JP2008155387A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which has heat resistance, rigidity, and an anti-Newton ring function. <P>SOLUTION: In the laminate, a transparent conductive film is formed on one surface (A) of a resin molding 0.1-1 mm thick which is obtained by curing a photopolymerizable composition [I]. Unevenness having the anti-Newton ring function is formed on the surface (A) of the molding. Its surface roughness (Ra) according to JIS B0601:2001 is 50-150 nm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laminate in which a transparent conductive film is formed on one surface of a resin molded body, and in particular, is a sheet-like or film-like laminate having an excellent anti-Newton ring function, and in particular, a touch panel The present invention relates to a laminate that is useful as a substrate with a transparent electrode.

Conventional technology

  Conventionally, glass, plastic films such as polyethylene terephthalate (PET) or polycarbonate have been widely used as substrates for touch panels. For example, a resistive film type touch panel is formed by forming a transparent conductive film (transparent electrode) such as indium tin oxide (ITO) on the surface of these substrates, and using the two substrates with transparent electrodes obtained, It is manufactured by forming cells so that the electrodes face each other. When glass is used as a substrate, a touch panel excellent in rigidity and heat resistance can be obtained, but there is a drawback that it is easily broken and heavy.

  On the other hand, when plastic is used as the substrate, a light touch panel that is hard to break can be obtained, but because it bends, other elements in the device are destroyed, or high-performance transparent electrodes cannot be formed due to insufficient heat resistance. There is a problem that the touch panel is deformed. In order to solve these problems, a plastic substrate having rigidity and heat resistance has been proposed (for example, see Patent Document 1).

  Further, in recent years, interference fringes (Newton rings) of touch panels have become a problem, and a touch panel in which interference fringes are present has a marked decrease in visibility. The interference fringes are generated because light undergoes multiple reflections on the surfaces (transparent electrode surfaces) of the two substrates facing each other, and the reflected lights interfere with each other in the gap between the two substrates. Alternatively, this occurs because the light undergoes multiple reflections on both sides of one substrate and the reflected lights interfere with each other inside the substrate. In order to eliminate the interference fringes, it is necessary to roughen the surface of the substrate, and in particular, it is necessary to appropriately roughen the transparent electrode surface. The function of eliminating the interference fringes is called an anti-Newton ring function, and a technique of providing a coating layer having irregularities on the surface of the substrate, a technique of crystallizing ITO to roughen the surface, etc. are proposed (for example, Patent Documents). 2).

JP-A-9-152510 JP 2006-190508 A

However, even with these disclosed technologies, it is difficult to say that all the performances are satisfied, and a plastic substrate with a transparent electrode having heat resistance and rigidity and having an advanced anti-Newton ring function is desired. It was.
Furthermore, in addition to the anti-Newton ring function of the inner surface (transparent electrode surface) of the touch panel, a plastic substrate with a transparent electrode that also has an anti-glare function of the outer surface of the touch panel for providing an easy-to-view image has been desired.

  In view of the above, an object of the present invention is to provide a plastic substrate with a transparent electrode that has heat resistance and rigidity and has an excellent anti-Newton ring function.

  However, as a result of intensive studies by the present inventors to solve the above problems, a resin obtained by curing a photopolymerizable composition, which is completely different from conventional plastic plates such as polyethylene terephthalate and polycarbonate. Using the molded body, a plastic substrate with a transparent electrode having heat resistance and rigidity and further having an anti-Newton ring function is obtained by forming fine irregularities on the surface of the resin molded body on which the transparent conductive film is formed. The present invention has been completed.

  That is, the gist of the present invention is a laminate in which a transparent conductive film is formed on one surface (A) of a resin molded body having a thickness of 0.1 to 1 mm obtained by curing the photopolymerizable composition [I]. And the surface (A) of the resin molded body is a surface on which irregularities having an anti-Newton ring function are formed, and the surface roughness (Ra) is 50 to 150 nm in JIS B0601: 2001 It is about the body.

  The laminate of the present invention is a laminate suitable for a plastic substrate for a display having excellent optical properties, thermal properties, mechanical properties, particularly excellent heat resistance and rigidity, and also having an anti-Newton ring function. It is useful as a substrate for liquid crystal display, liquid crystal display, and organic EL display.

Hereinafter, the present invention will be described in detail.
In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate.

The laminate of the present invention is a laminate in which a transparent conductive film is formed on one surface (A) of a resin molded body having a thickness of 0.1 to 1 mm obtained by curing the photopolymerizable composition [I]. And the surface (A) of the resin molded body is a surface on which irregularities having an anti-Newton ring function are formed, and the surface roughness (Ra) is 50 to 150 nm in JIS B0601: 2001. It is a feature.
In addition, the measurement length of the surface roughness (Ra) in this invention is 4 mm.
Further, the surface (A) on which the unevenness having the anti-Newton ring function is formed is a surface of a single resin molded body itself.

  The resin molded body used in the present invention is obtained by curing the photopolymerizable composition [I], and the photopolymerizable composition [I] is not particularly limited, but includes a polymerizable compound and light. It preferably contains a polymerization initiator. By photocuring the polymerizable compound, a resin molded article having excellent heat resistance and rigidity can be obtained.

Such polymerizable compounds include polyfunctional (meth) acrylate compounds, polyfunctional epoxy (meth) acrylate compounds, polyfunctional urethane (meth) acrylate compounds, polyfunctional polyester (meth) acrylate compounds, polyfunctional poly Examples include ether (meth) acrylate compounds.
Examples of the polyfunctional (meth) acrylate compound include a bifunctional (meth) acrylate compound and a tri- or higher functional (meth) acrylate compound.

Examples of the bifunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth). ) Acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol Aliphatic compounds such as glycidyl ether di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate diester, Bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane = di (meth) acrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = di (meth) acrylate Bis (hydroxy) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = di (meth) acrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = di (meth) acrylate, 2,2-bis [4- (β- (meth) acryloyloxyethoxy) cyclohexyl] propane, 1,3-bis ((meth) acryloyloxymethyl) cyclohexane, 1,3-bis ((meth) acryloyloxyethyloxymethyl) cyclohexane, 1,4-bis ((meth) acryloyloxymethyl) cyclohexane, 1,4-bis ((meth) acryloyloxyethyloxymethyl) cyclohexane, etc. Alicyclic compound, diglycidyl phthalate di (meth) acrylate, ethylene oxide modified bisphenol A (2,2'-diphenylpropane) type di (meth) acrylate, propylene oxide modified bisphenol A (2,2'-diphenyl) Propane) type di (meth) acrylate And aromatic compounds such as

  Examples of the trifunctional or higher functional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and di Pentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) Acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol Aliphatic compounds such as tri (meth) acrylate and ethylene oxide-modified pentaerythritol tetra (meth) acrylate, 1,3,5-tris ((meth) acryloyloxymethyl) cyclohexane, 1,3,5-tris ((meta And alicyclic compounds such as) (acryloyloxyethyloxymethyl) cyclohexane.

Among these polymerizable compounds, in terms of heat resistance, polyfunctional urethane (meth) acrylate compounds and bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane = di (meth) acrylate Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = di (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate are preferable, and further, shrinkage by curing Bis (hydroxy) tricyclo [5.2.1. Which is a polyfunctional urethane (meth) acrylate compound having an alicyclic structure and a polyfunctional (meth) acrylate compound having an alicyclic structure. 0 ^2,6 ] decane = di (meth) acrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = di (meth) acrylate Relate is preferable, and it is particularly preferable to use these in combination.

  As a polyfunctional urethane (meth) acrylate-based compound suitably used in the present invention, for example, a polyisocyanate-based compound and a hydroxyl group-containing (meth) acrylate-based compound may be used, if necessary, using a catalyst such as dibutyltin dilaurate. It is preferable that it is obtained by reacting.

Specific examples of the polyisocyanate compound include aliphatic polyisocyanate compounds such as ethylene diisocyanate and hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) tricyclo [5.2.1.0 ^2,6 ]. Decane, norbornane isocyanatomethyl, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, bis (4-isocyanatocyclohexyl) methane, 2,2-bis (4-isocyanate) Natocyclohexyl) propane, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, polyisocyanate compounds having an alicyclic structure such as isophorone diisocyanate trimer compound, and diphenylmethane diisocyanate Examples thereof include polyisocyanate compounds having an aromatic ring such as nate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate.

  Specific examples of the hydroxyl group-containing (meth) acrylate-based compound include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3- ( Examples include meth) acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tri (meth) acrylate, and the like.

  Two or more polyfunctional urethane (meth) acrylate compounds obtained by the reaction of a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound may be used in combination. Among these reactants, it is preferable to have an alicyclic skeleton from the viewpoint of water absorption, and acrylate compounds are more preferable from the viewpoint of curing speed, and 2 to 9 functional groups are particularly preferable from the viewpoint of heat resistance and bending elastic modulus. In particular, 2-6 functionalities are preferred.

Moreover, you may contain a monofunctional (meth) acrylate type compound as a polymeric compound to such an extent that heat resistance and rigidity are not inhibited.
Examples of monofunctional (meth) acrylate compounds include ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl ( Aliphatic compounds such as meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, tricyclodecyl (Meth) acrylate, tricyclodecyloxymethyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxymethyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2- Alicyclic compounds such as adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, aromatic compounds such as benzyl (meth) acrylate, monofunctional epoxy (meth) acrylate compounds, monofunctional urethanes Examples include (meth) acrylate compounds, monofunctional polyester (meth) acrylate compounds, and monofunctional polyether (meth) acrylate compounds.
These monofunctional (meth) acrylate compounds may be used alone or in combination of two or more.

  These monofunctional (meth) acrylate compounds are preferably used in a proportion of usually 50 parts by weight or less, more preferably 30 parts by weight or less, particularly 100 parts by weight of the photopolymerizable composition [I]. Is preferably 20 parts by weight or less. When there is too much this usage-amount, there exists a tendency for the heat resistance of the molded object obtained and rigidity to fall.

  Furthermore, you may add a polyfunctional mercaptan compound to the photopolymerizable composition [I] of this invention to such an extent that heat resistance and rigidity are not inhibited.

  Examples of the polyfunctional mercaptan compound include pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, and the like. These polyfunctional mercaptan-based compounds are preferably used in a proportion of usually 20 parts by weight or less, more preferably 10 parts by weight or less, particularly 5 parts by weight or less, based on 100 parts by weight of the photopolymerizable composition. preferable. When there is too much this usage-amount, there exists a tendency for the heat resistance of the molded object obtained and rigidity to fall.

  The photopolymerization initiator used in the present invention is not particularly limited as long as it can generate radicals by irradiation with active energy rays, and various photopolymerization initiators can be used. Examples include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like. Among these, photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are particularly preferable. These photopolymerization initiators may be used alone or in combination of two or more.

  These photopolymerization initiators are preferably used at a ratio of usually 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and particularly preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. 2-3 parts by weight are preferred. If the amount used is too small, the polymerization rate tends to decrease and polymerization does not proceed sufficiently. If the amount is too large, the light transmittance of the resulting resin molded product tends to decrease (yellowing).

  Moreover, you may use a thermal polymerization initiator together with a photoinitiator. As the thermal polymerization initiator, known compounds can be used, such as hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and the like. Hydroperoxides, dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide, peroxyesters such as t-butylperoxybenzoate, t-butylperoxy (2-ethylhexanoate), benzoylper Examples thereof include peroxides such as diacyl peroxides such as oxides, peroxycarbonates such as diisopropyl peroxycarbonate, peroxyketals, and ketone peroxides.

  The photopolymerizable composition [I] used in the present invention includes, in addition to the polymerizable compound and the photopolymerization initiator, an antioxidant, an ultraviolet absorber, a thickener, an antistatic agent, You may contain auxiliary components, such as a flame retardant, an antifoamer, a coloring agent, and various fillers.

In particular, the photopolymerizable composition [I] used in the present invention preferably contains an ultraviolet absorber from the viewpoint of light resistance of the touch panel.
Specific examples of the ultraviolet absorber are not particularly limited as long as they are soluble in the polymerizable compound, and various ultraviolet absorbers can be used. Specific examples include salicylic acid ester, benzophenone, triazole, hydroxybenzoate, and cyanoacrylate. These ultraviolet absorbers may be used in combination. Among these, in terms of compatibility with the polymerizable compound, benzophenone or triazole, specifically (2-hydroxy-4-octyloxy-phenyl) -phenyl-methanone, 2-benzotriazol-2-yl Ultraviolet absorbers such as -4-tert-octyl-phenol are preferred. It is preferable that the content rate of a ultraviolet absorber is 0.001-1 weight part normally with respect to 100 weight part of polymeric compounds, Most preferably, it is 0.01-0.1 weight part. When the amount of the ultraviolet absorber is too small, the light resistance of the resin molded product tends to be lowered. When the amount is too large, the light transmittance of the resin molded product is lowered and the photoelectric conversion efficiency tends to be lowered.

  Thus, the resin molding used by this invention is obtained by photocuring said photocurable composition [I].

  The thickness of the resin molding directly affects the rigidity of the plastic substrate. If the thickness is less than the lower limit, it is easy to bend and it is difficult to maintain the shape of the touch panel. Conversely, if the thickness exceeds the upper limit, it is difficult to reduce the weight of the touch panel. The preferable range of the thickness is 0.2 to 0.7 mm, more preferably 0.2 to 0.5 mm, and particularly preferably 0.2 to 0.4 mm.

  The anti-Newton ring function is imparted by forming fine irregularities on the surface (A) on the side where the transparent conductive film of the resin molded body is formed. When the surface roughness (Ra) of the uneven surface (A) is less than the lower limit value, sufficient anti-Newton ring function does not appear. Conversely, when the surface roughness (Ra) exceeds the upper limit value, the transparency of a panel such as a touch panel is caused by light scattering. Will be reduced. A preferable range of the surface roughness (Ra) is 60 to 120 nm, more preferably 70 to 110 nm, and particularly preferably 80 to 100 nm.

  In the present invention, the surface (A) on which irregularities having an anti-Newton ring function are formed is obtained by (1) bringing the photopolymerizable composition [I] into contact with the mold having irregularities and irradiating active energy rays. A method of forming by a transfer method of curing, (2) once forming a semi-cured resin molded body using the photocurable composition [I], and then transferring by pressing using a mold having irregularities, Further examples include a method of re-curing and the like. Although not particularly limited, the method (1) is particularly preferable from the viewpoint of cost reduction and productivity.

  That is, it is obtained by transferring the fine irregularities of the mold having a specific surface roughness to one surface (A) of the resin molded body. A preferable range of the surface roughness (Ra) of the mold is 50 to 150 nm, more preferably 60 to 120 nm, still more preferably 70 to 110 nm, and particularly preferably 80 to 100 nm.

  The material of the mold is not particularly limited, and those made of glass, metal, or resin can be used. Among these, a glass or transparent resin mold is preferable in terms of translucency of active energy rays. When an opaque mold is used, active energy rays are irradiated from the opposite surface. Further, a release agent can be applied to the surface of the mold in order to improve the demolding property of the resin molded body within the above-described range of the surface roughness of the mold.

  The resin molded body used in the present invention, once formed a semi-cured resin molded body using the photopolymerizable composition [I], then at least one surface of the semi-cured resin molded body has two surfaces. There is a method of placing between a mold having a fine uneven surface, transferring it by pressing or the like, and further re-curing, but preferably, the photopolymerizable composition [I] is applied to at least one surface of two sheets. Is provided between molds having fine irregular surfaces, and is produced by irradiating with active energy rays from both sides or one side and curing.

  The irradiation with active energy rays is preferably performed from the surface side of the mold having irregularities in order to improve the transfer accuracy of the fine irregularities. Further, it is preferable to complete the curing by irradiation from both sides. In order to accelerate or complete the curing, the resin molded body can be heated at the time of irradiation of active energy or after irradiation.

As the active energy rays used, far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays and other electromagnetic waves, X rays, γ rays and other electromagnetic waves, as well as electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous because of the availability of the irradiation device and the price. As a light source in ultraviolet irradiation, a chemical lamp, a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, or the like is usually used. Although it does not specifically limit as irradiation energy, Usually, what is necessary is just to irradiate about 1-100 J / cm < ² >.

  The photopolymerizable composition [I] used in the present invention is not particularly limited, but preferably has a viscosity of 10 to 1000 mPa · s at 23 ° C. from the viewpoint of accurately transferring fine irregularities from the mold. If the viscosity of the photopolymerizable composition is too low, it tends to be difficult to peel the resin molded product after polymerization from the mold. Conversely, if the viscosity is too high, the transfer accuracy tends to decrease. A preferable range of the viscosity is 20 to 800 mPa · s, more preferably 30 to 700 mPa · s, still more preferably 40 to 600 mPa · s, and particularly preferably 50 to 500 mPa · s.

  The resin molded body used in the present invention is preferably transparent and preferably has a haze of 5 to 15% from the viewpoint of the anti-Newton ring function. If the haze is too small, the sufficient anti-Newton ring function tends not to be exhibited, and if it is too large, the light transmittance of the touch panel tends to decrease. The preferable range of haze is 6 to 14%, more preferably 7 to 13%, and particularly preferably 8 to 12%.

  The resin molded body of the present invention preferably has a glass transition temperature of 150 ° C. or higher and a flexural modulus of 4 GPa or higher from the viewpoint of heat resistance and rigidity.

  If the glass transition temperature is too low, it tends to be difficult to form a high-performance transparent electrode. For example, crystallization of ITO is effective to ensure the sliding resistance and moisture resistance of the touch panel, but heating at 150 ° C. or higher is necessary for this crystallization, and the heat resistance of the plastic substrate When it is low, there is a tendency that undulation occurs or the hue deteriorates. The preferable range of the glass transition temperature is 180 to 500 ° C, more preferably 200 to 400 ° C, still more preferably 220 to 350 ° C. In adjusting the glass transition temperature to the above range, a method of appropriately controlling the type of the above-described photopolymerizable composition [I] and the blending amount of the components can be used. For example, an acrylate-based compound and a methacrylate-based compound are used in combination, and a larger amount of the methacrylate-based compound is blended in the mixing ratio.

  If the flexural modulus is too small, the rigidity of the resin molded body tends to be insufficient, and the touch panel tends to be easily deformed. The flexural modulus is preferably 4 to 6 GPa, more preferably 4.1 to 5.5 GPa, and still more preferably 4.2 to 5 GPa. In adjusting the bending elastic modulus to the above range, a method of appropriately controlling the kind of the above-described photopolymerizable composition [I] and the amount of the component is mentioned. For example, a bifunctional (meth) acrylate compound and a trifunctional or higher (meth) acrylate compound are used in combination, and the bifunctional (meth) acrylate compound is blended more in the mixing ratio.

  The transparent conductive film in the laminate of the present invention is preferably formed on the anti-Newton ring functional surface (A) of the resin molding and has a surface resistance value of 10 to 1000Ω / □. More preferably, it is 100-900 ohm / square, More preferably, it is 200-800 ohm / square, Especially preferably, it is 300-700 ohm / square. If the surface resistance value is too high, the conductivity tends to be insufficient, and if it is too small, the position detection accuracy of the touch panel tends to decrease.

  As the transparent conductive film, an ITO film which is an oxide of indium and tin is preferable. The film thickness is 50 to 500 mm, more preferably 100 to 400 mm, and still more preferably 150 to 300 mm. If the film thickness is too thin, the conductivity tends to be insufficient, and if it is too thick, the substrate tends to warp.

  Furthermore, in the present invention, the surface (B) (surface on which the transparent conductive film is not formed) opposite to the surface (A) on which the unevenness having the anti-Newton ring function of the resin molded body is formed is protected. It is preferable to form fine irregularities having a glare function, and the surface roughness (Ra) in JIS B0601: 2001 is preferably 50 to 150 nm. A more preferable range of the surface roughness (Ra) is 60 to 140 nm, more preferably 70 to 130 nm, and particularly preferably 80 to 120 nm.

  Fine irregularities on the opposite surface (B) can also be produced in the same manner as the irregular surface (A) having an anti-Newton ring function. In particular, it is preferable from the viewpoint of productivity and cost reduction that the photopolymerizable composition [I] is brought into contact with a mold having fine irregularities and is cured by an active energy ray. That is, it is obtained by transferring fine irregularities of a mold having a specific surface roughness (Ra) to the surface of the resin molded body. A preferable range of the surface roughness (Ra) of the mold is 50 to 150 nm, more preferably 60 to 140 nm, still more preferably 70 to 130 nm, and particularly preferably 80 to 120 nm.

  The material of the type | mold used for unevenness | corrugation formation of an opposite surface (B) is not specifically limited, The thing made from glass, metal, and resin can be used. Among these, a glass or transparent resin mold is preferable in terms of translucency of active energy rays. When using an opaque type | mold, an active energy ray is irradiated from an opposite surface (A surface). Further, a release agent can be applied to the surface of the mold in order to improve the demolding property of the resin molded body within the above-described range of the surface roughness of the mold.

  By using the laminate thus obtained, a substrate with a transparent electrode for a panel such as a touch panel can be obtained.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the examples, “parts” and “%” mean weight basis unless otherwise specified.

(1) Surface roughness (Ra) (nm)
According to JIS B0601: 2001, Ra on both surfaces of the resin molded product was measured using “Surfcom 570A” manufactured by Tokyo Seimitsu Co., Ltd. (cutoff: 0.8 μm, measurement length: 4 mm).

(2) Haze (%)
It measured using the color computer by Suga Test Instruments Co., Ltd.

(3) Glass transition temperature (° C)
Using a test piece having a length of 20 mm and a width of 5 mm, using a tensile mode of a dynamic viscoelastic device “DVE-V4 FT Rheospectr” manufactured by Rheology, a frequency of 10 Hz, a heating rate of 3 ° C./min, a strain Measurements were taken at 0.025%. The ratio (tan δ) of the imaginary part (loss elastic modulus) to the real part (storage elastic modulus) of the obtained complex elastic modulus was determined, and the maximum peak temperature of tan δ was defined as the glass transition temperature Tg.

(4) Flexural modulus (GPa)
Using a test piece of length 25 (mm) × width 10 (mm), bending modulus (GPa) at 25 ° C. with Autograph AG-5kNE (distance between fulcrums 20 mm, 0.5 mm / min) manufactured by Shimadzu Corporation ) Was measured.

(5) Viscosity (mPa · s)
Using a B-type viscometer “Bismetron VS-A1” manufactured by Shibaura System Co., Ltd., the measurement was performed at 23 ° C. and a rotational speed of 60 rpm (No. 3 rotor).

(6) Surface resistance (Ω / □)
It measured using the 4-terminal method resistance measuring device (Lorester MP) made from Mitsubishi Chemical Corporation using the test piece of 150 square mm.

(7) Anti-Newton ring function The touch panel was visually observed and evaluated as follows.
○ ・ ・ ・ Newton ring is not visible △ ・ ・ ・ Newton ring is slightly visible × ・ ・ ・ Newton ring is clearly visible

<Example 1>
[Preparation of Photopolymerizable Composition [I-1]]
10 parts of urethane acrylate having a hexafunctional interfacial skeleton (“UV7600B” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate (Shin Nakamura Chemical) "DCP", 87 parts, pentaerythritol tetrakisthiopropionate ("PETP", Sakai Chemical Co., Ltd.), benzophenone ultraviolet absorber (Kyogaku Co., Ltd., "biosorb 130") 0.1 part , 1 part of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals) was stirred until uniform at 60 ° C., and then filtered through a 10 μm filter to obtain a photopolymerizable composition [I-1] Got. The viscosity of this composition is 200 mPa · s.

[Preparation of molded resin]
The glass surface (A surface side) having fine irregularities with a surface roughness (Ra) of 80 nm and the smooth optical polishing glass surface (B surface side) with a surface roughness (Ra) of 6 nm are faced inward, A photopolymerizable composition [I-1] is injected at 23 ° C. into a mold using a silicon plate having a thickness of 0.2 mm as a spacer, and ultraviolet rays are applied from both sides with a light intensity of 10 J / cm ² using a metal halide lamp. Irradiated.
The obtained resin molded body was heated in a vacuum oven at 200 ° C. for 2 hours to obtain a resin molded body having a length of 400 mm, a width of 300 mm, and a thickness of 0.2 mm. The surface roughness (Ra) of the obtained resin molding was 80 nm for the anti-Newton ring functional surface (A surface) and 6 nm for the smooth surface (B surface). Moreover, the haze of the obtained resin molding was 8%, the glass transition temperature was 250 degreeC, and the bending elastic modulus was 4.2 GPa.

[Production of laminate]
An ITO film having a thickness of 200 mm was formed at 150 ° C. on the anti-Newton ring functional surface (A surface) of the obtained resin molded body by sputtering to obtain a laminate (substrate with a transparent electrode). The surface resistance value of the transparent electrode was 500Ω / □.

[Production of touch panel]
The transparent electrode surface of the obtained substrate with a transparent electrode was used as the upper electrode, the transparent electrode surface of the glass substrate with a general-purpose transparent electrode was used as the lower electrode, and both electrodes were placed facing each other with an interval of 0.2 mm to produce a touch panel. . Newton rings were not visible on this touch panel.

<Example 2>
[Preparation of molded resin]
A glass surface (A surface side) having fine irregularities with a surface roughness (Ra) of 100 nm and a smooth optical polished glass surface (B surface side) with a surface roughness (Ra) of 6 nm are faced inward, The photopolymerizable composition [I-1] obtained in Example 1 was poured at 23 ° C. into a mold using a silicon plate having a thickness of 0.2 mm as a spacer, and the amount of light was measured from both sides using a metal halide lamp. Ultraviolet rays were irradiated at 10 J / cm ² .
The obtained resin molded body was heated in a vacuum oven at 200 ° C. for 2 hours to obtain a resin molded body having a length of 400 mm, a width of 300 mm, and a thickness of 0.2 mm. The surface roughness (Ra) of the obtained resin molding was 100 nm for the anti-Newton ring functional surface (A surface) and 6 nm for the smooth surface (B surface). Moreover, the haze of the obtained resin molding was 10%, the glass transition temperature was 250 ° C., and the flexural modulus was 4.2 GPa.

[Production of laminate]
A laminate (substrate with a transparent electrode) was obtained in the same manner as Example 1. The surface resistance value of the transparent electrode was 500Ω / □.
[Production of touch panel]
A touch panel was produced in the same manner as in Example 1. Newton rings were not visible on this touch panel.

<Example 3>
[Preparation of molded resin]
A glass surface (A surface side) having fine irregularities with a surface roughness (Ra) of 50 nm and a smooth optical polished glass surface (B surface side) with a surface roughness (Ra) of 6 nm are faced inward, The photopolymerizable composition [I-1] obtained in Example 1 was poured at 23 ° C. into a mold using a silicon plate having a thickness of 0.2 mm as a spacer, and the amount of light was measured from both sides using a metal halide lamp. Ultraviolet rays were irradiated at 10 J / cm ² .
The obtained resin molded body was heated in a vacuum oven at 200 ° C. for 2 hours to obtain a resin molded body having a length of 400 mm, a width of 300 mm, and a thickness of 0.2 mm. The surface roughness (Ra) of the obtained resin molded body was 50 nm for the anti-Newton ring functional surface (A surface) and 6 nm for the smooth surface (B surface). Moreover, the haze of the obtained resin molding was 5%, the glass transition temperature was 250 degreeC, and the bending elastic modulus was 4.2 GPa.

[Production of laminate]
A laminate (substrate with a transparent electrode) was obtained in the same manner as Example 1. The surface resistance value of the transparent electrode was 500Ω / □.
[Production of touch panel]
A touch panel was produced in the same manner as in Example 1. I could see the Newton ring on this touch panel.

<Example 4>
[Preparation of molded resin]
The glass surface (A side) having fine irregularities with a surface roughness (Ra) of 80 nm and the glass surface (B side) having fine irregularities with a surface roughness (Ra) of 100 nm are facing inward. The photopolymerizable composition of Example 1 was poured into a mold using a silicon plate having a thickness of 0.2 mm as a spacer at 23 ° C., and ultraviolet rays were emitted from both sides with a light intensity of 10 J / cm ² using a metal halide lamp. Was irradiated.
The obtained resin molded body was heated in a vacuum oven at 200 ° C. for 2 hours to obtain a resin molded body having a length of 400 mm, a width of 300 mm, and a thickness of 0.2 mm. The surface roughness (Ra) of the obtained resin molding was 80 nm for the anti-Newton ring functional surface (A surface) and 90 nm for the antiglare functional surface (B surface). Moreover, the haze of the obtained resin molding was 15%, the glass transition temperature was 250 degreeC, and the bending elastic modulus was 4.2 GPa.

[Production of laminate]
A laminate (substrate with a transparent electrode) was obtained in the same manner as Example 1. The surface resistance value of the transparent electrode was 500Ω / □.
[Production of touch panel]
A touch panel was produced in the same manner as in Example 1. Newton rings were not visible on this touch panel. Moreover, the glare-proof function was also acquired and visibility was favorable.

<Example 5>
[Preparation of Photopolymerizable Composition [I-2]]
30 parts of urethane acrylate having a hexafunctional interfacial skeleton (“UV7600B” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate (Shin Nakamura Chemical) "DCP", 67 parts, pentaerythritol tetrakisthiopropionate ("PET", Sakai Chemical), 0.1 part of a benzophenone UV absorber (Kyo Pharmaceutical Co., Ltd., "biosorb 130") , 1 part of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals) was stirred until uniform at 60 ° C., and then filtered through a 10 μm filter to obtain a photopolymerizable composition [I-2] Got. The viscosity of this composition is 1500 mPa · s.

[Preparation of molded resin]
A resin molded body was obtained in the same manner as in Example 1 using the photocurable composition [I-2]. The surface roughness (Ra) of the obtained resin molded body was 70 nm for the anti-Newton ring functional surface (A surface) and 6 nm for the smooth surface (B surface). Moreover, the haze of the obtained resin molding was 7%, the glass transition temperature was 270 ° C., and the flexural modulus was 4.5 GPa.
[Production of laminate]
A laminate (substrate with a transparent electrode) was obtained in the same manner as Example 1. The surface resistance value of the transparent electrode was 500Ω / □.
[Production of touch panel]
A touch panel was produced in the same manner as in Example 1. Newton rings were not visible on this touch panel.

<Comparative Example 1>
[Preparation of molded resin]
A resin molded body was obtained in the same manner as in Example 1 except that smooth optically polished glass surfaces having a surface roughness (Ra) of 6 nm were used on both sides. The obtained resin molding was smooth on both sides, and the surface roughness (Ra) was 6 nm on both sides. Moreover, the haze of the obtained resin molding was 0.4%, the glass transition temperature was 250 degreeC, and the bending elastic modulus was 4.2 GPa.

[Production of laminate]
A laminate (substrate with a transparent electrode) was obtained in the same manner as Example 1. The surface resistance value of the transparent electrode was 500Ω / □.
[Production of touch panel]
A touch panel was produced in the same manner as in Example 1. A clear Newton ring was visible on this touch panel.

  The evaluation results of Examples and Comparative Examples are shown in Table 1.

  The laminate of the present invention can be advantageously used for various optical materials and electronic materials. For example, building materials such as window materials, liquid crystal substrates, organic / inorganic EL substrates, electronic paper substrates, light guide plates, phase difference plates, touch panels, optical filters, etc. It can be used for recording applications, energy applications such as thin film battery substrates and solar cell substrates, optical communication applications such as optical waveguides, and functional films / sheets and various optical films / sheets.

Claims (9)

A laminate in which a transparent conductive film is formed on one surface (A) of a resin molded body having a thickness of 0.1 to 1 mm obtained by curing the photopolymerizable composition [I], and resin molding A laminate having a surface (A) having an anti-Newton ring function and a surface roughness (Ra) of 50 to 150 nm in JIS B0601: 2001. The laminate according to claim 1, wherein the resin molded body has a haze of 5 to 15%. The laminated body according to claim 1 or 2, wherein the resin molded body has a glass transition temperature of 150 ° C or higher and a flexural modulus of 4 GPa or higher. The laminated body according to claim 1, wherein the photopolymerizable composition [I] has a viscosity at 23 ° C. of 10 to 1000 mPa · s. The laminate according to any one of claims 1 to 4, wherein the photopolymerizable composition [I] further contains an ultraviolet absorber. The surface (B) opposite to the surface (A) of the resin molded body is a surface on which irregularities having an antiglare function are formed, and the surface roughness (Ra) is 50 to 150 nm in JIS B0601: 2001. A laminate according to any one of claims 1 to 5. The unevenness of the surface (A) of the resin molded body is formed by a transfer method in which the photopolymerizable composition is brought into contact with a mold having unevenness, and the photopolymerizable composition is cured by irradiation with active energy rays to form unevenness. The laminate according to any one of claims 1 to 6, wherein: The surface resistance value of a transparent conductive film is 10-1000 ohms / square, The laminated body in any one of Claims 1-7 characterized by the above-mentioned. It uses as a board | substrate with a transparent electrode for touchscreens, The laminated body in any one of Claims 1-8 characterized by the above-mentioned.