JP2015013472A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that secures impact resistance, significantly improves surface slipperiness and durability, has excellent hardness, wear resistance, transparency and low curling property, and is also suitable as a display body cover.SOLUTION: The laminate at least comprises a substrate layer as a mold layer comprising polymethyl methacrylate, a first layer formed by curing a specific active energy ray-curable resin composition (I), and a second layer comprising a specific resin composition (II).

Description

  The present invention relates to a laminate having excellent sliding properties, scratch resistance, solvent resistance, pencil hardness, scratch resistance, and impact resistance, and is also suitable as a display body protective cover for industrial electronic devices such as mobile phones. It relates to a laminate.

  Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, ABS, MS resin, AS resin and other styrene resins, vinyl chloride resin, cellulose acetate such as triacetyl cellulose, etc. Lightweight, easy processability, impact resistance, etc. are especially excellent, so containers, instrument panels, packaging materials, various housing materials, optical disk substrates, plastic lenses, display devices such as liquid crystal displays and plasma displays It is used for various uses.

  In industrial electronic devices having display bodies such as mobile phones, with the diversification of design, thinning, and large area, there is an increasing demand for thinning the display body cover. A polycarbonate resin sheet is generally used. In the case of a polycarbonate resin sheet, although impact resistance is high, there is a disadvantage that pencil hardness is low. On the other hand, the acrylic resin sheet has a pencil hardness higher than that of polycarbonate, but has a drawback that it is easily cracked by impact.

  In addition, these plastic substrates have a surface hardness lower than that of glass and are easily damaged. Transparent resins such as polycarbonate and acrylic have the disadvantage that the original transparency or appearance of the resin is significantly impaired. It makes it difficult to use plastic substrates in fields that require wear. For this reason, there is a need for an active energy ray-curable hard coat material (coating material) that imparts wear resistance to the surface of these plastic substrates.

  In recent years, a transparent resin film coated with a hard coat is often used for video display devices such as TVs and touch panels. However, especially in touch panels, due to the widespread use of the capacitive type, the movement of sliding fingers (flip) is frequently performed in operation. Scratching (scratch resistance) during wiping is a problem, and further improvement in slipping and scratch resistance is required as compared with conventional hard coats.

  In an active energy ray-curable resin composition used for a hard coat layer with the aim of solving such problems, many attempts have been made to impart slipperiness by reducing the friction coefficient of the surface. For example, the invention described in Patent Document 1 cures an active energy ray-curable resin composition containing a polysiloxane structure or a compound having a perfluoroalkyl group and an acryloyl group together to form a hard coat layer. Improves hardness, scratch resistance, and stain resistance. In the invention described in Patent Document 2, a polysiloxane-containing compound having a specific structure is added to a solventless hard coat.

  Furthermore, in the resin base material which gave the hard coat, the trial which improves the pencil hardness of the base material which has impact resistance is made | formed. For example, in the invention described in Patent Document 3, the surface of an impact-resistant acrylic sheet is covered with a urethane acrylate hard coat to ensure impact resistance and improve pencil hardness.

JP 2010-33693 A JP 2007-046049 A JP 2008-1000042 A

  However, in the invention described in Cited Document 1, the coefficient of friction is not sufficiently lowered, and slipperiness and scratch resistance do not satisfy the performance required for the touch panel. In addition, the invention described in the cited document 2 is intended to solve the problem of antifouling properties, and its use is also limited to information recording media. For example, the technology is diverted to a solvent-based hard coat. However, since the amount of crosslinking groups in the polysiloxane-containing compound is small, it is unlikely that the performance required for the touch panel, particularly the scratch resistance requirement, will be satisfied as described above. Furthermore, in the invention described in Patent Document 3, the surface pencil hardness of the laminate is as low as 5H compared to the glass of the conventional cover base material, and it is difficult to think that the sliding and scratch resistance required for the touch panel is satisfied. .

  The problem to be solved by the present invention is that compared to these conventional technologies, while having impact resistance, at the same time, the surface slipperiness and its durability are greatly improved, and excellent hardness, wear resistance and transparency are achieved. It is to provide a laminate that can also realize low curling properties and to provide a laminate suitable as a display cover.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a layer obtained by curing a curable composition containing a specific copolymer, and a base material layer containing polymethyl methacrylate. It has been found that the above-mentioned problems can be solved by forming a laminate having a layer made of a resin composition containing a resin having an acrylic equivalent of 100 or more. That is, the present invention is as follows.

(1) A laminate having at least the following base material layer, the following first layer, and the following second layer.
Base material layer: Molding layer containing polymethyl methacrylate First layer: At least an acrylic copolymer (α) and an active energy ray-curable compound are contained, and the acrylic copolymer (α) is as follows: A layer copolymer (β) formed by curing the active energy ray-curable resin composition (I) obtained by adding the compound (γ) to the copolymer (β) of Copolymer compound (γ) of silicone monomer (A) represented by (I), (meth) acrylate (B) having an epoxy group and other copolymerizable monomer (C): carboxyl group and 1 in the molecule Compound having at least one (meth) acryloyl group

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, R ³ and R ⁴ are each a methyl group or a phenyl group, n is an integer of 10 to 100, and R ³ And R ⁴ may be the same as or different from each other, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.

Second layer: a layer comprising a resin composition (II) containing a resin having an acrylic equivalent of 100 or more

(2) The laminate according to (1), wherein the active energy ray-curable resin composition (I) contains 0.05 to 10% by weight of the acrylic copolymer (α).

(3) As the copolymerizable monomer (C), the copolymer (β) includes at least one (meth) acrylate selected from linear or branched alkyl (meth) acrylates having 4 to 22 carbon atoms, The laminate according to (1) or (2).

(4) The laminated body according to any one of (1) to (3), wherein the thickness of the first layer is 2 μm or more and 100 μm or less.

(5) The laminate according to any one of (1) to (4), wherein the resin composition (II) contains (meth) acrylate having one or more (meth) acryloyl groups in the molecule. body.

(6) When the resin composition (II) is 100 parts by weight of the total (weight) of (meth) acrylate and urethane (meth) acrylate having one or more (meth) acryloyl groups in the molecule, The laminate according to any one of (1) to (5), which contains 0.1% by weight to 99.9% by weight of (meth) acrylate.

(7) The laminated body according to any one of (1) to (6), wherein the thickness of the second layer is 2 μm or more and 100 μm or less.

(8) The laminate according to any one of (1) to (7), wherein the thickness of the base material layer is 0.01 mm or more and 2 mm or less.

  In the active energy ray-curable resin composition (I) used in the present invention, an acrylic copolymer having a low surface free energy is unevenly distributed on the surface in the solvent drying step during film formation, and the subsequent activity. Upon irradiation with energy rays, it is polymerized and cured to form a cured film.

  Since the acrylic copolymer (α) used in the present invention has a high molecular weight polysiloxane structure, it gives good slipperiness to the coating surface, and the acrylic copolymer (α) has an active energy. Since it contains a linear curable crosslinking group, it has high surface performance durability (less deterioration of surface slipperiness after wiping with a solvent and scratch resistance after steel wool). Furthermore, since other acrylic monomers are copolymerized in the polysiloxane structure, the compatibility with other components (solvent, photocurable compound) forming the film is good.

  As a result, by applying and curing the active energy ray-curable resin composition (I) on the surface of the base material, the surface slipperiness is improved, and the scratch resistance against nails, cloth and steel wool is good. It is possible to give molded products. In addition, by having a layer made of the resin composition (II) containing a resin having an acrylic equivalent of 100 or more, it is possible to reduce the deformation of the base material at the time of falling ball impact and improve the impact resistance of the laminate. It is. Furthermore, since it is also excellent in transparency, it can be used for optical use members.

Therefore, the present invention provides transparent articles for optical displays such as touch panels and liquid crystal televisions), automobile-related parts (lamp-related items, window-related items (rear windows, side windows, skylights, etc.)), life-related items (various types It can be suitably used as a surface protective cover for a wide range of articles such as casings of electrical equipment, decorative boards, furniture, and the like.

  In the following, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents. . In the present specification, the (meth) acryloyl group is a general term for an acryloyl group and a methacryloyl group. The same applies to (meth) acryl and (meth) acrylate. Further, in the present specification, “to” is used in the sense of including the numerical values described before and after it as a lower limit value and an upper limit value.

1. Laminate The laminate of the present invention comprises at least a substrate layer, a first layer formed by curing the active energy ray-curable resin composition (I), and a second layer comprising the resin composition (II). It is the laminated body which has. However, the second layer that can be understood as corresponding to the first layer shall not be regarded as the second layer.

Although the base material layer in this invention is a shaping | molding layer containing polymethylmethacrylate, the thing of arbitrary forms and shapes is employable, For example, molded objects, such as a film and a sheet | seat, etc. are mentioned.
The base material layer in the present invention preferably has a thickness of 0.01 mm or more, more preferably 0.1 mm or more, and most preferably 0.3 mm or more when importance is attached to hardness. In addition, it is preferably 2 mm or less, more preferably 1.5 mm or less, and most preferably 1 mm or less for thinning when used as a display body.

  The first layer in the present invention is a layer formed by curing the active energy ray-curable resin composition (I), but the cured layer has a thickness of 2 μm or more and has high hardness. It is preferable from the viewpoint of ensuring, more preferably 5 μm or more, and most preferably 8 μm or more. Moreover, it is preferable that it is 100 micrometers or less from the point that the distortion (crack) of the layer by hardening shrinkage does not generate | occur | produce more, It is more preferable that it is 50 micrometers or less, Most preferably, it is 25 micrometers or less.

  The second layer in the present invention is a layer made of the resin composition (II) and preferably has a thickness of 2 μm or more from the viewpoint of alleviating impact caused by falling balls, and more preferably 5 μm or more. Most preferably, it is 8 μm or more. Moreover, it is preferable that it is 100 micrometers or less from the point that importance is attached to transparency, it is more preferable that it is 50 micrometers or less, and it is most preferable that it is 25 micrometers or less.

  In the laminate of the present invention, the arrangement of the base material layer, the first layer, and the second layer is not particularly limited. Each layer may be formed so as to be directly adjacent to each other, and may have other layers such as a primer layer for further improving the adhesion between the layers. In order to obtain the effect of the present invention, the first layer needs to be the outermost layer. In addition, in order that the laminate of the present invention sufficiently obtains effects such as impact resistance, the second layer is preferably not directly adjacent to the first layer, and more preferably, the first layer, the base material layer, The second layer is preferably arranged in this order. Even in this case, it is the same that other layers may be provided between the layers.

2. Active energy ray-curable resin composition (I)
The active energy ray-curable resin composition (I) used in the present invention is an active energy ray-curable resin composition containing at least an acrylic copolymer (α) and an active energy ray-curable compound. The copolymer (α) is obtained by adding the compound (γ) to the following copolymer (β).

Copolymer (β): Copolymer compound (γ) of silicone monomer (A) represented by structural formula (I), (meth) acrylate (B) having an epoxy group and other copolymerizable monomer (C) ): Compound having a carboxyl group and one or more (meth) acryloyl groups in the molecule

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, R ³ and R ⁴ are each a methyl group or a phenyl group, n is an integer of 10 to 100, and R ³ And R ⁴ may be the same as or different from each other, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.

The active energy ray-curable resin composition (I) used in the present invention preferably contains 0.05% by weight or more of the acrylic copolymer (α), and sufficiently exhibits surface slipperiness in the cured film. From the viewpoint of good slipping and steel wool scratch resistance, it is preferably 0.1% by weight or more, particularly preferably 1% by weight or more. Further, it is preferably contained in an amount of 10% by weight or less, the compatibility with the photocurable compound that reacts with the acrylic copolymer (α) is ensured and the transparency of the cured film is good, and the photocuring From the point that the acrylic copolymer (α) that is relatively softer than the functional compound is not unevenly distributed on the surface and can ensure hardness and scratch resistance, it is preferably 9% by weight or less, and 8% by weight or less. It is particularly preferred.
The acrylic copolymer (α) and the active energy ray-curable compound will be described.

<Acrylic copolymer (α)>
The acrylic copolymer (α) used in the present invention is obtained by adding the compound (γ) to the following copolymer (β).

[Copolymer (β)]
The copolymer (β) used in the present invention is a copolymer of the silicone monomer (A) represented by the structural formula (I), the (meth) acrylate (B) having an epoxy group and other copolymerizable monomers (C). It is a polymer.

(Silicone monomer (A) represented by structural formula (I))
The silicone monomer (A) used in the present invention is a compound represented by the following structural formula (I).

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, R ³ and R ⁴ are each a methyl group or a phenyl group, n is an integer of 10 to 100, and R ³ And R ⁴ may be the same as or different from each other, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.

R ¹ is a hydrogen atom or a methyl group, and may be a methyl group because the glass transition temperature of the copolymer (hereinafter sometimes abbreviated as Tg) is increased and the hardness of the cured film surface is increased. preferable.

R ² is an alkylene group having 1 or more carbon atoms, and is preferably 2 or more, and particularly preferably 3 or more, from the viewpoint that acquisition of raw materials and production (reaction) are relatively easy. Moreover, it is 12 or less alkylene group, 10 or less is preferable and 8 or less is preferable.

R ³ and R ⁴ are each a methyl group or a phenyl group, and are preferably a methyl group from the standpoint that it is relatively easy to obtain and manufacture (react) the raw materials. Further, n is an integer of 10 or more, and is preferably 25 or more, particularly preferably 50 or more, from the viewpoint that the surface slipperiness is sufficiently expressed in the cured film and the slipperiness is good. Further, it is an integer of 100 or less, preferably 90 or less, and preferably 80 or less from the viewpoint of good solubility of the raw material and the acrylic copolymer (α) in a solvent and compatibility with the photocurable compound. Is particularly preferred.

R ⁵ is an alkyl group having 1 or more carbon atoms, and is preferably 2 or more, and particularly preferably 3 or more, from the viewpoint of relatively easy acquisition of raw materials and production (reaction). The alkyl group is 12 or less, preferably 10 or less, and preferably 8 or less.

  The specific structure is not particularly limited as long as the effects of the present invention can be obtained, but those having polydimethylsiloxane are preferable. For example, polydimethylsiloxane having a methacryloyl group at one end (for example, “Sila” manufactured by JNC). Plane (registered trademark) FM0711 "," Silaplane (registered trademark) FM0721 "," Silaplane (registered trademark) FM0725 ") and other radical polymerizable monomers may be used. These compounds may be used individually by 1 type, and may use 2 or more types. The number average molecular weight (g / mol) of the compound having the highest number average molecular weight among the silicone monomers (A) in the present invention is the one having the highest number average molecular weight when two or more kinds of (A) are used. Number average molecular weight (g / mol).

  Among the silicone monomers (A), the number average molecular weight (g / mol) of the compound having the highest number average molecular weight is not particularly limited, but is usually 1,000 or more, and the surface slipperiness in the cured film is good. In view of (low friction coefficient), 2,000 or more is preferable, and 3,000 or more is more preferable. Moreover, since it is normally 50,000 or less and compatibility with a solvent and an active energy ray hardening compound is favorable, 20,000 or less are preferable and 10,000 or less are more preferable. In particular, it is particularly preferably 4,000 or more and 7,000 or less because the antifouling property is specifically improved.

((Meth) acrylate (B) having epoxy group)
Examples of the (meth) acrylate (B) having an epoxy group used in the present invention include (meth) acrylate having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate; 3,4-epoxycyclohexyl acrylate, 3,4-epoxy Examples include (meth) acrylates in which an epoxy group is directly bonded to an alicyclic structure such as cyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate.

  Among these, glycidyl methacrylate and 3,4-epoxycyclohexyl are easy to obtain and easy to modify with a compound (γ) having a carboxyl group and one or more (meth) acryloyl groups in the molecule described later. Particularly preferred are acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and the like. These compounds may be used individually by 1 type, and may use 2 or more types.

  The weight ratio (%) of the (meth) acrylate (B) having an epoxy group in the copolymer (β) is not particularly limited, but is usually 1% by weight or more, and the durability of the surface slipperiness of the cured film is not limited. From the viewpoint of good properties, it is preferably 10% by weight or more, more preferably 20% by weight or more, still more preferably 40% by weight or more, and particularly preferably 50% by weight or more. In addition, the solubility of the acrylic copolymer (α) in a solvent is good, and gelation is unlikely to occur during the epoxy-acid reaction of the copolymer (β). However, it is preferably 90% by weight or less, more preferably 80% by weight or less, and particularly preferably 70% by weight or less.

(Other copolymerizable monomer (C))
The “other copolymerizable monomer (C)” used in the present invention is not particularly limited as long as the effects of the present invention can be obtained, but preferably has low reactivity with an epoxy group, and stability of the produced polymer Or a structure derived from a monomer having a rigid skeleton and not lowering the hardness. Examples of the monomer include (meth) acrylate having a linear or branched alkyl having 1 to 22 carbon atoms, styrene, or a lower alkyl group of styrene (for example, an alkyl group having 1 to 4 carbon atoms) or lower Substituted derivatives of alkenyl groups (for example, alkenyl groups having 2 to 4 carbon atoms), perfluoroalkyl (meth) acrylates, alkyl (meth) acrylamides, and cycloalkyls having 5 to 20 carbon atoms (poly) cycloalkyl side chains ( Examples thereof include meth) acrylate and (meth) acrylamides, and one kind may be used alone or two or more kinds may be used in combination.

For example, the following compounds are mentioned.
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) Acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, n-tridecyl (meth) acrylate, stearyl methacrylate , Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) ) Acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and a modified product thereof with a cationizing agent, diethylaminoethyl (meth) acrylate and a modified product with a cationizing agent, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate such as methoxypolypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2 Hydroxyethyl phthalate, (meth) acrylic acid, 2-acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloylpropyl phthalate, (meth) acryloyloxyethyl succinate, 2-isocyanate Ethyl (meth) acrylate, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyltrimethoxysilane, and 3- (meth) acryloyloxypropylmethyltriethoxysilane, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, vinylidene cyanide and the like Lilonitrile compound, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-ethyl (meth) acrylamide, N-methoxy (meth) acrylamide, N, N -Dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-ethoxy (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) Acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- (2-dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, N, N-ethylenebis (meth) acrylamide, etc. Acrylamide compound Things.

  Among these, the linear or branched alkyl group having 1 to 22 carbon atoms is used because the Tg of the copolymer is increased, the hardness of the cured film surface is increased, and the hardness of the cured surface is increased. (Meth) acrylate having, that is, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate , Sec-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, n-tridecyl (Meth) acrylate and stearyl methacrylate are preferred, copolymerized From the point that the hardness of the cured film surface is increased and the solubility of methyl (meth) acrylate and copolymer in the solvent is improved, 2-ethylhexyl (meth) acrylate and octyl (meth) A structure using acrylate, lauryl (meth) acrylate or stearyl methacrylate is particularly preferable. These structures may contain 1 type independently, and 2 or more types may contain them.

  In addition, the copolymerizable monomer (C) may have a molar ratio in the acrylic copolymer (α) of 1% by weight or more from the viewpoint that the solubility of the copolymer in a solvent is improved. It is preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and most preferably 30% by weight or more. Further, it is preferably 99% by weight or less, more preferably 95% by weight or less, from the viewpoint that the slipperiness of the coating film after curing, the SW resistance and the solubility of the acrylic copolymer (α) are good. 90% by weight or less is more preferable, 80% by weight or less is particularly preferable, and 70% by weight or less is most preferable.

In the present invention, among the silicone monomers (A), the number average molecular weight (g / mol) of the compound having the highest number average molecular weight and the (meth) acrylate (B) having an epoxy group in the copolymer (β) ) Is preferably 250,000 or more multiplied by the weight ratio (%). Here, the larger the number average molecular weight of the silicone monomer (A), the better the slipping property of the cured film, and the larger the weight ratio (%) in the copolymer (β) of the (meth) acrylate having an epoxy group, the harder the curing. From the viewpoint of preventing the copolymer (α) from falling off in the film and improving the durability of slipperiness, it is preferably 250,000 or more, more preferably 270,000 or more, and particularly preferably 300,000 or more. Further, the smaller the number average molecular weight of the silicone monomer (A) and the smaller the weight ratio (%) in the copolymer (β) of the (meth) acrylate having an epoxy group, the gelation in the acid-epoxy reaction at the time of synthesis. Is preferably 1,000,000 or less, more preferably 900,000 or less, and particularly preferably 700,000 or less.

  Of the silicone monomers (A), the number average molecular weight (g / mol) of the compound having the highest number average molecular weight and the weight of the (meth) acrylate (B) having an epoxy group in the copolymer (β). In order to adjust the value multiplied by the ratio (%), the number average molecular weight (g / mol) of the silicone monomer (A) is selected, or the epoxy group in the copolymer (β) is (meth) It can be adjusted by selecting the weight ratio (%) of the acrylate (B).

[Compound (γ)]
The compound (γ) used in the present invention is a compound having a carboxyl group and one or more (meth) acryloyl groups in the molecule.

(Compound having a carboxyl group and one or more (meth) acryloyl groups in the molecule)
Examples of the compound having a carboxyl group and one or more (meth) acryloyl groups in the molecule include (meth) acrylic acid and a reaction product of a hydroxyl group-containing polyfunctional acrylate and an acid anhydride. For example, (meth) acrylic acid, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipentaerythritol pentaacrylate maleic acid monoester, pentaerythritol Triacrylate phthalic acid monoester, dipentaerythritol pentaacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol Pentaacrylate tetrahydrophthalic acid monoester, and the like.

  When the total amount (total weight) of the components of the acrylic copolymer (α) and the active energy ray-curable compound is 100 parts by weight, the weight ratio of the acrylic copolymer (α) is usually 0.1 weight. %, But when the weight ratio of the acrylic copolymer (α) is increased, the slidability of the cured film surface is improved, preferably 0.2% by weight or more, more preferably 0.5% by weight or more, More preferably, it is 1.0% by weight or more. In addition, the amount is usually 10% by weight or less, but since the amount of the copolymer (α) unevenly distributed in the vicinity of the surface decreases as the weight ratio of the acrylic copolymer (α) decreases, the surface hardness increases and the scratch resistance. Is preferably 5% by weight or less, more preferably 3% by weight or less, and particularly preferably 2.5% by weight or less. The weight ratio of the acrylic copolymer (α) is not particularly limited as long as the desired physical properties are satisfied, and depends on the structure of the acrylic copolymer (α), particularly the molecular weight and content of the silicone monomer (A). It can be adjusted as appropriate.

<Active energy ray-curable compound>
The active energy ray-curable compound used in the present invention is a compound other than the acrylic copolymer (α) used in the present invention, and reacts with the acrylic copolymer (α) by irradiation with active energy rays. . A compound containing one or more (meth) acryloyl groups in the molecule is preferred. Further, the number of functional groups of the (meth) acryloyl group in the photocurable compound is preferably 3 or more from the viewpoint that the cured film has good hardness and scratch resistance and high reactivity at the time of curing. One or more is particularly preferred. Moreover, 9 or less are preferable from the point which the resin viscosity before hardening is suitable for coating, and 6 or less is especially preferable.

  Specifically, it is a polyfunctional (meth) acrylate and one or more polyfunctional (meth) acrylate derivatives selected from a urethane-modified product, an ester-modified product, and a carbonate-modified product. More specifically, the following can be exemplified, but the active energy ray-curable resin composition (I) used in the present invention is not limited to these as long as it can be obtained.

  For example, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate adduct to succinic anhydride, dipentaerythritol to succinic anhydride Polyfunctional acrylates such as pentaacrylate adducts; polyesters such as polyester oligomers (specifically, M8030, M7100, etc., manufactured by Toagosei Co., Ltd.) having side chains or side chain and terminal (meth) acryloyl groups Acrylates: Isophorone diisocyanate (IPDI) isocyanurate, polytetramethylene glycol (PTMG) and hydroxyethyl acrylate ( EA), polyfunctional urethane (meth) acrylates such as hexamethylene diisocyanate (HDI) isocyanate and PTMG reaction product of pentaerythritol triacrylate; oligoesters using polycarbonate diol and pentaerythritol tris Polyester (meth) acrylates having a carbonate bond such as a reaction product of acrylate; Polyurethane (meth) acrylates having a carbonate bond such as a reaction product of IPDI and polycarbonate diol and a reaction product of HEA; Acrylic acid adduct of bisphenol A (Specifically, polyepoxy (meth) acrylates such as EA-1025 manufactured by Shin-Nakamura Chemical Co., Ltd .; triethoxyisocyanuric acid diacrylate, triethoxyisocyanuric acid triac (Specifically, manufactured by Toagosei Co., Ltd. of Aronix M315, M313) Rate triethoxy (meth) acrylates having an isocyanurate ring such as; and their alkylene oxide modification products; polycaprolactone-modified products; and the like. Moreover, these may be used independently and may use 2 or more types together.

  Among them, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, due to viscosity and curability, hardness of the resulting cured film surface, etc. And dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, an alkylene oxide modified product, a caprolactone modified product, and the like are particularly preferable.

<Photopolymerization initiator>
As the photopolymerization initiator contained in the active energy ray-curable resin composition (I) used in the present invention, known photopolymerization initiators can be widely adopted, preferably α-hydroxyacetophenone (α-hydroxyphenyl ketone) type, Alkylphenone compounds such as α-aminoacetophenone and benzyl ketal compounds; acylphosphine oxide compounds; oxime ester compounds; oxyphenyl acetates; benzoin ethers; aromatic ketones (benzophenones); Benzoylformic acid and ester derivatives thereof;

Specifically, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2,4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butan-1-one, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoylformic acid, methyl benzoylformate, Zoirugi ethyl are preferred. Two or more of these photopolymerization initiators can be used in combination as appropriate.

  Among these, 2-hydroxy-2-methylpropio is used as at least a part of the photopolymerization initiator because it is possible to minimize a decrease in curability, is easily available, and hardly causes coloring and the like. It is preferable to use α-hydroxyphenyl ketones such as phenone and 1-hydroxycyclohexyl phenyl ketone.

  In order to obtain an active energy ray-curable resin composition (I) having particularly good curability, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl- Α-aminophenyl ketones such as 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzophenone, Michler's ketone, 2-chlorothioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, and the like And oxime esters such as CGI242 (manufactured by Ciba), OXE01 (manufactured by Ciba), and the like. Further, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzophenone, More preferably, methyl benzoylformate or the like is used, and 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butan-1-one and methyl benzoylformate are particularly preferred.

  When the total amount (total weight) of the components of the photocurable compound that reacts with the acrylic copolymer is 100 parts by weight, the photopolymerization initiator is 2 to 6.5 parts by weight, preferably 2.5. It is not less than 5.5 parts by weight. If it is less than 2 parts by weight, the curability of the obtained active energy ray-curable resin composition (I) is poor, and if it is 6.5 parts by weight or more, the physical properties of the cured film may be lowered.

  When the active energy ray-curable resin composition (I) used in the present invention is irradiated with active energy rays to obtain a cured film, when ultraviolet rays or soft X-rays are used as active energy rays, The composition to be used preferably contains the photopolymerization initiator as described above. However, when an electron beam or hard X-ray having a relatively high energy is used, the photopolymerization initiator may not be contained.

<Inorganic particles>
The active energy ray-curable resin composition (I) of the present invention can contain inorganic particles. By containing the inorganic particles and the (meth) acryloyl copolymer having a high crosslinking density, the active energy ray-curable resin composition (I) capable of forming a hard coat having higher hardness can be provided.

  The average primary particle diameter of the inorganic particles is preferably 1 nm to 200 nm, more preferably 150 nm or less, and more preferably 100 nm or less from the viewpoint of good transparency of the cured film. Although a lower limit is not specifically limited, Usually, 1 nm or more is preferable, From the point that the acquisition of a raw material is easy, More preferably, it is 5 nm or more, More preferably, it is 10 nm or more.

On the other hand, since the movement of inorganic particles in the above range is governed by thermal diffusion rather than sedimentation by gravity, it becomes possible to disperse particles stably in the hard coat liquid, and when the hard coat film is formed, the surface is effectively exposed to the surface. Inorganic particles can be present. Also, the smaller the average primary particle size of the inorganic particles, the better the optical properties.
The average primary particle diameter of the inorganic particles in the present invention refers to a diameter obtained by averaging the particle sizes observed with an electron microscope such as TEM.

  Examples of inorganic particles include silica (including organosilica sol), alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide) / Tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, antimony oxide and the like. These inorganic particles may be contained alone or in combination of two or more. Among these, silica (including organosilica sol) is preferably used because it is easy to obtain raw materials, the surface of the particles can be easily modified, and the dispersion stability is easily secured.

The colloidal silica in which silica is dispersed in water is preferably a surface-modified colloidal silica from the viewpoint of transparency of the coating film, weather resistance of the laminate, and laminate.
For the modification of colloidal silica, a compound having a hydrolyzable silicon group or a compound having a silicon group to which a hydroxyl group is bonded can be used. Each of these compounds may be one kind or two or more kinds. In a compound having a hydrolyzable silicon group, silanol groups are generated by hydrolysis, and these silanol groups react with and bind to silanol groups present on the surface of the colloidal silica to form surface-modified colloidal silica.

  Examples of the silicon group-containing compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and β- (meth) acryloyloxyethyltri. Methoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinyl orimethoxysilane, vinyltriethoxysilane, vinyl Methyldimethoxysilane, p-vinylphenyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimeth Shishiran, .gamma.-aminopropyltrimethoxysilane, .gamma. styryltrimethoxysilane, p- styryl trimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, and 3-mercaptopropyl trimethoxysilane.

  Alternatively, a derivative obtained by adding a polyfunctional (meth) acrylate or a high molecular weight (meth) acrylate to a silane having a mercapto group or a derivative obtained by adding a polyfunctional (meth) acrylate having a hydroxyl group to a silane having an isocyanate group is modified. Silicon group-containing compounds may be used.

  The surface modification of colloidal silica can be performed by reacting colloidal silica with a hydrolyzable silicon group-containing compound, catalyst, and water at 20 to 100 ° C. for 1 to 40 hours.

Examples of the catalyst used in the surface modification reaction include inorganic acids such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid; formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, acrylic Acids, organic acids such as methacrylic acid; alkalis; acetylacetone aluminum, aluminum 2,2,6,6, -tetramethyl-3,5-heptanedionate, aluminum diisopropoxide, BR> G tylacetoacetate, aluminum di Examples include isobutoxide ethyl acetoacetate, butoxide borate, dibutyltin dilaurate, and dibutyltin dioctate. The amount of these catalysts used is preferably 0.0001 to 5 parts by mass, and 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of colloidal silica and hydrolyzable silicon group-containing compound. It is more preferable. Moreover, it is preferable that it is 0.5-100 equivalent with respect to a hydrolysable silicon group, and, as for the quantity of the water in the said surface modification reaction, it is more preferable that it is 1-30 equivalent.

The colloidal silica is preferably acidic colloidal silica among acidic or basic colloidal silica.
The inorganic particles used in the present invention are preferably contained in an amount of 5 parts by weight or more, more preferably 10 parts by weight or more, based on 100 parts by weight of the active energy ray-curable resin composition (I) of the present invention. More preferably, it is 20 parts by weight or more. Further, it is preferably 70 parts by weight or less, more preferably 50 parts by weight or less, and still more preferably 40 parts by weight or less.

<Preparation method>
The method for preparing the active active energy ray-curable resin composition (I) of the present invention is not particularly limited. For example, an active energy ray-curable compound such as an acryloyl copolymer (α) and a polyfunctional (meth) acrylate is used. If necessary, it can be prepared by mixing together with a solvent, a polymerization initiator, an additive and the like.

  The solvent used in the preparation of the active energy ray-curable resin composition (I) of the present invention is not particularly limited, and becomes a (meth) acryloyl copolymer, a polyfunctional (meth) acrylate, and a base for coating. The material is appropriately selected in consideration of the material of the base material and the coating method of the composition. Specific examples of the solvent that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, and ethylene glycol. Ether solvents such as dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; dimethylformamide, Amide solvents such as diethylformamide and N-methylpyrrolidone; methyl Cellosolve, ethyl cellosolve, cellosolve solvents such as butyl cellosolve; methanol, ethanol, propanol, isopropanol, alcohol solvents such as butanol; and the like; dichloromethane, halogenated solvents such as chloroform.

  These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.

  Various additives can be added to the active energy ray-curable resin composition (I) of the present invention as necessary. Examples of such additives include conventional additives such as leveling agents, antistatic agents, plasticizers, surfactants, antioxidants, and ultraviolet absorbers.

Examples of the leveling agent include a compound containing a perfluoroalkyl group or a perfluoroalkylene skeleton, a compound containing a polydimethylsiloxane structure, and the like. The content of the leveling agent in the active energy ray-curable resin composition (I) is preferably 0 to 5 parts by mass from the viewpoint of transparency, coating appearance, adhesion, and hardness, and 0 to 2 parts by mass. It is more preferable that it is 0-1 mass part.

  Moreover, when the base material described later includes a functional group that can be cured by light or heat, it may be more preferable to cure the base material by irradiation with active energy rays or heating. The substrate may be in the form of a molded article (article), or another layer may be interposed between the substrate and the application surface.

The application method of the active energy ray-curable resin composition (I) of the present invention is not particularly limited, but spin coating, dip coating, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, and air knife. A coat etc. can be mentioned preferably.

  After the coating film is formed on the substrate by the above coating method, the cured film is obtained by such means as removing volatile components by heat drying and then irradiating the coating film with active energy rays. A layer formed by curing the active energy ray-curable resin composition (I), such as the cured film, is the first layer in the present invention.

  When using an active energy ray when obtaining a cured film, the irradiation method includes ultraviolet rays emitted from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like. Examples thereof include active energy rays (electron beams, EB) such as electron beams, α rays, β rays, and γ rays that are usually extracted from a particle accelerator of 20 to 2000 kV. A cured film cured with such active energy rays is particularly preferable because of its excellent balance between productivity and physical properties.

The haze can be calculated from the following formula in accordance with JIS K7136.
H (%) = (Td / Tt) × 100
H: Haze (cloudiness value) (%)
Td: Diffuse light transmittance (%)
Tt: Total light transmittance (%)
In addition, the measurement of haze can be measured, for example using a turbidimeter (made by Nippon Denshoku Industries Co., Ltd.).

3. Resin composition (II)
The resin composition (II) of the present invention is as follows.
That is, it is a resin composition containing a resin having an acrylic equivalent of 100 or more, and there are no particular limitations on the coating method, the presence or absence of solvent drying, the presence or absence of a curing step, and the curing method in creating a coating film. The acrylic equivalent in the present invention is a value obtained by dividing the molecular weight (g / mol) of the component constituting the resin composition (II) by the number of acryloyl groups present in one molecule of the component. In addition, when there is no acryloyl group, it becomes infinite, and this case is also included. In the case of a mixture, the sum of values obtained by multiplying the acrylic equivalent of each component by the weight ratio. The greater the acrylic equivalent, the lower the hardness of the resulting coating film. The acrylic equivalent is preferably 110 or more.

  The component of the resin composition (II) includes (meth) acrylate, polyolefin, polyester, polycarbonate, polyurethane, poly (meth) acrylate, polyepoxylate, poly (polyacrylate) having one or more (meth) acryloyl groups in the molecule. Examples thereof include resins having an acrylic equivalent of 100 or more such as siloxane and perfluoropolyether, and these one kind may be used alone or two or more kinds may be used in combination. Moreover, you may use the compound which introduce | transduced the acryloyl group into these compounds.

  Among these, from the viewpoint of ease of handling, (meth) acrylate, polyolefin, polyurethane and poly (meth) acrylate having one or more (meth) acryloyl groups in the molecule are preferable, and one or more ( (Meth) acrylate having a (meth) acryloyl group and poly (meth) acrylate are particularly preferred. The number of functional groups of the (meth) acryloyl group of the (meth) acrylate having one or more (meth) acryloyl groups in the molecule is usually 1 or more, preferably 2 or more, more preferably 3 or more. 4 or more are particularly preferable. These may be one kind or two or more kinds.

Specific examples of (meth) acrylate are as follows.
For example, as a (meth) acrylate compound having one (meth) acryl group in one molecule, a (meth) acrylate, cyclohexyl acrylate or isopropyl having a linear or branched alkyl group having 1 to 22 carbon atoms. Alicyclic (meth) acrylates such as bornyl methacrylate, (meth) acrylates having aromatic rings such as styrene and derivatives thereof, polyalkylene glycol chains, polydimethylsiloxane chains, (meth) acrylates having perfluoroalkyl groups, 2 -Hydroxyethyl (meth) acrylate, polyalkylene glycol chain, polyalkylene glycol chain in which the end of polydimethylsiloxane chain is substituted with a hydroxy group, or a hydroxy group such as (meth) acrylate having a polydimethylsiloxane chain (meth) Acrylate It is below.

  (Meth) acrylate compounds having two (meth) acryl groups in one molecule include (meth) acrylates at both ends of a linear or branched alkylene skeleton having 2 to 22 carbon atoms such as hexanediol diacrylate. Substituted aliphatic di (meth) acrylate, tricyclodecane dimethanol diacrylate and other di (meth) acrylates containing an alicyclic skeleton, polyethylene glycol diacrylate and other polyalkylene glycol di (meth) acrylates, and the like It is done.

  Examples of the (meth) acrylate compound having 3 or more (meth) acryl groups in one molecule include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, propionic acid modified dipentaerythritol tetra (meth) Acrylate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipenta Trifunctional or higher (meth) acrylates such as Sri Tall hexa (meth) acrylate.

Moreover, as long as the effects of the present invention are exhibited, the compound having one or more (meth) acryloyl groups in one molecule is not particularly limited to the above-mentioned compounds. From the hardness of the film surface, etc., trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Propionic acid modified dipentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, propionic acid modified dipentaerythritol tetra (meth) acrylate, propionic acid modified dipentaeryth Preferable are itolitol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and more preferably pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferable.

  Examples of the polyolefin include polyethylene, polypropylene, polybutadiene, hydrogenated polybutadiene, and polyisoprene.

  Polyesters include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, etc.) or anhydrides thereof and low molecular weight diols (ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl 1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl-1,3-pentanediol, 3,3-dimethylolheptane, 1,9- Nonanediol, 2-methyl-1,8-octane Ol, cyclohexanedimethanol, bishydroxyethoxybenzene, etc.) such as polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene sebacate, etc. Examples thereof include those obtained by ring-opening polymerization such as polycaprolactone and polymethylvalerolactone.

  As the polycarbonate, an aromatic dihydroxy compound or a small amount of a polyhydroxy compound is obtained by an interfacial polymerization method with phosgene, or branched by a transesterification reaction between the aromatic dihydroxy compound and the carbonic acid diester. For example, a carbonic acid ester polymer containing bisphenol A as a main raw material is used. Furthermore, polybutylene carbonate, polyhexamethylene carbonate, poly (3-methyl-1,5-pentylene) carbonate obtained by dealcoholization from a low molecular weight diol and alkylene carbonate or dialkyl carbonate may be used.

  Polyurethanes include alicyclic skeleton isocyanate compounds such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, (poly) butadiene diol, (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, and (poly) ester diol. , (Poly) caprolactone-modified diol, (poly) carbonate diol, (poly) spiroglycol, or the like, ((polyurethane)) or the like to which one or two or more compounds are added.

  The poly (meth) acrylate is a (meth) acrylate having a linear or branched alkyl group having 1 to 22 carbon atoms, styrene, or a lower alkyl group of styrene (for example, an alkyl group having 1 to 4 carbon atoms). Alternatively, a substituted derivative of a lower alkenyl group (for example, an alkenyl group having 2 to 4 carbon atoms), a perfluoroalkyl (meth) acrylate, an alkyl (meth) acrylamide, or a cyclo having a (poly) cycloalkyl side chain having 5 to 20 carbon atoms. Examples thereof include polymers containing (meth) acrylates such as alkyl (meth) acrylates and (meth) acrylamides as monomers. As long as the effects of the present invention are exhibited, these monomers may be polymerized alone or in combination of two or more, and polymerization methods such as radical polymerization, anionic polymerization, and cationic polymerization are not particularly limited. . Further, the structure of the polymer such as random, block or graft structure is not particularly limited.

Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl (meth). Acrylate, sec-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, n-tridecyl (meth) acrylate, stearyl methacrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and modified products thereof by cationizing agent, diethylamino Modified products of ethyl (meth) acrylate and its cationizing agent, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate , Alkoxypolyalkylene glycol (meth) acrylate such as methoxypolypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, (meth) acrylic acid, 2-acryloyloxyethyl phthalate, 2- (meth) acryloyl Oxyethyl hexahydrophthalate, 2- (meth) acryloylpropyl phthalate, (meth) acryloyloxyethyl succinate, 2-isocyanatoethyl (meth) acrylate, -(Meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyltrimethoxysilane, and 3- (meth) acryloyloxypropylmethyltriethoxysilane, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α -Acrylonitrile compounds such as trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, and vinylidene cyanide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide N, N-Emethyl (meth) acrylamide, N-methoxy (meth) acrylamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N N-ethoxy (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- ( Examples include acrylamide compounds such as 2-dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, and N, N-ethylenebis (meth) acrylamide. Among these, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meta) from the viewpoint of easy availability and ease of handling. ) Acrylate, lauryl (meth) acrylate, stearyl methacrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and its cation Modified with a oxidizer, diethylaminoethyl (meth) acrylate and a modified product with a cationizing agent thereof, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy Alkoxypolyalkylene glycol (meth) acrylates such as propylene glycol (meth) acrylate are preferred, and further methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl methacrylate, and cyclohexyl (meth) acrylate are particularly preferred.

Examples of polyepoxylates include bisphenol A diglycidyl ether, novolak type epoxy resins, trisphenol methane triglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, Trimethylolpropane triglycidyl ether, propylene glycol diglycidyl ether, 2,4-epoxycyclohexylmethyl-3,4-
Epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3 -Epoxycyclopentyl) ether, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), and polymers using these as monomers. Among these, bisphenol A diglycidyl ether, novolak-type epoxy resins, 2,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate due to availability 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, EHPE-3150, and bisphenol A diglycidyl Ether and novolac epoxy resins are particularly preferred.

  Examples of the polysiloxane include polydimethylsiloxane and derivatives having a structure for ensuring compatibility with polydimethylsiloxane, such as an alkyl group or a polyalkylene glycol chain.

  The resin composition (II) preferably contains a compound obtained by introducing an acryloyl group into these compounds from the viewpoints of hardness and scratch resistance. That is, it preferably contains polyolefin (meth) acrylate, polyester (meth) acrylate, polycarbonate (meth) acrylate, urethane (meth) acrylate, poly (meth) acryl acrylate, epoxy (meth) acrylate, and the like.

  Furthermore, it is preferable to contain polyurethane and urethane (meth) acrylate as the resin composition (II) from the viewpoint of availability, molecular design, and ease of synthesis, and urethane (meth) from the viewpoint of hardness and scratch resistance. It is preferable to contain an acrylate.

  Polyurethanes include alicyclic skeleton isocyanate compounds such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, aliphatic isocyanate compounds such as hexamethylene diisocyanate, aromatic isocyanate compounds such as tolylene diisocyanate and diphenylmethane diisocyanate, ) Butadiene diol, (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, 1,4- (poly) butanediol, 1,6- (poly) hexanediol, (poly) ester diol, ( One or more compounds such as poly) caprolactone-modified diol, (poly) carbonate diol, and (poly) spiroglycol are reacted, and the hydroxyl group is determined according to the reaction ratio. Or a compound synthesized so as to leave either of the isocyanate groups in the molecule, or a polyisocyanate having two or more isocyanate groups in one molecule with the polyurethane having the hydroxyl group left out of the aforementioned polyurethane. A cured product of a resin composition separately blended as a curing agent may be mentioned. In addition, a compound containing a urea bond obtained by reacting an amino group with an isocyanate group, a compound containing an allophanate bond generated by reacting an isocyanate group with a urethane bond, and an isocyanate group reacting with a urea bond In the present invention, a compound containing a burette bond that occurs and a compound containing an isocyanurate structure in which an isocyanate group is trimerized can also be used as polyurethane.

From the viewpoint of light resistance, aliphatic diisocyanates such as bis (isocyanate methyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and Aliphatic triisocyanates such as tris (isocyanatohexyl) isocyanurate are preferred, and isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate are more preferred.

  As the urethane (meth) acrylate, among the above-mentioned polyurethanes, those having an isocyanate group remained, the isocyanate group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate And a compound obtained by reacting a hydroxyl group of (meth) acrylate having a hydroxyl group, such as caprolactone-modified 2-hydroxyethyl acrylate and pentaerythritol triacrylate. In addition, a compound in which a hydroxyl group of (meth) acrylate having the same hydroxyl group as described above is reacted with a polyurethane that contains a urea bond, an allophanate bond, a burette bond, an isocyanurate structure and is synthesized so that an isocyanate group remains is also available. It can be illustrated.

  Among the polyurethanes and urethane (meth) acrylates described above, those having a high breaking elongation in a single film or a single cured film are particularly preferred in order to improve the (ball drop) impact resistance in the laminate of the present invention. The breaking elongation is preferably 10% or more, more preferably 20% or more, further preferably 30% or more, and most preferably 40% or more. Moreover, since the fall of the hardness of a coating film can be suppressed, 300% or less is preferable, 200% or less is more preferable, 150% or less is further more preferable, and 100% or less is the most preferable.

  Moreover, such urethane (meth) acrylate may use a commercial item, for example, U-108A, U-200AX, UA-511, U-412A, UA-4200, UA-4400, UA-340P, UA-2235PE, UA-160TM, UA-6100, U-108, UA-4000, UA-122P, UA-5201, UA-512, UA-W2A, UA-W2, UA-7000, UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd.) For example.

  The resin composition (II) is preferably a mixture of (meth) acrylate and urethane (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule from the viewpoints of hardness, scratch resistance, and falling ball impact resistance. Each may be used alone or in combination of two or more. Further, when the total (weight) of (meth) acrylate having one or more (meth) acryloyl groups in the molecule and urethane (meth) acrylate is 100 parts by weight, the content of urethane (meth) acrylate is usually 0. Although it is 1 part by weight or more, it is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, still more preferably 30 parts by weight or more, and most preferably 40 parts by weight or more because the falling ball impact resistance is good. . Further, it is usually 99.9 parts by weight or less, but 90 parts by weight or less is preferable, 80 parts by weight or less is more preferable, 70 parts by weight or less is further preferable, and 60 parts by weight because hardness and scratch resistance are improved. The part or less is most preferable.

<Photopolymerization initiator>
As the photopolymerization initiator contained in the resin composition (II) of the present invention, publicly known ones can be widely used. Preferably, α-hydroxyacetophenone (α-hydroxyphenyl ketone), α-aminoacetophenone, Alkylphenone type compounds such as benzyl ketals; acyl phosphine oxide type compounds; oxime ester compounds; oxyphenyl acetates; benzoin ethers; aromatic ketones (benzophenones); ketone / amine compounds; Derivatives and the like.

Specifically, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2,4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butan-1-one, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoylformic acid, methyl benzoylformate, Zoirugi ethyl are preferred. Two or more of these photopolymerization initiators can be used in combination as appropriate.

  Among these, 2-hydroxy-2-methylpropio is used as at least a part of the photopolymerization initiator because it is possible to minimize a decrease in curability, is easily available, and hardly causes coloring and the like. It is preferable to use α-hydroxyphenyl ketones such as phenone and 1-hydroxycyclohexyl phenyl ketone.

  In order to obtain a resin composition (II) having particularly good curability, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino- Α-aminophenyl ketones such as 1- (4-morpholinophenyl) -butan-1-one; benzophenones such as benzophenone, Michler's ketone, 2-chlorothioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone; benzoyl Benzoyl formic acids (esters) such as methyl formate, benzoyl formic acid, ethyl benzoyl formate; and oxime esters such as CGI 242 (manufactured by Ciba) and OXE01 (manufactured by Ciba) are preferred. Further, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzophenone, More preferably, methyl benzoylformate or the like is used, and 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butan-1-one and methyl benzoylformate are particularly preferred.

  When the total amount (total weight) of the components of the photocurable compound that reacts with the acrylic copolymer is 100 parts by weight, the photopolymerization initiator is 0.1 to 10 parts by weight, preferably 0.5. It is not less than 7 parts by weight and more preferably not less than 1 part by weight and not more than 6 parts by weight. If it is less than 0.1 parts by weight, the resulting resin composition (II) is inferior in curability, and if it is 10 parts by weight or more, the physical properties of the cured film may be lowered.

When the resin composition (II) of the present invention is irradiated with active energy rays to obtain a cured film, ultraviolet rays or soft X-rays are used as the active energy rays in the composition of the present invention. Such a photopolymerization initiator is preferably included. However, when an electron beam or a hard X-ray having a relatively high energy is used, the photopolymerization initiator may not be included.
The active energy ray-curable composition may further contain components other than the components described above. Such other components include, for example, colloidal silica, slipping or leveling agents, and solvents.

  For example, as the (meth) acrylate, an adduct of the trifunctional or higher functional (meth) acrylate and γ-mercaptopropyltrimethoxysilane, colloidal silica and / or silicate hydrolysis condensate; pentaerythritol triacrylate, dipentaerythritol Adducts of hydroxyl group-containing acrylates such as pentaacrylate and isocyanate propyltriethoxysilane, colloidal silica and / or silicate hydrolysis condensates may also be used.

As the colloidal silica, silica dispersed in a dispersion medium can be used. Examples of the dispersion medium include water, methanol, isopropanol, n-butanol, isobutanol, ethylene glycol, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone,
Examples thereof include methyl isobutyl ketone, dimethylacetamide, xylene and mixed solvents thereof.

  The volume average particle diameter of the silica is preferably 200 nm or less, more preferably 1 to 200 nm, and further preferably 5 to 50 nm, from the viewpoint of the transparency of the laminate and the uniformity of the coating film. preferable. The volume average particle diameter of the silica is obtained by photographing particles using a scanning electron microscope (JSM-7401F manufactured by JEOL Ltd.) and using image analysis software ImageProPlus (manufactured by Media Cybernetics) for 50 particles of this image. Can be measured.

  The content of the colloidal silica in the active energy ray-curable composition is 10 to 10 parts by weight, when the total amount of the polyfunctional (meth) acrylate and the urethane (meth) acrylate is 100 parts by mass as a solid content. It is preferable that it is 40 mass parts. In particular, the use of colloidal silica dispersed in an organic solvent is preferable because it exhibits high transparency when a coating film of an active energy ray-curable composition is formed. Typically, a solvent having a hydroxyl group, Alternatively, it is preferable to use an organosilica sol dispersed in a polar solvent having a ketone group.

  Examples of such colloidal silica include “IPA-ST” (IPA-dispersed organosilica sol, manufactured by Nissan Chemical Industries, Ltd.), “MEK-ST” (MEK-dispersed organosilica sol, manufactured by Nissan Chemical Industries, Ltd.), “ MIBK-ST "(MIBK-dispersed organosilica sol, manufactured by Nissan Chemical Industries, Ltd.) or the like, or a sol (for example, PGM-dispersed organosilica sol) obtained by replacing these with a solvent having another hydroxyl group as a raw material.

  The colloidal silica is preferably surface-modified colloidal silica from the viewpoints of transparency of the coating film, transparency of the laminate, weather resistance of the laminate, and water resistance of the laminate. Examples of such colloidal silica include colloidal silica surface-modified with a compound having a hydrolyzable silicon group.

  For the modification of colloidal silica, a compound having a hydrolyzable silicon group or a compound having a silicon group to which a hydroxyl group is bonded can be used. Each of these compounds may be one kind or two or more kinds. In a compound having a hydrolyzable silicon group, silanol groups are generated by hydrolysis, and these silanol groups react with and bind to silanol groups present on the surface of the colloidal silica to form surface-modified colloidal silica.

  Examples of the silicon group-containing compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and β- (meth) acryloyloxyethyltri. Methoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinyl orimethoxysilane, vinyltriethoxysilane, vinyl Methyldimethoxysilane, p-vinylphenyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimeth Shishiran, .gamma.-aminopropyltrimethoxysilane, .gamma. styryltrimethoxysilane, p- styryl trimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, and 3-mercaptopropyl trimethoxysilane.

  Alternatively, a modified silicon group-containing compound such as a derivative obtained by adding a polyfunctional (meth) acrylate to a silane having a mercapto group or a derivative obtained by adding a polyfunctional (meth) acrylate having a hydroxyl group to a silane having an isocyanate group is used. Also good.

  The surface modification of colloidal silica can be performed by reacting colloidal silica with a hydrolyzable silicon group-containing compound, catalyst, and water at 20 to 100 ° C. for 1 to 40 hours.

  Examples of the catalyst used in the surface modification reaction include inorganic acids such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid; formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, acrylic Acids, organic acids such as methacrylic acid; alkalis; aluminum acetylacetone, aluminum 2,2,6,6, -tetramethyl-3,5-heptanedionate, aluminum diisopropoxide ethyl acetoacetate, aluminum diisobutoxide ethyl aceto Acetate, butoxide borate, dibutyltin dilaurate, dibutyltin dioctate. The amount of these catalysts used is preferably 0.0001 to 5 parts by mass, and 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of colloidal silica and hydrolyzable silicon group-containing compound. It is more preferable. Moreover, it is preferable that it is 0.5-100 equivalent with respect to a hydrolysable silicon group, and, as for the quantity of the water in the said surface modification reaction, it is more preferable that it is 1-30 equivalent.

  The colloidal silica is preferably acidic colloidal silica among acidic or basic colloidal silica.

As the slipping agent or leveling agent, a slipping agent or leveling agent having a polydimethylsiloxane structure can be used. The content of the slipping agent or the leveling agent in the active energy ray hard / BR> SA composition is preferably 0 to 5 parts by mass from the viewpoint of transparency, coating appearance, adhesion, and hardness. The amount is more preferably 2 parts by mass, and still more preferably 0 to 1 part by mass.

  Examples of the slip agent include polydimethylsiloxane, a copolymer thereof, an acrylic polymer having a polydimethylsiloxane skeleton, a urethane polymer having a polydimethylsiloxane skeleton, and an acryloyl group or a methacryloyl group introduced into these, and active energy rays. The compound which provided the reactivity is mentioned.

  Examples of the leveling agent include polyether-modified polydimethylsiloxane and copolymers thereof, an acrylic polymer having a hydrophilic group such as an ether group and a hydroxyl group and having a polydimethylsiloxane skeleton, a hydrophilic group and a polydimethylsiloxane skeleton. And urethane compounds having acryloyl group or methacryloyl group introduced therein to give active energy ray reactivity.

  The content of the solvent in the active energy ray-curable composition can be appropriately determined from the viewpoint of handling the active energy ray-curable composition. One type or two or more types of solvents may be used. Examples of such solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol , Ethers such as 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, Ether esters such as 2-butoxyethyl acetate and 3-methoxypropyl acetate; aromatic hydrocarbons such as toluene and xylene; ethyl acetate and vinegar Propyl, esters such as ethyl acetate and butyl acetate; and the like.

  Moreover, when the base material described later includes a functional group that can be cured by light or heat, it may be more preferable to cure the base material by irradiation with active energy rays or heating. The substrate may be in the form of a molded article (article), or another layer may be interposed between the substrate and the application surface.

  The application method to the resin composition (II) of the present invention is not particularly limited, but spin coating, dip coating, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, air knife coating and the like are preferable. Can be mentioned.

  After the coating film is formed on the substrate by the above coating method, the cured film is obtained by such means as removing volatile components by heat drying and then irradiating the coating film with active energy rays.

  In addition, the layer which consists of resin composition (II) like this cured film is a 2nd layer in this invention. The resin composition (II) in the second layer is preferably a layer obtained by curing the resin composition (II) as in the cured film.

  Here, the thickness of the second layer is preferably 2 μm or more from the viewpoint of alleviating the impact caused by the falling ball, more preferably 5 μm or more, and most preferably 8 μm or more. Moreover, it is preferable that it is 100 micrometers or less from the point that importance is attached to transparency, it is more preferable that it is 50 micrometers or less, and it is most preferable that it is 25 micrometers or less.

  When using an active energy ray when obtaining a cured film, the irradiation method includes ultraviolet rays emitted from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like. Examples thereof include active energy rays (electron beams, EB) such as electron beams, α rays, β rays, and γ rays that are usually extracted from a particle accelerator of 20 to 2000 kV. A cured film cured with such active energy rays is particularly preferable because of its excellent balance between productivity and physical properties.

The haze can be calculated from the following formula in accordance with JIS K7136.
H (%) = (Td / Tt) × 100
H: Haze (cloudiness value) (%)
Td: Diffuse light transmittance (%)
Tt: Total light transmittance (%)
In addition, the measurement of haze can be measured, for example using a turbidimeter (made by Nippon Denshoku Industries Co., Ltd.).

4). Base material layer The base material layer in this invention is a layer which consists of a molded object containing polymethyl methacrylate. Here, as the molded product containing polymethyl methacrylate, the form and shape can be arbitrarily determined, and examples thereof include a film, a sheet, or a molded product, and more specifically, polymethacrylic acid. Examples thereof include molded products such as films and sheets containing methyl (PMMA). As the methacrylic resin constituting the base material, a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and another copolymerizable comonomer is applied. Examples of the copolymerizable comonomer include acrylic acid esters such as methyl acrylate and butyl acrylate, aromatic vinyl compounds such as styrene, vinylcyan compounds such as acrylonitrile, and the like. Moreover, what gave the characteristics, such as impact resistance, to the methacryl resin, or the commercial item manufactured by the well-known method can be used.

The base material layer in the present invention contains polymethyl methacrylate (PMMA), but may contain other resins. For example, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate, or polycarbonate, special polycarbonate (for example, “Pure Ace” (registered trademark) manufactured by Teijin), triacetyl cellulose, acrylonitrile butadiene styrene copolymer resin (ABS resin) , Modified polyolefin resin, hydrogenated polystyrene resin, cycloolefin-based transparent resin (for example, “Aton” (registered trademark) manufactured by JSR, “Zeonor” (registered trademark) manufactured by Nippon Zeon, etc.) and the like.

  As a base material layer containing other polymethyl methacrylate (PMMA), for example, a thermosetting or photocurable transparent resin (for example, a transparent epoxy resin, a transparent urethane resin, a thermosetting acrylic resin, photocuring) Curable acrylic resins, various thermosetting organic / inorganic hybrid resins, and photocurable various organic / inorganic hybrid resins).

  Among these, when used in optical article applications, that is, when a transparent film for optics, an optical sheet, and an optical plate are used as a transparent substrate, the substrate is coated, melt-extruded, solvent cast method It is desirable that it is a transparent resin molding formed of any of the above.

5. Rolled film laminate The laminate of the present invention is formed by, for example, curing the active energy ray-curable resin composition (I) of the present invention on a base material layer to form a first layer, and It can be manufactured by forming a second layer made of the resin composition (II) on the surface and winding it into a roll.

<Reason why the present invention is effective>
The reason why the present invention is effective is inferred as follows.
That is, in the laminate of the present invention, in the first layer formed by curing the active energy ray-curable resin composition (I), the acrylic copolymer (α) contains a high molecular weight polysiloxane structure. Therefore, good slipperiness is given to the coating surface. Further, since the acrylic copolymer (α) contains an active energy ray-curable crosslinking group, the surface after high pencil hardness and surface performance durability (after wiping with a solvent and resistance to steel wool scratching) Give a high surface). Moreover, although high hardness is ensured by using an acrylic base material, about impact resistance, the 2nd layer which consists of resin composition (II) whose acrylic equivalent formed in the back surface of a base material is 100 or more Thus, it is presumed that the deformation of the base material at the time of falling ball impact can be eased and the impact resistance of the laminate can be improved.

<Display device>
The present invention further relates to a display device including the laminate of the present invention and a light source. In this case, it is desirable that the base material included in the laminate is a translucent base material. Moreover, it is preferable that a light source is arrange | positioned on the back surface of a base material, ie, the surface on the opposite side to the fine uneven | corrugated layer of a base material, and irradiates light toward a base material there.

  In addition, although the thickness of a translucent base material can be selected timely according to a use, generally it is used at about 10-2000 micrometers.

  The light source that can be combined with the laminate is not particularly limited as long as it can emit light. Examples of the light source include a light emitting diode, a cold cathode tube, a hot cathode tube, and an EL. . The display device of the present invention may further include a retardation plate, a brightness enhancement film, a light guide plate, a light diffusing plate, a light diffusing sheet, a light collecting sheet, a reflecting plate, and the like. Further, a liquid crystal module, a backlight unit, or the like may be used as the light source.

As the light transmissive member, various light transmissive plates, light transmissive films, and the like can be used. For example, tempered glass, acrylic plate, triacetyl cellulose plate, polyethylene terephthalate plate, diacetylene cellulose plate, acetate butyrate cellulose plate, polyethersulfone plate, polyurethane plate, polyester plate, polycarbonate plate, polysulfone plate , Polyether plate, polymethylpentene plate, polyether ketone plate, (meth) acrylonitrile plate and the like. Examples of the light transmissive film include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, Examples include a polyester film, a polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyether ketone film, a (meth) acrylonitrile film, and a cycloolefin polymer (COP) film. As the light transmissive member, an acrylic plate, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a cycloolefin polymer (COP) film, and tempered glass are more preferably used. In addition, although the thickness of a light transmissive member can be selected timely according to a use, it is generally used at about 25-1000 micrometers.

In the case of a liquid crystal module, the light source is included, and a polarizing plate / liquid crystal cell / polarizing plate is arranged in this order on the light source. The liquid crystal cell is not particularly limited as long as it is generally used in a liquid crystal display device. For example, TN (Twisted Ne
magic) type liquid crystal cell, STN (Super Twisted Nematic) type liquid crystal cell, HAN (Hybrid Alignment Nematic) type liquid crystal cell, IPS (In Plane Switching) type liquid crystal cell, VA (Vertical Ali)
and a liquid crystal cell such as a multiple vertical alignment liquid crystal cell and an OCB (optically compensated bend) liquid crystal cell.

  The display device of the present invention is applied to a flat panel display such as a liquid crystal display device (liquid crystal display), LED (light emitting diode display), ELD (electroluminescence display), VFD (fluorescent display), PDP (plasma display panel), etc. can do. Moreover, since the active energy ray-curable composition of the present invention that can be used for the production of the display device of the present invention has weather resistance in addition to anti-blocking properties, the display device can be used outdoors. Is possible. For example, it can be installed outdoors or semi-outdoors as a panel display for the purpose of posting information such as advertisements.

  In addition, the outdoor or semi-outdoor use of the display device of the present invention includes a touch panel, which has a mechanism for operating equipment by holding down the display on the screen, for example, bank ATM, vending Machines, personal digital assistants (PDAs), copiers, facsimiles, game machines, information displays installed in facilities such as museums and department stores, car navigation systems, multimedia stations (multifunctional terminals installed in convenience stores), This is useful in mobile phones, railway vehicle monitoring devices, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “parts” means “parts by weight”.

The physical properties of the laminates obtained in the following examples and the like were evaluated for the first layer by the following method.
(1) Steel wool wear resistance (SW resistance):
The surface of the cured film was rubbed 400 times with # 0000 steel wool and a load of 160 g / cm ² , and the degree of damage of the cured film after the test was evaluated as follows.
○: 0 to 100 scratches ×: More than 100 scratches or whitening (2) Pencil hardness:
For the cured film, a JIS compliant pencil hardness meter (manufactured by Dazai Equipment Co., Ltd.) was used, and JIS K-5400
The measurement was performed based on the above conditions, and the evaluation was made with the hardest pencil count without scratches.
(3) Impact resistance:
Impact resistance was evaluated by a hard ball drop test in which a 50 g steel ball was naturally dropped from a height of 50 cm toward a center part on a test piece having a width of 12.6 cm, a length of 22.4 cm, and a thickness of 0.85 mm. In addition, as evaluation, (circle) shows that it was not cracked and x shows that it broke.
(4) Haze:
The haze value was measured with a haze meter ("HAZE METER HM-65W" manufactured by Murakami Color Research Laboratory) in accordance with JIS K-7136.
In addition, 0.3% or less was set as the pass.

<Synthesis Example 1>
A reactor equipped with a stirrer, a reflux condenser, and a thermometer has a weight average molecular weight of 10,000, one-end methacryloyl group-substituted polydimethylsiloxane (“Silaplane (registered trademark) FM-0725” manufactured by JNC), 20 weight. Parts, 30 parts by weight of glycidyl methacrylate (Mitsubishi Rayon “Acryester G”), 40 parts by weight of methyl methacrylate (Mitsubishi Rayon “Acryester M”), stearyl methacrylate (Mitsubishi Rayon “Acryester S”) 10 Part by weight and 150 parts by weight of methyl isobutyl ketone (MIBK) were charged. After the start of stirring, the system was purged with nitrogen, and the temperature was raised to 55 ° C. 0.06 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), 0.09 part by weight of 1-dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.) Then, the system was heated to 65 ° C. and stirred for 3 hours, and then 0.06 part by weight of V-65 was further added and stirred at 65 ° C. for 3 hours. The temperature inside the system is raised to 100 ° C. and stirred for 30 minutes, 68.8 parts by weight of MIBK is added, and the temperature inside the system is again raised to 100 ° C. After adding 0.05 parts by weight of p-methoxyphenol (manufactured by Wako Pure Chemical Industries) and 2.3 parts by weight of triphenylphosphine (manufactured by Wako Pure Chemical Industries), acrylic acid (manufactured by Mitsubishi Chemical Corporation) 15.5 Part by weight was added, the temperature was raised to 110 ° C., and the mixture was stirred for 6 hours. After cooling, 253 parts of MIBK was added to obtain a solution of copolymer (F1). The composition of the reaction solution was (F1) / MIBK = 20/80 (weight ratio).

<Formulation example I>
The solution of the copolymer (F1) obtained in Synthesis Example 1, the curable monomer DPHA, and Aronix M313 were blended at a solid content ratio of 2:86:12, and 1-hydroxy was used as a photopolymerization initiator. 4.0 parts by weight of cyclohexyl phenyl ketone (“Irgacure (registered trademark) 184” manufactured by BASF), 0.5% of α-aminophenyl ketone photopolymerization initiator (“Irgacure (registered trademark) 907” manufactured by BASF) After the addition of parts by weight, the mixture was diluted with a solution of propylene glycol monomethyl ether / methyl isobutyl ketone = 1/1 (weight ratio) so that the solid content was 40%, to obtain Formulation Liquid I. The acrylic equivalent of this liquid was 115 g / mol.

<Composition example II>
3. A curable monomer DPHA and a urethane acrylate UA122P are blended so as to have a solid content ratio of 40:60, and 1-hydroxycyclohexyl phenyl ketone (“Irgacure (registered trademark) 184” manufactured by BASF) is used as a photopolymerization initiator. After addition of 5 parts by weight, the mixture was diluted with a solution of propylene glycol monomethyl ether / methyl isobutyl ketone = 1/1 (weight ratio) so that the solid content would be 40%, to obtain Formulation Liquid II. The acrylic equivalent of this liquid was 370 g / mol.

<Formulation example III>
A polyester resin, Teslac (registered trademark) 2488, and a polyisocyanate curing agent, Mytec (registered trademark) NY730A-T, were blended in a solid content ratio of 53:47, and neostan (registered trademark) as a tin octylate catalyst. ) After adding 0.1 part by weight of U810, it was diluted with a methyl ethyl ketone solution to a solid content of 40% to obtain a polyurethane resin compounded liquid III. Since this liquid does not contain a compound having an acryloyl group, the acrylic equivalent is infinite.

<Example 1>
The coating liquid I obtained on a 0.65 mm thick PMMA sheet (“Acrylite” manufactured by Mitsubishi Rayon Co., Ltd.) on one side and the liquid II on the other side was 10 μm. The coating was applied by a bar coater and heated at 80 ° C. for 2 minutes to dry the coating film. Next, using a high-pressure mercury lamp with an output of 120 W / cm, irradiation with ultraviolet rays of 450 mW / cm ² and 500 mJ / cm ² was performed to obtain a laminated body 1 covered with a cured film.
When the laminate 1 was evaluated by the above evaluation method, the steel wool resistance (abrasion resistance) was ○, the pencil hardness was 9H, the impact resistance was ○, and the haze was 0.1%.

<Comparative Example 1>
The laminate 2 was a PMMA sheet (“Acrylite” manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 0.65 mm without a hard coat layer.
When the laminate 2 was evaluated by the above evaluation method, the steel wool resistance (abrasion resistance) was x, the pencil hardness was 3H, the impact resistance was x, and the haze was 0.1%.

<Comparative example 2>
The obtained compounded liquid I was applied on a 0.65 mm thick PMMA sheet (“Acrylite” manufactured by Mitsubishi Rayon Co., Ltd.) with a bar coater so that the coating film after drying was 10 μm, and then at 80 ° C. for 2 minutes. The coating was dried by heating. Next, using a high-pressure mercury lamp with an output of 120 W / cm, irradiation with 450 mW / cm ² and 500 mJ / cm ² of ultraviolet rays was performed to obtain a laminate 3 coated with a cured film.
When the laminate 3 was evaluated by the above evaluation method, the steel wool resistance (abrasion resistance) was ○, the pencil hardness was 9H, the impact resistance was ×, and the haze was 0.1%.

<Comparative Example 3>
The compound liquid I obtained on a 0.65 mm thick PMMA sheet (“Acrylite” manufactured by Mitsubishi Rayon Co., Ltd.) was applied on both sides with a bar coater so that the coating film after drying was 10 μm. The coating film was dried by heating at 0 ° C. for 2 minutes. Next, using a high-pressure mercury lamp with an output of 120 W / cm, irradiation with 450 mW / cm ² and 500 mJ / cm ² of ultraviolet rays was performed to obtain a laminate 4 coated with a cured film.
When the laminate 4 was evaluated by the above evaluation method, the steel wool resistance (abrasion resistance) was ◯, the pencil hardness was 9H, the impact resistance was x, and the haze was 0.1%.

<Comparative Example 4>
The compounded liquid I obtained on a PMMA sheet having a thickness of 0.65 mm (“Acrylite” manufactured by Mitsubishi Rayon Co., Ltd.) was applied with a bar coater so that the coating film after drying was 20 μm. The coating was dried by heating for a minute. Next, using a high-pressure mercury lamp with an output of 120 W / cm, irradiation with 450 mW / cm ² and 500 mJ / cm ² of ultraviolet rays was performed to obtain a laminate 5 coated with a cured film.
When the laminate 5 was evaluated by the above evaluation method, the steel wool resistance (abrasion resistance) was ○, the pencil hardness was 9H, the impact resistance was ×, and the haze was 0.1%.

<Example 2>
0.65 mm thick acrylic resin substrate: PMMA sheet (“Acrylite” manufactured by Mitsubishi Rayon Co., Ltd.) One surface of the compounded liquid III obtained with a bar coater so that the coating film after drying becomes 10 μm It was applied and heated at 80 ° C. for 10 minutes to dry the coating, and a second layer was formed on one side. Next, the coating liquid I is applied to the other surface with a bar coater so that the coating film after drying is 10 μm, heated at 80 ° C. for 1.5 minutes, dried, and output 120 W / cm A high pressure mercury lamp was used, irradiated with ultraviolet rays of 450 mW / cm ² and 500 mJ / cm ² to coat the cured film, and a first layer was formed on the acrylic resin layer, whereby a laminate 6 was obtained.
When the laminate 6 was evaluated by the above evaluation method, the steel wool resistance (abrasion resistance) was ◯, the pencil hardness was 9H, the impact resistance was ◯, and the haze was 0.2%.
The evaluation results for each laminate are summarized in Table 1.

PMMA (polymethyl methacrylate): Acrylite, DPHA (dipentaerythritol hexaacrylate) manufactured by Mitsubishi Rayon Co., Ltd .: KAYARAD (registered trademark)
DPHA Nippon Kayaku Co., Ltd. UA122P: UA122P, Shin-Nakamura Chemical Co., Ltd. M313: Aronix M313, Toagosei Co., Ltd. Teslac (registered trademark) 2488: Hitachi Chemical Co., Ltd. Mytec (registered trademark) NY730A-T: Mitsubishi Chemical Neostan (registered trademark) U810, manufactured by Nitto Kasei Co., Ltd. * SW resistance, pencil hardness, impact resistance, and haze evaluation are all preferably results of ◯ or more.

Comparing the examples and the comparative examples, the comparative example 1 is only the base material, and the SW resistance, pencil hardness and impact resistance are insufficient.
Since Comparative Example 2 does not have the second layer, the impact resistance is not satisfactorily improved.
In Comparative Example 3, the active energy ray resin composition (I) is used for the second layer, the active energy ray resin composition (II) is not used, and the impact resistance is satisfactorily improved. Absent.
In Comparative Example 4, the second layer was not provided and the first layer was thickened, but the impact resistance was not improved satisfactorily.

Claims (8)

A laminate having at least the following base material layer, the following first layer, and the following second layer.
Base material layer: Molding layer containing polymethyl methacrylate First layer: At least an acrylic copolymer (α) and an active energy ray-curable compound are contained, and the acrylic copolymer (α) is as follows: A layer copolymer (β) formed by curing the active energy ray-curable resin composition (I) obtained by adding the compound (γ) to the copolymer (β) of Copolymer compound (γ) of silicone monomer (A) represented by (I), (meth) acrylate (B) having an epoxy group and other copolymerizable monomer (C): carboxyl group and 1 in the molecule Compound having at least one (meth) acryloyl group

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, R ³ and R ⁴ are each a methyl group or a phenyl group, n is an integer of 10 to 100, and R ³ And R ⁴ may be the same as or different from each other, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms.
Second layer: a layer comprising a resin composition (II) containing a resin having an acrylic equivalent of 100 or more   The laminate according to claim 1, wherein the active energy ray-curable resin composition (I) contains 0.05 to 10% by weight of the acrylic copolymer (α).   The copolymer (β) contains (meth) acrylate selected from at least one linear or branched alkyl (meth) acrylate having 4 to 22 carbon atoms as the copolymerizable monomer (C). Or the laminated body of 2.   The laminate according to any one of claims 1 to 3, wherein the thickness of the first layer is 2 µm or more and 100 µm or less.   The laminated body as described in any one of Claims 1-4 in which the said resin composition (II) contains the (meth) acrylate which has a 1 or more (meth) acryloyl group in a molecule | numerator.   When the resin composition (II) is 100 parts by weight of the total (weight) of (meth) acrylate and urethane (meth) acrylate having one or more (meth) acryloyl groups in the molecule, urethane (meth) The laminated body as described in any one of Claims 1-5 containing 0.1 weight%-99.9 weight% of acrylates.   The laminated body according to any one of claims 1 to 6, wherein the thickness of the second layer is 2 µm or more and 100 µm or less.   The laminate according to any one of claims 1 to 7, wherein the base material layer has a thickness of 0.01 mm or more and 2 mm or less.