JP2009129802A - Transparent conductive substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent conductive substrate which has a small linear expansion coefficient and can be suitably used for a substrate for display and is excellent on transparency, flexibility, and electric characteristics (low resistance value). <P>SOLUTION: The transparent conductive substrate is obtained by performing formation of a transparent conductive film of indium oxide tin at 150°C or above on a cured surface of a three dimensionally bridged radical reactive resin composition wherein a flat plate-like inorganic material with a specific nature is distributed, suitably in particular, on the cured surface of an allyl ester resin composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a transparent conductive substrate excellent in transparency, conductivity, and heat resistance.

  Conventionally, a transparent conductive substrate used for a liquid crystal display or the like has been formed by sputtering a glass of indium tin oxide (hereinafter abbreviated as “ITO”) at a substrate temperature of 200 ° C. or more. It is known that as the substrate temperature at the time of ITO sputter deposition increases, the crystallization of ITO proceeds, and as a result, the resistance value decreases. If the resistance value is low, the ITO film can be made thinner accordingly, and a transparent conductive substrate with higher transparency can be obtained.

  On the other hand, in recent years, organic EL displays have attracted attention as flexible display devices. As a transparent conductive substrate used for organic EL, a substrate made of polyethylene terephthalate, polycarbonate, polyolefin, or polyethersulfone has been proposed (for example, Japanese Patent Application Laid-Open No. 2003-17244: Patent Document 1).

  However, since these materials for flexible display substrates are plastics having lower heat resistance than glass, ITO must be deposited at a substrate temperature of 100 ° C. or lower, and an ITO film having a low resistance value can be obtained. It was difficult.

  Moreover, the above-mentioned plastic has a large linear expansion coefficient with respect to a temperature change, and all have a linear expansion coefficient in a temperature range of 50 to 250 ° C. of about 30 to 200 ppm / ° C. When manufacturing a display substrate using these base materials, due to the difference in thermal expansion between the display substrate and the transparent electrode provided thereon, the transparent electrode cracks due to changes in ambient temperature, and the resistance increases. Further, there is a problem that disconnection occurs, and a transparent substrate for display having a low thermal expansion coefficient has been demanded.

  In order to solve these problems, Japanese Patent Laid-Open No. 2006-39530 (Patent Document 2) discloses a film made of a resin and an inorganic layered compound having a glass transition temperature (hereinafter abbreviated as Tg) such as polyethersulfone and the like of 150 ° C. The linear expansion coefficient of 20 to 150 ° C. is 20 ppm / ° C. or less. However, Patent Document 2 does not describe the linear expansion coefficient of the film at a temperature exceeding 150 ° C. In order to obtain a low-resistance conductive film, the ITO deposition temperature of 150 ° C. or higher is required, and a low linear expansion coefficient of at least 150 ° C. or higher is required. The patent does not mention that a transparent conductive film is formed, and it is unclear whether ITO can be formed.

JP 2003-17244 A JP 2006-39530 A

  An object of the present invention is to provide a transparent conductive substrate that has a small coefficient of linear expansion with respect to heat change and is excellent in heat resistance, transparency, flexibility, and electrical characteristics (low resistance value) that can be suitably used for a display substrate. It is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that a cured product of a radically reactive three-dimensional crosslinked resin composition in which a flat inorganic substance having a specific property is dispersed has a linear expansion coefficient. The present inventors have found that it becomes a small transparent composite material, and further completed the present invention by forming a transparent conductive film made of ITO at 150 ° C. or higher.

（式中、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は脂環式構造、芳香環構造及び脂肪族鎖状構造の少なくとも一種の構造を有するジカルボン酸に由来する有機残基を表す。）
で示される化合物の中から選ばれる少なくとも１種の化合物を含む前記８に記載の透明導電性基板。
［１０］ 前記一般式（１）におけるジカルボン酸が、脂環式構造を有するジカルボン酸である前記９に記載の透明導電性基板。
［１１］ アリルエステル化合物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は脂環式構造、芳香環構造及び脂肪族鎖状構造の少なくとも一種の構造を有するジカルボン酸に由来する有機残基を表す。）
で示される基を末端基として有し、かつ一般式（３）

（式中、Ａ³は脂環式構造、芳香環構造及び脂肪族鎖状構造の少なくとも一種の構造を有するジカルボン酸に由来する有機残基を表し、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、さらに前記一般式（２）を末端基とし、前記一般式（３）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８に記載の透明導電性基板。
［１２］ 前記一般式（２）及び（３）におけるジカルボン酸が、脂環式構造を有するジカルボン酸である前記１１に記載の透明導電性基板。
［１３］ 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７に記載の透明導電性基板。
［１４］ 平板状無機物質を含むラジカル反応性３次元架橋型樹脂組成物を硬化して得られる透明基板の５０〜２５０℃の温度範囲における面方向の平均線膨張率が５０ｐｐｍ／℃以下である前記１に記載の透明導電性基板。
［１５］ 透明導電膜がインジウム、スズ、アルミニウム、亜鉛、ゲルマニウム、及びガリウムからなる群から選ばれる少なくとも１つの元素を含む前記１に記載の透明導電性基板。
［１６］ 透明導電膜が酸化インジウムスズ（ＩＴＯ）膜である前記１５に記載の透明導電性基板。
［１７］ 平板状無機物質が面方向に配向している前記１に記載の透明導電性基板。

［１８］ 透明導電膜が酸化インジウムスズ（ＩＴＯ）膜であり、その膜を１５０〜３００℃の温度で形成する前記１に記載の透明導電性基板。 That is, the present invention relates to the following transparent conductive substrates [1] to [18].
[1] A group comprising a transparent composite material obtained by curing a radical-reactive three-dimensional crosslinked resin composition containing a plate-like inorganic substance having a number average particle diameter of 10 to 300 nm and an aspect ratio of 10 to 300 A transparent conductive substrate comprising a transparent conductive film formed on a material.
[2] The transparent conductive substrate as described in 1 above, wherein the tabular inorganic substance is an inorganic layered compound.
[3] The transparent conductive substrate according to 2 above, wherein the inorganic layered compound is at least one selected from the group consisting of smectite, talc, kaolinite, and mica (mica).
[4] The transparent conductive substrate according to 2 or 3 above, wherein the inorganic layered compound is a layered silicate that has been hydrophobized by a cation exchange method using a cationic surfactant.
[5] The transparent conductive substrate according to 1 above, wherein the content of the tabular inorganic substance in the base material made of the transparent composite material is 10 to 70% by mass.
[6] The transparent conductive substrate as described in 1 above, wherein the radical-reactive three-dimensional crosslinked resin composition is a resin composition containing no aromatic ring.
[7] The transparent conductive substrate as described in 6 above, wherein the resin composition not containing an aromatic ring is an allyl ester resin composition.
[8] The said allyl ester resin composition is the composition containing the allyl ester compound which has an allyl group and / or a methallyl group as an end group, and has the ester structure formed from the polyhydric alcohol and dicarboxylic acid. Transparent conductive substrate.
[9] The allyl ester resin composition further comprises the general formula (1)

(In the formula, R ¹ and R ² each independently represents an allyl group or a methallyl group, and A ¹ represents a dicarboxylic acid having at least ^one of an alicyclic structure, an aromatic ring structure and an aliphatic chain structure. Represents an organic residue derived from it.)
9. The transparent conductive substrate as described in 8 above, which comprises at least one compound selected from the compounds represented by:
[10] The transparent conductive substrate according to 9, wherein the dicarboxylic acid in the general formula (1) is a dicarboxylic acid having an alicyclic structure.
[11] At least one of the allyl ester compounds is represented by the general formula (2)

(Wherein R ³ represents an allyl group or a methallyl group, and A ² represents an organic residue derived from a dicarboxylic acid having at least one of an alicyclic structure, an aromatic ring structure and an aliphatic chain structure. )
And a group represented by the general formula (3)

(In the formula, A ³ represents an organic residue derived from a dicarboxylic acid having at least one of an alicyclic structure, an aromatic ring structure and an aliphatic chain structure, and X is one or more derived from a polyhydric alcohol. Wherein X may have a branched structure having an ester bond and further having the general formula (2) as a terminal group and the general formula (3) as a constituent unit.
9. The transparent conductive substrate according to 8 above, which has a structure represented by
[12] The transparent conductive substrate as described in 11 above, wherein the dicarboxylic acid in the general formulas (2) and (3) is a dicarboxylic acid having an alicyclic structure.
[13] The transparent conductive substrate as described in 7 above, wherein the allyl ester resin composition further contains a reactive monomer.
[14] The average linear expansion coefficient in the plane direction in a temperature range of 50 to 250 ° C. of a transparent substrate obtained by curing a radical-reactive three-dimensionally crosslinked resin composition containing a flat inorganic substance is 50 ppm / ° C. or less. 2. The transparent conductive substrate as described in 1 above.
[15] The transparent conductive substrate according to 1 above, wherein the transparent conductive film contains at least one element selected from the group consisting of indium, tin, aluminum, zinc, germanium, and gallium.
[16] The transparent conductive substrate as described in 15 above, wherein the transparent conductive film is an indium tin oxide (ITO) film.
[17] The transparent conductive substrate according to 1 above, wherein the planar inorganic substance is oriented in the plane direction.

[18] The transparent conductive substrate according to 1 above, wherein the transparent conductive film is an indium tin oxide (ITO) film, and the film is formed at a temperature of 150 to 300 ° C.

  In a conventional display substrate using a transparent composite material, a difference in thermal shrinkage occurs between the substrate and the transparent electrode provided on the substrate due to a change in ambient temperature, and the transparent electrode cracks, resulting in increased resistance or disconnection. However, the transparent conductive film or sheet using the transparent composite material having a low coefficient of linear expansion according to the present invention can solve such a problem and provide a highly durable display. Therefore, the present invention is extremely useful industrially.

Hereinafter, the present invention will be described in more detail.
The present invention relates to a transparent composite material in which a plate-like inorganic substance having a number average particle diameter of 10 to 300 nm and an aspect ratio of 10 to 300 is dispersed in a cured product of a radical reactive three-dimensional crosslinkable resin composition It is related with the transparent conductive substrate which formed the transparent conductive film on the base material which consists of.

[Base material made of transparent composite material]
The base material made of the transparent composite material of the present invention (hereinafter sometimes simply referred to as “transparent base material” or “transparent substrate”) has a number average particle diameter of 10 to 300 nm and an aspect ratio of 10 to 300. A certain flat inorganic substance has a radical-reactive three-dimensional cross-linked resin composition dispersed in a cured product. The substrate made of the transparent composite material according to the present invention can be generally obtained by mixing the flat inorganic substance with a radical-reactive three-dimensional crosslinked resin composition and curing.

  In the present invention, the transparency of the transparent substrate is evaluated by the total light transmittance. The transparent substrate of the present invention refers to a substrate having a total light transmittance of 70% or more and a haze value of 5% or less. However, the total light transmittance is preferably 80% or more, and more preferably 85% or more. If the total light transmittance is less than 70%, the loss of light increases, which is not preferable. Moreover, it is preferable that the haze value of a transparent base film and / or a transparent base material sheet is 5% or less of material. The haze value is preferably 3% or less. If the haze value is greater than 5%, the transmitted light may be distorted and lack of clarity. The total light transmittance is a value measured according to JIS K-7361-1, and the haze value is a value measured according to JIS K-7136.

  The shape of the substrate made of the transparent composite material in the present invention is not limited. A molded product having a shape such as a film, a sheet, and a flat plate is particularly suitable. These are simply categorized by thickness differences, but there is no clear standard for their thickness. In the present invention, a film having a thickness of 10 μm or more and 200 μm or less is classified as a film, a sheet having a thickness exceeding 200 μm and 5 mm or less is classified as a sheet, and a sheet having a thickness exceeding 5 mm is classified as a flat plate. The same applies to the transparent conductive substrate.

[Transparent conductive substrate]
The transparent conductive substrate of the present invention is obtained by forming a transparent conductive film on the transparent substrate. In the present invention, the conductivity of the transparent conductive substrate is evaluated by a resistance value and a specific resistance value. The transparent conductive substrate preferably has a sheet resistance value of 20Ω / □ or less and a specific resistance of 5.0 × 10 ⁻⁴ Ωcm or less. If the resistance value exceeds 20Ω / □, the power required for use as a display material increases, which is not preferable. More preferably, it is 15Ω / □ or less, and most preferably 10Ω / □ or less. It is known that the sheet resistance value is inversely proportional to the film thickness of the transparent conductive film, and it is possible to reduce the sheet resistance value by increasing the film thickness even for a material having a high specific resistance (sheet resistance value × Film thickness = specific resistance). However, when the film thickness is increased, a large amount of expensive material (for example, ITO) is used, which is not economical, and the light transmittance and flexibility may be lowered. It is preferable that the sheet resistance value is low even when the film thickness is small. That is, the specific resistance is preferably 5.0 × 10 ⁻⁴ Ωcm or less. More preferably, it is 4.0 × 10 ⁻⁴ Ωcm or less, and most preferably 3.0 × 10 ⁻⁴ Ωcm or less.

  The transparency of the transparent conductive substrate of the present invention is evaluated by the total light transmittance and / or the transmittance for each wavelength. The total light transmittance is preferably at least 60% or more. Preferably it is 70% or more, and most preferably 80% or more. When it is less than 60%, it is not preferable when used for a display or the like because the efficiency is deteriorated. Since a conventional transparent conductive substrate using glass as a substrate has a light transmittance of 80% or more, it is most preferably 80% or more, which is equivalent to a glass substrate.

In the transmittance of each wavelength, for example, the light transmittance at 550 nm is preferably 60% or more. More preferably, it is 70% or more, and most preferably 80% or more.
The flexibility of the transparent conductive substrate of the present invention can be evaluated by the following method, for example. A method of cutting a film or sheet into a strip shape having a width of 10 mm and a length of 100 mm, and winding the film or sheet 180 degrees around a cylinder having a different diameter to evaluate the presence or absence of a crack. It is preferable that the diameter of the cylinder which does not cause a crack in such an evaluation method is 10 mm or less. More preferably, it is 5 mm or less, and most preferably 1 mm or less.

[Flat inorganic material]
The flat inorganic substance used in the present invention is not particularly limited as long as it is an inorganic substance having a number average particle diameter of 10 to 300 nm and an aspect ratio of 10 to 300.

Number average particle diameter of flat inorganic substance When the transparent conductive substrate of the present invention is used for a display substrate or the like, the average particle diameter needs to be sufficiently smaller than the wavelength of visible light. The visible light here means light having a wavelength in the range of 400 to 800 nm. Therefore, the number average particle size of the tabular inorganic substance is preferably in the range of 10 to 300 nm, and more preferably in the range of 30 to 200 nm. When the number average particle size is less than 10 nm, the linear expansion coefficient in the plane direction of the transparent plate tends not to be sufficiently small, and when it exceeds 300 nm, those having a particle size that overlaps the visible light wavelength are included. It is not preferable.

In addition, the number average particle diameter of a flat inorganic substance here refers to the number average particle diameter calculated | required by the dynamic light scattering method, disperse | distributing in a solvent.
The number average particle diameter by the dynamic light scattering method can be determined by referring to pages 169 to 179 of “Particle Diameter Measurement Technology” (Edition of Powder Engineering, 1994), for example. As an example, a dynamic light scattering type particle size distribution measuring device (for example, LB-550, manufactured by Horiba, Ltd.) can be used. The number average particle size of the tabular inorganic material determined by the dynamic light scattering method is considered to be substantially the same as the number average particle size of the tabular inorganic material after being dispersed in the resin layer in the present invention. Can do.

Aspect ratio of flat inorganic substance The aspect ratio (Z) of the flat inorganic substance is represented by the relationship Z = L / a. Here, L is the number average particle diameter obtained by the dynamic light scattering method in a solvent, and a is the unit thickness of the tabular inorganic substance. The unit thickness a is a value that can be calculated by measuring a diffraction peak of a tabular inorganic substance by a powder X-ray diffraction method.

The flat inorganic substance used in the present invention has an aspect ratio in the range of 10 to 300 or less, and more preferably in the range of 30 to 200.
From the viewpoint of easy orientation in the plane direction of the transparent plate, the aspect ratio is preferably 10 or more. In the case of a flat inorganic material having an aspect ratio of less than 10, the linear expansion coefficient is within a predetermined range (preferably 50 ppm / ℃ or less). On the other hand, if a flat inorganic substance having an aspect ratio exceeding 300 is used, the transparency of the substrate may be lowered.

The content of the tabular inorganic substance The content of the tabular inorganic substance in the substrate made of the transparent composite material is preferably in the range of 10 to 70% by mass, and more preferably in the range of 20 to 60% by mass.
When the content of the tabular inorganic substance is less than 10% by mass, the average linear expansion coefficient from 50 to 150 ° C. of the substrate made of the transparent composite material increases and tends to exceed 50 ppm / ° C.
On the other hand, when the content of the tabular inorganic substance exceeds 70% by mass, it tends to be difficult to uniformly disperse the tabular inorganic substance in the resin.

[Inorganic layered compound]
The flat inorganic substance used in the present invention is preferably an inorganic layered compound.
The inorganic layered compound is an inorganic compound having a layered structure in which unit crystal layers are stacked on each other, and an inorganic layered compound that swells and cleaves with a solvent is preferably used.
As an example of such an inorganic layered compound, a layered clay mineral such as a layered clay mineral or hydrotalcite having swelling / cleavability in a solvent, or a layered polysilicate such as magadiite, kanemite, or kenyaite is preferable. Layered clay minerals include smectites such as montmorillonite, hectorite, stevensite, saponite, and beidellite, or kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, tetrasilic mica, sodium teniolite. , Muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite.

  Among these, more preferred are at least one inorganic layered compound selected from the group consisting of smectite, talc, kaolinite and mica (mica) in terms of dispersibility and size, and more preferred is smectite.

  Of the layered clay minerals, the layered silicate (for example, smectite) is preferably made hydrophobic by chemical treatment and improved in dispersibility in the resin. As such chemical treatment, various kinds of cationic metals such as cationic surfactants can be used for exchangeable metal cations such as sodium and calcium existing between layers of lamellar crystal surface layered silicates of layered silicates. For example, the material may be exchanged with a substance and inserted (intercalated) between crystal layers of the layered silicate.

The cation exchange capacity of the layered silicate in this case is not particularly limited, but is preferably 50 to 1200 meq / 100 g.
When the cation exchange capacity is less than 50 meq / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate is reduced by the cation exchange. May not be). When the cation exchange capacity exceeds 1200 meq / 100 g, the bonding force between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may be difficult to peel off.

  Specifically, the chemical treatment can be performed by the chemical modification method shown below. That is, the chemical modification method is also referred to as a cation exchange method using a cationic surfactant. Specifically, the chemical modification method is a method in which the layer of the layered silicate is previously subjected to cation exchange with a cationic surfactant to be hydrophobized. This method is effective when the resin component of the transparent composite material of the present invention has a low polarity, enhances the affinity between the layered silicate and the low polarity resin, and evenly finely disperses the layered silicate in the low polarity resin. Can be made.

  The cationic surfactant used here is not particularly limited, and examples thereof include quaternary ammonium salts and quaternary phosphonium salts. Among them, alkyl ammonium ion salts, aromatic quaternary ammonium ion salts or heterocyclic quaternary ammonium ion salts having 6 or more carbon atoms are preferably used because the crystal layers of the layered silicate can be sufficiently hydrophobized.

  The quaternary ammonium salt is not particularly limited, and examples thereof include trimethylalkylammonium salt, triethylalkylammonium salt, tributylalkylammonium salt, dimethyldialkylammonium salt, dibutyldialkylammonium salt, methylbenzyldialkylammonium salt, dibenzyldialkylammonium salt. , Trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt; benzylmethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl} ammonium chloride A quaternary ammonium salt having an aromatic ring such as: a quaternary ammonium salt derived from an aromatic amine such as trimethylphenylammonium; an alkylpyridinium salt, an imidazoli A quaternary ammonium salt having a heterocyclic ring such as a dimethyl salt; a dialkyl quaternary ammonium salt having two polyethylene glycol chains, a dialkyl quaternary ammonium salt having two polypropylene glycol chains, and a trialkyl quaternary having one polyethylene glycol chain Examples include ammonium salts and trialkyl quaternary ammonium salts having one polypropylene glycol chain. Among these, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl- N, N-dimethylammonium salt and the like are preferred. These quaternary ammonium salts may be used alone or in combination of two or more.

  The quaternary phosphonium salt is not particularly limited. For example, dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylmethylphosphonium salt, distearyldimethylphosphonium salt, distearyl And dibenzylphosphonium salts. These quaternary phosphonium salts may be used alone or in combination of two or more.

  Furthermore, by using a modifying compound, it is possible to highly disperse the layered silicate in the radical-reactive three-dimensional cross-linking resin composition, but it is clear which dispersibility is improved by using which modifying compound. It has not been. However, it is generally preferable to use an aliphatic modification compound for a three-dimensional crosslinked resin containing a large amount of aliphatic carbon chains, and for a three-dimensional crosslinked resin containing a large amount of aromatic carbon chains, an aromatic modification compound is used. It tends to be preferable to use compounds.

[Radically reactive three-dimensional cross-linked resin composition]
The radical-reactive three-dimensional crosslinkable resin composition used in the present invention is a conventional thermosetting resin composition as long as the cured product containing a flat inorganic substance (after the three-dimensional crosslink reaction) is transparent. A photocurable resin composition or the like can be used. The radical reactivity means that the active species of the three-dimensional crosslinking reaction (also called a curing reaction) is a radical. Specifically, polymerization and crosslinking reaction by reaction of ethylene-based carbon-carbon double bond are exemplified.
Specific examples include allyl ester resins, cross-linked acrylic resins, vinyl ester resins, and unsaturated polyester resins. These curable resins may be used alone or in combination of two or more. However, a curable resin that does not have an aromatic ring structure is more preferable from the viewpoint that it is compatible with a flat inorganic substance and can obtain higher transparency.

  Moreover, as long as the effect of the present invention is not impaired, epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, silicon resin, benzoxazine resin, melamine resin, urea resin, phenol resin, bismaleimide triazine resin, An alkyd resin, furan resin, polyurethane resin, aniline resin, or the like may be included. In this case, an operation for reacting these resins may be required in addition to the radical reaction. The content of these resins is desirably 10% by mass or less in the radical-reactive three-dimensional crosslinkable resin composition.

  In general, "thermosetting resin" refers to the prepolymer state (including oligomers, additives, and monomers) before curing, and there are two cases when the cured product is shown. In the present specification, the term “resin composition” indicates a prepolymer state before curing.

  The radical-reactive three-dimensional cross-linkable resin composition used in the present invention is a radical-reactive three-dimensional cross-linkable resin that essentially comprises an oligomer component having at least two radical-reactive functional groups such as vinyl groups and allyl groups. It consists of a composition (here, it refers to a resin component before curing. It is also referred to as a prepolymer or an oligomer. A monomer component may be included). You may contain a reactive diluent (reactive monomer), a hardening | curing agent (radical polymerization initiator), and various additives as needed. At the time of the resin composition, a solvent that does not participate in the crosslinking reaction may be included for the purpose of lowering the viscosity and improving processability. However, it is necessary to finally remove the solvent.

[Allyl ester resin composition]
The allyl ester resin composition used in the present invention contains an allyl group or a methallyl group (hereinafter, both may be referred to as a (meth) allyl group) and a compound having an ester structure as a main curing component. Composition.

A compound having a (meth) allyl group and an ester structure can be obtained by the following reactions (1) to (3).
(1) Esterification reaction between a compound containing a (meth) allyl group and a hydroxyl group (hereinafter collectively referred to as allyl alcohol) and a compound containing a carboxyl group,
(2) an esterification reaction between a compound containing a (meth) allyl group and a carboxyl group and a compound containing a hydroxyl group;
(3) Transesterification reaction between an ester compound composed of allyl alcohol and dicarboxylic acid and a polyhydric alcohol.
When the “compound containing a carboxyl group” in (1) and (2) is a polyester oligomer of a dicarboxylic acid and a diol, only the terminal can be an ester with allyl alcohol.

（式中、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は脂環式構造、芳香環構造及び脂肪族鎖状構造の少なくとも一種の構造を有するジカルボン酸に由来する有機残基を表す。）
で示される化合物の中から選ばれる少なくとも１種の化合物が挙げられる。この化合物は後述するアリルエステルオリゴマーの原料となるほか、反応性希釈剤（反応性モノマー）として本発明のアリルエステル樹脂組成物に含まれてもよい。一般式（１）中のＡ¹は後述の一般式（２）及び（３）におけるＡ²、Ａ³と同様のものが好ましい。 Moreover, as a specific example of "the ester compound which consists of allyl alcohol and dicarboxylic acid" in (3), following General formula (1)

(In the formula, R ¹ and R ² each independently represents an allyl group or a methallyl group, and A ¹ represents a dicarboxylic acid having at least ^one of an alicyclic structure, an aromatic ring structure and an aliphatic chain structure. Represents an organic residue derived from it.)
And at least one compound selected from the compounds represented by: This compound may be contained in the allyl ester resin composition of the present invention as a reactive diluent (reactive monomer) as well as a raw material for the allyl ester oligomer described later. A ¹ in the general formula (1) is preferably the same as A ² and A ³ in the general formulas (2) and (3) described later.

The compound having a (meth) allyl group and an ester structure, which is the main curing component of the allyl ester resin composition of the present invention, is formed from a polyhydric alcohol and a dicarboxylic acid with an allyl group and / or a methallyl group as a terminal group. It is preferable that the allyl ester compound having an ester structure (hereinafter, this may be referred to as “allyl ester oligomer”).
Moreover, 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は脂環式構造、芳香環構造及び脂肪族鎖状構造の少なくとも一種の構造を有するジカルボン酸に由来する有機残基を表す。）
で示される基を末端基として有し、かつ下記一般式（３） [Allyl ester oligomer]
As the allyl ester oligomer used in the present invention, the following general formula (2)

(Wherein R ³ represents an allyl group or a methallyl group, and A ² represents an organic residue derived from a dicarboxylic acid having at least one of an alicyclic structure, an aromatic ring structure and an aliphatic chain structure. )
And a group represented by the following general formula (3)

（式中、Ａ³は脂環式構造、芳香環構造及び脂肪族鎖状構造の少なくとも一種の構造を有するジカルボン酸に由来する有機残基を表し、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）を末端基とし、上記一般式（３）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。 General formula (3)

(In the formula, A ³ represents an organic residue derived from a dicarboxylic acid having at least one of an alicyclic structure, an aromatic ring structure and an aliphatic chain structure, and X is one or more derived from a polyhydric alcohol. Wherein X can have a branched structure having an ester bond and further having the above general formula (2) as a terminal group and 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 used in the present invention, the number of terminal groups represented by the general formula (2) is at least 2 or more, but 3 in the general formula (3) when X has a branched structure. That's it. In this case, although also R ³ at each end groups there are a plurality, each of these R ³ may not necessarily be the same type, some end there in the structure of an allyl group, the other terminal methallyl group It doesn't 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 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 an organic residue derived from a dicarboxylic acid having at least one of an alicyclic structure, an aromatic ring structure, and an aliphatic chain structure. 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. From the viewpoint of transparency, a dicarboxylic acid having an alicyclic structure or an aliphatic chain structure is preferred to a carboxylic acid having an aromatic structure.

The dicarboxylic acid for deriving the A ² structure is not particularly limited, but 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 Examples include terephthalic acid, tetrachlorophthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 2-methylsuccinic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and endic acid anhydride. Among these dicarboxylic acids, dicarboxylic acids having an aliphatic chain structure or an alicyclic structure are preferable. For example, malonic acid, succinic acid, glutaric acid, adipic acid, 2-methylsuccinic acid, 1,4-cyclohexanedicarboxylic acid Is mentioned. Furthermore, a dicarboxylic acid having an alicyclic structure is more preferable, and examples thereof include 1,4-cyclohexanedicarboxylic acid.

As the dicarboxylic acid to induce A ² structure, 1,4-cyclohexane flexible moldings when used as alicyclic structures such as dicarboxylic acid are obtained, easily molded into a transparent film. Moreover, the dispersibility of the resin of the inorganic substance on the flat plate is good, and a base material made of a transparent composite material that is superior in transparency and less colored than the aromatic dicarboxylic acid can be obtained.

  At least one structural unit represented by the general formula (3) is necessary in the allyl ester oligomer, but it is possible to obtain a suitable viscosity by repeating this structure to increase the molecular weight of the entire allyl ester oligomer to some extent. Therefore, workability is improved and the toughness of the cured product is also improved.

  However, if the molecular weight becomes too large, the molecular weight between cross-linking points of the cured product becomes too large, so that the glass transition temperature (Tg) is lowered and the heat resistance may be lowered. It is important to adjust to an appropriate molecular weight according to the application.

The allyl ester resin composition of the present invention contains a tabular inorganic substance having a number average particle diameter of 10 to 300 nm and an aspect ratio of 10 to 300.
By containing this flat inorganic substance, the glass transition temperature (Tg) and the linear expansion coefficient are improved while maintaining the transparency of the resin composition. However, if the molecular weight of the allyl ester oligomer is small, the cured product becomes brittle. There is a tendency. Therefore, in the allyl ester resin composition of the present invention, it is desirable to set the molecular weight of the allyl ester oligomer slightly higher. A preferable weight average molecular weight is 500 to 100,000, and more preferably 1000 to 50,000.

  The oligomer skeleton can be selected without particular limitation. If a linear oligomer having a large molecular weight is used, a relatively flexible and tough resin tends to be obtained. If a branched oligomer is selected, a resin having high hardness and heat resistance can be obtained. It is also possible to adjust the appropriate flexibility and hardness by mixing both.

A ³ in the general formula (3) is an organic residue derived from a dicarboxylic acid having at least one of an alicyclic structure, an aromatic ring structure and an aliphatic chain structure, and its definition and examples of preferred compounds Is the same as A ² in the general formula (2).

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 preferably a compound having two hydroxyl groups. X itself indicates a skeleton other than the hydroxyl group 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 adduct of isocyanuric acid, pentaerythritol, tricyclodecane dimethanol, glycerin, trimethylolpropane, ethylene oxide adduct of pentaerythritol, D-sorbitol and hydrogenated bisphenol A etc. are mentioned.

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. An example of a structural formula 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 (1,2-propanediol) and trimethylolpropane is shown below.

[Curing agent]
A curing agent may be used in the allyl ester resin composition of the present invention. 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 thermosetting the allyl ester resin composition of the present invention.

  As the organic peroxide, known compounds such as dialkyl peroxides, acyl peroxides, hydroperoxides, ketone peroxides, and peroxyesters can be used. Specific examples thereof include diisobutyryl peroxide, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3 , 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t- Butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-hexylperoxypivalate, t-butylperoxypivalate, di (3,5,5-trimethylhexanoyl peroxide, dilauroyl Peroxide, 1,1,3,3-te Lamethylbutylperoxy-2-ethylhexanoate, dissuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethyl Hexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide Oxide, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t- Butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2 2-bis [4,4-di (t-butylperoxy) cyclohexyl] propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5- Trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5 -Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-di (t-butyl) Peroxy) valerate, di (t-butylperoxyisopropyl) be , Dicumyl peroxide, di (t-hexyl) peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide , Cumene hydroperoxide, t-butyl hydroperoxide and 2,3-dimethyl-2,3-diphenylbutane.

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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-Methylpropan-1-one, oxyphenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester Oxyphenylacetic acid 2- [2-hydroxyethoxy] ethyl ester, phenylglyoxylic acid methyl ester, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine-4- Ylphenyl) butan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) )], Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), (4-methylphenyl) [4- ( 2-methylpropyl) phenyl] iodonium hexafluorophosphate, ethyl-4-dimethylaminobenzoe DOO, 2-ethylhexyl-4-dimethylaminobenzoate, and 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like.
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, It is preferable to mix | blend 0.1-10 mass parts with respect to 100 mass parts (except the mass of a flat inorganic substance) of allyl ester resin composition, 0 More preferably, 5 to 5 parts by mass is blended. 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, and 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 of 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.

  These reactive monomers are not particularly limited, and various types can be used. However, in order to react with an allyl ester oligomer, a monomer having a radical polymerizable carbon-carbon double bond such as a vinyl group or an allyl group is used. preferable. 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) ) (Meth) acrylic acid aromatic esters such as acrylates;
Haloalkyl (meth) acrylates such as fluoromethyl (meth) acrylate and chloromethyl (meth) acrylate;
Examples thereof include glycidyl (meth) acrylate, alkylamino (meth) acrylate, and α-cyanoacrylic acid ester.

  Examples of other vinyl compounds include styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene and vinyltoluene, vinyl acetate, vinyl propionate and vinyl benzoate, N-vinylformamide, N-vinylacetamide, N-vinylcaprolactam, N-vinylpyrrolidone, 1-vinylimidazole, N-vinylcarbazole, N-vinylmorpholine, N-vinylpyridine, acrylamide, acryloylmorpholine and the like can be mentioned.

  Crosslinkable polyfunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, oligoester di (meth) acrylate, polybutadiene di (meth) acrylate, 2, - bis (4- (meth) acryloyloxy) propane and 2,2-bis (4- (.omega. (meth) acryloyloxy polyethoxy) 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 chloride Trifunctional crosslinkable monomers such as lendates;
Furthermore, tetrafunctional cross-linkable monomers such as pentaerythritol tetra (meth) acrylate are exemplified.

  Said reactive monomer can be used individually by 1 type or in combination of 2 or more types. Although there is no restriction | limiting in particular in the usage-amount of the resin component of these reactive monomers, 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 decreasing the viscosity is small and workability may be deteriorated. When a large amount of a monofunctional monomer is used as a reactive monomer, the crosslinking density is lowered and heat resistance may be insufficient. 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 used in the present invention may contain a radical reactive resin component for the purpose of improving various physical properties. 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. Examples thereof include resins described in “Polyester Resin Handbook”, published by Nikkan Kogyo Shimbun, 1988, pages 16-18 and 29-37. This unsaturated polyester resin can be produced by a known method.

  The vinyl ester resin is also called epoxy (meth) acrylate, and is generally an open group between a compound having an epoxy group represented by an epoxy resin and a carboxyl group of a carboxyl compound having a polymerizable unsaturated group such as (meth) acrylic acid. By ring-opening reaction between a resin having a polymerizable unsaturated group produced by a ring reaction 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 The resin which has the polymerizable unsaturated group to produce | generate is pointed out. Details are described in “Polyester Resin Handbook”, published by Nikkan Kogyo Shimbun, 1988, pages 336-357. This vinyl ester resin 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 radical-reactive resin component 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 the workability is deteriorated or the moldability is deteriorated. It is not preferable. Moreover, when the usage-amount exceeds 1000 mass parts, the heat resistance of allyl ester resin itself may not appear, and it is unpreferable.

[Additive]
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, magnesium stearate and aluminum stearate. You may use these in combination of 2 or more types.

There is no restriction | limiting in particular as a ultraviolet absorber, The thing 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.
However, these additives are not limited to the specific examples described above, and any additive can be added within a range that does not impair the object or effect of the present invention.

[Allyl ester resin cured product]
The allyl ester resin composition can be obtained by mixing the allyl ester oligomer, reactive monomer, curing agent and various additives by a known method. The composition can be cured by coating a roll coater, spin coater, or the like using a heat coat, an ultraviolet ray, or an electron beam, or by a curing method such as a cast molding method or an optical modeling method after dispersing a flat inorganic substance. .

The curing temperature when the allyl ester resin composition in which the flat inorganic material is dispersed is molded into the transparent composite material of the present invention by heat curing is about 30 to 160 ° 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 curing temperature when the allyl ester resin composition in which the tabular inorganic substance is dispersed is cured and molded into the transparent composite material of the present invention by UV irradiation is about 0 to 150 ° C, preferably 10 to 130 ° C. Further, the UV irradiation time is 0.01 to 10 hours, preferably 0.05 to 1 hour, and more preferably 0.1 to 0.5 hours. The UV integrated light amount is 10 to 5000 mJ / cm ² . If it is less than 10 mJ / cm ² , incomplete curing is not preferable. At 5000 mJ / cm ² , the productivity becomes worse.

When the allyl ester resin composition of the present invention is cured by electron beam irradiation, a polymerization initiator is not necessary. However, when curing is completed by an after-curing operation, a thermal polymerization initiator may be used in combination.
The acceleration voltage of the electron beam during electron beam irradiation is 30 to 500 kV, preferably 50 to 500 kV. The irradiation dose is 1-1000 kGy, preferably 50-500 kGy. If the electron beam acceleration voltage is less than 30 kV, there is a risk that insufficient transmission of the electron beam may occur when the composition is thick, and if it exceeds 500 kV, the economic efficiency deteriorates. Further, if the irradiation dose exceeds 1000 kGy, the substrate may be damaged in some cases, which is not preferable.

[Crosslinked acrylic resin composition]
The cross-linked acrylic resin composition is a resin composition containing a compound having two or more (meth) acryloyloxy groups or a cured product thereof. As needed, the compound which has one (meth) acryloyloxy group which is a reactive monomer may be contained. Moreover, you may contain the hardening | curing agent similar to the said allyl ester resin composition, various additives, etc.

  The compound having two or more (meth) acryloyloxy groups is preferably a (meth) acrylic acid multiester compound. Specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene 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, -Bis (4-ω- (meth) acryloyloxypyriethoxy) phenyl) propane, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol S diacrylate, Dicyclopentadienyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate Relates and so on.

  Examples of the compound having one (meth) acryloyloxy group which is a reactive monomer include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like. A compound having one radical polymerizable carbon-carbon double bond such as styrene can also be used. In addition, the reactive monomer described in the section of the allyl ester resin composition can also be used.

  In the case of the cross-linked acrylic resin composition, the same curing agent, reactive monomer, additive and the like as those described in the section of the allyl ester resin composition can be used.

[Vinyl ester resin composition]
A vinyl ester resin composition is a resin composition which has the said vinyl ester resin as a main component, A well-known and usual thing can be used. In the case of the vinyl ester resin composition, the same curing agent, reactive monomer, additive and the like as those described in the section of the allyl ester resin composition can be used.

[Unsaturated polyester resin composition]
The unsaturated polyester resin composition is a resin composition containing the unsaturated polyester resin as a main component, and known and conventional ones can be used. In the case of the unsaturated polyester resin composition, the same curing agent, reactive monomer, additive and the like as those described in the section of the allyl ester resin composition can be used.

[solvent]
When the three-dimensional crosslinkable resin composition of the present invention is cured, a solvent may be used as long as it is necessary to reduce the viscosity during molding into a product. However, since it is necessary to remove the solvent later, the viscosity is preferably adjusted with the reactive monomer described above.

  Examples of the solvent that can be used for viscosity adjustment include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, mesitylene, n-propylbenzene, isopropylbenzene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate. Acetates such as acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone, ethers such as tetrahydrofuran and 1,4-dioxane, alcohols such as ethyl alcohol, (iso) propyl alcohol and butyl alcohol, dimethylformamide, Examples thereof include nitrogen-containing solvents such as N-methylpyrrolidone, N-vinylpyrrolidone, and pyridine.

  Further, when the tabular inorganic substance is an inorganic layered compound, it is preferable to use a solvent that can swell and cleave the inorganic layered compound. The inorganic layered compound swells and cleaves to form flaky crystals, and has a planar shape with a large aspect ratio. In order to easily cause the swelling and cleavage, it is preferable to use a layered silicate in which a cationic surfactant or the like is intercalated between crystal layers as described above.

  Solvents that can swell and cleave the inorganic layered compound include water, alcohols such as methanol, dimethylformamide, dimethyl sulfoxide, dichloromethane, chloroform, benzene, toluene, xylene, mesitylene, n-propylbenzene, isopropylbenzene, acetone , Methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, N-vinylpyrrolidone, pyridine and the like. Preferably, from the viewpoint of operability, water, alcohols such as methanol, toluene, xylene, and N-methylpyrrolidone are exemplified.

  Although the ratio with respect to the inorganic layered compound of a solvent is greatly dependent on the kind of solvent, it is 100-10000 mass parts with respect to 100 mass parts of inorganic layered compounds, More preferably, it is 200-5000 mass parts. If the ratio of the solvent is less than 100 parts by mass, the viscosity of the composition liquid of the mixture becomes high and difficult to apply, and if it exceeds 10,000 parts by mass, the viscosity of the liquid of the mixture becomes low, and a film thickness with a desired thickness is produced. It becomes difficult.

[Viscosity of Radical Reactive Three-dimensional Crosslinked Resin Composition]
The viscosity of the three-dimensional crosslinked resin composition can be measured by a method based on JIS K6901.
The viscosity of the three-dimensional crosslinkable resin composition for transparent material of the present invention is not particularly limited, but is preferably a viscosity suitable for a method for molding.
For example, in cast molding, the viscosity at 25 ° C. is preferably in the range of 0.01 to 1,000 Ps · s. When the viscosity is lower than 0.01 Pa · s or higher than 1,000 Pa · s, workability is deteriorated, which is not preferable.

  In the case of the roll coating method and the doctor knife method, the viscosity at 25 ° C. is preferably in the range of 0.01 to 1,000 Pa · s. When the viscosity is lower than 0.01 Pa · s or higher than 1,000 Pa · s, workability is deteriorated, which is not preferable. When the viscosity at normal temperature is high, workability can be improved by raising the temperature.

[Method for producing base material made of transparent composite material]
Next, the manufacturing method of the base material (a transparent film, a transparent sheet, and a transparent plate) which consists of a transparent composite material is demonstrated.

  In the transparent substrate of the present invention, a mixture of a tabular inorganic substance having a number average particle diameter of 10 to 300 nm and an aspect ratio of 10 to 300, a radical reactive three-dimensional crosslinkable resin composition and a solvent is applied on a coating plate. It can be manufactured by applying, drying and curing, and peeling off the resulting film.

  When the plate-like inorganic substance is an inorganic layered compound, the mixture of the inorganic layered compound, the three-dimensional cross-linkable resin composition, and the solvent is, for example, a solution obtained by dissolving a resin component in a solvent, and swelling / cleavage using the inorganic layered compound as a solvent. A method of mixing the dispersed liquid, a method of adding and dissolving the resin component in the dispersion obtained by swelling and cleaving the inorganic layered compound in a solvent, and adding the inorganic layered compound to a solution in which the resin component is dissolved in the solvent. It can be produced by a method of swelling and cleaving, or a method of dissolving and dispersing a kneaded product obtained by heating and kneading a resin component and an inorganic layered compound in a solvent, and the former three are preferred. Among these, from the viewpoint of dispersibility of the inorganic layered compound, a method of mixing a solution obtained by dissolving a resin component in a solvent and a dispersion obtained by swelling and cleaving the inorganic layered compound in a solvent is particularly preferable.

  Next, an inorganic layered compound is used as the plate-like inorganic substance, and a mixture of the resin component and the solvent is applied onto a coating plate and dried to obtain a resin film in which the inorganic layered compound is dispersed, and thermosetting Or after photocuring, it peels from an application board and it is set as a film, a sheet | seat, and a board. However, a flexible resin plate may be used as the coating plate, and the coating plate may be combined with the coating plate without peeling off the film formed on the coating plate.

  Application is the direct gravure method, reverse gravure method, micro gravure method, two roll beat coating method, bottom feed three reverse coating method, etc., using the mixture as a coating liquid, glass, metal, resin film or the like as a coating plate. The conventional roll coating method, doctor knife method, die coating method, dip coating method, bar coating method, and coating methods combining these methods can be used. And drying can be performed by methods usually used industrially, such as reduced-pressure drying, hot-air drying, and infrared drying.

  Among these, a roll coating method and a doctor knife method, which are methods for applying a force (shear) acting in a direction parallel to the surface of the transparent substrate so as to align the flat inorganic substance in the plane direction, are preferable.

  A transparent substrate composed of two or more layers is first coated on a coating plate and dried, and then another layer is coated on the obtained film, this is repeated, and after drying, it is peeled off from the coating plate. The method can be produced by producing two or more films and laminating the two or more films. When two or more films are laminated, the interface between the two sheets may be subjected to a treatment such as a corona treatment or an anchor coating agent.

  These tabular inorganic substances are preferably substantially aligned in the plane direction of the transparent substrate. That is, it is preferable that many of the respective particles of the tabular inorganic material are oriented so that the maximum surface thereof is substantially parallel to the surface of the transparent substrate (this is referred to as “orientation in the plane direction”). When the flat inorganic substance is oriented in the plane direction, the linear expansion coefficient in the plane direction of the transparent substrate can be effectively suppressed, and the linear expansion coefficient becomes particularly low. Further, when the tabular inorganic material is oriented in the plane direction, the visible light transmittance is increased even when the content of the tabular inorganic material is large.

  Moreover, when the solvent which can be volatilized is used for dilution of a flat inorganic substance and a resin component, it is possible to further orient the flat inorganic substance. That is, after applying a mixture of a flat inorganic substance, a resin component, and a solvent on a coating plate, if only the solvent is evaporated, the vertical and horizontal lengths in the surface direction of the transparent substrate composition remain the same in the normal direction. As a result, the flat inorganic substance remaining in the resin is further oriented in the plane direction. When using a reactive monomer, use a relatively low vapor pressure, use it in combination with a normal solvent with a high vapor pressure, and evaporate it at an appropriate temperature. The orientation can be balanced.

  The method of orienting the plate-like inorganic material in the plane direction by volatilizing the solvent can of course be used in combination with the roll coating method and the doctor knife method described above, and the method of coating without applying a share is performed alone. It is also possible to do.

  The temperature for volatilizing the solvent is preferably 0 to 200 ° C. A temperature lower than 0 ° C. is not preferable because the volatilization rate of the solvent is remarkably slow. When the temperature is higher than 200 ° C., foaming or resin gelation occurs, and the smoothness of the film is lowered, which is not preferable. More preferably, it is 10-100 degreeC.

  The pressure for volatilizing the solvent is preferably 1 Pa to 1 MPa. If it is less than 1 Pa, bumping may occur, which is not preferable. If it is higher than 1 MPa, the volatilization rate is extremely slow, which is not preferable. More preferably, it is 10 Pa to 0.2 MPa.

The time for volatilizing the solvent is preferably 1 to 120 minutes. If it is less than 1 minute, it may not volatilize sufficiently, which is not preferable. When it is longer than 120 minutes, productivity is deteriorated, which is not preferable.
When volatilizing the solvent, a gas such as nitrogen, argon, air or carbon dioxide may be used. These gases may contain a volatile component of the solvent.

  The gas flow rate when the solvent is volatilized is preferably 0.01 to 100 m / s. If it is less than 0.01 m / s, the volatilized solvent gas stays, which is not preferable. If it is faster than 100 m / s, the coating solution becomes non-uniform, which is not preferable. More preferably, it is 0.1-50 m / s.

  As a specific method for producing a transparent substrate, a radical-reactive three-dimensional crosslinkable resin composition before curing, in which a flat inorganic substance is dispersed and containing a solvent, is formed on a flat surface, for example, biaxially stretched polyethylene. An example is a method in which after applying to a terephthalate film while stretching it, the solvent is evaporated, and a biaxially stretched polyethylene terephthalate film having a smooth surface is sandwiched and cured.

[Linear expansion coefficient]
The transparent substrate of the present invention has a low linear expansion coefficient by containing a specific amount of a specific tabular inorganic substance. As a linear expansion coefficient of the transparent substrate of this invention, it is preferable that the average linear expansion coefficient between 50 degreeC and 250 degreeC is 50 ppm / degrees C or less, and it is further more preferable that it is 20 ppm / degrees C or less.
Here, the average linear expansion coefficient is a value measured in the tensile mode of the TMA method similar to JISK-7197.

[Transparent conductive film]
The transparent conductive film is obtained by forming a transparent conductive metal oxide on a glass or plastic film. 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 added with tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium, gallium, etc. as impurities, and oxide added with aluminum as impurities Examples thereof include metal oxide films such as zinc and 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.

[Film formation method]
In order to form the transparent conductive film, there are methods such as sputtering, ion plating, and vapor deposition. Although the film-forming method in this invention is not specifically limited, From the viewpoint of the uniformity of the electrically conductive film after film-forming, the method by sputtering is preferable.

  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.

  Although the film thickness of a transparent conductive 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.

[Deposition temperature]
When the ITO film is formed at a substrate temperature of 150 ° C. or higher, the degree of crystallinity increases and the conductivity of the film increases. In addition, the strength of the film is increased. The film formation temperature in the present invention is preferably a substrate temperature of 160 ° C. or higher. More preferably, the film is formed at 180 ° C. or higher, most preferably 200 ° C. or higher. If it is lower than 150 ° C., the degree of crystallinity is low, and there is a high possibility that the conductivity and strength are insufficient. The upper limit of the film formation temperature depends on the heat resistance of the resin, but the film formation temperature is preferably 300 ° C. or lower. If it exceeds 300 ° C., coloring or decomposition reaction due to deterioration of the resin may proceed, which is not preferable. More preferably, it is 250 degrees C or less.

[Processing before film formation]
Prior to film formation by sputtering or other methods, the transparent substrate is preferably washed with water or an organic solvent. It is conceivable that the conductivity and strength after film formation become non-uniform due to dust and contaminants adhering to the transparent substrate. This is not the case when working in a clean room, etc., to reduce the possibility of contaminants as much as possible.

  Generally, a plastic film absorbs moisture or absorbs or absorbs other substances to a small extent. In addition, a thermosetting resin is generally added with a catalyst in order to promote the reaction during polymerization. It is conceivable that those decomposition products remain on the transparent substrate. These adsorbents and decomposition products such as water are generated as outgas when forming a film at a high temperature, and there is a possibility that the inside of the sputtering chamber cannot reach a high vacuum. It is preferable to remove this outgas component in advance.

  The method for removing the outgas component in the present invention is not particularly limited, but heating at 150 ° C. or higher, which is the substrate temperature during film formation, is preferable. The same operation may be substantially heating before film formation. The pressure at the time of removal of the outgas component is preferably not more than normal pressure, more preferably not more than the degree of vacuum at the time of film formation.

  Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated, this invention does not receive any limitation by these description.

[Measurement of linear expansion coefficient and Tg]
The linear expansion coefficient was measured in a tensile mode using a thermo analyzer (TMA-50) manufactured by Shimadzu Corporation. The film-shaped test piece has a thickness of 50 μm × 3 mm × 12 mm (distance between chucks: 10 mm), tension: 0.001 kgf, and the temperature is raised to 300 ° C. at a temperature increase rate of 5 ° C./min in a nitrogen atmosphere of 50 mL / min. After that, the sample was cooled to 30 ° C. or lower, and the elongation percentage of the test piece was measured again from 30 ° C. to 300 ° C. at a temperature rising rate of 5 ° C./min. The average linear expansion coefficient in the plane direction between 50 ° C. and 250 ° C. was calculated from the difference in elongation rate between 50 ° C. and 250 ° C. and the temperature difference (100 ° C.). Moreover, the temperature of the discontinuity point of elongation rate was made into the glass transition temperature (Tg).

[Total light transmittance]
The total light transmittance was measured using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7361-1.

[Haze]
The haze value was measured according to JIS K-7136 using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.

[Flexibility]
For flexibility, a film or sheet was cut into strips having a width of 10 mm and a length of 100 mm, wound around a cylinder having a different diameter by 180 degrees, and the presence or absence of cracks was evaluated.

Synthesis example 1:
Into a 2-liter three-necked flask equipped with a distillation apparatus, 1625 g of diallyl 1,4-cyclohexanedicarboxylate, 327 g of propylene glycol and 0.813 g of dibutyltin oxide were charged and heated to 180 ° C. under a nitrogen stream. The allyl alcohol produced was distilled off. When the distilled allyl alcohol reached about 350 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 reaction system was brought to 0.5 kPa and further reacted for 1 hour to cool the reaction product. Hereinafter, the reaction product thus obtained is referred to as “oligomer (1)”.

Synthesis example 2:
In a 2-liter three-necked flask equipped with a distillation apparatus, 1655.0 g diallyl 1,4-cyclohexanedicarboxylate, 464.1 g diethylene glycol (Wako Pure Chemical Industries, Ltd.) and dioctyltin oxide (made by Hokuko Chemical Co., Ltd.) 2.40 g was charged and heated while distilling off the alcohol produced at 180 ° C. under a nitrogen stream. When the distilled alcohol reached about 256 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 almost no distillate came out, the pressure in the reaction system was reduced to 0.5 kPa, and the reaction was further allowed to proceed for 1 hour. Hereinafter, the reaction product thus obtained is referred to as “oligomer (2)”.

Example 1:
Into a 200 ml beaker, 90 g of toluene was added, and 10 g of lipophilic smectite (manufactured by Coop Chemical Co., synthetic smectite STN: number average particle size 50 nm, aspect ratio 50) which had been cation exchange treated with trioctylmethylammonium salt was stirred with a stirrer. Put in small amounts while. The mixture was sufficiently stirred at room temperature for 2 days with a stirrer to obtain a smectite dispersion.
4.2 g of oligomer (1), 1.8 g of oligomer (2), 4.0 g of 1,6-hexanediol diacrylate, photocuring agent (IRGACURE 651, manufactured by Ciba Specialty Chemicals Co., Ltd.) in the smectite dispersion. Was added and sufficiently stirred to obtain a composition.

The composition was applied on a polyethylene terephthalate film with a bar coater so that the cured film had a thickness of 500 μm. The solvent toluene was evaporated by drying with a hot air dryer at 80 ° C. for 2 hours. Furthermore, it was covered with a polyethylene terephthalate film from the top, and irradiated with about 1000 mJ / cm ² of ultraviolet rays by an ultraviolet irradiator (Toshikure 401 manufactured by Toshiba). Then, after peeling from the polyethylene terephthalate film, after-curing at 200 ° C. for 1 hour, a sample film having a thickness of about 50 μm was obtained. The linear expansion coefficient of this film was 18 ppm / ° C., and the total light transmittance was 91%. As for Tg, a clear discontinuity of elongation rate could not be detected in the measurement range of 50 to 250 ° C. Therefore, Tg is estimated to be 250 ° C. or higher.

This film 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 200 ° 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 film thickness of the ITO layer of the transparent conductive film obtained was 200 nm, the surface resistance value was 13Ω / □, and the light transmittance at 550 nm was 79%. The flexibility was 10 mm, and it had sufficient flexibility.

Example 2:
Into a 200 ml beaker, 90 g of toluene was added, and 10 g of lipophilic smectite (manufactured by Coop Chemical Co., synthetic smectite STN: number average particle size 50 nm, aspect ratio 50) which had been cation exchange treated with trioctylmethylammonium salt was stirred with a stirrer. Put in small amounts while. The mixture was sufficiently stirred at room temperature for 2 days with a stirrer to obtain a smectite dispersion.

To the smectite dispersion, 4.2 g of oligomer (1), 1.8 g of oligomer (2), and 4.0 g of 1,6-hexanediol diacrylate were added and stirred sufficiently to obtain a composition.
The composition was applied on a polyethylene terephthalate film with a bar coater so that the cured film had a thickness of 1000 μm. The solvent toluene was evaporated by drying with a hot air dryer at 80 ° C. for 2 hours. Furthermore, it was covered with a polyethylene terephthalate film from above and irradiated with an electron beam of 200 kV and 300 kGy by an electron beam irradiation device. Then, after peeling from the polyethylene terephthalate film, after-curing at 200 ° C. for 1 hour, a sample film having a thickness of about 100 μm was obtained. The linear expansion coefficient of the film was 22 ppm / ° C., and the total light transmittance was 90%. As for Tg, a clear discontinuity of elongation rate could not be detected in the measurement range of 50 to 250 ° C. Therefore, Tg is estimated to be 250 ° C. or higher.
An ITO film was formed on the obtained film in the same manner as in Example 1 at a substrate temperature of 200 ° C. to obtain a transparent conductive film. The film thickness of the ITO layer of the obtained transparent conductive film was 203 nm, the surface resistance value was 15Ω / □, and the light transmittance at 550 nm was 66%. The flexibility was 10 mm, and it had sufficient flexibility.

Comparative Example 1:
To 10 g of oligomer (1), 0.30 g of a radical polymerization initiator (Nippon Yushi Co., Ltd., Perhexa TMH) was added and sufficiently stirred to obtain a composition.
The composition was applied onto a polyethylene terephthalate film with a bar coater so that the cured film had a thickness of 50 μm. Cover with a polyethylene terephthalate film from above, and cure between a glass plate for 1 hour at 80 ° C, 1 hour at 100 ° C, 1 hour at 120 ° C, and then peel off from the polyethylene terephthalate film. Got. The linear expansion coefficient of this film was 145 ppm / ° C., Tg was 70 ° C., and the total light transmittance was 92%.
The obtained film was formed into an ITO film at a substrate temperature of 200 ° C. in the same manner as in Example 1. The obtained ITO film curled remarkably, and the desired ITO film could not be obtained.

Comparative Example 2:
An ITO film was formed in the same manner as in Example 1 except that the sample film obtained in Comparative Example 1 was changed to a substrate temperature of 60 ° C. The film thickness of the ITO layer of the obtained transparent conductive film was 200 nm, the surface resistance value was 33Ω / □, the light transmittance at 550 nm was 80%, and the flexibility was 10 mm.

Claims (18)

  On a substrate made of a transparent composite material obtained by curing a radical-reactive three-dimensional crosslinked resin composition containing a flat inorganic substance having a number average particle diameter of 10 to 300 nm and an aspect ratio of 10 to 300 A transparent conductive substrate formed by forming a transparent conductive film.   The transparent conductive substrate according to claim 1, wherein the flat inorganic substance is an inorganic layered compound.   The transparent conductive substrate according to claim 2, wherein the inorganic layered compound is at least one selected from the group consisting of smectite, talc, kaolinite, and mica (mica).   4. The transparent conductive substrate according to claim 2, wherein the inorganic layered compound is a layered silicate that has been hydrophobized by a cation exchange method using a cationic surfactant.   The transparent conductive substrate according to claim 1, wherein the content of the tabular inorganic substance in the base material made of the transparent composite material is 10 to 70% by mass.   The transparent conductive substrate according to claim 1, wherein the radical-reactive three-dimensional crosslinkable resin composition is a resin composition that does not contain an aromatic ring.   The transparent conductive substrate according to claim 6, wherein the resin composition not containing an aromatic ring is an allyl ester resin composition.   8. The transparent conductive material according to claim 7, wherein the allyl ester resin composition is a composition comprising an allyl ester compound having an ester structure formed from a polyhydric alcohol and a dicarboxylic acid, having an allyl group and / or a methallyl group as a terminal group. Substrate. The allyl ester resin composition further has the general formula (1)

(In the formula, R ¹ and R ² each independently represents an allyl group or a methallyl group, and A ¹ represents a dicarboxylic acid having at least ^one of an alicyclic structure, an aromatic ring structure and an aliphatic chain structure. Represents an organic residue derived from it.)
The transparent conductive substrate of Claim 8 containing the at least 1 sort (s) of compound chosen from the compound shown by these.   The transparent conductive substrate according to claim 9, wherein the dicarboxylic acid in the general formula (1) is a dicarboxylic acid having an alicyclic structure. At least one of the allyl ester compounds is represented by the general formula (2)

(Wherein R ³ represents an allyl group or a methallyl group, and A ² represents an organic residue derived from a dicarboxylic acid having at least one of an alicyclic structure, an aromatic ring structure and an aliphatic chain structure. )
And a group represented by the general formula (3)

(Wherein A ³ represents an organic residue derived from a dicarboxylic acid having at least one of an alicyclic structure, an aromatic ring structure and an aliphatic chain structure, and X is one or more derived from a polyhydric alcohol. Wherein X may have a branched structure having an ester bond and further having the general formula (2) as a terminal group and the general formula (3) as a constituent unit.
The transparent conductive substrate according to claim 8, having a structure represented by   The transparent conductive substrate according to claim 11, wherein the dicarboxylic acid in the general formulas (2) and (3) is a dicarboxylic acid having an alicyclic structure.   The transparent conductive substrate according to claim 7, wherein the allyl ester resin composition further contains a reactive monomer.   The average linear expansion coefficient in the plane direction in a temperature range of 50 to 250 ° C of a transparent substrate obtained by curing a radical-reactive three-dimensional crosslinkable resin composition containing a flat inorganic substance is 50 ppm / ° C or less. The transparent conductive substrate as described in 2.   The transparent conductive substrate according to claim 1, wherein the transparent conductive film contains at least one element selected from the group consisting of indium, tin, aluminum, zinc, germanium, and gallium.   The transparent conductive substrate according to claim 15, wherein the transparent conductive film is an indium tin oxide (ITO) film.   The transparent conductive substrate according to claim 1, wherein the flat inorganic substance is oriented in the plane direction.   The transparent conductive substrate according to claim 1, wherein the transparent conductive film is an indium tin oxide (ITO) film, and the film is formed at a temperature of 150 to 300 ° C.