WO2015152339A1

WO2015152339A1 - Photocurable composition for forming resin film or sheet

Info

Publication number: WO2015152339A1
Application number: PCT/JP2015/060373
Authority: WO
Inventors: 谷内　健太郎; 智隆松井
Original assignee: 東亞合成株式会社
Priority date: 2014-04-02
Filing date: 2015-04-01
Publication date: 2015-10-08
Also published as: JP6524999B2; KR20160140681A; JPWO2015152339A1; CN106459321A

Abstract

[Problem] To provide a photocurable composition enabling a resin film that does not exhibit coloring such as yellowing, has superior heat resistance, and is flexible as well as highly strong, to be obtained. Preferably, when the photocurable composition is used as a transparent conductive film, low resistance can be achieved without the occurrence of external defects. [Solution] A photocurable composition for forming a resin film or sheet that contains components (A) - (C) at a specified ratio, and the cured product of which has a glass transition temperature of equal to or greater than 200°C. (A): a mixture configured from an addition reaction product (a1) and an (meth)acrylate (a2), the product (a1) being obtained by a (meth)acrylate that contains one or more hydroxyl groups and two or more (meth)acryloyl groups being subjected to an addition reaction with an aliphatic polyisocyanate that does not contain an alicyclic group, and the (meth)acrylate (a2) not containing a hydroxyl group and containing three or more (meth)acryloyl groups; (B) a compound containing two or more (meth)acryloyl groups; and (C) a photopolymerization initiator having a molecular weight of equal to or greater than 350.

Description

Photocurable composition for resin film or sheet formation

The present invention relates to a photocurable composition for resin film or sheet formation, and the resin film obtained from the composition can be preferably used for the production of a transparent conductive film, particularly by the production of a transparent conductive film for a touch panel. It can be preferably used and belongs to these technical fields.
In the following, for convenience, “film or sheet” will be referred to as “film” unless otherwise specified.
Moreover, an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group, and an acrylate or methacrylate is represented as a (meth) acrylate.

In recent years, a touch panel integrated liquid crystal display device or a touch panel integrated organic EL display device has been widely applied to mobile devices such as smartphones, tablet terminals, and car navigation systems.
Conventionally, as a transparent conductive thin film of a touch panel, conductive glass in which a thin film of indium tin oxide (hereinafter referred to as “ITO”) is formed on glass is well known, but because the base material is glass, There exists a problem that it is inferior to flexibility and workability. For applications where a glass substrate is not preferred, a polyethylene terephthalate film (glass transition temperature of about 120 ° C.) is used as the substrate because of its advantages such as excellent impact resistance and light weight in addition to flexibility and workability. A transparent conductive film is used.

On the other hand, for the purpose of reducing the thickness and weight of the touch panel, improving the transmittance, and reducing the cost of components, a cover-integrated touch panel that directly forms a touch sensor such as ITO on the cover glass, so-called OGS (One Glass Solution), has been partially adopted. ing. However, since the OGS type touch panel has insufficient impact resistance of glass, there is a problem that when the mobile device is dropped, the cover glass is easily broken and the touch panel cannot be operated.
Therefore, so-called OPS (One Plastic Solution) has been proposed in which a plastic having excellent impact resistance is used instead of glass as a cover material, and a touch sensor such as ITO is directly formed on the plastic. However, conventional acrylic and polycarbonate sheets cannot be used for such applications because of insufficient heat resistance in the transparent conductor layer and metal electrode formation process.

Patent Document 1 discloses a plastic member for forming a transparent conductor layer obtained by photocuring a photocurable composition containing a bismethacrylate having an alicyclic skeleton and a mercapto compound.
However, although a toughness is imparted to the cured product by blending a mercapto compound, there is a problem that the pot life of the composition is shortened and the stability of the composition is lowered. It was. In addition, when a photopolymerization initiator having a molecular weight of less than 400, such as diphenyl- (2,4,6-trimethylbenzoyl) diphenylphosphine oxide described in the examples, is used, the decomposition product becomes a vacuum component of the transparent conductor layer. Since it is an outgas during film formation, it takes too much time to reach a high vacuum, and there is a problem that it is difficult to reduce resistance due to film quality deterioration of the conductive film.

In Patent Document 2, it is obtained by photocuring a photocurable composition containing a polyfunctional urethane (meth) acrylate having an alicyclic structure, a bifunctional (meth) acrylate having an alicyclic structure, and a photopolymerization initiator, A transparent resin molded body having a thickness of 50 to 500 μm is disclosed.
However, in the case where a photopolymerization initiator having a molecular weight of less than 400 such as 1-hydroxycyclohexyl phenyl ketone described in the examples is used, in addition to the same problem as described above, when the thickness is 500 μm or more, the yellow color of the film itself is increased. There was a problem that the change was great. Further, when the thickness is 500 μm or less, the same rigidity as that of glass cannot be exhibited, so that there is a problem that an appearance defect occurs in the heating step in the transparent conductor layer or metal electrode formation process.

As described above, a resin film manufactured from a photocurable composition that can reduce the resistance of a conductive film and does not cause appearance defects when forming a transparent conductor layer has not been found so far.

JP 2002-161113 A JP 2007-56180 A

The inventors of the present invention provide a photocurable composition in which the obtained resin film has excellent heat resistance, flexibility, and high strength without coloring such as yellowing, more preferably transparent. In order to find a photocurable composition that can be reduced in resistance without causing poor appearance when it is made into a conductive film, it has been intensively studied.

As a result of intensive studies to solve the above problems, the present inventors have found that an adduct obtained by reacting a specific (meth) acrylate having one or more hydroxyl groups with an isocyanate, and a compound having two or more (meth) acryloyl groups. And the composition containing a high molecular weight photoinitiator discovered that the said subject could be solved, and came to complete this invention.
Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, the obtained resin film has excellent heat resistance, flexibility, and high strength without coloring such as yellowing. Furthermore, when it is set as a transparent conductive film, it can be made low resistance without producing an appearance defect.

The present invention is a composition comprising the following components (A), (B) and (C) as essential components,
The total amount of (A) component and (B) component is 40 to 95% by weight based on the total amount of component (B) and component (B), and 5 to 60% by weight of component (B). Including 0.5 to 5 parts by weight of component (C) with respect to 100 parts by weight,
The present invention relates to a photocurable composition for forming a resin film or sheet in which the cured product has a glass transition temperature (hereinafter referred to as “Tg”) of 200 ° C. or higher.
(A) component: (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, (meth) acrylate and alicyclic having two or more (meth) acryloyl groups and one or more hydroxyl groups A (meth) acrylate derived from an addition reaction product (a1) with an aliphatic polyisocyanate not having a formula group and a trihydric or higher aliphatic polyhydric alcohol, and having three or more (meth) acryloyl groups (Meth) acrylate having no hydroxyl group (a2)
(Meth) acrylate mixture composed of (B) component: a compound having two or more (meth) acryloyl groups other than the component (A) (C) component: a photopolymerization initiator having a molecular weight of 350 or more Details of the composition will be described.

1. (A) component (A) component of this invention is
It is a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, and has no (meth) acrylate having two or more (meth) acryloyl groups and one or more hydroxyl groups, and no alicyclic group. An (meth) acrylate derived from an addition reaction product with an aliphatic polyisocyanate (a1) (hereinafter referred to as “component (a1)”) and a trihydric or higher aliphatic polyhydric alcohol, the (meth) acryloyl group (Meth) acrylate (a2) (hereinafter referred to as “component (a2)”) having 3 or more and having no hydroxyl group
(Meth) acrylate mixture composed of

The raw material compound of the component (a1) is a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having two or more (meth) acryloyl groups and one or more hydroxyl groups (meta ) Acrylate (hereinafter referred to as “hydroxyl-containing polyfunctional (meth) acrylate”).
Various compounds can be used as the trihydric or higher aliphatic polyhydric alcohol which is a raw material compound of a hydroxyl group-containing polyfunctional (meth) acrylate, and examples include trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol. .
As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, specifically, trimethylolpropane di (meth) acrylate, pentaerythritol di- or tri (meth) acrylate, ditrimethylolpropane di- or tri- Examples include (meth) acrylate and dipentaerythritol di, tri, tetra, or penta (meth) acrylate.
Among these, a compound having three or more (meth) acryloyl groups and one hydroxyl group is preferable in that the cured film is excellent in abrasion resistance and scratch resistance. Specifically, pentaerythritol trisitol is preferable. (Meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.
Among these compounds, pentaerythritol tri (meth) acrylate is more preferable because the obtained component (a1) can prevent warpage of the cured product.

Various compounds can be used as the aliphatic polyisocyanate having no alicyclic group (hereinafter simply referred to as “aliphatic polyisocyanate”), which is the other raw material for the synthesis of component (a1).
Examples of preferred aliphatic polyisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate.
In the case of a composition containing an addition reaction product of a polyisocyanate having an alicyclic group such as isophorone diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate, the cured product has sufficient toughness unless a polyfunctional mercaptan compound is used in combination. Don't be. Moreover, in the case of an addition reaction product of an aromatic polyisocyanate such as tolylene diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate, there is a problem that the yellowing of the cured product is large.
However, an addition reaction product of a polyisocyanate having an alicyclic group and a hydroxyl group-containing polyfunctional (meth) acrylate, or an addition reaction product of an aromatic polyisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate inhibits the effect of the present invention. If it is not a large amount within the range, it can be used as a component (B) described later.

The component (a1) is synthesized by an addition reaction between a hydroxyl group-containing polyfunctional (meth) acrylate and an aliphatic polyisocyanate. Although this addition reaction can be performed without a catalyst, a tin-based catalyst such as dibutyltin dilaurate, an amine-based catalyst such as triethylamine, or the like may be added in order to advance the reaction efficiently.

The component (a2) is a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol.
As the trihydric or higher aliphatic polyhydric alcohol which is a raw material compound of the component (a2), the same as those mentioned above can be used.
Specific examples of the component (a2) include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Among these, a compound having four or more (meth) acryloyl groups is preferable in that the cured film is excellent in wear resistance and scratch resistance. Specifically, pentaerythritol tetra (meth) acrylate and ditrimethylol are preferable. Examples include propanetetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Moreover, the caprolactone modified body of these compounds can also be used.
Among these compounds, pentaerythritol tetra (meth) acrylate is more preferable because it can prevent warpage of the cured product.

As a manufacturing method of (A) component, it can also manufacture by making the mixture of a hydroxyl-containing polyfunctional (meth) acrylate and the (a2) component react with aliphatic polyisocyanate.
Since the hydroxyl group-containing polyfunctional (meth) acrylate, which is the raw material of the component (A), is usually obtained as a mixture of the hydroxyl group-containing polyfunctional (meth) acrylate and the component (a2), the component (A) is easily produced. Can be preferable.
Examples of such mixtures include a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, a mixture of ditrimethylolpropane tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol penta. And a mixture of (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The component (A) of the present invention is a mixture of the component (a1) and the component (a2).
The proportion of the component (a1) and the component (a2) may be appropriately set according to the purpose, but a mixture containing (a1) :( a2) = 10: 90 to 75:25 is preferred, more preferably (A1): (a2) = a mixture containing a weight ratio of 30:70 to 70:30.
By setting the weight ratio of (a1) and (a2) within this range, a composition in which the cured film has an excellent balance between heat resistance and toughness can be obtained.

2. Component (B) The component (B) is a compound having two or more (meth) acryloyl groups other than the component (A).

As the component (B), various compounds can be used as long as they are compounds having two or more (meth) acryloyl groups other than the component (A).
Compound having two (meth) acryloyl groups [hereinafter referred to as “bifunctional (meth) acrylate”. Hereinafter, a compound having three or more (meth) acryloyl groups is represented in the same manner as “◯ functional (meth) acrylate”. ] Is a bifunctional (meth) acrylate having an aromatic skeleton such as di (meth) acrylate of bisphenol A alkylene oxide adduct and bisphenol A di (meth) acrylate;
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, propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, polybutylene glycol di (meth) acrylate, poly (1-methylbutylene glycol) di (meth) acrylate, 1 6- hexanediol di (meth) acrylate, 1,9-difunctional (meth) acrylates having an aliphatic skeleton such nonanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate;
Hydroxypivalate neopentyl glycol di (meth) acrylate;
A bifunctional (meth) acrylate having an alicyclic skeleton such as dimethylol tricyclodecane di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate and spiroglycol di (meth) acrylate;
Examples of the compound having a hydroxyl group include trimethylolpropane di (meth) acrylate, pentaerythritol di or tri (meth) acrylate, pentaerythritol di or tri (meth) acrylate, ditrimethylolpropane di or tri (meth) acrylate, and dipentaerythritol. Examples thereof include hydroxyl group-containing polyfunctional (meth) acrylates such as di-, tri-, tetra- or penta (meth) acrylates.
In the above, examples of the alkylene oxide adduct include ethylene oxide adduct and propylene oxide adduct.

As the component (B), oligomers can also be used, and specific examples include polyester (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, and the like.

Examples of the polyester (meth) acrylate include a dehydration condensate of polyester diol and (meth) acrylic acid.
Here, examples of the polyester diol include a reaction product of a diol and a dicarboxylic acid or an anhydride thereof.
Diols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, neo Examples thereof include low molecular weight diols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol and 1,6-hexanediol, and alkylene oxide adducts thereof.
Examples of the dicarboxylic acid or its anhydride include orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, and these An anhydride etc. are mentioned.

Epoxy (meth) acrylate is a compound obtained by addition reaction of (meth) acrylic acid to an epoxy resin. Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.

Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether, hydroquinone diglycidyl ether; diglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or an alkylene oxide adduct thereof; a phenol novolac type epoxy resin, and Examples thereof include novolak type epoxy resins such as cresol novolak type epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.

Specific examples of the aliphatic epoxy resin include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol, etc. Diglycidyl ethers of polyalkylene glycols; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adducts; diglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; tetrahydrophthalic acid diglycidyl esters Is mentioned.
In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide or propylene oxide.

Examples of the polyether (meth) acrylate include polyalkylene glycol (meth) diacrylate, and examples thereof include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate.

Urethane (meth) acrylate is a reaction product of polyol, organic polyisocyanate and hydroxyl group-containing (meth) acrylate.
As the polyol in the urethane (meth) acrylate, a diol is preferable.
As the diol, a low molecular weight diol, a diol having a polyester skeleton, a diol having a polyether skeleton, and a diol having a polycarbonate skeleton are preferable.
Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and the like.
Examples of the diol having a polyester skeleton include an esterification reaction product of a diol component such as the low molecular weight diol or polycaprolactone diol and an acid component such as dicarboxylic acid or an anhydride thereof.
Examples of the dicarboxylic acid or anhydride thereof include adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.
Examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polyetramethylene glycol.
Examples of the polycarbonate diol include a reaction product of the low molecular weight diol or / and bisphenol such as bisphenol A and a dialkyl ester carbonate such as ethylene carbonate and dibutyl ester carbonate.

Examples of organic polyisocyanates include aliphatic polyisocyanates having no alicyclic groups (hereinafter simply referred to as “aliphatic polyisocyanates”), aliphatic polyisocyanates having alicyclic groups (hereinafter referred to as “alicyclic polyisocyanates”). And polyisocyanates having aromatic rings and aromatic polyisocyanates.
Examples of the aliphatic polyisocyanate include the same compounds as described above.
Examples of alicyclic polyisocyanates include hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and isophorone diisocyanate trimer. It is done.
Examples of the aromatic polyisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,5-naphthalene diisocyanate, and the like.
In the present invention, the organic polyisocyanate is preferably an aliphatic polyisocyanate from the viewpoints of excellent physical properties of the cured product and little yellowing.

As the hydroxyl group-containing (meth) acrylate, a hydroxyl group-containing mono (meth) acrylate is preferable.
Examples of hydroxyl-containing mono (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and hydroxy And hydroxyalkyl (meth) acrylates such as octyl (meth) acrylate.

As the component (B), a compound other than the component (A) (hereinafter referred to as “urethane adduct”), which is an addition reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, can also be used.

In the urethane adduct, examples of the organic polyisocyanate and the hydroxyl group-containing (meth) acrylate include the compounds described above.
As the urethane adduct, both a hydroxyl group-containing polyfunctional (meth) acrylate and a hydroxyl group-containing mono (meth) acrylate can be used as the hydroxyl group-containing (meth) acrylate.

Specific examples of urethane adducts include addition reaction products of alicyclic polyisocyanates or aromatic polyisocyanates and hydroxyl group-containing polyfunctional (meth) acrylates.
As the alicyclic polyisocyanate and aromatic polyisocyanate, the same compounds as described above can be used.
As the hydroxyl group-containing polyfunctional (meth) acrylate, the same compounds as described above can be used, and the same compounds as described above are preferable.

Another specific example of the urethane adduct includes a reaction product of an organic polyisocyanate having three or more isocyanate groups and a hydroxyl group-containing mono (meth) acrylate.
Examples of the hydroxyl group-containing mono (meth) acrylate include the same compounds as those described above.
Examples of the organic polyisocyanate having three or more isocyanate groups include the aforementioned hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.
Examples of the urethane adduct include addition reaction products of hexamethylene diisocyanate trimer and hydroxybutyl acrylate.

(B) As a component, only 1 type of the above-mentioned compound may be used, or 2 or more types may be used together.

As the component (B), among the compounds described above, the storage elastic modulus and Tg of the cured product can be increased, and warpage can be prevented. ) Bifunctional (meth) acrylates having an alicyclic skeleton such as acrylate and spiroglycol di (meth) acrylate are preferred.

The content ratio of the component (A) and the component (B) is 40 to 95% by weight for the component (A) and 5 to 60% by weight for the component (B) based on the total amount of the component (A) and the component (B). Preferably, the component (A) is 50 to 95% by weight and the component (B) is 5 to 50% by weight. The content of the component (A) is less than 40% by weight, or the component (B) When the content ratio exceeds 60 parts by weight, the Tg of the resulting cured product is 200 ° C. or more, but the flexibility decreases, and the content ratio of the component (A) exceeds 95% by weight, or (B ) If the content ratio of the component is less than 5 parts by weight, the viscosity of the composition becomes too high, the coating property is lowered, and it becomes difficult to pour the composition into the recess.

3. Component (C) The component (C) is a photopolymerization initiator having a molecular weight of 350 or more, and a photopolymerization initiator having a molecular weight of 400 or more is preferable. In the case of a photopolymerization initiator having a molecular weight of less than 350, when the resin film obtained by the decomposition product after light irradiation is colored or used for the production of a transparent conductive film, the decomposition product is a vacuum component of the transparent conductor layer. Since it becomes outgas at the time of film | membrane, it will take time until it reaches high vacuum, and the film quality of a conductor layer will fall and it will become difficult to reduce resistance.

As the component (C), various compounds can be used as long as they have a molecular weight of 350 or more and can be polymerized by light such as ultraviolet rays and visible rays.
Specific examples of the component (C) include hydroxyketone polymers, and examples include compounds represented by the following formula (1). The said compound is also preferable at the point which is excellent in compatibility with (A) and (B) component.

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group, and n represents 2 to 5 numbers.
R ² is preferably a lower alkyl group such as a methyl group, an ethyl group and a propyl group as the alkyl group.

Specific examples of the compound represented by the formula (1) include oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone.
The compound is commercially available, and for example, ESACURE KIP 150 (manufactured by Lamberti) is known. ESACURE KIP 150 is a compound represented by the above formula (1), wherein R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, n is a 2 to 3 number, and [(204.3 × n + 16.0) or It is a compound having a molecular weight of (204.3 × n + 30.1)].

Examples of compounds other than the above include 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid.
The said compound is marketed and Irgacure 754 (made by BASF) is known. Irgacure 754 is a mixture of oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester.

The content ratio of the component (C) is 0.5 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). It is.
If the content ratio of the component (C) is less than 0.5 parts by weight, the curability of the composition is insufficient, and if it exceeds 5 parts by weight, the unreacted component (C) remains in the resin film, resulting in heat resistance. The nature will decline.

4). Photocurable composition for resin film formation The composition of the present invention essentially comprises the components (A) to (C).
The method for producing the composition of the present invention may be in accordance with a conventional method, and can be obtained by stirring and mixing the components (A) to (C) and, if necessary, other components described later. If necessary, the mixing time can be shortened by heating.

The composition of the present invention is a composition having a cured product having a Tg (glass transition temperature) of 200 ° C. or higher, preferably 200 to 350 ° C., more preferably 250 to 350 ° C. A composition whose Tg of the cured product is less than 200 ° C. has insufficient heat resistance.
In the present invention, Tg is a rate of temperature increase of 2 ° C./min. Means the temperature at which the main peak of the loss tangent (tan δ) of the dynamic viscoelastic spectrum of the cured product measured in (1) becomes maximum.

The composition of the present invention preferably does not contain a polyfunctional mercaptan compound.
Even if the composition of the present invention does not contain a polyfunctional mercaptan compound, the cured product is excellent in toughness. Furthermore, by not containing a polyfunctional mercaptan compound, the pot life of the composition is shortened, and the problem that the stability of the composition is reduced can be solved.
Examples of polyfunctional mercaptan compounds include ethylene glycol bisthioglycolate, butanediol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakis (3-mercaptopropionate), trimethylol. Propane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, tetraethylene glycol bis (3-thiopropionate), dipentaerythritol hexakis (3-mercapto Propionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4 6- (IH, 3H, 5H) - trione, trimethylolpropane tris (3-mercapto butyrate), trimethylolethane tris (3-mercapto butyrate), and the like.

The composition of the present invention comprises the components (A) to (C) as essential components, but various components can be blended depending on the purpose.
As other components, specifically, a compound having one ethylenically unsaturated group (hereinafter referred to as “component (D)”), an organic solvent (hereinafter referred to as “component (E)”), thermal polymerization initiation Agents, plasticizers, polymerization inhibitors or / and antioxidants, and light resistance improvers.
Hereinafter, these components will be described. In addition, the component mentioned later may be used only 1 type, and may use 2 or more types together.

4-1. Specific examples of the component (D) (D) include compounds having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”), N-vinyl-2-pyrrolidone, and the like. .

Specific examples of monofunctional (meth) acrylates include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 1- Adamantyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate , Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, о-phenylphenol EO modification (N = 1 to 4) (meth) acrylate, p-cumylphenol EO modified (n = 1 to 4) (meth) acrylate, phenyl (meth) acrylate, о-phenylphenyl (meth) acrylate, p-cumylphenyl ( And (meth) acrylate, N- (meth) acryloylmorpholine, N-vinylformamide, N- (meth) acryloyloxyethylhexahydrophthalimide, N- (meth) acryloyloxyethyltetrahydrophthalimide and the like.

The blending ratio of (D) may be set as appropriate, but with respect to a total of 100 weights of components (A), (B) and (D) (hereinafter collectively referred to as “curable components”). It is preferably 10% by weight or less, more preferably 1 to 5% by weight.

4-2. (E) Component The composition of the present invention preferably contains an organic solvent as the component (E) for the purpose of improving the coating property to the substrate.
In addition, when using the resin film obtained for a transparent conductive film use, what does not contain (E) component is preferable.

Specific examples of the organic solvent of component (E) include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene and cyclohexane;
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-butoxy Ethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1 -Methoxy-2-propanol, 1-ethoxy-2-propanol and propylene glycol monomethyl Alcohol solvents such as ether;
Ether solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis (2-methoxyethyl) ether, bis (2-ethoxyethyl) ether and bis (2-butoxyethyl) ether;
Acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, di-n-propyl ketone, diisobutyl ketone, phorone, isophorone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc. Ketone solvents;
Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol monomethyl ether acetate, cellosolve acetate;
Examples include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and γ-butyrolactone.

The ratio of the component (E) may be set as appropriate, but is preferably 10 to 90% by weight, more preferably 20 to 80% by weight in the composition.

4-3. Thermal Polymerization Initiator When the composition of the present invention is irradiated with light and then heated for the purpose of further improving the reaction rate, a thermal polymerization initiator can be blended.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.

Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, dilauroyl peroxide, t-hexylperoxyisopropyl monocarbonate, t-butyl Peroxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy Urate, t-butylperoxypivalate, t-hexylperoxypivalate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t- Butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2,2-bis (t-butyl Peroxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α'-bis (t-butyl) Peroxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2, -Di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexin-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide Examples include oxides.

Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, azodi-t-butane, and the like.
These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.

The use ratio of the thermal polymerization initiator is preferably 10 parts by weight or less with respect to 100 parts by weight of the total amount of the curable components.

4-4. For the purpose of imparting flexibility to the cured plasticizer and improving brittleness, a plasticizer can be added. Specific examples of the plasticizer include dialkyl phthalates such as dioctyl phthalate and diisononyl phthalate, dialkyl esters of adipic acid such as dioctyl adipate, phosphate esters such as sebacic acid ester, azelaic acid ester and tricresyl phosphate, polypropylene Examples thereof include liquid polyether polyols such as glycol, and liquid polyester polyols such as polycaprolactone diol and 3-methylpentanediol adipate.
The blending ratio of these plasticizers may be set as appropriate, but is preferably 5 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the total of the curable components.
When the blending ratio of the plasticizer is 5 parts by weight or more, flexibility is exhibited, and when it is 30 parts by weight or less, toughness is maintained.

4-5. Polymerization inhibitor or / and antioxidant It is preferable to add a polymerization inhibitor or / and an antioxidant to the composition of the present invention because the storage stability of the composition of the present invention can be improved.
As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and various phenolic antioxidants are preferable, but sulfur secondary antioxidants, phosphorus secondary antioxidants are preferable. A secondary antioxidant or the like can also be added.
The total blending ratio of these polymerization inhibitors and / or antioxidants is preferably 0.001 to 3 parts by weight, more preferably 0.01 to 0 parts per 100 parts by weight of the total amount of the curable components. .5 parts by weight.

4-6. The composition of the light resistance improver present invention, the light resistance improving agent such as an ultraviolet absorber or a light stabilizer may be added.
Examples of ultraviolet absorbers include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2 Benzotriazole compounds such as'-hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole;
Triazine compounds such as 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine;
2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 4, 4 ' -Trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3', 4,4'-tetrahydroxybenzophenone, or 2,2 Examples include benzophenone compounds such as'-dihydroxy-4,4'-dimethoxybenzophenone.
Examples of the light stabilizer include N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylhexamethylenediamine, bis (1,2,6,6). -) Pentamethyl-4-piperidyl) -2- (3,5-ditertiarybutyl-4-hydroxybenzyl) -2-n-butylmalonate, bis (1,2,2,6,6-pentamethyl-4- Low molecular weight hindered amine compounds such as piperidinyl) sebacate; N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylhexamethylenediamine, bis (1,2 Hindered amine light stabilizers such as high molecular weight hindered amine compounds such as 2,6,6-pentamethyl-4-piperidinyl) sebacate.
The blending ratio of the light fastness improver is preferably 0 to 5 parts by weight, more preferably 0 to 1 part by weight with respect to 100 parts by weight of the total amount of the curable components.

5. Using compositions of the manufacturing method of the present invention of a resin film, as a method for producing the resin film can be adopted various methods according to the purpose, for example, the following four manufacturing methods.
1) Manufacturing method 1
A method of applying a composition to a substrate and curing the composition by light irradiation
2) Manufacturing method 2
A method in which a composition is applied to a substrate and bonded to another substrate, followed by light irradiation to cure the composition.
3) Manufacturing method 3
A method of pouring a composition into a substrate having a space and curing the composition by light irradiation
4) Manufacturing method 4
A method in which a composition is poured into a base material having a space and bonded to another base material, and then the composition is cured by light irradiation. In the case of these production methods, heating can be performed after light irradiation.

5-1. As the base material , any of a peelable base material and a base material having no releasability (hereinafter referred to as “non-releasable base material”) can be used.
Examples of the peelable substrate include metal, glass, a release-treated film, and a surface untreated film having peelability (hereinafter, collectively referred to as “release material”).
Examples of the release material include silicone-treated polyethylene terephthalate film, surface untreated polyethylene terephthalate film, surface untreated cycloolefin polymer film, and surface untreated OPP film (polypropylene).
In order to suppress the haze of the cured product of the composition of the present invention to 1.0% or less, it is preferable to use a surface untreated polyethylene terephthalate film or a surface untreated OPP film (polypropylene).

In order to make the resin film obtained from the composition of the present invention, particularly an optical film, low haze or impart surface smoothness, the surface roughness (centerline average roughness) Ra is a peelable substrate. It is preferable to use a substrate having a thickness of 0.15 μm or less, and a substrate having a thickness of 0.001 to 0.100 μm is more preferable. Furthermore, the haze is preferably 3.0% or less.
Specific examples of the substrate include glass, untreated surface polyethylene terephthalate film, untreated surface OPP film (polypropylene), and the like.
In the present invention, the surface roughness Ra means a value obtained by measuring the surface roughness of the film and calculating an average roughness.

Examples of the non-releasable base material include various plastics other than the above, cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, acrylic resins, polyesters, polycarbonates, polyarylates, polyethersulfones, norbornene, etc. And cyclic polyolefin resins having a cyclic olefin as a monomer.

Examples of the base material having a space include a base material having a concave portion, in which a hole having a predetermined shape having a target film thickness is formed in a release material, and a concave portion is formed.
In this case, after pouring the composition into the substrate having a recess, another substrate can be stacked on the substrate having the recess.
As another example of the base material having a space portion, a material provided with a weir (spacer) on the mold release material so that the cured product has a desired film thickness (hereinafter referred to as “molding die”), and the like can also be mentioned. . In this case, another base material can be stacked on the weir.
As the release material in this case, glass and glass subjected to release treatment are preferable.
As an example of the molding die, a molding die composed of two base materials, two base materials excellent in releasability, and a base material for providing one weir (hereinafter referred to as “molding die 1”). And a molding die (hereinafter referred to as “molding die 2”) composed of two substrates and a substrate for providing one weir.
The substrate for providing the weir preferably has a shape having a hole for injecting the composition at the top. As a base material for providing the weir, various materials can be used, and silicone rubber can be exemplified.
A specific example of the mold 1 includes a mold composed of two substrates as a substrate, two films subjected to a release treatment, and a substrate for providing one weir.
The mold 2 is a case where glass or metal that has been subjected to a release treatment is used as a base material, and is excellent in the release properties of a cured product, so that two films subjected to a release treatment are not necessary.
Further, when the cured product of the composition itself is excellent in releasability, glass can be used as the substrate. An example in which the cured product of the composition is excellent in releasability includes an example in which a release agent is blended with the composition.

5-2. Pre-treatment of the composition In the application of the composition of the present invention, as a composition, the obtained resin film is made to prevent foreign matters from being mixed, to prevent generation of defects such as voids, or to have excellent optical properties. Therefore, it is preferable to use a purified product after stirring and mixing the raw material components.
As a method for purifying the composition, a method of filtering the composition is simple and preferable. Examples of the filtration method include pressure filtration.
The filtration accuracy is preferably 10 μm or less, more preferably 5 μm or less. The lower the filtration accuracy, the better. However, if the filter accuracy is too small, the filter is likely to be clogged, and the filter replacement frequency increases and the productivity is lowered. Therefore, the lower limit is preferably 0.1 μm.

In the production of the resin film, it is preferable to carry out defoaming treatment after blending each component in order to prevent bubbles from being contained in the cured product.
Examples of the defoaming treatment include standing, vacuum decompression, centrifugation, cyclone (automatic / revolving mixer), gas-liquid separation membrane, ultrasonic wave, pressure vibration, and defoaming with a multi-screw extruder.

5-3. As a coating method when the composition is applied to the coating or injection base material, it may be appropriately set according to the purpose, and conventionally known bar coater, applicator, doctor blade, knife coater, comma coater, reverse roll. Examples of the coating method include a coater, a die coater, a lip coater, a gravure coater, and a micro gravure coater.
In the case of injecting the composition into the substrate having the space, a method of injecting the composition into an injection device such as a syringe or an injection device can be used.

What is necessary is just to set suitably as a film thickness in this case according to the target film thickness of an above described resin film.
In the case of producing a resin film by production method 1 or production method 2, it is preferable that coating is performed so that the film thickness after drying an organic solvent or the like is 5 to 500 μm, more preferably 10 to 400 μm.
When producing a resin film by production method 3 or production method 4, particularly when used for glass replacement, preferably OPS, the thickness is preferably 100 μm to 5 mm, more preferably 200 μm to 3 mm, and particularly preferably 300 μm to 2 mm. is there.

When the composition contains an organic solvent or the like, it is heated and dried after coating to evaporate the organic solvent or the like.
As a heating / drying method, a method of passing through a furnace equipped with a heating device, or it can be carried out by blowing air,
The heating / drying conditions may be appropriately set according to the organic solvent used, and examples thereof include a method of heating to a temperature of 40 to 150 ° C.
As the composition after heating and drying, the proportion of the organic solvent is preferably 1% by weight or less.

5-4. Examples of the light irradiation light include ultraviolet rays and visible rays, and ultraviolet rays and visible rays are preferable and ultraviolet rays are more preferable in that the cured product can be formed into a thick film.
Examples of the ultraviolet irradiation device include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a black light lamp, a UV electrodeless lamp, and an LED.
What is necessary is just to set suitably irradiation conditions, such as a dose and irradiation intensity in light irradiation, according to the composition to be used, a base material, the objective, etc.

5-5. After the irradiation with heating light, the composition can be heated as necessary for the purpose of further curing the composition.
Examples of the heating method include a method of immersing in a heat medium bath such as heat and oil, a method using a hot press, a method of holding in a temperature-controlled thermostat, and the like.
What is necessary is just to set conditions, such as heating temperature in the case of heating suitably, according to the composition to be used, a base material, the objective, etc. The heating temperature is preferably 40 to 250 ° C. What is necessary is just to set a heat time suitably according to the composition to be used, the target resin sheet, etc., and 3 hours or more are mentioned. The upper limit of the heating time is preferably 24 hours or less in consideration of economy.
Also, the heating temperature can be changed according to the purpose. For example, the case where the thermal-polymerization initiator from which decomposition temperature differs is used. Specific examples of the temperature include a method of polymerizing at a relatively low temperature of about 40 to 80 ° C. for several hours and then polymerizing at a relatively high temperature of 100 ° C. or higher for several hours.

5-6. Preferred method for producing a resin film An example of a preferred method for producing a resin film comprising a release material / cured product will be described.
When the composition is a solventless type, the composition is applied to a release material. When the composition contains an organic solvent or the like, the composition is applied to a mold release material and then dried to evaporate the organic solvent or the like.
By irradiating light to the sheet in which the composition layer is formed on the release material, a resin film composed of the release material / cured material is obtained. Although light irradiation is normally irradiated from the composition layer side, it can also be irradiated from the mold release material side.
In the above, if a release material is used as the substrate, a resin film composed of the release material / cured product can be produced.
What is necessary is just to set suitably irradiation conditions, such as a dose and irradiation intensity in light irradiation, according to the composition to be used, a base material, the objective, etc.

An example of the preferable manufacturing method of the resin film comprised from a mold release material / hardened | cured material / mold release material is shown.

When the composition is a solventless type, the composition is applied to a release material. When the composition contains an organic solvent or the like, the composition is applied to a mold release material and then dried to evaporate the organic solvent or the like.
A resin film in which a release material, a cured product and a release material are formed in this order can be obtained by laminating a release material on the composition layer and then irradiating with light or laminating the release material after light irradiation.

Although the example which used the mold release material as the base material was described above, the resin film can also be manufactured using a non-mold release base material.
For example, it is possible to use a non-releasable base material in place of the above-mentioned release material, and to cure by irradiation with active energy in the same manner as described above to produce a resin film composed of a non-releasable base material / cured product. it can.
Moreover, a non-releasable base material is used as any of the above-mentioned release materials, and is cured by light irradiation in the same manner as described above, and is composed of a release material / cured product / non-releasable base material. It is also possible to produce a resin film or a resin film composed of a non-releasable substrate / cured product / non-releasable substrate.

In the above example, the resin film is produced by coating the composition on the substrate. However, when producing a resin film having a large film thickness, the composition is formed on a substrate having a specific recess. A resin film can also be produced by pouring an object and irradiating light in the same manner as described above to cure the composition.
Moreover, after pouring a composition into the base material which has a recessed part and bonding with another base material, it can also be irradiated with light and hardened and a resin film can also be manufactured.
This manufacturing method is preferable in that a relatively thick resin film can be manufactured. In this case, the film thickness is preferably 0.5 mm or more and 1.5 mm or less. The composition used in this case is preferably a solventless composition containing no organic solvent.

6). Use of Resin Film A resin film formed from the composition of the present invention can be preferably used as an optical film.
The optical film formed from the composition of the present invention can be used for various optical applications. More specifically, a film used for a liquid crystal display device such as a polarizer protective film for a polarizing plate, a support film for a prism sheet, and a light guide film, and a touch panel integrated liquid crystal display device, various functional films (for example, hard coat) Films, decorative films, transparent conductive films) and surface films (for example, moth-eye type antireflection films and films with a texture structure for solar cells), light resistance for outdoor use such as solar cells (weather resistance) ) Applications such as films, films for LED lighting / organic EL lighting, and transparent heat-resistant films for flexible electronics.

Since the optical film formed from the composition of the present invention is excellent in heat resistance, it can be preferably used for the production of a transparent conductive film. The composition used in this application is preferably a solventless composition that does not contain an organic solvent in that outgassing during the vacuum deposition of the transparent conductive layer can be suppressed.
Furthermore, since the optical film of the present invention is excellent in heat resistance even if it is a film thickness, it has flexibility and high strength, it can also be used as a transparent conductive film substrate for OPS. In this case, an optical film having a film thickness of 0.5 mm or more and 1.5 mm or less can be used more preferably.

The manufacturing method of a transparent conductive film should just follow a conventional method.
The metal oxide forming the transparent conductor layer is indium oxide, tin oxide, zinc oxide, titanium oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, indium-zinc composite. Examples thereof include oxides and titanium-niobium composite oxides. Of these, indium-tin composite oxide and indium-zinc composite oxide are preferable from the viewpoint of environmental stability and circuit processability.
As a method of forming the transparent conductor layer, a conventional method may be followed, and a method of forming by sputtering using a vacuum film forming apparatus using the metal oxide, using the optical film of the present invention. Etc.
More specifically, the metal oxide is used as a target material, dehydrated and degassed, and then evacuated and vacuumed, the optical film is brought to a predetermined temperature, and then sputtered onto the optical film. Examples include a method of forming a transparent conductor layer.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, “part” means part by weight, and “%” means% by weight.

1. Production Example 1 [Production of component (A)]
In a 0.5 L separable flask equipped with a stirrer and an air blowing tube, a mixture of pentaerythritol triacrylate (PETri) and pentaerythritol tetraacrylate (PETet) [Aronix M-305 manufactured by Toagosei Co., Ltd. Hereinafter, it is referred to as “M-305”. ] 159.2 g (containing 0.3 mol of PETri and 0.2 mol of PETet), 0.092 g of 2,6-di-tert-butyl-4-methylphenol, 0.055 g of dibutyltin dilaurate, and the liquid temperature was 70 to 75 ° C. 25.2 g (0.15 mol) of hexamethylene diisocyanate was added dropwise with stirring.
After completion of dropping, the mixture was stirred at 80 ° C. for 3 hours, and the reaction was completed after confirming that the isocyanate group had disappeared by IR (infrared absorption) analysis of the reaction product. Hereinafter, this reaction product is referred to as UA-1.
UA-1 is a mixture containing a urethane adduct compound (a1) of PETri and HDI and PETet (a2), wherein the weight ratio of (a1) and (a2) is (a1) :( a2) = 6: 4. is there.

2. Example 1 and 3 and Comparative Example 1 and 2
1) Production of composition After mixing the compounds shown in Table 1 in the proportions shown in Table 1, a composition was produced.

2) Manufacture of resin film Two glasses are opposed to each other, and the composition obtained above is poured into a mold using a 1.0 mm or 0.4 mm thick silicone plate as a spacer. Co., Ltd. UV irradiation device (high pressure mercury lamp, 365 nm irradiation intensity 200 mW / cm ² (measured value of UV POWER PUCK manufactured by Fusion UV Systems Japan Co., Ltd.), integrated light quantity 5J / from one glass plate side After irradiating ultraviolet rays at cm ² , it was turned upside down and irradiated with ultraviolet rays with an integrated light amount of 5 J / cm ² from the opposite side of the glass plate.
After curing, the resin film was peeled off to obtain a resin film.
About the obtained resin film, Tg, bending elastic modulus, and b * were evaluated according to the following method. The results are shown in Table 1.

(1) Evaluation method
a) Tg of resin film
The dynamic viscoelasticity measurement of the obtained resin film was performed at a temperature of 25 to 250 ° C. and a frequency of 10 Hz, and the temperature at which the tan δ value was maximum was defined as Tg (glass transition temperature).

b) Flexural modulus of resin film The obtained resin film was processed into a test piece of length 25 (mm) × width 10 (mm), and autograph “AG-5kNE” (distance between fulcrums) manufactured by Shimadzu Corporation. The flexural modulus (GPa) was measured at 25 ° C. at 20 mm and 0.5 mm / min.

c) Resin film b *
The b * of the obtained resin film was measured using a high-speed integrating sphere type spectral transmittance measuring device DOT-3C (manufactured by Murakami Color Research Laboratory Co., Ltd.).

3) Production of transparent conductive film (formation of ITO film)
A sintered body containing indium oxide and tin oxide in a weight ratio of 90:10 as a target material was attached to a single wafer magnetron sputtering apparatus (manufactured by Shibaura Mechatronics Co., Ltd.).
The resin film obtained above is set, dehydrated and degassed and evacuated to 5 × 10 ⁻³ Pa. Then, the heating temperature of the film is 120 ° C., and the pressure is 4 × 10 ⁻¹ Pa. As described above, argon gas and oxygen gas were introduced at a flow rate ratio of 98%: 2%, and a film was formed by DC sputtering to form an amorphous ITO film having a thickness of 20 nm on the substrate. Thereafter, the ITO film was crystallized by heating at 180 ° C. for 10 minutes.
About the obtained resin film with an ITO film | membrane, the external appearance and resistance were evaluated in accordance with the following method. The results are shown in Table 1.

(1) Evaluation method
a) Appearance of Resin Film with ITO Film Regarding the appearance of the obtained resin film with ITO film, the presence or absence of wrinkles was visually observed and evaluated according to the following criteria.
○: No wrinkles ×: Wrinkles
b) Resistance of Resin Film with ITO Film Regarding resistance of the obtained resin film with ITO film, four terminals using resistance meter Loresta GP MCP-T610 type (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) according to JIS K7194 Measured by the method.

The abbreviations in Table 1 mean the following.
DCP [dimethylol tricyclodecane dimethacrylate, light acrylate DCP manufactured by Kyoeisha Chemical Co., Ltd.]
KIP150 [poly [2-hydroxy-2-methyl- (4- (1-methylvinyl) phenyl) propanone, ESACURE KIP 150, Lamberti, molecular weight 424.6 to 643]
IRG184 [1-hydroxycyclohexyl phenyl ketone, Irgacure 184 manufactured by BASF Japan Ltd., molecular weight 204]

3. The compositions of General Examples 1 to 3 were excellent in Tg, flexural modulus, and b ^* of the resin film obtained.
Furthermore, it was excellent in the external appearance and film resistance of the resin film with an ITO film | membrane obtained from the resin film of Example 1 and the same 2. On the other hand, Example 3 used the same composition as Example 1, but the thickness was 0.5 mm, but the performance as a resin film with an ITO film is insufficient for the rigidity of the resin film. The appearance after ITO film formation was poor.
On the other hand, Comparative Example 1 is a composition using a compound having a molecular weight of less than 400 as a photopolymerization initiator, and although the obtained resin film is excellent in Tg and flexural modulus, photopolymerization is initiated. Since the decomposition product of the agent is outgas, yellowing becomes large and the film quality of the ITO film of the resin film with the ITO film is deteriorated, so that the resistance cannot be sufficiently lowered. Comparative Example 2 is a composition in which the component (A) is less than the lower limit of 40% by weight of the present invention [the component (B) exceeds the upper limit of 60% by weight of the present invention], but the resulting resin film is bent. Cracks occurred and the flexural modulus could not be evaluated.

The composition of the present invention can be preferably used for the production of a resin film, and the obtained resin film can be used for various applications, and can be preferably used as an optical film. The said optical film can be preferably used for manufacture of a transparent conductive film, and can be preferably used by manufacture of the transparent conductive film for touchscreens.

Claims

A composition comprising the following component (A), component (B) and component (C) as essential components,
The total amount of (A) component and (B) component is 40 to 95% by weight based on the total amount of component (B) and component (B), and 5 to 60% by weight of component (B). Including 0.5 to 5 parts by weight of component (C) with respect to 100 parts by weight,
A photocurable composition for resin film or sheet formation, wherein the cured product has a glass transition temperature of 200 ° C. or higher.
(A) component: (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, (meth) acrylate and alicyclic having two or more (meth) acryloyl groups and one or more hydroxyl groups A (meth) acrylate derived from an addition reaction product (a1) with an aliphatic polyisocyanate not having a formula group and a trihydric or higher aliphatic polyhydric alcohol, and having three or more (meth) acryloyl groups (Meth) acrylate having no hydroxyl group (a2)
(Meth) acrylate mixture composed of (B) component: Compound having two or more (meth) acryloyl groups other than component (A) (C) component: photopolymerization initiator having a molecular weight of 350 or more
The photocurable composition for resin film or sheet formation according to claim 1, wherein the cured product has a glass transition temperature of 200 to 350 ° C.
3. The photocurable composition for resin film or sheet formation according to claim 1, wherein the component (A) is a mixture containing (a1) :( a2) = 10: 90 to 75:25 in a weight ratio. object.
The component (A) is a mixture of (a1) an addition reaction product of pentaerythritol tri (meth) acrylate and an aliphatic polyisocyanate having no alicyclic group, and (a2) pentaerythritol tetra (meth) acrylate. Item 4. The photocurable composition for resin film or sheet formation according to any one of Items 1 to 3.
The photocurable composition for resin film or sheet formation according to any one of claims 1 to 4, wherein the component (C) is a compound represented by the following formula (1).

[In the formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group, and n represents 2 to 5 numbers. ]
The photocurable composition for resin film or sheet formation according to any one of claims 1 to 5, which does not contain a polyfunctional mercaptan compound.
The photocurable composition for resin film or sheet formation according to any one of claims 1 to 6, which does not contain an organic solvent.
A resin film or sheet in which the cured product of the composition according to any one of claims 1 to 7 is formed into a film shape or a sheet shape.
The resin film or sheet according to claim 8, wherein the cured product has a thickness of 0.5 mm to 1.5 mm.
An optical film or sheet comprising the resin film or sheet according to claim 8 or 9.
A transparent conductive film or sheet having a transparent conductor layer on one or both sides of the optical film or sheet according to claim 10.
A transparent conductive film or sheet for a touch panel having a transparent conductor layer on one or both sides of the optical film or sheet of claim 10.
A method for producing a resin film or sheet in which the composition according to any one of claims 1 to 7 is poured into a substrate having a space, and then irradiated with light from the poured surface or the substrate side. .
8. After pouring the composition according to any one of claims 1 to 7 into a substrate having a space, and pasting another substrate on the poured surface, any substrate The manufacturing method of the resin film or sheet | seat which irradiates light from the side.
The method for producing a resin film or sheet according to claim 14, wherein one or both of the base material having the space and the other base material is a peelable base material.
A resin film or sheet which is irradiated with light from the coated surface side or the film or sheet-like substrate side after applying the composition according to any one of claims 1 to 7 to the film or sheet-like substrate. Manufacturing method.
The method for producing a resin film or sheet according to claim 16, wherein the film or sheet-like substrate is a peelable substrate.
A sheet-like substrate is coated with the composition according to any one of claims 1 to 7, and another film or sheet-like substrate is bonded to the coating surface of the composition, and then the sheet-like substrate is coated. The manufacturing method of the resin film or sheet | seat which irradiates light from either side of a base material.
The method for producing a resin film or sheet according to claim 18, wherein either one or both of the film and the sheet-like substrate is a peelable substrate.