JP2010280092A - Laminate and application of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which is suitable for a lightweight, thin and flexible display and includes various excellent properties such as light transmittance, surface smoothness, flex resistance (no crack by bending), impact resistance, a linear expansion coefficient, a gas barrier property and the like. <P>SOLUTION: In the laminate having a construction of glass [I]/a cured resin layer [II], the glass [I] is 20-250 μm thick; the cured resin layer [II] is made by applying an active energy ray-curable composition on the glass [I] and curing the composition by the active energy ray; and the active energy ray-curable composition includes an alicyclic skeleton-containing polyfunctional urethane(meth)acrylate-based compound (A), a polyfunctional (meth)acrylate-based compound (B), a silane coupling agent (C) and a photopolymerization initiator (D). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a laminate comprising a thin film glass and a cured resin layer, and in particular, is a transparent laminate excellent in optical properties, surface smoothness, thermal properties, and mechanical properties. The present invention relates to a laminate useful as a transparent electrode substrate.

  Conventionally, as a substrate for a display, a glass substrate is often used. For example, in a liquid crystal display, an organic electroluminescence (EL) display, a touch panel or the like, a glass substrate having a thickness of about 300 to 1100 μm is widely used. The glass substrate has excellent properties such as transparency, low birefringence, surface smoothness, heat resistance, linear expansion coefficient, surface hardness, gas barrier properties, chemical resistance, and solvent resistance. This is the best substrate at the moment. Moreover, in recent years, with the reduction in thickness and weight of displays, the glass substrate has also been made thinner, and a thin glass having a thickness of 300 μm or less has been found. However, there is a problem that it is easy to break against impact and bending when manufacturing and using the display, so the range of use is limited, and it is particularly difficult to use it for large area displays and flexible displays. That is the situation.

  On the other hand, a resin substrate has been proposed from the viewpoint of light weight, thinness, and resistance to cracking. In particular, for the purpose of manufacturing a high-strength display for portable use, a resin substrate that is not easily broken by impact or bending is suitable. However, the performance of the glass substrate has not been achieved comprehensively, and there are many problems such as birefringence, surface smoothness, heat resistance, linear expansion coefficient, gas barrier property, chemical resistance and solvent resistance.

  In such a background, a laminate composed of glass and resin has also been proposed. For example, a laminate in which a glass film and a plastic film, a plastic sheet, or a plastic plate are laminated and fixed is proposed ( For example, see Patent Document 1.)

JP 2003-39597 A

  However, in the disclosed technique of Patent Document 1, although it is surely excellent in surface smoothness, heat resistance, gas barrier properties, chemical resistance / solvent resistance, etc., a relatively thick plastic film (in the example, 0.4 to 1 mm) is used. Since it adheres to the glass, it was still not sufficient in terms of adhesion and the total thickness of the laminate. In addition, although there is a disclosure of a laminate using a liquid polymerizable composition, in this case, the polymerizable composition is injected between two glass films to be cured, laminated and fixed, and glass film / plastic It is to produce a film / glass film laminate, and since it has glass on its surface, it is not possible to avoid the ease of cracking. For example, when a hard sphere falls on the glass surface, the laminate is easily broken, and even if the entire laminate is not broken, the glass surface is easily cracked or chipped. Moreover, in the Example of patent document 1, the thickness of a laminated body exceeds 0.5 mm, and there also exists a problem that it lacks in flexibility. Although a test method in which the length is 100 mm and the warp is 5 mm is described, the flexibility is insufficient at this level, and it is difficult to cope with a flexible display.

  Therefore, in the present invention, in such a background, the laminate is suitable for a lightweight, thin, and flexible display, and has impact resistance, bending resistance (that does not crack even when bent), light transmittance, multiple transmittance. It is an object of the present invention to provide a laminate having excellent physical properties such as refraction, surface smoothness, heat resistance, gas barrier properties, chemical resistance and solvent resistance, and a display substrate and a transparent electrode substrate.

  However, as a result of intensive studies by the present inventors to solve the above-described problems, a transparent laminate having a glass / cured resin layer configuration uses a thin glass, and as the cured resin layer, an alicyclic ring. By coating and curing an active energy ray-curable composition containing a skeleton-containing polyfunctional urethane (meth) acrylate compound as an essential component, impact resistance, flex resistance, birefringence, surface The present invention has been completed by discovering that it is excellent in smoothness, heat resistance, gas barrier properties, chemical resistance and solvent resistance, and is useful as a lightweight, thin and flexible display substrate and transparent electrode substrate.

  That is, the gist of the present invention is that in the laminate having the configuration of glass [I] / cured resin layer [II], the thickness (i) of glass [I] is 20 to 250 μm, and cured resin layer [II]. Is a cured resin layer obtained by applying an active energy ray-curable composition to glass [I] and curing with active energy rays, and the active energy ray-curable composition is an alicyclic skeleton-containing polyfunctional urethane (Metal). ) A curable composition comprising an acrylate compound (A), a polyfunctional (meth) acrylate compound (B), a silane coupling agent (C) and a photopolymerization initiator (D). It is related with the laminated body to perform.

  In the present invention, a display substrate using the laminate, or a transparent electrode substrate in which a transparent conductive film is further formed on the side opposite to the cured resin layer of the glass [I] of the laminate is provided. Is also provided.

  The laminate of the present invention uses a thin glass and is coated with an active energy ray-curable composition containing an alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound as an essential component as a cured resin layer. Because it is a cured layer, it is a laminate suitable for lightweight, thin, and flexible displays, impact resistance, bending resistance (does not break even when bent), light transmittance, birefringence, surface smoothness Excellent effects on various physical properties such as heat resistance, heat resistance, gas barrier properties, chemical resistance and solvent resistance.

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 has a configuration of glass [I] / cured resin layer [II]. Such a configuration is very useful because it has advantages such as surface smoothness, heat resistance, low linear expansion coefficient, and gas barrier properties in glass, and the advantage of being hard to crack in resin. In order to utilize these advantages, it is preferable to dispose the cured resin layer [II] on the outside of the display device and the glass [I] surface on the inside. For example, the liquid crystal device has a configuration in which a liquid crystal layer is sandwiched between two substrates, and a glass [I] surface is disposed on the liquid crystal layer side and a cured resin layer [II] is disposed on the outside. By arranging the glass [I] surface on the inner side of the display device, the smoothness, heat resistance, low linear expansion coefficient and gas barrier properties of the glass can be utilized, and the cured resin layer [II] is arranged on the outer side. Thus, the impact resistance and bending resistance of the resin can be utilized.

  Normally, a transparent electrode layer, a color filter layer, a TFT layer, and the like are formed between the liquid crystal layer and the glass, but it is possible to form a defect-free layer by taking advantage of the smoothness of the glass, Furthermore, the heat resistance and low linear expansion coefficient of glass enable each layer to be formed at a high temperature, and it is possible to produce a liquid crystal device with superior durability.

The arrangement described above is the same in the case of organic EL devices and resistive touch panels. By arranging the cured resin layer [II] outside the display device, a thin display excellent in impact resistance and flex resistance can be obtained. Can be manufactured.

  Examples of the thin glass [I] used in the present invention include soda lime glass and borosilicate glass. Among these, inexpensive soda lime glass is preferable. In addition, these glasses may be chemically strengthened, and an alkali elution preventing layer may be provided on the surface.

  In the present invention, the glass [I] has a thickness of 20 to 250 μm, preferably 70 to 200 μm, particularly preferably 100 to 200 μm, and more preferably 100 to 150 μm. When the thickness is too thin than the above range, the birefringence of the laminate tends to increase, and when it is too thick, the impact resistance of the laminate tends to decrease.

The cured resin layer [II] in the laminate of the present invention is obtained by curing an active energy ray-curable composition with active energy rays, and as such an active energy ray-curable composition, quick curing, glass It is necessary to contain the following component (A)-(D) from viewpoints, such as adhesiveness with this, and high strengthening of a laminated body.
(A) Alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound (B) Polyfunctional (meth) acrylate compound (C) Silane coupling agent (D) Photopolymerization initiator

  The alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound (A) used in the present invention is preferably a bifunctional urethane (meth) acrylate compound from the viewpoint of low curing shrinkage, and in particular. From the viewpoint of low water absorption, a compound represented by the following general formula (1) is preferable.

（ここで、Ｒ₁は水素又はメチル基であり、Ｒ₂は炭素数１〜５、好ましくは２〜３のアルキレン基である。）

(Here, R ₁ is hydrogen or a methyl group, and R ₂ is an alkylene group having 1 to 5 carbon atoms, preferably 2 to 3 carbon atoms.)

The alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound (A) comprises a polyisocyanate compound having an alicyclic skeleton and a hydroxyl group-containing (meth) acrylate compound, and a catalyst such as dibutyltin dilaurate as necessary. It can obtain by making it react.

Specific examples of the polyisocyanate compound having an alicyclic skeleton include, for example, isophorone diisocyanate, norbornene diisocyanate, cyclopentadiene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane. , Hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and isophorone diisocyanate trimer compound. Of these, isophorone diisocyanate is preferable.

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. Among them, monofunctional such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, etc. These hydroxyl group-containing (meth) acrylate compounds are preferred in terms of low cure shrinkage.

The alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound (A) may be used in combination of two or more.
In addition to the alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound (A), other polyfunctional urethane (meth) acrylate compounds can be used in combination.

The polyfunctional (meth) acrylate compound (B) used in the present invention is one excluding the polyfunctional urethane (meth) acrylate compound, and is a bifunctional (meth) compound from the viewpoint of low cure shrinkage. Acrylate compounds are preferred, and (meth) acrylate compounds containing an alicyclic skeleton are particularly preferred from the viewpoint of low birefringence. Examples of such bifunctional alicyclic skeleton-containing (meth) acrylate compounds include bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane = di (meth) acrylate, bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane = acrylate methacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = di (meth) acrylate, bis (hydroxymethyl) tricyclo [ 5.2.1.0 ^2,6 ] decane = acrylate methacrylate, bis (hydroxy) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . ^0,13 ] pentadecane = di (meth) acrylate, bis (hydroxy) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = acrylate methacrylate, bis (hydroxymethyl) 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 = acrylate methacrylate, 2,2-bis [4- (β- (meth) acryloyloxyethoxy) cyclohexyl] propane, 1,3-bis ((meth) acryloyloxymethyl) cyclohexane, 1,3 -Bifunctional (meth) acrylates such as bis ((meth) acryloyloxyethyl) cyclohexane, 1,4-bis ((meth) acryloyloxymethyl) cyclohexane, 1,4-bis ((meth) acryloyloxyethyl) cyclohexane Compounds and the like. Among these, from the viewpoint of chemical resistance and solvent resistance, 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.

  In the present invention, the content ratio of the alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound (A) and the polyfunctional (meth) acrylate compound (B) is 10/90 to 90/10 (weight ratio). It is preferable. The ratio is more preferably 15/85 to 80/20 (weight ratio), particularly preferably 20/80 to 70/30 (weight ratio), and still more preferably 20/80 to 40/60 (weight ratio). If the content of the alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound (A) is too small, the strength of the laminate tends to decrease. Conversely, if the content is too large, the viscosity of the active energy ray-curable composition is low. It tends to increase.

  Examples of the silane coupling agent (C) used in the present invention include acrylic silane coupling agents such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane, Examples include mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane, and among these, trialkoxysilane is preferable. From the viewpoint of adhesion to glass, a (meth) acryloxy group-containing trialkoxysilane such as 3- (meth) acryloxypropyltrimethoxysilane is particularly preferred. These may be used alone or in combination of two or more.

  The content of the silane coupling agent (C) is 1 with respect to the total amount of the alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound (A) and the polyfunctional (meth) acrylate compound (B). It is preferable that it is ˜50 wt%, more preferably 10 to 45 wt%, particularly 20 to 40 wt%. If the content is too large, the strength of the laminate tends to decrease. On the other hand, if the content is too small, the adhesion strength between the glass [I] and the cured resin layer [II] tends to be insufficient.

  Examples of the photopolymerization initiator (D) used in the present invention include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2, Examples include 4,6-trimethylbenzoyldiphenylphosphine oxide. Among these, radical-cleavage photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable. These may be used alone or in combination of two or more.

  Content of a photoinitiator (D) is 1-10 weight with respect to the sum total of an alicyclic skeleton containing polyfunctional urethane (meth) acrylate type compound (A) and a polyfunctional (meth) acrylate type compound (B). %, More preferably 2 to 8% by weight, particularly preferably 3 to 6% by weight. When the content is too large, the birefringence of the laminate increases and the light transmittance tends to decrease. On the other hand, when the content is too small, the polymerization rate decreases and the polymerization may not proceed sufficiently.

  The active energy ray-curable composition used in the present invention may contain a small amount of auxiliary components as long as the physical properties of the laminate of the present invention are not impaired. For example, polymerization inhibitors, thermal polymerization initiators, chain transfer agents, antioxidants, yellowing inhibitors, ultraviolet absorbers, bluing agents, dyes and pigments, antifoaming agents, leveling agents, thixotropic agents, flame retardants, A thickener, a filler, etc. are mentioned.

  It is important that the laminate of the present invention is transparent, and the term “transparent” in the present invention means that the light transmittance in the visible light region is usually 80% or more. The preferable range of the light transmittance is 85% or more, more preferably 90% or more. The upper limit is usually 99%.

  The laminate in the present invention is produced by applying an active energy ray-curable composition to thin glass [I] and curing with active energy rays to form a cured resin layer. As a coating method, a known method can be used. For example, an active energy ray-curable composition is applied onto glass [I] by a technique such as spin coating, bar coating, die coating, gravure coating, spray coating, or screen printing, and cured with active energy rays.

  The active energy ray-curable composition may be diluted with a solvent according to the coating method. By diluting with a solvent, the viscosity can be adjusted and the coatability can be improved. In this case, after coating on glass, the solvent is dried and then active energy ray curing is performed.

  Examples of the solvent include alcohol solvents such as isopropyl alcohol and diacetone alcohol, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the organic solvent include ketone solvents, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, and cellosolves.

  With respect to the amount of the organic solvent, the total concentration of the components (A) to (D) is 10 to 90% by weight, particularly 20 to 80% by weight, more preferably 30 to 70% by weight, particularly 40 to 60%. What is necessary is just to mix | blend so that it may become weight%. If the concentration is too high, the viscosity becomes high and the coating property tends to be poor. If the concentration is too low, the drying load tends to increase.

  In the present invention, the glass surface may be treated with a silane coupling agent in order to increase the adhesion strength between the glass [I] and the cured resin layer [II]. That is, the above-described silane coupling agent may be applied to the glass surface and then dried, and then the active energy ray-curable composition may be applied.

  As such active energy rays, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous from the viewpoint of easy availability and price.

As a method of curing by ultraviolet irradiation, the active energy ray-curable composition is preferably photocured with an irradiation light amount of 20 J / cm ² or less using ultraviolet rays having a wavelength of 150 to 450 nm. A more preferable range of the irradiation light amount is 0.5 to 15 J / cm ² , and more preferably 1 to 10 J / cm ² . If the amount of irradiation light is too large, productivity tends to be inferior. The illuminance of ultraviolet rays is usually 10 to 5000 mW / cm ² , preferably 100 to 1000 mW / cm ² . If the illuminance is too small, it may not be cured sufficiently. On the other hand, if the illuminance is too high, curing may run away and birefringence may increase.

Examples of the ultraviolet light source include a metal halide lamp, a high-pressure mercury lamp, an electrodeless mercury lamp, a carbon arc lamp, a xenon lamp, and a chemical lamp.
The cured resin layer [II] obtained in the present invention may be heat-treated for improving the degree of polymerization or releasing stress strain, and in that case, it is preferably heat-treated at 100 ° C. or higher.

  The curing shrinkage of the active energy ray-curable composition used for the laminate of the present invention is preferably 10% or less, more preferably 9% or less, and particularly preferably 8% or less from the viewpoint of reducing warpage of the laminate. . The lower limit of the cure shrinkage is usually 1%.

  In addition, the cure shrinkage said here means the volume shrinkage before and behind hardening of an active energy ray curable composition. Examples of the method for reducing the curing shrinkage rate include a method for specifying the component and content of the active energy ray-curable composition and a method for adding a filler as an auxiliary component.

In the laminate of the present invention, the thickness of the cured resin layer [II] is preferably 1 to 50 μm, particularly 2 to 40 μm, and more preferably 3 to 30 μm. If the thickness of the cured resin layer [II] is too thick, the birefringence of the laminate tends to increase. Conversely, if the thickness is too thin, the impact resistance of the laminate tends to be insufficient.

  Furthermore, in the laminate of the present invention, regarding the relationship between the thickness of the glass [I] and the thickness of the cured resin layer [II], the thickness of the glass [I] is 5 of the thickness of the cured resin layer [II]. It is preferably 50 to 50 times, particularly 10 to 45 times, and more preferably 20 to 40 times, from the viewpoint of securing a balance between mechanical strength such as impact resistance and flex resistance and heat resistance. If the glass [I] is too thin relative to the cured resin layer [II], the birefringence of the laminate tends to increase. Conversely, if the glass [I] is too thick, the impact resistance and flex resistance of the laminate are reduced. Tend to.

  The total thickness of the laminate of the present invention is preferably 30 to 300 μm. In particular, it is preferably 70 to 250 μm, more preferably 100 to 220 μm. If the total thickness is too thick, it tends to be difficult to reduce the weight and thickness of the display device. Conversely, if the total thickness is too thin, the display device tends to be difficult to manufacture due to insufficient rigidity.

  The retardation of the laminate in the present invention is preferably 1 nm or less from the viewpoint of high definition of the display device. More preferably, it is 0.5 nm or less, More preferably, it is 0.2 nm or less, Most preferably, it is 0.1 nm or less. As a technique for reducing retardation, a technique for specifying components and contents of the active energy ray-curable composition (for example, using an alicyclic skeleton monomer having a small curing shrinkage or adjusting the amount of a photopolymerization initiator). ), A method of adding a chain transfer agent such as a mercaptan compound as an auxiliary component, a method of controlling irradiation conditions of active energy rays at the time of curing (for example, do not increase illuminance excessively, Etc.).

  The light transmittance of the laminate in the present invention is preferably 90% or more from the viewpoint of increasing the brightness of the display device. More preferably, it is 90.5% or more, and particularly preferably 91% or more. The upper limit is usually 99%. As a technique for improving the light transmittance, a technique for specifying the components and content of the active energy ray-curable composition (for example, using a monomer that does not contain an aromatic ring as a polyfunctional (meth) acrylate, or a photopolymerization initiator) And the like, and a method of adding an antioxidant, an anti-yellowing agent, an ultraviolet absorber, etc. as an auxiliary component, a method of controlling the irradiation conditions of active energy rays during curing (for example, For example, not increasing the amount of light excessively or irradiating with inert gas).

  The pencil hardness on the cured resin layer [II] surface side of the laminate in the present invention is preferably H or more from the viewpoint of improving the quality of the display device. More preferably, it is 2H% or more, More preferably, it is 3H or more, Most preferably, it is 4H or more. The upper limit is usually 8H. Such pencil hardness is generally important in a resin layer lower than glass, and as a technique for improving the pencil hardness in the cured resin layer [II] of the present invention, the components and content of the active energy ray-curable composition are used. Techniques to identify (for example, using a hard alicyclic skeleton monomer, adjusting the amount of silane coupling agent or photopolymerization initiator, etc.), techniques for adding thermal polymerization initiators or fillers as auxiliary components And a method for controlling the irradiation conditions of the active energy rays at the time of curing (for example, irradiation with a sufficient amount of light, irradiation with inert gasification, etc.), and the like.

  In the laminate of the present invention, the interface between the glass [I] and the cured resin layer [II] is preferably in close contact with sufficient strength. The adhesion strength is evaluated by, for example, a peel test or a cross hatch test, but it is preferable that the adhesion strength is not removed even in a more severe cross hatch test.

  The laminate thus obtained is useful as a substrate for producing a high-strength, high-definition, high-reliability display substrate or transparent electrode substrate.

  A transparent electrode substrate can be obtained by further forming a transparent conductive film on the opposite surface side of the cured resin layer [II] of the glass [I] of the laminate of the present invention.

  Examples of the transparent conductive film include inorganic films such as indium and tin oxide (ITO) and organic films such as poly (3,4-ethylenedioxythiophene) (PEDOT). Among these, an ITO film is preferable in terms of conductivity and transparency. The film thickness of such a transparent conductive film is usually 100 to 5000 mm, preferably 1000 to 4000 mm, and more preferably 1500 to 3000 mm. If the film thickness is too thick, the substrate tends to warp, and if it is too thin, the conductivity tends to be insufficient.

  In forming the transparent conductive film, the film formation temperature is preferably 50 ° C to 300 ° C, more preferably 100 to 250 ° C, and still more preferably 130 to 200 ° C. If the film forming temperature is too low, the conductivity tends to be insufficient. Conversely, if the film forming temperature is too high, the light transmittance of the transparent electrode substrate tends to decrease.

  The conductivity of the obtained transparent electrode substrate is preferably 30 Ω / □ or less, more preferably 20 Ω / □ or less, and even more preferably 15 Ω / □ or less. If it is too high, the display performance of the display tends to deteriorate.

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.
The measuring method of each physical property is as follows.

(1) Light transmittance The light transmittance (%) at 550 nm was measured using a spectrophotometer (manufactured by JASCO Corporation, trade name: “Ubest-35”).

(2) Birefringence Retardation (nm) was measured at 25 ° C. with a birefringence measuring device manufactured by Oak.

(3) Surface roughness According to JIS B0601: 2001, Ra (nm) of the cured resin layer (front) and Ra (nm) of the glass (back) were measured using “Surfcom 570A” manufactured by Tokyo Seimitsu Co., Ltd. (Cutoff: 0.8 μm, measurement length: 1 mm).

(4) Bending resistance Using a test piece having a width of 10 cm and a length of 10 cm, first wound around a cylinder with a diameter of 1 cm with the cured resin layer side inward, and then wound around a cylinder with a diameter of 1 cm with the glass surface side inward. Those that did not break in the bending test were marked with ◯, and those that were broken were marked with ×.

(5) Impact resistance Using a test piece with a width of 10 cm and a length of 10 cm, placing the cured resin layer on top of an iron plate with a thickness of 1 cm, a steel ball with a height of 1 m to 100 g is naturally placed at the center of the test piece. Those that were dropped and not broken were marked with ◯, and those that were broken were marked with ×.

(6) Pencil hardness The pencil hardness of the cured resin layer [II] surface side of the laminate was measured according to JIS K 5600-5-4.

(7) Solvent resistance Using a test piece having a width of 10 cm and a length of 10 cm, immersed in N-methylpyrrolidone at 25 ° C. for 1 hour, ○ having no change in appearance, and × having a change in appearance. did.

(8) Oxygen permeability The oxygen permeability was measured under the conditions of 23 ° C. and 80% RH with an oxygen mocon measuring device manufactured by Oxytran.

(9) Surface resistance value The surface resistance value of the transparent conductive film was measured using a 4-terminal resistance measuring instrument (Lorestar MP) manufactured by Mitsubishi Chemical Corporation.

<Example 1>
[Production of alicyclic skeleton-containing polyfunctional urethane (meth) acrylate (A-1)]
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 53.34 g (0.24 mol) of isophorone diisocyanate, 55.73 g (0.48 mol) of 2-hydroxyethyl acrylate, polymerization Hydroquinone methyl ether 0.02 g as an inhibitor, 0.02 g of dibutyltin dilaurate and 500 g of methyl ethyl ketone as a reaction catalyst were charged and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group became 0.3%, The solvent was distilled off to obtain an isophorone skeleton-containing bifunctional urethane acrylate (A-1).

[Production of active energy ray-curable composition (a)]
40 parts of the above-mentioned isophorone skeleton-containing bifunctional urethane acrylate (A-1), bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate (B) (Shin-Nakamura Chemical Co., Ltd. “A- 37 parts of DCP ”, 15 parts of 3-acryloxypropyltrimethoxysilane (C) (“ KBM5103 ”manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts of 1-hydroxycyclohexyl phenyl ketone (D) (“ Irgacure 184 ”manufactured by Ciba Geigy) The mixture was stirred until uniform at 60 ° C. to obtain an active energy ray-curable composition (A).

[Production of laminate]
After 100 parts of propylene glycol monomethyl ether as a solvent was added to 100 parts of the active energy ray-curable composition (a) and stirred, spin coating was performed on thin glass [I] having a length of 100 mm, a width of 100 mm, and a thickness of 200 μm. And coated. Subsequently, the solvent was dried at 100 ° C. for 10 minutes, and the composition (A) was cured by irradiating ultraviolet rays with an illuminance of 100 mW / cm ² and a light amount of 5 J / cm ² with a high-pressure mercury lamp. The film thickness of the cured resin layer [II] was 5 μm, and there was no peeling in the cross hatch test, and the adhesion was good.
The structure of the obtained laminate is as shown in Table 1. The physical properties of the obtained laminate were as shown in Table 2 and had good characteristics.

[Manufacture of transparent electrode substrate]
An ITO film having a thickness of 2000 mm was formed at 150 ° C. on the glass [I] surface of the obtained laminate by a sputtering method to obtain a transparent electrode substrate.
Table 2 shows the surface resistance values of the obtained transparent electrode substrate.

<Examples 2 and 3>
[Manufacture of laminate and transparent electrode substrate]
A laminate was obtained in the same manner as in Example 1 except that the layer configuration shown in Table 1 was adopted. The physical properties of the obtained laminate are as shown in Table 2.
Further, a transparent electrode substrate was obtained in the same manner as in Example 1, and the surface resistance value of the obtained transparent electrode substrate was measured. The results are shown in Table 2.

<Example 4>
[Production of alicyclic skeleton-containing polyfunctional urethane (meth) acrylate (A-2)]
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 53.34 g (0.24 mol) of isophorone diisocyanate, pentaerythritol triacrylate (hydroxyl value 125.4 mg KOH / g) (Osaka Organic) Chemical Industry Co., Ltd., “Biscoat # 300”) 95.46 g (0.48 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate as a reaction catalyst, and 500 g of methyl ethyl ketone, 60 The reaction was terminated at 3 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate group became 0.3%, and the solvent was distilled off to obtain an isophorone skeleton-containing hexafunctional urethane acrylate (A-2).
In Example 1, instead of urethane acrylate (A-1), the active energy ray-curable composition (I) and the laminate were similarly used except that isophorone skeleton-containing hexafunctional urethane acrylate (A-2) was used. Obtained. The physical properties of the obtained laminate are as shown in Table 2.
Further, a transparent electrode substrate was obtained in the same manner as in Example 1, and the surface resistance value of the obtained transparent electrode substrate was measured. The results are shown in Table 2.

<Comparative Example 1>
Instead of the laminate of Example 1, only a 200 μm thick glass plate was used. The physical properties of the glass are as shown in Table 2.
Further, an ITO film having a thickness of 2000 mm was formed on one surface of this glass plate by sputtering at 150 ° C. to obtain a transparent electrode substrate, and the surface resistance value of the obtained transparent electrode substrate was measured. The results are shown in Table 2.

<Comparative example 2>
Instead of the laminate of Example 1, a cured resin molded body having a thickness of 200 μm was used. The manufacturing method of this cured resin molding is as follows.
Prepare two sheets of glass 110mm long, 110mm wide and 1mm thick. After the glass surface is fluorine coated with a fluorine release agent ("OPTOOL DSX" manufactured by Daikin Industries, Ltd.), silicon 200μm thick The plate is made to face as a spacer, the active energy ray-curable composition (A) is injected into this mold, and the composition is irradiated with ultraviolet rays having an illuminance of 100 mW / cm ² and a light amount of 5 J / cm ² with a high-pressure mercury lamp. (A) was cured. Next, the cured product was taken out from the mold and the periphery 10 mm was cut to obtain a cured resin molded body having a length of 100 mm, a width of 100 mm and a thickness of 200 μm.
Further, an ITO film having a thickness of 2000 mm was formed on one surface of the cured resin molded body at 150 ° C. by sputtering to obtain a transparent conductive sheet, and the surface resistance value of the obtained transparent conductive sheet was measured. The results are shown in Table 2.

<Comparative Example 3>
Instead of the laminate of Example 1, a laminate having a configuration of glass (thickness 100 μm) / cured resin layer (thickness 5 μm) / glass (thickness 100 μm) was used. The manufacturing method of this laminated body is as follows.
After 100 parts of propylene glycol monomethyl ether as a solvent was added to 100 parts of the active energy ray-curable composition (A) and stirred, it was applied on a thin glass having a length of 100 mm, a width of 100 mm, and a thickness of 200 μm by spin coating. . Next, the solvent was dried at 100 ° C. for 10 minutes, and a thin glass with a length of 100 mm, a width of 100 mm, and a thickness of 200 μm was stacked on the coated surface, and an illuminance of 100 mW / cm ² and a light amount of 5 J / cm ² with a high-pressure mercury lamp. The composition (a) was cured by irradiation with ultraviolet rays.
Further, an ITO film having a thickness of 2000 mm was formed on one surface of this laminate by sputtering at 150 ° C. to obtain a transparent conductive sheet, and the surface resistance value of the obtained transparent conductive sheet was measured. The results are shown in Table 2.

<Comparative example 4>
Instead of the laminate of Example 1, a laminate having a configuration of cured resin layer (thickness 5 μm) / glass (thickness 200 μm) / cured resin layer (thickness 5 μm) was used. The manufacturing method of this laminated body is as follows.
After 100 parts of propylene glycol monomethyl ether as a solvent was added to 100 parts of the active energy ray-curable composition (A) and stirred, it was applied on the glass surface of the laminate obtained in Example 1 by spin coating. Subsequently, the solvent was dried at 100 ° C. for 10 minutes, and the composition was cured by irradiating with ultraviolet rays at an illuminance of 100 mW / cm ² and a light amount of 5 J / cm ² with a high-pressure mercury lamp.
Further, an ITO film having a thickness of 2000 mm was formed on one surface of this laminate by sputtering at 150 ° C. to obtain a transparent conductive sheet, and the surface resistance value of the obtained transparent conductive sheet was measured. The results are shown in Table 2.

  The laminate of the present invention can be advantageously used for various optical materials and electronic materials. For example, liquid crystal substrates, organic / inorganic EL substrates, electronic paper substrates, light guide plates, phase difference plates, touch panels, etc., various display members, storage / recording applications including optical disk substrates, energy applications such as solar cell substrates It can be used for optical communication applications such as optical waveguides, and for various optical films, sheets and coatings such as functional films and sheets, antireflection films and optical multilayer films.

Claims (10)

In the laminate having the configuration of glass [I] / cured resin layer [II], the thickness of glass [I] is 20 to 250 μm, and cured resin layer [II] is an active energy ray curable composition made of glass. It is a cured resin layer that is applied to [I] and cured with active energy rays, and the active energy ray-curable composition comprises an alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound (A), polyfunctional ( A laminate comprising a curable composition comprising a (meth) acrylate compound (B), a silane coupling agent (C), and a photopolymerization initiator (D). The laminate according to claim 1, wherein the thickness of the cured resin layer [II] is 1 to 50 µm, and the total thickness of the laminate is 30 to 300 µm. The laminate according to claim 1 or 2, wherein the thickness of the glass [I] is 5 to 50 times the thickness of the cured resin layer [II]. The laminated body according to any one of claims 1 to 3, wherein the alicyclic skeleton-containing polyfunctional urethane (meth) acrylate compound (A) is a compound represented by the following general formula (1).

(Here, R ₁ is hydrogen or a methyl group, and R ₂ is an alkylene group having 1 to 5 carbon atoms.) Retardation is 1 nm or less, The laminated body in any one of Claims 1-4 characterized by the above-mentioned. The laminate according to any one of claims 1 to 5, wherein the light transmittance is 90% or more. The laminate according to any one of claims 1 to 6, wherein the pencil hardness of the cured resin layer [II] surface side is H or more. The laminate according to any one of claims 1 to 7, wherein the laminate is used as a substrate for a display. A display substrate using the laminate according to claim 1. A transparent electrode substrate, further comprising a transparent conductive film formed on the opposite side of the cured resin layer [II] of the glass [I] of the laminate according to any one of claims 1 to 8.