JP6045096B2 - Laminate and method for producing laminate - Google Patents

Description

  The present invention relates to a laminate having excellent adhesion between a resin substrate and a cured coating layer, both a cured coating layer and an inorganic material layer, and excellent in weather resistance and scratch resistance, and a method for producing the laminate. .

  Plastic materials such as polymethyl methacrylate resin, polystyrene resin, and polycarbonate resin are excellent in impact resistance, transparency, light weight, and easy to process. Used in windows, lamp lenses, and instrument covers. However, since plastic materials are inferior to glass in terms of surface properties such as scratch resistance, chemical resistance, and weather resistance, the surface properties of plastic materials have been improved. As methods for improving the surface properties of plastic materials, methods for applying polyorganosiloxane-based and melamine-based thermosetting coating compositions and methods for applying polyfunctional acrylate-based active energy ray-curable coating compositions have been proposed. ing.

  In recent years, as the use of plastic materials outdoors increases, further improvements in the surface properties (scratch resistance, weather resistance) of the plastic materials are required.

  As a method for improving the surface characteristics of plastic, a method of laminating an inorganic protective layer on the surface of the plastic can be mentioned. However, even if an inorganic substance such as silicon dioxide is laminated directly on a plastic material such as polycarbonate to form an inorganic protective layer, it is caused by mechanical or thermal effects due to the difference in properties from the plastic material. When subjected to excessive stress, performance problems such as poor adhesion and cracking occur.

  In view of this, the present applicant disclosed in Patent Document 1 a film comprising a composition comprising a compound and / or a resin having at least two acryloyl groups and / or methacryloyl groups in the molecule and a polymerizable unsaturated monomer on the surface of a plastic plate. The present inventors have proposed a cured film of an active energy ray-curable primer composition as a forming element, and a surface-modified plastic plate in which an inorganic substance layer is formed on the cured film by physical vapor deposition. However, in the method described in Patent Document 1, since the film thickness of the inorganic material layer is insufficient, in terms of scratch resistance, and the adhesion between the resin base material and the inorganic material layer is insufficient. There was a problem in terms of weather resistance.

  Also, in US Pat. No. 6,057,059, a coating characterized by a stepwise transition from a composition consisting essentially of an interfacial material to a composition consisting essentially of an inorganic wearable material on a plastic substrate by plasma enhanced chemical vapor deposition. A method of manufacturing a wear-resistant plastic article that forms a film is disclosed. As a primer used in this method, a composition comprising a polyfunctional acrylate monomer, colloidal silica, an acryloxy functional silane containing an ether bond, and an optical disclosure agent is disclosed.

  Further, in Patent Document 3, the surface of the amorphous polyolefin resin substrate is hydrophilized, and then a primer layer treatment liquid containing an organosilicon compound is applied to coat the primer layer, and then a polyfunctional acrylate, After applying a hard coat liquid containing aminosilane and colloidal silica, an active energy ray is irradiated to form a hard coat layer, and an inorganic film layer made of a metal or an inorganic compound is formed thereon. A method for producing a crystalline polyolefin resin article is disclosed. However, even if the methods of Patent Document 2 and Patent Document 3 are used, the adhesion between the resin base material and the inorganic material layer is excellent, but the transparency and weather resistance of the laminate are not satisfied.

JP-A-4-202240 Japanese Patent Publication No. 8-32958 Japanese Patent Laid-Open No. 2004-17410

  The present invention has been made in view of the above circumstances, and the object of the present invention is excellent in adhesion between the resin base material and the cured coating layer, the cured coating layer and the inorganic substance layer, and weather resistance. It is an object of the present invention to provide a laminate having a very excellent scratch resistance and a method for producing the laminate.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that the active energy ray-curable type contains a specific organic compound-modified silica particle polymerizable unsaturated compound, a photopolymerization initiator, an ultraviolet absorber, and a light stabilizer. It has been found that the above problem can be solved by laminating a cured coating film layer using the primer composition, and the present invention has been completed.

That is, the present invention is a laminate in which a cured coating layer (I) and an inorganic substance layer (II) are sequentially laminated on a resin base material with an active energy ray-curable primer composition,
The active energy ray-curable primer composition is
Organic-modified silica particles (A),
It contains a polymerizable unsaturated compound (B) and a photopolymerization initiator (C),
The present invention relates to a laminate and a method for producing the laminate, wherein the inorganic material layer (II) is formed by a dry film forming method.

  According to the present invention, by using a specific active energy ray-curable primer composition, the resin substrate and the cured coating layer, both the cured coating layer and the inorganic material layer are excellent in adhesion and weather resistance. A very excellent laminate can be obtained. Moreover, since the inorganic substance layer is an inorganic substance, it is possible to obtain a laminate having excellent weather resistance and scratch resistance that is not found in an organic film. Further, by sequentially laminating the inorganic material layer on the primer layer, the resulting laminate is very excellent in adhesion, weather resistance, water resistance and scratch resistance due to the synergistic effect of the primer layer and the inorganic material layer. You can get something.

  The laminate of the present invention is a laminate in which a cured coating layer (I) and an inorganic substance layer (II) made of an active energy ray-curable primer composition are sequentially laminated on a resin base material, The energy ray curable primer composition contains organic-modified silica particles (A), a polymerizable unsaturated compound (B), and a photopolymerization initiator (C), and the inorganic material layer (II) is dry-type. It is formed by a film forming method.

  The method for producing a laminate of the present invention comprises the steps of applying the active energy ray-curable primer composition, irradiating active energy rays to form a cured coating layer (I), and on the cured coating layer (I And a step of forming at least one inorganic material layer (II) by a dry film forming method.

≪Resin base material≫
The resin base material used for the laminate of the present invention is not particularly limited.

  Examples include polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin, and various plastic materials such as FRP. Of these, polycarbonate resin is preferred.

  In addition, the use of the laminate of the present invention is not particularly limited, for example, an outer plate portion of an automobile body such as a passenger car, a truck, a motorcycle, or a bus; an automobile part; A board part etc. are mentioned, Especially the outer-plate part of a motor vehicle body and a motor vehicle part are preferable.

≪Hardened coating layer (I) ≫
The cured coating film layer (I) of the present invention comprises an active energy ray-curable primer containing, on a resin substrate, organic matter-modified silica particles (A), a polymerizable unsaturated compound (B), and a photopolymerization initiator (C). It is formed by applying a composition and irradiating active energy rays. This will be described in more detail below.

≪Organic modified silica particles (A) ≫
The active energy ray-curable primer composition used for the laminate of the present invention contains organic-modified silica particles (A).

  Although it is not particularly limited as the organic substance-modified silica particles (A), reactive particles in which (meth) acryloyloxy groups are present on the surface of the silica fine particles (a-1) are preferable from the viewpoint of adhesion and weather resistance. In particular, reactive particles (a) having a group having both a (meth) acryloyloxy group and an isocyanurate ring structure on the surface of the silica fine particles (a-1) can be used in terms of transparency, adhesion and weather resistance. It can be used more suitably.

  In the reactive particles (a), the method for providing the silica fine particles (a-1) with a group having both a (meth) acryloyloxy group and an isocyanurate ring structure is not particularly limited. Fine particles (a-1) and hydrolyzable silane (a-2) having a group having both a (meth) acryloyloxy group and an isocyanurate ring structure in the molecule, or the hydrolyzable silane (a-2) Mixtures with hydrolyzable silanes (a-3) other than the hydrolyzable silane (a-2) [hereinafter referred to as “hydrolyzable silane (a-2)” and “hydrolyzable silane (a-3), respectively” "May be abbreviated. ] To obtain reactive particles (a).

Silica fine particles (a-1)
Examples of the silica fine particles (a-1) include colloidal silica fine particles and powdered fine particle silica.

  Colloidal silica fine particles are obtained by dispersing ultrafine particles of silica in a dispersion medium.

  As a dispersion medium, water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol; polyhydric alcohol solvents such as ethylene glycol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc. Polyhydric alcohol derivatives; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and tetrahydrofurfuryl acrylate. Of these, water, methanol, ethanol, isopropanol and the like are preferable from the viewpoint of ease of production.

  As colloidal silica fine particles, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, PGM-ST, ST-UP, ST-OUP, ST-20, ST-40, ST -C, ST-N, ST-O, ST-50, ST-OL (all manufactured by Nissan Chemical Industries, Ltd.) and the like.

  Examples of commercially available powdered fine particle silica include Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50 (all manufactured by Nippon Aerosil Co., Ltd.), E220A, E220 (all manufactured by Nippon Silica Kogyo Co., Ltd.), and SYLYSIA470 (Fuji Silysia). Chemical Co., Ltd.).

  The average primary particle diameter of the silica fine particles (a-1) is preferably 1 to 200 nm, and more preferably 5 to 100 nm. The lower limit of these ranges is significant in terms of suppressing gelation when reacted with hydrolyzable silane (a-2). The upper limit of these ranges is significant in terms of the transparency of the cured coating film obtained from the active energy ray-curable primer composition used in the laminate of the present invention.

  The average primary particle diameter in the present invention is a median diameter (d50) of a volume-based particle size distribution measured by a dynamic light scattering method, and can be measured using, for example, a nanotrack particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd. it can.

Hydrolyzable silane having a (meth) acryloyloxy group and an isocyanurate ring structure in the molecule (a-2)
Hydrolyzable silane (a-2) having both a (meth) acryloyloxy group and an isocyanurate ring structure in the molecule has a hydrolyzable silyl group. The hydrolyzable silyl group is a silanol group or a group that generates a silanol group by hydrolysis. Examples of the group that forms a silanol group include groups in which an alkoxy group, an aryloxy group, an acetoxy group, a halogen atom, or the like is bonded to a silicon atom. Here, the alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and the aryloxy group is preferably an aryloxy group having 6 to 18 carbon atoms.

  Examples of the hydrolyzable silane (a-2) include the following general formula (I)

[In Formula (I), R ¹ is the same or different and represents a hydrogen atom or a methyl group. R ² is the same or different and represents a divalent organic group. R ³ represents a divalent organic group. At least one of R ^a , R ^b and R ^c represents a halogen atom, a hydroxy group, an alkoxy group or an aryloxy group, and the remainder represents a hydrogen atom, an alkyl group or an aryl group. ] The hydrolysable silane represented by this is mentioned.

R ² and R ³ are not particularly limited as long as they are divalent organic groups. Examples of the divalent organic group include 1 to 100 carbon atoms, preferably 1 to 30 carbon atoms. The bivalent organic group of these is mentioned. The divalent organic group is not limited to a hydrocarbon group, and may have, for example, a urethane bond, an ester bond, an ether bond, or the like.

Examples of the alkoxy group represented by R ^a , R ^b and R ^c include those having 1 to 8 carbon atoms, and a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an octyloxy group and the like are preferable.

Examples of the alkyl group represented by R ^a , R ^b and R ^c include those having 1 to 8 carbon atoms, and a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like are preferable.

Examples of the aryloxy group represented by R ^a , R ^b and R ^c include those having 6 to 18 carbon atoms, and a phenoxy group, a xylyloxy group and the like are preferable.

Examples of the aryl group represented by R ^a , R ^b and R ^c include those having 6 to 18 carbon atoms, and a phenyl group, a xylyl group and the like are preferable.

Examples of the group represented by R ^a (R ^b ) (R ^c ) Si— include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. it can. Of these, a trimethoxysilyl group, a triethoxysilyl group, and the like are preferable.

  More specifically, examples of the hydrolyzable silane represented by the general formula (I) include a hydrolyzable silane represented by the following general formula (II) and a hydrolyzable silane represented by the following general formula (III). Degradable silanes are mentioned.

[In formula (II), R ⁴ is the same or different and represents a hydrogen atom or a methyl group. R ⁵ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ⁶ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. m is the same or different and represents an integer of 0 to 5. R ^a , R ^b and R ^c are the same as described above. In formula (III), R ⁷ is the same or different and represents a hydrogen atom or a methyl group. R ⁸ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ⁹ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. R ^a , R ^b and R ^c are the same as described above. ].

R ⁵ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Especially, it is preferable from the transparency point of the cured coating film obtained that it is a C2-C4 bivalent hydrocarbon group.

R ⁶ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 4 carbon atoms. Specific examples include ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group and the like.

As the organic group represented by the general formula (II), R ⁴ is a hydrogen atom from the viewpoint of better weather resistance, transparency, and active energy ray curability in the presence of a photopolymerization initiator, and R ⁵ Is an ethylene group, R ⁶ is a 1,3-propylene group, and m is 0.

R ⁸ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Especially, it is preferable from the transparency point of the cured coating film obtained that it is a C2-C4 bivalent hydrocarbon group.

R ⁹ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 4 carbon atoms. Specific examples include ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group and the like.

As the organic group represented by the general formula (III), R ⁷ is a hydrogen atom from the viewpoint of better weather resistance, transparency, and active energy ray curability in the presence of a photopolymerization initiator, and R ⁸ Is an organic group, and R ⁹ is a 1,3-propylene group.

Method for producing hydrolyzable silane (a-2)
A method for producing a hydrolyzable silane represented by the general formula (II) will be exemplified. The hydrolyzable silane represented by the general formula (II) is obtained by, for example, reacting a hydrolyzable silane represented by the following general formula (IV) with a compound represented by the following general formula (V). Can be obtained.

R ⁶ , R ^a , R ^b and R ^c in the general formula (IV) are the same as described above.

R ⁴ , R ⁵ and m in the general formula (V) are the same as described above.

  Specific examples of the hydrolyzable silane represented by the general formula (IV) include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

  The mixing ratio of the hydrolyzable silane represented by the general formula (IV) and the compound represented by the general formula (V) is not particularly limited. The reaction is carried out using equimolar amounts of the isocyanate group of the compound represented by the general formula (V) with respect to the number of moles of the amino group of the hydrolyzable silane represented by the formula (IV).

  This reaction can be performed according to a conventional method in which an amino group and an isocyanate group are reacted. The reaction temperature is, for example, -78 ° C to 200 ° C, preferably -78 ° C to 100 ° C, more preferably -10 ° C to 40 ° C. Further, this reaction can be carried out by applying pressure (or reduced pressure) as necessary, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  The compound represented by the general formula (V) can be obtained, for example, by reacting a compound represented by the following general formula (VI) with a compound represented by the following general formula (VII).

  The compound represented by the general formula (VI) is a so-called isocyanurate cycloadduct of 1,6-hexamethylene diisocyanate, and trade names include Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), Duranate TPA100 ( Asahi Kasei Chemicals).

R ⁴ , R ⁵ and m in the general formula (VII) are the same as described above. The compound represented by the general formula (VII) is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) when m is 0. Examples include acrylate and 4-hydroxybutyl (meth) acrylate. Examples of the compound when m is 1 to 5 include caprolactone-modified hydroxyalkyl (meth) acrylate. Specifically, “Placcel FA-1”, “Plaxel FA-2”, “Plaxel FA-2D”, “Plaxel FA-3”, “Plaxel FA-4”, “Plaxel FA-5” are trade names. , "Placcel FM-1", "Placcel FM-2", "Placcel FM-2D", "Placcel FM-3", "Placcel FM-4", "Placcel FM-5" (all manufactured by Daicel Chemical Industries, PLACCEL \ PLACCEL is a registered trademark).

  The mixing ratio of the compound represented by the general formula (VI) and the compound represented by the general formula (VII) is not particularly limited, but in the general formula (VI) The isocyanate group of the compound represented and the hydroxyl group of the compound represented by the general formula (VII) are usually in a molar ratio of NCO / OH = 1.05 to 2.00, preferably 1.10 to 1.50. The blending ratio is as follows.

  This reaction can be performed according to a conventional method in which an isocyanate group and a hydroxyl group are reacted. The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 ° C to 120 ° C. Further, this reaction can be carried out by applying pressure (or reduced pressure) as necessary, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 2 to 10 hours.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  In addition, the product obtained by reacting the compound represented by the general formula (VI) and the compound represented by the general formula (VII) includes the compound represented by the general formula (V). In addition, the following general formula (VIII)

[In the formula (VIII), R ⁴ , R ⁵ and m are the same as above. ] Or a compound in which two unreacted isocyanate groups remain in the compound represented by the general formula (V) may be included.

  And when manufacturing the hydrolysable silane represented by the said general formula (II), and when manufacturing a reactive particle (a) using the hydrolysable silane represented by the said general formula (II) Even if the compound represented by the general formula (VIII) is contained in the raw material for the production, there is no particular problem.

  Subsequently, a method for producing a hydrolyzable silane represented by the general formula (III) will be exemplified. The hydrolyzable silane represented by the general formula (III) is obtained by, for example, reacting a hydrolyzable silane represented by the following general formula (IX) with a compound represented by the following general formula (X). Can be obtained.

R ⁹ , R ^a , R ^b and R ^c in the general formula (IX) are the same as described above.

R ⁷ and R ⁸ in the general formula (X) are the same as described above.

  Specific examples of the hydrolyzable silane represented by the general formula (IX) include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.

  Examples of the compound represented by the general formula (X) include bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-acryloyloxypropyl) hydroxyethyl isocyanurate, and the like. Examples of product names include Aronix M-215 and Aronix M-313 (both manufactured by Toagosei Co., Ltd., Aronix is a registered trademark).

  The mixing ratio of the hydrolyzable silane represented by the general formula (IX) and the compound represented by the general formula (X) is not particularly limited. The reaction is carried out using equimolar amounts of the hydroxyl group of the compound represented by the general formula (X) with respect to the number of moles of the isocyanate group of the hydrolyzable silane represented by the formula (IX).

  This reaction can be performed according to a conventional method in which an isocyanate group and a hydroxyl group are reacted. The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 ° C to 120 ° C. Further, this reaction can be carried out by applying pressure (or reduced pressure) as necessary, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 2 to 10 hours.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  In addition, the compound represented by the general formula (X) is a name such as Aronix M-215 or Aronix M-313 (both manufactured by Toagosei Co., Ltd., Aronix is a registered trademark), and tris (2-acryloyloxyethyl). ) The following general formula (XI) such as isocyanurate, tris (2-acryloyloxypropyl) isocyanurate

[In formula (XI), R ⁷ and R ⁸ are the same as defined above. It is sold as a mixture with a compound represented by

  And when manufacturing the hydrolyzable silane represented by the said general formula (III), and when manufacturing a reactive particle (a) using the hydrolysable silane represented by the said general formula (III) Even if the compound represented by the general formula (XI) is contained in the raw material for the production, there is no particular problem.

Hydrolyzable silanes other than hydrolyzable silane (a-2) (a-3)
The reactive particles (a) are silica fine particles (a-1), hydrolyzable silanes (a-2), and hydrolyzable silanes (a-3) other than the hydrolyzable silanes (a-2). It can also be obtained by reacting with a mixture.

  As an example of the hydrolysable silane (a-3) in the said mixture, the hydrolysable silane which has a (meth) acryloyloxy group in molecules other than a hydrolysable silane (a-2) is mentioned, for example.

  When obtaining the reactive particles (a), the hydrolyzable silane (a-3) is hydrolyzed as compared with the case where only the hydrolyzable silane (a-2) is reacted with the silica fine particles (a-1). The reactive particles (a) obtained by reacting with the reactive silane (a-2) may be more excellent in active energy ray curability in the presence of a photopolymerization initiator.

  Examples of the hydrolyzable silane (a-3) include the following general formula (XII)

[In Formula (XII), X represents a (meth) acryloyloxy group. R ¹⁰ represents a divalent hydrocarbon group having 1 to 8 carbon atoms. R ^a , R ^b and R ^c are the same as described above. ] The hydrolysable silane represented by this is mentioned.

R ¹⁰ in the general formula (XII) is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 8 carbon atoms. Specifically, for example, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group, octylene group and the like can be mentioned. It is done.

  Examples of the hydrolyzable silane represented by the general formula (XII) include 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, and 2-acryloyloxy. Ethyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, Examples include at least one compound selected from 3-acryloyloxypropylmethyldimethoxysilane and the like.

  Examples of the hydrolyzable silane (a-3) include, in addition to the hydrolyzable silane represented by the general formula (XII), for example, a hydrolyzable silane having a (meth) acryloyloxy group and a urethane bond in the molecule. Is mentioned.

  Examples of the hydrolyzable silane having a (meth) acryloyloxy group and a urethane bond in the molecule include, for example, the following general formula (XIII)

[In formula (XIII), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ¹³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ^a , R ^b and R ^c are the same as described above. n shows the integer of 1-10. ] The hydrolysable silane represented by this is mentioned.

The R ¹² is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, for example, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and other alkylene groups; cyclohexylene group And aralkylene groups such as a phenylene group and a xylylene group. Especially, it is preferable that it is a C1-C6 bivalent hydrocarbon group, especially an ethylene group, a 1, 2- propylene group, and a 1, 4- butylene group.

The R ¹³ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, for example, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and other alkylene groups; cyclohexylene group And aralkylene groups such as a phenylene group and a xylylene group. Especially, it is preferable that it is a C1-C6 bivalent hydrocarbon group, especially an ethylene group and a 1, 3- propylene group.

  The n is not particularly limited as long as it is an integer of 1 to 10. n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1.

  The hydrolyzable silane represented by the general formula (XIII) is obtained by, for example, reacting a hydrolyzable silane represented by the following general formula (XIV) with a compound represented by the following general formula (XV). Can be obtained.

[In the formula (XIV), R ¹³ , R ^a , R ^b and R ^c are the same as defined above. ]

[In the formula (XV), R ¹¹ , R ¹² and n are the same as defined above. ]
Examples of the hydrolyzable silane represented by the general formula (XIV) include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.

  Examples of the compound represented by the general formula (XV) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples include acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and dipropylene glycol mono (meth) acrylate.

Method for producing hydrolyzable silane represented by general formula (XIII)
The reaction between the hydrolyzable silane represented by the general formula (XIV) and the compound represented by the general formula (XV) can be performed according to a conventional method in which an isocyanate group and a hydroxyl group are reacted.

  The use ratio of the hydrolyzable silane represented by the general formula (XIV) and the compound represented by the general formula (XV) in the above reaction formula is usually 0.90 to 1.10. About a mole, preferably about 0.95 to 1.05 mole.

  The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 to 120 ° C. Further, this reaction can be carried out by applying pressure (or reduced pressure) as necessary, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 2 to 10 hours.

  In the reaction, a catalyst may be appropriately used. Examples of the catalyst include tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, ethyl isoamyl ketone, diisobutyl ketone, and methyl hexyl ketone; ethyl acetate, butyl acetate, methyl benzoate, propion Esters such as methyl acid; Ethers such as tetrahydrofuran, dioxane and dimethoxyethane; Glycol ethers such as propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Aromatic hydrocarbons such as toluene and xylene; Aliphatic hydrocarbons And the like.

As the hydrolyzable silane (a-3), in addition to the hydrolyzable silane represented by the general formula (XII) and the general formula (XIII), an alkoxysilane or vinylsilane having an alkyl group having 1 or more carbon atoms. Etc.
By reacting an alkoxysilane having an alkyl group having 1 or more carbon atoms, the water resistance of the laminate obtained using the obtained reactive particles (a) may be improved. Examples of the alkoxysilane having an alkyl group having 1 or more carbon atoms include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, and dodecyltrimethoxy. Silane etc. are mentioned, The compound (for example, methyl triethoxysilane etc.) which substituted the methoxy group in these illustrated compounds by the ethoxy group is also mentioned. Examples of the vinyl silane having an alkyl group having 1 or more carbon atoms include vinyl trimethoxy silane and vinyl triethoxy silane.

Method for producing reactive particles (a)
The reactive particles (a) are obtained by reacting the silica fine particles (a-1) with the hydrolyzable silane (a-2), or the silica fine particles (a-1) and the hydrolyzable silane (a- 2) Mixture of hydrolyzable silane (a-3) [Hereinafter, in description of the manufacturing method of reactive particle | grains (a), hydrolysable silane (a-2) and hydrolysable silane (a-2) And a mixture of hydrolyzable silane (a-3) may be abbreviated as “hydrolyzable silane”. ] Can be obtained. The method for reacting the silica fine particles (a-1) with the hydrolyzable silane is not particularly limited. For example, [i] a method in which silica fine particles (a-1) and a hydrolyzable silane are mixed in the presence of an organic solvent containing water and hydrolytic condensation is performed, and [ii] in the presence of an organic solvent containing water. A method of condensing a hydrolyzate of hydrolyzable silane and silica fine particles (a-1) after hydrolyzing the hydrolyzable silane, [iii] silica fine particles (a-1) and hydrolyzable silane, Examples include a method of mixing in the presence of water, an organic solvent and other components such as a polymerizable unsaturated compound (B) described later, and performing hydrolytic condensation at a time. Here, the water used in these production methods may be water contained in the raw material, for example, water that is a dispersion medium of colloidal silica fine particles.

  The method for producing the reactive particles (a) will be described more specifically. The reactive particles (a) are, for example, colloidal in the presence of colloidal silica fine particles (silica fine particles (a-1)), hydrolyzable silane, optionally lower alcohol, and optionally polymerizable unsaturated compound. The dispersion medium in silica fine particles and lower alcohol (including lower alcohol produced by hydrolyzing hydrolyzable silane) are azeotropically distilled together with a solvent having a boiling point higher than that of lower alcohol under normal pressure or reduced pressure. After the dispersion medium is replaced with the solvent, it can be produced by a dehydration condensation reaction under heating.

  In this production method, a hydrolysis catalyst is added to a mixture of colloidal silica fine particles (silica fine particles (a-1)), hydrolyzable silane, optionally lower alcohol, and optionally polymerizable unsaturated compound as necessary. The hydrolyzable silane is hydrolyzed by a conventional method such as stirring at room temperature or under heating. Subsequently, the dispersion medium in the colloidal silica fine particles and the lower alcohol were azeotropically distilled together with a solvent having a boiling point higher than that of the lower alcohol under normal pressure or reduced pressure, and the dispersion medium was replaced with the solvent. The reaction is preferably carried out at a temperature of 80 to 130 ° C. with stirring for 0.5 to 10 hours while maintaining the nonvolatile content concentration in the range of 5 to 50 mass%. After the reaction, it is preferable to azeotropically distill water and lower alcohol generated by condensation reaction or hydrolysis together with a solvent having a boiling point higher than that of the lower alcohol.

  Examples of the solvent used in the above reaction include hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cyclohexane; halogenated hydrocarbons such as trichloroethylene and tetrachloroethylene; ethers such as 1,4-dioxane and dibutyl ether. Ketones such as methyl isobutyl ketone; esters such as n-butyl acetate, isobutyl acetate, ethyl acetate and ethyl propionate; and polyhydric alcohol derivatives such as ethylene glycol monobutyl ether.

  The non-volatile content concentration during the reaction is preferably in the range of 5 to 50% by mass. When the non-volatile concentration is less than 5% by mass, that is, when the solvent exceeds 95% by mass, the reaction between the silica fine particles (a-1) and the hydrolyzable silane is insufficient, and the active energy containing such reactive particles The cured film obtained by the curable composition may be inferior in transparency. On the other hand, if the nonvolatile content concentration exceeds 50% by mass, the product may be gelled.

  By these production methods, the silicon atom on the surface of the silica fine particle (a-1) and the silicon atom of the hydrolyzable silane are bonded via an oxygen atom, whereby the silica fine particle (a-1) and the hydrolyzable silane are combined. Chemically bound reactive particles (a) are obtained.

  The blending amount of the hydrolyzable silane (a-2) at the time of obtaining the reactive particles (a) varies depending on the particle diameter, but the obtained laminate is transparent with respect to 100 parts by mass of the silica fine particles (a-1). From a viewpoint of property, Preferably it is 1-99 mass parts, More preferably, it is 5-90 mass parts.

  Furthermore, when hydrolyzable silane (a-3) is used in addition to hydrolyzable silane (a-2) when obtaining reactive particles (a), hydrolyzable silane (a-2) The mixing ratio of hydrolyzable silane (a-3) is hydrolyzable silane (a-2) / hydrolyzable silane (a-) in terms of the active energy ray-curable primer in the presence of a photopolymerization initiator. 3) = 10/90 to 90/10 (mass ratio) is preferable, and 20/80 to 80/20 (mass ratio) is more preferable.

  Moreover, when an alkoxysilane having an alkyl group having 1 or more carbon atoms is used as a part of the hydrolyzable silane (a-3), the water resistance of the resulting laminate may be improved. The mixture ratio is 80 mass% or less with respect to the total mass of hydrolysable silane (a-2) and (a-3), Preferably it is the range of 50 mass% or less.

  The content of the organic substance-modified silica particles (A) in the cured coating layer (I) by the active energy ray-curable primer composition is not particularly limited. From the viewpoint of scratch resistance and wear resistance improvement, crack prevention and transparency of the obtained laminate, preferably 5 to 80 parts by mass with respect to 100 parts by mass of the nonvolatile content of the active energy ray-curable primer composition. Yes, more preferably 10 to 75 parts by mass, particularly preferably 20 to 70 parts by mass.

  Here, the non-volatile content of the active energy ray-curable primer composition is the sum of the non-volatile content of the organic material-modified silica particles (A) and the polymerizable unsaturated compound (B) described later.

≪Polymerizable unsaturated compound (B) ≫
The active energy ray-curable primer composition for forming the cured coating film layer (I) in the laminate of the present invention contains a polymerizable unsaturated compound (B).

  As the polymerizable unsaturated compound (B), when the organic modified silica (A) of the present invention is an organic modified silica particle having an unsaturated group, it is a compound other than that, and the polymerizable unsaturated compound (B) is not polymerizable in the chemical structure. The compound is not particularly limited as long as it is a compound having at least one saturated double bond.

  Examples of the polymerizable unsaturated compound (B) include monofunctional polymerizable unsaturated compounds and polyfunctional polymerizable unsaturated compounds.

  Examples of the monofunctional polymerizable unsaturated compound include esterified products of monohydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, N-acryloyloxyethylhexahydro Examples include phthalimide. Also, for example, hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid Carboxyl group-containing (meth) acrylates such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate and 5-carboxypentyl (meth) acrylate; glycidyl groups such as glycidyl (meth) acrylate and allyl glycidyl ether Containing polymerizable unsaturated compounds; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl Nitrogen-containing alkyl (meth) acrylates such as ru (meth) acrylate and Nt-butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- Methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Examples thereof include polymerizable amides such as dimethylaminoethyl (meth) acrylamide.

  Examples of the polyfunctional polymerizable unsaturated compound include an esterified product of a polyhydric alcohol and (meth) acrylic acid. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, Hexane dimethanol di (meth) acrylate, tricyclodencan dimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, hydrogenated hexafluorobisphenol A di (meth) Acrylate, bis (2- (meth) acryloyloxy) hexahydrophthalic acid, 5-ethyl-2- (2-hydroxy-1,1dimethylethyl) -5- (hydroxymethyl) -1,3-dioxanedi (meth) ) Di (meth) acrylate compounds such as acrylate; glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acrylate compounds such as ε-caprolactone modified tris (acryloxyethyl) isocyanurate; tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate Compound; Other examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Furthermore, polymerizable unsaturated group-containing acrylic resins, (meth) acryloyl group-containing urethane resins, (meth) acryloyl group-containing epoxy resins, (meth) acryloyl group-containing polyester resins and the like can be mentioned. Examples of the polymerizable unsaturated group-containing acrylic resin include a polymerizable unsaturated group-containing acrylic resin obtained by adding a glycidyl group-containing polymerizable unsaturated compound such as glycidyl (meth) acrylate to a carboxyl group-containing acrylic resin, hydroxyl group, and the like. Examples include polymerizable unsaturated group-containing acrylic resins obtained by adding a compound having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate and a polymerizable unsaturated group to the group-containing acrylic resin. These polymerizable unsaturated compounds can be used alone or in combination of two or more.

  Furthermore, examples of the polyfunctional polymerizable unsaturated compound include a polymerizable unsaturated compound represented by the following general formula (XVI) and / or a polymerizable unsaturated compound represented by the following general formula (XVII).

[In Formula (XVI), R ⁴ is the same or different and represents a hydrogen atom or a methyl group. R ⁵ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. m is the same or different and represents an integer of 0 to 5. In formula (XVII), R ⁷ are the same or different and each represents a hydrogen atom or a methyl group. R ⁸ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. ]
R ⁵ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Especially, it is preferable that it is a C2-C4 bivalent hydrocarbon group, especially an ethylene group.

R ⁸ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Especially, it is preferable that it is a C2-C4 bivalent hydrocarbon group, especially an ethylene group.

  The polymerizable unsaturated compound represented by the general formula (XVI) includes, for example, 1,6-hexamethylene diisocyanate isocyanurate cycloadduct and hydroxyalkyl (meth) acrylate or caprolactone-modified hydroxyalkyl (meth) acrylate. In the presence of a tin-based catalyst such as di-n-butyltin dilaurate, it can be obtained by heating at 60 to 70 ° C. for several hours by using the isocyanate group and the hydroxyl group so as to have approximately the same amount.

  Examples of the polymerizable unsaturated compound represented by the general formula (XVII) include tris (2-acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, and the like.

  Here, the polymerizable unsaturated compound represented by the general formula (XVI) is the same compound as the compound represented by the general formula (VIII) described in the method for producing the reactive particles (a) described above. . Moreover, the polymerizable unsaturated compound represented by the general formula (XVII) is the same compound as the compound represented by the general formula (XI) described in the method for producing the reactive particles (a) described above. Therefore, when producing the reactive particles (a), the polymerizable unsaturated compound represented by the general formula (XVI) or the polymerizable unsaturated compound represented by the general formula (XVII) is included. However, in the present invention, the polymerizable unsaturated compound represented by the general formula (XVI) and the polymerizable unsaturated compound represented by the general formula (XVII) are the polymerizable unsaturated compound (B ).

Furthermore, as the polyfunctional polymerizable unsaturated compound, for example, hexamethylene disissocyanate trimer having iminooxadiazinedione group and hydroxyalkyl (meth) acrylate are present in the presence of a catalyst, and the isocyanate group and the hydroxyl group are approximately equal. Urethane (meth) acrylates obtained by reacting with each other can also be used. Examples of commercially available hexamethylene disissocyanate trimer having an iminooxadiazinedione group include Desmodur ( ^{registered trademark)} XP2410 (manufactured by Bayer MaterialScience). Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. .

  The reaction of the hexamethylene disissocyanate trimer and the hydroxyalkyl (meth) acrylate can be performed at a temperature of, for example, 0 to 200 ° C, preferably 20 to 200 ° C, and more preferably 20 ° C to 120 ° C. The reaction is usually completed in about 2 to 10 hours. In the reaction, a catalyst may be appropriately used. Examples of the catalyst include tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  The active energy ray-curable primer composition used for the laminate of the present invention has a polymerizable property represented by the general formula (XVI) from the viewpoint of the weather resistance of the resulting cured coating film and the adhesion to an object to be coated. It is preferable to contain an unsaturated compound and / or a polymerizable unsaturated compound represented by the general formula (XVII).

  The use amount of the polymerizable unsaturated compound (B) in the active energy ray curable primer composition is preferably an active energy ray curable type from the viewpoint of the weather resistance of the obtained cured coating film and the adhesion to the article to be coated. It is 20-95 mass parts with respect to 100 mass parts of non volatile matters of a primer composition, More preferably, it is 25-90 mass parts, Most preferably, it is 30-80 mass parts.

  Among the polymerizable unsaturated compounds (B), the polyfunctional polymerizable unsaturated compound is particularly represented by the polymerizable unsaturated compound represented by the general formula (XVI) and / or the general formula (XVII). When a polymerizable unsaturated compound is used, from the viewpoint of weather resistance and adhesion to an object to be coated, the use ratio of the general formula (XVI) and / or the general formula (XVII) is determined based on the polymerizable unsaturated compound. It is 10 mass%-90 mass% with respect to the total amount of all the non volatile matters of (B), More preferably, it is the range of 15 mass%-85 mass%, More preferably, it is the range of 20-80 mass%.

≪Photopolymerization initiator (C) ≫
As a photoinitiator (C), if it is an initiator which absorbs an active energy ray and generate | occur | produces a radical, it can be used without being specifically limited.

  Examples of the photopolymerization initiator (C) include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, 4 -Thioxanthones such as diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; Benzophenones such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone; Michler's ketone Acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimeth Ci-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenones such as 1-butan-1-one, α-isohydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone; 2,4,6-trimethylbenzoyldiphenylphosphine Acylphosphine oxides such as oxide and bis (acyl) phosphine oxide; Quinones such as anthraquinone and 1,4-naphthoquinone; Halo such as phenacyl chloride, trihalomethylphenylsulfone, tris (trihalomethyl) -s-triazine Emissions compounds; peroxides such as di -t- butyl peroxide and the like. These can be used as one or a mixture of two or more.

  As a commercial item of a photoinitiator (C), Irgacure 184 (IRGACURE 184), Irgacure 127, Irgacure 261, Irgacure 500, Irgacure 651, Irgacure 754, Irgacure 819, Irgacure 907, Irgacure CGI-1700 Manufactured, trade name, IRGACURE and Irgacure are registered trademarks), Darocur 1173 (Darocur 1173), Darocur 1116, Darocur 2959, Darocur 1664, Darocur 4064 (trade name, Darocur \ Darocur \ registered trademark MB), Kayacure P , Kayacure DETX-S, Kayacure DMBI, Kayacure EPA, Kayacure OA (trade name, manufactured by Nippon Kayaku Co., Ltd.) KAYACURE \ Kayacure is a registered trademark), Vicure 10 (VICURE 10), Vicure 55 (trade name, manufactured by STAUFFER Co., LTD.), Trigonal P1 [TRIGONAL (registered trademark) P1]] [Akzo Corporation (AKZO Co., LTD., Product name), SANDORAY 1000 (SANDOZ Co., LTD., Product name), Deep (DEAP) [APJOHN Co., LTD Product name], CANTACURE PDO (QUANTACURE PDO), CANTACURE ITX, CANTACURE EPD (manufactured by WARD BLEKINSOP Co., LTD., Product name), ESACURE KIP150, ESACURE ONE (LAMBERTI) Trade name, esacure \ by lamberti is a registered trademark), lucillin TPO and the like.

  The photopolymerization initiator (C) is preferably one or a mixture of two or more of thioxanthones, acetophenones and acylphosphine oxides from the viewpoint of photocurability. Particularly preferred are mixtures with fin oxides.

The usage ratio of the photopolymerization initiator (C) is not particularly limited. 0.1 to 10 parts by mass, preferably 2 to 8 parts by mass is appropriate for 100 parts by mass of the nonvolatile content of the active energy ray-curable primer composition. Active energy ray curing used for the laminate of the present invention The mold primer composition can contain an ultraviolet absorber (D) and / or a light stabilizer (E) as necessary.

<Ultraviolet absorber (D)>
As the ultraviolet absorber, conventionally known ones can be used. For example, a benzotriazole-based absorbent, a triazine-based absorbent, a salicylic acid derivative-based absorbent, a benzophenone-based absorbent, or the like can be used.

  Specific examples of the benzotriazole-based absorbent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimi Methyl) -5'-methylphenyl} benzotriazole.

  Specific examples of the triazine-based absorbent include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine, 2- [4 ((2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 4-((2-hydroxy-3-tridecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.

  Specific examples of the salicylic acid derivative-based absorbent include phenyl salicylate, p-octylphenyl salicylate, 4-tert-butylphenyl salicylate, and the like.

  Specific examples of the benzophenone-based absorbent include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxy Benzophenone, sodium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2 -Hydroxybenzo Examples include phenone, resorcinol monobenzoate, 2,4-dibenzoyl resorcinol, 4,6-dibenzoyl resorcinol, hydroxydodecylbenzophenone, and the like. Examples of the ultraviolet absorber include known polymerizable ultraviolet absorbers such as 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, 2,2′-dihydroxy-4 (3- Methacryloxy-2-hydroxypropoxy) benzophenone and the like can also be used.

  Examples of commercially available ultraviolet absorbers include TINUVIN 900, TINUVIN 928, TINUVIN 348-2, TINUVIN 479, TINUVIN 405, TINUVIN 292 (trade name, TINUVIN / Tinuvin is a registered trademark), RUVA 93 ( Otsuka Chemical Co., Ltd., trade name).

  Although the usage-amount of the said ultraviolet absorber is not specifically limited, 0.1-20 mass parts with respect to 100 mass parts of non volatile matters of an active energy ray hardening-type primer composition, Preferably it is 1-10 masses. It is preferable that it is in the range of parts. These ranges are significant in terms of adhesion to the object to be coated and weather resistance.

<Light stabilizer (E)>
The light stabilizer is used as a radical chain inhibitor that traps active radical species generated during the deterioration process of the film. Among the light stabilizers, hindered piperidine is used as a light stabilizer that exhibits an excellent light stabilization effect. Kind.

  Examples of hindered piperidines include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and bis ( N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2 ′, 6,6′-tetramethylpiperidine, bis (1,2,2,6, Monomer type such as 6-pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl} butyl malonate; poly {[6- (1,1 , 3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethyl-4-piperidyl) iminol]} and the like; polyesters of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and succinic acid Examples thereof include, but are not limited to, polyester-bonded types. A known polymerizable light stabilizer can also be used as the light stabilizer.

  Commercially available products of the above light stabilizer include, for example, TINUVIN 123, TINUVIN 152, TINUVIN 292 (trade name, TINUVIN \ Tinuvin is a registered trademark), HOSTAVIN 3058 (manufactured by Clariant, and trade name Hostavin is a registered trademark). And ADK STAB LA-82 (manufactured by ADEKA Corporation, trade name, ADK STAB \ ADKSTAB and ADK STAB are registered trademarks), and the like.

  Although the usage-amount of the said light stabilizer is not specifically limited, 0.1-10 mass parts with respect to 100 mass parts of non volatile matters of an active energy ray hardening-type primer composition, Preferably 0.2- A range of 5 parts by mass is preferred. These ranges are significant in terms of weather resistance.

<Other ingredients>
The active energy ray-curable primer composition used in the laminate of the present invention may further contain various additives, saturated resins, and the like as necessary, and may be diluted with a solvent as required. Examples of the additive include a sensitizer, a polymerization inhibitor, an antioxidant, an antifoaming agent, a surface conditioner, a plasticizer, and a colorant. Examples of the saturated resin include saturated acrylic resin, saturated polyester resin, saturated urethane resin, and the like.

  Examples of the surface conditioner include a silicon-based surface conditioner (F), an acrylic-based surface conditioner, and a fluorine-based surface conditioner, and in particular, a silicon-based surface conditioner from the viewpoint of adhesion to a CVD layer. An agent is preferred, and a polymerizable unsaturated group-containing silicon-based surface conditioner (Fa) is particularly preferred from the viewpoint of interlayer adhesion between the CVD layer and the primer layer.

  Examples of the silicon-based surface conditioner (F) include organopolysiloxanes such as dimethylpolysiloxane, modified silicon obtained by modifying organopolysiloxane, and the like. Specific examples of the modified silicon include alkyl-modified polysiloxane, phenyl-modified polysiloxane, and polyether-modified polysiloxane. These can be used alone or in combination of two or more.

  Specifically, for example, dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified polydimethylsiloxane, polyether-modified dimethylpolysiloxane, polyester-modified dimethylpolysiloxane, polyester-modified polydimethylsiloxane, polymethylalkylsiloxane, polyester-modified polymethyl Examples thereof include alkyl siloxane and aralkyl-modified polymethylalkyl siloxane.

A commercially available product can be used as the silicon-based surface conditioner (F).
For example, DC11PA, ST80PA, DC3074, DC3037, SR2402 (above, trade names, manufactured by Toray Dow Corning); KP-321, KP-324, KP-327, KR-9218, X-40-9220 (above, merchandise Name, manufactured by Shin-Etsu Chemical Co., Ltd.); TSR165, XR-31B1763 (above, trade name, manufactured by Toshiba Silicon Corporation); BYK-341, BYK-344, BYK-306, BYK-307, BYK-325, BYK-315, BYK-320, BYK-322, BYK-323, BYK-300, BYK-302, BYK-330, BYK-333, BYK-335, BYK-370, BYK-SILCLEAN 3700 (above, trade name, manufactured by BYK Japan Corporation ); DISPARLON 1711, 1751N, 176 1, LS-001, LS-050 (above, trade name, manufactured by Enomoto Kasei Co., Ltd.); Polyflow KL-400HF, KL-401, KL-402, KL-403, KL-404 (above, trade name, Kyoeisha Chemical Co., Ltd.) Company name).

  Examples of the unsaturated group-containing silicon-based surface conditioner (Fa) include modified silicon obtained by introducing a polymerizable unsaturated group into the organopolysiloxane such as dimethylpolysiloxane.

  Examples of the polymerizable unsaturated group include a (meth) acryloyl group and a vinyl group. The number of polymerizable unsaturated groups is not particularly limited, but is preferably at least one, preferably two or more, from the viewpoint of active energy ray curability in the presence of a photopolymerization initiator.

  Specific examples of unsaturated group-containing silicon-based surface conditioners include (meth) acryloyl group-containing polysiloxanes, vinyl group-containing polysiloxanes and other polymerizable unsaturated group-containing polyether-modified polysiloxanes, and polymerizable unsaturated group-containing compounds. Examples include polyester-modified polysiloxane.

A commercially available product can be used as the polymerizable unsaturated group-containing silicon-based surface conditioner (Fa).
For example, as (meth) acryloyl group-containing polysiloxane, BYK-UV-3500, BYK-UV-3510, BYK-UV-3570 (above, trade name, manufactured by Big Chemie Japan); Silaplane FM-7711, FM -7721, FM-7725 (above, trade name, manufactured by JNC Corporation), X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22-1603 (above, Trade name, manufactured by Shin-Etsu Silicone Co., Ltd.); TEGO Rad-2100, -2200N, -2250, -2300, -2500, -2600, -2700 (above, TEGO Rad series, trade name, manufactured by Evonik Japan) It is done.

  Examples of the vinyl group-containing polysiloxane include Silaplane FM-2231 (trade name, manufactured by JNC Corporation).

  Among the above-mentioned polymerizable unsaturated group-containing silicon-based surface conditioners, (meth) acryloyl group-containing polysiloxane is preferable from the viewpoint of adhesion to the CVD layer and compatibility.

  In the case of using the polymerizable unsaturated group-containing silicon-based surface conditioner (Fa), from the viewpoint of adhesion to the CVD layer, 40 parts by mass with respect to 100 parts by mass of the nonvolatile content of the active energy ray-curable primer composition. It is below mass parts, preferably 0.05-35 mass parts, more preferably 1-35 mass parts. When the polymerizable unsaturated group-containing silicon-based surface conditioner (Fa) is blended, it crosslinks with other components having a polymerizable unsaturated group and works on the surface of the coating film to improve the adhesion to the CVD layer. Conceivable.

  The blending amount in the case of containing other surface conditioner is not particularly limited as long as the compatibility and the coating film performance are not significantly deteriorated. Usually, the non-volatile content of the active energy ray-curable primer composition is 100 parts by mass. On the other hand, it is 5 mass parts or less, Preferably it is the range of 0.01 mass part-3 mass parts.

  Examples of the solvent used for dilution include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, methyl benzoate, and methyl propionate; ethers such as tetrahydrofuran, dioxane, and dimethoxyethane Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons, aliphatic hydrocarbons and the like. These can be used in appropriate combination depending on the purpose such as adjustment of viscosity and adjustment of coating property.

  The nonvolatile content of the active energy ray-curable primer composition is not particularly limited. For example, Preferably it is 20-100 mass%, More preferably, it is 25-70 mass%. These ranges are significant in terms of smoothness of the cured coating layer and shortening of the drying time.

  The method for applying the active energy ray-curable primer composition to the resin substrate in the present invention is not particularly limited, and a known method can be adopted. The active energy ray-curable primer composition is applied, for example, by painting, and cured to obtain a cured coating film layer (I). Examples of the coating method include roller coating, roll coater coating, spin coater coating, curtain roll coater coating, slit coater coating, spray coating, electrostatic coating, immersion coating, silk printing, and spin coating.

  When the active energy ray-curable primer composition is applied to obtain the cured coating film layer (I), drying can be performed as necessary. The drying is not particularly limited as long as the solvent that is added can be removed. For example, it can be performed at a drying temperature of 20 to 120 ° C. for a drying time of 3 to 20 minutes.

  The thickness (hereinafter referred to as film thickness) of the cured coating film layer (I) is appropriately set according to the purpose. For example, the film thickness is preferably 3 to 30 μm, and more preferably 5 to 15 μm. When the film thickness is at least the lower limit of these ranges, the resulting laminate has excellent weather resistance (particularly adhesion to the object to be coated). Moreover, when it is below the upper limit of these ranges, the curability of the coating film is excellent.

  The irradiation source and irradiation amount of active energy ray irradiation are not particularly limited. For example, the active energy ray irradiation source includes ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, sunlight and the like.

Dose, for example preferably 100~10,000mJ / cm ^2, more preferably include a range of 300~5,000mJ / cm ^2.

  As described above, a cured coating layer is formed from the active energy ray-curable primer composition having excellent adhesion to both the resin substrate and the cured coating layer, and the cured coating layer and the inorganic material layer.

  Next, the inorganic material layer (II) will be described in detail.

Inorganic substance layer (II)
The inorganic material layer (II) in the present invention is not particularly limited as long as it is formed by a dry film forming method. For example, Si, Ti, Zn, Al, Ga, In, Ce, Bi, Examples thereof include a layer mainly composed of at least one kind of various metals or metal oxides, nitrides, sulfides, and the like having elements such as Sb, B, Zr, Sn, and Ta. In addition, for example, a diamond-like carbon (hereinafter referred to as DLC) film layer having high hardness and excellent insulating properties may be used. The DLC film is a carbon film with an amorphous structure mainly composed of carbon-to-carbon SP3 bonds. It is a diamond-like carbon film that is extremely hard, has a low coefficient of friction, wear resistance, corrosion resistance, and gas barrier properties, and is excellent in insulation. is there.

  The inorganic material layer (II) in the present invention may be at least one layer or more than one layer. When the inorganic material layer (II) is a multi-layer, the stacking order thereof and the type of the inorganic material layer (II) are not particularly limited. Further, the inorganic material layer (II) may be various functional layers such as an ultraviolet absorbing layer and a functional layer.

  Among these, the outermost inorganic substance layer (II) is a metal from the viewpoint of obtaining a surface layer having high hardness, adhesion with a cured coating film layer, transparency of the laminated film and excellent chemical stability. A layer made of an oxide, particularly a silicon oxide compound, is particularly preferable.

  When one layer of the inorganic material layer (II) is a DLC layer, it is preferable that the metal oxide layer is stacked and then the outermost layer is stacked from the viewpoint of the above performance.

  The method for laminating the inorganic material layer (II) in the present invention is not particularly limited as long as it is a dry film forming method. For example, resistance heating evaporation, electron beam evaporation, molecular beam epitaxy, ion beam deposition, ion plating, Physical vapor deposition methods such as sputtering (hereinafter also referred to as “PVD”) and chemical vapor deposition methods such as thermal CVD, plasma CVD, photo CVD, epitaxial CVD, atomic layer CVD, and catCVD (hereinafter also referred to as “CVD”). Among them, plasma CVD (Chemical Vapor Deposition) is particularly preferable from the viewpoint of film forming temperature and film forming speed. The dry film-forming method referred to here is generally called a dry process by treating the material surface using a gas phase or a molten state.

  As the inorganic material layer (II), when a silicon oxide layer is formed by plasma CVD, an organic silicon compound can be suitably used as a raw material. Specific examples include tetraethoxysilane, hexamethyldisiloxane, trimethoxysilane, methyltriethoxysilane, 1,1,3,3-tetramethyldisiloxane, tetramethoxysilane, methoxytrimethylsilane, tetramethylsilane, Examples include hexamethyltrisiloxane, tetrachlorosilane, trichloromethylsilane, trimethylchlorosilane, dimethyldichlorosilane, and dimethylchlorosilane.

  Further, when the DLC layer is formed by plasma CVD, a hydrocarbon compound is used as a raw material. Specific examples include toluene, acetylene, methane, hexane and the like. When the inorganic material layer (II) is formed by the plasma CVD method, in addition to the raw material organic silicon compound and hydrocarbon compound, as a decomposition gas, hydrogen gas, methane gas, ozone gas, oxygen gas, carbon monoxide gas, carbon dioxide Carbon gas, nitrogen gas, nitrogen dioxide gas, dinitrogen monoxide gas, or the like is used. Among these, any one of oxygen gas, ozone gas, nitrogen dioxide gas, dinitrogen monoxide gas, dioxide gas, monoxide gas, or a combination of two or more thereof can be suitably used.

  Thus, various inorganic material layers (II) can be formed by appropriately selecting a raw material containing various metal raw materials and a decomposition gas, and raw materials for forming the inorganic material layer (II). May be used alone or in combination of two or more.

  In addition, the thickness of the inorganic material layer (II) is preferably 1 μm or more from the viewpoint of scratch resistance, and more preferably 2 μm or more for maintaining sufficient wear resistance. The upper limit of the thickness of the inorganic material layer (II) is not particularly limited, but is preferably 25 μm or less, particularly preferably 15 μm or less. If the thickness of the inorganic material layer (II) is less than 1 μm, sufficient scratch resistance may not be exhibited. In order to adjust the thickness of the inorganic material layer (II), the processing time or the like may be adjusted in plasma CVD.

Since the inorganic material layer laminated as described above is an inorganic substance, the laminate according to the present invention has excellent appearance, weather resistance (particularly, coating film appearance after a weather resistance test) and scratch resistance that are not found in organic coatings. It has excellent adhesion to the cured coating layer (I) by the primer composition, and is extremely excellent in weather resistance, water resistance and scratch resistance.

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by mass” and “% by mass” unless otherwise specified. In addition, the structural analysis and measurement in the production examples were performed using the following analysis apparatus and measurement method in addition to the analysis apparatus described in this specification.

( ²⁹ Si-NMR, ¹ H-NMR analysis)
Apparatus: FT-NMR EX-400 manufactured by JEOL
Solvent: CDCl ₃
Internal standard: Tetramethylsilane (FT-IR analysis)
Apparatus: FT / IR-610 manufactured by JASCO Corporation.

≪Production of organic modified silica≫
(Production Example 1) A-1
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 179 parts of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), 87 parts of 2-hydroxyethyl acrylate, 205 parts of isobutyl acetate and p-methoxy 1.0 part of phenol was blended and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, the mixture was cooled to 5 ° C., and 41 parts of 3-aminopropyltriethoxysilane was added dropwise over 1 hour. At this time, the temperature of the reaction product in the flask was controlled so as not to exceed 20 ° C. Subsequently, 205 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour. Then, isobutyl acetate was removed by distillation under reduced pressure, and the nonvolatile content of the product (A-1) was 60 % Solution was obtained.

The obtained product (A-1) had an NCO value = 0 mgNCO / g and an amine value = 0 mgKOH / g. As a result of ¹ H-NMR analysis of the product (A-1), the molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si of the product (A-1) was 4. 0.0. Further, as a result of ²⁹ Si-NMR analysis of the product (A-1), hydrolysis of the ethoxysilyl group in the product (A-1) was not confirmed.

  From the above results, the product (A-1) is a mixture of a compound represented by the following formula (AI) and a compound represented by the following formula (A-II).

The ratio was the compound represented by the formula (AI) / the compound represented by the formula (A-II) = 60/40 (molar ratio).

(Production Example 2) A-2
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 333 parts (100 parts of silica fine particles), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 0.20 part of p-methoxyphenol and 227 parts of isopropanol were added, and the temperature was increased while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 17 parts of a 60% non-volatile solution of the product (A-1) obtained in Production Example 1 [6.0 parts of the compound represented by the above formula (AI)] were added, and 95 ° C. The mixture was subjected to a dehydration condensation reaction with stirring for 2 hours, then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixed solution of reactive particles and the compound represented by the formula (A-II) having a nonvolatile content of 30%. It was. The ratio between the reactive particles calculated from the blending amount and the compound represented by the formula (A-II) is: reactive particles / compound represented by the formula (A-II) = 100/4 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (A-II) is called a product (A-2).

(Production Example 3) A-3
Aronix ^{(registered trademark)} M-313 (manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified di- and triacrylate) is ^added to a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 179 parts, 3-isocyanatopropyl 38 parts of triethoxysilane, 145 parts of isobutyl acetate and 1.0 part of p-methoxyphenol were mixed and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, 145 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., the mixture was stirred at 80 ° C. for 1 hour, isobutyl acetate was removed by distillation under reduced pressure, and the nonvolatile content of the product (A-3) was 60 % Solution was obtained.

The obtained product (A-3) had an NCO value of 0 mg NCO / g. As a result of ¹ H-NMR analysis of the product (A-3), the molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si of the product (A-3) was 7 .7. As a result of ²⁹ Si-NMR analysis of the product (A-3), hydrolysis of the ethoxysilyl group in the product (A-3) was not confirmed.

  From the above results, the product (A-3) is a mixture of a compound represented by the following formula (A-III) and a compound represented by the following formula (A-IV),

The ratio was the compound represented by the formula (A-III) / the compound represented by the formula (A-IV) = 35/65 (molar ratio).

(Production Example 4) A-4
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 333 parts (100 parts of silica fine particles), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 0.20 part of p-methoxyphenol and 227 parts of isopropanol were added, and the temperature was increased while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 17 parts of a 60% non-volatile solution of the product (A-3) obtained in Production Example 3 [4.0 parts of the compound represented by the formula (A-III)] was added, and the temperature was 95 ° C. The mixture was subjected to a dehydration condensation reaction with stirring for 2 hours, then the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent is replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixed solution of reactive particles and a compound represented by the formula (A-IV) having a nonvolatile content of 30%. It was. The ratio between the reactive particles calculated from the blending amount and the compound represented by the formula (A-IV) is: reactive particles / compound represented by the formula (A-IV) = 100/5 (mass ratio). )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (A-IV) is called a product (A-4).

(Production Example 5) A-5
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) Manufactured) 333 parts (silica fine particles 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, p-methoxyphenol 0.20 parts and isopropanol 233 parts were mixed, and then the temperature was increased while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, after performing a dehydration condensation reaction with stirring at 95 ° C. for 2 hours, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, and a 30% non-volatile dispersion of reactive particles was obtained. In addition, the reactive particle obtained by this manufacture example is called a product (A-5).

<< Production of polymerizable unsaturated compound (B) >>
(Production Example 6) B-1
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 179 parts of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), 109 parts of 2-hydroxyethyl acrylate, 192 parts of isobutyl acetate and p-methoxy 1.0 part of phenol was blended and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, 192 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour, then isobutyl acetate was removed by distillation under reduced pressure, and the nonvolatile content of the product (B-1) was 60 % Solution was obtained.

  The obtained product (B-1) had an NCO value of 0 mg NCO / g. From the above results, the product (B-1) was a compound represented by the following formula (PI).

(Production Example 7) B-2
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 179 parts of Sumijour N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), 135 parts of 4-hydroxybutyl acrylate, 209 parts of isobutyl acetate and p- Methoxyphenol 0.20 part was blended and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, 209 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., the mixture was stirred at 80 ° C. for 1 hour, isobutyl acetate was removed by distillation under reduced pressure, and the nonvolatile content of the product (B-2) was 60 % Solution was obtained.

  The obtained product (B-2) had an NCO value of 0 mg NCO / g. From the above results, the product (B-2) was a compound represented by the following formula (P-II).

≪Preparation of active energy ray curable primer composition for cured coating layer (I) ≫
(Production Example 8) Active energy ray-curable primer composition No. 1
33 parts of the product (A-2) solution obtained in Production Example 2 (nonvolatile content 10 parts),
Ebecryl (registered trademark) 8804 (Note 1) 18 parts,
90 parts of the product (B-1) solution obtained in Production Example 6 (54 parts of non-volatile content),
Aronix ^{(registered trademark)} M-313 (Note 4) 18 parts,
Irgacure ^{(registered trademark)} 184 (Note 7) 3.0 parts,
Irgacure ^{(registered trademark)} 819 (Note 9) 0.40 part,
TINUVIN ^{(registered trademark)} 928 (Note 11) 3.0 parts,
TINUVIN ^{(registered trademark)} 292 (Note 14) 1.0 part,
And BYK ^(R) -333 (Note 15) 0.10 parts were mixed,
The nonvolatile content was adjusted with 1-methoxy-2-propanol, and the active energy ray-curable primer composition No. 30 having a nonvolatile content of 30% was obtained. 1 was obtained.

(Production Examples 9 to 32)
In Production Example 8, the active energy ray-curable primer composition No. 1 was prepared in the same manner as in Production Example 8 except that the types and amounts of each component were changed to the types and amounts of each component shown in Tables 1 and 2. 2-25 were obtained. In addition, the compounding quantity of Table 1 and Table 2 shows a nonvolatile content.

(Note 1) Ebecryl ^{(registered trademark)} 8804: Product name, bifunctional urethane acrylate manufactured by Daicel Cytec Co., Ltd. (Note 2) Ebecryl ^{(registered trademark)} 8402: Product name, product name, highly weather-resistant bifunctional urethane manufactured by Daicel Cytec Co., Ltd. Acrylate (Note 3) CN9001: Sartomer, trade name, bifunctional urethane acrylate (Note 4) Aronix ^{(registered trademark)} M-313: Toagosei Co., Ltd., trade name, isocyanuric acid EO-modified and diacrylate mixture , Diacrylate ratio (%) 30-40%
(Note 5) Aronix ^{(registered trademark)} M-315: manufactured by Toagosei Co., Ltd., trade name, isocyanuric acid EO-modified-di and triacrylate mixture, diacrylate ratio (%) 3-13%
(Note 6) Aronix ^{(registered trademark)} M-325: trade name, manufactured by Toagosei Co., Ltd., tris (2-acryloyloxyethyl) isocyanurate modified with one caprolactone per molecule.

(Note 7) Irgacure ^{(registered trademark)} 184: manufactured by BASF, trade name, photopolymerization initiator (C-1)
(Note 8) Irgacure ^{(registered trademark)} 754: manufactured by BASF, trade name, photopolymerization initiator (C-2)
(Note 9) Irgacure ^{(registered trademark)} 819: manufactured by BASF, trade name, photopolymerization initiator (C-3)
(Note 10) Lucillin TPO: manufactured by BASF, trade name, photopolymerization initiator (C-3).

(Note 11) TINUVIN ^{(registered trademark)} 928: manufactured by BASF, trade name, UV absorber (D-1)
(Note 12) TINUVIN ^{(registered trademark)} 384-2: BASF Corporation, trade name, UV absorber (D-2)
(Note 13) RUVA 93: manufactured by Otsuka Chemical Co., Ltd., trade name, UV absorber (D-3).

(Note 14) TINUVIN ^{(registered trademark)} 292: manufactured by BASF, trade name, light stabilizer (E-1).

(Note 15) BYK ^{(registered trademark)} -333: manufactured by BYK Chemie, trade name, surface conditioner (Note 16) BYK ^{(registered trademark)} -UV 3500: manufactured by BYK Chemie, trade name, surface conditioner.

Production of laminated body and evaluation results (Examples 1 to 25, Comparative Examples 1 and 2)
On the polycarbonate resin plate, the active energy ray-curable primer composition No. 1 to 25 were air spray coated so that the dry film thickness was 8 μm. Then, after preheating at 80 degreeC for 10 minute (s), the active energy ray was irradiated with the irradiation amount of 2,000 mJ / cm < ² > using the high pressure mercury lamp, and the cured coating film was produced. Next, an inorganic material layer (II) shown in Tables 3 and 4 was laminated thereon using a plasma CVD apparatus so as to have a film thickness of 5 μm. About each obtained test laminated body, it used for the following evaluation test. The evaluation results are shown in Tables 3 and 4.

(Note 17) "-" in Comparative Example 2 indicates that the compatibility with the polymerizable unsaturated compound was poor and the cured coating layer was cloudy, and subsequent evaluation could not be performed.
(Comparative Example 3)
On the polycarbonate resin plate, the active energy ray-curable primer composition No. 17 was applied by air spray so that the dry film thickness was 8 μm. Then, after preheating at 80 degreeC for 10 minute (s), the active energy ray was irradiated with the irradiation amount of 2,000 mJ / cm < ² > using the high pressure mercury lamp, and the cured coating film was produced. About each obtained test laminated body, it used for the following evaluation test. The evaluation results are shown in Table 4.

Performance test and evaluation criteria <Transparency>
Three drops of each primer composition are dropped on a glass plate, dried at 80 ° C. for 15 minutes, and then irradiated with active energy rays at a dose of 2,000 mJ / cm ² using a high-pressure mercury lamp metal halide lamp. A layer was made. Further, on the polycarbonate (PC) resin base material, each primer composition was air spray coated so as to have a dry film thickness of 8 μm as in Example 1, followed by preheating at 80 ° C. for 10 minutes, and then a high pressure mercury lamp. A cured coating layer was prepared by irradiating active energy rays at a dose of 2,000 mJ / cm ² using a metal halide lamp. Each cured coating layer was visually observed and evaluated according to the following criteria.

A: Turbidity cannot be confirmed in both the cured coating layer on the glass plate and the cured coating layer on the PC resin substrate. ○: Turbidity is confirmed in the cured coating layer on the glass plate, and on the PC resin substrate. Turbidity cannot be confirmed in the cured coating layer, and there is no problem when it is made into a product. ×: Turbidity is confirmed in both the cured coating layer on the glass plate and the cured coating layer on the PC resin substrate.

<Abrasion resistance>
Each specimen was subjected to a Taber abrasion test (abrasion wheel CF-10F, load 500 g, 1000 rotations) in accordance with ASTM D1044. The haze value was measured for the laminated film before and after the test to determine the change (ΔH) and evaluated according to the following criteria.

：: ΔH is less than 2 ○: ΔH is 2 or more and less than 5 Δ: ΔH is 5 or more and less than 10 ×: ΔH is 10 or more.

<Adhesiveness (initial)>
According to JIS K 5600-5-6 (1990), make a 100mm 1mm x 1mm gobang mesh on the laminated film until it reaches the substrate, stick an adhesive tape on the surface, and peel off rapidly, then on the coated surface The number of the remaining Gobanchi laminated films was evaluated.

A: Remaining number / total number = 100/100 and no edge defect ○: Remaining number / total number = 100/100 and no edge defect 5 or less Δ: Remaining number / total number = 99 to 90 Pieces / 100 pieces,
Alternatively, 100/100 and 6 or more missing edges X: remaining number / total number = 89 or less / 100.

<Water resistance>
About each test body, after immersing for 240 hours in 40 degreeC warm water, the external appearance and adhesiveness of the test body washed with water were evaluated on the following reference | standard. The appearance was evaluated visually, and the adhesion (after water resistance test) was evaluated by the same method and evaluation criteria as in the above << Adhesion (initial) >>.

[Appearance (after water resistance test)]
◎: No change in appearance with respect to the laminate film of the test specimen before the test. ○: Slight blurring or whitening is observed with respect to the laminate film of the test specimen before the test. No problem level Δ: Some gloss or whitening is observed with respect to the laminate film of the test specimen before the test. ×: Significant glossiness or whitening is observed with respect to the laminate film of the specimen before the test.

<Weather resistance>
For each test specimen, using a super UV tester (Dainippon Plastic Co., Ltd., W-13 type, accelerated weathering tester), a black panel temperature of 60 ° C., 24 hours of ultraviolet irradiation—24 hours of water spray cycle conditions are 1 The test was conducted up to 20 cycles. Appearance and adhesion were evaluated according to the following criteria. The appearance was evaluated visually, and the adhesion (after the weather resistance test) was evaluated by the same method and evaluation criteria as in the above <Adhesion (initial)>.

<Appearance (after weathering test)>
◎: No cracking occurred in the laminated film of the specimen, and almost no blur or discoloration was observed. ○: No cracking or discoloration was observed in the laminated film of the specimen, and slight gloss or discoloration was observed. However, there is no problem when it is made into a product. Δ: No cracking occurs in the laminated film of the test specimen, but noticeable gloss or discoloration is observed. ×: Cracking occurs in the laminated film of the specimen.

Claims (5)

A laminated body in which a cured coating layer (I) and an inorganic substance layer (II) are sequentially laminated on a resin base material with an active energy ray-curable primer composition,
The active energy ray-curable primer composition is
Organic-modified silica particles (A),
Polymerizable unsaturated compound (B),
The photopolymerization initiator (C) is contained, and the organic-modified silica particles (A) are formed on the surface of the silica fine particles (a-1) with (meth) acryloyloxy groups and isocyanurate ring structures and urea bonds or Reactive particles (a) having a group having a urethane bond , wherein the reactive particles (a) are silica fine particles (a-1), a (meth) acryloyloxy group and an isocyanurate ring structure in the molecule, and Hydrolyzable silane (a-2) having a group having a urea bond or a urethane bond, or a hydrolyzable silane other than the hydrolyzable silane (a-2) and the hydrolyzable silane (a-2) ( Reactive particles (a) obtained by reacting a mixture with a-3), wherein the hydrolyzable silane (a-2) is a hydrolyzable silane represented by the following general formula (II) and / or The following general formula Hydrolyzable silane represented by III)

[In formula (II), R ⁴ is the same or different and represents a hydrogen atom or a methyl group. R ⁵ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ⁶ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. m is the same or different and represents an integer of 0 to 5. At least one of Ra, Rb and Rc represents a halogen atom, a hydroxy group, an alkoxy group or an aryloxy group, and the remainder represents a hydrogen atom, an alkyl group or an aryl group. In formula (III), R ⁷ is the same or different and represents a hydrogen atom or a methyl group. R ⁸ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ⁹ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. Ra, Rb and Rc are the same as described above. ] Der is, laminate inorganic material layer (II) is characterized in that formed by a dry film formation method. The laminate according to claim 1, wherein the active energy ray-curable primer composition further contains an ultraviolet absorber (D) and / or a light stabilizer (E). The laminate according to claim 1 or 2 , wherein the dry film-forming method is a chemical vapor deposition method. The resin base material contains the organic substance-modified silica particles (A), the polymerizable unsaturated compound (B), and the photopolymerization initiator (C), and the organic substance-modified silica particles (A) contain silica fine particles ( a-1) Reactive particles (a) having a group having both a (meth) acryloyloxy group and an isocyanurate ring structure and a urea bond or a urethane bond on the surface, wherein the reactive particles (a) are silica fine particles ( a-1), a hydrolyzable silane (a-2) having a (meth) acryloyloxy group, an isocyanurate ring structure, and a urea bond or a urethane bond in the molecule, or the hydrolyzable silane (a -2) and a reactive particle (a) obtained by reacting a mixture of a hydrolyzable silane (a-3) other than the hydrolyzable silane (a-2), and the hydrolyzable silane (a- 2) Hydrolyzable silane represented by the general formula hydrolyzable silane and / or the following general formula represented by (II) (III)

[In formula (II), R ⁴ is the same or different and represents a hydrogen atom or a methyl group. R ⁵ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ⁶ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. m is the same or different and represents an integer of 0 to 5. At least one of Ra, Rb and Rc represents a halogen atom, a hydroxy group, an alkoxy group or an aryloxy group, and the remainder represents a hydrogen atom, an alkyl group or an aryl group. In formula (III), R ⁷ is the same or different and represents a hydrogen atom or a methyl group. R ⁸ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ⁹ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. Ra, Rb and Rc are the same as described above. The active energy ray curable primer composition is applied and irradiated with active energy rays to form a cured coating film layer (I), and on the cured coating film layer (I) by a dry film forming method. Forming at least one inorganic substance layer (II). The method for producing a laminate according to claim 4 , wherein the dry film forming method is a chemical vapor deposition method.