JP5090040B2 - Transparent conductive substrate - Google Patents

Description

  The present invention relates to a transparent conductive substrate using an allyl ester resin as a substrate. More specifically, the present invention relates to a transparent conductive substrate that has high heat resistance and excellent transparency and can be used for a transparent electrode plate for a touch panel, a transparent electrode plate for a liquid crystal, and a transparent conductive electrode plate for an organic EL display device.

In recent years, display devices have high demands such as thinning, weight reduction, large size, arbitrary shape, and curved display.
In particular, there is a strong demand for light weight and high durability for display elements used in portable devices, and as their use expands, display panels that use plastic as a substrate instead of conventional glass substrates are being considered, It has begun to be put into practical use in some areas.
However, along with the display color animation, demands for display devices such as TFT (Thin Film Transistor) display devices and organic EL (electroluminescence) display devices are increasing. Glass substrates are still used as substrates, and there is a demand for a shift to plastic substrates that are lightweight and highly durable.

However, conventional plastic substrates have insufficient heat resistance, and there has been a risk of warping and deformation in the process of forming a metal semiconductor or an insulating film by CVD (Chemical Vapor Deposition).
In addition, since the difference in coefficient of thermal expansion between the resin layer constituting the substrate and the electrode is large, in a TFT liquid crystal substrate that is exposed to a high temperature change during processing, the transparent electrode is likely to crack, and the electric resistance value is high. It may increase or sometimes break down, and its practical use has not yet been achieved.
Some thermosetting resins such as epoxy resins have improved heat resistance, but in that case the transparency is not sufficient. On the contrary, those having good transparency had a low glass transition temperature (Tg) and poor heat resistance.

Liquid crystal display devices include a transmissive liquid crystal display device and a reflective liquid crystal display device, and a transflective liquid crystal display device in which a reflective type and a transmissive type are integrated.
A transmissive liquid crystal display device is a type of liquid crystal display device that performs display using a backlight on the back of the screen as a light source, and is characterized by high saturation and easy viewing of the screen even in a dark room, but has the disadvantage of high power consumption. is there.

  On the other hand, the reflective liquid crystal display element is a type of liquid crystal display device that performs display by reflecting external light, and has attracted attention because of its low power consumption. Attempts have been made to make these substrates plastic. For example, Japanese Patent Laid-Open No. 11-2812 (Patent Document 1) discloses that a laminated plate including a fiber cloth impregnated with a resin such as a glass epoxy laminated plate is used for a reflective liquid crystal display substrate. However, the reflective conductive substrate exemplified here uses a white pigment in the reflective layer, and the recent demand for higher definition and higher contrast cannot be solved.

Japanese Patent Laid-Open No. 11-2812

  An object of the present invention is to provide a display device characterized by excellent heat resistance and chemical resistance, a low average linear expansion coefficient, high transparency, and less warpage, deformation, or wiring cracking in a thin film device formation process Another object of the present invention is to provide a conductive transparent resin substrate.

  As a result of intensive investigations, the present inventors have not only much higher heat resistance than thermosetting resins used in conventional transparent conductive substrates, but also excellent chemical resistance. The present invention has been completed by finding that it also provides adhesion and low linear expansion coefficient, high transparency, and excellent properties for use in transparent conductive substrates.

（Ｒ¹及びＲ²は、それぞれ独立してアリル基またはメタリル基を表し、Ａ¹はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）
で示される化合物の中から選ばれる少なくとも１種以上の化合物を含む前記２に記載の透明導電性基板。
４．アリルエステルオリゴマーの少なくとも一種が一般式（２）

（式中、Ｒ³はアリル基またはメタリル基を表し、Ａ²はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）
で示される基を末端基として有し、かつ一般式（３）

（式中、Ａ³はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表し、Ｘは多価アルコールから誘導された一種以上の有機残基を表す。ただし、Ｘはエステル結合によって、さらに上記一般式（２）で示される基を末端基とし、上記一般式（３）で示される基を構成単位とする分岐構造を有することができる。）
で示される構造を構成単位として有する前記２に記載の透明導電性基板。
５．前記一般式（２）及び（３）におけるジカルボン酸が、テレフタル酸、イソフタル酸、フタル酸及び１，４−シクロヘキサンジカルボン酸からなる群から選ばれる少なくとも一種である前記４に記載の透明導電性基板。
６．アリルエステル樹脂組成物が、さらに反応性モノマーを含む前記１〜５のいずれかに記載の透明導電性基板。
７．前記１〜６のいずれかに記載の透明導電性基板を電極として使用したタッチパネル用透明電極板。
８．前記７に記載の電極板を備えたタッチパネル。
９．前記１〜６のいずれかに記載の透明導電性基板を電極として使用した液晶表示装置用透明電極板。
１０．前記９に記載の電極板を備えた液晶表示装置。
１１．前記１〜６のいずれかに記載の透明導電性基板を電極として使用した有機ＥＬ表示装置用透明導電性電極板。
１２．前記１１に記載の電極板を備えた有機ＥＬ表示装置。 That is, the present invention relates to the following transparent conductive substrates [1] to [6] and uses of the transparent conductive substrates [7] to [12].
1. A transparent conductive substrate obtained by curing an allyl ester resin composition, wherein a transparent electrode is formed on an allyl ester resin substrate having a glass transition temperature of 160 ° C. or higher.
2. 2. The transparent conductive substrate as described in 1 above, wherein the allyl ester resin composition comprises an allyl ester oligomer having an allyl group and / or a methallyl group as an end group and having an ester structure formed from a polyhydric alcohol and a dicarboxylic acid.
3. The allyl ester resin composition further has the general formula (1)

(R ¹ and R ² each independently represent an allyl group or a methallyl group, and A ¹ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid.)
3. The transparent conductive substrate according to 2 above, comprising at least one compound selected from the compounds represented by:
4). At least one of the allyl ester oligomers is represented by the general formula (2)

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

(In the formula, A ³ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol. However, X may have a branched structure having an ester bond and a group represented by the above general formula (2) as a terminal group and a group represented by the above general formula (3) as a structural unit.
3. The transparent conductive substrate according to 2 above, having a structure represented by
5. 5. The transparent conductive substrate according to 4 above, wherein the dicarboxylic acid in the general formulas (2) and (3) is at least one selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid and 1,4-cyclohexanedicarboxylic acid. .
6). 6. The transparent conductive substrate according to any one of 1 to 5, wherein the allyl ester resin composition further contains a reactive monomer.
7). The transparent electrode plate for touchscreens which uses the transparent conductive substrate in any one of said 1-6 as an electrode.
8). A touch panel comprising the electrode plate according to 7 above.
9. The transparent electrode plate for liquid crystal display devices which uses the transparent conductive substrate in any one of said 1-6 as an electrode.
10. 10. A liquid crystal display device comprising the electrode plate as described in 9 above.
11. A transparent conductive electrode plate for an organic EL display device using the transparent conductive substrate according to any one of 1 to 6 as an electrode.
12 12. An organic EL display device comprising the electrode plate as described in 11 above.

  According to the present invention, by using an allyl ester resin cured product as a substrate, the electrical resistance is low, the heat resistance and the chemical resistance are excellent, the average linear expansion coefficient is low, and the transparency is high. Provided are various transparent conductive substrates for display elements that are less prone to cracking, deformation, and wiring cracking.

  Hereinafter, the present invention will be described in more detail.

<Allyl ester resin>
The allyl ester resin used in the transparent conductive substrate of the present invention is a kind of thermosetting resin.
In general, there are two cases where the term “allyl ester resin” refers to a prepolymer (including oligomers, additives, and monomers) before curing, and indicates a cured product thereof. Then, “allyl ester resin” indicates a cured product, and “allyl ester resin composition” indicates a prepolymer before curing.

<Allyl ester resin composition>
The allyl ester resin composition for a transparent conductive substrate according to the present invention contains an allyl group or a methallyl group (hereinafter sometimes referred to as a (meth) allyl group) and a compound having an ester structure as a main curing component. Composition.

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

（Ｒ¹及びＲ²は、それぞれ独立してアリル基またはメタリル基を表し、Ａ¹はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）
で示される化合物の中から選ばれる少なくとも１種以上の化合物を含むアリルエステル樹脂組成物が挙げられる。一般式（１）においてＲ¹及びＲ²はアリル基がより好ましい。また、Ａ¹の定義及び好ましい化合物の具体例は後述するＡ²と同様である。
さらに、その他の成分として、後述する硬化剤、反応性モノマー、添加剤、その他ラジカル反応性の樹脂成分等を含有してもよい。 The (meth) allyl group which is the main curing component of the allyl ester resin composition according to the present invention and the compound having an ester structure is composed of an allyl group and / or a methallyl group as a terminal group, and a polyhydric alcohol and a dicarboxylic acid. It is preferably an allyl ester compound having an ester structure formed (hereinafter, this may be referred to as “allyl ester oligomer”).
Moreover, the diallyl ester compound corresponding to the said oligomer is mentioned as a compound which has (meth) allyl groups and ester structures other than an allyl ester oligomer. Specific examples of the diallyl ester compound include the following general formula (1)

(R ¹ and R ² each independently represent an allyl group or a methallyl group, and A ¹ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid.)
An allyl ester resin composition containing at least one compound selected from the compounds represented by: In general formula (1), R ¹ and R ² are more preferably allyl groups. The definition of A ¹ and specific examples of preferred compounds are the same as those of A ² described later.
Furthermore, you may contain the hardening | curing agent mentioned later, a reactive monomer, an additive, other radical-reactive resin components, etc. as another component.

（式中、Ｒ³はアリル基またはメタリル基を表し、Ａ²はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）
で示される基を末端基として有し、かつ下記一般式（３）

（式中、Ａ³はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表し、Ｘは多価アルコールから誘導された一種以上の有機残基を表す。ただし、Ｘはエステル結合によって、さらに上記一般式（２）で示される基を末端基とし、上記一般式（３）で示される基を構成単位とする分岐構造を有することができる。）
で示される構造を構成単位として有する化合物が好ましい。 <Allyl ester oligomer>
As the allyl ester oligomer, the following general formula (2)

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

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

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

A ² in the general formula (2) is one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. The moiety derived from the dicarboxylic acid is indicated by a carbonyl structure adjacent to A ² . Therefore, A ² represents a benzene skeleton or a cyclohexane skeleton.
There are no particular limitations on the dicarboxylic acid to induce A ² structure, from the viewpoint of ready availability of raw materials, terephthalic acid, isophthalic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-naphthalenedicarboxylic Acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl-m, m′-dicarboxylic acid, diphenyl-p, p′-dicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, p- Phenylenediacetic acid, p-carboxyphenylacetic acid, methyl terephthalic acid and tetrachlorophthalic acid are preferred, and terephthalic acid, isophthalic acid, phthalic acid and 1,4-cyclohexanedicarboxylic acid are more preferred. From the viewpoint that the heat resistance temperature of the resin cured product evaluated by the glass transition temperature (Tg) and the heat distortion temperature can be increased, and a transparent electrode such as indium tin oxide (ITO) can be formed at a higher temperature, terephthalic acid, 1,4-cyclohexanedicarboxylic acid is most preferred.

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

At least one structural unit represented by the general formula (3) is required in the allyl ester oligomer. However, when this structure is repeated, the molecular weight of the allyl ester oligomer as a whole increases to some extent. Is preferable because workability is improved and the strength of the cured product is also improved.
The weight average molecular weight of the allyl ester oligomer is preferably 500 to 200,000, more preferably 1,000 to 100,000.

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

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

  Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6 -Hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, ethylene oxide 3 mol adduct of isocyanuric acid, pentaerythritol, tricyclodecane dimethanol, glycerin, trimethylolpropane, pentaerythritol ethylene oxide 3 mol adduct, D-sorbitol And hydrogenated bisphenol A and the like. Although there is no restriction | limiting in particular as a manufacturing method of these compounds, For example, it can manufacture by the method mentioned in Japanese Patent Publication No. 6-74239 (related application: US 4959451).

As the structural unit represented by the general formula (3) in the allyl ester oligomer, the same structural unit may be repeated, but different structural units may be included. That is, the allyl ester oligomer may be a copolymer type. In this case, several types of X exist in one allyl ester oligomer. For example, the structure may be such that one of X is a residue derived from propylene glycol and the other X is a residue derived from trimethylolpropane. In this case, the allyl ester oligomer will be branched at the trimethylolpropane residue. There may be several types of A ³ as well. The structural formula (4) in the case where R ³ is an allyl group, A ² and A ³ are residues derived from isophthalic acid, and X is propylene glycol and trimethylolpropane is shown below.

<Curing agent>
In order to cure the allyl ester resin composition of the present invention, radicals may be thermally generated by heating or may be cured, but it is preferable to use a curing agent. There is no restriction | limiting in particular as a hardening | curing agent which can be used, What is generally used as a hardening | curing agent of polymeric resin can be used. Among these, it is desirable to add a radical polymerization initiator from the viewpoint of starting polymerization of the allyl group. Examples of the radical polymerization initiator include organic peroxides, photopolymerization initiators, azo compounds and the like. Among these, organic peroxides are particularly preferable from the viewpoint of uniformly curing the allyl ester resin composition of the present invention.

  As the organic peroxide, known compounds such as dialkyl peroxides, acyl peroxides, hydroperoxides, ketone peroxides, peroxyesters and the like can be used. Specific examples thereof include benzoyl peroxide, 1,1 -Bis (t-butylperoxy) cyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (4,4-dibutylperoxycyclohexyl) propane , T-butylperoxy-2-ethylhexanate, 2,5-dimethyl2,5-di (t-butylperoxy) hexane, 2,5-dimethyl2,5-di (benzoylperoxy) hexane, t -Butyl peroxybenzoate, t-butyl cumyl peroxide, p-methyl hydroperoxy Id, t- butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, di -t- butyl peroxide and 2,5-dimethyl-2,5-dibutyl peroxy f relaxin -3, and the like.

Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2-methyl-1- (4-methylthiophenyl) -2- Morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,4,6- And trimethylbenzoyldiphenylphosphine oxide.
These radical polymerization initiators may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the compounding quantity of these hardening | curing agents, Allyl ester resin composition 100 mass part (When the below-mentioned reactive monomer and radical reactive resin component are included, these are the total mass of these and allyl ester resin components. ) To 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass. When the blending amount of the curing agent is less than 0.1 parts by mass, it is difficult to obtain a sufficient curing rate. When the blending amount exceeds 10 parts by mass, the final cured product becomes brittle and the mechanical strength decreases. There is a case.

<Reactive monomer>
A reactive monomer (reactive diluent) is added to the allyl ester resin composition according to the present invention for the purpose of controlling the curing reaction rate, adjusting the viscosity (improving workability), improving the crosslinking density, and adding functions. You can also.

  There is no restriction | limiting in particular as these reactive monomers, A various thing can be used. In order to react with the allyl ester oligomer, a monomer having a radically polymerizable carbon-carbon double bond such as a vinyl group or an allyl group is preferred. Examples thereof include unsaturated fatty acid esters, aromatic vinyl compounds, vinyl esters of saturated fatty acids or aromatic carboxylic acids and derivatives thereof, crosslinkable polyfunctional monomers, and the like. Especially, if a crosslinkable polyfunctional monomer is used, the crosslinking density of hardened | cured material can also be controlled. Preferred specific examples of these reactive monomers are shown below.

  As unsaturated fatty acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate Alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and methylcyclohexyl (meth) acrylate;

Phenyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, fluorophenyl (meth) acrylate, chlorophenyl (meth) acrylate, cyanophenyl (meth) acrylate, methoxyphenyl (meth) acrylate and biphenyl (meth) ) Acrylic acid aromatic esters such as acrylates;
Haloalkyl (meth) acrylates such as fluoromethyl (meth) acrylate and chloromethyl (meth) acrylate;
Furthermore, glycidyl (meth) acrylate, alkylamino (meth) acrylate, α-cyanoacrylic acid ester and the like can be mentioned.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, chlorostyrene, styrene sulfonic acid, 4-hydroxystyrene, vinyltoluene and the like.
Examples of vinyl esters of saturated fatty acids or aromatic carboxylic acids and derivatives thereof include vinyl acetate, vinyl propionate and vinyl benzoate.

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

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

<Radically reactive resin component>
The allyl ester resin composition according to the present invention may contain a radical reactive resin component for the purpose of improving various physical properties. The radical reactive resin means a polymer having a radical polymerizable functional group such as an ethylenic carbon-carbon double bond in the main chain or side chain. Examples of these resin components include unsaturated polyester resins and vinyl ester resins.

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

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

The epoxy resin used as the raw material for the vinyl ester resin includes bisphenol A diglycidyl ether and its high molecular weight homologue, glycidyl ether of bisphenol A alkylene oxide adduct, bisphenol F diglycidyl ether and its high molecular weight homologue, and bisphenol F alkylene oxide. Examples include adduct glycidyl ethers and novolac-type polyglycidyl ethers.
The above radical-reactive resin components can be used alone or in combination of two or more.

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

<Additives>
The allyl ester resin composition for transparent conductive substrates of the present invention has an ultraviolet absorber, an antioxidant, an antifoaming agent, a leveling agent, a release agent for the purpose of improving hardness, strength, moldability, durability and water resistance. Additives such as molds, lubricants, water repellents, flame retardants, low shrinkage agents, and crosslinking aids can be added as necessary.

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

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

There is no restriction | limiting in particular as a ultraviolet absorber, What is generally used can be used. Among these, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers are preferable, and benzophenone ultraviolet absorbers are particularly preferable. Examples of benzophenone ultraviolet absorbers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-butylphenyl) benzotriazole and 2- (2-hydroxy-3). '-T-butylphenyl) benzotriazole and the like.
These additives are not limited to the specific examples described above, and any additive can be added as long as the object or effect of the present invention is not impaired.

<Solvent>
When the allyl ester resin composition for a transparent conductive substrate of the present invention is cured, a solvent may be used if it is necessary to reduce the viscosity by a curing method. However, since it is necessary to remove the solvent later, the viscosity is preferably adjusted with the aforementioned reactive monomer.
Examples of solvents that can be used for viscosity adjustment include aromatic hydrocarbons such as toluene and xylene, acetates such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones, ethers such as tetrahydrofuran and 1,4-dioxane, alcohols such as ethyl alcohol, (iso) propyl alcohol, and butyl alcohol.

<Viscosity of allyl ester resin composition>
The viscosity of the allyl ester resin composition for a transparent conductive substrate of the present invention is not particularly limited, but is preferably a viscosity suitable for the molding method.
For example, in cast molding, the viscosity at 25 ° C. is preferably in the range of 0.01 to 1,000 (Ps · s). If the viscosity is lower than 0.01 (Pa · s) or higher than 1,000 (Pa · s), the workability deteriorates, which is not preferable.

Moreover, in transfer molding, it is preferable that the viscosity in 80 degreeC is the range of 0.01-1,000 (Pa * s). If the viscosity at 80 ° C. is lower than 0.01 (Pa · s) or higher than 1,000 (Pa · s), there is a high possibility of forming defects, which is not preferable.
The viscosity of the curable resin can be measured by a method based on JIS K6901.

<Allyl ester resin cured product>
The allyl ester resin composition can be obtained by mixing the allyl ester oligomer, the reactive monomer, the curing agent, and various additives by a known method. The composition can be cured using a coating method such as a roll coater or a spin coater, a casting method, a stereolithography method, or the like using heat, ultraviolet rays, or an electron beam.

The curing temperature when molding the allyl ester resin composition of the present invention is about 30 to 150 ° C, preferably 40 to 130 ° C.
In consideration of shrinkage and strain during curing, a method of gradually curing while heating is preferable, generally 0.5 to 100 hours, preferably 3 to 50 hours, more preferably 10 to 30 hours. It is better to cure.

  The glass transition temperature (Tg) of the cured allyl ester resin of the present invention is 160 ° C. or higher. Tg as used in the field of this invention is the value measured by the method described in the Example. Since the temperature of the resin substrate can be increased when a transparent conductive film such as indium tin oxide is formed on the resin substrate by a sputtering method, it is preferable that Tg is high as long as the transparency is not impaired. Tg is more preferably 180 ° C. or higher, and most preferably 200 ° C. or higher. Tg can be adjusted by changing the main chain structure of the allyl ester oligomer and the crosslinking density of the cured product. Tg is increased by blending a large amount of polyfunctional radical polymerizable monomers or by making the main chain structure of the allyl ester oligomer rigid such as an aromatic ring. Further, Tg can be adjusted by the kind, amount, and curing conditions of the polymerization initiator.

<Transparent conductive substrate>
In the transparent conductive substrate of the present invention, a transparent conductive film is formed on a substrate made of the allyl ester resin cured product.
As the transparent conductive film, a known metal film, metal oxide film, or the like can be applied. Among these, a metal oxide film is preferable from the viewpoint of transparency, conductivity, and mechanical characteristics. As these metal oxide films, for example, indium oxide, cadmium oxide and tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium and the like are added as impurities, zinc oxide to which aluminum is added as impurities, Examples thereof include metal oxide films such as titanium oxide. Among them, a thin film of indium tin oxide (ITO) containing 2 to 15% by mass of tin oxide is excellent in transparency and conductivity, and is preferably used.

  Although the film thickness of the said transparent conductive thin film is set according to the target surface resistance, generally it is the range of 4-800 nm, and 5-500 nm is especially preferable. When the thickness of the transparent conductive thin film is less than 4 nm, it tends to be difficult to form a continuous thin film, and it is difficult to show good conductivity. When it is thicker than 800 nm, the transparency tends to decrease.

Examples of the method for forming the transparent conductive film include sputtering, ion plating, and vacuum deposition. Further, it is preferable that the substrate heating temperature at the time of film formation is not higher than the thermal deformation temperature of the substrate.
In the case of ITO film formation, it is preferable that the substrate heating temperature is higher. The crystallization of ITO progresses as the film forming temperature increases, and the electrical resistance decreases. Therefore, it is desirable to form the film at a temperature as high as possible below the heat resistance temperature of the resin substrate evaluated by the heat distortion temperature or Tg. Since the allyl ester resin substrate of the present invention has high heat resistance, film formation at 150 ° C. or higher is possible.

  As the sputtering method, a normal sputtering method using an oxide target, a reactive sputtering method using a metal target, or the like is used. At this time, oxygen, nitrogen, or the like may be introduced as a reactive gas, or means such as ozone addition, plasma irradiation, or ion assist may be used in combination. In addition, a bias such as direct current, alternating current, and high frequency may be applied to the substrate as long as the object of the present invention is not impaired.

  The transparent conductive substrate of the present invention can be used as a transparent electrode plate for touch panels, a transparent electrode plate for liquid crystals, and a transparent conductive electrode plate for organic EL display devices.

Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is further demonstrated, this invention is not limited by these description.
In addition, the physical-property value described in the present Example and the comparative example was measured with the following method.

・ Glass transition temperature (Tg)
The glass transition temperature (Tg) was measured by the TMA method (thermomechanical analysis method) using a thermoanalyzer (TMA-50) manufactured by Shimadzu Corporation. The size of the test piece was 3 × 8 × 8 (mm), and the linear expansion coefficient from 30 ° C. to 300 ° C. was measured at a heating rate of 5 ° C./min in an atmosphere of nitrogen at 50 mL / min. The discontinuous point was defined as Tg. That is, as shown in FIG. 1, the horizontal axis represents temperature, the vertical axis represents the amount of deformation of the sample (the length of the sample), and the intersection of the extrapolated lines of the linear portion in the temperature region above and below Tg is defined as Tg. .

-Total light transmittance It measured using the JDH Kogyo Co., Ltd. NDH-2000 about the sample of thickness 3mm according to JISK7361-1.

-Surface resistance value It measured by pressing the HR probe of Hiresta IP MPC-HT260 made from Mitsubishi Chemical Corporation on the conductive film formed on the surface of the cured product.

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

Synthesis example 2:
A 2-liter three-necked flask equipped with a distillation apparatus is charged with 1400 g of diallyl 1,4-cyclohexanedicarboxylate, 165.4 g of trimethylolpropane, and 1.40 g of dibutyltin oxide, and is produced at 180 ° C. under a nitrogen stream. Heated while distilling off the alcohol. When the distilled alcohol reached about 150 g, the pressure in the reaction system was gradually reduced to 6.6 kPa over about 4 hours to increase the alcohol distillation rate. When the distillate almost disappeared, the pressure in the reaction system was reduced to 0.5 kPa and the reaction was further continued for 1 hour, and then the reaction product was cooled. Hereinafter, the reaction product thus obtained is referred to as “oligomer (2)”.

Synthesis Example 3:
Alcohol produced at 180 ° C. in a nitrogen stream, charged with 1400 g of diallyl 1,4-cyclohexanedicarboxylate, 125.91 g of pentaerythritol, and 1.40 g of dibutyltin oxide in a 2-liter three-necked flask equipped with a distillation apparatus Was heated while distilling off. When the distilled alcohol reached about 150 g, the pressure in the reaction system was gradually reduced to 6.6 kPa over about 4 hours to increase the alcohol distillation rate. When the distillate almost disappeared, the pressure in the reaction system was reduced to 0.5 kPa and the reaction was further continued for 1 hour, and then the reaction product was cooled. 700 g of the obtained reaction product was transferred to a plastic disposable cup, 300 g of triallyl isocyanurate was added, and the mixture was stirred with a stirrer until uniform. Hereinafter, the composition thus obtained is referred to as “oligomer (3)”.

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

Example 1:
1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane (trade name; Perhexa TMH, manufactured by NOF Corporation) with respect to 100 parts by mass of the oligomer (1) prepared in Synthesis Example 1 Add 3 parts by mass, stir well, pour into a mold with a 3 mm silicon rubber spacer sandwiched between two glass plates, hold at 80 ° C for 2 hours in an oven in an air atmosphere, and from 80 ° C to 100 ° C for 8 hours. The resin plate was prepared by curing under the temperature rising conditions of temperature rising, holding at 100 ° C. for 2 hours, heating from 100 ° C. to 120 ° C. for 4 hours, and holding at 120 ° C. for 2 hours. It was 273 degreeC when Tg of this hardened | cured material was measured.

This resin plate was set on a vacuum coater capable of sputtering, and a transparent conductive thin film was laminated by sputtering. As the target, 95% by mass of indium oxide and 5% by mass of tin oxide and having a filling degree of 95% were used. The substrate was heated by a micro heater and a halogen heater in the apparatus, and the substrate temperature was maintained at 150 ° C. After evacuating the inside of the vacuum coater to 1.3 mPa, a mixed gas having a volume ratio of argon: oxygen = 98.5: 1.5 was continuously introduced by a mass flow meter, a sputtering pressure of 0.27 Pa, and DC to the target. Sputtering was performed at an input power of 0.8 w / cm ² .
The obtained ITO thin film had a thickness of 150 nm and a surface resistance value of 30Ω / □. Further, the total light transmittance of this laminate was 91%.

Example 2:
A resin plate was produced in the same manner as in Example 1 except that the oligomer (2) produced in Synthesis Example 2 was used instead of the oligomer (1). It was 313 degreeC when Tg of this hardened | cured material was measured.
In addition, a transparent conductive thin film having a thickness of 150 nm was laminated on the resin plate by the same method as in Example 1. The obtained ITO thin film had a surface resistance of 30Ω / □, and the total light transmittance of this laminate was 90%.

Example 3:
A resin plate was produced in the same manner as in Example 1 except that the oligomer (3) produced in Synthesis Example 3 was used instead of the oligomer (1). It was 320 degreeC when Tg of this hardened | cured material was measured.
In addition, a transparent conductive thin film having a thickness of 150 nm was laminated on the resin plate by the same method as in Example 1. The obtained ITO thin film had a surface resistance of 30Ω / □, and the total light transmittance of this laminate was 91%.

Comparative Example 1:
Transparent with a film thickness of 150 nm in the same manner as in Example 1 except that the substrate temperature was set to 70 ° C. on a commercially available acrylic plate (polymethacrylate plate: manufactured by Sumitomo Chemical Co., Ltd., thickness: 3 mm, Tg: 80 ° C.) A conductive thin film was laminated. The obtained ITO thin film had a surface resistance value of 52Ω / □, and the total light transmittance of this laminate was 74%.

Comparative Example 2:
A transparent conductive thin film having a thickness of 150 nm was laminated on a commercially available polycarbonate plate (Takiron Co., Ltd., thickness: 3 mm, Tg: 150 ° C.) in the same manner as in Example 1 except that the substrate temperature was 100 ° C. The obtained ITO thin film had a surface resistance value of 48Ω / □. The total light transmittance of this laminate was 75%.

Comparative Example 3:
A resin plate was produced in the same manner as in Example 1 except that the oligomer (4) produced in Synthesis Example 4 was used instead of the oligomer (1). It was 87 degreeC when Tg of this hardened | cured material was measured.
A transparent conductive thin film having a thickness of 150 nm was laminated on the resin plate in the same manner as in Example 1 except that the substrate temperature was 75 ° C. The obtained ITO thin film had a surface resistance value of 50Ω / □, and the total light transmittance of this laminate was 90%.

Comparative Example 4:
Using the resin plate obtained in Comparative Example 3 and using the same method as Comparative Example 3 except that the substrate temperature was set to 150 ° C., an attempt was made to laminate a transparent conductive thin film having a thickness of 150 nm on the resin plate. A warp occurred.

The physical property measurement results of the substrate of the present invention (Example) and the conventional substrate (Comparative Example) are summarized in the following table.

  As can be seen from the results of Examples and Comparative Examples, the allyl ester substrate obtained by curing the allyl ester resin composition of the present invention has a Tg, total light transmittance, and surface resistivity much better than those of conventional substrates. showed that.

It is a graph which shows the TMA curve of the oligomer (1) hardened | cured material of Example 1.

Claims (11)

A transparent conductive substrate obtained by curing an allyl ester resin composition and having a glass transition temperature of 160 ° C. or higher and a transparent electrode formed on the allyl ester resin substrate , wherein the allyl ester resin composition has an allyl group and A transparent conductive substrate comprising an allyl ester oligomer having an ester structure formed from a polyhydric alcohol and a dicarboxylic acid and / or having a methallyl group as a terminal group . The allyl ester resin composition further has the general formula (1)

(R ¹ and R ² each independently represent an allyl group or a methallyl group, and A ¹ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid.)
The transparent conductive substrate according to claim 1 , comprising at least one compound selected from the compounds represented by: At least one of the allyl ester oligomers is represented by the general formula (2)

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

(In the formula, A ³ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol. However, X may have a branched structure having an ester bond and a group represented by the above general formula (2) as a terminal group and a group represented by the above general formula (3) as a structural unit.
The transparent conductive substrate of Claim 1 which has a structure shown by as a structural unit. The transparent conductivity according to claim 3 , wherein the dicarboxylic acid in the general formulas (2) and (3) is at least one selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid and 1,4-cyclohexanedicarboxylic acid. substrate.   The transparent conductive substrate according to claim 1, wherein the allyl ester resin composition further contains a reactive monomer. The transparent electrode plate for touchscreens which uses the transparent conductive substrate in any one of Claims 1-5 as an electrode. A touch panel comprising the electrode plate according to claim 6 . The transparent electrode plate for liquid crystal display devices which uses the transparent conductive substrate in any one of Claims 1-5 as an electrode. A liquid crystal display device comprising the electrode plate according to claim 8 . Transparent conductive organic EL display device for transparent conductive electrode plate using the substrate as an electrode according to any one of claims 1-5. An organic EL display device comprising the electrode plate according to claim 10 .

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