JP5895005B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate. More specifically, the present invention relates to a laminate having transparency and surface hardness suitable as an optical member and excellent in impact resistance.

  Conventionally, glass has been used as a substrate for display elements such as liquid crystal displays, organic EL displays, touch panels, etc., but alternatives to plastic substrates are being studied due to features such as light weight and resistance to cracking. Various thickness plastic substrates have been proposed. In particular, as a substitute for a glass substrate, a plastic substrate having a thickness (0.1 mm to 1 mm) and rigidity (high hardness, high elastic modulus) is required.

  Thermoplastic transparent plastic films such as PET (Poly (ethylene terephthalate)) and polyester such as PEN (Poly (ethylene naphthalate)), polycarbonate (PC), polymethyl methacrylate (PMMA), amorphous polyolefin (amorphous PO) Has excellent properties such as light weight, resistance to cracking and bending. Since these plastic films have low surface hardness and are easily damaged, a hard coat layer is provided. However, if the surface hardness of the plastic film itself is low, there is a tendency that sufficient surface hardness cannot be obtained even if a hard coat layer is provided, and a plastic substrate having a high surface hardness is desired.

  Since the curable resin film has a cross-linked structure, the surface hardness can be increased. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2001-114850) describes a cured product having a pencil hardness of H to 5H obtained by curing a polyfunctional acrylate. Such a polyfunctional acrylate base material has a high surface hardness, but has a relatively large volume shrinkage rate and is not sufficient in impact resistance, which is a mechanical property. If the impact resistance is low, cracking tends to occur, which is not preferable as a member for a display device.

JP 2001-114850 A

  An object of the present invention is to provide a transparent laminate excellent in surface hardness and impact resistance suitable as an optical member.

In order to achieve this object, the present inventors have intensively studied, and as a result, found that the object can be achieved by forming a laminated structure including a specific substrate, and completed the present invention.
That is, the present invention includes the following items [1] to [9].
[1] A laminate comprising at least one allyl ester resin layer, wherein at least one surface of the allyl ester resin layer is laminated with another resin layer or a glass layer via an adhesive layer.
[2] The other resin layer is an allyl ester resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, cycloolefin polymer, triacetyl cellulose, polyimide, polyaramid, polyethersulfone, siloxane polymer, or fluorine. 2. The laminate according to item 1, wherein the laminate is selected from a polymer, an amorphous polyolefin, an unsaturated polyester resin, a vinyl ester resin, an epoxy resin, and a urethane acrylate resin.
[3] The laminate according to item 2 above, wherein the other resin layer is selected from allyl ester resin, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and siloxane-based polymer.
[4] The laminate according to item 1 above, wherein the glass is float plate glass, tempered glass, or heat-resistant glass made of soda lime glass, borosilicate glass, or quartz glass.
[5] The laminate according to item 4 above, wherein the tempered glass is Gorilla glass manufactured by Corning Display Technology.
[6] The laminate according to any one of items 1 to 5, wherein the adhesive layer includes an acrylate-based material.
[7] The acrylate-based material includes an acrylic acid alkyl ester (monomer) as a main component, an alkyl (meth) acrylate having an alkyl group having 3 or less carbon atoms, acrylic acid, methacrylic acid, an acrylamide derivative, maleic acid, hydroxyl 7. The laminate according to item 6 above, which is obtained by copolymerizing at least one selected from ethyl acrylate and glycidyl acrylate.
[8] The laminate according to any one of items 1 to 7, wherein the total light transmittance is 85% or more.
[9] The laminate according to any one of items 1 to 8, wherein the total thickness is 0.1 mm to 1 mm.

ADVANTAGE OF THE INVENTION According to this invention, the transparent member excellent in surface hardness and impact resistance suitable for optical uses, such as a display substrate and a solar cell substrate, can be obtained.

Hereinafter, the present invention will be described in more detail.
The laminate of the present invention includes at least one allyl ester resin layer, and at least one surface of the allyl ester resin layer is laminated with another resin layer or a glass layer via an adhesive layer.

[Allyl ester resin]
The allyl ester resin constituting the allyl ester resin layer, which is an essential component in the present invention, is a kind of thermosetting resin.
In general, “allyl ester resin” refers to a prepolymer (including an oligomer, an additive, and a monomer) before curing, and a cured product in two cases. Then, “allyl ester resin” indicates a cured product, and “allyl ester resin composition” indicates a prepolymer before curing.

[Allyl ester resin composition]
The allyl ester resin composition used in the present invention is a composition containing an allyl group or a methallyl group (hereinafter sometimes referred to as a (meth) allyl group) and a compound having an ester structure as main curing components. is there.

  The compound having a (meth) allyl group and an ester structure is (1) an esterification reaction between a compound containing a (meth) allyl group and a hydroxyl group (herein collectively referred to as allyl alcohol) and a compound containing a carboxyl group, (2) It can be obtained by an esterification reaction between a compound containing a (meth) allyl group and a carboxyl group and a compound containing a hydroxyl group, or (3) an ester exchange reaction between an ester compound consisting of allyl alcohol and dicarboxylic acid and a polyhydric alcohol. When the compound containing a carboxyl group is a polyester oligomer of a dicarboxylic acid and a diol, only the terminal can be an ester with allyl alcohol.

（Ｒ¹及びＲ²は、それぞれ独立してアリル基またはメタリル基のいずれかの基を表し、Ａ¹はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）で示される化合物の中から選ばれる少なくとも１種以上の化合物が挙げられる。この化合物は後述のアリルエステルオリゴマーの原料となるほか、反応性希釈剤（反応性モノマー）として本発明のアリルエステル樹脂組成物に含まれていてもよい。一般式（１）中のＡ¹は後述の一般式（２）、一般式（３）におけるＡ²、Ａ³と同様のものが好ましい。As a specific example of the ester compound consisting of (meth) allyl alcohol and dicarboxylic acid, the following general formula (1)

(R ¹ and R ² each independently represents either an allyl group or a methallyl group, and A ¹ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. Represents at least one compound selected from the compounds represented by the formula: In addition to being a raw material for the allyl ester oligomer described below, this compound may be contained in the allyl ester resin composition of the present invention as a reactive diluent (reactive monomer). A ¹ in general formula (1) is preferably the same as A ² and A ³ in general formula (2) and general formula (3) described later.

  As a compound having an (meth) allyl group and an ester structure, which is the main curing component of the allyl ester resin composition, an ester formed from a polyhydric alcohol and a dicarboxylic acid having an allyl group and / or a methallyl group as a terminal group It is preferably an allyl ester compound having a structure (hereinafter, this may be referred to as “allyl ester oligomer”). The allyl ester resin composition may contain a curing agent, a reactive monomer, an additive, and other radical-reactive resin components described later as components other than the above compounds.

（式中、Ｒ³はアリル基またはメタリル基を表し、Ａ²はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）

（式中、Ａ³はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表し、Ｘは多価アルコールから誘導された一種以上の有機残基を表す。ただし、Ｘはエステル結合によって、さらに上記一般式（２）で示される基を末端基とし、上記一般式（３）で示される構造を構成単位とする分岐構造を有することができる。）[Allyl ester oligomer]
The main component of the allyl ester resin composition used in the present invention is an allyl ester having a group represented by the following general formula (2) as a terminal group and a structure represented by the following general formula (3) as a structural unit. An oligomer is preferable.

(Wherein R ³ represents an allyl group or a methallyl group, and A ² represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid.)

(In the formula, A ³ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol. However, X may have a branched structure having a group represented by the above general formula (2) as a terminal group and a structure represented by the above general formula (3) as a constituent unit by an ester bond.

In the allyl ester oligomer, the number of terminal groups represented by the general formula (2) is at least 2 or more, but when X in the general formula (3) has a branched structure, the number is 3 or more. In this case, although also R ³ at each end groups there are a plurality, each of these R ³ may not necessarily be the same type, some end there in the structure of an allyl group, the other terminal methallyl group It doesn't matter. Moreover, not all R ³ must be an allyl group or a methallyl group, and a part thereof may be a non-polymerizable group such as a methyl group or an ethyl group as long as the curability is not impaired. Similarly, the structure represented by A ² may be different for each terminal group. For example, A ^{2 at} one terminal may be a benzene ring and the other may be a cyclohexane ring.

A ² in the general formula (2) is one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. The moiety derived from the dicarboxylic acid is indicated by a carbonyl structure adjacent to A ² . Therefore, A ² represents a benzene skeleton or a cyclohexane skeleton.

There are no particular limitations on the dicarboxylic acid to induce A ² structure, from the viewpoint of ready availability of raw materials, terephthalic acid, isophthalic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic Acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl-m, m′-dicarboxylic acid, diphenyl-p, p′-dicarboxylic acid, benzophenone-4, 4′-dicarboxylic acid, p-phenylenediacetic acid, p-carboxyphenylacetic acid, methyl terephthalic acid and tetrachlorophthalic acid are preferred, and terephthalic acid, isophthalic acid, phthalic acid and 1,4-cyclohexanedicarboxylic acid are particularly preferred. Among these, it is preferable to use 1,4-cyclohexanedicarboxylic acid having no aromatic ring in the molecule from the viewpoint of light resistance, and it is preferable to use 1,4-cyclohexanedicarboxylic acid for applications requiring high transparency.

  In addition, within the range that does not impair the effects of the present invention, acyclic dicarboxylic acids (during the reaction) such as maleic acid, fumaric acid, itaconic acid, citraconic acid, endic acid anhydride and chlorendic acid are used. Also good.

  At least one structural unit represented by the general formula (3) is necessary in the allyl ester oligomer. However, when this structure is repeated, the molecular weight of the allyl ester oligomer as a whole increases to some extent. Since it is obtained, workability is improved, and the toughness of the cured product is also improved, which is preferable. However, if the molecular weight is too large, the molecular weight between cross-linking points is too large, so that the glass transition temperature (Tg) is lowered and the heat resistance may be lowered. It is important to adjust to an appropriate molecular weight according to the application. The weight average molecular weight of the allyl ester oligomer is preferably 500 to 200,000, more preferably 1,000 to 100,000.

In addition, A ³ in the general formula (3) is one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid, and examples of the definition and preferred compounds thereof are the general formula (2). The same as A ² in FIG.

  X in the general formula (3) represents one or more organic residues derived from a polyhydric alcohol. The polyhydric alcohol is a compound having two or more hydroxyl groups, and X itself represents a skeleton portion other than the hydroxyl groups of the polyhydric alcohol. Since at least two hydroxyl groups in the polyhydric alcohol need only be bonded, when the polyhydric alcohol used as a raw material is trivalent or more, that is, when there are three or more hydroxyl groups, an unreacted hydroxyl group may remain. Good.

  Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6 -Hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, ethylene oxide 3 mol adduct of isocyanuric acid, pentaerythritol, tricyclodecane dimethanol, glycerin, trimethylolpropane, pentaerythritol ethylene oxide 3 mol adduct, D-sorbitol And hydrogenated bisphenol A and the like. Although there is no restriction | limiting in particular as a manufacturing method of these compounds, For example, it can manufacture by the method mentioned in Japanese Patent Publication No. 6-74239 (US4959451).

As the structural unit represented by the general formula (3) in the allyl ester oligomer, the same structural unit may be repeated, but different structural units may be included. That is, the allyl ester oligomer may be a copolymer type. In this case, several types of X exist in one allyl ester oligomer. For example, the structure may be such that one of X is a residue derived from propylene glycol and the other X is a residue derived from trimethylolpropane. In this case, the allyl ester oligomer will be branched at the trimethylolpropane residue. There may be several types of A3 as well. The structural formulas in the case where R ³ is an allyl group, A ² and A ³ are residues derived from isophthalic acid, and X is propylene glycol and trimethylolpropane are shown below.

[Curing agent]
A curing agent may be used in the allyl ester resin composition used in the present invention. There is no restriction | limiting in particular as a hardening | curing agent which can be used, What is generally used as a hardening | curing agent of polymeric resin can be used. Among these, it is desirable to add a radical polymerization initiator from the viewpoint of starting polymerization of the allyl group. Examples of the radical polymerization initiator include organic peroxides, photopolymerization initiators, azo compounds and the like.

As the organic peroxide, known compounds such as dialkyl peroxides, acyl peroxides, hydroperoxides, ketone peroxides, peroxyesters and the like can be used. Specific examples thereof include benzoyl peroxide, 1,1 -Bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-dibutylperoxycyclohexyl) propane, t-butylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di (T-butylperoxy) hexane, 2,5-dimethyl2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, t-butylcumyl peroxide, p-methylhydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide Oki rhino de, Jikumi Peroxide, di -t- butyl peroxide and 2,5-dimethyl-2,5-dibutyl peroxy f relaxin -3, and the like.

  Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,4, Examples include 6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2 -Methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2-propenyl) ) -2-methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) and the like.

  These radical polymerization initiators may be used alone or in combination of two or more.

Although there is no restriction | limiting in particular in the compounding quantity of a hardening | curing agent, It is preferable to mix | blend 0.1-10 mass parts with respect to 100 mass parts of radical polymerization components in an allyl ester resin composition, 0.5-5 mass parts combination More preferably. When the blending amount of the curing agent is less than 0.1 parts by mass, it is difficult to obtain a sufficient curing rate. When the blending amount exceeds 10 parts by mass, the final cured product becomes brittle and the mechanical strength decreases. There is a case.

[Reactive monomer]
The allyl ester resin composition used in the present invention contains a reactive monomer (reactive diluent) for the purpose of controlling the curing reaction rate, adjusting the viscosity (improving workability), improving the crosslinking density, and adding functions. It can also be added. There is no restriction | limiting in particular as a reactive monomer, In order to make it react with an allyl ester oligomer, the monomer which has radically polymerizable carbon-carbon double bonds, such as a vinyl group and an allyl group, is preferable. Examples thereof include unsaturated fatty acid esters, aromatic vinyl compounds, vinyl esters of saturated fatty acids or aromatic carboxylic acids and derivatives thereof, crosslinkable polyfunctional monomers, and the like. Especially, if a crosslinkable polyfunctional monomer is used, the crosslinking density of hardened | cured material can also be controlled. Preferred specific examples of these reactive monomers are shown below.

As unsaturated fatty acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate Alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and methylcyclohexyl (meth) acrylate;
Phenyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, fluorophenyl (meth) acrylate, chlorophenyl (meth) acrylate, cyanophenyl (meth) acrylate, methoxyphenyl (meth) acrylate and biphenyl (meth) ) Acrylic acid aromatic esters such as acrylates;
Haloalkyl (meth) acrylates such as fluoromethyl (meth) acrylate and chloromethyl (meth) acrylate;
Furthermore, glycidyl (meth) acrylate, alkylamino (meth) acrylate, α-cyanoacrylic acid ester and the like can be mentioned.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, chlorostyrene, styrene sulfonic acid, 4-hydroxystyrene, vinyltoluene and the like.

  Examples of vinyl esters of saturated fatty acids or aromatic carboxylic acids and derivatives thereof include vinyl acetate, vinyl propionate and vinyl benzoate.

As the crosslinkable polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentadiol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, oligoester di (meth) acrylate, polybutadiene di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyphenyl) propane and 2,2-bis (4-ω- ( Meta) Leroy b carboxymethyl pyridinium) phenyl) di (meth) acrylates such as propane;
Diallyl phthalate, diallyl isophthalate, dimethallyl isophthalate, diallyl terephthalate, triallyl trimellitic acid, diallyl 2,6-naphthalenedicarboxylate, diallyl 1,5-naphthalenedicarboxylate, allyl 1,4-xylenedicarboxylate and 4,4 Difunctional aromatic carboxylates such as diallyl 4'-diphenyldicarboxylate; bifunctional such as diallyl 1,4-cyclohexanedicarboxylate, diallyl 1,2-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate and divinylbenzene Crosslinkable monomer: trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) allyl isocyanurate, tri (meth) Trifunctional crosslinkable monomers such as allyl cyanurate, triallyl trimellitate and diallyl chlorendate; and tetrafunctional crosslinkable monomers such as pentaerythritol tetra (meth) acrylate.

  Said reactive monomer can be used individually by 1 type or in mixture or combination of 2 or more types. Although there is no restriction | limiting in particular in the usage-amount of the resin component of these reactive monomers, It is preferable that it is 1-1000 mass parts with respect to 100 mass parts of allyl ester oligomers, and it is more preferable that it is 2-500 mass parts. Preferably, it is 5 mass parts-100 mass parts. When the amount of the reactive monomer used is less than 1 part by mass, the effect of decreasing the viscosity is small, workability is deteriorated, and when a polyfunctional monomer is used as the reactive monomer, the crosslinking density is lowered. Heat resistance may be insufficient. Moreover, when the usage-amount exceeds 1000 mass parts, the outstanding transparency of allyl ester resin itself may not be expressed, or the mechanical strength derived from allyl ester resin may fall.

[Radically reactive resin component]
The allyl ester resin composition used in the present invention may contain a radical reactive resin component for the purpose of improving various physical properties. Examples of these resin components include unsaturated polyester resins and vinyl ester resins.

  Unsaturated polyester resin can be obtained by converting a condensation product obtained by esterification reaction of a polyhydric alcohol and an unsaturated polybasic acid (and a saturated polybasic acid if necessary) into a polymerizable unsaturated compound such as styrene. For example, the resins described in “Polyester Resin Handbook”, published by Nikkan Kogyo Shimbun, 1988, pages 16 to 18, pages 29 to 37, etc. can be mentioned. This unsaturated polyester resin can be produced by a known method.

  Vinyl ester resin, also called epoxy (meth) acrylate, is a ring-opening reaction between a compound having an epoxy group typically represented by an epoxy resin and a carboxyl group of a carboxyl compound having a polymerizable unsaturated group such as (meth) acrylic acid. Polymerized by a ring-opening reaction between a resin having a polymerizable unsaturated group produced by the above, or a compound having a carboxyl group and an epoxy group of a polymerizable unsaturated compound having an epoxy group in the molecule such as glycidyl (meth) acrylate It refers to a resin having a polymerizable unsaturated group. Details are described in “Polyester Resin Handbook”, published by Nikkan Kogyo Shimbun, 1988, pp. 336 to 357, and can be produced by a known method.

  The epoxy resin used as the raw material for the vinyl ester resin includes bisphenol A diglycidyl ether and its high molecular weight homologue, glycidyl ether of bisphenol A alkylene oxide adduct, bisphenol F diglycidyl ether and its high molecular weight homologue, and bisphenol F alkylene oxide. Examples include adduct glycidyl ethers and novolac-type polyglycidyl ethers.

The above radical-reactive resin components can be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount of these radical reactive resin components, It is preferable that it is 1-1000 mass parts with respect to 100 mass parts of allyl ester oligomers, and it is more preferable that it is 2-500 mass parts. Preferably, it is 5 mass parts-100 mass parts. When the amount of the radical-reactive resin component used is less than 1 part by mass, the effect of improving the mechanical strength derived from the radical-reactive resin component is small, and the workability is deteriorated or the moldability is deteriorated. It is not preferable. Moreover, when the usage-amount exceeds 1000 mass parts, the heat resistance of allyl ester resin itself may not appear, and it is unpreferable.

[Additive]
In the allyl ester resin composition used in the present invention, for the purpose of improving hardness, strength, moldability, durability, and water resistance, an ultraviolet absorber, an antioxidant, an antifoaming agent, a leveling agent, a release agent, Additives such as lubricants, water repellents, flame retardants, low shrinkage agents, and crosslinking aids can be added as necessary.

  There is no restriction | limiting in particular as antioxidant, What is generally used can be used. Among them, phenolic antioxidants and amine antioxidants that are radical chain inhibitors are preferable, and phenolic antioxidants are particularly preferable. Phenol antioxidants include 2,6-t-butyl-p-cresol, 2,6-t-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6-t-butylphenol) and 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and the like can be mentioned.

There is no restriction | limiting in particular as a lubricant, What is generally used can be used. Among these, metal soap lubricants, fatty acid ester lubricants, aliphatic hydrocarbon lubricants and the like are preferable, and metal soap lubricants are particularly preferable. The metal soap-based lubricants, barium stearate, calcium stearate, zinc stearate, magnesium stearate and aluminum stearate, and the like. These may be used as a complex.

  There is no restriction | limiting in particular as said ultraviolet absorber, What is generally used can be used. Among these, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers are preferable, and benzophenone ultraviolet absorbers are particularly preferable. Examples of benzophenone ultraviolet absorbers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-butylphenyl) benzotriazole and 2- (2-hydroxy-3). '-Tert-butylphenyl) benzotriazole and the like.

  These additives are not limited to the specific examples described above, and any additive can be added as long as the object or effect of the present invention is not impaired.

[solvent]
When the allyl ester resin composition is cured, a solvent may be used if it is necessary to reduce the viscosity by a curing method. Examples of solvents that can be used for viscosity adjustment include aromatic hydrocarbons such as toluene and xylene, acetates such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones, ethers such as tetrahydrofuran and 1,4-dioxane, alcohols such as ethyl alcohol, (iso) propyl alcohol, and butyl alcohol. However, when a solvent is contained in the allyl ester resin composition, it is necessary to remove the solvent later. Therefore, the viscosity is preferably adjusted with the above-described reactive monomer.

[Viscosity of allyl ester resin composition]
The viscosity of the allyl ester resin composition of the present invention is not particularly limited, but is preferably a viscosity suitable for the method for molding. For example, in cast molding, the viscosity at 25 ° C. is preferably in the range of 0.01 (Pa · s) to 1,000 (Ps · s). When the viscosity is lower than 0.01 (Pa · s) or higher than 1,000 (Pa · s), workability is deteriorated. The viscosity of the curable resin can be measured by a method based on JIS K6901.

[Laminate]
Next, the laminate will be described in detail .
When using a laminated body for a display apparatus as an optical member, it is preferable that a total light transmittance is at least 85% or more, and it is more preferable that it is 90% or more. If it is less than 85%, the visibility deteriorates. The number of layers constituting the laminate is not particularly limited as long as the transmittance is not impaired, but at least one of the laminates is a film made of the allyl ester resin. Since allyl ester resin is a material having high transparency and heat resistance, for example, by laminating a film having high mechanical strength such as surface hardness and elastic modulus, it is free from deformation due to heat and a display member having high mechanical strength. Can be obtained.

  When using a layer made of a material other than a film made of an allyl ester resin (hereinafter sometimes referred to as another layer) as a layer constituting the laminate, it needs to be transparent. Examples of the film include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, cycloolefin-based polymer (for example, ZEONEX (registered trademark) of Nippon Zeon Co., Ltd.), triacetyl cellulose, polyimide (for example, Mitsubishi Gas Chemical Co., Ltd. Neoprim) L), polyaramid (for example, Toray Industries, Inc. Mikutron (registered trademark)), polyethersulfone (for example, Sumitomo Chemical Co., Ltd. Sumika Excel PES), siloxane-based polymer (for example, Nippon Steel Chemical Co., Ltd. Silplus (registered trademark)), Fluoropolymer (for example, Sumitomo 3M Ltd. Dyneon (TM) PTFE), amorphous polyolefin (e.g., Mitsui Chemicals, Inc. APEL (registered trademark)), unsaturated polyester resins, vinyl ester resins, epoxy resins, and urethane acrylate resins. In addition to these resin films, glass can be laminated as a constituent layer of the laminated film. Examples of glass types include soda-lime glass, borosilicate glass, float glass processed from quartz glass, tempered glass, and heat-resistant glass, among which Corning Display Technology's Gorilla glass is transparent. Property and smoothness are suitable as a laminated glass for a display.

  In addition, each layer used in the present invention may be provided with a hard coat, a gas barrier coat, an antireflection film, and a conductive film in order to impart functionality to the film as long as transparency is not impaired.

  In order to laminate the allyl ester resin film and other layers, an adhesive layer is interposed. The method of providing the adhesive layer is roughly divided into two methods: a method of applying a pre-formed adhesive layer and a method of forming an adhesive layer by directly applying an adhesive to the surface of the film. can do.

  In the former case, “a method of applying a pre-formed adhesive layer” means, for example, that an adhesive is applied to the surface of a release film having the same size as the transparent film, and one side of the release film In this method, an adhesive layer formed in a sheet shape is attached to a transparent film. In the above method, a conventionally known application means can be used as the adhesive application means. Specific examples include a spray method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method. When drying is required, conventionally known means such as heat drying and blow drying can be used as the means.

[adhesive]
As the adhesive, acrylic, rubber and silicone adhesives can be used, but acrylic adhesives are preferable from the viewpoint of transparency and durability. Such an acrylic adhesive is mainly composed of an acrylic acid alkyl ester (monomer) such as 2-ethylhexyl acrylate and n-butyl acrylate, and has a short carbon number of 3 or less in order to improve cohesion. A chain alkyl (meth) acrylate, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, and acrylic acid, methacrylic acid, acrylamide derivatives, maleic acid, hydroxyl ethyl acrylate, glycidyl acrylate, etc., which can serve as a crosslinking point of the crosslinking agent. It is preferable to use a polymerized one. The glass transition temperature (Tg) and the crosslinking density can be changed by appropriately adjusting the mixing ratio and type of the main component, the short chain component, and the component for adding a crosslinking point.

  Examples of the crosslinking agent used in combination with the adhesive include an isocyanate crosslinking agent, an epoxy resin crosslinking agent, a melamine resin crosslinking agent, a urea resin crosslinking agent, and a chelate crosslinking agent. Among these, an isocyanate crosslinking agent is used. An agent is more preferable. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, 4-4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine isocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, and the like. Isocyanates, products of these isocyanates with polyalcohols, and polyisocyanates formed by condensation of isocyanates can be used.

  The laminate of the present invention has a structure in which another resin layer (second resin layer) is laminated on at least one surface of an allyl ester resin layer (first resin layer) via an adhesive layer. That is, the structure in which another resin layer (second resin layer) is laminated on one side of the allyl ester resin layer is an allyl ester resin layer / first adhesive layer / second resin layer. Here, the second resin layer can be selected from any of the “other layers” described in the section “Laminate”, but can also be an allyl ester resin layer. The structure in which other resin layers (second and third resin layers) are laminated on both sides of the allyl ester resin layer via an adhesive layer is the second resin layer / first adhesive layer / allyl ester resin layer. / Second adhesive layer / third resin layer. It can also be set as the structure which contains two or more allyl ester resin layers in a laminated | multilayer film. For example, second resin layer / first adhesive layer / first allyl ester resin layer / second adhesive layer / second allyl ester resin layer / third adhesive layer / third resin layer The structure which becomes is mentioned. Here, the second and third resin layers can be selected from any of the above-mentioned “other layers”, but may be allyl ester resin layers. The second resin layer and the third resin layer may be the same material or different materials. Moreover, a 1st adhesive bond layer, a 2nd adhesive bond layer, and a 3rd adhesive bond layer can be selected from either of the said adhesive agents. These adhesive layers may be the same or different. It is preferable that the laminated structure has a symmetric configuration in terms of suppressing warpage of the laminated body.

  The total thickness of the laminate is preferably 0.1 mm to 1 mm. If it is less than 0.1 mm, the rigidity as a substrate is inferior, and if it exceeds 1 mm, the advantages of thinness and lightness as a member are lost.

  The thickness of the adhesive layer is 0.1 μm to 300 μm, preferably 10 μm to 200 μm. If the thickness is less than 0.1 μm, the impact resistance of the laminate tends to be insufficient, and if it exceeds 300 μm, the surface hardness may decrease.

  The transparent laminate of the present invention is suitable as an optical material, and is a display device member such as a liquid crystal display, an organic EL display, and a touch panel, and an illumination member, particularly a portable window, a touch panel cover, a touch panel substrate, a transparent printed substrate, and 3D glasses. It can use suitably for etc.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited by these description.
The total light transmittance, pencil hardness, and impact resistance of the laminates described in Examples and Comparative Examples were measured by the following methods.
[Total light transmittance]
The total light transmittance was measured according to JIS K7361-1, using a fully automatic haze meter TC-H3DPK manufactured by Tokyo Denshoku. The number of measurement samples was 5, and three average values excluding the first two were determined.
[Pencil hardness]
The pencil hardness was measured at 750 g based on JIS K5600-5-4.
[Shock resistance]
The impact resistance was measured in accordance with JIS K7211, using a steel ball having a mass of 130 g as a falling ball and using an 80 mm × 80 mm square test piece. The strength is indicated by 50% breaking height.

Synthesis Example 1: Synthesis of oligomer (1) A 2-liter three-necked flask equipped with a distillation apparatus was charged with 1625 g of diallyl terephthalate, 167 g of propylene glycol, and 0.813 g of dibutyltin oxide, and produced at 180 ° C. under a nitrogen stream. Heated while distilling off the alcohol coming. When the distilled alcohol reached about 170 g, the pressure in the reaction system was gradually reduced to 6.6 kPa over about 4 hours to increase the alcohol distillation rate. When the distillate almost disappeared, the pressure in the reaction system was reduced to 0.5 kPa and the reaction was further continued for 1 hour, and then the reaction product was cooled. Hereinafter, the reaction product thus obtained is referred to as “oligomer (1)”.

Example 1:
For 100 parts by mass of the oligomer (1) prepared in Synthesis Example 1, 10 parts by mass of pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester A-TMMT”), 1-hydroxycyclohexyl phenyl ketone (Ciba 3 parts by mass of “Irgacure 184” manufactured by Specialty Chemicals Co., Ltd.) was added and sufficiently stirred to obtain an allyl ester resin composition (2). This composition (2) was applied onto a glass substrate with a bar coater, UV cured at a UV (Eye Graphics Co., Ltd. ECS-4011GX-S, using a metal halide lamp) irradiation amount of 1200 mJ / cm ² , and thickness 0 A 2 mm allyl ester resin film was prepared.
This allyl ester resin film (film A) was affixed using 8146-4 (trade name: manufactured by Sumitomo 3M, thickness: 100 μm), which is an acrylate-based highly transparent adhesive transfer tape. After peeling off the release film, an allyl ester resin film (film B) having the same thickness was bonded to obtain a transparent laminate having a thickness of about 0.5 mm. As a result of measuring the characteristics of the obtained laminated laminate based on the evaluation method, the transmittance was 91%, the pencil hardness was 3H, and the falling ball impact height was 60 cm.

Example 2:
A transparent laminated laminate having a thickness of about 0.5 mm was obtained in the same manner as in Example 1 except that the film B was replaced with a polyethylene terephthalate film (Toray Co., Ltd. Lumirror T60) having a thickness of about 0.2 mm. As a result of measuring the characteristics of the obtained laminated laminate based on the evaluation method, the transmittance was 90%, the pencil hardness of the allyl ester resin film side (film A) surface was 3H, and the falling ball impact height was 80 cm.

Example 3:
A transparent laminate having a thickness of about 0.5 mm was obtained in the same manner as in Example 1 except that the film B was replaced with a polycarbonate film having a thickness of 0.2 mm (Teijin Chemicals Corporation Panlite). As a result of measuring the characteristics of the obtained laminate based on the evaluation method, the transmittance was 90%, the pencil hardness of the allyl ester resin film side (film A) surface was 3H, and the falling ball impact height was 70 cm.

Example 4:
A transparent laminate having a thickness of about 0.5 mm was obtained in the same manner as in Example 1 except that the film B was replaced with a 0.2-mm-thick polymethyl methacrylate film (Mitsubishi Rayon Co., Ltd.). As a result of measuring the characteristics of the obtained laminate based on the evaluation method, the transmittance was 90%, the pencil hardness of the allyl ester resin film side (film A) side was 3H, and the falling ball impact height was 65 cm.

Example 5:
A transparent laminate having a thickness of about 0.5 mm was obtained in the same manner as in Example 1 except that the film B was replaced with a siloxane polymer film having a thickness of 0.2 mm (Silplus J100, Nippon Steel Chemical Co., Ltd.). As a result of measuring the properties of the obtained laminate based on the evaluation method, the transmittance was 89%, the pencil hardness of the allyl ester resin film side (film A) surface was 3H, and the falling ball impact height was 55 cm.

Example 6:
A transparent laminate having a thickness of about 0.5 mm was obtained in the same manner as in Example 1 except that the film B was replaced with a float plate glass having a thickness of 0.2 mm. As a result of measuring the characteristics of the obtained laminate based on the evaluation method, the transmittance was 89%, the pencil hardness of the allyl ester resin film side (film A) surface was 3H, and the falling ball impact height was 45 cm.

Comparative Example 1:
A 0.5 mm allyl ester resin film (single layer) was obtained by the same UV curing method as in Example 1 using the allyl ester resin composition (2) of Example 1. As a result of measuring the characteristics of the obtained film based on the evaluation method, the transmittance of the film was 91%, the pencil hardness was 3H, and the falling ball impact height was 40.

  The laminated body obtained in Example 1 and the single-layer film obtained in Comparative Example 1 both have a member thickness of 0.5 mm. The transmittance and pencil hardness of both are the same level, but the falling ball impact height is higher in Example 1 than in Comparative Example 1. From this, it was suggested that even if it is a lamination of allyl ester resin composition films, impact resistance can be improved while maintaining transmittance and pencil hardness as compared with the case of a single layer.

Claims (8)

General formula (2)

(Wherein R ³ represents an allyl group or a methallyl group, and A ² represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid.)
And a group represented by the general formula (3)

(In the formula, A ³ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol. However, X may have a branched structure having a group represented by the above general formula (2) as a terminal group and a structure represented by the above general formula (3) as a constituent unit by an ester bond.
Comprising at least one allyl ester resin layer obtained by curing an allyl ester resin composition containing an allyl ester oligomer having a structure represented by
At least one surface of the first resin layer composed of the allyl ester resin layer is laminated with a second resin layer or a glass layer via an adhesive layer,
The second resin layer is an allyl ester resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, cycloolefin polymer, triacetyl cellulose, polyimide, polyaramid, polyethersulfone, siloxane polymer, fluorine polymer, Selected from amorphous polyolefin, unsaturated polyester resin, vinyl ester resin, epoxy resin and urethane acrylate resin,
A laminate having a total light transmittance of 85% or more. The laminate according to claim 1, wherein the second resin layer is selected from an allyl ester resin, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and a siloxane polymer.   The laminate according to claim 1 or 2, wherein the glass is float plate glass, tempered glass, or heat-resistant glass made of soda lime glass, borosilicate glass, or quartz glass.   The laminate according to any one of claims 1 to 3, wherein the adhesive layer is selected from an acrylic adhesive, a rubber adhesive, and a silicone adhesive.   The laminate according to any one of claims 1 to 3, wherein the adhesive layer contains an acrylic adhesive.   The acrylic adhesive comprises an alkyl acrylate ester (monomer) as a main component, an alkyl (meth) acrylate having an alkyl group having 3 or less carbon atoms, acrylic acid, methacrylic acid, an acrylamide derivative, maleic acid, hydroxyl ethyl acrylate And a laminate obtained by copolymerizing at least one selected from glycidyl acrylate.   The adhesive layer further includes a crosslinking agent selected from an isocyanate crosslinking agent, an epoxy resin crosslinking agent, a melamine resin crosslinking agent, a urea resin crosslinking agent, and a chelate crosslinking agent. The laminated body of crab.   The total thickness is 0.1 mm-1 mm, The laminated body in any one of Claims 1-7.