JP6524999B2 - Photocurable composition for forming resin film or sheet - Google Patents

Description

The present invention relates to a photocurable composition for forming a resin film or sheet, and a resin film obtained from the composition can be preferably used for producing a transparent conductive film, and in particular, by producing a transparent conductive film for touch panel It is preferably used and belongs to these technical fields.
In the following, for convenience, "film or sheet" will be described as "film" unless otherwise noted.
In addition, 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, many touch panel integrated liquid crystal display devices or touch panel integrated organic EL display devices have been applied to mobile devices such as smartphones, tablet terminals and car navigation systems.
Conventionally, as a transparent conductive thin film of a touch panel, a conductive glass in which a thin film of indium tin oxide (hereinafter referred to as "ITO") is formed on glass is well known, but since the substrate is glass, There is a problem that it is inferior in flexibility and processability. In the case where the glass substrate is not preferred, a polyethylene terephthalate film (glass transition temperature of about 120 ° C.) is used because of its advantages such as excellent impact resistance and light weight in addition to flexibility and processability. The transparent conductive film is used.

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

Patent Document 1 discloses a plastic member for forming a transparent conductive layer, which is obtained by photocuring a photocurable composition containing a bismethacrylate having an alicyclic skeleton and a mercapto compound.
However, although the toughness is given to the cured product by blending the mercapto compound, there is a problem that the pot life of the composition becomes short and the stability of the composition is lowered. The When a photopolymerization initiator having a molecular weight of less than 400 such as diphenyl- (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide described in the examples is used, the decomposition product thereof forms the vacuum of the transparent conductor layer. Since it becomes an outgas at the time of film formation, it takes a long time to reach a high vacuum, and there is a problem that it is difficult to reduce resistance due to deterioration of the film quality of the conductive film.

In Patent Document 2, it is obtained by photocuring a photocurable composition comprising a polyfunctional urethane (meth) acrylate having an alicyclic structure, a bifunctional (meth) acrylate having an alicyclic structure, and a photopolymerization initiator. A transparent resin molding having a thickness of 50 to 500 μm is disclosed.
However, when using a photopolymerization initiator having a molecular weight of less than 400 such as 1-hydroxycyclohexyl phenyl ketone described in the examples, in addition to the same problems as described above, the yellow color of the film itself when the thickness is 500 μm There was a problem that the change was large. Further, when the thickness is 500 μm or less, the same rigidity as that of glass can not be expressed, so there is a problem that appearance defects occur in the heating step in the transparent conductor layer or metal electrode forming process.

  As mentioned above, the resin film manufactured from the photocurable composition which can make resistance reduction of a conductive film and does not produce the appearance defect at the time of transparent conductor layer formation was not found until now.

JP, 2002-161113, A JP 2007-56180 A

  The present inventors have found that a photocurable composition is obtained in which the resulting resin film is excellent in heat resistance, flexible, and high in strength without having coloring such as yellowing, and more preferably transparent. The present inventors diligently studied to find a photocurable composition which can be made to have a low resistance without causing appearance defects when it is used as a conductive film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors made the compound which made the specific (meth) acrylate and isocyanate which have one or more hydroxyl groups react, and a compound which has two or more (meth) acryloyl groups. And the composition containing the photoinitiator of high molecular weight discovers that the said subject can 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 does not have coloring such as yellowing, is excellent in heat resistance, has flexibility, and also has high strength. Furthermore, when it is set as a transparent conductive film, it can be made low resistance, without producing appearance defect.

The present invention is a composition comprising the following components (A), (B) and (C) as essential components,
40 to 95% by weight of component (A) and 5 to 60% by weight of component (B) based on the total amount of component (A) and component (B), and the total of component (A) and component (B) 0.5 to 5 parts by weight of component (C) per 100 parts by weight of
The present invention relates to a photocurable composition for forming a resin film or sheet having a glass transition temperature (hereinafter referred to as “Tg”) of a cured product of 200 ° C. or higher.
Component (A): A (meth) acrylate derived from a trivalent or higher aliphatic polyhydric alcohol, which has two or more (meth) acryloyl groups and one or more hydroxyl groups (meth) acrylate and an alicyclic group A (meth) acrylate derived from an addition reaction product (a1) with an aliphatic polyisocyanate having no formula group and an aliphatic polyhydric alcohol having a valence of 3 or more and having three or more (meth) acryloyl groups , Hydroxyl group-free (meth) acrylate (a2)
(Meth) acrylate mixture (B) component: a compound having two or more (meth) acryloyl groups other than the (A) component (C) component: a photopolymerization initiator which is a polymer of hydroxy ketone having a molecular weight of 350 or more Agent Hereinafter, details of each component and composition will be described.

1. Component (A) The component (A) of the present invention is
(Meth) acrylates derived from trivalent or higher aliphatic polyhydric alcohols, which have two or more (meth) acryloyl groups and one or more hydroxyl groups (meth) acrylates and no alicyclic group (Meth) acrylate derived from addition reaction product (a1) with aliphatic polyisocyanate (hereinafter referred to as “component (a1)”) and aliphatic polyhydric alcohol having 3 or more valences, and (meth) acryloyl group (Meth) acrylate (a2) having three or more hydroxyl groups and no hydroxyl group (hereinafter referred to as "component (a2)")
And a (meth) acrylate mixture.

The raw material compound of the component (a1) is a (meth) acrylate derived from a trivalent or higher aliphatic polyhydric alcohol and has two or more (meth) acryloyl groups and one or more hydroxyl groups (Meta) 2.) Acrylate (hereinafter referred to as "hydroxyl group-containing polyfunctional (meth) acrylate").
Various compounds can be used as a trivalent or higher aliphatic polyhydric alcohol which is a raw material compound of a hydroxyl group-containing polyfunctional (meth) acrylate, and trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and the like can be mentioned. .
As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used. Specifically, trimethylolpropane di (meth) acrylate, di or tri (meth) acrylate of pentaerythritol, di or tri of ditrimethylolpropane Examples include di-, tri-, tetra- or penta (meth) acrylates of (meth) acrylate and dipentaerythritol.
Among these, a compound having three or more (meth) acryloyl groups and having one hydroxyl group is preferable in that the cured film is excellent in abrasion resistance and abrasion resistance, and specifically, pentaerythritol tritol. Examples include (meth) acrylate, ditrimethylolpropane tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.
Among these compounds, pentaerythritol tri (meth) acrylate is more preferable in that the component (a1) obtained can prevent the warp of the cured product.

Various compounds can be used as an aliphatic polyisocyanate having no alicyclic group (hereinafter simply referred to as “aliphatic polyisocyanate”), which is another synthetic raw material of the component (a1).
Examples of preferable aliphatic polyisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and the like.
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, a cured product having sufficient toughness unless used in combination with a polyfunctional mercaptan compound It does not. Moreover, in the case of the addition reaction product of aromatic polyisocyanate, such as tolylene diisocyanate, and a hydroxyl-containing polyfunctional (meth) acrylate, it has the problem that yellowing of hardened | cured material is large.
However, the addition reaction product of polyisocyanate having an alicyclic group and a hydroxyl group-containing polyfunctional (meth) acrylate, and the addition reaction product of an aromatic polyisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate inhibit the effect of the present invention. It can also be used together as a postscript (B) component, unless it is a large quantity of the range which is not.

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

The component (a2) is a (meth) acrylate derived from a trivalent or higher aliphatic polyhydric alcohol.
As a trivalent or more aliphatic polyhydric alcohol which is a raw material compound of (a2) component, the thing similar to what was mentioned above can be used.
Specific examples of the component (a2) include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
Among these, compounds having four or more (meth) acryloyl groups are preferable in that the cured film is excellent in abrasion resistance and abrasion resistance, and specifically, pentaerythritol tetra (meth) acrylate, ditrimethylol Examples include propane tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Also, caprolactone-modified products of these compounds can be used.
Among these compounds, pentaerythritol tetra (meth) acrylate is more preferable in that warpage of the cured product can be prevented.

The component (A) can also be produced by reacting a mixture of a hydroxyl group-containing polyfunctional (meth) acrylate and the component (a2) with an aliphatic polyisocyanate.
The hydroxyl group-containing polyfunctional (meth) acrylate which is a raw material of the component (A) is usually obtained as a mixture of the hydroxyl group-containing polyfunctional (meth) acrylate and the component (a2), so the component (A) is easily produced. Can be preferred.
Examples of such mixtures include mixtures of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, mixtures of ditrimethylolpropane tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol pentamer. And mixtures of (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The component (A) of the present invention is a mixture of the components (a1) and (a2).
Although the ratio of the component (a1) to the component (a2) may be appropriately set according to the purpose, a mixture containing a weight ratio of (a1) :( a2) = 10: 90 to 75:25 is preferable, and more preferably (A1): (a2) = It is a mixture containing by a weight ratio of 30:70-70:30.
By setting the weight ratio of (a1) to (a2) in this range, it is possible to obtain a composition in which the cured film is excellent in the balance between heat resistance and toughness.

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).
A compound having two (meth) acryloyl groups [hereinafter referred to as “bifunctional (meth) acrylate”. Hereinafter, the compound which has three or more (meth) acryloyl groups is described similarly to "(circle) functional (meth) acrylate." And difunctional (meth) acrylates 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 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-methyl butylene 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;
Bifunctional (meth) acrylates having an alicyclic skeleton such as dimethylol tricyclodecane di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate and spiroglycol di (meth) acrylate;
As the compound having a hydroxyl group, trimethylolpropane di (meth) acrylate, pentaerythritol di or tri (meth) acrylate, pentaerythritol di or tri (meth) acrylate, ditrimethylolpropane di or tri (meth) acrylate, dipentaerythritol Examples thereof include hydroxyl group-containing polyfunctional (meth) acrylates such as di, tri, tetra or penta (meth) acrylate.
In the above, examples of the alkylene oxide adduct include ethylene oxide adduct and propylene oxide adduct.

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

Examples of polyester (meth) acrylates include dehydrated condensates of polyester diols and (meth) acrylic acid.
Here, as polyester diol, the reaction product of diol and dicarboxylic acid or its anhydride, etc. are mentioned.
As a diol, 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 And low molecular weight diols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and alkylene oxide adducts thereof.
Examples of dicarboxylic acids or their anhydrides include dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, and Anhydride etc. are mentioned.

  Epoxy (meth) acrylate is a compound obtained by addition reaction of (meth) acrylic acid to an epoxy resin. As an epoxy resin, an aromatic epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

  Specifically as an aromatic epoxy resin, resorcinol diglycidyl ether, hydroquinone diglycidyl ether; bisphenol A, bisphenol F, bisphenol S, diglycidyl ether of bisphenol fluorene or its alkylene oxide adduct; phenol novolac epoxy resin, Novolak-type epoxy resins such as cresol novolac-type epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.

Specific examples of aliphatic epoxy resins 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; neopentyl glycol, diglycidyl ethers of dibromo neopentyl glycol and their alkylene oxide adducts; diglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ester, etc. Can be mentioned.
In the above, as the alkylene oxide of the alkylene oxide adduct, ethylene oxide, propylene oxide and the like are preferable.

  Examples of polyether (meth) acrylates include polyalkylene glycol (meth) diacrylates, such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate.

The urethane (meth) acrylate is a reactant of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate.
As a polyol in 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 low molecular weight diols 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 a dicarboxylic acid or an anhydride thereof.
Examples of dicarboxylic acids or their anhydrides include adipic acid, succinic acid, phthalic acid, tetrahydric phthalic acid, hexahydrophthalic acid and terephthalic acid, and their anhydrides and the like.
Examples of polyether diols include polyethylene glycol, polypropylene glycol, polyethylene glycol and the like.
Examples of polycarbonate diols include reaction products of bisphenols such as the low molecular weight diol and / or bisphenol A and dialkyl carbonates such as ethylene carbonate and carbonic acid dibutyl ester.

As the organic polyisocyanate, aliphatic polyisocyanate having no alicyclic group (hereinafter simply referred to as "aliphatic polyisocyanate"), aliphatic polyisocyanate having an alicyclic group (hereinafter "alicyclic polyisocyanate") And polyisocyanates having a heterocyclic ring and aromatic polyisocyanates.
Examples of aliphatic polyisocyanates 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, etc. Be
Examples of the aromatic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate and 1,5-naphthalene diisocyanate.
In the present invention, as the organic polyisocyanate, aliphatic polyisocyanate is preferable in that the physical properties of the cured product are excellent and yellowing is small.

The hydroxyl group-containing (meth) acrylate is preferably a hydroxyl group-containing mono (meth) acrylate.
As a hydroxyl group-containing mono (meth) acrylate, 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), it is also possible to use an addition reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate and a compound other than the component (A) (hereinafter referred to as "urethane adduct").

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

Specific examples of urethane adducts include addition reaction products of alicyclic polyisocyanate or aromatic polyisocyanate and hydroxyl group-containing polyfunctional (meth) acrylate.
As the alicyclic polyisocyanate and the 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 is a reaction product of an organic polyisocyanate having three or more isocyanate groups and a hydroxyl group-containing mono (meth) acrylate.
As the hydroxyl group-containing mono (meth) acrylate, the same compounds as the compounds described above can be mentioned.
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 an addition reaction product of hexamethylene diisocyanate trimer and hydroxybutyl acrylate, and the like.

  As the component (B), only one type of the above-mentioned compounds may be used, or two or more types may be used in combination.

  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. Thus, dimethylol tricyclodecane di (meth) acrylate, cyclohexane dimethanol di (meth Bifunctional (meth) acrylates having an alicyclic backbone, such as) acrylates and spiroglycol di (meth) acrylates are preferred.

The content ratio of the component (A) and the component (B) is 40 to 95% by weight of the component (A) and 5 to 60% by weight of the component (B) based on the total amount of the component (A) and the component (B). Preferably, 50 to 95% by weight of the component (A) and 5 to 50% by weight of the component (B), and the content of the component (A) is less than 40% by weight, or If the content ratio exceeds 60 parts by weight, the Tg of the obtained cured product will be 200 ° C. or higher, 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 coatability 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, preferably a photopolymerization initiator having a molecular weight of 400 or more. In the case of a photopolymerization initiator having a molecular weight of less than 350, if the resin film obtained by the decomposition product after light irradiation is colored or if it is used for the production of a transparent conductive film, the decomposition product is a vacuum conductor of the transparent conductor layer Since it becomes an outgas at the time of film formation, it takes too much time to reach high vacuum, and the film quality of the conductor layer is lowered to make it difficult to reduce resistance.

As the component (C), various compounds having a molecular weight of 350 or more and capable of initiating polymerization by light such as ultraviolet light and visible light can be used.
Specific examples of the component (C) include polymers of hydroxyketones, and examples thereof 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 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.
As the alkyl group, R ² is preferably a lower alkyl group such as a methyl group, an ethyl group and a propyl group.

Specific examples of the compound represented by the formula (1) include oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone and the like.
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 2 to 3 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.

Component (C) is used in an amount of 0.5 to 5 parts by weight, preferably 0.5 to 3 parts by weight, per 100 parts by weight of 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 becomes insufficient, and if it exceeds 5 parts by weight, the unreacted component (C) remains in the resin film and the heat resistance The sex is reduced.

4. Photocurable composition for forming resin film 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, the other components described later. If necessary, the mixing time can be shortened by heating.

Further, the composition of the present invention is a composition in which the Tg (glass transition temperature) of a cured product is 200 ° C. or higher, preferably 200 to 350 ° C., and more preferably 250 to 350 ° C. The composition having a Tg of 200 ° C. or less of the cured product has insufficient heat resistance.
In the present invention, Tg means a heating rate of 2 ° C./min. At 10 Hz. It means the temperature at which the main peak of the loss tangent (tan δ) of the dynamic viscoelasticity spectrum of the cured product measured in the above becomes the largest.

As the composition of the present invention, one not containing a polyfunctional mercaptan compound is preferable.
In the composition of the present invention, the cured product is excellent in toughness even if it does not contain a polyfunctional mercaptan compound. Furthermore, by not including the polyfunctional mercaptan compound, the pot life of the composition becomes short, and the problem that the stability of the composition is reduced can be solved.
As polyfunctional mercaptan compounds, 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 contains 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, light resistance improvers, etc. may be mentioned.
Hereinafter, these components will be described. The components to be described later may be used alone or in combination of two or more.

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 ( Meta) 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, ol-phenylphenol EO modified ( n = 1 to 4) (meth) acrylate, p-cumylphenol EO modified (n = 1 to 4) (meth) acrylate, phenyl (meth) acrylate, ol-phenylphenyl (meth) acrylate, p-cumylphenyl (meth) Acrylate, N- (meth) acryloyl morpholine, N-vinylformamide, N- (meth) acryloyloxyethyl hexahydrophthalimide, N- (meth) acryloyloxyethyl tetrahydrophthalimide and the like.

  The compounding ratio of (D) may be set as appropriate, but in the total 100 weight of (A), (B) and (D) components [hereinafter, these are collectively referred to as "curable component"]. 10 weight% or less is preferable, More preferably, it is 1 to 5 weight%.

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

Specific examples of the organic solvent of the 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, phohone, isophorone, cyclopentanone, cyclohexanone and methylcyclohexanone etc. Ketone solvents;
Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol monomethyl ether acetate, cellosolve acetate;
Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone and the like can be mentioned.

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

4-3. Thermal Polymerization Initiator In the case where 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 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2 , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, dilauroyl peroxide, t-hexylperoxyisopropyl monocarbonate, t-butyl Peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxira Rate, t-butylperoxypivalate, t-hexylperoxypivalate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t- Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 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-2,5 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 Etc.

Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile , Azo di-t-octane, azo di-t-butane and the like.
These may be used alone or in combination of two or more. Alternatively, the organic peroxide can be converted to 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 based on 100 parts by weight of the total of the curable components.

4-4. A plasticizer can be added for the purpose of imparting flexibility to the cured plasticizer and improving brittleness. Specific examples of the plasticizer include phthalic acid dialkyl esters such as dioctyl phthalate and diisononyl phthalate, adipic acid dialkyl esters such as dioctyl adipate, sebacic acid esters, azelaic acid esters, phosphoric acid esters such as tricresyl phosphate, and polypropylene Examples include liquid polyether polyols such as glycol, and liquid polyester polyols such as polycaprolactone diol and 3-methylpentanediol adipate.
The proportions of these plasticizers may be set appropriately, but it is preferably 5 to 30 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total of the curable components.
By setting the blending ratio of the plasticizer to 5 parts by weight or more, flexibility is developed, and by setting the blending ratio to 30 parts by weight or less, toughness is maintained.

4-5. Polymerization inhibitor or / and antioxidant The addition of a polymerization inhibitor or / and an antioxidant to the composition of the present invention can improve the storage stability of the composition of the present invention and is preferred.
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 Next antioxidants and 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, with respect to 100 parts by weight of the total amount of 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.
As a UV absorber, 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 and the like.
As a light stabilizer, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N'-diformyl hexamethylene diamine, bis (1,2,6,6) -) Pentamethyl-4-piperidyl) -2- (3,5-ditert-butyl-4-hydroxybenzyl) -2-n-butyl malonate, 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'-diformyl hexamethylene diamine, bis (1,2 And hindered amine light stabilizers such as high molecular weight hindered amine compounds such as 2,2,6,6-pentamethyl-4-piperidinyl) sebacate.
The compounding ratio of the light resistance improver is preferably 0 to 5 parts by weight, more preferably 0 to 1 parts by weight with respect to 100 parts by weight of the total amount of the curable components.

5. Method of Producing Resin Film As a method of producing a resin film using the composition of the present invention, various methods can be adopted according to the purpose, and the following four production methods can be mentioned, for example.
1) Manufacturing method 1
Method of applying a composition to a substrate and irradiating it with light to cure the composition
2) Manufacturing method 2
A method of applying a composition to a substrate and laminating it with another substrate, followed by light irradiation to cure the composition
3) Production method 3
Method of pouring a composition into a substrate having a space and irradiating it with light to cure the composition
4) Production method 4
The composition is poured onto a substrate having a space portion and bonded to another substrate, followed by light irradiation to cure the composition In the case of these production methods, heating may be performed after light irradiation.

5-1. As a base material , any of a peelable base material and a base material having no releasability (hereinafter, referred to as "non-releasing base material") can be used.
Examples of the releasable substrate include metal, glass, a film subjected to mold release treatment, and a surface untreated film having releasability (hereinafter collectively referred to as "mold 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 lower the haze or impart surface smoothness to a resin film obtained from the composition of the present invention, in particular to an optical film, the surface roughness (center line average roughness) Ra is a peelable substrate. It is preferable to use a substrate of 0.15 μm or less, and a substrate of 0.001 to 0.100 μm is more preferable. Furthermore, 3.0% or less is preferable as a haze.
Specific examples of the substrate include glass, surface untreated polyethylene terephthalate film, surface untreated 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 the average roughness.

  Examples of non-releasing base materials include various plastics other than the above, and cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, acrylic resins, polyesters, polycarbonates, polyarylates, polyether sulfones, norbornenes, etc. Cyclic polyolefin resin as a monomer.

As a base material which has a space part, as a base material which has a recessed part, the thing which formed the hole of the predetermined shape made into the target film thickness to a mold release material, and formed the recessed part is mentioned.
In this case, after the composition is poured into a substrate having a recess, another substrate can be overlaid on the substrate having the recess.
As another example of the base material having a space portion, one having a mold (spacer) provided on the mold release material so that the cured product has a desired film thickness (hereinafter referred to as "mold") may also be mentioned. . Again, another substrate can be overlaid on the crucible.
As the mold release material in this case, glass and glass subjected to mold release treatment are preferable.
As an example of a molding die, a molding die composed of two substrates, a substrate excellent in releasability of two sheets, and a substrate for providing one crease (hereinafter referred to as "molding die 1") And a molding die (hereinafter, referred to as “molding die 2”) configured by two substrates and a substrate for providing one crease.
The base material for providing a weir is preferably of a shape having a cavity for injecting the composition on the top. As a base material for providing the said wrinkles, various materials can be used and silicone rubber etc. can be mentioned.
Specific examples of the molding die 1 include a molding die composed of two sheets of glass, two sheets of release-treated film, and a base for providing one crease as a substrate.
The mold 2 is a case where a mold-released glass or metal is used as a base material, and since the mold-release property of the cured product is excellent, two mold-released films are unnecessary.
Moreover, glass can also be used as a base material, when the cured | curing material itself of a composition is excellent in mold release property. As an example in which the cured product of the composition itself is excellent in releasability, an example in which a release agent is blended in the composition can be mentioned.

5-2. Pretreatment of Composition In coating the composition of the present invention, as the composition, the resin film to be obtained is prevented from the inclusion of foreign matter, the occurrence of defects such as voids, or excellent in optical properties. Therefore, it is preferable to use the purified one after stirring and mixing the raw material components.
As a method of purifying the composition, a method of filtering the composition is simple and preferred. As a method of filtration, pressure filtration etc. are mentioned.
The filtration accuracy is preferably 10 μm or less, more preferably 5 μm or less. The smaller the filtration accuracy, the better. However, when the filtration accuracy is too small, the filter tends to be clogged, the frequency of replacement of the filter increases, and the productivity decreases, so the lower limit is preferably 0.1 μm.

In the production of the resin film, in order to prevent the inclusion of air bubbles in the cured product, it is preferable to carry out a defoaming treatment after blending the respective components.
The defoaming method may, for example, be stationary, vacuum pressure reduction, centrifugal separation, cyclone (autorotation / revolution mixer), gas-liquid separation membrane, ultrasonic wave, pressure vibration, defoaming by a multi-screw extruder, or the like.

5-3. Coating or Injection In the case of coating the composition on a substrate, it may be appropriately set according to the purpose, and a conventionally known bar coater, applicator, doctor blade, knife coater, comma coater, reverse roll Examples of the method include coating using a coater, a die coater, a lip coater, a gravure coater, and a microgravure coater.
In the case of injecting the composition into a substrate having a space portion, a method of injecting the composition into an injection device such as a syringe or an injection device may be mentioned.

The film thickness in this case may be appropriately set in accordance with the target film thickness of the resin film described above.
When manufacturing a resin film by the manufacturing method 1 or the manufacturing method 2, it is preferable to coat so that the film thickness after drying an organic solvent etc. may become 5-500 micrometers, More preferably, it is 10-400 micrometers.
In the case of producing a resin film according to production method 3 or production method 4, particularly when used for glass substitute applications, preferably for OPS application, 100 μm to 5 mm is preferable, more preferably 200 μm to 3 mm, and particularly preferably 300 μm to 2 mm is there.

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

5-4. The light irradiation light includes ultraviolet light and visible light, and is preferably ultraviolet light and visible light, and more preferably ultraviolet light in that the cured product can be made into a thick film.
Examples of the ultraviolet irradiation device include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, black light lamps, UV electrodeless lamps, LEDs and the like.
Irradiation conditions such as dose and irradiation intensity in light irradiation may be appropriately set according to the composition to be used, the substrate, the purpose and the like.

5-5. After the irradiation with the heating light, the composition may be heated as necessary for the purpose of further curing the composition.
Examples of the heating method include a method of immersing in heat and a heat medium bath such as oil, a method of using a heat press, and a method of holding in a temperature controlled thermostatic chamber.
Conditions such as the heating temperature in the case of heating may be appropriately set according to the composition to be used, the substrate, the purpose and the like. As heating temperature, 40-250 degreeC is preferable. The heating time may be appropriately set according to the composition to be used, the desired resin sheet, etc., and may be 3 hours or more. The upper limit of the heating time is preferably 24 hours or less in consideration of economy.
Moreover, heating temperature can also be changed according to the objective. For example, the case where the thermal polymerization initiator from which decomposition temperature differs is used etc. is mentioned. As a specific temperature, for example, a method of polymerizing at relatively low temperature of about 40 to 80 ° C. for several hours and then polymerizing at relatively high temperature of 100 ° C. or more for several hours can be mentioned.

5-6. Method for Producing Preferred Resin Film An example of a preferred method for producing a resin film composed of a release material / cured product is shown.
When the composition is of a non-solvent type, the composition is applied to a release agent. When the composition contains an organic solvent and the like, the composition is applied to a release material and then dried to evaporate the organic solvent and the like.
By irradiating the sheet in which the composition layer is formed on the release agent, a resin film composed of the release agent / the cured product is obtained. The light irradiation is usually performed from the composition layer side, but can also be performed from the release material side.
In the above, if a mold release material is used as a substrate, a resin film composed of a mold release material / cured product can be manufactured.
Irradiation conditions such as dose and irradiation intensity in light irradiation may be appropriately set according to the composition to be used, the substrate, the purpose and the like.

  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 of a non-solvent type, the composition is applied to a release agent. When the composition contains an organic solvent and the like, the composition is applied to a release material and then dried to evaporate the organic solvent and the like.
A mold release material is laminated on the composition layer and then irradiated with light or light is irradiated, and then the mold release material is laminated, whereby a resin film in which the mold release material, the cured product and the mold release material are formed in this order is obtained.

Although the example which used the mold release material as a base material above was described, a resin film can also be manufactured using a non-releasing base material.
For example, using a non-releasing base material instead of the above-mentioned mold release material, curing by irradiation with active energy in the same manner as described above to produce a resin film composed of non-releasing base material / cured product it can.
In addition, a non-releasing base material is used as any of the above-mentioned mold release materials, and it is irradiated with light and cured in the same manner as described above, and it is composed of mold release material / hardened product / non-releasing base material. It is also possible to produce a resin film and a resin film composed of non-releasing substrate / cured product / non-releasing substrate.

Moreover, although the example which coats a composition on a base material and manufactures a resin film was mentioned in the said example, when manufacturing a resin film with a large film thickness, it is composition to a base material etc. which has a specific crevice etc. It is also possible to pour a substance and irradiate the light in the same manner as described above to cure the composition to produce a resin film.
Moreover, after pouring a composition into the base material which has a recessed part, and bonding with another base material, it can also be light-irradiated and hardened and a resin film can also be manufactured.
The said manufacturing method is preferable at the point which can manufacture a relatively thick resin film. As a film thickness in this case, 0.5 mm or more and 1.5 mm or less are preferable. The composition used in this case is preferably a solventless composition containing no organic solvent.

6. Applications of Resin Film A resin film formed from the composition of the present invention can be particularly preferably used as an optical film.
Optical films formed from the compositions of the present invention can be used in a variety of optical applications. More specifically, films used for liquid crystal displays such as polarizer protective films of polarizing plates, support films for prism sheets, and light guide films, films used for touch panel integrated liquid crystal displays, various functional films (for example, hard coat) Base film of film, decoration film, transparent conductive film) and film with surface shape (for example, moth-eye type anti-reflection film or film with texture structure for solar cell), light resistance for outdoor use such as solar cell (weather resistance) And the like) films, films for LED illumination and organic EL illumination, 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. As a composition used for this use, the non-solvent type composition which does not contain an organic solvent is preferable at the point which can suppress outgas generation | occurrence | production at the time of vacuum film-forming of a transparent conductive material layer.
Furthermore, since the optical film of the present invention is excellent in heat resistance even if it has a film thickness, has flexibility and high strength, it can also be used as a transparent conductive film substrate for OPS, In the case, an optical film having a thickness of 0.5 mm or more and 1.5 mm or less can be more preferably used.

The method for producing the transparent conductive film may be in accordance with a conventional method.
As metal oxides for forming the transparent conductor layer, indium oxide, tin oxide, zinc oxide, titanium oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, indium-zinc composite Oxide, titanium-niobium complex oxide, etc. may be mentioned. Among these, indium-tin complex oxide and indium-zinc complex oxide are preferable from the viewpoint of environmental stability and circuit processability.
As a method of forming a transparent conductor layer, it may be in accordance with a conventional method, and is formed by sputtering using a vacuum film forming apparatus using the above-mentioned metal oxide using the optical film of the present invention Etc.
More specifically, after the metal oxide is used as a target material, dehydration and degassing are performed, the gas is evacuated and vacuumed, and the optical film is brought to a predetermined temperature, and then a sputtering apparatus is used to form the optical film. The method of forming a transparent conductor layer etc. are mentioned.

Hereinafter, the present invention will be described more specifically by showing Examples and Comparative Examples.
Also, in the following, "parts" means parts by weight, and "%" means% by weight.

1. Production Example 1 [Production of Component (A)]
A mixture of pentaerythritol triacrylate (PETri) and pentaerythritol tetraacrylate (PETet) in a 0.5 L separable flask equipped with a stirrer and an air blowing tube [Alonix M-305 manufactured by Toagosei Co., Ltd.]. Hereinafter, it is called "M-305". 159.2 g (containing 0.3 mol of PETtri and 0.2 mol of PETet), 0.092 g of 2,6-di-tert-butyl-4-methylphenol and 0.055 g of dibutyltin dilaurate, and the liquid temperature is 70 to 75 ° C. Under stirring with stirring, 25.2 g (0.15 mol) of hexamethylene diisocyanate was added dropwise.
After completion of the dropwise addition, the reaction mixture was stirred at 80 ° C. for 3 hours, IR (infrared absorption) analysis of the reaction product confirmed that the isocyanate group had disappeared, and the reaction was terminated. 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 a PETet (a2), and the weight ratio of (a1) to (a2) is (a1) :( a2) = 6: 4. is there.

2. Examples 1 to 3 and Comparative Examples 1 and 2
1) Preparation of Composition The compounds shown in Table 1 were stirred and mixed in the proportions shown in Table 1 to prepare a composition.

2) Production of resin film The composition obtained above is poured into a mold having two glass plates facing each other and a silicone plate having a thickness of 1.0 mm or 0.4 mm as a spacer. Using an ultraviolet irradiator (high-pressure mercury lamp, irradiation intensity of 200 nm / cm ^{2 of} 365 nm (measurement value of UV POWER PUCK manufactured by Fusion UV Systems Japan Ltd.)), integrated light quantity 5J / from one glass plate side After irradiating the ultraviolet ray with cm ² , it was turned over, and the ultraviolet ray was irradiated with an integrated light amount of 5 J / cm ² from the glass plate side of the surface opposite to the above.
After curing, the glass was peeled off to obtain a resin film.
The obtained resin film was evaluated for Tg, flexural modulus and b * 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 became maximum was taken as Tg (glass transition temperature).

b) Bending elastic modulus of resin film The obtained resin film is processed into a test piece of length 25 (mm) × width 10 (mm), and an autograph "AG-5 kNE" manufactured by Shimadzu Corp. (distance between supporting points) The flexural modulus (GPa) was measured at 25 ° C. at 20 mm, 0.5 mm / min).

c) b * of resin film
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).

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

(1) Evaluation method
a) Appearance of ITO Film-Coated Resin Film The appearance of the obtained ITO film-coated resin film was visually observed for the occurrence of wrinkles and evaluated according to the following criteria.
○: no wrinkles ×: wrinkles
b) Resistance of resin film with ITO film Regarding the 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 K 7194 It 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, Lamberti ESACURE KIP 150, molecular weight 424.6 to 643]
· IRG 184 (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 obtained resin film.
Furthermore, the appearance and the film resistance of the resin film with an ITO film obtained from the resin films of Examples 1 and 2 were excellent. 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 that the rigidity of the resin film is insufficient. The appearance after the ITO film formation was poor.
On the other hand, Comparative Example 1 is a composition using a compound having a molecular weight 204 less than the molecular weight 400 as the photopolymerization initiator, and although it is excellent in Tg and flexural modulus of the obtained resin film, photopolymerization start Since the decomposition product of the agent is outgassing, yellowing becomes large and the film quality of the ITO film of the resin film with an ITO film is lowered, so that the resistance can not be sufficiently lowered. Comparative Example 2 is a composition in which the component (A) does not reach 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). Cracking occurred and the flexural modulus could not be evaluated.

  The composition of the present invention can be preferably used for producing 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 (19)

A composition comprising the following components (A), (B) and (C) as essential components,
40 to 95% by weight of component (A) and 5 to 60% by weight of component (B) based on the total amount of component (A) and component (B), and the total of component (A) and component (B) 0.5 to 5 parts by weight of component (C) per 100 parts by weight of
The photocurable composition for resin film or sheet formation whose glass transition temperature of hardened | cured material is 200 degreeC or more.
Component (A): A (meth) acrylate derived from a trivalent or higher aliphatic polyhydric alcohol, which has two or more (meth) acryloyl groups and one or more hydroxyl groups (meth) acrylate and an alicyclic group A (meth) acrylate derived from an addition reaction product (a1) with an aliphatic polyisocyanate having no formula group and an aliphatic polyhydric alcohol having a valence of 3 or more and having three or more (meth) acryloyl groups , Hydroxyl group-free (meth) acrylate (a2)
(Meth) acrylate mixture (B) component: a compound having two or more (meth) acryloyl groups other than the (A) component (C) component: a photopolymerization initiator which is a polymer of hydroxy ketone having a molecular weight of 350 or more Agent   The photocurable composition for resin film or sheet formation of Claim 1 whose glass transition temperature of hardened | cured material is 200-350 degreeC.   The photocurable composition for forming a resin film or sheet according to claim 1 or 2, wherein the component (A) is a mixture containing a weight ratio of (a1) :( a2) = 10: 90 to 75:25. object.   The component (A) is an addition reaction product of (a1) pentaerythritol tri (meth) acrylate and an aliphatic polyisocyanate having no alicyclic group and a mixture of (a2) pentaerythritol tetra (meth) acrylate. The photocurable composition for resin film or sheet formation of any one of Claims 1-3. The component (C) is a compound represented by the following formula (1), The photocurable composition for resin film or sheet formation of any one of Claims 1-4.

In [Equation (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group, n represents the number 2-5. ]   The photocurable composition for resin film or sheet formation of any one of Claims 1-5 which does not contain a polyfunctional mercaptan compound.   The photocurable composition for resin film or sheet formation of any one of Claims 1-6 which do not contain the organic solvent.   The resin film or sheet in which the hardened | cured material of the composition of any one of Claims 1-7 is formed in a film form or sheet form.   The resin film or sheet according to claim 8, wherein the thickness of the cured product is 0.5 mm or more and 1.5 mm or less.   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 conductive layer on one side or both sides of the optical film or sheet according to claim 10.   A transparent conductive film or sheet for a touch panel, comprising a transparent conductive layer on one side or both sides of the optical film or sheet according to claim 10. The manufacturing method of the resin film or sheet which irradiates light from the surface or substrate side which poured in after pouring the composition of any one of Claims 1-7 into the base material which has a space part. After pouring the composition of any one of Claims 1-7 into the base material which has a space part, after bonding another base material to the poured-in side, either substrate side A method of producing a resin film or sheet which emits light from the above.   The method for producing a resin film or sheet according to claim 14, wherein one or both of the substrate having the space portion and the other substrate is a peelable substrate.   The resin film or sheet which irradiates light from the coated surface side or the film or sheet-like base material side, after applying the composition of any one of Claims 1-7 to a film or sheet-like base material. 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.   The 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 coated surface of the composition, and then the sheet-like substrate is formed. The manufacturing method of the resin film or sheet which irradiates light from any 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.