present invention (Z), add the occasion of inorganic fine particles (a-3), functional group's (hydroxyl with the surface of inorganic fine particles (a-3), carboxyl, silanol group etc.) Fan Ying base, for example, has the hydroxyl of being selected from intramolecularly, carboxyl, the vinyl polymerized monomer of at least a functional group in the group that halogenation silyl and alkoxysilyl are formed is owing to make the rigidity of the Photocurable resin composition that obtains, toughness, rerum naturas such as thermotolerance further improve, so also can contain such functional group, as the part of the vinyl polymerized monomer composition of free redical polymerization.

As the vinyl polymerized monomer that has so reactive base at intramolecularly, just like, 2-hydroxyethyl (methyl) methyl acrylate, 2-hydroxypropyl (methyl) methyl acrylate, (methyl) vinylformic acid, vinyl trichloro silane, vinyltrimethoxy silane, γ-acryloxy propyl trimethoxy silicane etc.

As the Photoepolymerizationinitiater initiater that uses among the present invention (z-2), just like the optical free radical polymerization starter that produces free radical by rayed.

As the optical free radical polymerization starter; can use known compound; and there is no particular limitation, but consider xanthochromia when solidifying and the deterioration when weather-proof, and it is better then to select for use methyl phenyl ketone system, benzophenone system, acyl group phosphine oxygen to be that such intramolecularly does not contain amino initiator.For example, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxyl-cyclohexyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2,4,6,-Three methyl Benzene formylphenyl phosphine oxygen, two (2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxygen is better.In these optical free radical polymerization starters, temporarily can reach the boiling point and its above temperature of compound because of manufacturing process, so should suitably select according to manufacturing process.Owing to will improve the surface hardness of molding, so also can add the additive that polymerizing curable that the inhibition oxygen of n-methyldiethanolamine etc. causes encumbers.In addition, except these Photoepolymerizationinitiater initiaters, consider to utilize the heat when being shaped, also can add various superoxide.In light solidified acrylic resin film or sheet, contain under the situation of superoxide, because need be 150 ℃ of curing of carrying out about 30 seconds, so adopt the low superoxide of critical temperature better, for example, lauroyl peroxide, tert-butyl peroxide-2-ethylhexanoate, 1, two (tert-butyl peroxide)-3,3 of 1-, 5-trimethyl-cyclohexane etc.

Because solidifying the back remaining quantity, the optical free radical polymerization starter can influence weathering resistance, so the addition of optical free radical polymerization starter has the compound of free-radical polymerised unsaturated group relatively on side chain, be preferably smaller or equal to 5 quality %, the relevant amine of xanthochromia during particularly with curing is that the optical free radical polymerization starter is preferably smaller or equal to 1 quality %.

Photocurable resin composition of the present invention (Z) can add inorganic fine particles (a-3) in order further to improve scuff resistance and wear resistant.For the inorganic fine particles of using among the present invention (a-3), be transparent as long as satisfy the Photocurable resin composition that obtains, its kind, particle diameter, form all there are not special restriction.As the example of inorganic fine particles (a-3), colloid silica, aluminum oxide, titanium oxide etc. are arranged.These can use separately, or two or more is used in combination.Wherein, consider preferred especially colloid silica from the transparency of the Photocurable resin composition layer that obtains complexity, low price, obtain and the performance of wear resistant.

Colloid silica can use the form and the form that is scattered in the organic solvent of common aqueous liquid dispersion, but for the thermoplastic resin that has free-radical polymerised unsaturated group on side chain with conduct (z-1) composition evenly and stably disperses jointly, the then preferred colloid silica that is scattered in the organic solvent that uses.

Organic solvent as such for example has, methyl alcohol, Virahol, propyl carbinol, ethylene glycol, dimethylbenzene/butanols, ethyl cellosolve, ethylene glycol butyl ether, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene etc.Wherein, in order to disperse the preferred organic solvent that is dissolved in the thermoplastic resin (z-1) that has free-radical polymerised unsaturated group on the side chain of levying jointly equably with thermoplastic resin.In addition, as described later, because when making light solidified acrylic resin film of the present invention and sheet, to make it volatilization to these organic solvent heat dryings, so preferably have boiling point second-order transition temperature high 80 ℃ or its above, preferred 30 ℃ or its above organic solvent unlike the resinous principle of the main composition composition of the membranaceous thing of acrylic resin (A), like this, it is difficult to remain in light solidified acrylic resin film and the sheet.

As having the colloid silica that is scattered in form in the organic solvent, can use the commercially available product that is scattered in the solvent, for example, methyl alcohol silicon sol MA-ST, Virahol silicon sol IPA-ST, propyl carbinol silicon sol NBA-ST, ethylene glycol silicon sol EG-ST, dimethylbenzene/butanols silicon sol XBA-ST, ethyl cellosolve silicon sol ETC-ST, ethylene glycol butyl ether silicon sol BTC-ST, dimethyl formamide silicon sol DBF-ST, N,N-DIMETHYLACETAMIDE silicon sol DMAC-ST, methyl ethyl ketone silicon sol MEK-ST, methyl iso-butyl ketone (MIBK) silicon sol MIBK-ST (above is trade(brand)name, produces chemical society system daily) etc.

The particle diameter of inorganic fine particles (a-3) is considered from the transparency of the light solidified acrylic acid resin composition layer that obtains, usually smaller or equal to 200 μ m, is more preferably less than and equals 100 μ m, further smaller or equal to 50 μ m.

The addition of inorganic fine particles (a-3), solid shape with respect to the thermoplastic resin that has free-radical polymerised unsaturated group on side chain (z-1) is divided 100 mass parts, the solid shape of inorganic fine particles divide preferred in the scope of 5～400 mass parts, preferred especially in the scope of 10～200 mass parts.Under the situation of addition less than 5 mass parts of inorganic fine particles (a-3), can't confirm the effect that wear resistant improves, in addition, surpass under the situation of 400 mass parts at addition, not only the storage stability of Photocurable resin composition (Z) reduces, and the plasticity of light solidified acrylic resin film that obtains and sheet is low.

In addition, as the inorganic fine particles of using among the present invention (a-3), the particle that also can use the silane compound with following structural formula (a3-1) expression to carry out surface preparation.Use surface-treated inorganic fine particles, because the storage stability of Photocurable resin composition (Z) becomes better, and the surface hardness of light solidified acrylic resin film that obtains and sheet and weathering resistance also become better.

SiR ¹ _aR ² _b(OR ³) _c (a3-1)

(in the following formula, R ¹And R ²Expression can have the hydrocarbyl residue of the carbonatoms 1～10 of ehter bond, ester bond, epoxy bond or carbon-carbon double bond, R respectively ³The expression hydrogen atom maybe can have the hydrocarbyl residue of the carbonatoms 1～10 of ehter bond, ester bond, epoxy bond or carbon-carbon double bond, and a and b are respectively 0～3 integer, and c is 1～4 the integer that satisfies 4-a-b)

In the silane compound of said structure formula (a3-1) expression, the silane compound that can enumerate following structural formula (a3-2)～(a3-7) expression is as preferred compound.

SiR ⁴ _aR ⁵ _b(OR ⁶) _c (a3～2)

SiR ⁴ _n(OCH ₂CH ₂OCO(R ⁷)C＝CH ₂) _4-n (a3-3)

CH ₂＝C(R ⁷)COO(CH ₂) _pSiR ⁸ _n(OR ⁶) _3-n (a3-4)

CH ₂＝CHSiR ⁸ _n(OR ⁶) _3-n (a3-5)

HS(CH ₂) _pSiR ⁸ _n(OR ⁶) _3-n (a3-6)

(in the following formula, R ⁴And R ⁵Expression can have the hydrocarbyl residue of the carbonatoms 1～10 of ehter bond, ester bond or epoxy bond, R respectively ⁶The hydrocarbyl residue of expression hydrogen atom or carbonatoms 1～10, R ⁷Expression hydrogen atom or methyl, R ⁸The alkyl and the phenyl of expression carbonatoms 1～3, a and b are respectively 0～3 integer, and c is 1～4 the integer that satisfies 4-a-b, and n is 0～2 integer, p is 1～6 integer)

Silane compound as said structure formula (a3-2) expression, for example have, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, phenyltrimethoxysila,e, Ethoxysilane on the phenyl, dimethyldimethoxysil,ne, dimethoxydiphenylsilane, the methylethyl diethoxy silane, aminomethyl phenyl dimethoxy silane, trimethylethoxysilane, the methoxy ethyl triethoxyl silane, the acyloxy ethyl triethoxysilane, diethoxy ethyl dimethoxy silane, four acyloxy silanes, methyl three acyloxy silanes, four (2-methoxy ethoxy) silane, γ-acryloxy propyl trimethoxy silicane, γ-acryloxy propyl group methyldiethoxysilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane etc.

Silane compound as said structure formula (a3-3) expression, four (acryloyl-oxy base oxethyl) silane, four (methacryloxy oxyethyl group) silane, methyl three (acryloyl-oxy base oxethyl) silane, methyl three (methacryloxy oxyethyl group) silane etc. are for example arranged.

Silane compound as said structure formula (a3-4) expression, β-acryloxy ethyl dimethoxy-methyl silane, γ-acryloxy propyl group methoxyl group dimethoxy silane, γ-acryloxy propyl trimethoxy silicane, Beta-methyl acryloxy ethyl dimethoxy-methyl silane, γ-methacryloxypropyl trimethoxy silane etc. are for example arranged.

Silane compound as said structure formula (a3-5) expression for example has vinyl methyl dimethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane etc.

Silane compound as said structure formula (a3-6) expression for example has γ-sulfydryl propyl group dimethoxy-methyl silane, γ-Qiu Jibingjisanjiayangjiguiwan etc.

Silane compound as said structure formula (a3-7) expression for example has, to the ethenylphenyl methyl dimethoxysilane, to the ethenylphenyl Trimethoxy silane etc.

These silane compounds with respect to the solid shape branch of 1 molar part inorganic fine particles (a-3), preferably use with the ratio of 0～3 molar part.When the usage quantity of silane compound surpassed 3 molar part, the big wear resistant of light solidified acrylic resin film that obtains and sheet reduced.The molar part here is meant the mass parts of inorganic fine particles or silane compound and the ratio of molecular weight.For example, inorganic fine particles colloid silica (SiO ₂) solid shape divide 100 mass parts to be equivalent to 100 ÷ 60=1.666 molar part.

Carry out the surface-treated inorganic fine particles with silane compound, can utilize commercially available product, in addition, also can carry out surface treatment to inorganic fine particles and obtain by known method.

As the method for inorganic fine particles (a-3) being added in the thermoplastic resin (z-1) that on side chain, has free-radical polymerised unsaturated group, can synthesize in advance behind the thermoplastic resin that has free-radical polymerised unsaturated group on the side chain (z-1), be mixed into inorganic fine particles (a-3), in addition, can be to carry out polymerization under polymerizable monomer and inorganic fine particles (a-3) the blended condition at the ethene that will be formed in the thermoplastic resin (z-1) that has free-radical polymerised unsaturated group on the side chain also, these methods can be selected for use arbitrarily.

In the Photocurable resin composition that uses among the present invention (Z), thermoplastic resin that on side chain, has free-radical polymerised unsaturated group (z-1) and Photoepolymerizationinitiater initiater (z-2) except neccessary composition, and as required and outside the spendable above-mentioned inorganic fine particles (a-3), can also fit into the additive of sensitive agent, sex change resin, dyestuff, pigment and homogenize agent, impact modifier, UV light absorber, photostabilizer, oxidation stabilizer etc. as required.

Above-mentioned sensitive agent promotes photocuring reaction, its example as, benzophenone, benzoin isobutyl propyl group ether, thioxanthone etc.

But Photocurable resin composition (Z) should not contain in fact except that above-mentioned cross-linked compound the thermoplastic resin that has free-radical polymerised unsaturated group on the side chain (z-1).Should not contain especially in fact 40 ℃ for liquid cross-linkable monomer, oligopolymer, molecular weight smaller or equal to 2000 low-molecular-weight cross-linkable monomer, oligopolymer.Especially, when containing at 40 ℃ for liquid cross-linkable monomer, oligopolymer and molecular weight during smaller or equal to 2000 low-molecular-weight cross-linkable monomer, oligopolymer, when long-term keeping and heating shaping, the surface produces tackiness, in typography, go wrong, when inserts shaping or mould internal shaping, pollute problems such as mould sometimes.Even more ideal is should not contain in fact at 50 ℃ to be liquid cross-linkable monomer, oligopolymer.Further even more ideal is should not contain in fact at 60 ℃ to be liquid cross-linkable monomer, oligopolymer.

Among the present invention, owing to used above-mentioned Photocurable resin composition (Z), even stacked Photocurable resin composition on membranaceous thing of acrylic resin (A) or acrylic resin stack membrane, under the situation that forms light solidified acrylic resin film or sheet, the surface of light solidified acrylic resin film or sheet is non-adhesiveness also, and Biao Mian tackiness can not change in time yet yet, with the good stability of reeling condition preservation.

Light solidified acrylic resin film of the present invention or sheet be owing to have above-mentioned formation, thereby be to take into account the good plasticity before photocuring and the light solidified acrylic resin film or the sheet of storage stability and the good surface texture behind photocuring (hardness, weathering resistance etc.) on the high level.As described later, usually, light solidified acrylic resin film of the present invention or sheet are by the solvent with Photocurable resin composition (Z) and organic solvent etc., solution after the dissolving is coated with on membranaceous thing of acrylic resin (A) or acrylic resin stack membrane by various coating processes, carries out then being that the heat drying of purpose is made except that desolvating.At this moment, if remaining a large amount of solvents in light solidified acrylic resin film or the sheet, then the Photocurable resin composition before rayed (Z) laminar surface produces tackiness, yield rate in printing process is low, problems such as mould perhaps take place to pollute in the poor stability so that reeling condition is preserved when inserts shaping or mould internal shaping.In addition, even inserts molding or mould internal shaping product process photocuring that light solidified acrylic resin film or sheet obtain by inserts shaping or mould internal shaping, the surface physical property of its scuff resistance, resistance to chemical reagents, weathering resistance etc. also can variation.For addressing these problems, preferably the quantity of solvent in light solidified acrylic resin film or the sheet is few as much as possible.

As the light solidified acrylic resin film of the present invention with membranaceous thing of acrylic resin (A) or acrylic resin stack membrane and Photocurable resin composition (Z) layer or the manufacture method of sheet, for example have, the thermoplastic resin that on side chain, has free-radical polymerised unsaturated group (z-1) and the Photoepolymerizationinitiater initiater (z-2) that will contain neccessary composition, and the Photocurable resin composition (Z) of inorganic fine particles as required (a-3) abundant stirring and dissolving in the organic solvent equal solvent, pass through woodburytype, silk screen print method, the known printing process of offset printing method etc., and flow coat method, spraying method, rod is coated with method, the recessed method that is coated with, rolling method, spread coating, bar is coated with method, the scraper rolling method, air knife is coated with method, comma (コ Application マ) rolling method, two-sided rolling method, transform rolling method, touch rolling method, the curtain coating method, the known coating process of dip coating etc., on the membranaceous thing of acrylic resin (A), be coated with, the behavior of going forward side by side removes the heat drying that desolvates, and obtains the method for stack membrane or sheet.Boiling point unlike second-order transition temperature high 80 ℃ or more than it, preferred 30 ℃ or organic solvent more than it since difficulty remain in light solidified acrylic resin film and the sheet, thereby preferred.

Make it the dissolved solvent as stirring Photocurable resin composition (Z), preferably can make each the composition dissolving of Photocurable resin composition (Z) and homodisperse, the membranaceous thing of acrylic resin (A) or acrylic resin stack membrane are not had very big detrimentally affect and boiling point second-order transition temperature high 80 ℃ or its above, preferred 30 ℃ or its above volatile solvent unlike the resinous principle of the main component that constitutes membranaceous thing of acrylic resin (A) or acrylic resin stack membrane in the use.As such solvent, for example spendable pure series solvent that methyl alcohol, ethanol, Virahol, propyl carbinol, ethylene glycol etc. are arranged; The aliphatic hydrocarbon series solvent of the aromatic series series solvent of dimethylbenzene, toluene, benzene etc., hexane, pentane etc.; The halon series solvent of chloroform, tetracol phenixin etc.; The phenol series solvent of phenol, cresols etc.; The ketone series solvent of methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetone etc.; Anaesthetie Ether, methoxy toluene, 1,2-glycol dimethyl ether, 1,2-dibutoxy ethane, 1,1-Methylal(dimethoxymethane), 1,1-glycol dimethyl ether, 1, the ether series solvent of 4-dioxan, THF etc.; Formic acid, acetate, propionic acid or the like fatty acid series solvent; The acid anhydrides series solvent of diacetyl oxide etc.; The ester series solvent of ethyl acetate, butylacetate, butyl formate etc.; The nitrogen-containing solvent of ethamine, Tolylamine, dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.; The sulfur-bearing solvent of thiophene, dimethyl sulfoxide (DMSO) etc.; The solvent with two or more functional group of Pyranton, 2-methyl cellosolve (methylcyclohexane), cellosolvo (ethyl cellosolve), butoxy ethanol (ethylene glycol butyl ether), Diethylene Glycol, 2-monoethanolamine, acetone cyanohydrin, diethanolamine, morpholine etc.; Or various known solvents such as water.

Here, in order to eliminate the foregoing problem that causes because of remaining solvent in light solidified acrylic resin film or sheet, and enhance productivity with low cost, can in the shorter time, make light solidified acrylic resin film or sheet, must strengthen the heat drying condition of desolvating, carry out thorough drying for removing.Yet, this moment is if the continuous heat drying of the temperature more than the heat-drawn wire of membranaceous thing of acrylic resin (A) or acrylic resin stack membrane is more than 20 seconds to light solidified acrylic resin film or sheet, even small tension force also can be extended, thereby the not only thickness attenuation of Photocurable resin composition (Z) layer and membranaceous thing of acrylic resin (A) or acrylic resin stack membrane, and can cause the big scuff resistance of curable resin composition (Z) behind the photocuring, the reduction of surface hardness etc.

The heat drying condition of light solidified acrylic resin film or sheet, preferably carry out heat drying in the temperature of the scope of the heat-drawn wire that is no more than membranaceous thing of acrylic resin (A) or acrylic resin stack membrane, when perhaps under the hot conditions of the heat-drawn wire that is higher than membranaceous thing of acrylic resin (A) or acrylic resin stack membrane, carrying out drying, below heat-drawn wire+15 of membranaceous thing of acrylic resin (A) or acrylic resin stack membrane ℃, preferably+10 ℃, and the heat drying time under this temperature below 20 seconds, preferably, more preferably carrying out below 5 seconds below 10 seconds.

As drying machine, when using flammable organic solvent as solvent, from security consideration, use utilizes the drying machine of the thermal source with air heating formula of steam, the mode that can adopt the hot blast generation convection current in the drying machine to touch mode and blow to light solidified acrylic resin film or sheet by nozzle.The shape of drying machine has arc formula, flat formula etc., can select known shape as required for use.

＜have band the layer (B) the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet

For giving the aesthetic property of the membranaceous thing of acrylic resin of the present invention (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet, can on various base materials, be provided with and band layer (B).For example, can use the printed matter of suitable print process printing as required.At this moment, preferably a side that one of is selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form is carried out printing treatment, as on one side, having the film that bands layer (B).In addition, from the protection that adds facing with give feeling of high class and consider, be preferably in and band layer (B) when being shaped and be configured on the commissure with substrate resin.Band the available known method of layer (B) and form, but preferably adopt print process to form printed layers, form the evaporation layer with vapour deposition method.

Banding the printed layers of layer (B), is to form pattern and literal etc. on inserts molding or mould internal shaping product surface.Printed patterns can be arbitrarily, and painting of wood grain, bag, woven design, sand streak, geometric patterns, literal, comprehensive compact composing etc. for example arranged.Adhesive material as printed layers, just like, polyethylene-based resin, polyamide-based resin, polyester based resin, polyacrylic resin, polyurethane series resin, the polyvinyl acetal of vinylchlorid/vinyl acetate between to for plastic based copolymers etc. are that resin, poly ester urethane are that resin, cellulose ester are the resin of resin, Synolac, chlorinated polyolefin resin etc.As the polyacrylic resin, for example multi-ply construction polymkeric substance (I) or resin combination (III) and resin combination (IV) can be used as adhesive material.Printed layers also can further be used the pigment that contains appropriate color or the dyestuff coloring printing ink as tinting material.

Mill pigment as being used for printed layers can use following raw material.Usually, as pigment, can use pigment, the different Yin of polyazo as yellow ultramarine etc. to cut mineral dyes such as the pigment dyestuff of quinoline ketone etc. and lead and yellow-collation, as the mineral dye of the pigment dyestuff of the pigment of polyazo of red pigment etc., quinacridone etc. and ferric oxide etc., as the mineral dye of the pigment dyestuff of phthalocyanine blue of blue pigments etc. and cobalt blue etc., as the pigment dyestuff of nigrosine of black pigment etc., as the mineral dye of titanium oxide of white pigment etc.

As the mill pigment that is used for printed layers, can in the scope that does not impair effect of the present invention, use various known dyestuffs.

In addition, as the formation method of printed layers, can use the known print process of offset printing method, intaglio plate transhipment print process, silk screen print method etc. and the known coating process of rolling method, spraying method etc., the flexographic printing method.The thickness of printed layers should be decided according to application, but is generally about 0.5～30 μ m.Because light solidified acrylic resin film of the present invention or sheet do not use low-molecular-weight cross-linked compound, and what use is to make polymkeric substance that the Photocurable resin composition of crosslinked formation take place between mutually, therefore, the problem when surperficial non-adhesiveness, printing is few, and yield rate is good.

The evaporation layer is set on one of in addition, also can be in being selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form bands layer and evaporation layer as banding layer (B), also can being provided with simultaneously.The evaporation layer is with at least a metal or their alloy or compound formation in the group that is selected from compositions such as aluminium, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc.As the method that forms the evaporation layer, the method for vacuum vapour deposition and gunite, ion plating, electrochemical plating etc. is arranged.These are to band the printed layers of usefulness and the thickness of vapour deposition method, and the inserts that is obtained by hope is shaped or the appearance of mould internal shaping product, and the degree of drawing when engagement insert shaping or mould internal shaping and suitably selecting.

In the occasion that 60 ° of surface glosses of few one side are printed smaller or equal to the membranaceous thing of 100% acrylic resin (A), consider from reducing the printing omission, preferably the high one side of 60 ° of surface glosses of film is carried out printing treatment.

To one of being selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form the number that the printing of having carried out the face of printing treatment is omitted, from aesthetic property, the consideration of banding property, preferably smaller or equal to 10/m ²The number that printing is omitted is smaller or equal to 10/m ², then the outward appearance of the lamination molding of this film is good.Carried out number that the printing of the face of printing treatment omits more preferably smaller or equal to 5/m ², most preferably be smaller or equal to 1/m ²

In addition, at the tone that utilizes the base material plastics, when being used for substituting transparent coating, can take advantage of its transparent direct use.Especially, when utilizing the tone of such base material, one of be selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form and compare with polyester resin film with vinylchlorid, better on the transparency, depth perception and feeling of high class.

Also can carry out painted processing back use to of the present invention one of be selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form.

One of at least also following layer (D) can be set as required to of the present invention being selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form.

Following layer (D) is so long as have the adaptation of banding layer (B) and thermoplastic resin described later (C), or the material of character that bands the adaptation of layer (B) and base material described later (E) gets final product, and can selected use in the synthetic resins shape material arbitrarily.For example, be under the situation of polyester based resin at thermoplastic resin (C), use polyacrylic resin better.In addition, when thermoplastic resin (C) is under the situation of resin (acrylonitrile-butadiene-styrene resin), AS resin (acrylonitrile styrene resin (AS)), vinyl chloride resin, polydiphenyl ether polystyrene, polycarbonate-based resin, styrene copolymerized system resin, polystyrene blending resin for ABS, so that to use the polyacrylic resin, polystyrene resin, polyamide-based resin, the ABS that have an affinity with these resins be resin, vinyl chloride resin etc. for well.And, be under the situation of polyolefin-based resins of polypropylene-based resin etc. when thermoplastic resin (C), can adopt heat curing-type urethane resin that has used chlorinated polyolefin resin, ethylene chloride-vinyl acetate copolymer resin, thermoprene, coumarone-indene resin, blocked isocyanate etc.For the tackiness that reduces following layer and improve thermotolerance, also can further contain hydrophobic silica and Resins, epoxy, petroleum resin etc.

In addition, on of the present invention one of be selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form, also protective membrane can be set.This protective membrane is effectively dustproof to the surface one of in the group that is selected from the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet and forms; in addition, effective to the anti-injury of Photocurable resin composition (Z) laminar surface of active energy beam pre-irradiation.

Using on light solidified acrylic resin film or the sheet under the situation of said protection film; be shaped preceding driving fit in Photocurable resin composition (Z) layer to inserts; when being shaped, directly peels off inserts, so need the adaptation of appropriateness and good detachment be arranged Photocurable resin composition (Z) layer.If the film that satisfies such condition is arranged, then can select arbitrarily.As such film, if any polyethylene mesentery, polypropylene mesentery, polyester mesentery etc.

＜stack membrane or sheet and lamination molding 〉

Among the present invention, of the present invention one of being selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form on the lamination group base material (E) can be made the lamination molding.Perhaps of the present invention one of be selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form is stacked in base material (E) with stack membrane with thermoplastic resin (C) or sheet and goes up as the lamination molding.For example, after carrying out vacuum forming and pressing the empty preliminary shaping that is shaped etc., insert preformed articles in other moulds, the injection molding substrate resin, when obtaining the inserts moulding method of vinylformic acid laminated forming product, preferably stack membrane or sheet.

Stack membrane of the present invention or sheet have of the present invention one of being selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form and thermoplastic resin (C).Preferred building materials are with stack membrane or sheet, and the external force of its impact and sex change etc. shows full intensity.For example, in inserts shaping etc., treat the film vacuum forming after, from mould, take out, these vacuum forming product are packed injection molding into when using mould, even impacted and sex change, also difficultly break, operability is good.Perhaps, also can use to improve and the thermoplastic resin (C) as purpose such as the adaptation of base material (E).And then, by using thermoplastic resin (C), for example, the transmission of the surface imperfection of giving the injection molding product one of in being selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form becomes minimum advantage, perhaps when injection molding base material (E), give and band the advantage that layer (B) is difficult to disappear.

Thermoplastic resin (C) is that purpose is considered from the adaptation that improves with base material (E), preferably selects from having the material of consistency with base material (E).In fact, thermoplastic resin (C) is preferably selected from the polymer materials identical with base material (E), can use known thermoplastic resin film or sheet.For example, acrylic resin, ABS is resin (acrylonitrile-butadiene-styrene resin), AS resin (acrylonitrile styrene resin (AS)), vinyl chloride resin, polyethylene, polypropylene, polybutene, the polyolefin-based resins of polymethylpentene etc., ethylene-vinyl acetate copolymer or its are saponified, the polyolefin multipolymer of ethene-(methyl) acrylate copolymer etc., polyethylene terephthalate, polybutylene terephthalate, poly-to (ethylene naphthalate), polyarylate, the polyester based resin of polycarbonate etc., 6-nylon, 6,6-nylon, 6,10-nylon, the polyamide resin of 12-nylon etc., polystyrene resin, the cellulose acetate resin, the derivatived cellulose of Nitrocellulose etc., fluorinated ethylene propylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene, the fluorine resin of ethylene-tetrafluoroethylene copolymer etc. etc., perhaps therefrom select multipolymer and mixture more than two kinds or three kinds, complex body, multilayer body etc.As thermoplastic resin (C), from banding the post forming consideration of formation, stack membrane or sheet of layer (B), preferred acrylic resins, ABS resin, vinyl chloride resin, polyethylene, polycarbonate.

But be used for the occasion of building materials, the preferred resin that uses halogenss such as not chloride and fluorine, promptly non-halogen is a resin.Among, the each side of the surface physical property of flexibility of operation, wear resistant and the solvent resistance etc. of the easiness of price from the market and circulation supply, the flexibility that arrives appropriateness and intensity balance, bending and cut-out cutting etc., weathering resistance etc. is considered, preferably uses the thermoplastic resin that is selected from polyolefin-based resins, acrylic resin and polyester based resin.

In thermoplastic resin (C), can contain stablizer, antioxidant, lubrication prescription, processing aid, softening agent, shock-resistant dose, whipping agent, weighting agent, antiseptic-germicide, anti-Fungicide, remover, static inhibitor, tinting material, UV light absorber, photostabilizer, thermo-stabilizer, fire retardant etc. as required.

Can be from as phenol being as antioxidant, sulphur system, phosphorus system etc., as UV light absorber as benzophenone, benzotriazole, salicylate, cyanoacrylate, carbonamidine, oxanilide, triazine system etc., as photostabilizer be as hindered amine, nickel complex system etc., as thermo-stabilizer be as hindered phenol, sulphur system, hydrazine system etc., (though they are different and different according to the resin kind) as softening agent as phthalic acid ester are, phosphoric acid ester system, fatty acid ester system, aliphatic diacid ester system, oxidation benzoate system, epoxy system, polyester system etc., as lubrication prescription be as fatty acid ester, fatty acid series, metallic soap system, fatty acid amide system, higher alcohols system, paraffin series, as static inhibitor be as positively charged ion, negatively charged ion system, nonionic system, zwitter-ion system, as fire retardant be as bromine, phosphorus system, chlorine system, nitrogen system, aluminium system, antimony system, magnesium system, boron system, zirconium system etc., as weighting agent as lime carbonate, barium sulfate, talcum, alabaster, a kind of and the two or more mixed stocker of selecting in the kaolin etc. is used.

Addition means as above-mentioned Synergist S-421 95, have the thermoplastic resin that forms thermoplastic resin (C) is together supplied with the method for forcing machine with raw material, and will add mixture mixing blended method in various mixing rolls of the thermoplastic resin of Synergist S-421 95 in advance.Mixing roll as using in one method of back has single shaft mixing roll, twin shaft mixing roll, Banbury, roll-type mixing roll etc. usually.

Stack membrane of the present invention or sheet generally need have disguise to the color and the defective on the surface of being pasted base material in many occasions.For stack membrane or the sheet that makes purpose has sufficient disguise, can in the thermoplastic resin that constitutes thermoplastic resin (C), add disguised pigment, thus the generation disguise of thermoplastic resin (C).In addition, be the disguise that replaces thermoplastic resin (C) to produce, the hidden contact print printed layers that can the printing ink composition that contain disguised pigment be set in the surface or the inside of thermoplastic resin (C), but also both also use.

As above-mentioned disguised pigment, desired use be high refractive index and disguised good mineral dye.Particularly, can use yellow lead, Zh 1, cadmium yellow, titan yellow, baryta yellow, quinoline a word used for translation ketone, Aureolin, molybdate orange, cadmium red, ferric oxide, red lead, cinnabar, Mars purple, manganese violet, cobalt blue, sky blue, ultramarine is indigo, the white pigment of the pigment dyestuff of emerald, sulfuric acid molybdic acid lead chromate, chromic oxide, chrome green, iron oxide black, carbon black etc. and for example titanium oxide (titanium white (Titanium white)), zinc oxide (flowers of zinc), basic lead white, zinc sulphide, lithopone, チタノッ Network ス etc. etc.

Thermoplastic resin of the present invention (C) also can be by of the same race or many laminations layer body that the xenogeneic thermoplastic resin constitutes and is constituted.

Manufacture method when thermoplastic resin (C) uses as film or sheet in advance is preferably by the melting extrusion molding and the casting method of polishing roll.When melting is extruded,, generally extrude the resin of melting state on one side foreign matter is removed with 200 orders or its above filter mesh in preferred limit.At this moment, if adopt several rollers be selected from metallic roll, nonmetal roller and metal strip or with on seize the method for system film on both sides by the arms, the film of the thermoplastic resin that then obtains (C) or the surface smoothing raising of sheet, thus preferred.Like this, can reduce the white point of the macroscopic irregularity that causes printing omission etc.

The thickness of thermoplastic resin (C), as required and suitably decision, but usually preferably about 20～500 μ m.The thickness of thermoplastic resin (C) is necessary to make the outward appearance one of be selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form to present the surface of complete slyness, absorb the surface imperfection of base material (E) or band layer (B) when injection molding and do not disappear.

For obtaining stack membrane or sheet, (1) can carry out film or the sheet that one of is selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form with thermoplastic resin (C) by known method such as lamination such as heat lamination, dried lamination, wet lamination, hot melt layer platen presses.

In addition, also can extrude and carry out lamination by lamination.Concrete, just like lower floor's platen press: (2) are on the film or sheet of thermoplastic resin (C), be extruded into membranaceous or sheet with one side meltings such as T modulus methods membranaceous thing of acrylic resin (A) or acrylic resin film, the laminated method in one side, (3) on one of in being selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form, (C) is extruded into membranaceous or sheet with one side meltings such as T modulus methods with thermoplastic resin, Yi Bian laminated method.

In addition, also have (4) that membranaceous thing of acrylic resin (A) and thermoplastic resin (C) melting are on one side extruded, simultaneously the method for lamination.Particularly, then method and the laminating method that the coextrusion of then method etc. is shaped is set outside the mould of a plurality of die lips is arranged in the mould of feed head method and many material Dow process etc. on a mould.

In addition, have acrylic resin stack membrane and the stack membrane of thermoplastic resin (C) or the method for sheet as obtaining, have with the membranaceous thing of acrylic resin (A) with and other acrylic resin film shape thing (A ') or the membranaceous thing of fluoro-resin (A ") and thermoplastic resin (C) when melting is extruded, carry out the method for lamination.Particularly, then method and the laminating method that the coextrusion of then method etc. is shaped is set outside the mould of a plurality of die lips is arranged in the mould of feed head method and many material Dow process etc. on a mould.

One of be selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form and thermoplastic resin (C) between aforesaid layer (B) and/or the pigmented layer (F) of banding can be set.

One of will being selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form of aforementioned (1) carried out preformed situation with thermoplastic resin (C), can form on any film or sheet and band layer (B).At this moment, preferred use a side at film or sheet to be formed with to band layer (B), when forming stack membrane and sheet, band layer (B) and be configured on the non-surface because of can layer (B) is protected and to give its feeling of high class preferred to banding.

In the method that thermoplastic resin (C) is pre-formed lamination after film or the sheet of aforementioned (2), make band layer (B) be formed at thermoplastic resin (C) after, make and band layer (B) side and be stacked in the opposite that one of is selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form.

One of will being selected from advance in the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form in the laminating method after being shaped of aforementioned (3), make band layer (B) side be stacked in one of be selected from the group that the membranaceous thing of acrylic resin (A), acrylic resin stack membrane, light solidified acrylic resin film or sheet form go up after, make and band the opposite that layer (B) side is stacked in thermoplastic resin (C).

As required, can carry out handling, fix the surface treatment of processing, prime treatment etc. to the one side of the membranaceous thing of acrylic resin (A), thermoplastic resin (C) etc. as corona treatment, ozonize, plasma treatment, ionizing ray processing, dichromic acid.At thermoplastic resin (C) and band between the layer (B), the adaptation between the membranaceous thing of acrylic resin (A) and the thermoplastic resin (C) etc. also can improve.

The position that is provided with for pigmented layer (F) has no particular limits, and one of can be arranged in the group that is selected from the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet and band between the layer (B) to wait, and band the position that joins between layer (B).

By one of transparent pigmented layer (F) being arranged in the group that is selected from the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet and banding between the layer (B), its outward appearance can become at the same layer (B) that bands and has various tones.

For example, in the occasion etc. of banding layer (B) by the print process setting, can obtain easily that version and printing ink do not change and different stack membrane attractive in appearance or the sheet of tone in printing engineering.Particularly using metal style and metal level when banding layer (B),, can obtain having the metal appearance of the various form and aspect of silvery white metal, golden metal and blue metal etc., thereby be preferred by transparent pigmented layer (F) is set.

By pigmented layer (F) being set banding between layer (B) and the thermoplastic resin (C), can banding layer (B) formation and have the outward appearance of the background colour of various tones same.

For example, in the occasion etc. of banding layer (B) by the print process setting, background colour utilizes the color of pigmented layer (F), only prints the design pattern beyond the background colour, like this, can easily obtain in printing engineering version and printing ink does not change and different stack membrane attractive in appearance or the sheet of tone.Particularly band layer when banding layer (B),, can obtain having the metal appearance of the various form and aspect of silvery white metal, golden metal and blue metal etc., thereby be preferred by transparent pigmented layer (F) is set in the metal style of using perviousness.

In addition, following layer (D) can be set as required.For example, can be at pigmented layer (F) or band between layer (B) and the thermoplastic resin (C), and base material (E) join and be provided with on thermoplastic resin (C) face of side.

One of the feature of lamination molding of the present invention is to follow etc. by melting, in base material (E) the superimposed layer group that is selected from the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet of the present invention.

Form the resin of base material (E), can use various known resins.As such resin, for example, polyethylene-based resin, polypropylene-based resin, polybutene are that resin, polymethylpentene are that resin, ethylene-propylene are that ethylene series resin, polystyrene resin, the ABS of resin, ethylene-propylene-butylene copolymer resin, ethylene series thermoplastic elastomer etc. is that resin (acrylonitrile-butadiene-styrene resin), AS are that resin (acrylonitrile styrene resin (AS)), acrylic resin, urethane are that resin, unsaturated polyester are that resin, epoxy are general thermoplasticity or thermosetting resins such as resin.In addition, also can use polydiphenyl ether polystyrene resin, polycarbonate-based resin, poly-acetal is that resin, polycarbonate sex change polyphenylene oxide are that general engineering resin such as resin, polyethylene terephthalate and polysulfones are that resin, Polyphenylene Sulfone are that resin, polyphenylene oxide are that resin, polyetherimide are that resin, polyimide are that resin, liquid crystal polyester are that resin, polyarylate are the super engineering resin of heat stable resin etc.And, also can use the compound resin and the various denatured resin of the modification agent of the strongthener that added glass fibre and mineral filler (talcum, lime carbonate, silicon oxide, mica etc.), rubber constituent etc.

Wherein, preferably can with the group that is selected from the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet in one of, or when stack membrane or sheet and the resin followed of thermoplastic resin (C) melting.For example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, polyvinyl chloride (PVC) RESINS, acrylic resin, polyester based resin or be the resin of principal constituent with them.From then property consideration, preferred ABS resin, AS resin, polycarbonate resin, polyvinyl chloride (PVC) RESINS or be the resin of principal constituent, preferred especially ABS resin, polycarbonate resin or be the resin of principal constituent with them with them.

But, even on the substrate resin that the non-hot melt of polyolefin resin etc., use following layer, also can one of be selected from the group of the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet and follow during base material (E) in shaping.

When the multilayer body of the lamination molding of the present invention that is shaped, two-dimensional shapes, but the base material that hot melt

Can adopt the known method of heat lamination etc.For example, the non-hot melt of metal of the woodboard of the timber plate of wood single-plate, timber plywood, shaving board, medium density fibre board (MDF) (MDF) etc., wood fibre board etc., iron, aluminium etc. base material (E), (D) can fit by following layer.

When being configured as the multilayer body of 3D shape, can adopting the known method of inserts shaping or mould internal shaping method etc., but consider preferred mould internal shaping method from generative nature.

Mould internal shaping method is to after the heating one of in the group that is selected from the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet, carries out vacuum forming in the mould with vacuum traction function.This method is because film is shaped and injection molding carries out in same operation, thereby operation, economical.

Have the membranaceous thing of known acrylic resin when carrying out the mould internal shaping that bands layer (B) in use, because the condition of mold shape, injection molding, near banding layer and can the disappear cast gate.Cast gate is divided into basically at the constant narrow unrestricted cast gate of gate part resin stream and the restriction cast gate of stream stenosis.These gate shapes because diminish near the residual stress the cast gate, cast gate by the temperature of resin rise simultaneously, near the ejaculation resin pressure of the membranaceous object plane per unit area of acrylic resin cast gate becomes big, so band layer (B) easily dissolved.But, use the membranaceous thing of acrylic resin of the present invention (A), compare with the situation of using the membranaceous thing of knowing of acrylic resin in the past, can alleviate the disappearance of banding layer (B).

Have that the stack membrane of thermoplastic resin (C) or sheet carry out that inserts is shaped or during the mould internal shaping,, therefore, be preferred in this in use because the existence of thermoplastic resin (C) can further alleviate the disappearance of banding layer (B).

Heating temperature during the mould internal shaping, the preferably softening temperature one of in the group that is selected from the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet or more than it.Concrete, decide with the thermal characteristics of film or the shape of molding, but usually at 70 ℃ or be good more than it.In addition, if the residual temperature height, the trend that then oriented appearance worsens, separability worsens development.Though this also decides with the thermal characteristics of film or the shape of molding, usually at 170 ℃ or be good below it.Have, consider from energy efficiency, the pre-heating temperature during vacuum forming is better low.Concrete, preferably smaller or equal to 135 ℃.In addition, for the low also shapable film of pre-heating temperature, can shorten the time of preheating and replace reducing pre-heating temperature.At this moment, can realize vacuum-formed high circulationization, its industrial utilization is worth high.

So,, one of be selected from the group of the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet and when high temperature, have sufficient extensibility in the occasion of giving the film 3D shape by vacuum forming, highly beneficial.

Seize the membranaceous thing of acrylic resin (A) that the system film obtains in use on both sides by the arms with several rollers or the band that are selected from metallic roll, nonmetal roller and metal strip, and use the high membranaceous thing of acrylic resin (A) that bands layer (B) of briliancy with metal tone etc., carry out vacuum-formed situation, produce the situation of bad order sometimes because of the white point in the membranaceous thing of acrylic resin (A).It is different that bad order described here and printing are omitted, and is meant the defective of depression of the surface appearance of vacuum forming product.At this moment,, can reduce the generation of such bad order, thereby be preferred by having the stack membrane or the sheet of thermoplastic resin (C).

As the base material (E) of injection molding, but can use the resin of any injection molding.If the shrinking percentage after shaping resin is shaped and the shrinking percentage of aforementioned films or sheet are close, problem such as the peeling off and also can be eliminated of the bending of inserts molding and film or sheet then, thereby be preferred.

When stack membrane of the present invention or sheet are used for the building materials purposes, except that inserts shaping or mould internal shaping,, circumvolution processing, V-arrangement cutting processing etc. can also be arranged as the method for laminated stack film or sheet.

Circumvolution processing is interval following layer (D) on the long axis direction of the column base material of cylinder, polygon prism etc., supply with stack membrane or sheet, by the different roller of several directions, pressurize in turn in a plurality of sides that constitute column then stack membrane or sheet obtain the method for lamination molding.

The V-arrangement cutting processing is a following layer (D) at first at interval, stacked stack membrane or sheet on plate-like substrate, then with the opposition side of the stack membrane or the sheet of plate-like substrate, the degree of depth with the interface that reaches stacked tunic or sheet and plate-like substrate cuts into the ditch that section is V word shape or U word dress, in ditch, be coated with tackiness agent then, bend ditch, obtain the lamination molding of casing or column.

Use contains the stack membrane or the sheet of the membranaceous thing of acrylic resin of the present invention (A), and the albinism of the acrylic film when circumvolution processing and V-arrangement cutting processing is alleviated.

When the lamination molding that uses light solidified acrylic resin film of the present invention or sheet to obtain, make the Photocurable resin composition on lamination molding surface by photocuring by rayed.As the light of irradiation, just like electron rays, ultraviolet ray, gamma-rays etc.Illuminate condition is decided by the photocuring characteristic of light-cured resin (Z) layer, but irradiation dose is generally 500～10,000mJ/cm ²About.Like this, just can obtain the lamination molding that Photocurable resin composition (Z) hardens, formed the tunicle of hard on the surface.

As required, can carry out to giving the surface treatment of its various functions the surface one of in the group that is selected from the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet.As the surface treatment of giving its function, have that the surface hardening that printing treatment, the metal tone of silk quality printing, ink jet printing etc. are given or surface hardness is handled, improved in metal evaporation, sputter, the wet plating of antireflection is handled, antipollution hydrophobization is handled or photocatalyst layer form handle, dustproof handle or for the electromagnetic anti-charged processing of blocking-up, prevent reflecting layer formation, non-glare treated etc.

The lamination molding that carries out lamination one of in the group that is selected from the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet of the present invention is specially adapted to vehicular applications, building materials purposes.Concrete, applicable to following various uses: device panel, control enclosure, the instrument lid, door lock ペゼ Le, steering wheel, automatic window conversion panel, center bunch (center cluster), the automobile inside purposes of dashboard etc., weather strip, collision bumper, the collision bumper baffle plate, side mudguard, bodyshell, spoiler, preceding grid, supporting bracket, axle cap, newel, peephole, the center is decorated, the limit mould, the door mould, the window mould, window, the front truck lampshade, back lamp shade, the automobile of the anti-parts of wind etc. is adorned purposes outward, the frontend panels of AV machine and article of furniture, button, mark, purposes such as surface cosmetic material, the shell of mobile telephone etc., display window, the purposes of button etc., and furniture is with adorning purposes outward, wall, the roof, the for building interior dress material purposes on floor etc., the outer wall of wallboard etc., fence, the roof, door, the structural exterior material purposes of the cover plate of pediment yardarm etc., window frame, door, fence, threshold, the surface cosmetic material purposes of the furniture of lintel etc., various indicating meters, lens, mirror, eye-protection glasses, the optics portion material purposes of window glass etc., perhaps electric car, the aviation machine, the inside and outside dress purposes of the various vehicles except that automobile of boats and ships etc., bottle, cosmetics containers, the various packaging vessels and the material of little container etc., other purposes such as the groceries of gift and little thing etc.

Satisfy the performance of anti-shaping albefaction, surface hardness and thermotolerance, the transparency or extinction one of in the group that is selected from the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film or sheet of the present invention, expanded use in the past greatly.Especially, good aspect the anti-shaping albefaction when carrying out inserts shaping or mould internal shaping, the membranaceous thing of the acrylic resin of the application of the invention (A), with regard to not needing to carry out the part that when replacing stamping-out (punching) processing to remove the film that overflows by hand style is constituted the albefaction of restriction is heated once again removing the operation of the part of turning white (white flavor), so industrial utilization is worth high.

Embodiment

By the following examples the present invention is elaborated, but embodiment is not construed as limiting the present invention." part " expression " mass parts " among the embodiment, " % " expression " quality % ".In addition, among the embodiment write a Chinese character in simplified form as follows:

Methyl methacrylate MMA

Methyl acrylate MA

N-butyl acrylate n-BA

Vinylbenzene St

Dimethacrylate 1,3 butylene glycol ester 1,3-BD

Allyl methacrylate(AMA) AMA

Cumene hydroperoxide CHP

Tertbutyl peroxide t-BH

Uncle's hexyl hydrogen peroxide t-HH

Octyl mercaptan n-OM

Sodium ethylene diamine tetracetate EDTA

Methacrylic acid 2-hydroxyethyl HEMA

Lauric acid superoxide LPO

(mensuration of rerum natura, evaluation method)

By following mensuration, the gel containing ratio of rerum natura, resin combination (III) and the resin combination (IV) of the multi-ply construction polymkeric substance (I) that evaluation obtains, thermoplastic polymer (II), the polymkeric substance (V-1) that contains hydroxyl and thermoplastic polymer (VII-1), and the rerum natura of membranaceous thing of acrylic resin (A) that obtains in embodiment 1～61 and the comparative example 1～28 and lamination molding etc.

The evaluation of lamination molding is to carrying out as the lamination molding in the evaluation of anti-shaping albefaction.But, be that the lamination molding made from the method for record is herein carried out to the evaluation of embodiment 24～27 and comparative example 13 and 14.

(1) weight average particle diameter of multi-ply construction polymkeric substance (I)

To the light-scattering photometer DLS-700 (trade(brand)name) of polymer emulsion Yong Da mound Electricity (strain) system of the multi-ply construction polymkeric substance (I) that obtains through emulsion polymerization, according to dynamic light scattering determination.

(2) the gel containing ratio of multi-ply construction polymkeric substance (I), resin combination (III) and resin combination (IV)

The multi-ply construction polymkeric substance (I) that to stipulate (quality before extracting) is (after the polymerization, what obtain solidifies powder), resin combination (III) is (after extruding, the little saccharoid that obtains) in acetone solvent, extracts processing under the backflow, this treatment solution is carried out centrifugation respectively, to quality measurement after the acetone insoluble components drying (extracting the back quality), the value that calculates by the following method then:

Quality (g) * 100 before gel containing ratio (%)=extraction back quality (g)/extraction.

(3) multi-ply construction polymkeric substance (I) and contain the second-order transition temperature (Tg) of the polymkeric substance (V) of hydroxyl

(value of record calculates with the FOX formula among the Polymer HandBook (J.Brandrup, Interscience, 1989) to adopt polymer handbook.

(4) reducing viscosity of thermoplastic polymer (II), the intrinsic viscosity of polymkeric substance (V) that contains hydroxyl and the reducing viscosity of thermoplastic polymer (VII)

Polymkeric substance 1.0g is dissolved in the 100mL chloroform, 25 ℃ of mensuration

(5) turbidity value before and after the tension test of the membranaceous thing of acrylic resin (A)

The tension test of the membranaceous thing of acrylic resin (A) is to use the smart mechanism of Japan to make the ストログラ Off T (trade(brand)name) of society of institute system, under 23 ℃ of in the early stage chuck spacing 25mm, speed 50mm/min, the temperature, use the test film of wide 20mm, thickness 125 μ m to make under the condition a of chuck spacing as 33mm of terminal point, and under 15 ℃ of in the early stage chuck spacing 25mm, speed 300mm/min, the temperature, the chuck spacing that makes terminal point is under the condition b of 33mm, carries out according to the test method of JIS K7127.

Turbidity value is according to the determination of test method of JISK7136 to the test film before the above-mentioned tension test and the test film after the tension test.And, surpass 40% the membranaceous thing of acrylic resin (A) for turbidity value, also carry out according to same test method.

In addition, to the inserts shaping molding of record in embodiment 24～27 and comparative example 13 and 14, also according to the determination of test method of JIS K7136.

(6) surface luster of the membranaceous thing of acrylic resin (A)

Use glossmeter (system ラカミカラ one リサ one チラ Block ラトリ one system, GM-26D type (trade(brand)name)), 60 ° of surface lusters of the one side that does not contact when surveying customised films with mirror roller.

(7) HTD (heat-drawn wire) of the membranaceous thing of acrylic resin (A)

The granule of resin combination behind injection molding, is configured as heat-drawn wire determination test sheet based on ASTM D648, carries out annealing in 4 hours at 60 ℃.Then, use this test film, under low loading (0.45MPa), measure according to ASTM D648.

(8) near the printing state cast gate when the anti-shaping albefaction of the membranaceous thing of acrylic resin (A), acrylic resin stack membrane and light solidified acrylic resin film, mould internal shaping

On the membranaceous thing of the acrylic resin that obtains (A) or acrylic resin stack membrane and light solidified acrylic resin film or sheet, form band layer (B) of wood grain style and pitch-dark style with intaglio printing.

The mold bottom that employing will have vacuum traction function, film chamber one side has 1cm ²The foursquare degree of depth be that the die assembly of groove (beginning the position of horizontal 3cm from central cast gate) of 1mm is to J85ELII type emission forming machine (society of JSW system, trade(brand)name) and ホットパッ Network システ system (Japan description printing society system, trade(brand)name) the mould internal shaping device that constitutes carries out the mould internal shaping.

The box that is shaped as long 150mm * wide 120mm * high 2mm, dark 10mm of detailed molding, the cast gate of mould be 3 places altogether, in molding central authorities 1 place is arranged respectively, respectively there is 1 place at (molding vertically) 40mm place about central cast gate, gate shape is the needlepoint type cast gate of diameter 1mm.

To having the vacuum forming of film of banding layer (B), be to be 260 ℃, 15 seconds heat-up times, well heater and intermembranously under the condition of 15mm, to heat in heater temperature, make the non-course of banding mould and join and carry out vacuum forming.

In addition, the injection molding that carries out in same mould continuously is at 250 ℃ of barrel temperatures, issuing velocity 30%, penetrates under the condition of 60 ℃ of pressure 43%, die temperature, penetrates a substrate resin from banding layer side.As substrate resin, use be thermotolerance ABS resin (UMG ABS society system, trade(brand)name " バ Le Network サ system TM25B ").

The 1cm of observable lamination molding ²The state of four directions convex part is estimated according to the following stated.In addition, also observe near the printing state that bands layer (B) of cast gate, estimate according to the following stated.

(about albefaction)

Zero: the albefaction of no film

△: the faint albefaction of film is arranged

*: the strong albefaction of film is arranged

^*When using matt film (embodiment 7～16, comparative example 4,5)

Zero: the albefaction of no film

*: the albefaction of film is arranged

(about fracture)

Zero: the fracture of no film

*: the fracture of film is arranged

(about near the printing state the cast gate)

Zero: do not have the disappearance of printing

*: the disappearance of printing is arranged

(9) the anti-shaping albefaction of stack membrane

The stack membrane that obtains is configured in the mould with vacuum traction function, makes the membranaceous thing of acrylic resin (A) side, carry out vacuum forming after 1 minute, the part of not wanting is pruned away 140 ℃ of heating in film chamber side.Mold bottom in the film chamber of film chamber side one side has 1cm ²The foursquare degree of depth be that the stack membrane in that configuration vacuum in the bottom of mould becomes makes the membranaceous thing side of acrylic resin be positioned at film chamber side the mould of groove (beginning the position of horizontal 3cm from central cast gate) of 1mm.Then, in the thermoplastic resin film side injection molding base material ABS resin (UMGABS society system, trade(brand)name " ダィヤペット ABS バ Le Network サ system TM25B ") of stack membrane), adopt inserts to be shaped and obtain the lamination molding.

Injection molding is to use society of JSW system J85ELII type emission forming machine, at 250 ℃ of barrel temperatures, issuing velocity 30%, penetrate and carry out under the condition of 60 ℃ of pressure 43%, die temperature.

The 1cm of observable lamination molding ²The state of four directions convex part is estimated by the benchmark identical with (8).

(10) heat-resistant aging of lamination molding test

To estimating by following standard in the outward appearance of 400 hours molding of 80 ℃ of heating

Zero: no change

*: albefaction is arranged, send out turbid

In addition, to using the molding of matt film (embodiment 7～16, comparative example 4,5), the outward appearance that heats 400 hours molding at 100 ℃ is estimated by following standard

Zero: no light echo

*: light echo is arranged

(11) pencil hardness of acrylic resin film and lamination molding

Measure according to JIS K5400

(12) lamination molding, the building materials scuff resistance of stack membrane

On 5 eclipsed gauzes, apply the loading of 0.049MPa, at stroke be between 100mm with 30 times back and forth/minute speed back and forth the lamination molding after the scratch 200 times, the outward appearance of stack membrane are estimated by following.

Zero: do not have and hinder

△: wound is arranged, and the scratch part is not seen albefaction

*: wound is arranged, and the scratch part is seen albefaction

In addition, to having used the lamination molding of matt film (embodiment 7～16,52～61, comparative example 4,5,25～28), estimate by following outward appearance to the molding after reciprocal 100 scratches.

Zero: do not have and hinder

△: weak wound is arranged

*: strong wound is arranged

(13) the anti-aromaticity of lamination molding

Place the polyethylene rounding tube of internal diameter 38mm, high 15mm on the surface of molding, with pressing device to make it tight driving fit on test film, inject the automobile perfume compound (ダィャケミカ Le society system, trade(brand)name " ダレィスメィト Port ピ one " oranges and tangerines system) of 5mL to its peristome.Then, after peristome is added a cover sheet glass, put into the thermostatic bath that keeps 55 ℃ and placed 4 hours.Then, remove and pressing device, air-dry behind the water-wash test sheet, the condition of surface of viewing test portion is performed as follows evaluation.

Zero: no change

*: there is crystal mass to separate out

(14) outward appearance of lamination molding

By visual, following evaluation is carried out in the wood grain style printing of molding or the outward appearance of pitch-dark style printing.

Zero: observe distinct printing

△: very little observe the printing that the part of turning white weakens

*: observe the printing that the part of turning white weakens

(15) thickness of light solidified acrylic resin film

With transmission electron microscope JEM100S (Jeol Ltd.'s system, trade(brand)name), the section of light solidified acrylic resin film is observed, measure the thickness of Photocurable resin composition (Z) layer and the membranaceous thing of acrylic resin (A) layer.

(16) wear resistant of the lamination molding that obtains by the light solidified acrylic resin film

Use テ one バ, one wear test (sheet side 500g loading, CS-10F (trade(brand)name)) abrasion wheel, measure the turbidity behind the speed of rotation 60rpm, test number (TN) 100 times and 500 times.Use then (turbidity value after the test)-the numeric representation wear resistant (%) of (test before turbidity value) expression.

(17) adaptation of inserts shaping molding

Based on JIS K5400, estimate with grid band method.

(18) crooked elastic rate of resin combination (III)

Use the smart mechanism of Japan Japan to make the ストログラ Off T of society of institute system, the test method according to ASTM D790 under the condition of length of support 100mm, rate of bending 3mm/min is carried out.

The granule of resin combination (III) behind injection molding, is configured as heat-drawn wire determination test sheet based on ASTM D648, uses this test film to measure.

(19) the building materials anti-shaping albefaction of stack membrane

Demonstrate to obtaining the outward appearance that circumvolution that the lamination molding carries out adds the lamination molding surface in man-hour.Be expressed as follows.

(about albefaction)

Zero: the albefaction of no film

△: the faint albefaction of film is arranged

*: the strong albefaction of film is arranged

(about fracture)

Zero: the fracture of no film

*: the fracture of film is arranged

(20) the building materials anti-light echo of stack membrane

Demonstrate outward appearance at the stack membrane of surface temperature after keeping 24 hours under 90 ℃ the state of stack membrane.Be expressed as follows.

Zero: no light echo

*: light echo is arranged

(21) the anti-crooked albefaction of the membranaceous thing of acrylic resin (A) (index of anti-shaping albefaction) is under 20 ℃ atmosphere gas, demonstrates at the membranaceous thing of acrylic resin (A) of thickness 125 μ m than under the fast speeds, makes 180 ° of albefaction states when crooked.Be expressed as follows.

◎: unconfirmed have an albefaction

Zero: few albefaction is only arranged

△: can confirm has some albefactions

*: albefaction takes place

* *: produces fracture

(22) the system film of the membranaceous thing of acrylic resin (A)

Situation when demonstrating the membranaceous thing of acrylic resin (A) the system film of thickness 125 μ m in the T modulus method.Be expressed as follows.

Zero: have at 5 hours or more than it possibility that film does not rupture

△: in 5 hours, the cut-out of film for several times takes place.

(23) total light transmittance of the membranaceous thing of acrylic resin (A)

Estimate according to JIS K6714.

(24) the anti-light echo of lamination molding

Demonstrate the casting mold that is the delustring shape with the surface, through the vinyl chloride sheet of membranaceous thing of the acrylic resin of 125 μ m (A) and thick 3mm being carried out the outward appearance of lamination molding when heating 15 hours for 85 ℃ that die forming obtains.Be expressed as follows.

Zero: no light echo

*: light echo is arranged

(25) the anti-hair cosmetic agent of lamination molding

On the acrylate resin layer side surface of lamination molding, with 2g/105cm ²Be coated with Block ラバスヘァリキッ De (trade(brand)name, Shiseido society system) as hair cosmetic agent with finger equably, on test film, place very little flannel, place 80 ℃ baking box.After one week, take out washing (can use a spot of neutral detergent), air-dry after, the visual observation condition of surface is pressed following evaluation albefaction and convexo-concave occurrence degree.

(albefaction)

Zero: do not see albefaction

*: see the part albefaction

(concavo-convex)

Zero: do not see concavo-convex

*: on one side, see concavo-convex

The manufacturing of＜multi-ply construction polymkeric substance (I-1) 〉

In the container that has been equipped with stirrer, add 10.8 parts of deionized waters after, drop into again by 4.5 parts of 0.3 part of MMA, n-BA, 1, the monomer component of 0.05 part of 0.2 part of 3-BD, AMA and 0.025 part of formation of CHP at room temperature mixes.Then, stir on the limit, and 1.3 parts of emulsifying agents (chemical industry society of eastern nation system, trade(brand)name " Off ォス Off ァノ one Le RS10NA ") are dropped on the limit in said vesse, continues to stir 20 minutes, modulates emulsion.

Then, in the aggregation container that has water cooler, drop into 139.2 parts of deionized waters, be warmed up to 75 ℃.And then, in aggregation container, be dropped in simultaneously and added the mixture that 0.20 part of methane amide sodium hydrosulfite 90min, 0.0001 part in ferrous sulfate and the modulation of EDTA0.0003 part form in 5 parts of ion exchanged waters.Then, under nitrogen, while stirring synthetic emulsion was splashed in the aggregation container in 8 minutes, continue reaction 15 minutes then, treat innermost layer polymkeric substance la m (I-1-A ₁) polymerization finish.Then, will be by 14.4 parts of 9.6 parts of MMA, n-BA, 1, the monomer component of 1.0 parts of 3-BD and 0.25 part of formation of AMA and CHP0.016 part one coexist and splash in the aggregation container in 90 minutes, continue reaction 60 minutes then, obtain containing innermost layer polymkeric substance outside layer (I-1-A ₂) innermost layer polymkeric substance (I-1-A).Innermost layer polymkeric substance la m (I-1-A ₁) independent Tg be-48 ℃, innermost layer polymkeric substance outside layer (I-1-A ₂) independent Tg be-10 ℃.

Then, will be coexisted by 4 parts of 6 parts of MMA, MA and 0.075 part of monomer component that constitutes of AMA and CHP0.125 part 1 splashed in the aggregation container in 45 minutes, continued reaction 60 minutes then, made it to form intermediate layer polymer (I-1-B).The independent Tg of intermediate layer polymer (I-1-B) is 60 ℃.

Then, to in 140 minutes, splash in the aggregation container by 0.264 part of 3 parts of 57 parts of MMA, MA, n-OM and 0.075 part of monomer component that constitutes of t-BH, continue reaction 60 minutes then, form outermost layer polymkeric substance (I-1-C), obtain the polymer emulsion of multi-ply construction polymkeric substance (I-1).The independent Tg of outermost layer polymkeric substance (I-1-C) is 99 ℃.

The weight average particle diameter of the multi-ply construction polymkeric substance of measuring after the polymerization (I-1) is 0.11 μ m.

With the mesh that the SUS system has been installed (average mesh: oscillating mode filtration unit 62 μ m), filter the polymer emulsion of the multi-ply construction polymkeric substance (I-1) that obtains after, in the aqueous solution that contains 3.5 parts of calcium acetates, saltout, after drying is reclaimed in washing.Obtain the multi-ply construction polymkeric substance (I-1) of powder shaped.The gel containing ratio of multi-ply construction polymkeric substance (I-1) is 70%.

In addition, filter multi-ply construction polymkeric substance (I-1) 214.3g that obtains with the nylon mesh of mesh 25 μ m and put among the acetone 1500ml, stirred 3 hours, be modulated into the acetone dispersion liquor of multi-ply construction polymkeric substance (I-1).Then, after this dispersion liquid filtered with the nylon mesh of mesh 32 μ m, in chloroform, carry out 15 minutes ultrasonic cleaning, thereby clean seizure thing on the nylon mesh with chloroform with the nylon mesh.Follow seizure thing and filtering net behind the above-mentioned ultrasonic cleansing of input in the filtering 150ml acetone of nylon mesh of mesh 25 μ m, this liquid is carried out removing the nylon mesh after the ultrasonication in 15 minutes, be modulated into the acetone dispersion liquor 150ml of the seizure thing on the mesh.Then, this dispersion liquid 70ml is measured down at 25 ℃ with the sub-tester of self acting liquid particle (KL-01) of リォ Application Co., Ltd. system, trying to achieve diameter is 10 more than or equal to the particle number of 55 μ m.

＜2. the manufacturing of multi-ply construction polymkeric substance (I-2) 〉

With innermost layer polymkeric substance la m (I-1-A1) that contains multi-ply construction polymkeric substance (I-1) and innermost layer polymkeric substance outside layer (I-1-A ₂) same the obtaining of innermost layer polymkeric substance (I-1-A) contain innermost layer polymkeric substance la m (I-2-A ₁) and innermost layer polymkeric substance outside layer (I-2-A ₂) innermost layer polymkeric substance (I-2-A).Innermost layer polymkeric substance la m (I-2-A ₁) independent Tg be-48 ℃, innermost layer polymkeric substance outside layer (I-2-A ₂) independent Tg be-10 ℃.

Then, the formation intermediate layer polymer (I-2-B) same with the intermediate layer polymer (I-1-B) of multi-ply construction polymkeric substance (I-1).The independent Tg of intermediate layer polymer (I-2-B) is 60 ℃.

Then, to in 140 minutes, splash in the aggregation container by 0.264 part of 0.6 part of 59.4 parts of MMA, MA, n-OM and 0.075 part of monomer component that constitutes of t-BH, continue reaction 60 minutes then, form outermost layer polymkeric substance (I-2-C), obtain the polymer emulsion of multi-ply construction polymkeric substance (I-2).The independent Tg of outermost layer polymkeric substance (I-2-C) is 104 ℃.

The weight average particle diameter of the multi-ply construction polymkeric substance of measuring after the polymerization (I-2) is 0.11 μ m.

With the mesh that the SUS system has been installed (average mesh: oscillating mode filtration unit 62 μ m), filter the polymer emulsion of the multi-ply construction polymkeric substance (I-2) that obtains after, in the aqueous solution that contains 3.5 parts of calcium acetates, saltout, after drying is reclaimed in washing.Obtain the multi-ply construction polymkeric substance (I-2) of powder shaped.The gel containing ratio of multi-ply construction polymkeric substance (I-2) is 70%.

In addition, be 11 with the same diameter of obtaining the multi-ply construction polymkeric substance (I-2) that obtains of multi-ply construction polymkeric substance (I-1) more than or equal to the particle number of 55 μ m.

＜3. the manufacturing of multi-ply construction polymkeric substance (I-3) 〉

Drop into by 4.5 parts of 0.3 part of MMA, n-BA, 1 add 8.5 parts of deionized waters in possessing the container of stirrer after, the monomer component of 0.05 part of 0.2 part of 3-BD, AMA and 0.025 part of formation of CHP at room temperature mixes.Then, in said vesse, drop into 1.3 parts of emulsifying agents (chemical industry society of eastern nation system, trade(brand)name " Off ォス Off ァノ one Le RS610NA ") while stirring, continue stirring and be modulated into emulsion in 20 minutes.

Then, in the aggregation container that has water cooler, drop into 186.5 parts of deionized waters, be warmed up to 70 ℃.And then, in aggregation container, be dropped in simultaneously and added the mixture that 0.20 part of methane amide sodium hydrosulfite 90min, 0.0001 part in ferrous sulfate and the modulation of EDTA0.0003 part form in 5 parts of ion exchanged waters.Then, under nitrogen, while stirring synthetic emulsion was splashed in the aggregation container in 8 minutes, continue reaction 15 minutes then, treat innermost layer polymkeric substance la m (I-3-A ₁) polymerization finish.Then, will be by 22.5 parts of 1.5 parts of MMA, n-BA, 1, the monomer component of 1.0 parts of 3-BD and 0.25 part of formation of AMA and CHP0.016 part one coexist and splash in the aggregation container in 90 minutes, continue reaction 60 minutes then, obtain containing innermost layer polymkeric substance outside layer (I-3-A ₂) innermost layer polymkeric substance (I-3-A).Innermost layer polymkeric substance la m (I-3-A ₁) independent Tg be-48 ℃, innermost layer polymkeric substance outside layer (I-3-A ₂) independent Tg be-48 ℃.

Then, will be coexisted by 0.125 part 1 of 6 parts of MMA, n-BA4 part and 0.075 part of monomer component that constitutes of AMA and CHP splashed in the aggregation container in 45 minutes, continued reaction 60 minutes then, made it to form intermediate layer polymer (I-3-B).The independent Tg of intermediate layer polymer (I-3-B) is 20 ℃.

Then, to in 140 minutes, splash in the aggregation container by 0.19 part of 4.8 parts of MMA 55.2, n-BA, n-OM and 0.08 part of monomer component that constitutes of t-BH, continue reaction 60 minutes then, form outermost layer polymkeric substance (I-3-C), obtain the polymer emulsion of multi-ply construction polymkeric substance (I-3).The independent Tg of outermost layer polymkeric substance (I-3-C) is 84 ℃.

The weight average particle diameter of the multi-ply construction polymkeric substance of measuring after the polymerization (I-3) is 0.12 μ m.

With the mesh that the SUS system has been installed (average mesh: oscillating mode filtration unit 62 μ m), filter the polymer emulsion of the multi-ply construction polymkeric substance (I-3) that obtains after, in the aqueous solution that contains 3 parts of calcium acetates, saltout, after drying is reclaimed in washing.Obtain the multi-ply construction polymkeric substance (I-3) of powder shaped.The gel containing ratio of multi-ply construction polymkeric substance (I-3) is 60%.

＜4. the manufacturing of multi-ply construction polymkeric substance (I-4) 〉

Under nitrogen atmosphere, in the reactor that has reflux cooler, add 310 parts of deionized waters, be warmed up to 80 ℃.Then, add (one) shown below, add the raw material (two) of innermost layer polymkeric substance (I-4-A) usefulness shown below while stirring continuously, then, carry out polymerization in 120 minutes, obtain the latex of innermost layer polymkeric substance (I-4-A).The independent Tg of innermost layer polymkeric substance (I-4-A) is-35 ℃.

Then, in this latex, add the methane amide sodium hydrosulfite 90min of 10 parts of deionized waters and 0.15 part, kept 15 minutes.Then, under nitrogen atmosphere in 80 ℃ of raw materials (three) that in 100 minutes, add innermost layer polymkeric substance (I-4-A) usefulness shown below while stirring continuously, keep carrying out in 60 minutes polymerization at 80 ℃ then, form outermost layer polymkeric substance (I-4-C), obtain the polymer emulsion of outermost layer polymkeric substance (I-4-C).The independent Tg of outermost layer polymkeric substance (I-4-C) is 99 ℃.

The weight average particle diameter of the multi-ply construction polymkeric substance (I-4) that obtains is 0.12 μ m.

Polymer emulsion to the multi-ply construction polymkeric substance (I-4) that obtains carries out condensation, aggegation, curing reaction with calcium acetate, filters, the washing after drying obtains multi-ply construction polymkeric substance (I-4).

(1) single (Empilan NP) phosphatase 24 0% and two (0.5 part of polyoxyethylene nonylbenzene

Base ether) the part corrective of the mixture of the sodium hydroxide of phosphoric acid 60%

0.1 part in yellow soda ash

0.5 part of methane amide sodium hydrosulfite 90min

0.00024 part in ferrous sulfate

0.00072 part of EDTA

(2) n-BA is 81.0 parts

19.0 parts of St

1.0 parts of AMA

0.25 part of t-BH

Single (Empilan NP) phosphatase 24 0% and two (1.1 parts of polyoxyethylene nonylbenzenes

(3) MMA is 57.0 parts

3.0 parts of MA

0.2 part of n-OM

0.1 part of t-BH

＜5. the manufacturing of multi-ply construction polymkeric substance (I-5) 〉

Under nitrogen atmosphere, in the reactor that has reflux cooler, add 244 parts of deionized waters, be warmed up to 80 ℃.Then, add (four) shown below, add innermost layer polymkeric substance la m (I-5-A shown below while stirring ₁) usefulness raw material (four) 1/15, kept 15 minutes.Then, be to add continuously in 8%/time remaining raw material (five) in increment rate with respect to the monomer component [raw material (five)] of water.Kept 60 minutes, and obtained innermost layer polymkeric substance la m (I-5-A ₁) latex.Innermost layer polymkeric substance (I-5-A ₁) independent Tg be 24 ℃.

Then, in this latex, add 0.6 part methane amide sodium hydrosulfite 90min, kept 15 minutes.Then, under nitrogen atmosphere, be to add innermost layer polymkeric substance outside layer (I-5-A shown below in 4%/time continuously in increment rate while stirring with respect to the monomer component [raw material (six)] of water in 80 ℃ ₂) raw material (six) of usefulness, kept 120 minutes, obtain innermost layer polymkeric substance outside layer (I-5-A ₂) latex.Innermost layer polymkeric substance outside layer (I-5-A ₂) independent Tg be-38 ℃.

Then, in this latex, add 0.4 part methane amide sodium hydrosulfite 90min, kept 15 minutes.Then, under nitrogen atmosphere, be to add the raw material (seven) of outermost layer polymkeric substance (I-5-C) usefulness shown below in 10%/time continuously in increment rate while stirring with respect to the monomer component [raw material (seven)] of water in 80 ℃, kept 60 minutes, carry out the polymerization of outermost layer polymkeric substance (I-5-C), obtain the polymer emulsion of outermost layer polymkeric substance (I-5-C).The independent Tg of outermost layer polymkeric substance (I-5-C) is 99 ℃.

The weight average particle diameter of the multi-ply construction polymkeric substance (I-5) that obtains is 0.28 μ m.

Polymer emulsion to the multi-ply construction polymkeric substance (I-5) that obtains carries out condensation, aggegation, curing reaction with calcium acetate, filters, the washing after drying obtains multi-ply construction polymkeric substance (I-5).

(4) the methane amide sodium hydrosulfite 90min is 0.6 part

0.000124 part in ferrous sulfate

0.0003 part of EDTA

(5) MMA is 22.0 parts

15.0 parts of n-BA

15.0 parts of St

0.4 part of AMA

1,0.14 part of 3-BD

0.18 part of t-BH

Single (Empilan NP) phosphatase 24 0% and two (1.0 parts of polyoxyethylene nonylbenzenes

(6) n-BA is 50.0 parts

10.0 parts of St

0.4 part of AMA

1,0.14 part of 3-BD

0.2 part of t-HH

(7) MMA is 57.0 parts

3.0 parts of MA

0.3 part of n-OM

0.06 part of t-BH

＜contain the manufacturing of the polymkeric substance (V-1) of hydroxyl 〉

In the reactor that possesses stirrer, reflux cooler, nitrogen inlet etc., add following mixture.

(8) MA is 1 part

79 parts of MMA

20 parts of HEMA

0.14 part of n-OM

0.5 part of LPO

0.05 part of methyl methacrylate/methacrylate/Jia Jibingxisuanyizhi sulfonate

Multipolymer

0.5 part in sodium sulfate

250 parts of ion exchanged waters

After fully replacing with nitrogen in the container, be heated to 75 ℃ while stirring, in stream of nitrogen gas, carry out polymerization.Be warmed up to 90 ℃ after 2 hours, and then keep finishing in 45 minutes polymerization.Then to the polymeric beads that obtains dewater, drying, obtain containing the polymkeric substance (V-1) of hydroxyl.

The intrinsic viscosity of the polymkeric substance that contains hydroxyl (V-1) that obtains is 0.076L/g, and second-order transition temperature is 93 ℃.

＜7. the manufacturing of thermoplastic polymer (VII-1) 〉

200 parts of ion exchanged waters that add nitrogen replacement in reaction vessel add 1 part of the emulsifying agent of the commodity " ラテ system Le ASK " by name of flower king system, 0.15 part of Potassium Persulphate again.

Then, add 0.004 part of 2 parts of 40 parts of MMA, n-BA and n-OM, under nitrogen atmosphere,, finish polymerization in 65 ℃ of stirrings 3 hours.

Then, in 2 hours, drip behind the monomer component of forming by MMA44 part and n-BA14 part, kept 2 hours, finish polymerization.

The polymer emulsion of the thermoplastic polymer (VII-1) that obtains is added in 0.25% aqueous sulfuric acid, make the polymkeric substance acid out after, dewater, washing, drying, reclaim the thermoplastic polymer (VII-1) of powder shaped.

The reducing viscosity of the thermoplastic polymer that obtains (VII-1) is 0.38L/g.

＜8. the manufacturing of multi-ply construction polymkeric substance (I-6) 〉

In 8 minutes, in reaction vessel, add following (nine) and (ten), under nitrogen atmosphere, add while stirring in 75 ℃.Kept then 60 minutes, and obtained innermost layer polymkeric substance la m (I-6-A ₁) latex.Innermost layer polymkeric substance la m (I-6-A ₁) independent Tg be-37 ℃.Then, under nitrogen atmosphere, in 120 minutes, drip while stirring following (11) in 75 ℃, kept then 60 minutes, polymerization is finished, form innermost layer polymkeric substance outside layer (I-6-A ₂) latex.Innermost layer polymkeric substance outside layer (I-6-A ₂) independent Tg be-49 ℃.

Then, under nitrogen atmosphere, in 45 minutes, drip while stirring following (12) in 75 ℃, kept then 60 minutes, polymerization is finished, form middle layer (I-6-B).The independent Tg in middle layer (I-6-B) is-10 ℃.

At last, under nitrogen atmosphere, in 90 minutes, drip while stirring following (13) in 75 ℃, drip finish after, stirred 60 minutes at 75 ℃, the reaction of outermost polymer layer (I-6-C) is finished.The independent Tg of outermost polymer layer (I-6-C) is 68 ℃.

The median size of the multi-ply construction polymkeric substance (I-6) that obtains is 0.11 μ m.

With the mesh that the SUS system has been installed (average mesh: oscillating mode filtration unit 62 μ m), filter the polymer emulsion of the multi-ply construction polymkeric substance (I-6) that obtains after, in the aqueous solution that contains 3.5 parts of calcium acetates, saltout, after drying is reclaimed in washing.Obtain the multi-ply construction polymkeric substance (I-6) of powder shaped.The gel containing ratio of multi-ply construction polymkeric substance (I-6) is 75%.

(9) deionized water is 200 parts

0.2 part of methane amide sodium hydrosulfite 90min

0.0001 part in ferrous sulfate

0.0003 part of EDTA

(10) MMA is 1.6 parts

8.0 parts of n-BA

1,0.4 part of 3-BD

0.0003 part of EDTA

0.1 part of AMA

0.05 part of CHP

East chemical industry society of nation system: 0.9 part of Off ォス Off ァノ one Le RS610NA

(trade(brand)name)

2 parts of (11) MMA

37 parts of n-BA

1,1 part of 3-BD

0.5 part of AMA

0.5 part of CHP

4 parts of (12) MMA

6 parts of n-BA

0.01 part of AMA

0.05 part of CHP

34 parts of (13) MMA

6 parts of n-BA

0.5 part of t-BH

0.13 part of n-OM

＜9. on side chain, have a manufacturing of the thermoplastic resin (z-1) of free-radical polymerised unsaturated group 〉

In the four-hole boiling flask of the 1L that possesses nitrogen inlet, stirrer, condenser and thermometer, add 50 parts of methylethylketones, be warming up to 80 ℃.The mixture of 0.5 part of 79.9 parts of methyl methacrylates, 20.1 parts of glyceral methacrylate and Diisopropyl azodicarboxylate dripped in 3 hours under nitrogen atmosphere.Then, add the mixture of 0.2 part of 80 parts of methylethylketones 80 parts (79.6 ℃ of boiling points) and Diisopropyl azodicarboxylate, carry out polymerization.After 4 hours, add 10.1 parts in 74.4 parts of methylethylketones, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphines and vinylformic acid, be blown into air on one side 80 ℃ of stirrings 30 hours.Then, after the cooling, from flask, take out reactant, obtain on side chain, having the solution of the thermoplastic resin (z-1) of free-radical polymerised unsaturated group.

The monomeric percent polymerization that has the thermoplastic resin (z-1) of free-radical polymerised unsaturated group on side chain is more than or equal to 99.5%, the solid about 35 quality % of shape component of polymkeric substance, number-average molecular weight is about 30,000, about 105 ℃ of second-order transition temperature, two key equivalent average out to 788g/mol.

＜10. colloid silica (manufacturing of inorganic fine particles (a-3)) 〉

In the flask that possesses stirrer, condenser and thermometer, add IPA-ST (Virahol dispersoid silicon-dioxide) (daily output chemical industry (strain) system of dividing the molar part that converts by solid shape, silicon-dioxide particle diameter=15nm) 1 part, KBM503 (γ-methacryloxypropyl trimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry (strain) system), molecular weight=248) 0.1 part, 0.3 part in water, bath temperature is elevated to 75 ℃ while stirring, this thermotonus 2 hours, obtain being scattered in the colloid silica that handle with silane compound on the surface in the Virahol thus.Then, heat up in a steamer Virahol after, add toluene (110.6 ℃ of boiling points), this operation is carried out repeatedly, by replacing Virahol fully with toluene, obtains being scattered in surface in the toluene with the colloid silica of silane compound processing.

The manufacturing of＜11. light-cured resin solution 〉

Be modulated into by the mass parts of solid shape branch conversion, by 100 parts of the thermoplastic resins that on side chain, has free-radical polymerised unsaturated group (z-1), 3 parts of 1-hydroxycyclohexylphenylketones (Photoepolymerizationinitiater initiater (z-2)), (66 parts of light-cured resin solution of forming of inorganic fine particles (a-3) with the propeller type mixer stirring.

The manufacturing of＜12. multi-ply construction polymkeric substance (I-7) 〉

In possessing the aggregation container of water cooler, add 150 parts of deionized waters, be warmed up to 75 ℃.And then, in aggregation container, be dropped in simultaneously and added the mixture that 0.20 part of methane amide sodium hydrosulfite 90min, 0.0001 part in ferrous sulfate and the modulation of EDTA0.0003 part form in 5 parts of ion exchanged waters.Then, under nitrogen, add while stirring by 22.5 parts of 6 parts of MMA, n-BA, 1,0.3 part of 1.2 parts of 3-BD, AMA, CHP0.041 part, emulsifying agent (chemical industry society of eastern nation system: Off ォス Off ァノ one Le RS610NA (trade(brand)name)) 1/6 of the monomer component of 1.3 parts of compositions, kept 15 minutes.Then, in 90 minutes, the residual monomers composition is added continuously.Again, kept 60 minutes, obtain the latex of innermost layer polymkeric substance (I-7-A).The independent Tg of innermost layer polymkeric substance (I-7-A) is-33 ℃.

Then, will be coexisted by 0.0125 part 1 of 0.07 part of monomer component of forming of 3.97 parts of 5.96 parts of MMA, MA, AMA and CHP splashed in aggregation container in 45 minutes, continued reaction 60 minutes then, formed intermediate layer polymer (I-7-B).The independent Tg of intermediate layer polymer (I-7-B) is 60 ℃.

Then, to in 140 minutes, splash in the aggregation container by 0.264 part of 3 parts of 57 parts of MMA, MA, n-OM and 0.075 part of monomer component that constitutes of t-BH, continue reaction 60 minutes then, form outermost layer polymkeric substance (I-7-C), obtain the polymer emulsion of multi-ply construction polymkeric substance (I-7).The independent Tg of outermost layer polymkeric substance (I-7-C) is 99 ℃.

The weight average particle diameter of measuring after the polymerization is 0.11 μ m.

With the mesh that the SUS system has been installed (average mesh: oscillating mode filtration unit 62 μ m), filter the polymer emulsion of the multi-ply construction polymkeric substance (I-7) that obtains after, in the aqueous solution that contains 3.5 parts of calcium acetates, saltout, after drying is reclaimed in washing.Obtain the multi-ply construction polymkeric substance (I-7) of powder shaped.The gel containing ratio of multi-ply construction polymkeric substance (I-7) is 70%.

The manufacturing of＜13. multi-ply construction polymkeric substance (I-8)～(I-16) 〉

With with the same method of manufacturing of multi-ply construction polymkeric substance (I-7), produce multi-ply construction polymkeric substance (I-8), (I-9) that each layer constitutes with monomer component shown in the table 1.

With with the same method of manufacturing of multi-ply construction polymkeric substance (I-1), produce the multi-ply construction polymkeric substance (I-10)～(I-2) that each layer constitutes with monomer component shown in the table 1.

With with the same method of manufacturing of multi-ply construction polymkeric substance (I-3), produce the multi-ply construction polymkeric substance (I-13)～(I-16) that each layer constitutes with monomer component shown in the table 1.In the manufacturing of (I-15), (I-16), each polymerization single polymerization monomer rate of addition is consistent with creating conditions of (I-3), and the polymerization of innermost layer polymkeric substance (I-A) makes outermost layer polymkeric substance (I-C) polymerization after finishing immediately.

The Tg that constitutes the polymkeric substance of each layer is shown in table 1.

(embodiment 1)

In 100 parts in multi-ply construction polymkeric substance (I-1), interpolation is as 2.7 parts of チバスペシャリティケミカ Le ズ society system trade(brand)names " チヌ PVC Application 234 ", Xu Dianhuagongyeshe system trade(brand)name " the ァデカスタ Block AO-50 " 0.1 part of Synergist S-421 95, and after 0.3 part of the Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block LA-57 ", mix with the Henschel mixing tank.After this mixture (resin combination (III-1)) is heated to 230 ℃, supply with degassing formula forcing machine (pond shellfish ironworker (strain) makes PCM-30 (trade(brand)name)), carry out mixingly, obtain granule.

The granule that to make with aforesaid method is at 80 ℃ of dry diels, with the crooked screwe-type xtruder (L/D=26) of the nothing of the 40mm φ that the wide T mould of 300mm has been installed, under the condition of 180～240 ℃ of barrel temperatures, 240 ℃ of T mould temperature, make film, obtain the thick membranaceous thing of acrylic resin (A) of 125 μ m.The formation of banding layer (B) is good, and printing is omitted few.

(embodiment 2)

Except using 100 parts in 90 parts in multi-ply construction polymkeric substance (I-1) and thermoplastic polymer (II-1) (MMA/MA=99/1 (mass ratio), reducing viscosity η sp/c=0.06L/g) 10 parts of replacements multi-ply construction polymkeric substance (I-1), obtain mixture (resin combination (III-2)) similarly to Example 1, make film, obtain the membranaceous thing of acrylic resin (A).The formation of banding layer (B) is good, and printing is omitted few.

(embodiment 3)

Except using 100 parts in 75 parts in multi-ply construction polymkeric substance (I-1) and thermoplastic polymer (II-1) 25 parts of replacements multi-ply construction polymkeric substance (I-1), obtain mixture (resin combination (III-3)) similarly to Example 1, make film, obtain the membranaceous thing of acrylic resin (A).The formation of banding layer (B) is good, and printing is omitted few.

(embodiment 4)

Except using 100 parts in 90 parts in multi-ply construction polymkeric substance (I-2) and thermoplastic polymer (II-1) 10 parts of replacements multi-ply construction polymkeric substance (I-1), obtain mixture (resin combination (III-4)) similarly to Example 1, make film, obtain the membranaceous thing of acrylic resin (A).The formation of banding layer (B) is good, and printing is omitted few.

(embodiment 5)

Replace 2.7 parts of チバスペシャリティケミカ Le ズ society's system trade(brand)names " チヌ PVC Application 234 " as the Synergist S-421 95 except adding 2.1 parts of Xu Dianhuagongyeshe system trade(brand)names " ァデカスタ Block LA-31 ", obtain mixture (resin combination (III-5)) similarly to Example 3, make film, obtain the membranaceous thing of acrylic resin (A).The formation of banding layer (B) is good, and printing is omitted few.

(embodiment 6)

Except in 25 parts of 75 parts in multi-ply construction polymkeric substance (1-I) and thermoplastic polymers (II-1), add 0.3 part of 0.1 part of Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AO-50 " and Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block LA-67 " as Synergist S-421 95, obtain the granule of mixture (resin combination (III-6)) similarly to Example 3.Use the granule of this mixture (resin combination (III-6)) then, further make film, at the wide membranaceous thing of acrylic resin for the melting state extruded under the condition of 0.5mm of the sealing of T mould by two metal cooling but between the roller, state with no dumping tower tray (pitch) is seized on both sides by the arms, do not prolong and press and after duplicating, with up-coiler it is wound on the paper roll, obtains making film similarly to Example 3 outside the membranaceous thing of acrylic resin (A) of 125 μ m.The formation of banding layer (B) is good, and printing is omitted few.

(comparative example 1)

In multi-ply construction polymkeric substance (I-3), interpolation as 0.3 part of 2.1 parts of the Xu Dianhuagongyeshe of Synergist S-421 95 system trade(brand)names " ァデカスタ Block LA-31 ", 0.1 part of Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AO-50 " and Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block LA-57 " after, mix with the Henschel mixing tank.After this mixture (resin combination (III-7)) is heated to 230 ℃, supply with degassing formula forcing machine (pond shellfish ironworker (strain) makes PCM-30 (trade(brand)name)), carry out mixingly, obtain granule.Then, except using this mixture (resin combination (III-7)), similarly make film, obtain the membranaceous thing of acrylic resin (A) with embodiment 1.

(comparative example 2)

Except replacing multi-ply construction polymkeric substance (I-3) 100 especially for 68 parts with 32 parts in multi-ply construction polymkeric substance (I-4) and thermoplastic polymer (II-1), similarly obtain mixture (resin combination (III-8)) with comparative example 1, the system film obtains the membranaceous thing of acrylic resin (A).

(comparative example 3)

Except replacing multi-ply construction polymkeric substance (I-3) 100 especially for 84 parts with 16 parts in multi-ply construction polymkeric substance (I-5) and thermoplastic polymer (II-1), similarly obtain mixture (resin combination (III-9)) with comparative example 1, the system film obtains the membranaceous thing of acrylic resin (A).

(embodiment 7)

With the Henschel mixing tank to 100 parts in multi-ply construction polymkeric substance (I-1), contain 10 parts in the polymkeric substance (V-1) of hydroxyl, as 2.7 parts of the チバスペシャリティケミカ Le ズ society of Synergist S-421 95 system trade(brand)names " チヌ PVC Application 234 ", Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AO-50 " 0.1 part, and Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block LA-57 " 0.3 part mixes.After this mixture (resin combination (IV-1)) is heated to 230 ℃, supply with degassing formula forcing machine (pond shellfish ironworker (strain) makes PCM-30 (trade(brand)name)), carry out mixingly, obtain granule.

With the above-mentioned granule that obtains at 80 ℃ of dry diels, with the crooked screwe-type xtruder (L/D=26) of the nothing of the 40mm φ that the wide T mould of 300mm has been installed, under the condition of 180～240 ℃ of barrel temperatures, 240 ℃ of T mould temperature, make film, obtain the thick membranaceous thing of acrylic resin (A) of 125 μ m.

(embodiment 8)

Except replacing multi-ply construction polymkeric substance (I-1) 100 especially for 10 parts with the thermoplastic polymer (II-1) that uses among 90 parts in multi-ply construction polymkeric substance (I-1), the embodiment 2, obtain mixture (resin combination (IV-2)) similarly to Example 7, make film, obtain the membranaceous thing of acrylic resin (A).

(embodiment 9)

Except replacing multi-ply construction polymkeric substance (I-1) 100 especially for 25 parts with the thermoplastic polymer (II-1) that uses among 75 parts in multi-ply construction polymkeric substance (I-1), the embodiment 2, obtain mixture (resin combination (IV-3)) similarly to Example 7, make film, obtain the membranaceous thing of acrylic resin (A).

(embodiment 10)

Except using 2.7 parts of チバスペシャリティケミカ Le ズ society system trade(brand)names " チヌ PVC Application 234 ", 0.1 part of Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AO-50 ", 0.3 part of Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block LA-57 " and Xu Dianhuagongyeshe to make trade(brand)name " ァデカスタ Block 260 " 0.4 especially as Synergist S-421 95, obtain mixture (resin combination (IV-4)) similarly to Example 8, make film, obtain the membranaceous thing of acrylic resin (A).

(embodiment 11)

Obtain granule similarly to Example 8.

The above-mentioned granule that obtains at 80 ℃ of dry diels, with the crooked screwe-type xtruder (L/D=26) of the nothing of the 40mm φ that the wide T mould of 300mm has been installed, under the condition of 180～240 ℃ of barrel temperatures, 240 ℃ of T mould temperature, is melt extruded by the T mould.The resin of extruding is seized on both sides by the arms with mirror roller (surface roughness of chromium plating processing is the roller of 0.25S) and the silica rubber roller that contains 50 parts in the aluminium of mean particle size 40 μ m with the cooling of temperature adjustment to 75 ℃, makes film and obtains the thick membranaceous thing of acrylic resin (A) of 125 μ m.In the occasion of the film that uses embodiment 11, do not have printing and omit generation.

(embodiment 12)

Except using 2.1 parts of Xu Dianhuagongyeshe system trade(brand)names " ァデカスタ Block LA-31 ", 0.1 part of Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AO-50 " and Xu Dianhuagongyeshe to make trade(brand)name " ァデカスタ Block LA-57 " 0.3 especially as Synergist S-421 95, obtain mixture (resin combination (IV-5)) similarly to Example 9, make film, obtain the membranaceous thing of acrylic resin (A).

(embodiment 13)

With the Henschel mixing tank to 70 parts in multi-ply construction polymkeric substance (I-1), thermoplastic polymer (II-2) (MMA/MA multipolymer (MMA/MA=90/10) (mass ratio), reducing viscosity η sp/c=0.056L/g) 20 part, 10 parts in the polymkeric substance (V-1) that contains hydroxyl, as 3 parts of the thermoplastic polymers (VII-1) of Synergist S-421 95, チバスペシャリティケミカ Le ズ society system trade(brand)name " チヌ PVC Application 234 " 1.4 parts, Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AO-60 " 0.1 part, 0.3 part of Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block LA-67 " and system trade(brand)name " JP333E " 0.3 part of north of the city chemical industry society mix.After this mixture (resin combination (IV-6)) is heated to 230 ℃, supply with degassing formula forcing machine (pond shellfish ironworker (strain) makes PCM-30 (trade(brand)name)), carry out mixingly, obtain granule.Then, except the granule that uses this mixture (resin combination (IV-6)), make the membranaceous thing of acrylic resin (A) similarly to Example 11.

With the above-mentioned granule that obtains at 80 ℃ of dry diels, with the crooked screwe-type xtruder (L/D=26) of the nothing of the 40mm φ that the wide T mould of 300mm has been installed, under the condition of 180～240 ℃ of barrel temperatures, 240 ℃ of T mould temperature, make film, obtain the thick membranaceous thing of acrylic resin (A) of 125 μ m.In the occasion of the film that uses embodiment 13, do not have printing and omit generation.

(embodiment 14)

Except the proportioning of multi-ply construction polymkeric substance (I-1) and thermoplastic polymer (II-2) is 25 parts in 65 parts in multi-ply construction polymkeric substance (I-1), thermoplastic polymer (II-2), obtain mixture (resin combination (IV-5)) similarly to Example 13, make film, obtain the membranaceous thing of acrylic resin (A).In the occasion of the film that uses embodiment 14, do not have printing and omit generation.

(embodiment 15)

With ABS resin (UMG ABS society system, trade(brand)name " ダィャペット ABS SW7 ") as thermoplastic resin (C), with the crooked screwe-type xtruder (L/D=26) of the nothing of the 40mm φ that is provided with 400 purpose filter mesh that the wide T mould of 300mm has been installed, under the condition of 180～240 ℃ of barrel temperatures, 230 ℃ of T mould temperature, melt extrude by the T mould.The resin of extruding is made the thermoplastic resin film (C) of thick 125 μ m by 3 polishing rolls of temperature regulation to 75 ℃.

Then, the printing of silver metal style is carried out in receiving mutually with mirror roller of the membranaceous thing of the acrylic resin of making in embodiment 13 (A) on the one side, form and band layer (B).The membranaceous thing of acrylic resin (A) after this printing is joined with above-mentioned thermoplastic resin film, carries out heat lamination by scoring roller, make thermoplastic resin film with band layer and join, obtain stack membrane.

(embodiment 16)

The membranaceous thing of in using embodiment 8, making of acrylic resin (A), implement similarly to Example 15, obtain stack membrane.

(comparative example 4)

Except use 100 parts in multi-ply construction polymkeric substance (I-3), contain 84 parts in the polymkeric substance (V-1) of hydroxyl, 2.1 parts of Xu Dianhuagongyeshe system trade(brand)names " ァデカスタ Block AL-31 ", 0.1 part of Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AO-50 " and 0.3 part of composite mixture (resin combination (IV-8)) of Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AL-57 " as Synergist S-421 95, make film similarly to Example 7, obtain the membranaceous thing of acrylic resin (A).

(comparative example 5)

Except using multi-ply construction polymkeric substance (I-5) 16 parts, 84 parts of thermoplastic polymers (II-1), 10 parts in the polymkeric substance (V-1) that contains hydroxyl, Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AL-31 " 2.1 parts as Synergist S-421 95, Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AO-50 " 0.1 part, outside 0.3 part of Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AL-57 " and Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block 260 " the composite mixture (resin combination (IV-9)), make film similarly to Example 7, obtain the membranaceous thing of acrylic resin (A).

(embodiment 17)

With the granule that obtains among the embodiment 1 (resin combination (III-1)) as the membranaceous thing of acrylic resin (A), with the granule that obtains in the comparative example 3 (resin combination (III-9), but replace 2.1 parts of Xu Dianhuagongyeshe system trade(brand)names " ァデカスタ Block LA-31 " for 2.7 parts with チバスペシャリティケミカ Le ズ society system trade(brand)name " チヌ PVC Application 234 "), the system film obtains the acrylic resin stack membrane.

Concrete, with granule at 80 ℃ of dry diels, use the crooked single-bolt type forcing machine of nothing, the crooked single-bolt type forcing machine of nothing of 40mm φ, the wide many material road pattern of 300mm of 65mm φ respectively, coextrusion is shaped under the condition of 180～240 ℃ of barrel temperatures, 240 ℃ of T mould temperature, obtain being positioned at the top layer the membranaceous thing of acrylic resin (A '-a) thickness is that the total thickness that the big thickness of 10 μ m and the membranaceous thing of acrylic resin (A) that is positioned at lower floor is 115 μ m is the acrylic resin stack membrane of 125 μ m.With the membranaceous thing of acrylic resin (A) and the membranaceous thing of acrylic resin (A '-a) extrude by the forcing machine of 65mm φ and 40mm φ respectively.

(embodiment 18～20)

Except the granule (resin combination (III-2)～(III-4)) that use embodiment 2～4 obtains, make film similarly to Example 17, obtain the acrylic resin stack membrane.

(embodiment 21)

Except multi-ply construction polymkeric substance (I-1) and thermoplastic polymer (II-1) mix with the ratio shown in the table 7 respectively, implement similarly to Example 1, obtain granule (resin combination (II-A '-1)), except use this granule as the membranaceous thing of acrylic resin (A '-a), make film similarly to Example 18, obtain the acrylic resin stack membrane.

(embodiment 22)

Except with Mitsubishi Li Yang society system acrylic resin " ァ Network リペット MD " (trade(brand)name) as the membranaceous thing of acrylic resin (A '-a), make film similarly to Example 18, obtain the acrylic resin stack membrane.The membranaceous thing of this acrylic resin (A '-a) be 3H as the pencil hardness of the occasion of the film of 125 μ m individually.

(embodiment 23)

Except the partial fluorine ethylene polymer " HYLAR460 " (trade(brand)name) with Solvay Solexis society system replace the membranaceous thing of acrylic resin (A '-a) membranoid substance is as the membranaceous thing of fluoro-resin (A "); make film similarly to Example 17, obtain the acrylic resin stack membrane.

(comparative example 6)

With the granule that obtains in the comparative example 3 (resin combination (III-9), but replace 2.1 parts of Xu Dianhuagongyeshe system trade(brand)names " ァデカスタ Block LA-31 " for 2.7 parts with チバスペシャリティケミカ Le ズ society system trade(brand)name " チヌ PVC Application 234 ") as the membranaceous thing of acrylic resin (A '-a) and with the granule that obtains in the comparative example 1 (resin combination (III-7)) as the membranaceous thing of acrylic resin (A '-b), except the thickness of each layer is the value shown in the table 8, implement similarly to Example 17.Respectively with the membranaceous thing of acrylic resin (A '-b) and the membranaceous thing of acrylic resin (A '-a) extrude by the forcing machine of 65mm φ and 40mm φ.

(comparative example 7)

Except to multi-ply construction polymkeric substance (I-6), thermoplastic polymer (II-3) (MMA/n-BA multipolymer (MMA/n-BA=77/23) (mass ratio), reducing viscosity η sp/c=0.08L/g) respectively with in the table 7 expression mixed, adding is as Xu Dianhuagongyeshe system trade(brand)name " the ァデカスタ Block LA-31 " 1.5 parts of Synergist S-421 95, Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AO-50 " 0.1 part, after 0.3 part of Xu Dianhuagongyeshe system trade(brand)name " ァデカスタ Block AL-57 " and Sanyo change into 2 parts of industrial society's system trade(brand)names " Port リェチレ Application グリコ one Le PEG20000 ", outside the mixing of Henschel mixing tank, implement similarly to Example 1, obtain the membranaceous thing of acrylic resin (A '-b) with granule (resin combination (II-A '-2)).Except using this granule, similarly implement with comparative example 6.

(comparative example 8)

Except with the granule that obtains in the comparative example 2 (resin combination III-8) as the membranaceous thing of acrylic resin (A '-b), similarly implement with comparative example 6.

(comparative example 9)

Except multi-ply construction polymkeric substance (I-4) and thermoplastic polymer (II-3) mix with the vast scale shown in the table 7, implement similarly to Example 1, obtain the membranaceous thing of acrylic resin (A '-b) with granule (resin combination (II-A '-3)).Except use this granule as the membranaceous thing of acrylic resin (A '-b), similarly implement with comparative example 6.

(comparative example 10)

Except with the granule that obtains in this comparative example 3 (resin combination (III-9), but replace 2.1 parts of Xu Dianhuagongyeshe system trade(brand)names " ァデカスタ Block LA-31 " for 2.7 parts with チバスペシャリティケミカ Le ズ society system trade(brand)name " チヌ PVC Application 234 "), make the membranaceous beyond the region of objective existence of acrylic resin of 125 μ m, similarly implement with comparative example 3.

(comparative example 11)

Except with Mitsubishi Li Yang society system acrylic resin " ァ Network リペット MD " (trade(brand)name) as the membranaceous thing of acrylic resin (A '-a), similarly make film with comparative example 6, obtain the acrylic resin stack membrane.

(comparative example 12)

Except the partial fluorine ethylene polymer " HYLAR460 " (trade(brand)name) with Solvay Solexis society system replace the membranaceous thing of acrylic resin (A '-a) membranoid substance is as the membranaceous thing of fluoro-resin (A "); similarly make film with comparative example 6, obtain the acrylic resin stack membrane.

(embodiment 24)

On the membranaceous thing of the acrylic resin that in embodiment 1, obtains (A), light-cured resin solution is carried out the coating of 250mm with the comma roll-coater.Then, the round tube type drying oven under the temperature condition in setting following table 2 for (wide 800mm, high 100mm, long 8m is divided into 4 drying zones (each head of district 2m), relatively sends into hot blast with the motion of sheet) in, pass through with the speed that 10m/ divides, make solvent evaporates, form light-cured resin (Z) layer.The residence time of each drying zone of this moment is remembered in following table 2.

Table 2

Then, it is wide to be divided into 200mm, long at ABS coremaking top roll shape coiling 20m.

This light solidified acrylic resin film is configured in the mould, make Photocurable resin composition fit towards the inner-wall surface of mould, then, with infrared heater temperature be 350 ℃ the light solidified acrylic resin film carried out preheating of 10 seconds after, while heat again the light solidified acrylic resin film is chased after from mold shape by vacuum attraction.The shape of this mould is that the size of butt pyramid shape, butt face is 100mm * 100mm, bottom surface size 108mm * 117mm, the radius-of-curvature of the end of 10mm, butt face is respectively 3,5,7,10mm deeply.Visual assessment mould following this moment, the following of each end is all good.

Then, under the condition of 280～300 ℃ of forming temperatures, 40～60 ℃ of die temperatures, as shaping resin, carry out inserts and be shaped, obtain the driving fit of light solidified acrylic resin film as the lip-deep laminated forming product of moulding product with polycarbonate resin.

Then, with the about 700mJ/cm of UV irradiation equipment irradiation ²Ultraviolet ray, Photocurable resin composition is solidified, estimate the surface physical property of lamination molding.

(embodiment 25)

The membranaceous thing of acrylic resin (A) that in using embodiment 2, obtains, implement similarly to Example 24.

(embodiment 26)

The membranaceous thing of acrylic resin (A) that in using embodiment 3, obtains, implement similarly to Example 24.

(embodiment 27)

The membranaceous thing of acrylic resin (A) that in using embodiment 4, obtains, implement similarly to Example 24.

(embodiment 28)

Use ABS resin (UMG ABS society system, trade(brand)name " ダィャペット ABS SW7 ") as thermoplastic resin (C), the crooked screwe-type xtruder (L/D=26) of nothing of the wide 40mm φ T mould, that be provided with 400 purpose filter mesh of 300mm has been installed in use, under the condition of 180～220 ℃ of barrel temperatures, 230 ℃ of T mould temperature, melt extrude by the T mould.The resin of extruding obtains the thick thermoplastic resin film of 200 μ m with 3 polishing roll system films of temperature adjustment to 75 ℃.

Then, the membranaceous thing of acrylic resin (A) side of the light solidified acrylic resin film that obtains in embodiment 26 is with band layer (B) of intaglio printing formation silver metal style.

This light solidified acrylic resin film band layer (B) side, the above-mentioned thermoplastic resin film that obtains of heat lamination obtains the stack membrane of light solidified.

With the stack membrane of this light solidified, implement inserts with the method for record in (9) of (mensuration of rerum natura, evaluation method) and be shaped, make the lamination molding.

The lamination molding that obtains is to have printing drawing style, molding that aesthetic property is good.

(comparative example 13)

The membranaceous thing of acrylic resin (A) that in using comparative example 2, obtains, implement similarly to Example 24.

(comparative example 14)

The membranaceous thing of acrylic resin (A) that in using comparative example 3, obtains, implement similarly to Example 24.

(embodiment 29)

On the membranaceous thing of the acrylic resin that in embodiment 1, obtains (A), print wood grain style and pitch-dark style as banding layer (B) with intaglio printing, by warming mill, will band layer (B) and join on the thermoplastic resin film (C) that obtains among the embodiment 15 at last, heat lamination and obtain stack membrane.

(embodiment 30～33)

The membranaceous thing of acrylic resin (A) that in using embodiment 2～5, obtains, implement similarly to Example 29.

(embodiment 34)

On the thermoplastic resin film that in embodiment 15, obtains (C), print wood grain style and pitch-dark style as banding layer (B) with intaglio printing, by warming mill, will band layer (B) and join on the membranaceous thing of the acrylic resin that obtains among the embodiment 3 (A) at last, heat lamination and obtain stack membrane.

(embodiment 35)

Except the layer molding made from the method enforcement inserts shaping of record in the hurdle (8) of (mensuration of rerum natura, evaluation method), similarly implement with embodiment 31.

(embodiment 36)

The membranaceous thing of acrylic resin (A) that in using embodiment 6, obtains, implement similarly to Example 29.

The formation of banding layer (B) is good, does not have printing and omits.

(comparative example 15～17)

The membranaceous thing of acrylic resin (A) that in using comparative example 1～3, obtains, implement similarly to Example 29.

(embodiment 37)

On the surface as the painted Atactic Polypropelene resin molding (reason is ground PVC ニ Le industry society system) of the thick 90 μ m of thermoplastic resin (C), using at polyester polyol is that the biliquid sclerotic type urethane resin that has cooperated the isocyanate hardener of 3 quality % to form in matchmaker's liquid is printing ink " ラミスタ one " (Japan ィ Application キ society system; Trade(brand)name), band layer (B) (a wood grain style and a pitch-dark style) by the woodburytype printing, and then, on printing surface, be the hot joining property resin by intaglio plate coating method coating vinylformic acid-polyester-ethylene chloride, make that dried glue spread is 1.5g/m ², form following layer.Then; in the aspect of following; as sealer; to with the membranaceous thing of acrylic resin (A) of the 50 μ m that obtain with the same method of embodiment 1; under the condition of 120 ℃ of film surface temperatures, carry out heat lamination; carry out the embossing processing of catheter design with the metal system grain roller of 180 ℃ of surface temperatures, obtain the building materials stack membrane.Then, these building materials with stack membrane on, spraying water-based biliquid urethane be solid as following layer (D), make that dried glue spread is 10g/m ², be on the 3D shape base material at the vibrin of the shape of dried radius-of-curvature 0.5R, building materials are carried out under 80 ℃ condition with stack membrane three-dimensional laminated, the lamination molding that obtains having 3D shape.

(embodiment 38～40)

Except the membranaceous thing of acrylic resin (A) that uses the 50 μ m that the method identical with embodiment 2～4 obtain, similarly implement with embodiment 37.

(comparative example 18～20)

Except the membranaceous thing of acrylic resin (A) that uses the 50 μ m that the method identical with comparative example 1～3 obtain, similarly implement with embodiment 37.

(embodiment 41)

Implement similarly to Example 1 the multi-ply construction polymkeric substance (I-1) except replacing with multi-ply construction polymkeric substance (I-7).

(embodiment 42～46)

Similarly implement with embodiment 41 the multi-ply construction polymkeric substance (I-7) except replacing with multi-ply construction polymkeric substance (I-8)～(I-12).

(embodiment 47 and 48)

Except the proportioning of multi-ply construction polymkeric substance (I-1) and thermoplastic polymer (II-1) changes to shown in the table 12, implement similarly to Example 2.

(embodiment 49 and 50)

The trade(brand)name " チヌ PVC Application 1577 " of producing except trade(brand)name " チヌ PVC Application 329 " 2.5 parts of (embodiment 49), the チバスペシャリティケミカ Le ズ societies that produce with チバスペシャリティケミカ Le ズ society respectively 1.0 parts (embodiment 50) replaces trade(brand)name " チヌ PVC Application 234 " 2.7 that the チバスペシャリティケミカ Le ズ society as one of Synergist S-421 95 usefulness produces especially, implements similarly to Example 3.

(embodiment 51)

Except not adding the trade(brand)name " ァデカスタ Block LA-67 " of producing, implement similarly to Example 6 as the Xu Dianhuagongyeshe of one of Synergist S-421 95 usefulness.

(comparative example 21～24)

Implement similarly to Example 2 the multi-ply construction polymkeric substance (I-1) except replacing with multi-ply construction polymkeric substance (I-13)～(I-16).

(embodiment 52 and 59)

Except add again when the blend contain hydroxyl polymkeric substance (V-1) 10 especially, similarly implement with embodiment 41～48.

(embodiment 60 and 61)

Except according to the addition shown in the table 15, making trade(brand)name " ェ Port スタ one MA1004 " with Nippon Shokubai Co., Ltd is that crosslinked particle replaces containing the polymkeric substance (V-1) of hydroxyl and not using north of the city chemical industry society system trade(brand)name " JP333E " 0.3 especially as PMMA, implements similarly to Example 13.

(comparative example 25～28)

Except add again when the blend contain hydroxyl polymkeric substance (V-1) 10 especially, similarly implement with comparative example 21～24.

The composition and the gel containing ratio of the resinous principle of the resin combination (III) (resin combination (III-1～9)) that uses in embodiment 1～6 and the comparative example 1～3 are shown in Table 3.The evaluation result of membranaceous thing of the acrylic resin that obtains in addition, (A) and lamination molding is shown in table 4.

The composition and the gel containing ratio of the resinous principle of the resin combination (IV) (resin combination (IV-1～9)) that uses in embodiment 7～16 and comparative example 4 and 5 are shown in Table 5.The evaluation result of membranaceous thing of the acrylic resin that obtains in addition, (A) and lamination molding is shown in table 6.

Resin combination (III-1～4) and (III-7～9), and the composition of the resinous principle of resin combination (III-A '-1～3), gel containing ratio, crooked elastic rate and be shown in Table 7 with the evaluation result of the membranaceous thing of its acrylic resin of making (A).In addition, the evaluation result of the kind of the membranoid substance that the acrylic resin stack membrane is used and the lamination molding that obtains is shown in table 8.

The evaluation result of the membranaceous thing of acrylic resin (A), light solidified acrylic resin film and the lamination molding that obtains in embodiment 24～28 and comparative example 13 and 14 is shown in Table 9.

The evaluation result of the membranaceous thing of acrylic resin (A), stack membrane and the lamination molding that obtains in embodiment 29～36 and the comparative example 15～17 is shown in Table 10.

Membranaceous thing of acrylic resin (A) that obtains in embodiment 37～40 and the comparative example 18～20 and building materials are shown in Table 11 with the evaluation result of stack membrane.

The membranaceous thing of acrylic resin (A) of embodiment 1～3,5,6,41～51 and comparative example 1,3,21～24 and the evaluation result of lamination molding are shown in table 12～14.

Embodiment 7～9 and 52～61, and the composition of the resin combination of comparative example 4 and 25～28 (IV) and gel containing ratio, and the evaluation result of membranaceous thing of acrylic resin (A) and lamination molding is shown in Table 15.

Pencil hardness is good more than or equal to the scuff resistance of the membranaceous thing of acrylic resin (A) of the embodiment 1～16 of 2B.Pencil hardness demonstrates especially good scuff resistance more than or equal to the embodiment 2～6 of F and 8～16 the membranaceous thing of acrylic resin (A), does not see damage.And, under the condition that in the early stage chuck spacing 25mm, speed 50mm/min, temperature are 23 ℃, after making the chuck spacing of terminal point be the tension test of 33mm to the test film of wide 20mm, according to the value of this test film of determination of test method of JIS K7136 (measuring method of turbidity) and difference according to the value of test film before the determination of test method test of JIS K7136 (measuring method of turbidity) be smaller or equal to the membranaceous thing of acrylic resin (A) of 30% embodiment 1～16 anti-shaping albefaction and wood grain, pitch-dark in all no problem generations.In addition, near also no problem generation of the printing state of the membranaceous thing of the acrylic resin of embodiment 1～16 (A) cast gate.

On the other hand, pencil hardness is not good enough less than the scuff resistance of the membranaceous thing of acrylic resin (A) of 2B comparative example 1,4, and because heat-drawn wire is 79 ℃, can not satisfy the requirement of ageing resistance, so the utility value of industry is low.The difference of the turbidity value of each test film before and after the above-mentioned tension test surpasses 30% comparative example 2,3 and 5 the membranaceous thing of acrylic resin (A), can not fully satisfy anti-shaping albefaction, in wood grain.Shaping albefaction under the pitch-dark situation is obvious, and the printing style disappears, and industrial utilization is worth step-down.

In addition, the lamination molding of embodiment 17～40 with membranaceous thing of any one acrylic resin (A) of embodiment 1～16 all has good characteristic.

And, use the membranaceous thing of acrylic resin (A) of embodiment 1～3,5,7～9,41～61 of multi-ply construction polymkeric substance of the present invention (I) or resin combination (III) or resin combination (IV) and the lamination molding with it all to have good characteristic.

Embodiment 17～23 obtained known in the past acrylic resin multilayer film can not be getable the good acrylic resin multilayer film of anti-shaping albefaction, scuff resistance, heat-resistant aging during grain printing.

Utilize possibility on the industry

Lamination formed products with membranaceous thing of acrylic resin of the present invention (A) is specially adapted to vehicular applications and building materials purposes. Particularly, applicable to following various uses: device panel, control box, the instrument lid, door lock ペゼ Le, steering wheel, the automatic window conversion panel, center bunch (center cluster), the automobile inside purposes of instrument board etc., weather strip, bumper, the bumper baffle plate, side mudguard, bodyshell, spoiler, front grid, supporting bracket, axle cap, newel, peephole, the center is decorated, the limit mould, the door mould, the window mould, window, the front truck lampshade, rear lamp shade, the exterior purposes of automobile of the anti-parts of wind etc., the frontend panels of AV machine and article of furniture, button, mark, the purposes such as surface cosmetic material, the shell of mobile phone etc., display window, the purposes of button etc., and the exterior purposes of furniture, wall, the roof, the for building in-built material purposes on floor etc., the outer wall of wallboard etc., fence, the roof, door, the structural exterior material purposes of the cover plate of pediment yardarm etc., window frame, door, fence, threshold, the surface cosmetic material purposes of the furniture of lintel etc., various displays, lens, mirror, goggles, the optics section material purposes of glass pane etc., perhaps electric car, the aviation machine, the interior exterior purposes of the various vehicles except automobile of boats and ships etc., bottle, cosmetics containers, various packing containers and the material of little container etc., other purposes such as the groceries of gift and little thing etc.

Claims

1. the membranaceous thing of acrylic resin (A), it is characterized in that, its thickness is 10～500 μ m, and under the condition that in the early stage chuck spacing 25mm, speed 50mm/min, temperature are 23 ℃, it is the tension test of 33mm that the test film of wide 20mm is made the chuck spacing of terminal point, be smaller or equal to 30% and is more than or equal to 2B based on the pencil hardness that JISK5400 measures according to the value of this test film of determination of test method of the measuring method of the turbidity of JIS K7136 and difference according to the value of test film before the determination of test method test of the measuring method of the turbidity of JIS K7136.

2. the membranaceous thing of acrylic resin (A) of claim 1 record, its at least 60 ° of surface glosses of one side smaller or equal to 100%.

3. the membranaceous thing of acrylic resin (A) of claim 1 record, its heat-drawn wire of measuring based on ASTM D648 is more than or equal to 80 ℃.

4. the membranaceous thing of acrylic resin (A) of claim 1 record, it also has the layer of banding at least on one side.

5. acrylic resin stack membrane, it is the acrylic resin stack membrane with membranaceous thing of acrylic resin (A) of claim 1 record, it further has other membranaceous thing of acrylic resin (A ') or the membranaceous thing of fluoro-resin (A ").

6. light solidified acrylic resin film or sheet, it has the membranaceous thing of acrylic resin (A) of claim 1 record and contains the thermoplastic resin (z-1) that has free-radical polymerised unsaturated group on side chain and the Photocurable resin composition (Z) of Photoepolymerizationinitiater initiater (z-2) layer.

7. stack membrane or sheet, it has the membranaceous thing of acrylic resin (A) and the thermoplastic resin (C) of record in the claim 1.

8. building materials are with stack membrane or sheet, and it has the membranaceous thing of acrylic resin (A) and the thermoplastic resin (C) of claim 1 record.

9. the lamination molding is characterized in that, the membranaceous thing of acrylic resin (A) of claim 1 record is stacked on the base material (E) form.

10. the lamination molding of claim 9 record, it is by at least the membranaceous thing of described acrylic resin (A) being carried out vacuum forming in ejection shaping mould or press empty the shaping, and the resin that will constitute above-mentioned base material (E) then in this ejection shaping mould carries out behind the injection molding integrated and obtain.

11. the lamination molding of claim 9 record, it is by at least the membranaceous thing of described acrylic resin (A) being carried out vacuum forming or presses empty the shaping, insert then in the ejection shaping mould, the resin that will constitute above-mentioned base material (E) in this ejection shaping mould carries out injection molding and obtains.