JP2015221510A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in pencil hardness, scratch resistance, transparency, interlayer adhesion, antifouling property and the like.SOLUTION: The laminate has the following layer (A) and the following layer (B) in this order on a substrate layer. The layer (A): a layer is produced through a step of coating (α) a curable composition including a compound having an acryloyl group in a thickness of 2-40 μm on the substrate layer and irradiating with an active energy ray so as to adjust the reaction rate of acryloyl group to not less than 5% to less than 60% to cure the curable composition. The layer (B): a layer is produced through a step of coating (β) a curable composition including a compound having an acryloyl group in a thickness of 2-40 μm on the layer (A) and irradiating with an active energy ray so as to adjust the reaction rate of acryloyl group to not less than 60% to cure the curable composition.

Description

  The present invention relates to a laminate excellent in pencil hardness, scratch resistance (abrasion resistance), transparency, interlayer adhesion, antifouling property and the like. Moreover, this invention relates to the display body cover which consists of this laminated body.

  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) Various resin base materials such as resin, styrene resin such as acrylonitrile-styrene (AS) resin; vinyl chloride resin; cellulose acetate resin such as triacetyl cellulose are excellent in light weight, 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, substrates of display devices such as liquid crystal displays and plasma displays.

  Since these plastic products generally have a low pencil hardness, they are easily scratched and have insufficient wear resistance. Therefore, in transparent resins such as polycarbonate resin and polyethylene terephthalate resin, the resin inherently has scratches due to scratches on the surface. The transparency or appearance of the film is greatly impaired, and it is difficult to use it in fields that require wear resistance. For this reason, a hard coat material (coating material) that imparts pencil hardness and abrasion resistance to the surface of these plastic products is required.

  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, the movement of flipping fingers (flip) is frequently performed due to the prevalence of capacitance type, and the feeling of slipping by fingers and fingerprints by fingernails or attached with tissue or cloth are used. Scratch resistance (scratch resistance) when wiping off is required, and further improvement in slipperiness and scratch resistance is required as compared with conventional hard coats.

  In order to solve such problems, many attempts have been made to reduce the friction coefficient of the surface and impart slipperiness. For example, Patent Document 1 discloses that a hard coat material containing a polysiloxane structure or a compound having a perfluoroalkyl group and an acryloyl group imparts hardness, scratch resistance, and stain resistance. Patent Document 2 discloses that a polysiloxane-containing compound having a specific structure is used as a solvent-free hard coat material.

JP 2010-033693 A JP 2007-046049 A

According to detailed studies by the present inventors, the pencil hardness is insufficient with the techniques disclosed in Patent Documents 1 and 2 described above. Also, for use as a surface cover for optical display components such as touch panels and liquid crystal televisions, it is desirable to increase pencil hardness while maintaining good scratch resistance (abrasion resistance), transparency, antifouling properties, etc. It is.
That is, an object of the present invention is to provide a laminate excellent in pencil hardness, scratch resistance (abrasion resistance), transparency, interlayer adhesion, antifouling property, and the like, and a display cover comprising the laminate. is there.

  As a result of intensive studies by the present inventors to solve the above problems, a laminate having a specific layer structure formed through a specific curing step on the base material layer has a pencil hardness, scratch resistance (scratch resistance). ), Transparency, interlayer adhesion, antifouling property, etc. were found. That is, the gist of the present invention resides in the following [1] to [10].

[1] A laminate having the following layer (A) and the following layer (B) in this order on at least one surface of the base material layer from the base material layer side.
Layer (A): A curable composition (α) containing at least a compound having an acryloyl group is applied on a substrate layer with a thickness of 2 to 40 μm, and the reaction rate of the acryloyl group of the curable composition (α) is 5 % (B): a curable composition (β) containing at least a compound having an acryloyl group. It is applied on the layer (A) with a thickness of 2 to 40 μm, and is obtained through a step of curing by irradiation with active energy rays so that the reaction rate of the acryloyl group of the curable composition (β) is 60% or more. layer

[2] The curable composition (β) of the layer (B) contains at least one of a perfluoroalkyl structure, a perfluoroalkylene structure, a perfluoropolyether structure, and a polysiloxane structure, and 1 in the molecule. The laminate according to [1], containing 0.05 to 10% by weight of a compound having one or more acryloyl groups with respect to the total of the compounds having acryloyl groups in the curable composition (β).

[3] The curable composition (β) of the layer (B) is obtained by copolymerizing at least a silicone-containing (meth) acrylate represented by the following formula (1) and a (meth) acrylate having an epoxy group. The (meth) acrylic copolymer obtained by reacting the obtained copolymer with a compound having a carboxyl group and an acryloyl group is 0 with respect to the total of the compounds having an acryloyl group in the curable composition (β). The laminate according to [1] or [2], containing 0.05 to 10% by weight.

（上記式（１）中、Ｒ^１は水素原子又はメチル基であり、Ｒ^２は炭素数１〜１２のアルキレン基であり、Ｒ^３及びＲ^４はそれぞれ独立してメチル基又はフェニル基であり、Ｒ^５は炭素数１〜１２のアルキル基であり、ｎは平均値であり、１０〜１００の数である。）

(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.)

[4] The laminate according to [3], wherein the (meth) acrylic copolymer is obtained by further copolymerizing an alkyl (meth) acrylate having an alkyl group having 4 to 22 carbon atoms.

[5] The laminate according to any one of [1] to [4], wherein the curable composition (α) includes silica particles having an average primary particle diameter of 1 to 100 nm.

[6] The layer (A) coats the curable composition (α) on the substrate layer with a thickness of 2 to 40 μm, and the acryloyl group reaction rate of the curable composition (α) is 5% or more and 60. The laminate according to any one of [1] to [5], which is obtained by performing the step of irradiating and curing active energy rays so as to be less than 2% at least twice.

[7] The laminate according to any one of [1] to [6], wherein the thickness of the layer (A) is 2 to 100 μm.

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

[9] The base layer is a layer made of at least one resin selected from polyethylene terephthalate resin, polymethyl methacrylate resin, polycarbonate resin, hydrogenated polyimide resin, and polycycloolefin resin. [8] The laminate according to any one of [8].

[10] A display cover comprising the laminate according to any one of [1] to [9].

The laminate of the present invention is excellent in pencil hardness, scratch resistance (abrasion resistance), transparency, interlayer adhesion, antifouling property and the like.
For this reason, the laminated body of the present invention includes optical display parts such as touch panels and liquid crystal televisions; automobile-related parts such as lamp-related articles and window-related articles (rear windows, side windows, skylights, etc.); It can be suitably used for the surface cover of a wide range of articles such as decorative articles and daily life-related articles such as furniture. Among these, it can be particularly suitably used as a surface cover for optical display components such as a touch panel and a liquid crystal television, that is, a display body cover.

  Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is limited to the following description unless it exceeds the gist. is not. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression. In the present invention, when the expression “(meth) acryl” is used, it means one or both of “acryl” and “methacryl”. The same applies to “(meth) acrylate” and “(meth) acryloyl”.

[Laminate]
The laminated body of this invention has the following layer (A) and the following layer (B) in this order from the base material layer side in the at least one surface on a base material layer.
Layer (A): A curable composition (α) containing at least a compound having an acryloyl group is applied on a substrate layer with a thickness of 2 to 40 μm, and the reaction rate of the acryloyl group of the curable composition (α) is 5 % (B): a curable composition (β) containing at least a compound having an acryloyl group. It is applied on the layer (A) with a thickness of 2 to 40 μm, and is obtained through a step of curing by irradiation with active energy rays so that the reaction rate of the acryloyl group of the curable composition (β) is 60% or more. layer

  In the present invention, the “acryloyl group” in the curable composition (α) and the curable composition (β) is directly bonded to the C═C carbon atom in the acryloyl group as well as the acryloyl group itself. A hydrogen atom is used in the sense of including other atoms or substituents. For example, a group in which a hydrogen atom directly bonded to C = C of an acryloyl group is substituted with a methyl group or a halogen element, more specifically, a methacryloyl group, a fluoroacryloyl group or the like is also included in the “acryloyl group”. Shall be used.

  The laminate of the present invention has the effect of being excellent in pencil hardness and interlayer adhesion. In the present invention, the degree of internal cross-linking in the vicinity of the base material can be improved by curing each layer as a two-layer structure of layer (A) and layer (B), rather than curing any one layer at a time. It is thought that pencil hardness is obtained. Furthermore, when the reaction rate of the curable composition (α) is controlled, the degree of crosslinking of the layer (A) does not become too high, and when the curable composition (β) is subsequently applied on the layer (A), It is considered that interlayer adhesion between the layer (A) and the layer (B) can be obtained by impregnating the surface of the layer (A) with the curable composition (β) and curing it. That is, the inventors set the pencil hardness of the laminate by setting the curable composition (α), the layer (B), and the curable composition (β) of the layer (A) to specific reaction rates, respectively. It has been found that the interlayer adhesion is excellent.

[Base material layer]
Although there is no restriction | limiting in particular about the constituent material of a base material layer, It is preferable that the base material layer of the laminated body of this invention is a thermoplastic resin, especially a polyethylene terephthalate (PET) resin, a polymethyl methacrylate (PMMA). Resin (in the present invention, “polymethyl methacrylate resin” means a resin obtained by using methyl methacrylate in an amount of 50 mol% or more), polycarbonate (PC) resin (in the present invention, “polycarbonate resin”) The term “means not only aromatic polycarbonate resins”, but also general resins whose structural units are linked by a carbonate bond), hydrogenated polyimide (hydrogenated PI) resin (in the present invention, “hydrogenated polyimide”). Is a polyimid obtained using a compound having at least an aromatic ring hydrogenated as a raw material. In a.), And it is a layer made of at least one resin selected from the polycycloolefin (COP) resin, transparency, optical properties, heat resistance, preferable in viewpoint of easy availability.
The base material layer may have a laminated structure of two or more layers made of these resins.

  In the laminate of the present invention, the thickness of the base material layer (when the base material layer has a laminated structure of two or more layers, the total thickness) is preferably thicker from the viewpoint of the mechanical strength of the laminate, In view of demands for reduction in thickness and weight for use as a display body or the like, a thinner one is preferable. From these viewpoints, the thickness of the base material layer is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 15 μm or more, while preferably 250 μm or less, more preferably 180 μm or less. More preferably 130 μm or less, and particularly preferably 110 μm or less.

  The base material layer may be formed on another resin base material. In this case, examples of the other resin base material include polyethylene naphthalate, triacetyl cellulose, acrylonitrile-butadiene-styrene (ABS resin). ), Modified polyolefin, hydrogenated polystyrene, and the like.

[Layer (A)]
In the layer (A), a curable composition (α) containing at least a compound having an acryloyl group is applied on the substrate layer with a thickness of 2 to 40 μm, and the reaction rate of the acryloyl group of the curable composition (α) is It is a layer obtained by performing the process of irradiating and curing the active energy ray so as to be 5% or more and less than 60% at least once. A curable composition ((alpha)) is demonstrated below and the formation method and suitable thickness of a layer (A) are mentioned later.

<Curable composition (α)>
The curable composition (α) contains at least a compound having an acryloyl group. In addition, the acrylic equivalent of the curable composition (α) is preferably 100 g / mol or more from the viewpoint of preventing cracks when the layer (A) is cured. On the other hand, 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, more preferably 3,000 g / mol. Or less, more preferably 2,000 g / mol or less, and particularly preferably 1,000 g / mol or less.

  In the present invention, the “acryl equivalent” in the curable composition (α) and the curable composition (β) described later is the molecular weight (g / mol) of the compound having an acryloyl group contained in these compositions. In the case of a composition containing two or more compounds having an acryloyl group divided by the number of acryloyl groups present in one molecule of the compound, the acrylic equivalent of each compound is multiplied by the weight ratio. Defined as the sum of the values. Note that a compound having no acryloyl group is not considered.

(Compound having acryloyl group)
Examples of the compound having an acryloyl group contained in the curable composition (α) include monofunctional (meth) acrylate and derivatives thereof, polyfunctional (meth) acrylate and derivatives thereof, and silica whose surface is modified with a compound having acryloyl groups. Particles and the like. 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 polyfunctional (meth) acrylate and derivatives thereof and silica particles whose surface is modified with a compound having an acryloyl group. Furthermore, it is more preferable that at least two of them are included.

  Examples of the monofunctional (meth) acrylate 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 ( (Meth) 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 modified products thereof with cationizing agent, diethylaminoethyl (meth) acrylate and cationization thereof Modified products by agents, alkoxypolyalkylene glycol (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-phenoxy Propyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2 -(Meth) acryloylpropyl phthalate, (meth) acryloyloxyethyl succinate, 2-isocyanatoethyl (meth) acrylate and the like. These may be used alone or in combination of two or more.

  Examples of the polyfunctional (meth) acrylate and polyfunctional (meth) acrylate derivatives include pentaerythritol triacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and trimethylolpropane. Multifunctional acrylates such as triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate adduct to succinic anhydride, dipentaerythritol pentaacrylate adduct to succinic anhydride; side chain or side chain and acryloyl group at the end Polyester (meth) acrylates such as polyester oligomers (specifically, M8030, M7100 manufactured by Toagosei Co., Ltd.) Isopentone diisocyanate (IPDI) isocyanurate, polytetramethylene glycol (PTMG) and hydroxyethyl acrylate (HEA) reaction, hexamethylene diisocyanate (HDI) isocyanate and PTMG reactant pentaerythritol triacrylate Polyfunctional urethane (meth) acrylates such as reactants of polyesters; Polyester (meth) acrylates having carbonate bonds such as reactants of oligoesters and pentaerythritol triacrylates using polycarbonate diols; Reactants of IPDI and polycarbonate diols , Polyurethane (meth) acrylates having carbonate bond such as HEA reaction product; acrylic acid adduct of bisphenol A (specifically, Shin-Nakamura Chemical Co., Ltd.) Polyethoxy (meth) acrylates such as EA-1025); triethoxyisocyanuric acid diacrylate, triethoxyisocyanuric acid triacrylate (specifically, Aronix (registered trademark) M315, M313 manufactured by Toagosei Co., Ltd.) Examples thereof include triethoxy (meth) acrylates having an isocyanurate ring; these alkylene oxide modified products; these polycaprolactone modified products. 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, due to viscosity, curability, hardness of the resulting cured product surface, etc. Tetraacrylate, dipentaerythritol triacrylate; these alkylene oxide modified products; these caprolactone modified products are particularly preferred.

  Silica particles whose surface is modified with a compound having an acryloyl group can be produced, for example, by subjecting silica particles dispersed in a solvent and a silane compound having an acryloyl group to a hydrolytic condensation reaction. Silica particles 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, and more specifically, the surface is made of a compound having an acryloyl group. In the modified silica particles, first, a silane compound having an acryloyl group is added to silica particles using an organic solvent as a dispersion medium, and water and acetylacetone aluminum are added as a hydrolysis catalyst. 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, Examples thereof include silica particles dispersed in one or more solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, toluene, and cyclohexanone. These can be obtained as commercial products. Examples thereof include methanol silica sol MA-ST-M, isopropyl alcohol silica sol IPA-ST, ethylene glycol silica sol EG-ST, xylene / manufactured by Nissan Chemical Industries, Ltd. 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.

Further, 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, further preferably 5 nm or more, and 200 nm or less. It 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 not less than the above lower limit value, the scratch resistance and pencil hardness tend to be improved, and when it is not more than the above upper limit value, the transparency of the cured product tends to be good. . In addition, the average primary particle diameter of the silica particles dispersed in the solvent in the present invention is a value obtained as a converted value from the following formula by obtaining a specific surface area measurement value (based on JIS Z8830) by the BET adsorption method. For commercial products, standard values (catalog values) based on these measured values can be adopted.
[Average primary particle size (nm)] =
6,000 / [[specific surface area (m ² / g)] × [density (g / cm ³ )]]

Examples of the silane compound having an acryloyl group include 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 Liloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, and the like can be used. These may be used alone or in combination of two or more.
The amount of acryloyl group modified on the surface of silica particles whose surface is modified with a compound having acryloyl group (the amount of double bonds per 1 g of silica particles whose surface is modified with a compound having acryloyl group (mol)) The calculated value from the charged value is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, still more preferably 0.3 mmol / g or more, It is preferably 0 mmol / g or less, more preferably 1.5 mmol / g or less, and still more preferably 1.0 mmol / g or less.

  When the curable composition (α) contains silica particles whose surface is modified with a compound having an acryloyl group, the content thereof is based on 100 parts by weight of the total of the compound having an acryloyl group in the curable composition (α). It is preferably 1 part by weight or more, more preferably 5 parts by weight or more, still more preferably 10 parts by weight or more, on the other hand, preferably 200 parts by weight or less, and 100 parts by weight or less. It is more preferable that it is 60 parts by weight or less. By including silica particles whose surface is modified with a compound having an acryloyl group in the curable composition (α), the pencil hardness and scratch resistance of the layer (A) and the laminate can be improved. If the content of the silica particles whose surface is modified with a compound having a lower limit than the above upper limit, the resin curability, transparency, and stability of the blending solution are good, and if the content is higher than the lower limit, an acryloyl group is present. The above effect can be sufficiently obtained by the silica particles whose surface is modified with the compound having the above.

  In addition, as described above, the silica particles are preferably included as those whose surfaces are modified with a compound having an acryloyl group, but as a component of the mixture, a curable composition in a state where the surfaces are not modified. The silica particles that may be contained in the product (α) can be used in this case, and for example, the same silica particles as those dispersed in the solvent mentioned above can be used. Thus, in the curable composition (α), the content of the silica particles and the average primary particle diameter when they are contained as one component of the mixture are the silica particles whose surface is modified with a compound having an acryloyl group. It is the same.

(Photopolymerization initiator)
The curable composition (α) used in the present invention preferably contains a photopolymerization initiator in order to improve curability. Known photopolymerization initiators can be used. Examples of the photopolymerization initiator include a photo radical generator and a photo acid generator.

  Among the photopolymerization initiators that can be used for the curable composition (α), examples of the photo radical generator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and 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 [for example, 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- ON, 2-methyl-1- [4- (meth Acetophenones such as thio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone; 2,4,6-trimethylbenzoyl Phosphine oxides such as diphenylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Anthraquinones such as chloroanthraquinone and 2-amylanthraquinone; benzophenone and various derivatives thereof; formic acid derivatives such as methyl benzoylformate and ethyl benzoylformate; These may be used alone or in combination of two or more.

  Among these photo radical generators, acetophenones, phosphine oxides and formic acid derivatives are preferable from the viewpoint of light resistance of the cured product, and 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1 are more preferable. -[4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethyl Pentylphosphine oxide and methyl benzoylformate are preferable, and 1-hydroxycyclohexyl phenyl ketone and methyl benzoylformate are particularly preferable.

Known photoacid generators can be used. Among them, diaryliodonium salts and triarylsulfonium salts are preferable from the viewpoint of curability and acid generation efficiency. Specific examples include di (alkyl-substituted) phenyliodonium anion salts (specifically, PF ₆ salts, SbF ₅ salts, tetrakis (perfluorophenyl) borate salts, etc.). As a specific example of the anion salt of (alkyl-substituted) phenyliodonium, 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, the content thereof is a viewpoint of improving curability with respect to a total of 100 parts by weight of the compound having an acryloyl group in the curable composition (α). Therefore, it is preferably 0.01 parts by weight or more, 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 used as 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 organic solvents that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone (MIBK), and cyclohexanone; diethyl ether and isopropyl ether. , Tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether (PGM), anisole, phenetol and other ether solvents; ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol di Ester solvents such as acetate; dimethylformamide, diethylformamide, N-methylpyrrolide Amide solvents like; methyl cellosolve, 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.

  These organic solvents may be used individually by 1 type, and may use 2 or more types together. Of these organic solvents, ester solvents, ether solvents, alcohol solvents, and ketone solvents are preferably used.

  There is no restriction | limiting in particular in the usage-amount of an organic solvent, Considering the applicability | paintability of the prepared curable composition ((alpha)), the viscosity and surface tension of a liquid, compatibility of solid content, etc., it determines suitably. The curable composition (α) is prepared using the above-mentioned solvent, preferably as a coating liquid having a solid content concentration of 20 to 95% by weight, more preferably 30 to 80% by weight. Here, the “solid content” in the curable composition (α) means a component excluding the 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) described later.

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

[Layer (B)]
In the laminate of the present invention, the layer (B) is formed by applying a curable composition (β) containing at least a compound having an acryloyl group onto the layer (A) with a thickness of 2 to 40 μm. It is a layer obtained through a step of curing by irradiating active energy rays so that the reaction rate of the acryloyl group of β) is 60% or more. The curable composition (β) will be described below, and the formation method and suitable thickness of the layer (B) will be described later.
In addition, the curable composition (β) may be the same as or different from the curable composition (α).

<Curable composition (β)>
The curable composition (β) contains at least a compound having an acryloyl group. The acrylic equivalent of the curable composition (β) is preferably 100 g / mol or more from the viewpoint of preventing cracks when the layer (B) is cured. On the other hand, the upper limit of the acrylic equivalent of the curable composition (β) is not particularly limited, but is usually 10,000 g / mol or less, preferably 6,000 g / mol or less, more preferably 3,000 g / mol. Or less, more preferably 2,000 g / mol or less, and particularly preferably 1,000 g / mol or less.

(Compound having acryloyl group)
The compound having an acryloyl group contained in the curable composition (β) is not particularly limited, and examples thereof include the following (1) to (5).
(1) Monofunctional (meth) acrylate and its derivatives
(2) Polyfunctional (meth) acrylate and its derivatives
(3) Silica particles whose surface is modified with a compound having an acryloyl group
(4) A compound containing at least one of a perfluoroalkyl structure, a perfluoroalkylene structure, a perfluoropolyether structure and a polysiloxane structure and having one or more acryloyl groups in the molecule, hereinafter referred to as “(meth) acrylate” (Β) ”. )
(5) Reaction of a compound having a carboxyl group and an acryloyl group to a copolymer obtained by copolymerizing a silicone-containing (meth) acrylate represented by the following formula (1) and a (meth) acrylate having an epoxy group (Meth) acrylic copolymer (hereinafter, referred to as “(meth) acrylic copolymer (β)”).

(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.)

  Any one of the above-mentioned compounds having an acryloyl group (1) to (5) may be used alone, or two or more thereof may be mixed and used. Moreover, what was chosen from 2 or more types of compound groups in said (1)-(5) can also be used in mixture of multiple types.

  Among these, from the viewpoint of increasing the hardness of the layer (B), at least one of the group consisting of (2) polyfunctional (meth) acrylate and derivatives thereof and (3) silica particles whose surface is modified with a compound having an acryloyl group. In addition to these, (4) (meth) acrylate (β) and (5) (meth) acrylic copolymer (in terms of improving scratch resistance and antifouling properties) Preferably it comprises at least one of the group consisting of β).

  (1) Monofunctional (meth) acrylate and derivatives thereof, (2) Polyfunctional (meth) acrylate and derivatives thereof, and (3) Silica particles whose surface is modified with a compound having an acryloyl group include curable compositions (α ) Include those described above, and preferable ones are the same as those in the curable composition (α), but the hardness and scratch resistance of the cured film are improved, and the reactivity at the time of curing is also included. The number of acryloyl groups in the silica particles whose surface is modified with a polyfunctional (meth) acrylate and its derivative in the curable composition (β) and a compound having an acryloyl group is 3 or more. Preferably, it is 4 or more. Further, from the viewpoint of suitable viscosity for coating, it is preferably 9 or less, more preferably 7 or less.

  (4) Of the (meth) acrylate (β), the perfluoroalkyl group of the compound having a perfluoroalkyl structure and one or more acryloyl groups is preferably a perfluoroalkyl group having 4 to 12 carbon atoms. When the carbon number of the perfluoroalkyl group is 4 or more, it is preferable from the viewpoint of antifouling properties. On the other hand, when the carbon number is 12 or less, the solubility is good and the transparency and appearance of the resulting cured film are good. It is preferable because of its tendency. Specific examples of the compound having a perfluoroalkyl structure and one or more acryloyl groups include perfluorobutylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, perfluorohexylethyl (meth) acrylate, and the like. .

  The perfluoroalkylene group of the compound having a perfluoroalkylene structure and one or more acryloyl groups is preferably a C 4-12 perfluoroalkylene group. When the perfluoroalkylene group has 4 or more carbon atoms, it is preferable from the viewpoint of antifouling properties, and when the perfluoroalkylene group has 12 or less carbon atoms, the solubility is improved, This is preferable because the appearance tends to be good. Specific examples of the compound having a perfluoroalkylene structure and one or more acryloyl groups include perfluorooctanediol di (meth) acrylate, perfluorohexanediol sidi (meth) acrylate, perfluorobutanediol di (meth) acrylate, etc. Is mentioned.

  Examples of the compound having a perfluoropolyether structure and one or more acryloyl groups include those represented by the following formula (2).

(In said formula (2), X represents a hydrogen atom or a fluorine atom, and m is a number of 0-100.)

  The compound represented by the above formula (2) is preferably m = 1 to 20 and X = F in order to sufficiently exhibit its function. The compound represented by the above formula (2) can be produced by the method described in JP-A-2009-9138.

  A compound having a perfluoropolyether structure and one or more acryloyl groups can also be obtained as a commercial product. Examples of commercially available products include “OPTOOL (registered trademark) DAC-HP” manufactured by Daikin Industries, Ltd. Illustrated.

  As the compound having a polysiloxane structure and one or more acryloyl groups, those having a polydimethylsiloxane structure are preferred as the polysiloxane structure. Examples of such compounds include polydimethylsiloxane having an acryloyl group at one end (for example, As commercial products, Silaplane (registered trademark) FM0711, FM0721, FM0725, etc. manufactured by JNC), polydimethylsiloxane having an acryloyl group at both ends (for example, X-22-164A manufactured by Shin-Etsu Chemical Co., Ltd.) , Polydimethylsiloxane having an epoxy group at both ends and an acryloyl group in the side chain, polydimethylsiloxane in the main chain and / or side chain, and 1 to 2 acryloyl in the side chain and / or terminal And a copolymer having a group. Among these, polydimethylsiloxane having an acryloyl group at one terminal and / or both terminals is particularly preferable.

  The number average molecular weight (Mn) of the compound having a polysiloxane structure and one or more acryloyl groups is preferably 500 or more, more preferably 1,000 or more, while preferably 10,000 or less, More preferably, it is 8,000 or less. When the number average molecular weight of this compound is not less than the above lower limit value, it is preferable from the viewpoint of antifouling properties and slipperiness, and when it is not more than the above upper limit value, it is preferable from the viewpoint of maintaining compatibility with other components. .

(5) In the formula (1) representing a silicone-containing (meth) acrylate used as a raw material for the (meth) acrylic copolymer (β), R ¹ represents a hydrogen atom or a methyl group. R ¹ is preferably a methyl group in order to increase the glass transition temperature (Tg) of the resulting (meth) acrylic copolymer and increase the surface hardness when the layer (B) is cured. .

In formula (1), ^{R 2} is an alkylene group having 1 to 12 carbon atoms. The number of carbon atoms is preferably 2 or more, more preferably 3 or more, on the other hand, preferably 10 or less, and preferably 8 or less, in order to easily obtain the raw materials and to produce easily. It is more preferable.

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 is easy to produce.

In formula (1), R ⁵ is an alkyl group having 1 to 12 carbon atoms. The number of carbon atoms in R ⁵ is preferably 2 or more, more preferably 3 or more. On the other hand, the number of carbon atoms in R ⁵ is preferably 10 or less, and more preferably 8 or less. It is preferable for the carbon number of R ⁵ to be in the above range because the raw materials are easily available and are easy to produce.

  In Formula (1), n is an average value and is a number of 10-100. When n is 10 or more, the surface slipperiness of the cured film obtained by curing the curable composition (β) is sufficiently expressed and the slipperiness 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, when n is 100 or less, the solubility in a solvent is good. 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 obtained by calculation 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 sufficient to express the slipperiness of the cured film obtained by curing the curable composition (β). From the viewpoint of improving the quality, it is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 3,000 or more. 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 improving the solubility in a solvent. Is more preferably 10,000 or less, and still more preferably 10,000 or less.

  Among the silicone-containing (meth) acrylates represented by the formula (1), those having a polydimethylsiloxane structure are preferable, and polydimethylsiloxane having a methacryloyl group at one end as a particularly preferable one (as a specific example of a commercially available product, And "Silaplane (registered trademark) FM0711", "Silaplane (registered trademark) FM0721", "Silaplane (registered trademark) FM0725", etc.). In addition, the silicone-containing (meth) acrylate represented by the formula (1) may be used alone or in combination of two or more.

  Examples of the (meth) acrylate having an epoxy group used as a raw material for the (meth) acrylic copolymer include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( And (meth) acrylate. 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, other monomers may be further copolymerized. Other monomers are particularly limited as long as they have a carbon-carbon double bond and can be copolymerized with the silicone-containing (meth) acrylate represented by the formula (1) and the (meth) acrylate having an epoxy group. Although not mentioned, (meth) acrylates other than these, (meth) acrylamide, etc. can be mentioned, for example.

  Examples of other monomers 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 (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethyl (meth) ) 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 (Meth) acrylates such as: N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N- Tylmethyl (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-methylenebis 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. Other monomers are preferably alkyl (meth) acrylates having an alkyl group having 4 to 22 carbon atoms.

  The (meth) acrylic copolymer (β) is obtained by copolymerizing the silicone-containing (meth) acrylate represented by the formula (1), the (meth) acrylate having an epoxy group, and other monomers used as necessary. Although there is no restriction | limiting in particular in the usage-amount of each monomer at the time of manufacture, Preferably the silicone containing (meth) acrylate represented by Formula (1) is 5-90 weight%, (meth) acrylate 10-epoxy having an epoxy group. 95% by weight, and 0 to 80% by weight of other monomers used as necessary (however, a silicone-containing (meth) acrylate represented by the formula (1), a (meth) acrylate having an epoxy group, and as necessary The total of other monomers used is 100% by weight.), Particularly preferably a silicone-containing (meth) acrylate represented by the formula (1) 10 to 80% by weight, 20 to 90% by weight of (meth) acrylate having an epoxy group, and 5 to 60% by weight of other monomers used as necessary are used for scratch resistance and antifouling property. It is preferable from the viewpoint.

  The reaction of copolymerizing the silicone-containing (meth) acrylate represented by the formula (1), the (meth) acrylate having an epoxy group, and other monomers used as necessary is usually a radical polymerization reaction. Can be carried out in an organic solvent in the presence of a radical polymerization initiator. The reaction time of this reaction is usually 1 to 50 hours, preferably 3 to 12 hours. The organic solvents and radical polymerization initiators that can be used here 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; aromatic hydrocarbon solvents such as toluene and the like. 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. Organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2′-azobisbutyl Examples include azo compounds such as nitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more.

  The (meth) acrylic copolymer (β) is a copolymer of at least a silicone-containing (meth) acrylate represented by the formula (1), a (meth) acrylate having an epoxy group, and other monomers used as necessary. In this reaction, the reaction temperature is preferably 50 to 110 ° C, more preferably 55 to 100 ° C. The copolymer obtained by reacting a compound having a carboxyl group and an acryloyl group with the copolymer thus obtained. It is. Moreover, reaction time becomes like this. Preferably it is 3 to 50 hours, More preferably, it is 4 to 30 hours. This reaction is usually an addition reaction between the epoxy group of the (meth) acrylic copolymer (β) and a compound having a carboxyl group and an acryloyl group.

  Examples of the compound having a carboxyl group and an acryloyl group that 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 ( Examples include adducts of meth) acrylate and succinic anhydride, adducts of pentaerythritol tri (meth) acrylate and phthalic anhydride, and the like. Among these, an adduct of (meth) acrylic acid, pentaerythritol tri (meth) acrylate and succinic anhydride is preferable. In addition, the compound which has a carboxyl group and an acryloyl group may be used individually by 1 type, or may be used in combination of 2 or more type.

  The compound having a carboxyl group and an acryloyl group is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, as the mol% of the carboxyl group with respect to the epoxy group in the (meth) acrylic copolymer (β). Particularly preferably, it is used in a proportion of 50 to 110 mol%. It is preferable to react the compound having an acryloyl group with the (meth) acrylic copolymer (β) in the above range from the viewpoint of allowing the reaction to proceed without excess and deficiency and reducing the residue of the raw material.

  Moreover, in order to accelerate | stimulate the reaction which adds the compound which has a carboxyl group and an acryloyl group to (meth) acrylic-type copolymer ((beta)), it can be made to react 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, more preferably 0.05 to 1% by weight, based on the total amount of raw materials. In addition, in this reaction, you may make it react using the organic solvent used for reaction in manufacture of a (meth) acrylic-type copolymer ((beta)) as it is, and you may make it react by adding an organic solvent suitably. The organic solvents that can be used for this reaction are the same as those listed above.

  When curable composition (β) contains (meth) acrylate (β), the content of (meth) acrylate (β) relative to the total of compounds having an acryloyl group in curable composition (β) is 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and preferably 10% by weight or less. It is more preferably 5% by weight or less, and further preferably 3% by weight or less. When the content of (meth) acrylate (β) is not less than the above lower limit value, it is preferable from the viewpoint of antifouling properties and scratch resistance, and on the other hand, the solution stability of the curable composition is not more than the above upper limit value. It tends to be good, and the surface hardness is not too soft, which is preferable from the viewpoint of scratch resistance.

  When the curable composition (β) contains the (meth) acrylic copolymer (β), the (meth) acrylic copolymer is used for the total of the compounds having an acryloyl group in the curable composition (β). The content of the combination (β) is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, further preferably 0.2% by weight or more, It is preferably no more than wt%, more preferably no more than 5 wt%, and even more preferably no more than 3 wt%. When the content of the (meth) acrylic copolymer (β) is not less than the above lower limit value, it is preferable from the viewpoint of antifouling properties and scratch resistance, and on the other hand, it is not more than the above upper limit value of the curable composition. The solution stability tends to be good, and the surface hardness is not too soft, which is preferable from the viewpoint of scratch resistance.

  The curable composition (β) is, as a compound having an acryloyl group, (2) a polyfunctional (meth) acrylate and a derivative thereof and (3) a silica particle whose surface is modified with a compound having an acryloyl group. And (4) (meth) acrylate (β) and (5) (meth) acrylic copolymer (β) at least one (hereinafter sometimes referred to as “mainly responsible for curability”) When including at least one of the groups (hereinafter sometimes referred to as “mainly responsible for antifouling properties”), the proportion of the main component responsible for curability in the total of these is 90 to 99.95 wt. The proportion of the component mainly responsible for antifouling is preferably 0.05 to 10% by weight, more preferably the proportion of the component mainly responsible for curability is 95 to 99.9% by weight. Contaminant ingredient The ratio of the component mainly responsible for curability is 97 to 99.8% by weight, and the ratio of the component mainly responsible for antifouling is preferably 0.2 to 3%. It is preferable in terms of balance between curability, antifouling property and scratch resistance.

(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 photopolymerization initiator that can be used here is the same as that mentioned in the curable composition (α).

  When the curable composition (β) contains a photopolymerization initiator, the content thereof is from the viewpoint of improving curability with respect to a total of 100 parts by weight of the compounds having an acryloyl group in the curable composition (β). The amount is preferably 0.01 parts by weight or more, and more preferably 0.1 parts by weight or more. On the other hand, from the viewpoint of maintaining the stability of the liquid when the curable composition (β) is used as a solution and the scratch resistance when the curable composition (β) is cured, it is preferably 10 parts by weight or less. More preferably, it is 8 parts by weight or less.

(Organic solvent)
The curable composition (β) used in the present invention is preferably an organic solvent. The kind and amount of the organic solvent that 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 may contain other components other than the compound having an acryloyl group, the photopolymerization initiator, and the organic solvent as long as the effects of the present invention are not impaired. Other components include UV absorbers, hindered amine light stabilizers, fillers, silane coupling agents, reactive diluents, antistatic agents, organic pigments, slip agents, dispersants, thixotropic agents (thickeners). ), Antifoaming agents, antioxidants, leveling agents and the like.

[Manufacturing method of laminate]
The laminated body of this invention can be manufactured by laminating | stacking each layer one by one 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).
In the laminate of the present invention, the layer (A) and the layer (B) may be formed only on one surface of the base material layer, and the layer (A) and the layer (B) are formed on both surfaces. May be.

In the layer (A) of the laminate of the present invention, the curable composition (α) described above is applied on the substrate layer with a thickness of 2 to 40 μm, and the reaction rate of the acryloyl group of the curable composition (α) is high. It is formed by performing at least one step of irradiating and curing the active energy ray so as to be 5% or more and less than 60%.
In addition, the layer (B) is obtained by applying the curable composition (β) described above on the layer (A) with a thickness of 2 to 40 μm, and the acryloyl group reaction rate of the curable composition (β) is 60% or more. It forms through the process of irradiating and curing an active energy ray.
In addition, the reaction rate of an acryloyl group is calculated | required by the method described in the term of the below-mentioned Example.

  For example, each of the layers (A) and (B) includes a curable composition (α) and a curable composition (β) on a base material layer (in the case of the layer (B), on the layer (A)). It can be formed by irradiating with active energy rays so as to satisfy the above-mentioned curing conditions. Examples of a method for applying these curable compositions onto the substrate or layer (A) include, for example, reverse coating, gravure coating, rod coating, bar coating, Mayer bar coating, die coating, and spray coating. Law. In the present invention, “application” means a step of applying a curable composition (α) or a curable composition (β) before curing.

  In the laminate of the present invention, active energy rays that can be used when curing the curable compositions (α) and (β) include ultraviolet rays, electron beams, 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.

When the curable compositions (α) and (β) are cured by ultraviolet irradiation when the laminate of the present invention is produced, various ultraviolet irradiation devices can be used, and the light source thereof is a xenon lamp, a high pressure Mercury lamps, metal halide lamps, LED-UV lamps, and the like can be used. Irradiation amount of the ultraviolet (in mJ / cm ²⁾ is usually 10~10,000mJ / cm ^2, the flexible curable composition (alpha), curable, the cured product of the (beta) (cured film) From the viewpoint of properties and the like, it is preferably 15 to 5,000 mJ / cm ² , more preferably in the range of ^{20 to} 3,000 mJ / cm ² , depending on the reaction rate of the acryloyl group required in each curing step. It is determined.

  Moreover, when manufacturing the laminated body of this invention, when hardening curable composition ((alpha)) and ((beta)) by electron beam irradiation, a various electron beam irradiation apparatus can be used. The irradiation amount (Mrad) of the electron beam is usually 0.5 to 20 Mrad, and the viewpoints such as curability of the curable compositions (α) and (β), flexibility of the cured product, and prevention of damage to the substrate, etc. To preferably in the range of 1 to 15 Mrad, depending on the reaction rate of the acryloyl group required in each curing step.

<Layer (A)>
As described above, the layer (A) is formed by applying the curable composition (α) on the base material layer with a thickness of 2 to 40 μm, and the reaction rate of the acryloyl group of the curable composition (α) is 5% or more 60 It is formed by performing the step of curing by irradiating active energy rays so as to be less than 1% at least once.

In forming the layer (A), if the coating thickness in one curing step is not less than the above lower limit, inhibition of the crosslinking reaction due to oxygen at the time of curing can be suppressed and the hardness becomes high, and conversely below the above upper limit. A cured film having a uniform film thickness distribution can be obtained. Further, when the reaction rate of the acryloyl group in one curing step is not less than the above lower limit, blocking at the time of winding during production can be suppressed, and a film with high hardness can be formed. On the contrary, when it is not more than the above upper limit, a laminate excellent in interlayer adhesion can be obtained. That is, in the laminate of the present invention, the reaction rate of the acryloyl group in the curing step of the lower layer (A) is set to less than 60%, and the curable composition (β) is applied thereon in a state where the curing is not completed. By curing with an acryloyl group reaction rate of 60% or more, the curing of the layer (A) is completed at the time of curing of the layer (B) and unreacted in the curable composition (α) of the layer (A). By reacting the acryloyl group with the acryloyl group in the curable composition (β) of the layer (B), interlayer adhesion between the layer (A) and the layer (B) is enhanced. From the viewpoint of the hardness of the layer (A) and the interlayer adhesion with the layer (B), the reaction rate of the acryloyl group in one curing step is preferably 10% or more, and more preferably 15% or more. More preferably, it is particularly preferably 20% or more. Moreover, it is preferable that it is 55% or less, and it is more preferable that it is 50% or less. The irradiation amount of the active energy ray when curing is performed so as to achieve such a reaction rate of the acryloyl group is usually about ²⁰ to 200 mJ / cm ² .

  In forming the layer (A), the curable composition (α) is applied on the substrate layer with a thickness of 2 to 40 μm, and the reaction rate of the acryloyl group of the curable composition (α) is 5% or more and less than 60%. The step of curing by irradiating with active energy rays is preferably performed twice or more, and by performing such a curing step twice or more, the degree of internal cross-linking in the vicinity of the base material layer is increased, and more pencil A laminate having high hardness can be obtained. However, from the viewpoint of productivity, this step is usually 4 times or less, preferably 3 times or less.

  In addition, although the kind of curable composition ((alpha)) used in each process, the application | coating thickness of a curable composition ((alpha)), and the reaction rate of acryloyl group may be the same or different, acryloyl group As for the reaction rate, it is preferable that the active energy ray irradiation conditions for achieving the desired acryloyl group reaction rate are the same in all steps, and the same in order to simplify the apparatus specifications and operation. Moreover, it is preferable that the curable composition (α) is the same in order to improve the interlayer adhesion of the layer formed in each step.

  The thickness of the layer (A) thus formed is preferably thicker from the viewpoint of pencil hardness of the resulting laminate, and thinner from the viewpoint of crack resistance. Therefore, the thickness of the layer (A) is preferably 2 μm or more, more preferably 10 μm or more, still more preferably 23 μm or more, particularly preferably 30 μm or more, while preferably 100 μm or less, More preferably, it is 90 micrometers or less, More preferably, it is 80 micrometers or less, Most preferably, it is 70 micrometers or less. In addition, when forming a layer (A) through two or more hardening processes, it is 2-40 micrometers as above-mentioned about the thickness of the layer formed by one hardening process, Preferably it is 4 micrometers or more. More preferably, it is 5 μm or more, while it is preferably 30 μm or less, more preferably 18 μm or less.

<Layer (B)>
As described above, in the tank (B), the curable composition (β) was applied on the layer (A) with a thickness of 2 to 40 μm, and the reaction rate of the acryloyl group of the curable composition (β) was 60%. It forms through the process of irradiating and curing an active energy ray so that it may become the above.

A layer (B) is normally formed by performing said process once. The unreacted acryloyl group of the layer (A) is reacted by curing so that the reaction rate of the acryloyl group in the curing step when forming the layer (B) is 60% or more, preferably 70% or more. At the same time, the reaction of the acryloyl group in the curable composition (β) of the layer (B) can be sufficiently advanced to form a good cured film having excellent scratch resistance and high pencil hardness. The irradiation amount of the active energy ray when curing is performed so as to obtain such a reaction rate of the acryloyl group is usually about 300 to 2,000 mJ / cm ² .

  The thickness of the layer (B) thus formed is preferably thicker from the viewpoint of pencil hardness and scratch resistance of the resulting laminate, and thinner from the viewpoint of crack resistance. Therefore, the thickness of the layer (B) is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, particularly preferably 5 μm or more, while preferably 100 μm or less, More preferably, it is 40 micrometers or less, More preferably, it is 30 micrometers or less, Especially preferably, it is 15 micrometers or less, Especially preferably, it is 10 micrometers or less.

  Further, the total thickness of the layer (A) and the layer (B) is preferably 10 μm or more, more preferably 30 μm or more, on the other hand, preferably 100 μm or less, and 50 μm or less. It is more preferable.

  In addition, in the laminated body of this invention, in a range which does not inhibit the effect of this invention in each between a base material layer and a layer (A) and between a layer (A) and a layer (B), It may be laminated.

  Further, the total thickness of the laminate of the present invention is preferably 30 μm or more, more preferably 60 μm or more, more preferably 80 μm or more from the viewpoint of ensuring the thickness of each layer and fully exhibiting each function. It is particularly preferred. On the other hand, the thickness is preferably 300 μm or less, more preferably 250 μm or less, and particularly preferably 150 μm or less from the viewpoint of reducing the thickness and weight of the product to which the laminate of the present invention is applied.

[Usage]
The laminate of the present invention is excellent in pencil hardness, scratch resistance, transparency, interlayer adhesion, antifouling property and the like. For this reason, the laminated body of the present invention includes optical display parts such as touch panels and liquid crystal televisions; automobile-related parts such as lamp-related articles and window-related articles (rear windows, side windows, skylights, etc.); It can be suitably used for the surface cover of a wide range of articles such as life-related articles such as decorative panels and furniture. Among these, it can be particularly suitably used as a surface cover for optical display components such as a touch panel and a liquid crystal television, that is, a display body cover.

  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”.

(Evaluation of laminate)
The laminates obtained in the following Examples / Comparative Examples (only the base material in Comparative Example 7) were evaluated by the following methods.

(1) Adhesiveness A cross-cut peel test (10 × 10 squares) was performed once in accordance with JIS K-5400 on the layer (B) of the laminate, and the following evaluation was performed according to the number of squares where the film remained. .
◎: 90 or more ○: 80-89 △: 50-79 ×: 49 or less

(2) Pencil hardness The layer (B) or substrate of the laminate is measured based on the conditions of JIS K-5400 using a JIS-compliant pencil hardness tester (manufactured by Dazai Equipment Co., Ltd.) I checked the count of the hard pencil. A pencil hardness of 4H or higher was accepted.

(3) Transparency (haze)
According to JIS K-7136, the haze value of the laminate or the substrate was measured with a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory) and evaluated as follows.
○: Less than 1.0 Δ: 1.0 or more and less than 2.0 ×: 2.0 or more

(4) Steel wool wear resistance (abrasion resistance)
# 0000 steel wool with a load of 200 g / cm ² , the layer (B) of the laminate or the surface of the substrate was rubbed 20 times, and the degree of damage to the cured film or substrate of the layer (B) after the test was as follows: It evaluated as follows. In addition, △ or more was considered as a pass.
◎: 0 to 10 scratches ○: 11 to 20 scratches △: 21 to 100 scratches ×: countless scratches or whitening

(5) Antifouling With black magic (“Mackey Care Black” manufactured by Zebra Corporation), the layer (B) of the laminate or the surface of the substrate is painted in a 1 cm × 1 cm range in black, and after standing for 10 seconds, the surface The operation of wiping with a nonwoven fabric (“KURAFLEX CLEAN WIPER” manufactured by Kuraray Co., Ltd.) was repeated, and the number of times until the wiping was impossible (the written magic remained black) was examined and evaluated as follows.
◎: 10 times or more ○: 2-9 times △: 1 time ×: 0 times

(Synthesis example)
<Synthesis Example 1>
To a reactor equipped with a stirrer, a reflux condenser, and a thermometer, a methyl ethyl ketone (MEK) solution of colloidal silica (catalog value: average primary particle size 10 to 20 nm (catalog value)) ("MEK-ST" manufactured by Nissan Chemical Co., Ltd.) ”, 303.3% by weight (non-volatile content), 293.3 parts by weight, 12 parts by weight of 3- (acryloyloxy) propyltrimethoxysilane (“ KBM-5103 ”manufactured by Shin-Etsu Chemical Co., Ltd.), and 16.5 parts by weight of MEK were added, and stirring was started. Later, dry air was passed through the system, and the temperature was raised to 70 ° C. To this, 0.05 parts by weight of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.), 1 part by weight of water, 0.5 parts by weight of acetylacetone aluminum (manufactured by Kishida Chemical Co., Ltd.) and 1 part by weight of MEK were added. The mixture was stirred for a time to obtain a MEK solution of colloidal silica (Ac-Si) whose surface was modified with an acryloyl group. The composition of the reaction solution was Ac-Si / MEK = 31/69 (weight ratio). The amount of acryloyl group modified on the surface of the silica particles was 0.49 mmol / g.

<Synthesis Example 2>
To a reactor equipped with a stirrer, a reflux condenser, and a thermometer, a one-terminal methacryloyl group-substituted polydimethylsiloxane having a number average molecular weight of 5,000 ("Silaplane (registered trademark) FM0721" manufactured by JNC, the above formula (1) 10 parts by weight of a compound containing a silicone-containing (meth) acrylate represented by the formula: 60 parts by weight of glycidyl methacrylate (Mitsubishi Rayon “Acryester G”), methyl methacrylate (Mitsubishi Rayon “Acryester M”) 20 Part by weight, 10 parts by weight of stearyl methacrylate (“Acryester S” manufactured by Mitsubishi Rayon Co., Ltd.), and 150 parts by weight of methyl isobutyl ketone (MIBK) were charged, and after the start of stirring, the system was purged with nitrogen and heated to 55 ° C. Here, 0.02 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), 1-dodecanethiol (manufactured by Wako Pure Chemical Industries), 0. After adding 09 parts by weight, the system was heated to 65 ° C. and stirred for 3 hours, and then 0.06 parts by weight of V-65 was added and stirred at 65 ° C. for 3 hours. The temperature inside the system was raised to 100 ° C. and stirred for 30 minutes, after which 98.2 parts by weight of MIBK was added, and the temperature inside the system was again raised to 100 ° C. After adding 0.05 parts by weight of p-methoxyphenol (manufactured by Wako Pure Chemical Industries) and 2.6 parts by weight of triphenylphosphine (manufactured by Wako Pure Chemical Industries), acrylic acid (manufactured by Mitsubishi Chemical) 31 parts by weight was added, the temperature was raised to 110 ° C. and the mixture was stirred for 6 hours, and 64.1 parts by weight of MIBK was added to obtain a copolymer (PDMS-Ac) solution. The composition of the reaction solution was PDMS-Ac / MIBK = 30/70 (weight ratio).

[Examples and Comparative Examples]
[Examples 1-12, Comparative Examples 1-7]
<Preparation of coating liquid>
Coating liquids (curable compositions) HC-1, HC-2, HC-3 and HC-4 were prepared according to the composition shown in Table-1.

In addition, the symbol in Table-1 is as follows.
DPHA: Dipentaerythritol penta / hexaacrylate (“Kayarad (registered trademark) DPHA” manufactured by Nippon Kayaku)
M313: Bis / Tris (acryloxyethyl) isocyanurate ("Aronix (registered trademark) M-313" manufactured by Toa Gosei)
PF77: Acrylic leveling agent (“Polyflow No. 77” manufactured by Kyoeisha Chemical Co., Ltd.)
PFPE-Ac: Compound having a perfluoropolyether structure and an acryloyl group (non-volatile content of “OPTOOL (registered trademark) DAC-HP” manufactured by Daikin)
HFCP: 1,1,2,2,3,3,4-heptafluorocyclopentane (50% by weight contained in the “OPTOOL® DAC-HP” product)
Irg184: 1-hydroxycyclohexyl phenyl ketone ("Irgacure (registered trademark) 184" manufactured by BASF)

<Manufacture and evaluation of laminate>
Using the obtained coating solution, after coating on a PET film having a thickness of 100 μm (“O321E100 (CE SE98-)” manufactured by Mitsubishi Plastics, Inc.) according to the conditions described in Table 2, a high-pressure mercury lamp was used. The process of irradiating with ultraviolet rays and curing was repeated to obtain a cured film of each layer. In addition, coating conditions A to C in Table-2 are as follows.
Coating condition A: high pressure mercury lamp output 80 W, UV illuminance 100 mW / cm ² ,
UV irradiation 50mJ / cm ²
Coating condition B: high-pressure mercury lamp output 120W, illuminance 450mW / cm ² ,
UV irradiation amount 500 mJ / cm ²
Coating condition C: high-pressure mercury lamp output 120 W, UV illuminance 450 mW / cm ² ,
UV irradiation 700mJ / cm ²

Moreover, the reaction rate of acryloyl group in Table-2 (indicated as “reaction rate” in Table-2) is the total reflection type FT from the coating film surface side before and after curing after applying and drying the coating liquid in each step. -IR (ATR FT-IR) is used to measure the spectrum on the cured film surface side, and the intensity of the acryloyl group C = O-derived peak (1722 cm ^-1 ) and the C = C double bond-derived peak (808 cm ^-1 ) It calculated from the ratio using the following formula.
Reaction rate [%] = [1- (Sa ₈₀₈ / Sa ₁₇₂₂ ) / (Sb ₈₀₈ / Sb ₁₇₂₂ )] × 100
Sa _860: peak intensity of 808cm ^-1 after curing sa _1700: peak intensity Sb ₈₆₀ of 1722 cm ^-1 after curing: peak intensity of uncured 808cm ^-1 Sb _1700: peak strength of a cured before 1722 cm ^-1

In addition, the apparatus and measurement conditions used for the measurement of ATR FT-IR are as follows.
Device name: FT-IR Spectrometer manufactured by Perkin Elmer
Option “Universal ATR” to “Spectrum100”
Sampling Accessory "Replacing the light source: MIR [800-30] ^{cm -1}
Beam splitter: OptKBr [7800-400] cm ⁻¹
Detector: MIR TGS [15000-370] cm ⁻¹
Window material: Opt KBr
Optimal scanning range: [7800-650] cm ⁻¹
Crystal: Diamond / ZnSe
Number of reflections: 1
Measurement range: 4000-600 cm ⁻¹
Resolution: 4cm ^-1
Integration count: 4 scans

  About the obtained laminated body, said (1)-(5) evaluation was performed. The results are shown in Table-3. In addition, the comparative example 7 is a result of only the base material in which nothing is applied.

From Tables 2 and 3, according to the present invention, the interlaminar adhesion, pencil hardness, transparency and scratch resistance are excellent. In particular, the curable composition (β) constituting the layer (B) has the above-mentioned (meta ) Use acrylic copolymer (β) or (meth) acrylate (β), or use silica particles whose surface is modified with a compound having an acryloyl group in the curable composition (α) constituting the layer (A). Thus, it can be seen that the laminate can be more excellent in antifouling property and scratch resistance.
On the other hand, pencil hardness is low in Comparative Examples 1 to 4 having only the layer (B) and no layer (A).
In Comparative Example 5 in which the reaction rate of the compound having an acryloyl group in the curable composition of the layer (A) or the layer (B) does not satisfy the present invention even if the layer (A) and the layer (B) are included. Interlayer adhesion was inferior, and the coating film was peeled off at the time of measuring the pencil hardness, and thus could not be evaluated. In Comparative Example 6, the scratch resistance is inferior.

Claims (10)

The laminated body which has the following layer (A) and the following layer (B) in this order from the base material layer side at least on one surface on a base material layer.
Layer (A): A curable composition (α) containing at least a compound having an acryloyl group is applied on a substrate layer with a thickness of 2 to 40 μm, and the reaction rate of the acryloyl group of the curable composition (α) is 5 % (B): a curable composition (β) containing at least a compound having an acryloyl group. It is applied on the layer (A) with a thickness of 2 to 40 μm, and is obtained through a step of curing by irradiation with active energy rays so that the reaction rate of the acryloyl group of the curable composition (β) is 60% or more. layer   The curable composition (β) of the layer (B) includes at least one of a perfluoroalkyl structure, a perfluoroalkylene structure, a perfluoropolyether structure, and a polysiloxane structure, and one or more in the molecule. The laminated body of Claim 1 which contains 0.05-10 weight% of compounds which have an acryloyl group with respect to the sum total of the compound which has an acryloyl group in a curable composition ((beta)). A copolymer obtained by copolymerizing the curable composition (β) of the layer (B) with at least a silicone-containing (meth) acrylate represented by the following formula (1) and a (meth) acrylate having an epoxy group. The (meth) acrylic copolymer obtained by reacting the polymer with a compound having a carboxyl group and an acryloyl group is from 0.05 to the total of the compounds having an acryloyl group in the curable composition (β). The laminate according to claim 1 or 2, comprising 10% by weight.

(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 laminate according to claim 3, wherein the (meth) acrylic copolymer is obtained by copolymerizing an alkyl (meth) acrylate having an alkyl group having 4 to 22 carbon atoms.   The laminated body of any one of Claims 1 thru | or 4 in which the said curable composition ((alpha)) contains a silica particle with an average primary particle diameter of 1-100 nm.   The layer (A) is formed by coating the curable composition (α) on the substrate layer with a thickness of 2 to 40 μm, and the reaction rate of the acryloyl group of the curable composition (α) is 5% or more and less than 60%. The laminate according to any one of claims 1 to 5, which is obtained by performing the step of irradiating and curing the active energy ray at least twice.   The laminate according to any one of claims 1 to 6, wherein the layer (A) has a thickness of 2 to 100 µm.   The laminated body of any one of Claims 1 thru | or 7 whose thickness of the said layer (B) is 2-100 micrometers.   The said base material layer is a layer which consists of at least 1 sort (s) of resin chosen from polyethylene terephthalate resin, polymethyl methacrylate resin, polycarbonate resin, hydrogenated polyimide resin, and polycycloolefin resin. The laminate according to claim 1.   The display body cover which consists of a laminated body of any one of Claims 1 thru | or 9.