JP6511811B2 - Laminate - Google Patents

Description

  The present invention relates to a laminate excellent in scratch resistance, hardness, crack resistance, impact resistance, low curlability, transparency and the like. The present invention also relates to a display cover made of this laminate.

  Plastic products, such as polycarbonate (PC) resin; polymethyl methacrylate (PMMA) resin; polyethylene terephthalate (PET) resin; polybutylene terephthalate (PBT) resin, acrylonitrile-butadiene-styrene (ABS) resin, styrene-methyl methacrylate (MS) Resins, styrene resins such as acrylonitrile-styrene (AS) resins; vinyl chloride resins; various resin substrates such as cellulose acetate resins such as triacetyl cellulose are excellent in lightness, easy processability, impact resistance, etc. Therefore, they are used in various applications such as containers, instrument panels, packaging materials, various housing materials, optical disk substrates, plastic lenses, and substrates of display devices such as liquid crystal displays and plasma displays.

  In industrial electronic devices having displays such as mobile phones and PHS (Personal Handy-phone System), with the progress of diversification of design, thickness reduction, and increase in area, the thickness and weight of the display cover itself are also reduced. There is a growing demand for cost reduction and so on. Although a glass substrate is generally used as the display cover, the thickness of the display itself can be maintained at a certain thickness so that the substrate itself can stand by itself in response to demands for thinning, weight reduction and cost reduction of the display cover itself. Various uses of PMMA resin sheet, PC resin sheet, etc. which have On the other hand, since these plastic substrates are inferior to scratch resistance and hardness compared with the glass substrates conventionally used, the resin sheet which coat | covered various hard-coat materials is examined.

  Heretofore, the following technologies have been disclosed mainly as laminates for display covers such as mobile phones and PHSs. For example, Patent Document 1 discloses that the scratch resistance of the surface is improved by a laminate in which a PMMA substrate is coated with a hard coating material containing urethane acrylate and silicone oil. Further, Patent Document 2 discloses that a scratch resistance of the surface is improved by a laminate in which a PMMA substrate is coated with a hard coat material containing a polyfunctional acrylate. Further, in Patent Document 3, the laminate is obtained by covering a PMMA base material having a weight average molecular weight of 100,000 or more and a glass transition temperature of 100 ° C. or more on a hard coat material containing polyfunctional acrylate and silicone oil. It has been disclosed to improve gender. Furthermore, in Patent Document 4, impact resistance, curling property, and the like are improved by a laminate obtained by coating a hard coat material containing an impact resistant PMMA substrate with a bifunctional urethane acrylate and a polyfunctional acrylate and / or a polyfunctional urethane acrylate. Is disclosed.

Unexamined-Japanese-Patent No. 2004-299199 JP, 2008-006811, A JP, 2008-049697, A JP 2008-100422 A

According to the detailed study of the present inventors, it has been found that the techniques as disclosed in the above-mentioned Patent Documents 1 to 4 have the following problems.
All of these conventional techniques are mainly directed to display covers for mobile phones and PHSs, and are required for the touch panels such as smartphones and tablets that have become widespread in recent years, such as impact resistance, scratch resistance, hardness, etc. The function is insufficient for the characteristic. That is, the display cover in a touch panel such as a smartphone or a tablet is not only required to have sufficient shock resistance per se, but a finger sliding motion (flip) is frequently performed in operation. Conventional display covers for cellular phones and PHS are insufficient in scratch resistance, hardness and the like, and their functions are insufficient for these display covers.

  The present inventors repeated studies in view of the problems of the above-mentioned prior art, and in order to enhance the hardness while maintaining the impact resistance and the scratch resistance, the scratch resistance and the hardness to a high degree with respect to the PMMA substrate etc. It was considered to apply a thick coating of a hard coating material consisting of a specific silicone compound and an active energy ray curable compound capable of imparting Was found to cause cracks in the

  The present invention aims to solve the various problems as mentioned above. That is, an object of the present invention is to provide a laminate excellent in scratch resistance, hardness, impact resistance, crack resistance, impact resistance, low curlability, transparency and the like, and a display cover made of the laminate. It is.

  As a result of intensive investigations by the present inventors to solve the above problems, a laminate having a specific layer configuration on a base material layer having a specific type and thickness has scratch resistance, hardness, impact resistance, and crack resistance. And excellent in impact resistance, low curling property, transparency and the like. That is, the gist of the present invention resides in the following [1] to [13].

[1] The following layer (A) and the following layer (B) are provided in this order from the base layer side on at least the following base layer and one side of the base layer, and the thickness of the base layer is Laminate which is 0.3-30 mm.
Base layer: Layer layer consisting of polymethyl methacrylate (A): Curable composition (α) containing at least a compound having an acryloyl group and having an acrylic equivalent of 100 g / mol or more and / or a cured product thereof (with the proviso that Layer (B) consisting of a curable composition (β) and / or a cured product thereof (B): A silicone-containing (meth) acrylate represented by the following formula (1) and a (meth) acrylate having an epoxy group A curable composition (β) comprising an acrylic copolymer obtained by reacting a compound having a carboxyl group and an acryloyl group with a copolymer obtained by copolymerizing with an acrylic resin and an active energy ray-curable compound And / or a layer comprising the cured product

(In the above formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ are each independently a methyl group or a phenyl group , R ⁵ is an alkyl group having 1 to 12 carbon atoms, n is an average value, and is a number of 10 to 100.)

[2] The laminate according to [1], having the following layer (C) on the other surface of the base material layer.
Layer (C): A layer comprising a curable composition (γ) having an acrylic equivalent of 100 g / mol or more and / or a cured product thereof

[3] The laminate according to [1] or [2], wherein the curable composition (α) contains silica modified with a compound having a multifunctional (meth) acrylate and / or an acryloyl group.

[4] The curable composition (β) contains the acrylic copolymer in an amount of 0.05 to 10% by weight based on the total amount of the acrylic copolymer and the active energy ray-curable compound. The laminated body in any one of 1] thru | or [3].

[5] [1] to [4], wherein the copolymer contained in the curable composition (β) is further obtained by copolymerizing an alkyl (meth) acrylate having an alkyl group having 4 to 22 carbon atoms. ] The laminated body in any one of.

[6] The laminate according to any one of [2] to [5], wherein the curable composition (γ) contains silica modified with a compound having a polyfunctional (meth) acrylate and / or an acryloyl group. .

[7] The laminate according to any one of [2] to [6], wherein the curable composition (γ) contains a polyurethane.

[8] The laminate according to any one of [1] to [7], wherein the thickness of the layer (B) is 2 to 100 μm.

[9] The laminate according to any one of [2] to [8], wherein the thickness of the layer (C) is 2 to 100 μm or less.

[10] The laminate according to any one of [1] to [9], wherein the base material layer is composed of two layers of at least a layer composed of polymethyl methacrylate and a layer composed of polycarbonate.

[11] The base material layer is composed of at least a layer consisting of polymethyl methacrylate and a layer consisting of polycarbonate, and the layer consisting of polymethyl methacrylate is in contact with the layer (A) The laminate according to any one of [2] to [10], wherein a layer comprising the polycarbonate is in contact with the layer (C).

[12] A display cover comprising the laminate according to any one of [1] to [11].

[13] A display cover comprising the laminate according to [2], [6], [7], [9] or [11], having a layer (B) side on the front side, C) Display body cover having the back side.

  The laminate of the present invention is excellent in scratch resistance, hardness, impact resistance, crack resistance, impact resistance, low curling property, transparency and the like. Therefore, the laminate of the present invention is a component for an optical display such as a touch panel, a liquid crystal television, etc .; an automobile related component such as a lamp related article, a window related article (rear window, side window, skylight etc.); It can be suitably used for the surface cover of a wide range of articles such as lifestyle-related articles such as decorative boards and furniture. Among these, it can be particularly suitably used as a surface cover for components for optical displays such as touch panels and liquid crystal televisions, that is, as a display cover.

  The embodiment of the present invention will be described in detail below, but the following description is an example of the embodiment of the present invention, and the present invention is limited to the following contents unless the gist is exceeded. is not. In addition, when using the expression "-" in this specification, it shall use as an expression containing the numerical value or physical-property value before and behind that. In the present invention, when the expression "(meth) acrylic" is used, it means one or both of "acrylic" and "methacrylic". The same applies to “(meth) acrylate” and “(meth) acryloyl”.

[Laminate]
The laminate of the present invention comprises at least the following base layer, and the following layer (A) and the following layer (B) in this order from the base layer side on one side of the base layer, the base The thickness of the layer is 0.3 to 30 mm.
Base layer: Layer layer consisting of polymethyl methacrylate (A): Curable composition (α) containing at least a compound having an acryloyl group and having an acrylic equivalent of 100 g / mol or more and / or a cured product thereof (with the proviso that Layer (B) consisting of a curable composition (β) and / or a cured product thereof (B): A silicone-containing (meth) acrylate represented by the following formula (1) and a (meth) acrylate having an epoxy group And a copolymer obtained by reacting a compound having a carboxyl group and an acryloyl group with a copolymer obtained by copolymerizing a copolymer and a curable composition (β) containing an active energy ray-curable compound and / or Or a layer comprising the cured product

(In the above formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ are each independently a methyl group or a phenyl group , R ⁵ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 10 to 100.)

  In the present invention, the “acrylic equivalent” in the curable composition (α), the curable composition (β) described later, and the curable composition (γ) described later are the acryloyl groups contained in these compositions. It is a value obtained by dividing the molecular weight (g / mol) of the compound having a group by the number of acryloyl groups present in one molecule of the compound, and in the case of a composition containing two or more compounds having an acryloyl group It is defined as the sum of the value obtained by multiplying the weight ratio by the acrylic equivalent of each compound. In addition, it shall not consider about the compound which does not have an acryloyl group. Moreover, the methacryloyl group is also included in the "acryloyl group".

[Base layer]
The base material layer used in the laminate of the present invention is a layer made of polymethyl methacrylate. In the present invention, "polymethyl methacrylate" of the base material layer means a base material of an acrylic polymer having at least methyl methacrylate as a constitutional unit, and "polymethyl methacrylate layer" It is used in the meaning including what laminated | stacked the layer which consists of a polymethylmethacrylate base material layer and another resin base material.

  Other resin base materials that can be used for the base layer include, for example, polyethylene terephthalate resin (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, acrylonitrile-butadiene-styrene (ABS resin), modified polyolefin, hydrogenation Polystyrene, cycloolefin resin, etc. are mentioned. Among these, polycarbonate is preferable from the viewpoint of imparting impact resistance to the laminate. When the base material layer according to the present invention has a layer laminated structure of a base material layer made of polymethyl methacrylate and a base material layer made of polycarbonate, the layer (A) described later is a base material layer made of polymethyl methacrylate. The layer (C) described later is preferably provided in contact with the substrate layer made of polycarbonate.

  In the laminate of the present invention, the total thickness of the substrate layer is 0.3 to 30 mm. In order for the laminate of the present invention to be self-supporting, the total thickness of the substrate layer needs to be 0.3 mm or more. From this viewpoint, the total thickness of the base material layer is preferably 0.4 mm or more. Moreover, in order to use for a display body etc. in thickness reduction and weight reduction, it is necessary for the total thickness of a base material layer to be 2.0 mm or less. From this viewpoint, the total thickness of the substrate layer is preferably 1.8 mm or less.

  The thickness of the polymethyl methacrylate substrate layer in the substrate layer used in the present invention is preferably 30 μm or more. On the other hand, the thickness of the polymethyl methacrylate base layer is preferably 1.2 mm or less from the viewpoint of hardness, and more preferably 1.0 mm or less.

[Layer (A)]
Layer (A) is a layer comprising at least a compound having an acryloyl group, and a curable composition (α) having an acrylic equivalent of 100 g / mol or more and / or a cured product thereof. Here, the curable composition (α) is used in the meaning excluding those corresponding to the curable composition (β) described later. The upper limit of the acrylic equivalent of the curable composition (α) is not particularly limited, but is usually 10,000 g / mol or less, preferably 6,000 g / mol or less, and more preferably 3,000 g / mol or less It is more preferably 2,000 g / mol or less, particularly preferably 1,000 or less. Moreover, when the layer (A) is hardened as the acrylic equivalent of a curable composition ((alpha)) is 100 g / mol or more, it can prevent that a crack is generated.

(Compound having an acryloyl group)
Examples of the compound having an acryloyl group include monofunctional (meth) acrylates and derivatives thereof, polyfunctional (meth) acrylates and derivatives thereof, and silica whose surface is modified with a compound having an acryloyl group. Among these, from the viewpoint of increasing the hardness of the layer (A), it is preferable to include at least one of the group consisting of multi-functional (meth) acrylates and derivatives thereof and silica particles whose surface is modified with a compound having acryloyl group. .

  Examples of monofunctional (meth) acrylates and derivatives thereof include 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 ( Meta) acrylate, n-tridecyl (meth) acrylate, stearyl (meth) acrylate, 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 its modified product with cationizing agent, diethylaminoethyl (meth) acrylate and its cationization Polyalkyleneglycol (meth) acrylates such as cyanoethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenol Propyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2 -(Meth) acryloyl propyl phthalate, (meth) acryloyl oxyethyl succinate, 2-isocyanate ethyl (meth) acrylate etc. are mentioned. These may be used alone or in combination of two or more.

  As polyfunctional (meth) acrylates and polyfunctional (meth) acrylate derivatives, for example, pentaerythritol triacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane Polyfunctional acrylates such as triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate adduct to succinic anhydride, dipentaerythritol pentaacrylate adduct to succinic anhydride; side chains or side chains and terminal acryloyl groups Polyester (meth) acrylates such as polyester oligomers (specifically, M8030 and M7100 manufactured by Toagosei Co., Ltd.) Isocyanurate of isophorone diisocyanate (IPDI), reaction product of polytetramethylene glycol (PTMG) and hydroxyethyl acrylate (HEA), and pentaerythritol triacrylate to isocyanate product of hexamethylene diisocyanate (HDI) and PTMG reactant Reactive substances of the following: Polyfunctional urethane (meth) acrylates such as polycarbonates; Polyesters (meth) acrylates having a carbonate bond such as reactive substances of oligoesters and pentaerythritol triacrylates using polycarbonate diols; Reactive substances of IPDI and polycarbonate diols And polyurethane (meth) acrylates having a carbonate bond such as a reactant of HEA; acrylic acid adduct of bisphenol A (specifically, Shin-Nakamura Chemical Co., Ltd. EA-1025) and the like, polyepoxy (meth) acrylates such as triethoxyisocyanuric acid diacrylate, triethoxyisocyanuric acid triacrylate (specifically, Tolonago Ltd. Alonics M315, M313) and the like. Triethoxy (meth) acrylates; modified products of these alkylene oxides; modified products of these polycaprolactones. These may be used alone or in combination of two or more.

  Among these, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane from the viewpoint of viscosity, curability and hardness of the surface of the obtained cured product. Particularly preferred are tetraacrylate, dipentaerythritol triacrylate; modified alkylene oxide thereof; and modified caprolactone thereof.

  The silica particle whose surface is modified with a compound having an acryloyl group can be produced, for example, by subjecting a silica particle dispersed in a solvent and a silane compound having an acryloyl group to a hydrolytic condensation reaction. The silica particle whose surface is modified with a compound having an acryloyl group can be produced, for example, by the method described in JP-A-2006-249322. More specifically, the compound has an acryloyl group on the surface. In the modified silica particles, first, a silane compound having an acryloyl group is added to silica particles in which an organic solvent is used as a dispersion medium, water and aluminum acetylacetone are further added as a hydrolysis catalyst, and water is added while stirring under heating. It can be obtained by advancing the decomposition reaction.

  Examples of silica particles dispersed in a solvent include methanol, ethanol, propanol, butanol, isopropyl alcohol, ethylene glycol, xylene, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono n-propyl ether, propylene glycol monomethyl ether, Silica particles dispersed in one or more solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, toluene, cyclohexanone and the like can be mentioned. These can be obtained as commercial products, and examples thereof include, for example, methanol silica sol MA-ST-M manufactured by Nissan Chemical Industries, Ltd., isopropyl alcohol silica sol IPA-ST, ethylene glycol silica sol EG-ST, xylene / Butanol silica sol XBA-ST, dimethylacetamide silica sol DMAC-ST, methyl ethyl ketone silica sol MEK-ST, methyl isobutyl ketone silica sol MIBK-ST, ethylene glycol mono n-propyl ether silica sol NPC-ST-30, propylene glycol monomethyl ether silica sol PGM-ST Ethyl acetate silica sol EAC-ST, propylene glycol monomethyl ether acetate PMA-ST, toluene silica sol TOL-ST, cyclohexano It can be used silica sol CHO-ST-M, or the like. These may be used alone or in combination of two or more.

The silica particles dispersed in the solvent preferably have an average primary particle diameter of 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, and 200 nm or less. Is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less. When the average primary particle diameter of the silica particles is at least the lower limit, the abrasion resistance and the surface hardness tend to be improved, and when it is at the upper limit or less, the transparency of the cured product tends to be good. . The average primary particle diameter of the silica particles dispersed in the solvent in the present invention is a value determined as a converted value from the following equation by determining the specific surface area measurement value (based on JIS Z8830) by the BET adsorption method. Catalog values can be adopted for commercial products.
[Average primary particle size (nm)] =
6,000 / [[specific surface area (m ² / g)] × [density (g / cm ³ )]]

In addition, as the silane compound having an acryloyl group, for example, β- (meth) acryloyloxyethylmethyldimethoxysilane, β- (meth) acryloyloxyethylmethyldiethoxysilane, β- (meth) acryloyloxyethyldimethylmethoxysilane, β- (Meth) acryloyloxyethyldimethylethoxysilane, β- (Meth) acryloyloxyethyltrimethoxysilane, β- (Meth) acryloyloxyethyltriethoxysilane, γ- (Meth) acryloyloxypropyldimethylmethoxysilane, γ- (Meth) acryloyloxypropyldimethylethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acrylic It is possible to use ryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, and the like. These may be used alone or in combination of two or more.
Amount of acryloyl group modified on the surface of silica particle of silica particle whose surface is modified with compound having acryloyl group (amount of double bond per 1 g of silica particle whose surface is modified by compound having (meth) acryloyl group ( mol), preferably 0.1 to 2.0 mmol / g, more preferably 0.2 to 1.5 mmol / g, still more preferably 0.3 to 1.0 mmol / g, as calculated from the charge value preferable.

(Photopolymerization initiator)
The curable composition (α) used in the present invention preferably contains a photopolymerization initiator in order to improve the curability. A well-known photoinitiator can be used. Examples of the photopolymerization initiator include a photo radical generator, a photo acid generator and the like.

  Among the photopolymerization initiators that can be used for the curable composition (α), examples of the photoradical generator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and alkyl ethers thereof; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone [eg, trade name "IRGACURE (registered trademark) 184" Manufactured by BASF], 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one On, 2-methyl-1- [4- (meth) Acetophenones such as thio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone; 2,4,6-trimethylbenzoyl Phosphine oxides such as diphenyl phosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide; 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1- Anthraquinones such as chloroanthraquinone and 2-amyl anthraquinone; benzophenone and its various derivatives; formic acid derivatives such as methyl benzoyl formate and ethyl benzoyl formate, and the like. These may be used alone or in combination of two or more.

  Among these photo-radical generators, preferred are acetophenones, phosphine oxides and formic acid derivatives from the viewpoint of light resistance of the cured product, and more preferred are 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethyl Particular preference is given to pentyl phosphine oxide, methyl benzoyl formate, and 1-hydroxycyclohexyl phenyl ketone, methyl benzoyl formate.

As the photoacid generator, known photoacid generators can be used. Among them, diaryliodonium salts and triarylsulfonium salts are preferable from the viewpoint of curability and acid generation efficiency. As a specific example, an anion salt of di (alkyl substituted) phenyl iodonium (specifically, a PF ₆ salt, a SbF ₅ salt, a tetrakis (perfluorophenyl) borate salt, etc.) can be exemplified. As a specific example of the (alkyl-substituted) phenyliodonium anion salt, PF ₆ salt of dialkylphenyliodonium [trade name “IRGACURE (registered trademark) 250”, manufactured by BASF] is particularly preferable. These photoacid generators may be used alone or in combination of two or more.

  When the curable composition (α) contains a photopolymerization initiator, its content is preferably 0.01 parts by weight from the viewpoint of improving the curability with respect to a total of 100 parts by weight of the compound having an acryloyl group. It is the above, more preferably 0.1 parts by weight or more. On the other hand, it is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, from the viewpoint of maintaining the stability of the solution when the curable composition (α) is a solution.

(Organic solvent)
The curable composition (α) preferably contains an organic solvent. The organic solvent is not particularly limited, and can be appropriately selected in consideration of the types of components contained in the curable composition (α). Specific examples of the organic solvent which can be used include, for example, 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, ethylene Ether solvents such as glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; Amide solvents such as diethylformamide, N-methylpyrrolidone and the like; Bed, ethyl cellosolve, cellosolve solvents butyl cellosolve and the like; methanol, ethanol, propanol, isopropanol, alcohol solvents butanol; dichloromethane, halogenated solvents such as chloroform and the like.

  One of these organic solvents may be used alone, or two or more thereof may be used in combination. Among these organic solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.

  The amount of the organic solvent used is not particularly limited, and is appropriately determined in consideration of the coatability of the curable composition (α) to be prepared, the viscosity and surface tension of the liquid, the compatibility of the solid content, and the like. Usually, the curable composition (α) is prepared as a coating solution having a solid content concentration of 20 to 95% by weight, preferably 30 to 80% by weight, using the above-mentioned solvent. Here, "solid content" in the curable composition (α) means a component excluding a solvent, and includes not only a solid component but also a semi-solid or viscous liquid material . The same applies to the curable composition (β) and the curable composition (γ) described later.

(Other ingredients)
The curable composition (α) used in the present invention may contain other components other than the above-described acryloyl group-containing compound, a photopolymerization initiator, and an organic solvent, as long as the effects of the present invention are not inhibited. Other components include UV absorbers, hindered amine light stabilizers, fillers, silane coupling agents, reactive diluents, antistatic agents, organic pigments, slip agents, dispersants, thixotropy agents (thickeners ), Antifoaming agents, antioxidants and the like.

  The thickness of the layer (A) is preferably 2 μm or more, preferably 5 μm or more, and particularly preferably 10 μm or more from the viewpoint of hardness. On the other hand, from the viewpoint of crack resistance, it is preferably 100 μm or less, more preferably 60 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less.

[Layer (B)]
In the laminate of the present invention, the layer (B) is a layer comprising the curable composition (β) and / or a cured product thereof. The curable composition (β) contains an acrylic copolymer and an active energy ray curable compound described below.

(Acrylic copolymer)
The curable composition (β) is a copolymer obtained by copolymerizing a silicone-containing (meth) acrylate represented by at least the following formula (1) with a (meth) acrylate having an epoxy group: It includes an acrylic copolymer obtained by reacting a compound having an acryloyl group.

(In the above formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ are each independently a methyl group or a phenyl group , R ⁵ is an alkyl group having 1 to 12 carbon atoms, n is an average value, and is a number of 10 to 100.)

In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ¹ is preferably a methyl group because the glass transition temperature (Tg) of the resulting acrylic copolymer becomes high and the hardness of the surface when the layer (B) is cured becomes high.

In formula (1), ^{R 2} is an alkylene group having 1 to 12 carbon atoms. In order to easily obtain raw materials and to easily produce them, the carbon number thereof is preferably 2 or more, more preferably 3 or more, and preferably 10 or less, and 8 or less. Is more preferred.

In formula (1), R ³ and R ⁴ are each independently a methyl group or a phenyl group. A methyl group is preferable because the raw material is easily available and easily manufactured.

Wherein (1), ^{R 5} is an alkyl group having 1 to 12 carbon atoms. The carbon number of R ⁵ is preferably 2 or more, more preferably 3 or more, while the carbon number of R ⁵ is preferably 10 or less, more preferably 8 or less. When the carbon number of R ⁵ is in the above range, it is preferable because the raw materials are easily available and easily manufactured.

  In Formula (1), n is an average value and is a number of 10-100. When n is 10 or more, the surface lubricity of the cured film obtained by curing the curable composition (β) is sufficiently developed, and the lubricity is improved. From the viewpoint of making this effect better, n is preferably 25 or more, and more preferably 50 or more. On the other hand, the solubility to a solvent becomes favorable for n to be 100 or less. From the viewpoint of making this effect better, n is preferably 90 or less, and more preferably 80 or less. The value of n can be calculated from the number average molecular weight (Mn).

  The number average molecular weight (Mn) of the silicone-containing (meth) acrylate represented by the formula (1) is such that the surface slipperiness of the cured film obtained by curing the curable composition (β) is sufficiently developed to exhibit slipperiness. From the viewpoint of making it favorable, it is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 3,000 or more. Further, the number average molecular weight (Mn) of the silicone-containing (meth) acrylate represented by the formula (1) is preferably 50,000 or less, from the viewpoint of making the solubility in a solvent good. Is more preferably 1,000 or less, and still more preferably 10,000 or less.

  Among silicone-containing (meth) acrylates represented by the formula (1), those having a polydimethylsiloxane structure are preferable, and polydimethylsiloxanes having a methacryloyl group at one end are particularly preferable (as a specific example of a commercially available product, JNC Corporation "Syllaplane FM 0711", "Syllaplane FM 0721", "Syraplane FM 0725", etc. may be mentioned. The silicone-containing (meth) acrylate represented by the formula (1) may be used alone or in combination of two or more.

  Examples of epoxy group-containing (meth) acrylates used as raw materials for acrylic copolymers include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate Etc. Among these, glycidyl (meth) acrylate is preferable. The (meth) acrylate having an epoxy group may be used alone or in combination of two or more.

  When the silicone-containing (meth) acrylate represented by the formula (1) and the (meth) acrylate having an epoxy group are copolymerized, another monomer may be further copolymerized. Other monomers are particularly limited as long as they can be copolymerized with the silicone-containing (meth) acrylate represented by the formula (1) and the (meth) acrylate having an epoxy group represented by the formula (1). For example, other than these (meth) acrylates, (meth) acrylamides, etc. can be mentioned.

  As other monomers, for example, 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 (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) acrylate 2) Acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 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 N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N- Ethylmethyl (meth) acrylamide, N-methoxy (meth) acrylamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-diethoxy (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- methylene bis Examples include (meth) acrylamide, and (meth) acrylamide such as N, N-ethylenebis (meth) acrylamide. These may be used alone or in combination of two or more. As another monomer, the alkyl (meth) acrylate which has a C4-C22 alkyl group is preferable.

  When producing an acrylic copolymer by copolymerizing the silicone-containing (meth) acrylate represented by the formula (1), the (meth) acrylate having an epoxy group, and other monomers optionally used The amount of the monomer used is not particularly limited, but preferably 5 to 90% by weight of the silicone-containing (meth) acrylate represented by the formula (1), 10 to 95% by weight of the (meth) acrylate having an epoxy group, and necessary 0 to 80% by weight of other monomers used according to (wherein the silicone-containing (meth) acrylate represented by the formula (1), (meth) acrylate having an epoxy group, and other monomers optionally used The total amount is 100% by weight), particularly preferably 10 to 80 weight silicone-containing (meth) acrylates represented by the formula (1) %, Having an epoxy group (meth) acrylate 20 to 90% by weight, and other monomers 5-60 wt% scratch resistance is used in an amount of optionally used, from the viewpoint of antifouling property.

  The reaction for copolymerizing the silicone-containing (meth) acrylate represented by the formula (1), the (meth) acrylate having an epoxy group, and the other monomer optionally used is usually a radical polymerization reaction, and it is specific Can be carried out in the presence of a radical polymerization initiator in an organic solvent. The reaction time of this reaction is usually 1 to 50 hours, preferably 3 to 12 hours. The organic solvent which can be used here, and a radical polymerization initiator are as follows.

  Examples of the organic solvent include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA) and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether Ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate and 2-ethoxyethyl acetate; and aromatic hydrocarbon solvents such as toluene. These organic solvents may be used alone or in combination of two or more.

  As the radical polymerization initiator, for example, known initiators generally used for radical polymerization can be used, and organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, etc .; Examples include azo compounds such as ronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like. These radical polymerization initiators may be used alone or in combination of two or more.

  The acrylic copolymer used in the present invention comprises copolymerizing at least a silicone-containing (meth) acrylate represented by the formula (1), a (meth) acrylate having an epoxy group, and other monomers optionally used. The obtained copolymer is obtained by reacting a compound having a carboxyl group and an acryloyl group, and in this reaction, the reaction temperature is preferably 50 to 110 ° C., more preferably 55 to 100 ° C. . The reaction time is preferably 3 to 50 hours, more preferably 4 to 30 hours. This reaction is usually an addition reaction of an epoxy group in the copolymer with a compound having a carboxyl group and an acryloyl group.

Examples of the compound having a carboxyl group and an acryloyl group which can be used in this reaction include (meth) acrylic acid, carboxyethyl (meth) acrylate, an adduct of glycerin di (meth) acrylate and succinic anhydride, pentaerythritol tri ( An adduct of meta) acrylate and succinic anhydride, an adduct of pentaerythritol tri (meth) acrylate and phthalic anhydride, and the like can be mentioned. Among these, (meth) acrylic acid and an adduct of pentaerythritol tri (meth) acrylate and succinic anhydride are preferable. The compound having a carboxyl group and an acryloyl group may be used alone or in combination of two or more.
The above-mentioned compound having a carboxyl group and an acryloyl group is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, particularly preferably 50 to 110 mol%, as mol% of carboxyl group to epoxy group in the copolymer. It is preferable to use it in the proportion of mol% from the viewpoint of advancing the reaction without excess and deficiency and from the viewpoint of reducing the residue of the raw material.

  Moreover, in order to accelerate the reaction in which a compound having a carboxyl group and an acryloyl group is added to the copolymer, the reaction can be performed using a catalyst. Examples of the catalyst include triethylamine, tributylamine, triethylenediamine, N, N-dimethylbenzylamine, benzyltrimethylammonium chloride, triphenylphosphine and the like. The amount of the catalyst used is preferably 0.01 to 2% by weight, and more preferably 0.05 to 1% by weight, based on the total amount of the raw materials. In this reaction, the organic solvent used for the reaction in the production of the copolymer may be used as it is, or the reaction may be performed by adding an organic solvent as appropriate. Organic solvents which can be used for this reaction are the same as those mentioned above.

  The number average molecular weight (Mn) of the acrylic copolymer is preferably 500 or more, more preferably 1,000 or more, and one, preferably 10,000 or less, more preferably 8,000 or less. is there. It is preferable from the viewpoint of antifouling property and slipperiness expression that this number average molecular weight is more than the above lower limit value, and it is preferable from the viewpoint that compatibility with other components is maintained as it is less than the above upper limit value.

  In the curable composition (β), the content of the acrylic copolymer is from the viewpoint of making the scratch resistance favorable relative to the total amount of the acrylic copolymer and the active energy ray curable compound described later. It is preferable that it is 0.05 weight% or more, It is preferable that it is 0.1 weight% or more, It is more preferable that it is 0.5 weight% or more. On the other hand, from the viewpoint of making the curability of the curable composition (β) good, it is preferably 10% by weight or less, more preferably 8% by weight or less, and 6% by weight or less More preferable.

(Active energy ray curable compound)
The active energy ray-curable compound contained in the curable composition (β) is a compound other than the above-mentioned acrylic copolymer, and is particularly limited as long as it has a functional group capable of curing reaction upon irradiation with active energy rays. I will not.

  The active energy ray curable compound is preferably a compound containing an acryloyl group, and the hardness and abrasion resistance of the cured film are good, and the reactivity at the time of curing is also high. The number of acryloyl groups in the group is preferably 3 or more, and more preferably 4 or more. Moreover, it is preferable that it is nine or less from a viewpoint suitable for coating for the viscosity before hardening, and it is more preferable that it is seven or less.

  Specifically, as the active energy ray-curable compound having an acryloyl group, polyfunctional (meth) acrylates; polyfunctional (meth) acrylates such as urethane modified products, ester modified products, carbonate modified products, etc. of polyfunctional (meth) acrylates Acrylate derivatives; silica having a surface modified with a compound having an acryloyl group and the like can be mentioned.

  As polyfunctional (meth) acrylates and polyfunctional (meth) acrylate derivatives, for example, pentaerythritol triacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane Polyfunctional acrylates such as triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate adduct to succinic anhydride, dipentaerythritol pentaacrylate adduct to succinic anhydride; side chains or side chains and terminal acryloyl groups Polyester (meth) acrylates such as polyester oligomers (specifically, M8030 and M7100 manufactured by Toagosei Co., Ltd.) Isocyanurate of isophorone diisocyanate (IPDI), reaction product of polytetramethylene glycol (PTMG) and hydroxyethyl acrylate (HEA), and pentaerythritol triacrylate to isocyanate product of hexamethylene diisocyanate (HDI) and PTMG reactant Reactive substances of the following: Polyfunctional urethane (meth) acrylates such as polycarbonates; Polyesters (meth) acrylates having a carbonate bond such as reactive substances of oligoesters and pentaerythritol triacrylates using polycarbonate diols; Reactive substances of IPDI and polycarbonate diols And polyurethane (meth) acrylates having a carbonate bond such as a reactant of HEA; acrylic acid adduct of bisphenol A (specifically, Shin-Nakamura Chemical Co., Ltd. EA-1025) and the like, polyepoxy (meth) acrylates such as triethoxyisocyanuric acid diacrylate, triethoxyisocyanuric acid triacrylate (specifically, Tolonago Ltd. Alonics M315, M313) and the like. Triethoxy (meth) acrylates; modified products of these alkylene oxides; modified products of these polycaprolactones. These may be used alone or in combination of two or more.

  Among these, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane from the viewpoint of viscosity, curability and hardness of the surface of the obtained cured product. Particularly preferred are tetraacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate; modified products of these alkylene oxides; and modified products of caprolactone.

(Photopolymerization initiator)
The curable composition (β) used in the present invention preferably uses a photopolymerization initiator in order to improve the curability of the layer (B). The photoinitiator which can be used here is the same as that mentioned in the curable composition (α).

  When the curable composition (β) contains a photopolymerization initiator, its content is preferably 0.01 parts by weight or more from the viewpoint of improving the curability with respect to 100 parts by weight of the active energy ray-curable compound. And more preferably 0.1 parts by weight or more. On the other hand, from the viewpoint of maintaining the stability of the solution when the curable composition (β) is a solution and maintaining the scratch resistance when the curable composition (β) is cured, it is preferably 10 parts by weight or less. And more preferably 8 parts by weight or less.

(Organic solvent)
It is preferable to use an organic solvent for the curable composition (β) used in the present invention. The kind and amount of the organic solvent which can be used here, that is, the solid content concentration of the curable composition (β) are the same as those mentioned in the curable composition (α).

(Other ingredients)
The curable resin composition (β) used in the present invention contains other components other than the acrylic copolymer, the active energy ray curable compound, the photopolymerization initiator and the organic solvent within the range not inhibiting the effects of the present invention. It may be. Other components include UV absorbers, hindered amine light stabilizers, fillers, silane coupling agents, reactive diluents, antistatic agents, organic pigments, slip agents, dispersants, thixotropy agents (thickeners ), Antifoaming agents, antioxidants and the like.

  The thickness of the layer (B) is preferably 2 μm or more from the viewpoint of hardness, and particularly preferably 4 μm or more. On the other hand, from the viewpoint of crack resistance, it is preferably 100 μm or less, more preferably 60 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less.

[Layer (C)]
The laminate of the present invention preferably has the following layer (C) on the side opposite to the side on which the layer (A) and the layer (B) are laminated on the base material layer.
Layer (C): A layer comprising a curable composition (γ) having an acrylic equivalent of 100 g / mol or more and / or a cured product thereof

  The laminate of the present invention is useful as a display cover for a touch panel or the like. However, when used for such an application, the laminate is formed and then used through several printing / drying steps and an assembly step. For this reason, the laminate of the present invention is preferably prevented from being damaged by handling or the like in a plurality of steps. Since a load may be applied not only to the front surface but also to the back surface at the time of handling, it is preferable that a hard coat layer be laminated on both sides of the base material layer.

  The curable composition (γ) used in the layer (C) corresponds to the curable composition (β) described above as long as it corresponds to a curable composition having an acrylic equivalent of 100 g / mol or more. It may be. Except for this point, when the curable composition contains a compound having an acryloyl group, the curable composition (γ) can be the same as the curable composition (α) described above. Moreover, although the above-mentioned curable composition (α) contains a compound having an acryloyl group, when the curable composition (γ) has an acrylic equivalent of 100 g / mol or more, the layer (C) is cured. The curable composition (γ) may be one which does not contain a compound having an acryloyl group (one having an infinite acrylic equivalent) because it is possible to prevent the occurrence of cracks in the above.

  The compound which does not have an acryloyl group which can be used for curable composition ((gamma)) WHEREIN: A polyurethane is illustrated as a preferable thing from a viewpoint of crack resistance, hardness, etc. Specifically as polyurethane, what is obtained by making polyisocyanate and a polyol react is mentioned. Examples of polyisocyanate and polyol which can be used as a raw material of polyurethane are listed below, but in the curable composition (γ), polyurethane may be used alone or in combination of two or more.

  Examples of polyisocyanate which can be used as a raw material of polyurethane include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and 2,4-diphenylmethane. Aromatic polyisocyanates such as diisocyanates and 4,4-diphenylmethane diisocyanate; ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate Linear aliphatic polyisocyanates such as; isophorone diisocyanate; dicyclohexylmethane-4, 4-diisocyanate; Alicyclic polyisocyanates such as hexylene diisocyanate; alkylene arylene alkylene polyisocyanates such as xylylene diisocyanate or tetramethyl xylylene diisocyanate (wherein "alkylene arylene alkylene" means aliphatic hydrocarbon group-aromatic hydrocarbon) It means a group bonded in the order of group-aliphatic hydrocarbon group) and the like. The polyisocyanate may be used alone or in combination of two or more.

  Examples of the polyol that can be used as a raw material of polyurethane include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3- Methyl-1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl- 1,6-hexanediol, 2,2,4-trimethyl-1,6- Aliphatic diols such as xanthdiol, 3,3-dimethylolheptane, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol; bishydroxyethoxybenzene, bishydroxyethyl terephthalate Aromatic diols such as bisphenol-A; dialkanolamines such as N-methyldiethanolamine; low molecular weight polyols such as pentaerythritol, sorbitol, mannitol, glycerin, and trimethylolpropane; polyester polyols, polyetherester polyols, polycarbonate polyols And high molecular weight polyols such as C.I. Here, the low molecular weight polyol means one having a molecular weight of 500 or less, and the high molecular weight polyol means one having a molecular weight exceeding 500. The polyols may be used alone or in combination of two or more.

  The thickness of the layer (C) is preferably 2 μm or more from the viewpoint of hardness, and particularly preferably 4 μm or more. On the other hand, from the viewpoint of crack resistance, it is preferably 100 μm or less, more preferably 60 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less.

[Method of manufacturing laminate]
The laminate of the present invention can be produced by sequentially laminating each layer on a base material layer. Although the manufacturing method in particular of the laminated body of this invention is not restrict | limited, Usually, it can obtain by forming a layer (A) on a base material layer, and then forming a layer (B). When the laminate of the present invention has the layer (C), the order of forming the layer (C) is not particularly limited. For example, the layer (A) and the layer (B) may be formed sequentially after the layer (C) Layer (C) and then layer (A) and layer (B) may be formed sequentially, or layer (C) may be formed after layer (A) is formed. The layer (B) may be formed after formation.

  Each layer of the layers (A) to (C) is, for example, a curable composition (α), a curable composition (β), a curable composition (γ) on a substrate (in the case of the layer (B) Can be formed by applying (coating) the layer (A)) and drying at about 40 to 100 ° C. if necessary, and then irradiating the layer with an active energy ray as required . As a method of applying (coating) these curable compositions on a substrate, for example, reverse coating method, gravure coating method, rod coating method, bar coating method, Mayer bar coating method, die coating method, spray coating method Etc. In addition, the form of a cured product obtained by curing the curable composition of the present invention is not particularly limited, but generally, the cured product obtained by irradiating and curing an active energy ray on a substrate is a substrate It can be obtained as a cured film (cured film) on at least a part of one side.

  In the laminate of the present invention, the present invention is applied to each of the base layer and the layer (A), the layer (A) and the layer (B), and the base layer and the layer (C). Other layers may be laminated as long as the effects of the invention are not impaired.

  The total thickness of the laminate of the present invention is preferably 0.3 mm or more, more preferably 0.4 mm or more, from the viewpoint of ensuring the thickness of each layer and sufficiently exhibiting each function. It is particularly preferable that the diameter is 0.5 mm or more. On the other hand, the thickness is preferably 2.0 mm or less, more preferably 1.9 mm or less, and 1.8 mm or less from the viewpoint of thinning and weight reduction of the product to which the laminate of the present invention is applied. Particularly preferred.

  In the laminate of the present invention, active energy rays which can be used when curing the curable compositions (α) to (γ) include ultraviolet rays, electron rays, X-rays, infrared rays and visible rays. Among these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoints of curability and prevention of resin deterioration.

In the case of producing the laminate of the present invention, when curing the curable compositions (α) to (γ) by ultraviolet irradiation, various ultraviolet irradiation devices can be used, and as the light source, xenon lamp, high pressure A mercury lamp, a metal halide lamp, an LED-UV lamp etc. can be used. Irradiation amount of the ultraviolet (in mJ / cm ²⁾ is usually 10~10,000mJ / cm ^2, the flexible curable, the cured product of the curable composition (alpha) ~ (gamma) (cured film) It is preferably 15 to 5,000 mJ / cm ² , and more preferably 200 to 3,000 mJ / cm ² from the viewpoint of properties and the like.
In addition, after forming a layer (A) by a curable composition ((alpha)) on a base material layer, when forming a layer (B) by a curable composition ((beta)), a curable composition ((alpha)) When the composition is applied to the substrate layer and cured, the composition is cured to a certain extent with a small dose of about ²⁰ to 200 mJ / cm ² , and then the curable composition (β) is applied, and the radiation of about 300 to 500 mJ / cm ² It is also possible to make the layer (A) and the layer (B) completely cured together in amounts.

  Moreover, when manufacturing the laminated body of this invention, when hardening curable composition ((alpha))-((gamma)) by electron beam irradiation, various electron beam irradiation apparatuses can be used. The irradiation dose (Mrad) of the electron beam is usually 0.5 to 20 Mrad, and in view of the curability of the curable compositions (α) to (γ), the flexibility of the cured product, the prevention of damage to the substrate, etc. Preferably it is 1-15 Mrad.

[Use]
The laminate of the present invention is excellent in scratch resistance, hardness, impact resistance, crack resistance, impact resistance, low curling property, transparency and the like. Therefore, the laminate of the present invention is a component for an optical display such as a touch panel, a liquid crystal television, etc .; an automobile related component such as a lamp related article, a window related article (rear window, side window, skylight etc.); It can be suitably used for the surface cover of a wide range of articles such as lifestyle-related articles such as decorative boards and furniture. Among these, it can be particularly suitably used as a surface cover for components for optical displays such as touch panels and liquid crystal televisions, that is, as a display cover.
In addition, when using the laminated body of this invention as a display body cover, it is preferable to have especially the above-mentioned layer (C), and at this time, a display body cover has the function of high hardness, abrasion resistance, antifouling property in the front. The layer (B) of the laminate of the present invention is provided on the front side, since it is preferable to have the back surface, and it is preferable to have the functions of impact resistance, hardness to withstand processing steps, and scratch resistance. It is particularly preferable to use a display cover having the layer (C) on the back side.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following examples, "parts" means "parts by weight".

[Evaluation of laminate]
The laminates obtained in the following Examples and Comparative Examples were evaluated by the following methods.

(1) Scratch resistance The surface of the layer cured with # 0000 steel wool and a load of 160 g / cm ² was rubbed back and forth 300 times, and the degree of scratching of the cured film after the test was evaluated as follows.
○: Less than 100 scratches ×: More than 100 scratches

(2) Hardness (pencil hardness)
(PMMA side)
Measure the surface of the cured layer on the PMMA side using a JIS JIS pencil hardness tester (manufactured by Taiyo Kikai Co., Ltd.), based on the conditions of JIS K-5400, and confirm the hardness of the hardest pencil that is not scratched. The following criteria were evaluated.
○: Pencil hardness 8H or more ×: Pencil height 7H or less (PC side)
Measure the surface of the hardened layer on the PC side using a JIS JIS pencil hardness tester (manufactured by Taiyo Kikai Co., Ltd.), based on the conditions of JIS K-5400, and check the hardness of the hardest pencil that does not get scratched. The following criteria were evaluated.
:: pencil hardness H or more ○: pencil hardness 2B or more ×: pencil hardness 3B or less

(3) Crack resistance After curing, the presence or absence of cracks (cracks) in the coating of layer (A) and layer (B) was visually confirmed and evaluated as follows.
○: no cracks in both layer (A) and layer (B) ×: cracks in at least one of layer (A) and layer (B)

(4) Impact resistance A test piece of width 12.6 cm, length 22.4 cm, thickness 0.85 mm, layer (B (if there is no layer (B), layer (A)) on top, layer ( C) (if there is no layer (C), the surface opposite to the layer (A) -forming surface of the base layer) is placed on the lower surface, and 50 g of steel is directed toward the center of this test piece The ball was subjected to a hard ball drop test in which the ball was allowed to fall spontaneously from a height of 50 cm, and the impact resistance was evaluated as follows.
○: not damaged by falling ball ×: damaged by falling ball

(5) Transparency (Haze)
The haze value was measured with a haze meter ("HAZE METER HM-65W" manufactured by Murakami Color Research Laboratory) according to JIS K-7136, and evaluated as 0.3% or less as a pass.
○: the haze value is 0.3 or less ×: the haze value is greater than 0.3

(6) Recoatability It was evaluated as follows by whether it can coat (recoat) layer (B) on the cured film of layer (A).
○: A layer (B) can be recoated ×: A layer (B) can not be recoated

Synthesis Example
Synthesis Example 1
A single-end methacryloyl group-substituted polydimethylsiloxane having a number average molecular weight of 5,000 (represented by "Syraplane FM 0721" manufactured by JNC, formula (1)) in a reactor equipped with a stirrer, a reflux condenser and a thermometer 20 parts by weight of a compound corresponding to a silicone-containing (meth) acrylate, 60 parts by weight of glycidyl methacrylate ("Acryester G" manufactured by Mitsubishi Rayon), 10 parts by weight methyl methacrylate ("Acryester M" manufactured by Mitsubishi Rayon), Stearyl 10 parts by weight of methacrylate ("Aklyester S" manufactured by Mitsubishi Rayon Co., Ltd.) and 151 parts by weight of methyl isobutyl ketone (MIBK) are charged, the system is purged with nitrogen after stirring is started, and the temperature is raised to 55 ° C. '-Azobis (2,4-dimethyl valeronitrile) (Wako Pure Chemical Industries, Ltd.' V-65 )) After adding 1.2 parts by weight and 0.9 parts by weight of 1-dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.), the temperature in the system is raised to 65 ° C. and after stirring for 3 hours, V-65 is further added .6 parts by weight were added and stirred at 65.degree. C. for 3 hours. The system was heated to 100 ° C. and stirred for 30 minutes, then 163 parts by weight of MIBK was added, and the system was heated again to 100 ° C. To this, 0.5 parts by weight of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.6 parts by weight of triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd.) are added, and then acrylic acid (manufactured by Mitsubishi Chemical Corporation) 31.0 parts by weight was added, the temperature was raised to 110 ° C., and the mixture was stirred for 6 hours. After cooling, 4.8 parts by weight of MIBK was added to obtain a MIBK solution of a copolymer (F1) having a number average molecular weight of 6,500. The composition of the MIBK solution of the copolymer (F1) was made to be [weight of copolymer (F1)] / [weight of MIBK] = 30/70 (solid content 30% by weight).

Synthesis Example 2
In a reactor equipped with a stirrer, reflux condenser, dropping funnel and thermometer, MEK-ST (methyl ethyl ketone (MEK) dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd. trade name MEK-ST, average primary particle diameter: 15 nm (catalog) Value, solid content of silica: 30% by weight)), 88 parts by weight, and 12 parts by weight of KBM-5103 (γ- (meth) acryloyloxypropyltrimethoxysilane (trade name KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.)) Furthermore, methyl ethyl ketone is added, diluted and stirred so that the solid concentration becomes 30% by weight, then 0.05 parts by weight of methyl hydroquinone, 1 part by weight of water, 0.5 parts by weight of aluminum acetylacetone, and 1 part by weight of methyl ethyl ketone A reaction is conducted for 4 hours while heating to 70 ° C. in an oil bath, and the compound has an acryloyl group on the surface A silica particle (F2) modified with a substance was obtained. The amount of acryloyl groups to be modified on the surface of the silica particles was 0.51 mmol / g.

[Base materials, raw materials, etc.]
In the following, the used base materials, raw materials, etc. and their abbreviations are as follows.

(Base material)
PMMA / PC sheet: ShineTech AW-10 (thickness: 1.0 mm (thickness of PMMA layer: 0.054 mm, thickness of PC layer: 0.95 mm)) manufactured by Nippon Wayblock Co., Ltd. PC sheet: Yupiron (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Registered trademark NF-2000 (thickness 1.0 mm)

(Acrylic copolymer)
Copolymer (F1): Copolymer (F1) obtained in Synthesis Example 1
(Compound having an acryloyl group)
DPHA: Nippon Kayaku Co., Ltd. KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
UA-160TM: Shin-Nakamura Chemical Co., Ltd. UA-160TM (urethane acrylate having a polytetramethylene glycol structure, 2 acryloyl groups)
M313: Toho Gosei Co., Ltd. Alonix M 313 (a mixture of isocyanuric acid ethylene oxide (EO) modified diacrylate (a kind of urethane acrylate) and a mixture of isocyanuric acid ethylene oxide (EO) modified triacrylate (a kind of urethane acrylate)))
Silica particle (F2): Surface acryloyl group modified silica particle (F2) obtained in Synthesis Example 2

(Additive)
BYK-306: BYK-306 manufactured by ALTANA (silicone additive having no acryloyl group (not corresponding to the acrylic copolymer contained in the curable composition (β) in the present invention))

[Preparation of Curable Composition (β)]
<Composition liquid 1>
The solution of the copolymer (F1) obtained in Synthesis Example 1, DPHA and M313 are blended in a solid content weight ratio of 1.5: 86.5: 12, and 1-hydroxy as a photopolymerization initiator. After adding 2.5 parts by weight of cyclohexyl phenyl ketone ("Irgacure (registered trademark) 184" manufactured by BASF), [weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1 (weight ratio) The resulting solution was diluted to a solid content of 40% by weight with a solution of The acrylic equivalent of this solution was 110 g / mol.

[Preparation of Curable Composition (α), (γ)]
<Composition liquid 2>
DPHA and M313 were blended so that the solid content weight ratio would be 95: 5, and 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone ("Irgacure (registered trademark) 184" manufactured by BASF) as a photopolymerization initiator After the addition, the mixture was diluted with a solution of [weight of propylene glycol monomethyl ether acetate] / [weight of methyl isobutyl ketone] = 1/1 so as to have a solid content of 60% by weight, to obtain a liquid mixture 2. The acrylic equivalent of this solution was 103 g / mol.

<Composition liquid 3>
A solution of the surface acryloyl group-modified silica particles (F2) obtained in Synthesis Example 2, DPHA and M313 are blended so as to have a solid content weight ratio of 70: 25: 5, and 1-hydroxycyclohexyl as a photopolymerization initiator After 2.5 parts by weight of phenyl ketone ("Irgacure (registered trademark) 184" manufactured by BASF Corp.) was added, the mixture was diluted with propylene glycol monomethyl ether so as to have a solid content of 60% by weight to obtain Formulation Liquid 3. The acrylic equivalent of this solution was 566 g / mol.

<Composition liquid 4>
BYK-306, DPHA and M313 are blended so as to have a solid content ratio of 1.5: 86.5: 12, and 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF "Irgacure (registered trademark)" as a photopolymerization initiator) After adding 2.5 parts by weight of 184 "), a solution of [weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1 (weight ratio) is brought to a solid content of 40% by weight Dilution was performed to obtain a combination solution 4.

<Composition liquid 5>
DPHA and UA-160TM were blended so as to have a solid content weight ratio of 60:40, and further 4.5 weight of 1-hydroxycyclohexyl phenyl ketone ("Irgacure (registered trademark) 184" manufactured by BASF) as a photopolymerization initiator After the addition of a portion, the mixture was diluted with a solution of [weight of propylene glycol monomethyl ether] / [weight of methyl isobutyl ketone] = 1/1 so as to have a solid content of 50% by weight, thereby obtaining a mixed solution 5. The acrylic equivalent of this solution was 380 g / mol.

<Composition liquid 6>
Adipic acid-based polyester polyol ("Teslac 2488" manufactured by Hitachi Chemical Co., Ltd.) and polyisocyanate curing agent ("Mitec (registered trademark) NY 730A-T" manufactured by Mitsubishi Chemical Co., Ltd.) are blended so as to have a solid content weight ratio of 53:47. And 0.1 parts by weight of a octylate tin catalyst (“Neostan U-810” manufactured by Nitto Kasei Co., Ltd.), and then diluted with a methyl ethyl ketone solution to a solid content of 40% by weight and reacted in the solution Thus, a mixture solution 6 of polyurethane was obtained. Since each raw material component of this liquid does not have an acryloyl group, the acrylic equivalent was infinite.

[Examples and Comparative Examples]
Example 1
It applied with the bar coater so that the coating film after drying the compound liquid 5 might be set to 20 micrometers on PC base material side of a PMMA / PC sheet. The coated film is dried by heating at 80 ° C. for 1.5 minutes, and then the coated film is coated with ultraviolet light of 450 mW / cm ² and 500 mJ / cm ² using a high pressure mercury lamp with an output of 120 W / cm. A layer (C) was formed on the surface of the PC substrate of the substrate.

Next, the mixed solution 2 was applied to the PMMA substrate surface of the substrate by a bar coater such that the coating after drying was 15 μm, and the coating was dried by heating at 80 ° C. for 1.5 minutes. Then, using a high-pressure mercury lamp with an output of 80 W / cm, the cured film was coated by irradiation with ultraviolet light of 100 mW / cm ² and 50 mJ / cm ² to form a layer (A) on the PMMA substrate surface.

Furthermore, the coating liquid was apply | coated by the bar coater so that the coating film after drying might be 5 micrometers on layer (A), and it heated at 80 degreeC for 1.5 minutes, and dried the coating film. Thereafter, using a high-pressure mercury lamp with an output of 120 W / cm, a cured film is coated by irradiation with ultraviolet light of 450 mW / cm ² and 500 mJ / cm ² to form a layer (B) on the layer (A) to form a laminate I got

Example 2
With respect to the layer (A), a laminate was obtained in the same manner as in Example 1 except that the liquid mixture 3 was used instead of the liquid mixture 2.

Example 3
A laminate was obtained in the same manner as in Example 1 except that the layer (C) was not formed.

Example 4
The mixed liquid 6 is applied to the PC substrate surface of the PMMA / PC sheet by a bar coater so that the coating after drying becomes 20 μm, heated at 80 ° C. for 10 minutes to dry and cure the coating, and PC group A layer (C) was formed on the surface of the material.

  Subsequently, in the same manner as in Example 1, a layer (A) and a layer (B) were sequentially formed on a PMMA substrate to obtain a laminate.

Comparative Example 1
A layer (C) was formed in the same manner as in Example 1 on the PC base surface of the PMMA / PC sheet. Next, the compounded liquid 1 is applied to the PMMA substrate surface with a bar coater so that the coating after drying becomes 20 μm, and the coating is dried by heating at 80 ° C. for 1.5 minutes, and the output 120 W / cm Using a high pressure mercury lamp of the above, ultraviolet rays of 450 mW / cm ² and 500 mJ / cm ² were irradiated to coat the cured film, and a layer was formed on the surface of the PMMA substrate to obtain a laminate.

Comparative Example 2
A layer (C) was formed in the same manner as in Example 1 on the PC base surface of the PMMA / PC sheet. Next, the compounded liquid 1 is applied to the PMMA substrate surface with a bar coater so that the coating after drying becomes 15 μm, and the coating is dried by heating at 80 ° C. for 1.5 minutes, and the output 80 W / cm of using a high pressure mercury lamp ^was irradiated with ultraviolet light of 100mW / cm 2, 50mJ / cm 2, is coated with a cured film to form a layer. Furthermore, when it was going to form a layer further using the liquid mixture 1 on this layer, since the liquid compound 1 was repelled on the layer surface, the layer could not be formed.

Comparative Example 3
A layer (C) was formed in the same manner as in Example 1 on the PC base surface of the PMMA / PC sheet. Next, the compounded liquid 1 is applied to the PMMA substrate surface with a bar coater so that the coating after drying becomes 15 μm, and the coating is dried by heating at 80 ° C. for 1.5 minutes, and the output 80 W / cm of using a high pressure mercury lamp ^was irradiated with ultraviolet light of 100mW / cm 2, 50mJ / cm 2, is coated with a cured film to form a layer. Furthermore, when it was going to form a layer further using the liquid mixture 2 on this layer, the layer could not be formed because the liquid layer 2 was repelled on the layer surface.

Comparative Example 4
A layer (C) was formed in the same manner as in Example 1 on the PC base surface of the PMMA / PC sheet. Next, the compounded liquid 1 is applied to the PMMA substrate surface with a bar coater so that the coating after drying becomes 15 μm, and the coating is dried by heating at 80 ° C. for 1.5 minutes, and the output 80 W / cm of using a high pressure mercury lamp ^was irradiated with ultraviolet light of 100mW / cm 2, 50mJ / cm 2, is coated with a cured film to form a layer. Furthermore, when it was going to form a layer further using the liquid mixture 3 on this layer, since the liquid compound 3 was repelled in the layer surface, the layer was not able to be formed.

Comparative Example 5
With respect to the layer (B), a laminate was obtained in the same manner as in Example 1 except that the formulation solution 2 was used instead of the formulation solution 1.

Comparative Example 6
With respect to the layer (B), a laminate was obtained in the same manner as in Example 2 except that the liquid mixture 3 was used instead of the liquid mixture 1.

Comparative Example 7
With respect to the layer (B), a laminate was obtained in the same manner as in Example 1 except that the liquid mixture 4 was used instead of the liquid mixture 1.

Comparative Example 8
A laminate was obtained in the same manner as in Example 1 except that a PC sheet was used instead of the PMMA / PC sheet.

  The laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 8 were evaluated for the above (1) to (6), and the results are shown in Table 1.

〔Evaluation results〕
As can be seen from Table 1, the laminates of Examples 1 to 4 were all excellent in scratch resistance, hardness on the layer (A) side, crack resistance, impact resistance, transparency, and recoatability. In Examples 1, 2 and 4, since the layer (C) was formed, the hardness on the layer (C) side was also good, and particularly in Example 4, a high hardness of hardness H was obtained.

In Comparative Example 1, when a layer consisting of the curable composition (β) and / or its cured product was formed to 20 μm without forming a layer corresponding to the layer (A) on the base material layer, cracks occurred.
In Comparative Examples 2 to 4, after a layer obtained by curing the mixed solution 1 corresponding to the layer consisting of the curable composition (β) and / or the cured product thereof is formed on the base material layer, When it was going to form the layer which hardened | cured 3 respectively, since recoat property was bad, other evaluation was not implemented.
In Comparative Examples 5 to 7, after the layer corresponding to the layer (A) was formed on the substrate, the layer not corresponding to the layer (B) was formed, and the scratch resistance was poor. Furthermore, in Comparative Example 8, when a layer corresponding to layer (A) and a layer corresponding to layer (B) were formed without using a layer made of PMMA as a base material layer, the hardness on the layer (A) side was poor. The

Claims (13)

The following layer (A) and the following layer (B) are provided in this order from the base layer side on a layer consisting of at least the following base layer and the following polymethyl methacrylate on one side of the base layer, The laminated body whose total thickness of a base material layer is 0.3-30 mm.
Base layer: Layer layer (A) containing layer comprising polymethyl methacrylate: curable composition (α) containing at least a compound having an acryloyl group and having an acrylic equivalent of 100 g / mol or more and 1,000 g / mol or less And / or a layer of the cured product thereof (but excluding the following curable composition (β) and / or the cured product thereof): Layer (B): silicone-containing (meth) acrylate represented by at least the following formula (1) Acrylic copolymer obtained by reacting a compound having a carboxyl group and an acryloyl group with a copolymer obtained by copolymerizing a monomer and a (meth) acrylate having an epoxy group, an active energy ray-curable compound, and Layer comprising the curable composition (β) containing the compound and / or its cured product

(In the above formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ are each independently a methyl group or a phenyl group , R ⁵ is an alkyl group having 1 to 12 carbon atoms, n is an average value, and is a number of 10 to 100.) The laminated body of Claim 1 which has the following layer (C) on the other side of the said base material layer.
Layer (C): A layer comprising a curable composition (γ) having an acrylic equivalent of 100 g / mol or more and / or a cured product thereof   The laminated body of Claim 1 or 2 in which the said curable composition ((alpha)) contains the silica modified by the compound which has a polyfunctional (meth) acrylate and / or an acryloyl group.   The curable composition (β) contains 0.05 to 10% by weight of the acrylic copolymer based on the total amount of the acrylic copolymer and the active energy ray-curable compound. The layered product according to any one of 3.   The copolymer contained in the said curable composition ((beta)) is further what copolymerized the alkyl (meth) acrylate which has a C4-C22 alkyl group in any one of Claims 1-4. The laminated body as described in a term.   The laminate according to any one of claims 2 to 5, wherein the curable composition (γ) contains silica modified with a compound having a polyfunctional (meth) acrylate and / or an acryloyl group.   The laminate according to any one of claims 2 to 6, wherein the curable composition (γ) comprises a polyurethane.   The layered product according to any one of claims 1 to 7 whose thickness of said layer (B) is 2-100 micrometers.   The layered product according to any one of claims 2 to 8 whose thickness of said layer (C) is 2-100 micrometers or less.   The laminate according to any one of claims 1 to 9, wherein the base material layer is composed of two layers of at least a layer composed of polymethyl methacrylate and a layer composed of polycarbonate.   The base layer is composed of at least two layers of a layer composed of polymethyl methacrylate and a layer composed of polycarbonate, and the layer composed of polymethyl methacrylate is in contact with the layer (A), and the polycarbonate The layered product according to any one of claims 2 to 10, wherein the layer which consists of a layer touches said layer (C).   The display body cover which consists of a laminated body of any one of Claims 1-11.   A display cover comprising the laminate according to claim 2, 6, 7, 9, or 11, wherein the layer (B) side is on the front side and the layer (C) side is on the back side .