JP2014124786A - Resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate and a scratch-resistant resin laminate which are hardly warped under a high-temperature and high-humidity environment.SOLUTION: The resin laminate of the present invention is formed by laminating a thermoplastic resin layer which contains as resin components a copolymer of an alkenyl cyanide monomer and a styrene monomer, and a methacrylic resin on at least one surface of a polycarbonate resin layer. The contents of the copolymer and the methacrylic resin are 20-90 pts.wt. and 80-10 pts.wt. respectively based on 100 pts.wt. of the total of the copolymer and the methacrylic resin.

Description

  The present invention relates to a resin laminate including a polycarbonate resin layer and a thermoplastic resin layer containing an acrylonitrile-styrene copolymer. Furthermore, it is related with the abrasion-resistant resin laminated board which equips at least one surface of this resin laminated body with a cured film.

As a resin laminate having excellent impact resistance and surface hardness, Patent Document 1 discloses a resin laminate comprising a polycarbonate resin layer and a layer made of an acrylic resin laminated on one or both surfaces of the polycarbonate resin layer. Has been.
However, this resin laminate tends to warp in a high temperature and high humidity environment.

International Publication No. 2008/047940

  An object of the present invention is to provide a resin laminate and a scratch-resistant resin laminate that are difficult to warp in a high temperature and high humidity environment.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, this invention consists of the following structures.
(1) A thermoplastic resin layer containing a copolymer of a alkenyl cyanide monomer and a styrene monomer as a resin component is laminated on at least one surface of a polycarbonate resin layer. Resin laminate.
(2) The resin laminate according to (1), wherein the thermoplastic resin layer further contains a methacrylic resin as a resin component.
(3) The content of the copolymer and methacrylic resin in the thermoplastic resin layer is 20 to 90 parts by weight based on a total of 100 parts by weight of the copolymer and methacrylic resin. The resin laminate according to (2), which is 80 to 10 parts by weight.
(4) The weight ratio of the alkenyl cyanide monomer and the styrenic monomer in the copolymer is based on a total of 100% by weight of the alkenyl cyanide monomer and the styrenic monomer. The resin laminate according to any one of (1) to (3), wherein the monomer is 10 to 25% by weight and the styrene monomer is 90 to 75% by weight.
(5) The resin laminate according to any one of (1) to (4), wherein the alkenyl cyanide monomer is acrylonitrile and the styrenic monomer is styrene.
(6) The resin laminate according to any one of (1) to (5), wherein the polycarbonate resin layer and the thermoplastic resin layer are laminated by melt coextrusion molding.
(7) A scratch-resistant resin laminate comprising a cured coating on at least one surface of the resin laminate according to any one of (1) to (6).
(8) A protective plate for a display comprising the scratch-resistant resin laminate according to (7).
(9) A touch panel protective plate comprising the scratch-resistant resin laminate according to (7).
(10) A protective plate for a display window of a portable information terminal comprising the scratch-resistant resin laminate according to (7).

  The resin laminate of the present invention has an effect that it is difficult to warp in a high temperature and high humidity environment.

It is a schematic explanatory drawing which shows the manufacturing method of the resin laminated board which concerns on one Embodiment of this invention.

[Resin laminate]
The resin laminate of the present invention is formed by laminating a predetermined thermoplastic resin layer on at least one surface of a polycarbonate resin layer. That is, the resin laminate of the present invention is a three-layer resin laminate comprising a polycarbonate resin layer and a thermoplastic resin layer laminated on both sides of the polycarbonate resin layer; or a polycarbonate resin layer and the polycarbonate resin layer. It is a resin laminated board of the 2 layer structure provided with the thermoplastic resin layer laminated | stacked on one side.

The thickness of the resin laminate is usually 0.1 to 3000 μm, preferably 0.3 to 2000 μm, and more preferably 0.5 to 1500 μm.
The ratio of the thickness of the polycarbonate resin layer and the thermoplastic resin layer (the thickness of the polycarbonate resin layer / the thickness of the thermoplastic resin layer, where the thickness of the thermoplastic resin layer is a thermoplastic resin laminated on one surface of the polycarbonate resin layer) The thickness of the layer is preferably 2 to 100, more preferably 3 to 70, and still more preferably 4 to 50. If the ratio of the thickness of the polycarbonate resin layer and the thermoplastic resin layer is within the above range, a resin laminate having excellent impact resistance and surface hardness can be obtained.

<Thermoplastic resin layer>
The thermoplastic resin layer contains a copolymer of an alkenyl cyanide monomer and a styrene monomer (hereinafter sometimes referred to as an AS copolymer) as a resin component. In addition, when a thermoplastic resin layer is laminated on both surfaces of a polycarbonate resin layer, the thickness and composition of the thermoplastic resin layers on both surfaces may be the same or different from each other, but may be a high temperature and high humidity environment. From the viewpoint of the difficulty of warping below, they are preferably the same as each other.

(Alkenyl cyanide monomer)
Examples of the alkenyl cyanide monomer include acrylonitrile and methacrylonitrile, and a mixture of two or more of these may be used, and acrylonitrile is particularly preferable.

(Styrene monomer)
Examples of the styrenic monomer include styrene; methyl styrene such as α-methyl styrene, 2-methyl styrene, 4-methyl styrene; dimethyl styrene such as 2,4-dimethyl styrene; ethyl styrene; 4-tert-butyl. Styrene; Methoxystyrene; Bromostyrene; Fluorostyrene; Nitrostyrene; Chloromethylstyrene; Acetoxystyrene; 4- (Dimethylaminomethyl) styrene and the like, and a mixture of two or more of these may be used. Styrene is preferred.

  The weight ratio of the alkenyl cyanide monomer and the styrene monomer in the AS copolymer is not particularly limited, but the thermoplastic resin layer described later together with the AS copolymer, the methacrylic resin as the resin component From the viewpoint of transparency, the alkenyl cyanide monomer is 10 to 25 wt% based on the total of 100 wt% of the alkenyl cyanide monomer and styrene monomer, and the styrene It is preferable that the monomer is 90 to 75% by weight.

  The AS copolymer may be a copolymer of an alkenyl cyanide monomer, a styrene monomer, and another monomer component. Examples of other monomer components include butadiene monomers. Examples of the butadiene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and the like. May be. A copolymer containing an alkenyl cyanide monomer, a styrene monomer, and a butadiene monomer, that is, an ABS copolymer, is an alkenyl cyanide monomer, a styrene monomer, and a butadiene monomer. Is polymerized at a desired ratio by a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method or the like.

(Methacrylic resin)
The thermoplastic resin layer may contain only the AS copolymer as a resin component, or may contain a methacrylic resin as a resin component together with the AS copolymer. A resin laminate including a thermoplastic resin layer containing an AS copolymer and a methacrylic resin as a resin component is superior in surface hardness to a resin laminate including a thermoplastic resin layer containing only an AS copolymer as a resin component. .

The methacrylic resin is a polymer mainly composed of a methacrylic acid ester, and may be a homopolymer of a methacrylic acid ester, or a methacrylic acid ester of 50% by weight or more and other monomers of 50% by weight or less. A copolymer may also be used. Here, as the methacrylic acid ester, an alkyl ester of methacrylic acid is usually used.
From the viewpoint of heat resistance, the methacrylic resin preferably has a glass transition temperature of 70 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 90 ° C. or higher. This glass transition temperature can be appropriately set by adjusting the type of monomer and the ratio thereof.

The methacrylic resin can be prepared by polymerizing the following monomer components by a method such as suspension polymerization, emulsion polymerization or bulk polymerization. At that time, in order to obtain a suitable glass transition temperature, it is preferable to adjust the polymerization by adding an appropriate chain transfer agent. What is necessary is just to determine the addition amount of a chain transfer agent suitably according to the kind of monomer, its ratio, etc.
The monomer composition of the methacrylic resin is preferably 50 to 100% by weight of alkyl methacrylate, 0 to 50% by weight of alkyl acrylate, and 0% of other monomers than the total amount of all monomers. It is -49 weight%, More preferably, an alkyl methacrylate is 50-99.9 weight%, an alkyl acrylate is 0.1-50 weight%, and a monomer other than these is 0-49 weight%.

Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and the like, and the carbon number of the alkyl group is usually 1 to 8, preferably 1 to 4, If necessary, a mixture of two or more of these may be used, and methyl methacrylate is particularly preferable.
Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like, and the carbon number of the alkyl group is usually 1 to 8, preferably 1 to 4, If necessary, a mixture of two or more of these may be used.
Examples of monomers other than alkyl methacrylate and alkyl acrylate include, for example, a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule, and a polymerizable carbon-carbon double in the molecule. Examples thereof include a polyfunctional monomer having at least two bonds, and if necessary, a mixture of two or more of these may be used, and among them, a monofunctional monomer is preferable.

Examples of monofunctional monomers that are examples of monomers other than alkyl methacrylate and alkyl acrylate include, for example, styrene monomers such as styrene, α-methylstyrene, and vinyl toluene; acrylonitrile, methacrylonitrile, and the like. Examples include alkenyl cyanide; acrylic acid; methacrylic acid; maleic anhydride; N-substituted maleimide.
Examples of polyfunctional monomers that are examples of monomers other than alkyl methacrylate and alkyl acrylate include polyunsaturated polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, and trimethylolpropane triacrylate. Carboxylic acid ester; alkenyl ester of unsaturated carboxylic acid such as allyl acrylate, allyl methacrylate, allyl cinnamate; polybasic acid poly, such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate Alkenyl esters; aromatic polyalkenyl compounds such as divinylbenzene.

(Contents of AS copolymer and methacrylic resin in thermoplastic resin layer)
The content of the AS copolymer and the methacrylic resin in the thermoplastic resin layer is the sum of the AS copolymer and the methacrylic resin, that is, the total amount of the alkenyl cyanide monomer, the styrenic monomer, and the methacrylic resin. Preferably, the AS copolymer is 20 to 90% by weight, the methacrylic resin is 80 to 10% by weight, and more preferably, the AS copolymer is 30 to 80% by weight and the methacrylic resin is 70 to 20% by weight. is there. When the content of the AS copolymer and the methacrylic resin is within the above range, it is difficult to warp even when exposed to a high temperature and high humidity environment, and a resin laminate having excellent surface hardness can be obtained.
Further, the higher the content ratio of the AS copolymer, the more difficult it is to warp even when exposed to a high temperature and high humidity environment, while the higher the content ratio of the methacrylic resin, the more excellent the surface hardness. Since it can be set as a laminated board, you may adjust suitably content of AS copolymer and a methacryl resin according to the objective.

<Resin composition>
The thermoplastic resin layer is composed of a resin composition containing an AS copolymer and, if necessary, a methacrylic resin. The resin composition containing an AS copolymer and a methacrylic resin can be obtained by mixing the AS copolymer and a methacrylic resin by a known method.
The resin composition further includes other thermoplastic resins such as polyester resin, polycarbonate resin, polycyclic olefin resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), and polyvinylidene fluoride resin (PVDF resin); organic or inorganic System fine particles; rubbery polymer; ultraviolet absorbers, organic dyes, inorganic dyes, pigments, antioxidants, antistatic agents, surfactants and other additives.
When the resin composition contains another thermoplastic resin, the total amount of the other thermoplastic resin is usually 30% by weight or less based on the total amount of all monomer components to be subjected to AS copolymerization. Good.
When the resin composition contains fine particles, the thermoplastic resin layer becomes a light diffusive mat layer, so that a mat-like design can be expressed. Examples of the organic fine particles include cross-linked acrylic polymer particles and cross-linked styrene polymer particles, and examples of the inorganic fine particles include silica and alumina. The content of these fine particles may be appropriately adjusted depending on the desired degree of surface gloss, design, etc., but is usually about 0.1 to 50% by weight with respect to the total material constituting the thermoplastic resin layer.
When a resin composition contains an additive, content of an additive should just be a range which does not impair the effect of this invention.

<Polycarbonate resin layer>
As a material constituting the polycarbonate resin layer, for example, a resin obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method, a melt transesterification method, or the like; a carbonate prepolymer by a solid phase transesterification method, or the like And a resin obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

  Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis { (4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) ) Phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4- Hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4 -Methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3 5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy- -Methyl) phenyl} fluorene, α, α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis ( 4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4, 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, and the like. If necessary, a mixture of two or more of these may be used. It can also be used.

  Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3 -Methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) A dihydric phenol selected from the group consisting of −3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene is used alone or a mixture of two or more thereof is used. In particular, bisphenol A is used alone; bisphenol A and 1,1-bis (4-hydroxyphenyl) -3 The group consisting of 3,5-trimethylcyclohexane, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene The combined use with one or more dihydric phenols selected from the above is preferred.

  Examples of the carbonylating agent include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, and haloformates such as dihaloformates of dihydric phenols. A mixture of two or more of these may be used as necessary. it can.

[Manufacture of resin laminates]
The resin laminate is preferably formed by laminating and integrating a polycarbonate resin layer and a thermoplastic resin layer by melt coextrusion molding. In this way, the resin laminate produced by melt coextrusion molding has two components compared to a resin laminate produced by bonding a polycarbonate resin layer and a thermoplastic resin layer via an adhesive or adhesive. Easy to form next.
In the melt coextrusion molding, for example, the above-described polycarbonate resin layer material and thermoplastic resin layer material (resin composition) are separately fed into two or three uniaxial or biaxial extruders, respectively. In this molding method, after melt-kneading, a polycarbonate resin layer and a thermoplastic resin layer are laminated and integrated through a feed block die, a multi-manifold die or the like, and extruded. The extruded sheet-like or film-like molten resin laminate is preferably cooled and solidified by, for example, a roll unit.

[Abrasion resistant resin laminate]
The scratch-resistant resin laminate of the present invention includes a cured coating on at least one surface of the above-described resin laminate. Thereby, scratch resistance can be imparted to the resin laminate.

Examples of the layer structure of the scratch-resistant resin laminate include the following (i) to (vi). The polycarbonate resin is abbreviated as PC layer and the thermoplastic resin layer is abbreviated as TR layer.
(I) TR layer / PC layer / cured film (ii) Cured film / TR layer / PC layer (iii) Cured film / TR layer / PC layer / cured film (iv) TR layer / PC layer / TR layer / cured film (V) Cured film / TR layer / PC layer / TR layer (vi) Cured film / TR layer / PC layer / TR layer / cured film When forming a cured film on both sides of the resin laminate, The composition and thickness of the cured coating may be the same or different from each other.

  The thickness of the cured coating is preferably 0.5 to 50 μm, more preferably 1 to 20 μm. The thinner the cured coating, the more difficult it is to crack, but too thin a cured coating is not preferable because the scratch resistance is insufficient.

  If necessary, the surface of the scratch-resistant resin laminate may be subjected to antireflection treatment by a coating method, a sputtering method, a vacuum deposition method, or the like. In addition, for the purpose of imparting an antireflection effect, a separately prepared antireflection sheet may be bonded to one side or both sides of the scratch resistant resin laminate.

[Method for producing scratch-resistant resin laminate]
As a method for producing the scratch-resistant resin laminate, for example, a curable coating composition is applied to at least one surface of the resin laminate to form a curable coating, and then the curable coating is cured. And a method of forming a cured coating.

<Curable coating composition>
The curable coating composition contains a curable compound that provides scratch resistance as an essential component, and contains a curing catalyst, conductive particles, a solvent, a leveling agent, a stabilizer, an antioxidant, a colorant, and the like as necessary. To do.

(Curable compound)
Examples of the curable compound include acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds, carboxyl group-modified epoxy acrylate compounds, polyester acrylate compounds, copolymer acrylate compounds, alicyclic epoxy resins, glycidyl ether epoxy resins, vinyl ether compounds, Examples include oxetane compounds. Among these, from the viewpoint of scratch resistance of the cured film, radical polymerization curable compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds, and polyfunctional epoxy acrylate compounds; thermal polymerization systems such as alkoxysilanes and alkylalkoxysilanes The curable compound is preferable. These curable compounds are preferably cured by irradiating energy beams such as electron beam, radiation, and ultraviolet rays, or cured by heating. These curable compounds may be used alone or in combination of a plurality of compounds.

  Particularly preferred curable compounds are those having at least three (meth) acryloyloxy groups in the molecule. Here, the (meth) acryloyloxy group means an acryloyloxy group or a methacryloyloxy group. In addition, in the present specification, “(meth)” such as (meth) acrylate has the same meaning.

  Examples of the compound having at least three (meth) acryloyloxy groups in the molecule as an example of the curable compound include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerin tri (meth) ) Acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri- or tetra- (meth) acrylate, dipentaerythritol tri-, tetra-, penta- or hexa- (meth) acrylate, tripentaerythritol tetra-, penta- A poly (meth) acrylate of a trihydric or higher polyhydric alcohol such as hexa- or hepta- (meth) acrylate; a compound having at least two isocyanato groups in the molecule, a (meth) acrylate having a hydroxyl group, Urethane (meth) acrylate obtained by reacting at a ratio of hydroxyl groups to equimolar or more with respect to the soocyanato group, and having 3 or more (meth) acryloyloxy groups in the molecule [for example, diisocyanate and pentaerythritol A hexafunctional urethane (meth) acrylate is obtained by the reaction of tri (meth) acrylate]; and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid. In addition, although the monomer was illustrated here, you may use these monomers as it is, for example, you may use what was in the form of oligomers, such as a dimer and a trimer. Moreover, you may use a monomer and an oligomer together. These (meth) acrylate compounds may be used alone or in combination of two or more.

  A commercially available compound can be used as the compound having at least three (meth) acryloyloxy groups in the molecule, which is an example of the curable compound. Specific examples thereof include “U-6HA” (urethane acrylate oligomer), “NK Hard M101” (urethane acrylate series), “NK Ester A-TMM-3L” manufactured by Shin-Nakamura Chemical Co., Ltd. (Pentaerythritol triacrylate), "NK ester A-TMMT" (pentaerythritol tetraacrylate), "NK ester A-9530" (dipentaerythritol pentaacrylate) and "NK ester A-DPH" (dipentaerythritol hexaacrylate) , "KAYARAD DPCA" (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., "Nopcocure 200" series manufactured by San Nopco Co., Ltd., "Unidic" series manufactured by Dainippon Ink & Chemicals, Inc. Can be mentioned.

(Other curable compounds)
When a compound having at least three (meth) acryloyloxy groups in the molecule is used as the curable compound, other curable compounds such as ethylene glycol di (meth) acrylate and diethylene glycol are used as necessary. A compound having two (meth) acryloyloxy groups in the molecule, such as di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. may be used in combination. . The amount used is usually up to 20 parts by weight per 100 parts by weight of the compound having at least 3 (meth) acryloyloxy groups in the molecule.

(Photopolymerization initiator)
When the curable coating film is cured with ultraviolet rays, the curable coating composition preferably contains a photopolymerization initiator as a curing catalyst. Examples of the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethyl ketals, α-hydroxyalkylphenones, hydroxyketones, aminoalkylphenones, acylphosphine oxides, and the like. Depending on the above, a mixture of two or more of these may be used. The usage-amount of a photoinitiator is 0.1-5 weight part normally with respect to 100 weight part of sclerosing | hardenable compounds.

  Commercially available photopolymerization initiators can be used, and specific examples include “IRGACURE 651”, “IRGACURE 184”, “IRGACURE 500”, “IRGACURE 1000” manufactured by Ciba Specialty Chemicals Co., Ltd. "IRGACURE 2959", "DAROCUR 1173", "IRGACURE 907", "IRGACURE 369", "IRGACURE 1700", "IRGACURE 1800", "IRGACURE 819", "IRGACURE 784", etc. DAROCUR series, all of which are “KAYACURE ITX”, “KAYACURE DETX-S”, “KAYACURE BP-100”, “KAYACUREBMS”, “KA” manufactured by Nippon Kayaku Co., Ltd. ACURE 2-EAQ "such as, KAYACURE (Kayacure) series, and the like.

(Conductive particles)
The curable coating composition may contain conductive particles. Thereby, antistatic property can be provided to a cured film. Examples of the conductive particles include antimony-tin composite oxide, tin oxide containing phosphorus, antimony oxide such as antimony pentoxide, antimony-zinc composite oxide, titanium oxide, indium-tin composite oxide (ITO), etc. Inorganic particles are preferably used. The conductive particles can also be used in the form of a sol having a solid content concentration of about 10 to 30% by weight.

The particle diameter of the conductive particles is usually 0.5 μm or less, and is preferably 0.001 μm or more and preferably 0 in terms of the average particle diameter from the viewpoint of antistatic properties and transparency of the cured coating. 0.1 μm or less, more preferably 0.05 μm or less. The smaller the average particle diameter of the conductive particles, the lower the haze of the scratch-resistant resin laminate, and the higher the transparency.
The usage-amount of electroconductive particle is 2-50 weight part normally with respect to 100 weight part of sclerosing | hardenable compounds, Preferably it is 3-20 weight part. As the amount of the conductive particles used increases, the antistatic property of the cured coating tends to improve. However, when the amount of the conductive particles used excessively decreases the transparency of the cured coating, it is not preferable.

  The conductive particles can be produced by, for example, a gas phase decomposition method, a plasma evaporation method, an alkoxide decomposition method, a coprecipitation method, a hydrothermal method, or the like. The surface of the conductive particles may be surface-treated with, for example, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicon coupling agent, an aluminum coupling agent, or the like.

(solvent)
The curable coating composition may contain a solvent for the purpose of adjusting the viscosity thereof. In particular, when the curable coating composition contains conductive particles, it is preferable to contain a solvent for the dispersion. When preparing a curable coating composition containing conductive particles and a solvent, for example, the conductive particles and the solvent are mixed and the conductive particles are dispersed in the solvent, and then the dispersion is used as the curable compound. Alternatively, after mixing the curable compound and the solvent, the conductive particles may be dispersed in the mixed solution.

  The solvent should be one that can dissolve the curable compound and can easily volatilize after coating, and can disperse it when conductive particles are used as a coating component. There should be. Examples of such a solvent include alcohols such as diacetone alcohol, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol; Examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; water and the like. What is necessary is just to adjust the usage-amount of a solvent suitably according to the property etc. of a curable compound.

(Leveling agent)
Silicone oil is preferably used when the curable coating composition contains a leveling agent. Specific examples include dimethyl silicone oil, phenylmethyl silicone oil, alkyl / aralkyl-modified silicone oil, fluorosilicone oil, polyether-modified silicone oil, fatty acid ester-modified silicone oil, methylhydrogen silicone oil, silanol group-containing silicone oil, alkoxy Group-containing silicone oil, phenol group-containing silicone oil, methacryl-modified silicone oil, amino-modified silicone oil, carboxylic acid-modified silicone oil, carbinol-modified silicone oil, epoxy-modified silicone oil, mercapto-modified silicone oil, fluorine-modified silicone oil, polyether Examples include modified silicone oil. These leveling agents may be used alone or in combination of two or more. The amount of the leveling agent used is usually 0.01 to 5 parts by weight with respect to 100 parts by weight of the curable compound.

  Commercially available leveling agents can be used, and specific examples include "SH200-100cs", "SH28PA", "SH29PA", "SH30PA", "Toray Dow Corning Silicone Co., Ltd." "ST83PA", "ST80PA", "ST97PA" and "ST86PA", all of which are BYK-302, "BYK-307", "BYK-320" and "BYK-330" manufactured by Big Chemie Japan, Inc. Etc.

<Method of applying curable coating composition>
Examples of the method for applying the curable coating composition to at least one surface of the resin laminate include, for example, a bar coating method, a micro gravure coating method, a roll coating method, a flow coating method, a dip coating method, a spin coating method, and a die coating method. And a coating method such as a spray coating method.

<Curing method of curable coating film>
In order to cure the curable coating film, it may be performed by irradiation with energy rays, heating, or the like according to the type of the curable coating composition.

Examples of energy rays for curing the curable coating film by irradiation with energy rays include ultraviolet rays, electron beams, and radiation. Conditions such as strength and irradiation time are appropriately selected according to the type of the curable coating composition.
Further, when curing the curable coating film by heating, conditions such as temperature and time are appropriately selected according to the type of the curable coating composition, and the heating temperature is set so that the resin substrate does not deform. In general, the temperature is preferably 100 ° C. or lower. When the curable coating composition contains a solvent, after application, the solvent may be volatilized and then the curable coating film may be cured, or the solvent may be volatilized and the curable coating film may be cured simultaneously. Also good.

[Application of scratch-resistant resin laminate]
Since the scratch-resistant resin laminate is excellent in transparency, surface hardness, impact resistance, and color unevenness, it can be used in various applications. Among these, the scratch-resistant resin laminate is suitably used as a display protective plate, a touch panel protective plate, and a protective plate for a display window of a portable information terminal.

  Examples of the type of display to be protected include a cathode ray tube (CRT) display, a liquid crystal display, a plasma display, and an EL display. In addition, display applications to be protected include, for example, a display window of a portable information terminal such as a TV or computer monitor, a mobile phone, a personal handy-phone system (PHS), or a PDA (Personal Digital Assistant), a digital camera, or a handy device. Finder part of a portable video camera, display window of a portable game machine, etc.

  Examples of the use of the touch panel to be protected include a car navigation system, a portable information terminal, an automatic teller machine (ATM) of a bank, an operation panel of an industrial machine, a touch panel of a personal computer screen, a portable game machine, etc. Etc.

  In order to produce the display protection plate and the touch panel protection plate, first, if necessary, the scratch-resistant resin laminate may be subjected to processing such as printing and drilling, and then cut to a required size. Then, if it sets to a display or a touch panel, a display and a touch panel can be protected effectively. In that case, when the cured film is formed in one surface of the resin laminated board, it is good to install so that the surface in which the cured film is formed may become the front side (viewer side). Further, when a cured coating is formed on both surfaces of a resin laminate in which a thermoplastic resin layer is laminated on one surface of a polycarbonate resin layer, the thermoplastic resin layer is on the front side (viewer side) and It is good to install so that it becomes.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the examples, “%” and “part” representing the content or amount used are based on weight unless otherwise specified.

The surface hardness and warpage of the resin laminate and the evaluation of the adhesion between the resin laminate and the cured film in the scratch-resistant resin laminate were performed under the following conditions.
<Surface hardness of resin laminate (pencil hardness)>
According to JIS K5600, it measured about the thermoplastic resin layer surface of the obtained resin laminated board.
<War amount of resin laminate>
The resin laminate was cut to a size of 200 mm in the extrusion direction and 200 mm in the direction orthogonal to the extrusion direction to obtain a test piece. With this test piece suspended, it was placed in a thermo-hygrostat with a temperature of 85 ° C. and a humidity of 85% and held for 72 hours. Thereafter, the test piece was taken out from the thermo-hygrostat and held in an atmosphere of 25 ° C. for 4 hours in a suspended state. Then, place the test piece on the surface plate with the convex warped surface as the ground contact surface side, and measure the amount of lifting of the four corners of the test piece from the surface plate surface on which the test piece is mounted using the position sensor. The average value was calculated. The difference between the average value and the average value measured and calculated in the same manner before placing the test piece in the thermo-hygrostat was taken as the amount of warpage.
<Adhesion between Resin Laminate and Cured Film in Scratch Resistant Laminate>
After 100 pieces of 2 mm × 2 mm cross hatches were put on the surface of the cured film formed on the thermoplastic resin layer side of the scratch-resistant resin laminate with a cutter, and cellophane tape (manufactured by Nichiban Co., Ltd.) was applied thereon. The cellophane tape was peeled off. After pasting the cellophane tape, the operation of peeling the cellophane tape was further repeated twice, and the number of squares in which the cured coating was peeled off from the resin laminate was repeated three times in total. The case where there was no peeled cell was designated as “◯”, and the case where there was a peeled cell was designated as “x”.

In the following examples and comparative examples, the following polycarbonate resins, methacrylic resins and acrylonitrile-styrene copolymers were used.
<Polycarbonate resin>
As the polycarbonate resin, “Caliber 301-10” manufactured by Sumika Stylon Polycarbonate Co., Ltd. was used.
<Methacrylic resin>
As the methacrylic resin, pellets of a thermoplastic polymer (glass transition temperature 104 ° C.) obtained by bulk polymerization of a monomer composed of 97.8% methyl methacrylate and 2.2% methyl acrylate were used. This glass transition temperature is an extrapolated glass transition start temperature obtained at a heating rate of 10 ° C./min by differential scanning calorimetry according to JIS K7121: 1987.
<Acrylonitrile-styrene copolymer>
As an acrylonitrile-styrene copolymer, “Cebian N 050SF” manufactured by Daicel Polymer Co., Ltd. was used. In this “Cebian N 050SF”, the ratio of the acrylonitrile monomer to the total weight of the acrylonitrile monomer and the styrene monomer is 24% by weight.

The structure of the cooling roll in the extrusion apparatus used in the following examples and comparative examples is as follows. Moreover, the 1st cooling roll 5, the 2nd cooling roll 6, and the 3rd cooling roll 7 were arrange | positioned by the horizontal array, as shown in FIG.
<Configuration of cooling roll>
First cooling roll 5: metal elastic roll (surface temperature: 100 ° C.)
Second cooling roll 6: metal roll (surface temperature: 125 ° C.)
Third cooling roll 7: metal roll (surface temperature: 110 ° C.)
<Metal elastic roll, metal roll>
The metal elastic roll has a 2 mm thick stainless steel thin film with one side mirrored so as to cover the outer periphery of the shaft roll made of stainless steel so that the mirror finished surface is the outer surface of the roll. It is a metal elastic roll having an outer diameter of 250 mm, in which a fluid made of heat transfer oil is sealed between the metal thin film. The metal roll is a spiral roll made of stainless steel having a mirror-finished surface and having an outer diameter of 250 mm.
The surface temperature of the cooling roll is a value obtained by actually measuring the surface of the roll.

[Examples 1 to 4 and Comparative Example 1]
(Production of resin laminate)
First, as a material for forming the thermoplastic resin layer, a methacrylic resin and an acrylonitrile-styrene copolymer were mixed in the combinations and proportions shown in Table 1 to obtain a resin composition. Next, the polycarbonate resin was melted with a 65 mmφ single screw extruder 1 [Toshiba Machine Co., Ltd.], and the resin composition was melted with a 45 mmφ single screw extruder 2 [manufactured by Hitachi Zosen Corporation]. Next, these were laminated and extruded through a multi-manifold die 3 (manufactured by Hitachi Zosen Co., Ltd., 2-type 2-layer distribution) having a set temperature of 260 ° C. to obtain a film-like molten resin 4. Then, the obtained film-like molten resin 4 is sandwiched between the first cooling roll 5 and the second cooling roll 6 that are arranged to face each other, and then wound around the second roll 6 while the second roll 6 and the third roll. 7, the product was wound around a third cooling roll 7, molded and cooled to obtain a resin laminate 8 having a two-layer structure with the thickness of each layer shown in Table 1. The obtained resin laminate 8 was colorless and transparent when visually observed.
The surface hardness and warpage of each obtained resin laminate were evaluated, and the results are shown in Table 1.

(Preparation of curable paint)
25 parts of urethane acrylate oligomer ("U-6HA" manufactured by Shin-Nakamura Chemical Co., Ltd.), 1 part of photopolymerization initiator ["IRGACURE 184" manufactured by Ciba Specialty Chemicals Co., Ltd.], 1-methoxy as a solvent A curable coating was prepared by mixing 37 parts of 2-propanol and 37 parts of isobutyl alcohol.

(Manufacture of scratch-resistant resin laminates)
Each resin laminated board obtained in Examples 1-4 and Comparative Example 1 was cut into a size of 100 mm × 80 mm, and a coating film of a curable coating was formed on both surfaces of each resin laminated board by a dipping method. Next, each resin laminate on which this coating film was formed was dried at room temperature for 1 minute, further dried in a hot air oven at 50 ° C. for 3 minutes to volatilize the solvent, and then 120 W of high-pressure mercury was applied to this coating film. Using a lamp, 0.5 J / cm ² ultraviolet rays were irradiated and cured to obtain each scratch-resistant resin laminate having a cured film having a thickness of 3.5 μm formed on both sides.
The adhesion between the resin laminate and the cured film in each obtained scratch-resistant resin laminate was evaluated, and the results are shown in Table 1.

  Both the scratch-resistant resin laminate using the resin laminate obtained in the examples and the scratch-resistant resin laminate using the resin laminate obtained in the comparative example are adhesion between the resin laminate and the cured film. Was excellent. Further, as is apparent from Table 1, it was found that the resin laminates obtained in the examples were less likely to warp after being exposed to a high temperature and high humidity environment than the resin laminates obtained in the comparative examples.

DESCRIPTION OF SYMBOLS 1, 2 Extruder 3 Multi-manifold die 4 Molten resin laminated board 5 1st cooling roll 6 2nd cooling roll 7 3rd cooling roll 8 Resin laminated board

Claims (10)

  A resin laminate comprising a thermoplastic resin layer containing a copolymer of a alkenyl cyanide monomer and a styrene monomer as a resin component on at least one surface of a polycarbonate resin layer .   The resin laminate according to claim 1, wherein the thermoplastic resin layer further contains a methacrylic resin as a resin component.   The content of the copolymer and the methacrylic resin in the thermoplastic resin layer is 20 to 90 parts by weight based on a total of 100 parts by weight of the copolymer and the methacrylic resin, and 80 to 10 parts by weight for the methacrylic resin. The resin laminate according to claim 2, wherein the resin laminate is part by weight.   The weight ratio of the alkenyl cyanide monomer and the styrene monomer in the copolymer is based on a total of 100% by weight of the alkenyl cyanide monomer and the styrene monomer, based on the alkenyl cyanide monomer. The resin laminate according to any one of claims 1 to 3, wherein 10 to 25% by weight and styrene monomer is 90 to 75% by weight.   The resin laminate according to any one of claims 1 to 4, wherein the alkenyl cyanide monomer is acrylonitrile and the styrenic monomer is styrene.   The resin laminate according to any one of claims 1 to 5, wherein the polycarbonate resin layer and the thermoplastic resin layer are laminated by melt coextrusion molding.   A scratch-resistant resin laminate comprising a cured coating on at least one surface of the resin laminate according to any one of claims 1 to 6.   A protective plate for a display comprising the scratch-resistant resin laminate according to claim 7.   A protective plate for a touch panel comprising the scratch-resistant resin laminate according to claim 7.   A protective plate for a display window of a portable information terminal, comprising the scratch-resistant resin laminate according to claim 7.

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