JP2014061672A - Laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet achieving both spontaneous peeling-off suppression during processing and easy peelability after molding.SOLUTION: There is provided a laminated sheet which has a (B) layer comprising a curable resin as a main component on at least one side of a substrate (A) layer comprising a cyclic olefin resin as a main component, wherein the substrate (A) layer contains a petroleum resin. The substrate (A) layer has an a1 layer and an a2 layer, the a1 layer is mainly composed of a cyclic olefin resin and the a2 layer is mainly composed of a cyclic olefin resin and further contains 0.1 to 15 mass% of a petroleum resin in the total 100 mass% of the a2 layer.

Description

  The present invention relates to a laminated sheet, and has a (B) layer containing a curable resin as a main component on at least one side of a base material (A) layer containing a cyclic olefin resin as a main component. (A) It is related with the laminated sheet from which a base material (A) layer and a (B) layer do not peel naturally during a process but can peel easily after shaping | molding because it is set as the structure containing a petroleum resin.

  In recent years, with the growing awareness of the environment, there has been an increasing demand for solvent-free painting and plating alternatives for building materials, automobile parts, mobile phones, electrical appliances, etc., and the introduction of decoration methods using films has progressed. As a method for decorating a substrate, a method is known in which a decoration layer is laminated on a thermoplastic resin film and transferred to the substrate simultaneously with molding. Moreover, the proposal of the film containing polyolefin resin is also made | formed with respect to such a decorating method (for example, refer patent document 1, 2).

  On the other hand, the proposal which improves adhesiveness with printing ink and a coating film by giving various surface treatments to a film is also made (for example, refer patent documents 3-5). In addition, various studies on other applications using cyclic olefin-based resins and petroleum resins have been performed (see, for example, Patent Documents 6 to 8).

JP 2000-355082 A JP 2004-188708 A JP 2008-101110 A JP 2006-290108 A JP 2011-190378 A JP 2007-21756 A JP 2006-27052 A JP 2004-250469 A

  The film described in Patent Document 1 assumes adhesion with an acrylic resin or adhesive with an olefin resin in a molten state via an adhesive, and is used by peeling the film after molding like a transfer foil. It was not designed to be used.

  Patent Document 2 describes a film in which a release layer is formed and peeled off from a topcoat layer after molding in addition to being bonded to a polyester resin via an adhesive. However, depending on the material of the topcoat layer, there is a problem that the film and the topcoat layer are spontaneously peeled during the molding process, and the surface appearance after molding is lowered.

  The films described in Patent Documents 3 to 5 are subjected to corona treatment or UV treatment on the olefin film to improve the adhesion with the printing ink and the coating film, but the adhesiveness is high because the strength of the surface treatment is high. There is a problem that the film is strong or the film is easily deformed, and the design is not sufficiently considered for the use in which the film is peeled off after use as in the case of a transfer foil.

  The films described in Patent Documents 6 to 8 are packaging films made of a cyclic olefin resin and a petroleum resin, and have improved moisture resistance and processability compared to conventional packaging olefin films. However, since the surface layer is composed mainly of polyethylene resin or polypropylene, when it is applied to applications where the film is peeled off after molding, such as transfer foil, the undulations specific to polyethylene resin and polypropylene resin are transferred. As a result, there is a problem that the surface appearance after molding is deteriorated.

  Accordingly, an object of the present invention is to eliminate the above-described problems. That is, the present invention is to provide a laminated sheet that achieves both natural peeling suppression during the process and easy peeling after molding without reducing the surface appearance after molding when used in applications such as transfer foil.

The present invention for solving the above problems has the following configuration.
(1) It has (B) layer which has curable resin as a main component in the at least one side of base material (A) layer which has cyclic olefin system resin as the main component, and this base material (A) layer contains petroleum resin. A laminated sheet comprising the laminated sheet.
(2) The base material (A) layer has an a1 layer and an a2 layer, the a1 layer is a layer containing a cyclic olefin resin as a main component, and the a2 layer is a cyclic olefin resin as a main component. Furthermore, it is a layer which contains 0.1-15 mass% of petroleum resins in 100 mass% of the whole a2 layer, The laminated sheet as described in (1) characterized by the above-mentioned.
(3) The a1 layer has a cyclic olefin copolymer resin (hereinafter referred to as COC) as a main component, and the a2 layer has a cyclic olefin resin (hereinafter referred to as COP) as a main component. The laminated sheet according to 2).
(4) The laminated sheet according to (2) or (3), wherein the a2 layer, the a1 layer, and the a2 layer are directly laminated in this order.
(5) Any of (2) to (4), wherein the a1 layer contains 1 to 40% by mass of a polyethylene resin and / or a polypropylene resin with respect to 100% by mass of the entire a1 layer. The laminated sheet of crab.
(6) The peel strength between the base material (A) layer and the (B) layer is 0.01 to 0.5 N / 10 mm, according to any one of (1) to (5) The laminated sheet as described.
(7) Any one of (1) to (6), characterized in that, on at least one side of the base material (A) layer, a (B) layer, a decoration (C) layer, and an adhesive (D) layer are provided in this order. The laminated sheet of crab.
(8) The laminated sheet according to any one of (1) to (7), which is used for molding applications.

  In this invention, it has (B) layer which has curable resin as a main component in at least one side of the base material (A) layer which has cyclic olefin resin as a main component, and this base material (A) layer is petroleum resin. Therefore, the base material (A) layer and the (B) layer are not naturally separated during the process, and can be easily separated after molding.

  This invention has the (B) layer which has a curable resin as a main component in the at least one side of the base material (A) layer which has a cyclic olefin resin as a main component, and this base material (A) layer is a petroleum resin. It is the structure containing. Hereinafter, the laminated sheet of the present invention will be specifically described.

(Base material (A) layer)
The laminated sheet of the present invention needs to have a substrate (A) layer from the viewpoints of moldability and self-holding property. As the resin constituting the base material (A) layer, from the viewpoint of adjusting the glass transition temperature according to the moldability, processability, easy peelability after molding, and molding temperature when used as a molding transfer foil, it is cyclic. It is necessary to have an olefin resin as a main component.

  Here, the cyclic olefin-based resin refers to a resin having an alicyclic structure in the main chain of a polymer obtained by polymerization from a cyclic olefin as a monomer.

  Further, the cyclic olefin resin in the present invention is a resin obtained by polymerizing a cyclic olefin monomer and the like, and the total of the components derived from the cyclic olefin monomer is 50% in 100% by mass of the polymer of the cyclic olefin resin. The polymer of the aspect which is 100 mass% or less exceeding the mass% is meant.

Cyclic olefin monomers include monocyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclopentadiene, 1,3-cyclohexadiene,
Bicyclo [2,2,1] hept-2-ene, 5-methyl-bicyclo [2,2,1] hept-2-ene, 5,5-dimethyl-bicyclo [2,2,1] hept-2-ene Ene, 5-ethyl-bicyclo [2,2,1] hept-2-ene, 5-butyl-bicyclo [2,2,1] hept-2-ene, 5-ethylidene-bicyclo [2,2,1] Hept-2-ene, 5-hexyl-bicyclo [2,2,1] hept-2-ene, 5-octyl-bicyclo [2,2,1] hept-2-ene, 5-octadecyl-bicyclo [2, 2,1] hept-2-ene, 5-methylidene-bicyclo [2,2,1] hept-2-ene, 5-vinyl-bicyclo [2,2,1] hept-2-ene, 5-propenyl- Bicyclic olefins such as bicyclo [2,2,1] hept-2-ene;
Tricyclo [4,3,0,1 ^2.5] dec-3,7-diene, tricyclo [4,3,0,1 ^2.5] dec-3-ene, tricyclo [4,3,0,1 ^{2 .5]} undec-3,7-diene, tricyclo [4,3,0,1 ^2.5] undec-3,8-diene, tricyclo [4,3,0,1 ^2.5] undec-3-ene 5-cyclopentyl-bicyclo [2,2,1] hept-2-ene, 5-cyclohexyl-bicyclo [2,2,1] hept-2-ene, 5-cyclohexenylbicyclo [2,2,1] hept 2-ene, 5-phenyl - bicyclo [2,2,1] tricyclic olefins such hept-2-ene, tetracyclo ^{[4,4,0,1 2.5, 1 7.10]} dodeca-3 ene, 8-methyl tetracyclo ^[4,4,0,1 2.5, ^{1 7 10]} dodeca-3-ene, 8-ethyl-tetracyclododecene ^{[4,4,0,1 2.5, 1 7.10]} dodeca-3-ene, 8-methylidene-tetracyclo [4,4,0,1 ^{2.5, 1 7.10]} dodeca-3-ene, 8-ethylidene tetracyclododecene ^{[4,4,0,1 2.5, 1 7.10]} dodeca-3-ene, 8-vinyl-tetracyclo [4 , ^{4,0,1 2.5, 1 7.10]} dodeca-3-ene, 8-propenyl - tetracyclo ^{[4,4,0,1 2.5,} four such ^{1 7.10]} dodeca-3-ene Cyclic olefins,
8-cyclopentyl-- tetracyclo ^{[4,4,0,1 2.5, 1 7.10]} dodeca-3-ene, 8-cyclohexyl - tetracyclo ^{[4,4,0,1 2.5, 1 7.10]} dodeca-3-ene, 8-cyclohexenyl - tetracyclo ^{[4,4,0,1 2.5, 1 7.10]} dodeca-3-ene, 8-phenyl - cyclopentyl - tetracyclo [4,4,0,1 ^{2.5, 1 7.10]} dodeca-3-ene, tetracyclo ^{[7,4,1 3.6,} 0 ^{1.9, 0 2.7]} tetradeca -4,9,11,13- tetraene, tetracyclo [ 8,4,1 ^{4.7, 0} 1.10 ^{0 3.8]} pentadeca -5,10,12,14- tetraene, pentacyclo ^{[6,6,1 3.6, 0} 2.7, ^{0 9. 14} ] -4-hexadecene, pentacyclo [6, 5,1,1 ^{3.6, 0 2.7, 0 9.13]} -4-pentadecene, pentacyclo ^{[7,4,0,0 2.7,} 1 ^{3.6, 1 10.13]} -4- pentadecene, heptacyclo ^{[8,7,0,1 2.9,} 1 ^{4.7, 1 11.17, 0 3.8, 0 12.16]} -5-eicosene, heptacyclo [8,7,0,1 ^{2 .9, 0 3.8,} 1 ^4.7, 0 ^{12.17, 1 13.16]} 14-eicosene, etc. polycyclic olefin tetramer, etc. such cyclopentadiene and the like. These cyclic olefin monomers can be used alone or in combination of two or more.

  Among the above mentioned cyclic olefin monomers, bicyclo [2,2,1] hept-2-ene (hereinafter referred to as norbornene), tricyclo [4,3,0,12. 5] Tricyclic olefins having 10 carbon atoms (hereinafter referred to as tricyclodecene), tetracyclo [4,4,0,12.5,17.10] dodec-3-ene, such as deca-3-ene Of these, a tetracyclic olefin having 12 carbon atoms (hereinafter referred to as tetracyclododecene), cyclopentadiene, or 1,3-cyclohexadiene is preferably used.

  The cyclic olefin-based resin polymerized only the cyclic olefin monomer when the total of the components derived from the cyclic olefin monomer exceeds 50% by mass and 100% by mass or less in 100% by mass of the polymer of the cyclic olefin-based resin. Any resin of resin and resin obtained by copolymerizing the cyclic olefin monomer and the chain olefin monomer may be used.

  Examples of a method for producing a resin obtained by polymerizing only a cyclic olefin monomer include known methods such as addition polymerization or ring-opening polymerization of a cyclic olefin monomer. For example, norbornene, tricyclodecene, tetracyclodecene, and derivatives thereof Ring-opening metathesis polymerization followed by hydrogenation, norbornene and its derivatives by addition polymerization, cyclopentadiene, cyclohexadiene after 1,2-, 1,4-addition polymerization and hydrogenation It is done. Among these, from the viewpoint of productivity, surface property, and moldability, a resin obtained by hydrogenating norbornene, tricyclodecene, tetracyclodecene, and derivatives thereof after ring-opening metathesis polymerization is most preferable.

  In the case of a resin obtained by copolymerizing a cyclic olefin monomer and a chain olefin monomer, preferred chain olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-1-butene. 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl- 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc. Can be mentioned. Among these, ethylene can be particularly preferably used from the viewpoint of productivity and cost. Examples of the method for producing a resin obtained by copolymerizing a cyclic olefin monomer and a chain olefin monomer include known methods such as addition polymerization of a cyclic olefin monomer and a chain olefin monomer. For example, norbornene and its derivatives Examples include a method of addition polymerization of ethylene. Among these, from the viewpoints of productivity, surface properties, and moldability, a copolymer of norbornene and ethylene is most preferable.

  The base material (A) layer in the present invention is required to have a cyclic olefin-based resin as a main component. Here, the main component is 100% by mass of the total of all components of the base material (A) layer. In that case, it means containing 100 mass% or less of cyclic olefin resin exceeding 50 mass%. The aspect containing 70 mass% or more and 100 mass% or less is preferable, as for the cyclic olefin resin contained in a base material (A) layer, the sum total of all the components of a base material (A) layer is 100 mass%, and 80 mass% or more and 100 are included. It is more preferable if it is an embodiment containing not more than mass%, and it is particularly preferable if it is an embodiment containing not less than 90 mass% and not more than 100 mass%. And when a cyclic olefin resin is a main component in a base material (A) layer, even if a base material (A) layer is comprised only from cyclic olefin resin, other olefin resin is contained, Moreover, you may contain resin other than an olefin resin.

  Examples of the olefin resin other than the cyclic olefin resin include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, and ethylene-α / olefin copolymer polymerized using a metallocene catalyst. Various polypropylene resins such as polyethylene resin, polypropylene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, and polyolefin resins such as methylpentene polymer can be used. Further, a polymer composed of an α-olefin monomer such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and a random copolymer composed of the α-olefin monomer. Also, a block copolymer comprising the α-olefin monomer can be used. Among these, from the viewpoint of compatibility with the cyclic olefin resin, various polyethylene resins and various polypropylene resins are preferably used as the olefin resin other than the cyclic olefin resin.

  In the present invention, the base material (A) layer containing a cyclic olefin resin as a main component can reduce the shear stress in the extrusion process by containing a polyethylene resin and a polypropylene resin, and foreign matter due to crosslinking. Generation | occurrence | production can be suppressed, and also toughness can be improved, and it is preferable. On the other hand, when the content of polyethylene resin or polypropylene resin increases, the self-holding property tends to decrease. From the viewpoint of quality, toughness, and self-holding property, the content of the polyethylene resin and / or the polypropylene resin is 1 to 40% by mass with respect to 100% by mass in total of all the components of the base material (A) layer. 1 to 30% by mass is more preferable, and 1 to 20% by mass is most preferable. Among polyethylene resins and polypropylene resins, polyethylene resins are preferably used from the viewpoint of compatibility with cyclic olefin resins, and low density polyethylene and linear low density polyethylene are particularly preferably used. Density polyethylene is most preferably used. When the substrate (A) layer contains both a polyethylene resin and a polypropylene resin, the total amount of the polyethylene resin and the polypropylene resin is within the above range, that is, all the components of the substrate (A) layer. It is preferable to set it as 1-40 mass% with respect to 100 mass% in total, More preferably, it is 1-30 mass%, Most preferably, it is 1-20 mass%.

  In addition, the polyethylene-type resin in this invention means the polymer of the aspect whose sum total of an ethylene origin component exceeds 100 mass% in 100 mass% of polymers of a polyethylene-type resin.

  In addition, the polypropylene resin in the present invention means a polymer in an aspect in which the total of propylene-derived components is more than 50% by mass and 100% by mass or less in 100% by mass of the polymer of the polypropylene resin.

  In the present invention, the base material (A) layer preferably has a total thickness of 100% and a total thickness of layers having a glass transition temperature of 80 ° C. or higher of 50% or more from the viewpoint of self-holding property. Here, “the total thickness of the layers having a glass transition temperature of 80 ° C. or higher” means the thickness of the layer when the glass transition temperature is 80 ° C. or higher, and the glass transition temperature is 80 ° C. or higher. When there are a plurality of layers, this is the total thickness of those layers. The method for controlling the glass transition temperature of each layer is not particularly limited. For example, when a copolymer of norbornene and ethylene is used as the cyclic olefin resin, the glass transition temperature can be increased by increasing the content of norbornene in the layer. The temperature can be increased. Furthermore, the glass transition temperature of the layer can also be adjusted by blending two kinds of cyclic olefin resins having different norbornene contents. In addition, for example, when a cyclic olefin resin (eg, norbornene, tricyclodecene, tetracyclododecene, and derivatives thereof) that has been hydrogenated and then hydrogenated is used as the cyclic olefin-based resin, It is possible to increase the glass transition temperature by increasing the molecular weight of the cyclic olefin or increasing the number of rings to form a rigid structure. Furthermore, the glass transition temperature of the layer can also be adjusted by blending two kinds of norbornene derivatives having different glass transition temperatures and then hydrogenating resins after ring-opening metathesis polymerization.

  When the total thickness is 100%, the base material (A) layer is more preferably a total thickness of layers having a glass transition temperature of 85 ° C or higher of 50% or higher, and a layer having a glass transition temperature of 90 ° C or higher. It is particularly preferable if the total thickness is 50% or more. When there are a plurality of glass transition temperatures, such as when a plurality of resins are mixed in one layer, the glass transition temperature on the high temperature side is set as the glass transition temperature of the layer.

  The base material (A) layer in the present invention contains a petroleum resin from the viewpoint of suppressing natural peeling during the process with the (B) layer containing a curable resin as a main component and improving the quality of the base material (A) layer. It is necessary to. Here, the petroleum resin is obtained by polymerization of a part of by-product oil of naphtha decomposition used in the petrochemical industry (C5 (carbon number 5) fraction, C9 (carbon number 9) fraction, etc.). A C5 petroleum resin obtained by cationic polymerization of a C5 chain olefin mixture, a dicyclopentadiene petroleum resin obtained by thermal polymerization of a dicyclopentadiene fraction, and a C9 petroleum obtained by cationic polymerization of a C9 aromatic olefin mixture. Examples thereof include a resin, a C5C9 copolymerized petroleum resin, a petroleum resin called pure monomer resin produced from pure alphamethylstyrene by extracting alphamethylstyrene contained in a C9 fraction, and a resin obtained by hydrogenating these. Petroleum resin has a structure close to the cyclic olefin-based resin that is the main component of the base material (A) layer, is highly compatible with the cyclic olefin-based resin, and maintains transparency with the (B) layer. The effect of suppressing natural peeling during the process can be imparted. From the viewpoint of adhesion during the step (B), C9 aromatic olefins are more preferable for C9 petroleum resins and C5C9 copolymer petroleum resins because they have higher adhesion to polar components.

  Specific examples of petroleum resins include “Imabe” manufactured by Idemitsu Kosan, “Escollet” manufactured by Tonex, “Arcon” manufactured by Arakawa Chemical, “Petocol” manufactured by Tosoh, and “Petrotac”.

  The petroleum resin contained in the base material (A) layer in the present invention preferably has a softening point of 80 to 150 ° C. from the viewpoint of improving the moldability and processability of the base material (A), and 90 to 125 More preferably, it is ° C. When the softening point of the petroleum resin is less than 80 ° C., the petroleum resin portion may be deformed during heating such as a drying process, resulting in insufficient flatness. Further, when the softening point of the petroleum resin exceeds 150 ° C., the petroleum resin portion may not follow the deformation at the molding temperature, which may cause the sheet to break.

  The base material (A) layer in the present invention preferably contains 0.1% by mass or more and 15% by mass or less of petroleum resin when the total of all components of the base material (A) layer is 100% by mass. More preferably, they are 1 mass% or more and 12 mass% or less, Especially preferably, they are 5 mass% or more and 10 mass% or less. When the petroleum resin contained in the base material (A) layer is less than 0.1% by mass, the adhesion with the layer (B) during the process may be insufficient. Moreover, when the petroleum resin contained in a base material (A) layer exceeds 15 mass%, a base material (A) layer may become weak or peelability from a (B) layer may become inadequate. .

  The laminated sheet of the present invention has a curable resin as a main component on at least one side of the base material (A) layer from the viewpoint of appearance and durability of the molded body after molding when used as a transfer foil (B). It is necessary to have a layer. By having the curable resin, durability such as weather resistance, scratch resistance, impact resistance, and water resistance can be imparted to the molded body. Here, the curable resin refers to a resin that is cured by three-dimensional crosslinking by applying heat or an electron beam. In the (B) layer, the main component of the curable resin is that it contains 50% by mass or more and 100% by mass or less of the curable resin in 100% by mass of all the components of the resin (B) layer. Point to.

  (B) From the viewpoint of appearance and durability, the curable resin of the layer (B) is preferably cured after molding. Before molding, the moldability can be maintained and the semi-cured state is maintained so that the handleability does not deteriorate. Preferably there is.

  As the thermosetting resin preferably used as the curable resin, unsaturated polyester resin, phenoxy resin, epoxy resin, phenol resin, melamine resin, urea resin, polyurethane resin, diallyl phthalate resin, Examples thereof include silicon-based resins and alkyd-based resins, and a mixture of one or more selected from them may be used.

  In addition, photocurable resins (mainly UV curable resins) and electron beam curable resins that are preferably used as curable resins include polyurethane acrylate resins, polyester acrylate resins, unsaturated polyester resins, and silicone acrylates. 1 type or more selected from resin, epoxy acrylate resin and the like. Moreover, when using a photocurable resin and an electron beam curable resin, you may use what mixed the photoinitiator etc. as needed.

  These thermosetting resins, photocurable resins, and electron beam curable resins include curing agents, curing accelerators, binders, surface conditioners, pigments, plasticizers, ultraviolet absorbers, and light as necessary. A stabilizer or the like may be mixed.

  The thermosetting resin, photocurable resin, and electron beam curable resin may be a copolymer or a mixture of different resins.

  In the present invention, the thickness of the layer (B) is preferably from 2 μm to 100 μm, more preferably from 5 μm to 80 μm, most preferably from 10 μm to 70 μm from the viewpoint of appearance and durability. preferable.

  The resin (B) layer in the present invention is on one side of the base material (A) layer (that is, in one side of the base material (A) layer or in the laminate comprising the base material (A) layer and another layer). (On one side of another layer), (B) a method of applying the raw material composition used to form the layer, or extruding the resin of the base (A) layer and (B) layer with separate extruders Then, it can be obtained by a method of laminating with a feed block and solidifying the resin discharged from the T die with a cooling roll. The former coating method is not particularly limited, and for example, it can be applied using a gravure coater, bar coater, comma coater, die coater, knife coater, or the like. The latter coextrusion method requires that the extrusion temperature of the resin constituting the base material (A) layer and the (B) layer be close, but the adhesion of the base material (A) layer can be increased to some extent. From the point that blocking does not occur when only the substrate (A) layer is wound up first. In addition, when blocking occurs when only the base material (A) layer is wound first by the former method, a known polyethylene-based self-adhesive film (for example, manufactured by Toray Film Processing Co., Ltd.) is used for the base material (A) layer. It is also possible to use a method in which the self-adhesive film is peeled off immediately before the (B) layer is laminated, after the “Tretec” or the like is wound.

  In the present invention, the base material (A) layer and the (B) layer can achieve both adhesion in the process and easy peelability after molding by the petroleum resin contained in the base material (A) layer. Depending on the material of the (B) layer, the adhesion may be insufficient. Therefore, the surface modification treatment of the substrate (A) layer is carried out within the range that does not impair easy peelability, Adhesion may be improved. Examples of such methods include, but are not limited to, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, laser treatment, flame treatment, high frequency treatment, glow discharge treatment, ozone oxidation treatment, and the like, from the viewpoint of cost and simplicity. Therefore, a corona discharge treatment and an ultraviolet irradiation treatment are preferably used, and an ultraviolet irradiation treatment is preferably used particularly when high-precision adhesion control is required. The ultraviolet irradiation treatment and the corona discharge treatment may be performed in air, nitrogen, carbon dioxide, and a mixture thereof.

  In the present invention, the base material (A) layer and the (B) layer can achieve both adhesion in the process and easy peelability after molding by the petroleum resin contained in the base material (A) layer. Depending on the material of the (B) layer, the adhesiveness may be insufficient. Therefore, an adhesive resin other than petroleum resin is applied to the base material (A) layer within a range that does not impair easy peelability. ) Adhesion with the layer may be improved.

  Examples of adhesive resins other than petroleum resins include rosin resins such as rosin, rosin ester, hydrogenated rosin, and polymerized rosin, or α-pinene polymers, β-pinene polymers, dipene polymers, terpene / phenol polymers, etc. Terpene resins, cyclic olefin resins containing polar groups, polyolefin resins other than cyclic olefin resins containing polar groups, and the like. Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, and a hydroxyl group.

  Examples of the method of incorporating a polar group into the cyclic olefin resin include a method of grafting and / or copolymerizing an unsaturated compound having a polar group. As unsaturated compounds having a polar group, (meth) acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (1 to 10 carbon atoms) ester, maleic acid Alkyl (C1-C10) ester, (meth) acrylamide, (meth) acrylic acid-2-hydroxyethyl etc. can be mentioned.

  The polar group in the cyclic olefin resin containing the polar group is selected from the viewpoints of cost and handling at the time of extrusion, and each alicyclic portion in the resin (for example, the cyclic olefin resin is a copolymer of norbornene and ethylene). In this case, a state in which the same number to 3 times the number of norbornene portions) is included is preferable, and the same number is more preferable.

  Examples of the cyclic olefin-based resin containing a polar group include “ARTON” manufactured by JSR.

  Examples of polyolefin resins other than cyclic olefin resins containing polar groups include ethylene-vinyl acetate copolymers, ionomer resins, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylic resins. Polyolefin copolymers containing polar groups such as acid copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, low density polyethylene, medium density polyethylene, high density polyethylene, linear Low-density polyethylene, ethylene-α-olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-propylene copolymer, methylpentene polymer, other random copolymers composed of α-olefin monomers, block copolymers Polyolefin resin such as Polyolefin resins modified by acrylic acid, methacrylic acid, maleic anhydride, fumaric acid or other unsaturated carboxylic acids, or modified by oxidative decomposition of the resin can be used.

  Examples of the α-olefin monomer include ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and the like, and are randomly composed of such α-olefin monomers. As the copolymer, for example, a propylene copolymer is a polymer obtained by random copolymerization of propylene and one or more α-olefin monomers excluding propylene from the α-olefin monomer. Polypropylene obtained by copolymerizing one or more α-olefin monomers excluding propylene in a range of 2 to 15% by mass by a method.

  However, cyclic olefin-based resins containing polar groups, polyolefin resins other than cyclic olefin-based resins have high adhesiveness to metals, adhere to piping and caps of production equipment, and cause poor film appearance, Since productivity may decrease due to pipe and base washing, the resin containing a polar group is 5% by mass or less when the total of all components of the base material (A) layer is 100% by mass. Preferably, it is 2% by mass or less, more preferably 1% by mass or less, and the steps of the base material (A) layer and the (B) layer with only petroleum resin, rosin resin, and terpene resin. It is particularly preferable to exhibit the adhesiveness inside.

  In this invention, a base material (A) layer has a1 layer and a2 layer, a1 layer is a layer which has cyclic olefin resin as a main component, and a2 layer has cyclic olefin resin as a main component. Furthermore, a layer containing 0.1 to 15% by mass of a petroleum resin is preferable.

  About a1 layer, having cyclic olefin resin as a main component means that the sum total of all the components of a1 layer is 100 mass%, and contains cyclic olefin resin exceeding 50 mass% and 100 mass% or less. The a1 layer is more preferably an aspect containing 70% by mass or more and 100% by mass or less of a cyclic olefin-based resin, with the total of all components of the layer being 100% by mass, and further if it is an aspect containing 80% by mass or more and 100% by mass or less. An embodiment containing 90% by mass or more and 100% by mass or less is particularly preferable.

  About a2 layer, having cyclic olefin resin as a main component means that the sum total of all the components of a2 layer is 100 mass%, and contains cyclic olefin resin exceeding 50 mass% and 100 mass% or less. The a2 layer is more preferably an aspect containing 70% by mass or more and 100% by mass or less of the cyclic olefin-based resin, with the total of all components of the layer being 100% by mass, and further if it is an aspect containing 80% by mass or more and 100% by mass or less An embodiment containing 90% by mass or more and 100% by mass or less is particularly preferable. When the a2 layer is a single layer, the total amount of all the components of the a2 layer is 100% by mass, and the cyclic olefin-based resin is contained in an amount exceeding 50% by mass and 100% by mass or less. When there are two a2 layers, it is determined whether each layer has a cyclic olefin-based resin as a main component. That is, for one of the two a2 layers, when the total of all components of the a2 layer is 100% by mass, the cyclic olefin-based resin is contained in an amount exceeding 50% by mass and 100% by mass or less. The a2 layer is the main component, and the other a2 layer is similarly determined.

  The petroleum resin contained in the a2 layer has a petroleum resin content of 0.1 to 15 masses with the total of all components of the a2 layer being 100 mass% from the viewpoint of adhesion to the (B) layer, easy peelability, and brittleness resistance. %, More preferably 1 to 12% by mass of petroleum resin, and particularly preferably 5 to 10% by mass.

  In addition, the laminated sheet of this invention WHEREIN: When a base material (A) layer has a1 layer and a2 layer, it does not need to contain petroleum resin in a1 layer. However, since the adhesion to the (B) layer is expressed by the petroleum resin contained in the a2 layer, the a1 layer should not contain a petroleum resin, particularly when brittle resistance is required. Is preferred.

  In the present invention, the a1 layer has a cyclic olefin copolymer resin (hereinafter sometimes referred to as COC) as a main component, and the a2 layer has a cyclic olefin resin (hereinafter sometimes referred to as COP) as a main component. It is preferable. With this configuration, particularly excellent moldability, surface appearance, and toughness can be achieved.

  In the present invention, COC and COP both refer to the above-mentioned cyclic olefin-based resin, and COP means a resin in an embodiment in which only “a repeating unit containing a cyclic olefin in the main chain” is polymerized. The COC in the present invention is an embodiment in which at least two types of repeating units of “a repeating unit containing a cyclic olefin in the main chain” and “a repeating unit made of an olefin not containing a cyclic olefin in the main chain” are polymerized. (A repeating unit containing a cyclic olefin may be referred to as a cyclic olefin monomer).

  Here, in the a1 layer, COC as a main component means that the total of all components of the a1 layer is 100% by mass, and the a1 layer contains COC more than 50% by mass and 100% by mass or less. The aspect which contains 70 mass% or more and 100 mass% or less of COC is more preferable when the sum total of all the components of a1 layer is 100 mass%, It is further more preferable if it is an aspect containing 80 mass% or more and 100 mass% or less, 90 mass% or more and 100 It is particularly preferable if it is an embodiment containing at most mass%.

  In addition, C2 is mainly used in the a2 layer, and the total of all components of the a2 layer of the thermoplastic resin substrate (A) layer is 100% by mass, and the COP exceeds 50% by mass and is contained by 100% by mass or less. Means that. More preferably, the total content of all components of the a2 layer is 100% by mass, and COP is 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less. It is particularly preferable if it is an embodiment containing at most mass%. In the case where the a2 layer is a single layer, the sum of all components of the a2 layer is 100% by mass, and COP is contained in the amount of more than 50% by mass and 100% by mass or less. When there are two layers, it is determined whether each layer has COP as a main component. That is, for one of the two a2 layers, when the total of all components of the a2 layer is 100% by mass, and COP is contained more than 50% by mass and 100% by mass or less, the a2 The layer is the main component, and the same determination is made for the other a2 layer.

  The base material (A) layer preferably has a configuration in which the a2 layer, the a1 layer, and the a2 layer are directly laminated in this order from the viewpoint of handleability. Here, being directly laminated means that the layers are laminated without any other layer such as an adhesive layer interposed between the a1 layer and the a2 layer.

  When the base material (A) layer has an a1 layer and an a2 layer, the stacking ratio (total thickness of the a2 layer / thickness of the a1 layer) is 0.00 from the viewpoint of toughness, self-holding property, and surface appearance. It is preferable that it is 25-1. The stacking ratio (total thickness of a2 layers / a1 layer thickness) is the sum of the thicknesses of a2 layers existing when there are two a2 layers / thickness of a1 layers. The total thickness of the a2 layer / the thickness of the a1 layer is the thickness of the a2 layer / the thickness of the a1 layer when the a2 layer is one layer. The lamination ratio (total thickness of a2 layers / thickness of a1 layers) is more preferably 0.4 to 0.8. The lamination ratio can be measured by observing the cross section of the base material (A) layer with a scanning electron microscope, a transmission electron microscope, an optical microscope or the like at a magnification of 500 to 10,000 times.

  The cyclic olefin-based resin has lower toughness than the polyethylene-based resin and the polypropylene-based resin, but the toughness can be improved by including the polyethylene-based resin and the polypropylene-based resin. On the other hand, when a polyethylene resin or a polypropylene resin is contained, the surface appearance may be lowered. For this reason, in order to achieve both toughness and surface appearance, the base material (A) layer has a cyclic olefin resin as a main component on at least one side of a cyclic olefin layer (a1 layer) having a cyclic olefin resin as a main component. It is preferable to have a cyclic olefin layer (a2 layer), and the a1 layer preferably contains 1 to 40% by mass of polyethylene resin and / or polypropylene resin with respect to 100% by mass of (a1 layer) as a whole. . Here, when the a1 layer includes a polyethylene resin and a polypropylene resin, the a1 layer is 1 to 40% by mass in total of the polyethylene resin and the polypropylene resin with respect to 100% by mass of the entire (a1 layer). It is preferable to include.

  In addition, from the viewpoint of toughness and self-holding property, the polyethylene resin and / or polypropylene resin in (a1 layer) is preferably 1 to 30% by mass with 100% by mass as a whole (a1 layer), 1 to 20% by mass is most preferable.

  Further, from the viewpoint of surface appearance, the content of the polyethylene resin and / or the polypropylene resin in the cyclic olefin layer (a2 layer) mainly composed of the cyclic olefin resin is based on 100 mass% of the total (a2 layer). The content is preferably 0% by mass or more and 10% by mass or less, more preferably 0% by mass or more and 5% by mass or less, and most preferably 0% by mass of polyethylene resin and / or polypropylene resin.

  The laminated sheet of the present invention comprises a base material (A) layer and a base material (B) from the viewpoint of achieving both the adhesion in the process between the base material (A) layer and the (B) layer, and easy peelability after molding. ) The peel strength between the layers is preferably 0.01 to 0.5 N / 10 mm. When the peeling strength at 25 ° C. is less than 0.01 N / 10 mm, the peeling strength is too low, and natural peeling may occur during processes such as sheet conveyance and winding. On the other hand, when the peel strength is greater than 0.5 N / 10 mm, peeling after molding may be difficult. The peel strength at 25 ° C. between the base material (A) layer and the (B) layer is more preferably 0.02 to 0.3 N / 10 mm, and particularly preferably 0.05 to 0.1 N / 10 mm.

  In the laminated sheet of the present invention, the method of setting the peel strength between the base material (A) layer and the (B) layer at 25 ° C. to 0.01 to 0.5 N / 10 mm is not particularly limited. In addition to the method of containing 0.1 to 15% by mass of a petroleum resin in the layer), the surface modification treatment of the base material (A) layer, the inclusion of an adhesive resin other than the petroleum resin, and the like are preferable.

  In the laminated sheet of the present invention, the glass transition temperature of the base material (A) layer is 80 ° C. or higher from the viewpoint of moldability and self-holding property, and the “glass transition temperature −20” ° C. of the base material (A) layer. It is preferable that the elongation at break is 200% or less, and the elongation at break of the base material (A) layer at “glass transition temperature + 20” ° C. is 500% or more. By making the glass transition temperature of the base material (A) layer 80 ° C. or higher and the elongation at break at “glass transition temperature −20” ° C. of the base material (A) layer 200% or lower, sufficient self-holding property is obtained. Can be secured, and handling is improved.

  The glass transition temperature of the substrate (A) layer is preferably 85 ° C. or higher, and particularly preferably 90 ° C. or higher. Moreover, it is preferable that the glass transition temperature of a base material (A) layer is 160 degrees C or less. The elongation at break of the base material (A) layer at “glass transition temperature −20” ° C. is more preferably 190% or less, and most preferably 180% or less from the viewpoint of self-holding property and brittleness resistance. The elongation at break of the base material (A) layer at “glass transition temperature −20” ° C. is preferably 3% or more, more preferably 90% or more, and particularly preferably 100% or more. Moreover, the outstanding moldability can be made compatible by making the breaking elongation in the "glass transition temperature +20" degreeC of a base material (A) layer into 500% or more. The elongation at break of the substrate (A) layer at “glass transition temperature + 20” ° C. is more preferably 600% or more, and most preferably 700% or more from the viewpoint of moldability and dimensional stability. The breaking elongation of the base material (A) layer at “glass transition temperature + 20” ° C. is preferably 2,000% or less, more preferably 1,000% or less, and 970% or less. Particularly preferred.

  The glass transition temperature of the base material (A) layer is 80 ° C. or more, the elongation at break of the base material (A) layer at “glass transition temperature−20” ° C. is 200% or less, and the “glass” of the base material (A) layer As a preferable base material (A) layer for setting the elongation at break at a transition temperature of +20 ”° C. to 500% or more, a cyclic olefin resin, a polyester resin, an acrylic resin, a polycarbonate resin, a polyvinyl chloride resin, An ABS (acrylonitrile / butadiene / styrene copolymer) resin or the like can be preferably used.

  In the present invention, the glass transition temperature of the base material (A) layer as in the case where the base material (A) layer is a laminated film or a plurality of resins are mixed even if it is a single layer film. When a plurality of glass transition temperatures are observed when the value is measured, the glass transition temperature on the high temperature side is adopted as the glass transition temperature of the substrate (A) layer.

  The laminated sheet of the present invention is a “glass” of the base material (A) layer of the sheet containing the resin (B) layer obtained by peeling the base material (A) layer from the laminated sheet in order to suppress natural peeling during heat molding. The stress at 100% elongation (F100 value) at the transition temperature +20 "° C is preferably 3 MPa or less. When the 100% elongation stress (F100 value) of the sheet including the resin (B) layer is greater than 3 MPa at the “glass transition temperature + 20” ° C. of the base material (A) layer, when the laminated sheet is thermoformed, The sheet portion including the resin (B) layer is less likely to follow the molding of the base material (A) layer, and peeling may occur between the base material (A) layer and the resin (B) layer. “Glass transition of the base material (A) layer of the sheet containing the resin (B) layer obtained by peeling the base material (A) layer from the laminated sheet in order to further improve the molding followability to the base material (A) layer. The stress at 100% elongation (F100 value) at a temperature of + 20 ° C. is preferably 2.5 MPa or less, and most preferably 0.01 MPa or more and 2 MPa or less.

  100% elongation stress (F100 value) of 3 MPa or less at the “glass transition temperature + 20” ° C. of the base material (A) layer of the sheet containing the resin (B) layer from which the base material (A) layer is peeled from the laminated sheet For example, when the sheet including the resin (B) layer from which the substrate (A) layer is peeled is a sheet comprising a resin (B) layer, a decoration (C) layer, and an adhesive (D) layer For this, it is preferable to select a flexible resin as the resin used for the resin (B) layer, the decoration (C) layer, and the adhesive (D) layer. In addition, when a curable resin is used in each layer of the resin (B) layer, the decorative (C) layer, and the adhesive (D) layer, the laminated sheet of the present invention is prepared and stored at as low a temperature as possible. In the case where the curable resin is an electron beam curable resin, it is preferably stored in an environment where no electron beam is applied.

  The laminated sheet of the present invention has a configuration in which the (B) layer is laminated on at least one side of the substrate (A) layer. The structure is not particularly limited as long as the resin (B) layer is laminated on at least one side of the substrate (A) layer, but from the viewpoint of cost, the substrate (A) layer and the (B) layer are directly laminated. Are preferred. For example, a configuration having a base (A) layer, a (B) layer, a decoration (C) layer, and an adhesion (D) layer in this order (the configuration is the base (A) layer / (B) layer / decoration (C ) Layer / adhesion (D) layer, and so on.), Base material (A) layer / (B) layer / decoration (C) layer, base material (A) layer / (B) layer / adhesion ( D) layer, base material (A) layer / resin (B) layer, and the like. The laminated sheet of the present invention particularly preferably has a (B) layer, a decoration (C) layer, and an adhesive (D) layer in this order on at least one side of the base material (A) layer.

  The laminated sheet of the present invention preferably has a decoration (C) layer from the viewpoint of design. In particular, it is preferable to have a (B) layer, a decoration (C) layer, and an adhesion (D) layer in this order on at least one side of the base material (A) layer.

  In this invention, a decoration (C) layer is a layer different from a base material (A) layer and a (B) layer, and decorations, such as coloring, an unevenness | corrugation, a pattern, woodgraining, a metallic tone, and a pearl tone, are given. It is a layer intended to be added, and is constituted by, for example, a binder resin and a colorant, or in the case of a metallic tone, is constituted by a metal thin film layer.

When the decoration (C) layer includes a binder resin and a colorant, a thermoplastic resin and / or a curable resin can be used as the binder resin. As a thermoplastic resin suitable as the binder resin, a resin obtained by mixing a solvent with a resin such as polyethylene resin, polypropylene resin, polycarbonate resin, acrylic resin, or polystyrene resin can be used. Moreover, as a curable resin suitable as a binder resin, it is preferable that it is cured after molding from the viewpoint of appearance and durability, and before molding, the moldability can be maintained, and the handling property is not lowered. A cured state is preferred. In addition, it is preferable that binder resin has a curable resin as a main component. Here, the binder resin having a curable resin as a main component means that the content of the curable resin is more than 50% by mass and 100% by mass or less in 100% by mass of all components of the binder resin. As the curable resin, the resins listed in the resin (B) layer are preferably used. The binder resin may be a copolymer or a mixture of different resins. In the present invention, since it is easy to handle and inexpensive, a thermosetting resin is preferably used. In particular, from the viewpoint of moldability, a mixture containing a urethane resin and an acrylic resin can be used as a binder resin. preferable.

  The decorative (C) layer is preferably cured after molding from the viewpoint of durability after molding and surface glossiness. Before molding, the moldability can be maintained, and the semi-cured state is such that the handleability does not deteriorate. It is preferable that

  In addition, as a colorant, from the viewpoint of dispersibility, appearance, and concealment, in particular, black pigments such as carbon black and black iron oxide, white pigments such as titanium oxide, barium sulfate, zinc white, and zinc sulfate, metal powder pigments, metal It is preferable to contain a metallic pigment such as a foil pigment or a metal-deposited foil pigment in an amount of 5% by mass to 30% by mass with respect to 100% by mass of all the components of the decoration (C) layer.

  In addition, when the decoration (C) layer is a metal thin film layer, a method for producing the metal film is not particularly limited, but a vacuum deposition method, an EB deposition method, a sputtering method, an ion plating method, or the like can be used. As the metal to be used, it is preferable to deposit a metal compound having a melting point of 150 to 400 ° C. from the viewpoint of molding followability and appearance. Although it does not specifically limit as a metal compound whose melting | fusing point is 150-400 degreeC, Indium (157 degreeC) and tin (232 degreeC) can use preferably.

  In the present invention, the thickness of the decoration (C) layer should be 0.5 μm or more and 50 μm or less from the viewpoint of base concealability and thickness unevenness when the decoration (C) layer includes a binder resin and a colorant. Is preferably 1 μm or more and 40 μm or less. In the case where the decoration (C) layer is a metal thin film layer, the thickness of the decoration (C) layer is preferably 0.05 μm or more and 1.5 μm or less from the viewpoint of moldability and appearance after molding, preferably 0.1 μm. More preferably, it is 1 μm or less.

  The laminated sheet of the present invention preferably has an adhesive (D) layer from the viewpoint of adhesion to the adherend. The adhesion (D) layer means a layer having adhesion to an adherend. The adhesive (D) layer is preferably adjusted as appropriate according to the material of the adherend. For example, a phenol resin adhesive, a resorcinol resin adhesive, a phenol-resorcinol resin adhesive, an epoxy resin adhesive A radical-reactive adhesive comprising a thermosetting resin adhesive such as an adhesive, a urea resin adhesive, a polyurethane adhesive and a polyaromatic adhesive, or a radical polymerizable composition such as an unsaturated polyester or acrylate, Thermoplastic resin adhesive such as vinyl acetate resin, acrylic resin, acrylic urethane resin, ethylene vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, vinyl chloride, nylon and cyanoacrylate resin, polyolefin resin, chloroprene adhesive, nitrile rubber Adhesive, SBR adhesive and natural rubber Rubber adhesives such as wear agents.

  The thickness of the adhesive (D) layer in the present invention is preferably 0.1 μm or more and 50 μm or less, more preferably 1 μm or more and 40 μm or less from the viewpoint of adhesiveness and thickness unevenness, and 2 μm or more and 30 μm or less. Is most preferable.

  The method for forming the colored (D) layer of the present invention is not particularly limited. For example, it can be formed by coating using a gravure coater, bar coater, comma coater, die coater, knife coater, or the like.

  The laminated sheet of the present invention has a (B) layer containing a curable resin as a main component on at least one side of a base material (A) layer containing a cyclic olefin resin as a main component. Since it is a structure containing petroleum resin, it is used suitably for the use which transfers the sheet | seat containing (B) layer to a to-be-adhered body simultaneously with shaping | molding, and obtains a decoration molded object. (B) Although it does not specifically limit as a method of transferring the sheet | seat containing a layer to a to-be-adhered body, For example, the method of transferring to a to-be-adhered body simultaneously with vacuum forming is mentioned. In this method, as the adherend, for example, polypropylene resin, acrylic resin, polystyrene resin, AS (acrylonitrile / styrene copolymer) resin, ABS (acrylonitrile / butadiene / styrene copolymer) resin, polycarbonate Resins such as polyester resins, polyester resins, and the like, alloy resins thereof, and resins reinforced with carbon fibers, glass fibers, and the like. Furthermore, a metal member, a glass member, etc. are mentioned.

  Moreover, the method of transferring simultaneously with injection molding can also be used. In this case, the above-mentioned resin is preferably used as the adherend.

  In addition, since the lamination sheet of this invention is excellent in the moldability at the time of a heating, it can be used suitably for various shaping | molding uses, such as vacuum forming, pressure forming, and press molding. And it is particularly suitably used for vacuum forming applications.

  The laminated sheet of the present invention has a (B) layer containing a curable resin as a main component on at least one side of a base material (A) layer containing a cyclic olefin resin as a main component. Since the base material (A) layer and the (B) layer do not spontaneously peel off during the process and can be easily peeled off after the molding, for example, building materials and mobile devices. It can be suitably used for decorating molded members such as electrical products, automobile parts, and gaming machine parts.

The laminate sheet was produced and evaluated by the following method.

(1) Laminated sheet total thickness and thickness of each layer When measuring the total thickness of the laminated sheet, the dial gauge is used to measure the thickness of five arbitrary locations of a sample cut out of the sheet of length 50 mm × width 10 mm. The average value was obtained by measurement.
Moreover, when measuring the layer thickness of each layer of the laminated sheet, the transmitted light was photographed using a Leica DMLM manufactured by Leica Microsystems under the condition that the cross section of the sheet was 100 times magnification. And from the photograph | photographed photograph, arbitrary five places thickness was measured for every layer of the lamination sheet, and the average value was made into the layer thickness of each layer.

(2) Glass transition temperature of substrate (A) layer Measurement and analysis were performed according to JIS K7121-1987 and JIS K7122-1987 using a differential scanning calorimeter (Seiko Denshi Kogyo RDC220).
A substrate (A) layer of 5 mg was used as a sample. The specific heat change based on the transition from the glass state to the rubber state when the sample was heated from 25 ° C. to 300 ° C. at 20 ° C./min was read. An intermediate point where the straight line parallel to the straight line (intermediate point) at the same distance (intermediate point) in the direction of the vertical axis (the axis indicating the heat flow) from the straight line obtained by extending each base line intersects with the curve of the step change portion of the glass transition The point glass transition temperature was determined and used as the glass transition temperature. In addition, when multiple glass transition temperatures existed, the glass transition temperature of the high temperature side was employ | adopted as a glass transition temperature of a base material (A) layer. Moreover, about the film which confirmed the laminated structure about the base material (A) layer by the method of (1), the surface layer and the inner layer were shaved and the glass transition temperature of each layer was also measured.

(3) Peel strength Using a metal halide lamp (M04-L41, manufactured by iGraphics), an ultraviolet irradiation treatment is performed from the base (A) layer side so that the integrated light quantity is 1000 mJ / cm ^2, and (B) layer Was cured.

Next, an NPP-manufactured OPP adhesive tape (Dumplon Ace No. 375) was bonded to the sheet side including the layer (B) in the laminated sheet, and cut into a rectangular shape having a width of 10 mm and a length of 150 mm. The sample was forcibly separated between the base material (A) layer and the (B) layer, and using a tensile tester (Orientec Tensilon UCT-100), the initial tensile chuck distance was 100 mm, and the tensile speed was 20 mm / As a minute, a 180 ° peel test was performed. The measurement was performed until the peel length reached 130 mm (distance between chucks 230 mm), and the average value of the loads having a peel length of 25 mm to 125 mm was defined as the peel strength. In addition, the measurement was performed 5 times and the average value was adopted.
The peel strength at 25 ° C. was measured in a room adjusted to 25 ° C., and the breaking strength at 100 ° C. was set in a constant temperature layer previously set at 100 ° C., and pre-heated for 60 seconds and then subjected to a 180 ° peel test. Went.

(4) Breaking elongation at “glass transition temperature−20 ° C.” and “glass transition temperature + 20 ° C.” of base material (A) layer After peeling only the base material (A) layer from the laminated sheet, any one Samples were cut into rectangles having a length of 100 mm and a width of 10 mm in the direction and the direction perpendicular thereto. Using a tensile tester (Orientec Tensilon UCT-100), an initial tensile chuck distance was 20 mm, a tensile speed was 200 mm / min, and a tensile test was performed in an arbitrary direction and a direction orthogonal thereto.
The measurement was performed at a constant temperature set in advance at predetermined temperatures (in the case of the present invention, “glass transition temperature−20” ° C. of the substrate (A) layer and “glass transition temperature + 20” ° C. of the substrate (A) layer). A sample was set in the layer and a tensile test was performed after 60 seconds of preheating. The elongation when the sample broke was defined as the breaking elongation. In addition, the measurement was performed 5 times in each sample and in each direction, and the average value (average value obtained from the average value in each direction) was evaluated.

(5) Stress at 100% elongation of substrate (A) layer (F100 value)
After peeling off only the base material (A) layer from the laminated sheet, the sample was cut into a rectangular shape having a length of 100 mm and a width of 10 mm in an arbitrary direction and a direction orthogonal to the direction. Using a tensile tester (Orientec Tensilon UCT-100), an initial tensile chuck distance was 20 mm, a tensile speed was 200 mm / min, and a tensile test was performed in an arbitrary direction and a direction orthogonal thereto. The measurement is performed by setting a sample in a constant temperature layer set in advance at a predetermined temperature (in the case of the present invention, “glass transition temperature + 20” ° C. of the base material (A) layer), and performing a tensile test after preheating for 60 seconds. went. Read the load applied to the sheet when the sample is stretched 100% (when the distance between chucks is 40 mm), and divide by the cross-sectional area (sheet thickness (mm) x 10 mm) of the sample before the test. Time stress (F100 value) was used. In addition, the measurement was performed 5 times for each sample and each direction, and the average value was evaluated.

(6) Winding property A laminated sheet having a width of 500 mm and a length of 200 m (6 inch diameter, 550 mm length core winding) is prepared, and rolled back to a 3 inch diameter, 550 mm length core under the following conditions, and evaluated according to the following criteria. Went.
Unwinding: upper unwinding, tension 200 N / m, winding: upper unwinding, tension 100 N / m
Speed: 5m / min
A: Peeling did not occur at all between the base material (A) layer / (B) layer.
B: Peeling was observed between the base material (A) layer / (B) layer, but no air was caught in the peeled portion.
C: Peeling was observed between the base material (A) layer / (B) layer, and some air entrainment occurred at the delamination site (air entrapment rate (air when the total area of the laminated sheet was 100%) Is less than 5%).
D: Peeling was observed between the base material (A) layer / (B) layer, and air entrainment occurred at the delamination site (air entrapment ratio (air when the total area of the laminated sheet was 100%) The ratio of the biting area) was 5% or more) or completely peeled off.

(7) Natural peeling at the time of heating A laminated sheet was cut out to A4 size, and was set in the sheet clamp frame in the upper part in a vacuum forming apparatus (the NGF-0406-T made from cloth application vacuum). Subsequently, the degree of vacuum in the upper and lower boxes was reduced to 99.0 kPa, and the behavior when heated using an infrared heater was evaluated according to the following criteria.
A: Even at a sheet temperature of 140 ° C., no peeling occurred between the base material (A) layer / (B) layer.
B: Peeling occurred between the base material (A) layer / (B) layer at a sheet temperature of 120 ° C. or higher and lower than 140 ° C.
C: Peeling occurred between the base material (A) layer / (B) layer at a sheet temperature of 100 ° C. or higher and lower than 120 ° C.
D: Peeling occurred between the base material (A) layer / resin (B) layer at a sheet temperature of less than 100 ° C.

(8) Formability The laminated sheet was cut into a size of 200 mm x 300 mm at an arbitrary position to prepare a sample. On the (B) layer side of the laminated sheet, a coating composition for a decorative layer described later was applied using an applicator and dried at 80 ° C. for 10 minutes to form a decorative (C) layer having a coating thickness of 25 μm. . Further, an adhesive layer coating composition described later is applied on the decorative layer using an applicator, dried at 80 ° C. for 10 minutes to form an adhesive (D) layer having a coating thickness of 20 μm, and decorated. A sheet was produced. A polypropylene shaped body (length: 100 mm x width: 100 mm, height: 20 mm, 25 mm, 30 mm) is placed on the top / bottom lifting table in a vacuum forming apparatus (Nagyo 0406-T manufactured by Fuse Vacuum). A decorative sheet (length 300 mm × width 200 mm) was set on a sheet clamp frame at the top of the shaped body in the apparatus. Subsequently, the degree of vacuum in the upper and lower boxes is reduced to 99.0 kPa, and the decorative sheet surface temperature is heated using an infrared heater until the glass transition temperature of the thermoplastic resin substrate (A) layer becomes “glass transition temperature + 20” ° C. Then, the shape body was raised, and the shape body and the laminated sheet were brought into close contact with each other and held for 3 seconds. Then, the laminated sheet was shaped by releasing only the upper box to atmospheric pressure, and a decorative molded body was obtained.
The decorated molded body obtained as described above was evaluated as follows.
A: Molding was possible at a height of 30 mm.
B: Although it was able to be molded at a height of 25 mm, the shape could not be reproduced at 30 mm.
C: Although it was able to be molded at a height of 20 mm, the shape could not be reproduced at 25 mm.
D: The shape could not be reproduced at a height of 20 mm.

(9) Peeling after molding Decorative molding of the structure of base material (A) layer / (B) layer / decoration (C) layer / adhesion (D) layer / polypropylene shaped body obtained as in (8) The body was peeled between the base material (A) layer / (B) layer and evaluated according to the following criteria. In addition, this evaluation performed the ultraviolet irradiation process from the base-material (A) layer side so that it may become integrated light quantity 1000mJ / cm < ² > using a metal halide lamp (the product made from iGraphics, M04-L41), (B) This was done after the layer was cured.
A: It was able to peel without a problem.
B: Although there was some resistance, it was able to peel off without leaving the adhesion trace in the molding.
C: It peeled off when taking out from the molding machine.
D: Resistance was strong, or the (B) layer was not cured, and adhesion marks were attached to the molded body during peeling. Or it did not come off.

(10) Surface appearance after molding The film was stretched under the following conditions using a film stretcher (manufactured by Bruckner, KARO-IV). The surface appearance of the stretched film was evaluated according to the following criteria.
Initial sample: 100 mm × 100 mm, preheating / stretching temperature: temperature 20 ° C. higher than the glass transition temperature of the substrate (A) measured based on (2), preheating time: 20 seconds, stretching temperature: 20% / second, stretching Magnification 2x2
A: The surface gloss was very high and no unevenness was observed. B: The surface gloss was high and almost no unevenness was observed. C: Some undulating unevenness was observed on the surface.
D: Remarkable wavy unevenness was observed on the surface.

(11) Tear resistance at the time of peeling The obtained molded transfer foil is molded in the same manner as (8), and the base material (A) layer / (B) layer / decoration (C) layer / adhesion (D ) A decorative molded body having the structure of layer / polypropylene shaped body was obtained. Using a metal halide lamp (M04-L41, manufactured by iGraphics), the decorative molded body is subjected to ultraviolet irradiation treatment from the base material (A) layer side so that the integrated light quantity becomes 1000 mJ / cm ^2, and (B) layer After curing, the base material (A) layer was peeled off from the molded member by hand. In addition, a peeling location is between a base material (A) layer and a (B) layer. The same operation was performed 10 times, and evaluation was performed by the number of times that the base material (A) layer was torn and the film was not peeled off from the (B) layer.
A: None B: 1 to 2 times C: 3 to 4 times D: 5 times or more.

(12) Resin (cyclic olefin copolymer resin A (COC-A)) used for the production of the thermoplastic resin substrate (A) layer in the present invention
“TOPAS 8007F-04” (a resin obtained by copolymerizing ethylene and norbornene having a glass transition temperature of 78 ° C.) made of Polyplastics was used.
(Cyclic olefin copolymer resin B (COC-B))
“TOPAS 6013F-04” (a resin obtained by copolymerizing ethylene and norbornene having a glass transition temperature of 138 ° C.) was used.
(Cyclic olefin resin C (COP-C))
“ZEONOR 1060R” (cyclic olefin resin having a glass transition temperature of 105 ° C.) manufactured by Nippon Zeon was used.
(Cyclic olefin resin D (COP-D))
“ZEONOR 1430R” (cyclic olefin resin having a glass transition temperature of 135 ° C.) manufactured by Nippon Zeon was used.
(Polyethylene resin E (PE-E))
“Evolue SP2540” (a linear low-density polyethylene resin having an MFR of 3.8 g / 10 min according to JIS K7210-1999 and a melting point of 123 ° C. according to JIS K7121-1987) was used.
(Petroleum resin F)
Idemitsu Kosan "Imabu P100" (fully hydrogenated petroleum resin mainly composed of C5 fraction having a softening point of 100 ° C according to JIS K2207-1996) was used.
(Petroleum resin G)
“Scollets 213” manufactured by Tonex (unhydrogenated petroleum resin of C5 fraction / C9 fraction copolymerization having a softening point of 104 ° C. according to JIS K2207-1996) was used.
(Petroleum resin H)
“Arcon P100” manufactured by Arakawa Chemical Co., Ltd. (fully hydrogenated petroleum resin mainly composed of C9 fraction having a softening point of 100 ° C. according to JIS K2207-1996) was used.
(Terpene resin I)
“YS Resin PX1000” (terpene polymer resin having a softening point of 100 ° C. according to JIS K2207-1996) was used.
(Antioxidant)
“Irganox 1010” manufactured by Ciba Specialty Chemicals was used.

(13) Resin (curable resin J) used in the production of layer (B) in the present invention
What mixed the following ultraviolet curable resin and the solvent with the following compounding ratios was used.
-UV curable resin: DIC "V-4025" (UV curable urethane acrylate resin, solid content: 80%) 50 parts by mass-Solvent: butyl acetate 50 parts by mass (curable resin K)
What mixed the following ultraviolet curable resin and the solvent with the following compounding ratios was used.
・ UV curable resin: “beam set 1200” manufactured by Arakawa Chemical Co., Ltd. (UV, electron beam curable epoxy acrylate resin, solid content 100%) 40 parts by mass. Solvent: methyl ethyl ketone 60 parts by mass (non-curable resin L)
“LG-517” manufactured by Toray Fine Chemical (room temperature drying resin, solid content: 50 mass%) was used.

(14) The resin composition used in the production of the decorative (C) layer in the present invention was prepared by mixing the main agent and the curing agent in the following blending ratio to obtain a decorative layer coating composition.
・ Main agent: “R2325” manufactured by Nippon Bee Chemical (solid component: 36%) 100 parts by mass ・ Curing agent: “D-178N” manufactured by Mitsui Chemicals (solid component: 100%) 2 parts by mass (15) Adhesion in the present invention (D) Resin used for production of layer A coating composition for an adhesive layer was prepared by mixing the following polyolefin hot-melt adhesive and a solvent in the following blending ratio.
Polyolefin hot melt adhesive: “M-28” (maleic anhydride-modified chlorinated polypropylene) manufactured by Toyobo 20 parts by mass. Solvent: 80 parts by mass of toluene.

Example 1
The substrate (A) layer has a single layer configuration. Resin is mixed in the composition as shown in the table, fed to a single screw extruder (L / D = 28), melted at a feed part temperature of 235 ° C. and a temperature thereafter of 250 ° C., and a leaf disk filter with a filtration accuracy of 20 μm. Was passed. Next, the sheet was discharged from a T die (lip gap: 0.4 mm) onto a metal roll whose temperature was controlled at 75 ° C. At that time, a nip was made with a rubber roll (nip pressure: 0.2 MPa) to obtain a substrate (A) layer having a thickness of 100 μm.

  On one side of the obtained base material (A) layer, the curable resin J is applied with a slot die coater, and dried at 80 ° C. for 10 minutes to form the (B) layer. A sheet was obtained. About the obtained sheet | seat, it evaluated by the method as described in (1)-(11).

  The laminated sheet of Example 1 was good in all such as natural peeling upon heating, moldability, and evaluation of peeling after molding.

  Of the evaluations described in (1) to (11), (3), (8), (9), and (11) are (B) by a metal halide lamp (M04-L41, manufactured by Eye Graphics). Evaluation is performed after the layer is subjected to ultraviolet curing treatment, and for other evaluations, the state before the (B) layer is cured, or the substrate (A) layer before the (B) layer is cured (B) Evaluation is performed after the layer is peeled off, and the same applies to other examples and comparative examples.

(Examples 2 and 3)
A laminated sheet was obtained in the same manner as in Example 1 except that the composition of the substrate (A) layer was as shown in the table. The obtained laminated sheet was evaluated by the method described in (1) to (11).

  Since the laminated sheet of Example 2 had a higher concentration of petroleum resin than that of Example 1, natural peeling during heating was improved, and tear resistance during peeling was lowered. Moreover, since the laminated sheet of Example 3 had a higher petroleum resin concentration than Example 2, the winding property was improved, and the peel evaluation after molding was lowered.

Example 4
The substrate (A) layer has a three-layer structure. The composition of each layer is as shown in the table, and each is supplied to a single screw extruder (L / D = 28), the supply part temperature is 235 ° C., the subsequent temperature is melted at 250 ° C., and a leaf disk filter with a filtration accuracy of 20 μm is obtained. After passing, after laminating so as to be a2 layer / a1 layer / a2 layer (see the table for the lamination thickness ratio) in the feed block installed on the top of the die, the temperature was controlled to 75 ° C. from the T die. The sheet was discharged on a metal roll. At that time, a nip was made with a rubber roll (nip pressure: 0.2 MPa) to obtain a substrate (A) layer having a thickness of 100 μm.
On one side of the obtained base material (A) layer, the curable resin J is applied with a slot die coater, and dried at 80 ° C. for 10 minutes to form the (B) layer. A sheet was obtained. About the obtained sheet | seat, it evaluated by the method as described in (1)-(11).

  In the laminated sheet of Example 4, the substrate (A) layer was laminated and the main component of the a2 layer was COP compared to Example 2, so that the surface appearance after molding and tear resistance at the time of peeling Improved.

(Examples 5 to 15)
A laminated sheet was obtained in the same manner as in Example 4 except that the composition of the substrate (A) layer was as shown in the table. The obtained laminated sheet was evaluated by the method described in (1) to (11).

  The laminated sheet of Example 5 has a configuration in which petroleum resin F is petroleum resin G, as compared with Example 4, and the evaluation is equivalent.

  The laminated sheet of Example 6 has a configuration in which the petroleum resin F is changed to the petroleum resin H as compared with Example 4, and the winding property is improved.

  Compared with Example 4, the laminated sheet of Example 7 has a configuration in which the a1 layer also contains petroleum resin F, and the tear resistance at the time of peeling was lowered.

  Compared with Example 7, the laminated sheet of Example 8 has a configuration that does not contain petroleum resin F in the a2 layer, and the roll-up property, the natural peeling evaluation during heating, and the peeling evaluation after molding decreased. .

  The laminated sheet of Example 9 has a higher ratio of the a2 layer petroleum resin F than that of Example 4, so that the winding property is improved. On the other hand, the evaluation after peeling, the surface appearance after molding, and the peeling The tear resistance of the was reduced.

  In the laminated sheet of Example 10, as compared with Example 4, the main component of the a2 layer was COC, and the tear resistance at the time of peeling was lowered.

  In the laminated sheet of Example 11, compared with Example 4, the main component of the a1 layer is COP, and the glass transition temperature is high in both the a1 layer and the a2 layer, and the surface appearance after molding is reduced. The tear resistance during peeling improved.

  The laminated sheet of Example 12 has a two-layer configuration of a1 layer / a2 layer as compared with Example 4, and curling was somewhat observed in the base material (A) layer, so that the winding property was lowered. .

  The laminated sheet of Example 13 has a structure that does not contain PE-E in the a1 layer as compared with Example 4, and the tear resistance at the time of peeling was lowered.

  Since the laminated sheet of Example 14 increased the proportion of PE-E in the a1 layer as compared with Example 4, the surface appearance after molding was lowered and the tear resistance at the time of peeling was improved.

  Compared with Example 4, the laminated sheet of Example 15 has a structure in which the terpene resin I is contained in the a2 layer in addition to the petroleum resin F, and the winding property is improved.

(Example 16)
A base material (A) layer was obtained in the same manner as in Example 4 except that the composition of the base material (A) layer was as shown in the table. To one surface of the resulting substrate layer (A), after irradiation time 40 seconds so that the integrated light quantity 100 mJ / cm ² at an excimer lamp (Iwasaki Electric Ltd. "EVUV-200"), cured irradiated surface The conductive resin J was coated with a slot die coater and dried for 10 minutes at 80 ° C. to form the layer (B) to obtain a laminated sheet of the present invention. About the obtained sheet | seat, it evaluated by the method as described in (1)-(11).

  The laminated sheet of Example 16 was subjected to UV treatment with an excimer lamp as compared with Example 4, and the winding property and natural peeling during heating were improved. On the other hand, since the adhesion between the base material (A) layer and the (B) layer was increased, peeling evaluation after molding was lowered. In addition, since the base material (A) layer was slightly deformed by heat during the UV treatment with the excimer lamp, the surface appearance after molding was deteriorated.

(Example 17)
A laminated sheet of the present invention was obtained in the same manner as in Example 16 except that the cumulative amount of light with the excimer lamp applied to the base material (A) was 110 mJ / cm ² and the irradiation time was 44 seconds. About the obtained sheet | seat, it evaluated by the method as described in (1)-(11).

  In the laminated sheet of Example 17, the integrated light quantity of the excimer lamp was increased as compared with Example 16, and the surface appearance after molding was deteriorated.

(Example 18)
(B) Except having changed the layer into curable resin K, it carried out similarly to Example 4, and obtained the laminated sheet of this invention. About the obtained sheet | seat, it evaluated by the method as described in (1)-(11).

  The laminated sheet of Example 18 obtained the same evaluation as in Example 4.

(Comparative Examples 1 and 2)
A substrate (A) was obtained in the same manner as in Example 1 except that the composition of the substrate (A) layer was as shown in the table. The obtained laminated sheet was evaluated by the method described in (1) to (11).

  Comparative Example 1 has a configuration that does not contain petroleum resin F as compared with Example 1, and the rollability and the natural peeling evaluation during heating were greatly reduced, and the performance as a transfer foil was insufficient.

  In Comparative Example 2, the cyclic olefin-based resin is not the main component compared to Example 2, so the tear resistance at the time of peeling was improved, but the surface appearance after molding was greatly reduced, and the performance as a transfer foil Was insufficient.

(Comparative Example 3)
A base material (A) was obtained in the same manner as in Example 4 except that the composition of the base material (A) layer and the composition of the (B) layer were as shown in the table. The obtained laminated sheet was evaluated by the method described in (1) to (11).

  In Comparative Example 3, compared with Example 2, the (B) layer is composed of a resin that is not curable, and the components of the (B) layer remain adhered during the post-molding peeling, and the post-molding peeling evaluation Decreased significantly.

Claims (8)

It has (B) layer which has curable resin as a main component in at least one side of base material (A) layer which has cyclic olefin system resin as the main component, and this base material (A) layer contains petroleum resin. A laminated sheet that is characterized. The substrate (A) layer has an a1 layer and an a2 layer, the a1 layer is a layer mainly composed of a cyclic olefin resin, the a2 layer is composed mainly of a cyclic olefin resin, The laminated sheet according to claim 1, wherein the layer is a layer containing 0.1 to 15% by mass of a petroleum resin in 100% by mass of the entire a2 layer. The a1 layer has a cyclic olefin copolymer resin (hereinafter referred to as COC) as a main component, and the a2 layer has a cyclic olefin resin (hereinafter referred to as COP) as a main component. The laminated sheet as described. The laminated sheet according to claim 2 or 3, wherein the a2 layer, the a1 layer, and the a2 layer are directly laminated in this order. The laminate according to any one of claims 2 to 4, wherein the a1 layer contains 1 to 40% by mass of a polyethylene resin and / or a polypropylene resin with respect to 100% by mass of the entire a1 layer. Sheet. The laminate sheet according to any one of claims 1 to 5, wherein the peel strength between the base material (A) layer and the (B) layer is 0.01 to 0.5 N / 10 mm. It has a (B) layer, a decoration (C) layer, and an adhesion | attachment (D) layer in this order on the at least one side of a base material (A) layer, The lamination | stacking in any one of Claims 1-6 characterized by the above-mentioned. Sheet. The laminated sheet according to any one of claims 1 to 7, which is used for molding.