JP4673038B2 - Acrylic resin laminate, transparent electrode plate, and touch panel manufacturing method - Google Patents

Description

  The present invention relates to a method for producing an acrylic resin laminate excellent in scratch resistance and heat resistance, a method for producing a transparent electrode plate using the acrylic resin laminate, and a touch panel using the transparent electrode plate. Regarding the method.

<Acrylic resin laminate>
Acrylic resin plates are used in lenses, automobile parts, lighting parts, various electronic displays and the like because of their excellent optical properties. However, since the acrylic resin plate has lower scratch resistance than glass, scratches due to scratching or the like are likely to occur. Moreover, when heat processing is performed at high temperature, there exists a fault that heat resistance is inadequate.

  As a technology to improve the scratch resistance and heat resistance of acrylic resin plates, first a resin plate with excellent heat resistance is produced by photocuring polyfunctional methacrylate, and then the polyfunctional acrylate is applied to the surface of this resin plate. A method of forming a cured coating film by photocuring has been proposed (see, for example, Patent Document 1). However, this method does not provide sufficient adhesion between the resin plate and the cured coating film.

  In addition, a polysiloxane-based cured coating film forming material is applied to the inner surface of the mold, dried, and thermally cured, and then a base resin material containing an alkyl methacrylate as a main component and containing a polyfunctional methacrylate is injected into the mold and polymerized. There has been proposed a method for obtaining a scratch-resistant heat-resistant plate (see, for example, Patent Document 2). However, this method requires a long time for drying and thermal curing of the cured coating film, and the productivity is low.

  Further, a cured coating film forming raw material mainly composed of urethane acrylate is applied to the inner surface of the mold and photocured, and then the ethylenically unsaturated monofunctional monomer, ethylenically unsaturated polyfunctional monomer and A method has been proposed in which a synthetic resin raw material liquid composed of a radical polymerization initiator is injected and polymerized to obtain a scratch-resistant heat-resistant plate (for example, see Patent Document 3). However, this method has a drawback that the cured coating film is easily peeled off from the mold during the polymerization of the synthetic resin raw material liquid, and the appearance of the resin plate is deteriorated.

<Transparent electrode plate for touch panel and touch panel>
A display device-integrated input device in which a transparent touch panel is arranged on a display device such as a liquid crystal display or a cathode ray tube touches the display screen with an input pen or a finger, so that the touch panel acts as an input device to facilitate an input operation. Therefore, it is used as an operation screen of an automatic teller machine such as a portable information terminal or a bank. In particular, a resistive film type analog touch panel is most widely used because it can be applied to any operation screen.

  A resistance film type analog touch panel generally includes an upper transparent electrode plate and a lower transparent electrode plate, and the upper and lower transparent electrode plates have a transparent substrate and a transparent conductive film formed on the transparent substrate. It is an electrode plate, and the upper and lower transparent electrode plates have a configuration in which the transparent conductive films are arranged so as to face each other.

  When the upper transparent electrode plate of the touch panel having such a configuration is pressed with an input pen or a finger, the upper transparent electrode plate is bent and the transparent conductive films of the upper and lower transparent electrode plates are in contact with each other at the pressing point. And the coordinate of this contact point is detected by the measurement of electrical resistance, and input information is read.

  As a transparent electrode plate of such a touch panel, a resin plate is generally used as an upper transparent electrode plate, and a glass plate or a resin plate is used as a transparent substrate for a lower transparent electrode plate, and vacuum deposition is performed on the surface of these transparent substrates. A method in which a transparent conductive film is formed by a vacuum film forming method such as a sputtering method, a CVD (chemical vapor deposition) method, or an ion plating method is used.

  However, the lower electrode plate using a glass plate as a transparent substrate is prone to cracking when assembling and transporting the touch panel, or pressing with a pen or hand, making it difficult to reduce the thickness, making it difficult to reduce the weight, etc. There's a problem.

  On the other hand, when a resin plate is used as a transparent substrate, the problems of substrate breakage, thickness reduction, and weight reduction that occur when a glass plate is used as a transparent substrate can be easily solved. Actually, various studies have been made on upper and lower electrode plates using resin plates as transparent substrates (see, for example, Patent Documents 4, 5, and 6). However, the transparent substrate using a resin plate such as polyethylene terephthalate resin disclosed in Patent Documents 4, 5, and 6 has insufficient transparency. In addition, since the heat resistance is insufficient, the transparent substrate surface is easily deformed easily when a transparent conductive film is formed on the transparent substrate. The adhesion of the transparent conductive film is low and the durability is insufficient. There is a problem that further processing is required.

Further, a methacrylic resin molding material obtained by polymerizing methyl methacrylate and neopentyl glycol dimethacrylate, which is a polyfunctional (meth) acrylate, as monomers is disclosed (for example, see Patent Document 7). However, here, it is not disclosed at all that this methacrylic resin molding material can be used as a transparent substrate of a transparent electrode plate for a touch panel, and it is not suggested at all what composition is suitable as a transparent electrode plate for a touch panel. . Furthermore, since the methacrylic resin molding material described in Patent Document 7 has a low polymerization rate of 4 to 62% by mass, when this molding material is made into a product, the polymerization rate is further increased by a process such as compression molding or extrusion molding. It needs to be high. For this reason, distortion occurs and it is not suitable for use on a touch panel.
JP 11-314313 A JP-A-1-238911 JP-A-6-87129 JP 2000-276301 A JP 2001-14951 A JP 2001-34418 A Japanese Patent Publication No. 5-6570

  An object of the present invention is to provide a method for producing an acrylic resin laminate excellent in scratch resistance and heat resistance. Furthermore, the objective of this invention is providing the manufacturing method of the transparent electrode plate which has a resin laminated body excellent in heat resistance and transparency, and the manufacturing method of a touch panel which has this transparent electrode plate.

  In the present invention, the monomer (a-1) having 3 to 30% by mass of at least one hydroxyl group, carboxyl group or amino group and at least one (meth) acryloyl group in the molecule, ) A curable composition (A) containing 70 to 97% by mass of a polyfunctional (meth) acrylate (a-2) having an acryloyl group is applied and cured on at least one inner surface of the mold, and then in the mold, Monoethylenically unsaturated monomer (b-1) containing 5 to 95% by mass of a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms and a polyfunctional compound having two or more (meth) acryloyl groups ( It is a manufacturing method of the acrylic resin laminated body which has the process of inject | pouring the polymeric mixture (B) containing 5-95 mass% of (meth) acrylate (b-2), and performing cast polymerization.

  The present invention also relates to a monomer (a-1) having 3 to 30% by mass of at least one hydroxyl group, carboxyl group or amino group and at least one (meth) acryloyl group in the molecule, and two or more ( A curable composition (A) containing 70 to 97% by mass of a polyfunctional (meth) acrylate (a-2) having a (meth) acryloyl group is applied to and cured on at least one inner surface of the mold, and then into the mold Monoethylenically unsaturated monomer (c-1) containing 70 to 99% by mass of a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, and an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms 5 to 95 parts by mass of syrup (d-1) consisting of 1 to 30% by mass of (co) polymer (c-2) consisting of monoethylenically unsaturated monomer units containing an ester, and two or more ( T) Acrylic resin laminate having a step of casting polymerization by injecting 100 parts by mass of a polymerizable mixture (D) containing 5 to 95 parts by mass of polyfunctional (meth) acrylate (d-2) having an acryloyl group It is a manufacturing method.

  Furthermore, this invention is a manufacturing method of the transparent electrode plate which forms a transparent conductive film further on at least one surface of the acrylic resin laminated body obtained by one of said manufacturing methods.

  The present invention further includes an upper transparent electrode plate and a lower transparent electrode plate, wherein the upper transparent electrode plate and the lower transparent electrode plate are formed on a transparent substrate and at least one surface of the transparent substrate. In the method of manufacturing a touch panel in which the upper transparent electrode plate and the lower transparent electrode plate are arranged so as to face each other, the upper transparent electrode plate and the lower transparent electrode plate, The touch panel manufacturing method is characterized in that at least one of the lower transparent electrode plates is a transparent electrode plate obtained by the above manufacturing method.

  According to the method for producing an acrylic resin laminate of the present invention, the scratch resistance, heat resistance, and appearance can be greatly improved while maintaining the excellent optical properties of the acrylic resin. This acrylic resin laminate is used, for example, on nameplates of various electric devices, various glazings such as partitions, front plates of various displays such as CRTs, liquid crystal televisions, projection televisions, etc., and front plates of information display units such as liquid crystals of information terminals. It can be suitably used. In addition, a transparent electrode plate formed by forming a transparent conductive film such as an ITO film on the acrylic resin laminate is very useful as a transparent electrode plate for a touch panel.

  This transparent electrode plate for a touch panel has heat resistance capable of withstanding an inorganic thin film forming process and an electrode thermosetting process while maintaining the excellent optical properties inherent in acrylic resins. Furthermore, because the resin plate can be used for the substrate of the transparent electrode plate for the touch panel, it is possible to easily prevent damage to the touch panel, to reduce the weight, and to reduce the wall thickness. Application to shapes is possible.

<Acrylic resin laminate>
In the method for producing an acrylic resin laminate of the present invention, the curable composition (A) is applied and cured on at least one inner surface of the mold. First, this curable composition (A) is demonstrated.

  The curable composition (A) comprises a monomer (a-1) having at least one hydroxyl group, carboxyl group or amino group and at least one (meth) acryloyl group in the molecule, and two or more (meta) And a polyfunctional (meth) acrylate (a-2) having an acryloyl group.

  Content of a monomer (a-1) is 3-30 mass% in curable composition (A). When the content is 3% by mass or more, the appearance is improved, and when the content is 30% by mass or less, the scratch resistance tends to be improved. Furthermore, this content is preferably 5 to 30% by mass, and more preferably 10 to 30% by mass.

  The monomer (a-1) may be any monomer having at least one (meth) acryloyl group and having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, and an amino group. . Specific examples of the monomer (a-1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, and 2-hydroxy-3. -Phenoxypropyl (meth) acrylate, 1,2,3-propanetriol-1- (meth) acrylate, 1,2,3-propanetriol-1,3-di (meth) acrylate, 3-acryloyloxy-2- Hydroxypropyl methacrylate, 1,6-hexanediyl-bis (2-hydroxypropane-1,3-diyl) di (meth) acrylate, pentaerythritol tri (meth) acrylate, hydrogen (meth) acrylate, β- (meth) acryloyl Oxyethyl hydrogen succinate, β- (meth) acrylate Iroxyethyl hydrogen maleate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl Examples thereof include tetrahydrohydrogen phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate. These can also be used in combination. Among these, pentaerythritol tri (meth) acrylate, 2-hydroxyethyl (meth) acrylate, β- (meth) acryloyloxyethyl hydrogen succinate, and dimethylaminoethyl (meth) acrylate are preferable. In the present invention, “(meth) acryloyl” is a generic term for “methacryloyl” and “acryloyl”, and similarly, “(meth) acrylate” is a generic term for “methacrylate” and “acrylate”. It is.

  Content of polyfunctional (meth) acrylate (a-2) is 70-97 mass% in curable composition (A). When the content is 70% by mass or more, the scratch resistance is improved, and when the content is 97% by mass or less, the appearance tends to be improved. Furthermore, this content is preferably 70 to 95% by mass, and more preferably 70 to 90% by mass.

  The polyfunctional (meth) acrylate (a-2) may be a monomer having two or more (meth) acryloyl groups [excluding those corresponding to the monomer (a-1)]. . Specific examples of the polyfunctional (meth) acrylate (a-2) include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

  Further, as the polyfunctional (meth) acrylate (a-2), an esterified product obtained from a polyhydric alcohol, a polyvalent carboxylic acid or an anhydride thereof, and (meth) acrylic acid or a derivative thereof can also be used. . Specific examples of the polyhydric alcohol include trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and the like. Specific examples of the polyvalent carboxylic acid or anhydride thereof include polyvalent carboxylic acids such as malonic acid, succinic acid, adipic acid, glutaric acid, sebacic acid, fumaric acid, itaconic acid, maleic anhydride, and anhydrides thereof. It is done.

  Further, as the polyfunctional (meth) acrylate (a-2), the following general formula (1)

(In the formula, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms.)
It is also possible to use a urethane compound which is a reaction product of a compound having three isocyanate groups in the molecule and a compound having a hydroxyl group and a (meth) acryloyloxy group in the molecule. In this case, it has a (meth) acryloyloxy group by the reaction of the isocyanate group of the compound represented by the general formula (1) with the hydroxyl group of a compound having a hydroxyl group and a (meth) acryloyloxy group in the molecule. A urethane compound is produced.

  The compound represented by the general formula (1) is preferably composed of a trimer of a compound having two isocyanate groups. Specific examples of the compound having two isocyanate groups in the molecule include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, toluylene diisocyanate, or these diisocyanates. Examples of the compound include diisocyanate compounds obtained by hydrogenating aromatic isocyanates (for example, hydrogenated xylylene diisocyanate). By trimerizing these, the compound represented by the general formula (1) can be obtained.

  In the compound having a hydroxyl group and a (meth) acryloyloxy group in the molecule to be reacted with the compound represented by the general formula (1), the number of (meth) acryloyloxy groups in the molecule may be one or 2 There may be more than one. Specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, 1,2,3-propanetriol-1,3- Examples include dimethacrylate and 3-acryloyloxy-2-hydroxypropyl (meth) acrylate.

  In particular, hexamethylene diisocyanate trimer and 1,2,3-propanetriol-1,3-dimethacrylate or 3-acryloyloxy-2-hydroxypropyl in terms of the balance between scratch resistance and substrate adhesion Urethane compounds obtained by reaction with (meth) acrylates are preferred.

  The above-mentioned various compounds can be used in combination of two or more as required.

  Various additives, such as a surface smoothing agent, surfactant, a ultraviolet absorber, and a storage stabilizer, can be further added to the curable composition (A) as necessary.

  As a method for curing the curable composition (A), for example, a method of blending a thermal polymerization initiator such as an azo type or a peroxide type and heat curing, or a method of blending a photopolymerization initiator and irradiating ultraviolet rays to light. Various radical polymerization methods conventionally known, such as a curing method, can be mentioned. In particular, a photocuring method is preferable.

  Examples of the photopolymerization initiator used in the photocuring method include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, 2, 2-diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1 -Carbonyl compounds such as phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine Kisaido, benzo dichloride ethoxy phosphine oxide; and the like. The addition amount of the photopolymerization initiator is preferably 0.1 parts by mass or more from the viewpoint of curability by ultraviolet rays with respect to 100 parts by mass of the curable composition (A), from the viewpoint of maintaining a good color tone of the coating film. 10 parts by mass or less is preferable.

  In the present invention, the curable composition (A) described above is applied to at least one inner surface of the mold, and the coating film is cured. By this step, a cured coating film of the curable composition (A) is formed on at least one inner surface of the mold.

  The material of the mold is not particularly limited. For example, stainless steel, a glass plate, etc. are preferable. Further, the surface state of the mold may be a mirror surface or may have fine irregularities.

  The method for applying the curable composition (A) to the inner surface of the mold is not particularly limited. For example, various conventionally known methods such as brush coating, casting, roller coating, bar coating, spray coating, air knife coating, and dipping can be used. A method for curing the curable composition (A) applied to the inner surface is not particularly limited, and a radical polymerization method can be used as described above. Moreover, the surface of the coating film of the curable composition (A) apply | coated to the surface of a casting_mold | template can also be covered with a film, and the method of removing a film after hardening of a curable composition (A) can also be used.

  The inner surface of the mold on which the curable composition (A) is applied is preferably an inner surface of the mold corresponding to at least one of two surfaces (a front surface and a back surface) in the obtained acrylic resin laminate. When the area of the mold inner surface corresponding to at least one surface is 100%, the area to which the curable composition (A) is applied is preferably 50% or more, more preferably 80% or more, 100 % Is most preferred. The curable composition (A) can also be applied to the entire interior of the mold corresponding to the front and back surfaces.

  The thickness of the coating film after application of the curable composition (A) is preferably in the range of 1 to 100 μm. If the thickness is 1 μm or more, the scratch resistance of the acrylic resin laminate tends to be good, and if it is 100 μm or less, cracks tend not to occur.

  In the present invention, the curable composition (A) is applied to at least one inner surface of a mold and cured, and then the polymerizable mixture (B) or the polymerizable mixture (D) is used as a substrate material in the mold. And casting polymerization.

  First, the polymerizable mixture (B) will be described. The polymerizable mixture (B) has a monoethylenically unsaturated monomer (b-1) containing a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms and two or more (meth) acryloyl groups. It is a mixture containing polyfunctional (meth) acrylate (b-2).

  Content of a monomer (b-1) is 5-95 mass% in a polymeric mixture (B). When the content is 5% by mass or more, the appearance is improved, and when it is 95% by mass or less, the heat resistance tends to be improved. Furthermore, this content is preferably 10 to 70% by mass, and more preferably 15 to 50% by mass when used as a transparent electrode plate for a touch panel. Further, when the total amount of the monomer (b-1) is 100 parts by mass, the proportion of the alkyl methacrylate having 1 to 4 carbon atoms in the monomer (b-1) When imparting high transparency to the body, the amount is preferably 50 parts by mass or more, and the ratio of other monoethylenically unsaturated monomers is preferably 50 parts by mass or less. When the ratio is set, transparency tends to be improved, and heat resistance may be further improved.

  In the monomer (b-1), examples of the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n methacrylate. -Butyl, i-butyl methacrylate, t-butyl methacrylate and the like. These can also be used in combination. Of these, methyl methacrylate is particularly preferred.

  In the monomer (b-1), examples of the monoethylenically unsaturated monomer other than the methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms include styrene, α-methylstyrene, acrylonitrile, and acrylic acid. , Methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, isostearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacryl Examples include isobornyl acid, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, and the like. . These can also be used in combination. In particular, in order to reduce the water absorption rate, alkyl methacrylate having an alkyl group having 8 to 20 carbon atoms such as 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, and isostearyl methacrylate is preferable. .

  Content of polyfunctional (meth) acrylate (b-2) is 5-95 mass% in polymeric mixture (B). When this content is 5% by mass or more, the heat resistance is improved, and when it is 95% by mass or less, the appearance tends to be good. This content is preferably 30 to 90% by mass, and more preferably 50 to 85% by mass when used as a transparent electrode plate for a touch panel.

  As polyfunctional (meth) acrylate (b-2), for example, the following general formula (2)

(In the formula, R ² and R ³ represent H or CH _3. )
A compound represented by the following general formula (3)

(Wherein R ⁴ and R ⁵ represent H or CH ₃ , R ⁶ and R ⁷ represent H or a hydrocarbon group having 3 or less carbon atoms, and n represents an integer of 0 to 4)
, Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These can also be used in combination.

  In these, the compound represented by General formula (2) or General formula (3) is preferable.

Examples of the compound represented by the general formula (2), for example, bis (oxymethyl) tricyclo [5,2,1,0 ^2,6] decane acrylate, bis (oxymethyl) tricyclo [5, 2, 1, 0 ^2,6 ] decanedimethacrylate and the like. These can also be used in combination. By using these compounds, the hygroscopicity of the obtained resin can be reduced.

  Examples of the compound represented by the general formula (3) include ethylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butylene glycol dimethacrylate, and 1,6-hexanediol. Di (meth) acrylate, 2-methyl-1,3-propanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2′-dimethyl-1,4-butanediol di (meth) acrylate, etc. Is mentioned. These can also be used in combination. Among the compounds represented by the general formula (3), neopentyl glycol dimethacrylate is most preferable from the viewpoint of improving transparency.

  In general formula (3), when n is 1 or more, the appearance is good, and when n is 4 or less, the heat resistance tends to be improved. In addition, compared with the compound represented by the general formula (2), when the compound represented by the general formula (3) is used, the polymerization shrinkage tends to increase, so that the content thereof is a polymerizable mixture (B ) Is preferably 5 to 70% by mass. When this content is 5% by mass or more, the heat resistance is improved, and when it is 70% by mass or less, the appearance tends to be good. Furthermore, when using as a transparent electrode plate for touch panels, it is preferable that the content is 45 mass% or more.

  Moreover, when using the compound represented by General formula (3) as polyfunctional (meth) acrylate (b-2), content of a monomer (b-1) is in polymerizable mixture (B). 30 to 95% by mass is preferable. When the content is 30% by mass or more, the appearance is improved, and when it is 95% by mass or less, the heat resistance tends to be improved. Furthermore, when using as a transparent electrode plate for touch panels, it is preferable that content of a monomer (b-1) is 55 mass% or less.

  For polymerization of the polymerizable mixture (B), conventionally known various radical polymerization initiators can be used. Specific examples of the radical polymerization initiator include t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, and t-butylperoxide. Oxyisopropyl carbonate, t-hexylperoxyisopropyl monocarbonate, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2 2,2'-azobisisobutyronitrile and the like. The addition amount of the radical polymerization initiator is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the polymerizable mixture (B).

  If necessary, the polymerizable mixture (B) may further include a colorant, a release agent, an antioxidant, a stabilizer, an antistatic agent, an antibacterial agent, a flame retardant, an impact modifier, a light stabilizer, and an ultraviolet ray. Various additives such as an absorbent, a light diffusing agent, a polymerization inhibitor, a chain transfer agent, a polymerization regulator (such as terpinolene) can be added.

  Next, the polymerizable mixture (D) will be described. The polymerizable mixture (D) includes a monoethylenically unsaturated monomer (c-1) containing a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, and a methacryl having an alkyl group having 1 to 4 carbon atoms. A syrup (d-1) composed of a (co) polymer (c-2) composed of a monoethylenically unsaturated monomer unit containing an acid alkyl ester, and a polymer having two or more (meth) acryloyl groups It is a mixture containing a functional (meth) acrylate (d-2).

  Content of syrup (d-1) in 100 mass parts of polymeric mixtures (D) is 5-95 mass parts. Furthermore, this content is preferably 10 to 70 parts by mass, and more preferably 15 to 50 parts by mass when used as a transparent electrode plate for a touch panel.

  Content of the monomer (c-1) which comprises syrup (d-1) is 70-99 mass% in syrup (d-1). When this content is 70% by mass or more, the heat resistance is improved, and when it is 99% by mass or less, the appearance tends to be improved. Specific examples of methacrylic acid alkyl esters having an alkyl group having 1 to 4 carbon atoms in monomer (c-1), specific examples of other monoethylenically unsaturated monomers, and preferred composition ratios of the two The same as those described in the description of the monomer (b-1) of the polymerizable mixture (B).

  Content of the (co) polymer (c-2) which comprises syrup (d-1) is 1-30 mass% in syrup (d-1). When this content is 1% by mass or more, the appearance is improved, and when it is 30% by mass or less, the heat resistance tends to be improved. The (co) polymer (c-2) is composed of a monoethylenically unsaturated monomer unit containing a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms. That is, a methacrylic acid alkyl ester homopolymer having an alkyl group having 1 to 4 carbon atoms, or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms and a monoethylenically unsaturated monomer that can be copolymerized therewith It is a copolymer with the body. The “(co) polymer” means “homopolymer or copolymer”. Specific examples of methacrylic acid alkyl esters having an alkyl group having 1 to 4 carbon atoms used in this (co) polymer (c-2), other specific examples of monoethylenically unsaturated monomers, and both As a suitable composition ratio, the same thing as what was described in description of the monomer (b-1) of a polymeric mixture (B) is mentioned.

  Content of the polyfunctional (meth) acrylate (d-2) in 100 mass parts of polymeric mixtures (D) is 5-95 mass parts. When this content is 5 parts by mass or more, the heat resistance is improved, and when it is 95 parts by mass or less, the appearance tends to be good. Furthermore, this content is preferably 30 to 90 parts by mass, and more preferably 50 to 85 parts by mass when used as a transparent electrode plate for a touch panel. Specific examples of the polyfunctional (meth) acrylate (d-2) include the same as those described in the description of the polyfunctional (meth) acrylate (b-2) of the polymerizable mixture (B). Moreover, when using the compound represented by the said General formula (2) as polyfunctional (meth) acrylate (d-2), content of the compound is 5-70 in 100 mass parts of polymeric mixture (D). It is preferable that it is a mass part. When this content is 5 parts by mass or more, the heat resistance is improved, and when it is 70 parts by mass or less, the appearance tends to be good. Furthermore, when using as a transparent electrode plate for touch panels, it is preferable that the content is 45 mass parts or more.

  For polymerization of the polymerizable mixture (D), various conventionally known polymerization initiators can be used. Moreover, various additives can be added as needed. Specific examples of the polymerization initiator and additive include the same as those described in the description of the polymerizable mixture (B).

  In the present invention, the polymerizable mixture (B) or the polymerizable mixture (D) described above is injected into a mold in which a cured coating film of the curable composition (A) is previously formed on at least one inner surface. Perform type polymerization. By this step, the cured coating film is transferred to at least one surface of the resin base material obtained by polymerization of the polymerizable mixture (B) or the polymerizable mixture (D). As a result, an acrylic resin laminate is obtained in which a cured coating film of the curable composition (A) is laminated on a substrate composed of the polymer of the polymerizable mixture (B) or the polymerizable mixture (D).

  What is necessary is just to select suitably the polymerization temperature and polymerization time in this casting polymerization as needed. For example, it is performed by pouring into a mold constituted by sandwiching a gasket between a pair of tempered glass sheets, putting it in a heating furnace and polymerizing at 40 to 70 ° C. for 2 to 5 hours and at 100 to 150 ° C. for 1 to 6 hours. Can do. Instead of this tempered glass sheet, for example, a mirror surface stainless steel sheet can be used.

  This cast polymerization can also be carried out continuously. For example, a polymerizable mixture (B) or a mixture formed in a mold formed by facing surfaces of a pair of stainless steel endless belts that run facing each other at a predetermined interval and two gaskets that run following the running of the endless belts. A so-called continuous casting method can be used in which the polymerizable mixture (D) is injected, polymerized and cured continuously, and the polymer is peeled off from the endless belt and taken out. In this case, the curable composition (A) may be applied to the surface of the endless belt and cured. This method is excellent in productivity.

  The plate thickness of the acrylic resin laminate of the present invention is preferably 0.5 to 5 mm. When the plate thickness is 0.5 mm or more, cracks tend not to occur when the acrylic resin laminate is peeled from the mold. Moreover, when it is 5 mm or less, there is a tendency that it is difficult to break the plate during polymerization.

  The acrylic resin laminate obtained according to the present invention has greatly improved scratch resistance, heat resistance and appearance while maintaining the excellent optical properties of the acrylic resin. Such acrylic resin laminates include, for example, peripheral materials of heat-generating light sources such as incandescent lamp covers and halogen lamp covers, parts of heating household appliances such as clothes dryers, microwave ovens, ovens, eyeglass lenses, sunglasses lenses, cameras For automotive materials such as automotive lenses, video camera lenses, goggles lenses, contact lenses and other optical lenses, in-vehicle parts such as meter covers, in-vehicle audio equipment parts, in-vehicle display device parts, in-vehicle navigation system parts, etc. Furthermore, it can be used for various display members such as a front plate of various display devices such as a plasma display device, a liquid crystal display device, and a projection display device, and a light guide plate of a liquid crystal display.

<Transparent electrode plate>
A transparent electrode plate can be produced by forming a transparent conductive film on at least one surface of the acrylic resin laminate obtained in the present invention. The transparent conductive film may be a transparent and conductive thin film. For example, an inorganic thin film or an organic polymer thin film can be used.

  Examples of the material for the inorganic thin film include transparent metal oxides such as tin oxide, indium oxide, and ITO (tin-added indium oxide). Of these, ITO is preferable. Examples of the material for the organic polymer thin film include polyisothianaphthene.

  Moreover, the transparent electrode plate in which a transparent conductive film such as ITO is formed on at least one surface on the acrylic resin laminate can be used for the use of a transparent conductive material. For example, electrical component circuit materials such as capacitors and resistors, copying materials such as electrophotography and electrostatic recording, transparent electrodes for signal input for liquid crystal displays, electrochromic displays, electroluminescence displays, touch panels, etc. In addition to photoelectric conversion elements such as batteries and optical amplifiers, it can be used for various applications such as antistatic members, electromagnetic wave shielding members, surface heating elements, and sensors. Especially, it is preferable to utilize as a transparent electrode plate for touch panels.

  The transparent electrode plate obtained by the present invention is very useful particularly as a transparent electrode plate for a touch panel.

  As a method of forming a transparent conductive film on the acrylic resin laminate, various conventionally known film forming methods can be used. Examples of film forming methods include vacuum film forming methods such as vacuum deposition, sputtering, CVD, and ion plating. Here, a specific example of film formation by sputtering of an ITO thin film will be described. First, in the cleaning step, the transparent substrate is washed with pure water or alkaline water, and dried in the atmosphere at a temperature of 120 ° C. or higher, preferably 120 to 130 ° C. for 1 to 4 hours. Then, ITO is sputtered at a temperature of 100 to 140 ° C., preferably 120 ° C. under vacuum. Thereafter, the electrode and the lead electrode are applied with a silver paste and cured at a temperature of 130 to 170 ° C., preferably 150 ° C.

  The transparent electrode plate for a touch panel preferably has a deflection temperature under load of 150 ° C. or higher. If the deflection temperature under load is 150 ° C. or higher, the resin substrate tends to be difficult to deform when the silver paste is cured. The deflection temperature under load of the transparent electrode plate is the same as the deflection temperature under load of the acrylic resin laminate constituting the transparent electrode plate when the thickness of the transparent conductive film is as thin as 1 μm or less. Therefore, in this case, the deflection temperature under load of the acrylic resin laminate may be measured and used as the deflection temperature under load of the transparent electrode plate.

  0.5-2 mm is preferable and, as for the thickness of the acrylic resin laminated body used for the transparent electrode plate for touchscreens, 0.5-1 mm is more preferable. Moreover, 10-50 nm is preferable and, as for the thickness of a transparent conductive film, 25-40 nm is more preferable. If the thickness within these ranges is adopted, it is possible to reduce the weight and thickness as compared with the transparent electrode plate for a touch panel using a glass substrate.

  The acrylic resin laminate used for the transparent electrode plate for a touch panel is preferably uncolored. Further, an antireflection film can be formed on the side without the transparent conductive film. When the thickness of the transparent electrode plate for a touch panel is 1 mm, the total light transmittance is a value based on the total light transmittance measurement method shown in JIS-K7361, and is preferably 91% or more. If the total light transmittance is 91% or more, sufficient transparency as a transparent electrode plate for a touch panel can be obtained.

<Touch panel>
The touch panel obtained in the present invention includes an upper transparent electrode plate and a lower transparent electrode plate, and the upper transparent electrode plate and the lower transparent electrode plate are formed on at least one surface of the transparent substrate and the transparent substrate. A transparent electrode plate having a conductive film, wherein the upper transparent electrode plate and the lower transparent electrode plate are arranged such that the transparent conductive films face each other, the upper transparent electrode plate At least one of the electrode plate and the lower transparent electrode plate is a transparent electrode plate for a touch panel obtained by the present invention.

  Hereinafter, the suitable example of the transparent electrode plate for touchscreens obtained by this invention and a touchscreen using the same is demonstrated using FIGS. 1-3. FIG. 1 is a schematic sectional view showing an example of a transparent electrode plate for a touch panel obtained by the present invention, and FIG. 2 is a schematic plan view thereof. FIG. 3 is a schematic cross-sectional view showing an example of a touch panel using the transparent electrode plate shown in FIGS. 1 and 2 as a lower transparent electrode plate.

  The touch panel shown in FIG. 3 has a structure in which a lower transparent electrode plate 1 and an upper transparent electrode plate 7 are arranged to face each other with a spacer 6 therebetween. As shown in FIGS. 1 and 2, the lower transparent electrode plate 1 includes a transparent substrate 2, a transparent conductive film 3 formed on one surface of the transparent substrate 2, and end portions on the transparent conductive film 3. The electrode 4 is connected to the electrode 4, and the lead electrode 5 is connected to the electrode 4. The upper transparent electrode plate 7 has the same structure as the lower transparent electrode plate 1. That is, the upper transparent electrode plate 7 similarly has a transparent substrate 8, a transparent conductive film 9, an electrode 10, and the like.

  The lower transparent electrode plate 1 and the upper transparent electrode plate 7 have the transparent conductive films 3 and 9 inside, a dot spacer 11 interposed between the transparent electrode plates 1 and 7, and the electrodes 4 and 10. It arrange | positions through the spacer 6 at fixed intervals so that a direction may cross | intersect. When the touch panel having such a configuration is pressed from above the upper transparent electrode plate 7 with a pen or a finger, the upper transparent electrode plate 7 is deformed and the lower transparent conductive film 3 and the upper transparent conductive film 9 are brought into contact conduction. The input is complete.

  The transparent electrode plate for a touch panel obtained by the present invention is suitable for use as the lower transparent electrode plate 1 because it has high transparency, scratch resistance and high rigidity. 1 to 3 show such an example. However, the present invention is not limited to this. For example, the transparent electrode plate for a touch panel obtained in the present invention may be used as the upper transparent electrode plate 7 or may be used for both the lower transparent electrode plate 1 and the upper transparent electrode plate 7.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the following description, “part” is based on mass. Each evaluation in the table was performed according to the following method.

(1) Evaluation of acrylic resin laminate:
(1-1) Deflection temperature under load:
In order to evaluate the heat resistance of the acrylic resin laminate, the deflection temperature under load was measured according to the measurement method described in JIS-K7207.

(1-2) Haze:
In order to evaluate the optical properties of the acrylic resin laminate, haze was measured in accordance with the measurement method shown in JIS-K7136.

(1-3) Scratch resistance In order to evaluate the scratch resistance of the acrylic resin laminate, the change in haze before and after the scratch test was measured. That is, a circular pad with a diameter of 25.4 mm with # 000 steel wool was placed on the cured coating film of the sample, and under a load of 9.8 N, a 20 mm distance was reciprocally scratched 100 times, before and after scratching. The haze increment was calculated from the following equation.
[Haze increment (%)] = [haze value after abrasion (%)] − [haze value before abrasion (%)].

(1-4) Appearance:
In order to evaluate the appearance of the acrylic resin laminate, ten samples were prepared, and the number of samples free from defects such as whitening and sink marks was visually shown as n / 10.

(1-5) Adhesiveness In order to evaluate the adhesiveness of the cured coating film of the acrylic resin laminate, using a cutter, the cured coating film of the sample is arranged in a grid pattern with 11 pieces vertically and horizontally at 1 mm intervals. Scratches were made so as to reach the resin substrate, and 100 1 × 1 mm squares were produced. Adhesive tape (manufactured by Nichiban Co., Ltd., cellophane tape) was closely adhered on the mesh, and was peeled off rapidly by 45 °. At this time, the number (n) of the cells remaining without peeling of the cured coating film was displayed as n / 100. Specifically, the value of n is preferably 96 or more, more preferably 100. It can be said that the larger the value of n, the higher the adhesion of the cured coating film, and the better the acrylic resin laminate.

(2) Evaluation of transparent electrode plate for touch panel:
(2-1) Total light transmittance:
In order to evaluate the transparency of the transparent electrode plate for a touch panel, the total light transmittance was measured according to the measurement method shown in JIS-K7361.

(2-2) Deformation of substrate:
A series of touch panels for determining whether or not the acrylic resin laminate (substrate) is deformed, drying the substrate before forming the transparent conductive film (ITO), then forming the film by sputtering, and applying and curing the silver paste after forming the film When the acrylic resin laminate was not deformed, it was evaluated as “◯” (good), and when deformation occurred, it was evaluated as “x” (defective).

(2-3) ITO state:
The state of the transparent conductive film (ITO) was observed in a series of manufacturing processes for transparent electrode plates for touch panels such as film formation by sputtering and silver paste coating and curing after film formation, and optical distortion and cracks were observed. When it was not, it was evaluated as “◯” (good), and when optical distortion or crack was observed, it was evaluated as “x” (bad).

(2-4) Adhesiveness:
Using a cutter, scratches are made on the transparent conductive film of the transparent electrode plate for touch panels in a grid pattern of 11 pieces vertically and horizontally at intervals of 1 mm so as to reach the cured coating, and 100 squares of 1 × 1 mm are produced. did. Adhesive tape (manufactured by Nichiban Co., Ltd., cellophane tape) was closely adhered on the mesh, and was peeled off rapidly by 45 °. At this time, the number (n) of the cells remaining without peeling off the transparent conductive film was indicated as n / 100. Specifically, the value of n is preferably 96 or more, more preferably 100. It can be said that the larger the value of n, the higher the adhesiveness of the transparent conductive film, and the better the transparent electrode plate for touch panel.

<Manufacture of acrylic resin laminate>
[Example 1]
It is obtained by reacting 3 parts of 3-acryloyloxy-2-hydroxypropyl methacrylate with 18 parts of pentaerythritol triacrylate, 12 parts of pentaerythritol tetraacrylate, and 1 mole of triisocyanate composed of a trimer of hexamethylene diisocyanate. A curable composition was prepared by mixing and dissolving 35 parts of a urethane compound, 35 parts of 1,6-hexanediol diacrylate, and 1.5 parts of benzoin ethyl ether as a photopolymerization initiator.

Next, this curable composition is applied onto a tempered glass sheet as a mold, covered with a 12 μm thick PET (polyethylene terephthalate) film, and an excessive curable composition is squeezed out using a rubber roll having a JIS hardness of 40 °. However, it was pressure-bonded so as not to contain bubbles, and its thickness was 22 μm. Next, with the PET film surface facing upward, curing was performed by passing a position 20 cm below a fluorescent ultraviolet lamp (FL40BL manufactured by Toshiba Corporation) with an output of 40 w at a speed of 0.3 m / min. And the PET film was peeled leaving the cured coating film on the tempered glass sheet. Next, with the cured coating film surface of the tempered glass sheet facing upward, the coating film is further cured by passing a position 20 cm below the high-pressure mercury lamp with an output of 30 w / cm ² at a speed of 0.3 m / min. A cured coating film of 20 μm was obtained.

The two tempered glass sheets thus formed with a cured coating film face each other so that the cured coating film is on the inside, and the periphery is sealed with a gasket made of soft polyvinyl chloride to produce a casting polymerization mold. did. In this mold, 10 parts of isostearyl methacrylate (“NK ester S-1800M” manufactured by Shin-Nakamura Chemical Co., Ltd.), 10 parts of methyl methacrylate, and bis (oxymethyl) tricyclo [5,2,1, ^0,6 ] per 100 parts of a mixture with 80 parts of decanedimethacrylate, 0.05 part of 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile) as a polymerization initiator, t-hexylperoxy A polymerizable mixture consisting of 0.05 parts of pivalate, 0.05 parts of t-hexylperoxyisopropyl monocarbonate and 0.03 part of terpinolene as a polymerization regulator was injected, and the distance between opposing tempered glass sheets was set to 1.7 mm. After adjusting and removing bubbles, the mixture was placed in a heating furnace and polymerized at 55 ° C. for 1 hour, at 50 ° C. for 1 hour, and then at 135 ° C. for 3 hours. Then, when the mold was cooled and peeled off, the cured coating film on the inner surface of the mold was transferred to the resin plate surface, and an acrylic resin laminate having a thickness of 1 mm having the cured coating film on the surface was obtained.

  This acrylic resin laminate had a good appearance without whitening or sinking without the cured coating film peeling off from the mold during polymerization and curing. When the haze was measured, it was 0.2%, indicating good transparency. Further, the haze increment after scratching was 0.0%, and the scratch resistance was excellent. Moreover, the deflection temperature under load exceeded 200 ° C., indicating good heat resistance. Furthermore, the adhesion of the cured coating film was also good. Table 1 shows main raw material compositions and evaluation results of the curable composition and the polymerizable mixture of this example.

[Examples 2 to 14]
An acrylic resin laminate was produced in the same manner as in Example 1 except that the raw material compositions shown in Table 1 and Table 2 were adopted. The evaluation results are shown in Tables 1 and 2.

[Examples 15 to 18]
As polymerization initiator for the polymerizable mixture, 0.03 part of 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 0.01 part of t-hexylperoxypivalate, t-butylperoxyisopropyl An acrylic resin laminate was produced in the same manner as in Example 1, except that 0.01 part of monocarbonate, 0.03 part of terpinolene as a polymerization regulator, and the raw material composition shown in Table 3 were adopted. The evaluation results are shown in Table 3.

[Examples 19 to 21]
As polymerization initiator, 0.01 part of t-hexylperoxypivalate, 0.08 part of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 0.08 part of t-hexylperoxyisopropyl monocarbonate. 05 parts, 0.03 part of terpinolene as a polymerization regulator, 0.05 part of n-dodecyl mercaptan, and a casting mixture comprising a raw material composition shown in Table 3 having a cured coating film comprising a raw material composition shown in Table 3 Pour into the mold for polymerization, adjust the distance between the opposing tempered glass sheets to 1.7 mm, remove air bubbles, put in a water bath, put into a water bath at 80 ° C. for 1 hour, then put into a heating furnace, at 135 ° C. for 1 hour An acrylic resin laminate was produced in the same manner as in Example 1 except that the polymerization was performed. The evaluation results are shown in Table 3.

[Comparative Examples 1 to 7]
An acrylic resin laminate was produced in the same manner as in Example 1 except that the raw material composition shown in Table 4 was adopted. The evaluation results are shown in Table 4.

[Comparative Examples 8-12]
An acrylic resin laminate was produced in the same manner as in Example 15 except that the raw material composition shown in Table 5 was adopted. The evaluation results are shown in Table 5.

[Comparative Example 13]
An acrylic resin plate was produced in the same manner as in Example 15 except that the cured coating film was not formed and the raw material composition shown in Table 5 was adopted. The evaluation results are shown in Table 5.
<Transparent electrode plate>
Each acrylic resin laminate or acrylic resin plate obtained in Examples 1 to 21 and Comparative Examples 1 to 13 was washed with pure water, placed in a hot air drying furnace, and dried in the atmosphere at 120 ° C. for 2 hours. Next, ITO was formed as a transparent conductive film on one cured coating film or one resin plate by a sputtering method to obtain a transparent electrode plate. The film thickness of the transparent conductive film was adjusted to about 30 nm. Moreover, in this sputtering, In ₂ O ₃ / SnO ₂ having a mass ratio of 95/5 is used as a target, exhausted to 10 ⁻³ Pa, argon / oxygen having a volume ratio of 92.5 / 7.5 is used as an introduction gas, RF sputtering was performed under heating at 120 ° C.

<Manufacture of transparent electrode plate for touch panel>
Each of the transparent electrode plates is cut into a width of 250 mm and a length of 180 mm, and a silver paste is applied to the transparent electrode plate in a predetermined pattern and cured at 150 ° C. to form electrodes and lead electrodes. The touch panel having the configuration shown in FIGS. A transparent electrode plate for each was manufactured. The film thickness of this electrode and the lead electrode was adjusted to about 10 μm. The evaluation result of each obtained transparent electrode plate for touch panels is shown in Tables 1-5.

<Touch panel>
Each of the touch panel transparent electrode plates was used as the lower transparent electrode plate 1 to fabricate touch panels having the configuration shown in FIG. Specifically, each of the transparent electrode plates for a touch panel was used as the lower transparent electrode plate 1. As the upper transparent electrode plate 7, an ITO film having a film thickness of about 25 nm is formed on a 188 μm thick polyethylene terephthalate film (product name: Tetron film, manufactured by Teijin Ltd.) in the same manner as the lower transparent electrode plate. What was done was used. As the spacer 6, a double-sided tape having a thickness of 100 μm was used.

  Further, the lower transparent conductive film 3 is coated with a photocurable acrylic resin in a predetermined pattern and cured by irradiating with ultraviolet rays, whereby dot spacers 11 having a height of 10 μm and a diameter of 50 μm are staggered at a pitch of 3 mm. It was formed so that it might be arranged in. Further, an insulating film (not shown) was formed on the electrode 4 and the electrode 10. Then, by assembling a structure in which the lower transparent electrode plate 1 and the upper transparent electrode plate 7 are arranged to face each other with a spacer 6 therebetween, a touch panel having a size corresponding to 12 types, that is, 250 mm wide × 180 mm long is manufactured. did.

The abbreviations in the table indicate the following compounds.
“PE3A”: pentaerythritol triacrylate “HEA”: 2-hydroxyethyl acrylate “SA”: β-acryloyloxyethyl hydrogen succinate “DM”: dimethylaminoethyl methacrylate “PE4A”: pentaerythritol tetraacrylate “UA”: hexa Urethane compound [TAS] obtained by reacting 3 mol of 3-acryloyloxy-2-hydroxypropyl methacrylate with 1 mol of triisocyanate consisting of trimer of methylene diisocyanate: condensation of trimethylolethane / succinic acid / acrylic acid Polyester acrylate “C6DA” obtained by reaction (molar ratio 2: 1: 4): 1,6-hexanediol diacrylate “MMA”: methyl methacrylate “ISMA”: methacrylate Isostearyl "TDMA": bis (oxymethyl) tricyclo [5,2,1,0 ^2,6] decane dimethacrylate "PMMA" number-average molecular weight 450,000 methyl methacrylate polymer "NPG": neopentyl glycol Dimethacrylate.

  As shown in Tables 1 to 3, in Examples 1 to 21, good results were obtained with respect to heat resistance, transparency, scratch resistance, appearance, and film adhesion of the acrylic resin laminate. Furthermore, in Examples 1-12 and 15-19, the favorable result was obtained about transparency, external appearance, and adhesiveness of the transparent electrode plate for touch panels. The touch panel also worked properly.

  On the other hand, as shown in Tables 4 and 5, in Comparative Examples 1 to 4 and 8 to 10, the cured coating film was peeled off in the production process (polymerization process) of the acrylic resin laminate, and the appearance deteriorated. In Comparative Examples 5, 6, 11, and 13, the scratch resistance of the acrylic resin laminate and the acrylic resin plate was deteriorated. Moreover, in Comparative Examples 7 and 12, the heat resistance of the acrylic resin laminate was low.

It is typical sectional drawing which shows an example of the transparent electrode plate for touchscreens obtained by this invention. It is a schematic plan view which shows an example of the transparent electrode plate for touchscreens obtained by this invention. It is typical sectional drawing which shows an example of the touchscreen which uses the transparent electrode plate shown in FIG. 1 and FIG. 2 as a lower transparent electrode plate.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Lower transparent electrode plate 2 Transparent substrate 3 Transparent conductive film 4 Electrode 5 Lead electrode 6 Spacer 7 Upper transparent electrode plate 8 Transparent substrate 9 Transparent conductive film 10 Electrode 11 Dot spacer

Claims (4)

3 to 30% by mass of monomer (a-1) having at least one hydroxyl group, carboxyl group or amino group and at least one (meth) acryloyl group in the molecule, and two or more (meth) acryloyl groups Applying and curing a curable composition (A) containing 70 to 97% by mass of a polyfunctional (meth) acrylate (a-2) having at least one inner surface of a mold;
Next, in the template, 5 to 95% by mass of a monoethylenically unsaturated monomer (b-1) containing a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, and two or more (meth) acryloyl The manufacturing method of the acrylic resin laminated body which inject | pours the polymeric mixture (B) containing 5-95 mass% of polyfunctional (meth) acrylate (b-2) which has a group, and performs cast polymerization. 3 to 30% by mass of monomer (a-1) having at least one hydroxyl group, carboxyl group or amino group and at least one (meth) acryloyl group in the molecule, and two or more (meth) acryloyl groups Applying and curing a curable composition (A) containing 70 to 97% by mass of a polyfunctional (meth) acrylate (a-2) having at least one inner surface of a mold;
Next, in the template, 70 to 99% by mass of a monoethylenically unsaturated monomer (c-1) containing a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms 5 to 95 parts by mass of syrup (d-1) consisting of 1 to 30% by mass of a (co) polymer (c-2) consisting of a monoethylenically unsaturated monomer unit containing a methacrylic acid alkyl ester having A step of injecting 100 parts by mass of a polymerizable mixture (D) containing 5 to 95 parts by mass of a polyfunctional (meth) acrylate (d-2) having two or more (meth) acryloyl groups and performing cast polymerization. The manufacturing method of the acrylic resin laminated body which has.   The manufacturing method of the transparent electrode plate which forms a transparent conductive film further on at least one surface of the acrylic resin laminated body obtained by the manufacturing method of Claim 1 or 2. A transparent electrode comprising an upper transparent electrode plate and a lower transparent electrode plate, the upper transparent electrode plate and the lower transparent electrode plate having a transparent substrate and a transparent conductive film formed on at least one surface of the transparent substrate In the method of manufacturing a touch panel, wherein the upper transparent electrode plate and the lower transparent electrode plate are arranged at intervals so that the transparent conductive films face each other,
A method for manufacturing a touch panel, wherein at least one of the upper transparent electrode plate and the lower transparent electrode plate is a transparent electrode plate obtained by the manufacturing method according to claim 3.

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