JP5307511B2 - Radical polymerizable resin composition for film formation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film-forming radically polymerizable resin composition which excels in workability and handling properties and can form a film having a low refractive index, good flexibility, and high hardness. <P>SOLUTION: The film-forming radically polymerizable resin composition contains a resin (A) having a polysiloxane structure and two or more polymerizable unsaturated double bonds in the molecule and a fluorine-containing polymerizable unsaturated monomer (B) represented by formula (I) at a compounding mass ratio of the resin (A) to the fluorine-containing polymerizable unsaturated monomer (B) in the range of 2/98 to 50/50. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a film-forming radical polymerizable resin composition capable of forming a film having a low refractive index.

  For optical products such as liquid crystal displays, for example, a high refractive index resin layer (hereinafter referred to as “high refractive index resin layer”) is formed on the surface of the image display unit in order to prevent contrast reduction and image reflection due to reflection of external light. And a functional layer such as a low refractive index resin layer (hereinafter referred to as “low refractive index resin layer”).

  Conventionally, among such functional layers, a low refractive index resin layer often contributes greatly to improving the visibility of images and the like, and therefore, development of a resin composition capable of forming a low refractive index resin layer has been made. It is being advanced.

  As an example of a resin composition capable of forming a low refractive index resin layer, for example, a specific fluorine-containing di (meth) acrylic acid ester, a specific fluorine-containing (meth) acrylic acid ester and / or a specific fumaric acid diester A fluorine-curable coating liquid containing a polymer obtained by polymerization in combination with is known (see, for example, Patent Document 1).

  However, the polymer contained in this fluorine curable coating solution is soluble in a specific organic solvent such as trifluoromethylbenzene, but is difficult to handle in general-purpose esters and ketones, so it is easy to handle. It was not. Furthermore, when forming a film using a fluorine curable coating liquid, in order to advance radical polymerization of the resin composition to a practically sufficient level, it is necessary to irradiate with an electron beam, and industrial production efficiency is high. There wasn't.

  Other examples of the resin composition capable of forming a low refractive index resin layer include, for example, fluorine-containing polyfunctional (meth) acrylic acid esters, silane coupling agents having a (meth) acryloyloxy group, and fluorine-containing compounds. A fluorine-containing curable coating liquid containing colloidal silica modified with a silane coupling agent is known (for example, see Patent Document 2).

  However, in order to form a cured coating film using a fluorine-containing curable coating liquid, for example, ultraviolet irradiation may be necessary in a low oxygen concentration atmosphere such as a nitrogen atmosphere, and the efficiency of the film formation work There was a problem in trying to make it easier.

By the way, the material for optical applications may not only form a resin layer having a predetermined refractive index, but also may require an appropriate hardness according to the usage scene.
For example, in a technical field related to an optical waveguide, a material having a low refractive index may be used as a clad portion constituting the optical waveguide. The material constituting the clad portion is required to have a low refractive index and good flexibility.

  In addition, among the technical fields related to image display devices, organic EL display materials may require low flexibility and good flexibility. On the other hand, materials for plasma displays and liquid crystal displays may be required to have a low refractive index and a certain degree of hardness.

As described above, there is a demand from the industry for a resin composition that has a low refractive index and can arbitrarily adjust the hardness and flexibility of the coating film depending on the application.
However, with conventional resin compositions, it is often difficult to arbitrarily adjust the hardness of the coating if the low refractive index of the coating is to be maintained. As a result, it is necessary to respond to various requests from customers. There was a case that could not be.
JP-A-8-48935 JP 2001-262011 A

The present invention has been made in view of the above circumstances, and an object thereof is to provide a film-forming radical polymerizable resin composition that is excellent in workability and handleability and can form a low refractive index film. To do.
Another object of the present invention is to provide a film-forming radical polymerizable resin composition capable of forming a low refractive index film having good flexibility.
It is another object of the present invention to provide a film-forming radical polymerizable resin composition capable of forming a film having a high hardness and a low refractive index.

While the present inventors have studied in order to solve the above problems, various fluorine atom-containing polymerizable monomers are combined with a polysiloxane resin that has been conventionally known as a material capable of forming a resin layer having a low refractive index. Therefore, we considered that the refractive index could be further reduced, and proceeded with the study. However, many fluorine atom-containing polymerizable monomers are difficult to be compatible with the polysiloxane resin, and thus may be difficult to handle industrially.
Accordingly, as a result of further studies to solve the above problems, the present inventors have made a combination of a fluorine atom-containing polymerizable monomer having a specific structure and a resin having a specific polysiloxane structure. The composition was found to be excellent in compatibility and capable of forming a cured resin layer having a low refractive index, thereby completing the present invention.
In addition, as a result of investigations to solve the above problems, the present inventors have further found that one homopolymer having a glass transition temperature of −30 ° C. or lower can be formed on the resin composition. Monomer having a radically polymerizable unsaturated double bond, a polymer having one polymerizable unsaturated double bond and a glass transition temperature of -30 ° C. or lower, or 3 or more polymerizable unsaturateds It has been found that by adding a crosslinking agent having a double bond, the hardness of the cured resin layer obtained by the resin composition can be arbitrarily adjusted, and the present invention has been completed.

That is, the present invention relates to a resin (A) having a polysiloxane structure and two or more polymerizable unsaturated double bonds in the molecule, and a fluorine atom-containing polymerizable compound represented by the following general formula (I). It contains a saturated monomer (B), and the resin (A) is one or more selected from the group consisting of urethane (meth) acrylate (a1) and epoxy (meth) acrylate (a2). There, the resin (a) and the fluorine atom-containing polymerizable unsaturated film-forming radical polymer, characterized in that blending weight ratio in the range of 2 / 98-50 / 50 and the monomer (B) A functional resin composition is provided.

However, in the above general formula (I), _{R 1} is H or _CH 3, _{R 2} represents H or F, n = 1 to 3 integers, m = 1 to 4 integer.

  According to the radically polymerizable resin composition for film formation of the present invention, a cured resin having a low refractive index can be obtained without complicated operations and handling. In addition, the cured resin obtained using the radical-polymerizing resin composition for film formation according to the present invention is excellent in transparency and its hardness can be adjusted arbitrarily, so that, for example, optical components such as liquid crystal displays and optical waveguides can be used. Can be used for product applications.

The best mode of the radically polymerizable resin composition for film formation of the present invention will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

  The radically polymerizable resin composition for film formation of the present invention comprises a resin (A) having a polysiloxane structure and two or more polymerizable unsaturated double bonds in the molecule, and the following general formula (I): It contains the fluorine atom-containing polymerizable unsaturated monomer (B) shown, and the blending mass ratio of the resin (A) and the fluorine atom-containing polymerizable unsaturated monomer (B) is 2 / 98-50. / 50, and contains other additives as required.

However, in the above general formula (I), _{R 1} is H or _CH 3, _{R 2} represents H or F, n = 1 to 3 integers, m = 1 to 4 integer.

The radical-polymerizing resin composition for film formation of the present invention has a specific resin (A) and a specific fluorine atom-containing polymerization in forming a relatively low refractive index cured product having a refractive index of about 1.45 or less. It is essential to use the unsaturated unsaturated monomer (B) in combination.
Here, the refractive index in the present invention refers to a cured product formed by almost completely curing a film-forming radical polymerizable resin composition in a 25 ° C. environment under a measuring instrument (universal Abbe refractometer, It is a refractive index measured using ERMA Inc.).

Moreover, the radically polymerizable resin composition for film formation of the present invention is not simply a combination of the resin (A) and the fluorine atom-containing polymerizable unsaturated monomer (B). The blending mass ratio of A) to the fluorine atom-containing polymerizable unsaturated monomer (B) is in the range of 2/98 to 50/50, and the blending mass ratio is in the range of 4/96 to 30/70. More preferably. If this blending mass ratio is in the range of 4/96 to 30/70, it becomes possible to further reduce the refractive index of the cured product obtained from the film-forming radical polymerizable resin composition.
Further, when the blending mass ratio of the resin (A) and the fluorine atom-containing polymerizable unsaturated monomer (B) is outside the range of 2/98 to 50/50, the refractive index is generally 1.45 or less. Rate cured product may not be formed.

  The resin (A) constituting the radical-polymerizing resin composition for film formation of the present invention is a resin having a polysiloxane structure in the main chain, and has two or more polymerizable unsaturated double bonds in the molecule. Is.

As the resin (A), in order to obtain a film-forming radical polymerizable resin composition capable of forming a cured product having a low refractive index, it is essential to use a resin having a polysiloxane structure in the main chain.
The polysiloxane structure is a chain structure composed of a bond of a silicon atom and an oxygen atom.
As the resin (A), a resin in which an alkyl group such as a methyl group is bonded to a silicon atom can be used as necessary.

  Here, when a resin having no polysiloxane structure is used instead of the resin (A), the refractive index of the cured product formed using the resin composition containing the resin not having the polysiloxane structure is It becomes approximately 1.46 or more, and the refractive index of this cured product may not be adjusted to 1.45 or less.

Moreover, it is preferable that the ratio of a polysiloxane structure is the range of 35-95 mass% with respect to the whole resin (A), More preferably, it is 40-90 mass%.
When the ratio of the polysiloxane structure to the entire resin (A) is within this range, a radically polymerizable resin composition for film formation capable of forming a cured product having a low refractive index can be obtained.

Resin (A) has two or more polymerizable unsaturated double bonds in the molecule.
These polymerizable unsaturated double bonds present in the resin (A) are the polymerizable unsaturated double bonds of the fluorine atom-containing polymerizable unsaturated monomer (B) described later, or the resin (A). It radically polymerizes with other polymerizable unsaturated double bonds possessed by and contributes to the formation of a cured product.
Moreover, since the radically polymerizable resin composition for film formation of this invention contains resin (A), the hardening reaction can fully be advanced by the ultraviolet irradiation in the air. Therefore, it is not necessary to perform ultraviolet irradiation under specific conditions such as in a nitrogen atmosphere as in the prior art.

The number of polymerizable unsaturated double bonds is 2 or more, preferably 3 or more, more preferably 3 to 10 with respect to the main chain of the resin (A).
When the number of polymerizable unsaturated double bonds with respect to the main chain of the resin (A) is within this range, the reactivity of the radical polymerization reaction of the film-forming radical polymerizable resin composition can be improved.

Moreover, it is preferable that the number average molecular weights of resin (A) are 1000-5000, More preferably, it is 1000-3000.
When the number average molecular weight of the resin (A) is within this range, the transparency of the cured product obtained from the film-forming radical polymerizable resin composition can be improved.

  Specifically, as the resin (A), a urethane (meth) acrylate (a1) having a polysiloxane structure having a predetermined polymerizable unsaturated double bond, and an epoxy (meth) acrylate having a polysiloxane structure One or more selected from the group consisting of (a2) are used.

The urethane (meth) acrylate (a1) includes a polyurethane containing two or more isocyanate groups produced by reacting a polysiloxane having active hydrogen atom-containing groups at both molecular terminals and a polyisocyanate, and an active hydrogen atom-containing group. It is produced by reacting with a (meth) acrylate having bismuth and having two or more polymerizable unsaturated double bonds in the molecule.
Examples of the polysiloxane include a chain having an active hydrogen atom-containing group such as a hydroxyl group, a carboxyl group, or an amino group at both molecular ends.
Moreover, as (meth) acrylate, what has active hydrogen atom containing groups, such as a hydroxyl group, a carboxyl group, and an amino group, is mentioned.
Here, the reaction ratio between the active hydrogen atom-containing group of the polysiloxane and the isocyanate group of the polyisocyanate is within a range of [isocyanate group / active hydrogen atom-containing group] = 1.1 to 1.5. preferable.

  Examples of the polysiloxane having an active hydrogen atom-containing group in the molecule that can be used in the production of the urethane (meth) acrylate (a1) include an active hydrogen atom-containing group directly bonded to a silicon atom constituting the polysiloxane chain. And those in which a silicon atom and an active hydrogen atom-containing group are bonded via an organic group such as an alkylene group.

  Here, in the resin composition using urethane (meth) acrylate prepared using polyalkylene oxide instead of polysiloxane, the refractive index of the film (cured product) formed using the resin composition is It is difficult to reduce it to about 1.45 or less. On the other hand, if urethane (meth) acrylate (a1) prepared using the above polysiloxane is used, a film-forming radical polymerizable resin composition capable of forming a cured product having a low refractive index can be obtained.

Examples of the polysiloxane include polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polyethylphenylsiloxane, and polydiphenylsiloxane.
Among these polysiloxanes, from the viewpoint that the refractive index of the cured product comprising the radical-polymerizing resin composition for film formation of the present invention can be further reduced, from a silicon atom to which two or more alkyl groups are bonded. Polydimethylsiloxane, polydiethylsiloxane, and polyethylmethylsiloxane are preferred, and polydimethylpolysiloxane is particularly preferred.

The molecular weight of the polysiloxane is preferably 700 to 4500, more preferably 900 to 2700.
When the molecular weight of the polysiloxane is within this range, a film-forming radical polymerizable resin composition that is excellent in transparency and can form a cured product having a low refractive index can be obtained.

  Although it does not specifically limit as a commercial item of the polysiloxane which has an active hydrogen atom containing group applicable to the radically polymerizable resin composition for film formation of this invention, For example, X-22-160AS by Shin-Etsu Chemical Co., Ltd. KF-6001, KF-6002, and FZ-2191 manufactured by Toray Dow Corning.

  The polyisocyanate used for producing the urethane (meth) acrylate (a1) will be described.

  Examples of the polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, 2,4-tolylene diisocyanate, isomers of 2,4-tolylene diisocyanate, and isomers of these isomers. Mixture, diisocyanate such as 4,4-diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”), xylylene diisocyanate, norbornene diisocyanate, and the above-mentioned diisocyanates and trihydric or higher aliphatic polyhydric alcohols such as trimethylolpropane. Adducts, isocyanurate structures that are trimers of diisocyanates, burettes formed by the reaction of diisocyanates and water, or polymers Tsu, such as click MDI is used.

  The polyisocyanate has two or more isocyanate groups from the viewpoint of preventing discoloration of a cured product obtained using the radically polymerizable resin composition for film formation of the present invention and further reducing the refractive index. It is preferable to use an aliphatic polyisocyanate. From the viewpoint of improving the compatibility between the urethane (meth) acrylate (a1) and the fluorine atom-containing polymerizable unsaturated monomer (B), it is more preferable to use a polyisocyanate having a cyclohexane ring. .

  The (meth) acrylate having an active hydrogen atom-containing group used for producing the urethane (meth) acrylate (a1) will be described.

The (meth) acrylate having an active hydrogen atom-containing group is used when a polymerizable unsaturated double bond is introduced into the resin (A).
Here, instead of the (meth) acrylate having an active hydrogen atom-containing group, a radical polymerization reaction proceeds rapidly even when an active hydrogen-containing compound having no polymerizable unsaturated group, such as diethylene glycol, which is generally known, is used. I can't let you.

  As the (meth) acrylate having an active hydrogen atom-containing group, one having at least one polymerizable unsaturated double bond is preferably used. From the viewpoint of promptly proceeding the radical polymerization reaction, the polymerizable unsaturated double bond is used. It is more preferable to use one having 2 to 5 bonds.

Examples of the (meth) acrylate having an active hydrogen atom-containing group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, or addition of ethylene oxide thereof. , Propylene oxide adduct, ε-caprolactan adduct, ε-caprolactam adduct, or trimethylolpropane di (meth) acrylate, trimethylolpropane methacrylate, acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra ( One or more selected from (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. The top is used.
Among these (meth) acrylates, trimethylolpropane di (meth) acrylate, trimethylolpropane methacrylic acid, from the viewpoint of improving the reactivity of the radical curing reaction of the film-forming radical-curable resin composition of the present invention. It is preferable to use rate acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hepta (meth) acrylate, or the like. In particular, when the radical polymerization reaction is allowed to proceed by ultraviolet irradiation, it is preferable to use trimethylolpropane diacrylate, trimethylolpropane methacrylate acrylate, pentaerythritol triacrylate, dipentaerythritol heptaacrylate, or the like.

  Moreover, when producing | generating urethane (meth) acrylate (a1), it has an active hydrogen atom containing group for the purpose of preventing that the radical curable resin composition for film formation of this invention inhibits hardening by air (meta ) In addition to acrylate, a hydroxyl group-containing allyl ether compound may be used in combination.

  Examples of the hydroxyl group-containing allyl ether compound include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, and tripropylene glycol. Monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, Many types such as glyceryl diallyl ether and pentaerythritol triallyl ether Allyl ether compounds alcohols are used.

  Moreover, when producing | generating urethane (meth) acrylate (a1), 2- (meta) which has a polymerizable unsaturated double bond and an isocyanate group instead of polyisocyanate and (meth) acrylate which has an active hydrogen atom containing group. ) Acryloyloxyethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate, Karenz MOI-EG manufactured by Showa Denko KK and the like can also be used.

  Urethane (meth) acrylate (a1) can be produced by the following two-step reaction process.

  The first stage reaction step is a step of producing a polyurethane having a polysiloxane structure by reacting 1 equivalent of a hydroxyl group of polysiloxane with 2 equivalents or more of an isocyanate group of polyisocyanate.

The first-stage reaction step is preferably performed in a range of room temperature to about 100 ° C. in a nitrogen atmosphere.
Moreover, although this reaction process can also be performed under a non-solvent, an organic solvent and a fluorine atom containing polymerizable unsaturated monomer (B) can also be used as a solvent as needed.

In the first reaction step, a catalyst may be used as necessary.
Examples of the catalyst include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, organotin compounds such as tin octylate, dibutyltin oxide, and sibutyltin dilaurate, and further, stannous chloride, stannous bromide Known catalysts such as acids and alkalis such as tin and stannous iodide can be used.
It is preferable that the addition amount of a catalyst is 10-10000 ppm with respect to the whole preparation amount of the raw material of urethane (meth) acrylate (a1).

  The second stage reaction step includes an isocyanate group possessed by the polyurethane produced in the first stage reaction step and an active hydrogen atom-containing group such as a hydroxyl group possessed by a (meth) acrylate having an active hydrogen atom-containing group. This is a reaction step.

  The (meth) acrylate having an active hydrogen atom-containing group is in the range of 1 to 1.5 equivalents of an active hydrogen atom-containing group such as a hydroxyl group of the (meth) acrylate with respect to 1 equivalent of the isocyanate group of the polyurethane. It is preferable to use in proportion.

The second stage reaction step is preferably carried out in an air atmosphere in the range of room temperature to 90 ° C.
Moreover, although this reaction process can also be performed under a non-solvent, an organic solvent and a fluorine atom containing polymerizable unsaturated monomer (B) can also be used as a solvent as needed.

In the second stage reaction step, a catalyst similar to the catalyst that can be used in the first stage reaction step may be used as necessary.
In addition, during the second stage reaction step, a radical polymerization inhibitor is added as necessary for the purpose of preventing gelation due to radical polymerization reaction of the polymerizable unsaturated double bond of the urethane (meth) acrylate (a1). Can be used.

As the radical polymerization inhibitor, for example, hydroquinone monomethyl ether, dt-butyl hydroquinone, pt-butyl catechol, phenothiazine and the like are used.
The addition amount of the radical polymerization inhibitor is preferably 10 to 10,000 ppm with respect to the total amount of raw materials of the urethane (meth) acrylate (a1).

The epoxy (meth) acrylate (a2) used as the resin (A) will be described.
Examples of the epoxy (meth) acrylate (a2) include those obtained by reacting an epoxy group-containing polysiloxane with a polymerizable unsaturated double bond-containing monocarboxylic acid such as (meth) acrylic acid, or a carboxyl group. Those obtained by reacting the containing polysiloxane with an epoxy group and a polymerizable unsaturated double bond-containing compound are used.

As the epoxy group-containing polysiloxane, for example, a compound in which a silicon atom of dimethylpolysiloxane and an epoxy group are bonded via an organic group is used. Among these compounds, those having an epoxy equivalent of 400 to 2500 are used. It is preferable to use it.
Specific examples of the epoxy group-containing polysiloxane include KF-105, X-22-163A, and X-22-163B manufactured by Shin-Etsu Chemical Co., Ltd.

  Examples of the polymerizable unsaturated double bond-containing monocarboxylic acid that can react with the epoxy group-containing polysiloxane include monocarboxylic acids such as acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, and sorbic acid, monomethyl malate, Unsaturated dicarboxylic acid monoalkyl esters such as monomethyl fumarate, monopropyl malate, monobutyl malate, or mono (2-ethylhexyl) malate are used.

  In addition, as the carboxyl group-containing polysiloxane, for example, a compound in which a silicon atom of dimethylpolysiloxane and a carboxyl group are bonded via an organic group is used, and among these compounds, the carboxyl group equivalent is 400 to 2500. It is preferable to use those.

  Specific examples of the carboxyl group-containing polysiloxane include X-22-162C manufactured by Shin-Etsu Chemical Co., Ltd.

  Examples of the epoxy group capable of reacting with the carboxyl group-containing polysiloxane and the polymerizable unsaturated double bond-containing compound include glycidyl (meth) acrylate.

The fluorine atom-containing polymerizable unsaturated monomer (B) will be described.
As the fluorine atom-containing polymerizable unsaturated monomer (B), those having a specific structure represented by the following general formula (I) are used.
For example, instead of the fluorine atom-containing polymerizable unsaturated monomer (B), 2-perfluorohexylethyl (meth) acrylate and 2-perfluorooctylethyl (meth) acrylate not included in the following general formula (I) Even if a fluorine atom-containing polymerizable unsaturated monomer such as is used, the radical polymerization reaction may not proceed rapidly.

However, in the above general formula (I), _{R 1} is H or _CH 3, _{R 2} represents H or F, n = 1 to 3 integers, m = 1 to 4 integer.

  Specific examples of the fluorine atom-containing polymerizable unsaturated monomer (B) include 2,2,2-trifluoroethyl (meth) acrylate and 2,2,3,3-tetrafluoropropyl (meth) acrylate. 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, and the like. Among these fluorine atom-containing polymerizable unsaturated monomers (B), 2,2,2-trifluoroethyl (meth) acrylate is excellent in compatibility with the resin (A) and promptly performs radical polymerization reaction. This is particularly preferable because it can be advanced.

Next, the manufacturing method of the radically polymerizable resin composition for film formation of this invention is demonstrated.
The film-forming radical polymerizable resin composition of the present invention is, for example, a resin (A) and a fluorine atom-containing polymerizable unsaturated monomer (B) mixed together in a container adjusted to 60 ° C., Manufactured by stirring.
In addition, you may use a fluorine atom containing polymerizable unsaturated monomer (B) as a solvent at the time of producing | generating resin (A).

  Moreover, when using the various additives mentioned later, it is preferable to mix and stir an additive collectively with resin (A) and a fluorine atom containing polymerizable unsaturated monomer (B).

The radically polymerizable resin composition for film formation of the present invention is exclusively used for film formation. Specifically, a coating film is formed on the surface of the substrate by applying the radical-polymerizing resin composition for film formation of the present invention to the surface of various substrates and curing it.
Further, by applying the radical-polymerizing resin composition for film formation of the present invention to the surface of various base materials, and then placing another base material on the coating surface and curing it, [base material layer / It is possible to form a laminate composed of a cured resin layer / base material layer].
In addition, after coating and curing the film-forming radical polymerizable resin composition of the present invention on the surface of various substrates, the coating obtained by peeling the cured product from the surface of the substrate is used as a film or It can be used as a sheet or the like.

  When the hardness of the film formed using the radically polymerizable resin composition for film formation of the present invention is increased, for example, when a film that can be used for an image display device of a plasma display or a liquid crystal display is formed, the resin (A) In addition to the fluorine atom-containing polymerizable unsaturated monomer (B), it is preferable to further add a crosslinking agent having three or more polymerizable unsaturated double bonds.

  As the crosslinking agent, (meth) acrylate having 3 or more (meth) acrylate groups is used, for example, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dihexaerythritol hexa (meth). Examples include acrylate, dihexaerythritol tetra (meth) acrylate, dihexaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and ditrimethylolpropane tri (meth) acrylate.

It is preferable that the compounding quantity of a crosslinking agent is 10-20 mass parts with respect to a total of 100 mass parts of resin (A) and a fluorine atom containing polymerizable unsaturated monomer (B).
If the compounding quantity of a crosslinking agent exists in this range, the refractive index of the hardened | cured material obtained using the radically polymerizable resin composition for film formation of this invention can be maintained low.

  In addition, the film formed using the radical-polymerizing resin composition for film formation of the present invention may require chemical resistance, heat resistance, solvent resistance, etc. in addition to low refractive index. . These characteristics can be achieved by maintaining the refractive index of the coating and increasing the hardness of the coating.

  Examples of the film-forming radical polymerizable resin composition capable of forming such a film include, in addition to the resin (A) and the fluorine atom-containing polymerizable unsaturated monomer (B), three or more ( It is preferable to use one containing a crosslinking agent having a (meth) acrylate group.

On the other hand, in addition to having a low refractive index, a film formed using the radical-forming resin composition for film formation may be required to have good flexibility.
Examples of the film-forming radical polymerizable resin composition capable of forming such a film include, in addition to the resin (A) and the fluorine atom-containing polymerizable unsaturated monomer (B), and further a temperature of −30 ° C. or lower. A monomer having one radically polymerizable unsaturated double bond capable of forming a homopolymer having a glass transition temperature, one polymerizable unsaturated double bond, and a glass transition temperature of −30 ° C. or lower; It is preferable to use one containing at least one selected from the group consisting of polymers having a

  Examples of the monomer having one radical polymerizable unsaturated double bond capable of forming a homopolymer having a glass transition temperature of −30 ° C. or lower include isodecyl (meth) acrylate, n-lauryl (meth) acrylate, Tridecyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butyl acrylate, 2-ethylhexyl acrylate, isoamyl acrylate, methoxyethyl acrylate, ethoxyethyl methacrylate, hydroxyethyl (meth) acrylate, and Those ethylene oxide adducts, propylene oxide adducts, ε-caprolactam adducts, acrylonitrile and the like are used.

Moreover, as a monomer which has one radical polymerizable unsaturated double bond which can form the homopolymer which has a glass transition temperature of -30 degrees C or less, (meth) acryloyl group, styryl group, aryl group, vinyl ether group And the like having a compound at the end of the molecule.
The polymer having one (meth) acryloyl group and a glass transition temperature of −30 ° C. or lower contains a carboxyl group having a glass transition temperature of −30 ° C. or lower in the presence of a chain transfer agent such as mercaptoacetic acid. It can be produced by reacting a polymer with glycidyl (meth) acrylate or the like.

The polymer having one styryl group and a glass transition temperature of −30 ° C. or lower is obtained by reacting, for example, a neutralized carboxyl group of a carboxyl group-containing polymer with chloromethylstyrene. Can be generated.
In addition, a polymer having one aryl group and a glass transition temperature of −30 ° C. or lower can be produced, for example, by reacting a carboxyl group-containing polymer with an aryl glycidyl ether.
In addition, a polymer having one vinyl ether group and a glass transition temperature of −30 ° C. or lower is, for example, a hydroxyl group-containing polymer, a diisocyanate such as tolylene diisocyanate, and butanediol in the presence of a chain transfer agent such as mercaptoethanol. It can be produced by reacting with glycol monovinyl ether such as monovinyl ether.

The number average molecular weight of the polymer having one polymerizable unsaturated double bond and a glass transition temperature of −30 ° C. or lower is preferably 1000 to 40000, and more preferably 2000 to 25000.
In addition, the number average molecular weight in this invention is a number average molecular weight of polystyrene conversion by gel permeation chromatography (GPC).

  In addition, as a polymer having one polymerizable unsaturated double bond and a glass transition temperature of −30 ° C. or lower, one (meth) acryloyl group and a glass transition temperature of −30 ° C. or lower are used. It is preferable to use the polymer which has, and specifically, it is preferable to use macromonomer AB-6 (methacryloyl group containing polybutylacrylate) by Toagosei Co., Ltd.

A monomer having one radical polymerizable unsaturated double bond capable of forming a homopolymer having a glass transition temperature of −30 ° C. or less, and one polymerizable unsaturated double bond, and −30 ° C. or less The blending amount of the polymer having a glass transition temperature of 10 to 20 parts by mass with respect to 100 parts by mass in total of the resin (A) and the fluorine atom-containing polymerizable unsaturated monomer (B). Is preferred.
A monomer having one radical polymerizable unsaturated double bond capable of forming a homopolymer having a glass transition temperature of −30 ° C. or less, and one polymerizable unsaturated double bond, and −30 ° C. or less If the blending amount of the polymer having a glass transition temperature within this range is within this range, the low refractive index and improved flexibility of the cured product obtained by using the radical-polymerizing resin composition for film formation of the present invention. Can be compatible.

  The radical-polymerizing resin composition for film formation of the present invention is cured by any of the curing methods of curing by active energy rays, heat curing by using a peroxide, and room temperature curing by using a peroxide and a reducing agent. be able to. In addition, the radically polymerizable resin composition for film formation of the present invention is not cured only by ultraviolet irradiation under a specific environment such as a nitrogen atmosphere, but can be cured sufficiently by ultraviolet irradiation in an air atmosphere. In this respect, there is an advantage over the prior art.

  When the radically polymerizable resin composition for film formation of the present invention is cured by active energy rays, it is preferable to use a photopolymerization initiator as a curing agent.

  Examples of the photopolymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, Thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxy Cyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone Which acetophenones; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 Acylphosphine oxides such as 1,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate, 1,7-bisacridinylheptane, 9-phenylacridine and the like Is used.

  When the radically polymerizable resin composition for film formation of the present invention is cured by active energy rays, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, 4-dimethylaminobenzoate, together with a photopolymerization initiator as necessary. Known photosensitizers such as methyl acid, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone may be used.

  When the film-forming radical polymerizable resin composition of the present invention is cured by heating, examples of the curing agent include diacyl peroxide, peroxy ester, hydroperoxide, dialkyl peroxide, and ketone peroxide. Peroxyketal-based, alkyl perester-based and percarbonate-based peroxides are used.

  In addition, when the film-forming radical polymerizable resin composition of the present invention is cured at room temperature, a peroxide and an organic metal salt such as cobalt naphthenate or cobalt octenoate which are curing accelerators, dimethylaniline or diethylaniline are used. , And aromatic amine compounds such as paratoluidine can be used in combination.

  It is preferable that the compounding quantity of a hardening | curing agent is 0.1-10 mass parts with respect to 100 mass parts of the radically polymerizable resin composition for film formation of this invention, More preferably, it is 1-6 mass parts. .

Moreover, the polymerization inhibitor for film formation of this invention may add a polymerization inhibitor as needed.
As the polymerization inhibitor, for example, trihydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, toluhydronone, p-tert-butylcatechol, 2,6-tert-butyl-4-methylphenol and the like are used.
It is preferable that the compounding quantity of a polymerization inhibitor is 10-1000 ppm in the radically polymerizable resin composition for film formation of this invention.

  In addition, the radically polymerizable resin composition for film formation of the present invention includes generally known polymerizable unsaturated monomers, unsaturated polyester resins, epoxy acrylate resins, within a range not impairing the effects of the present invention. Polyurethane resins, acrylic resins, alkyd resins, urea resins, melamine resins, polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyester resins, saturated polyethers, celluloses and their derivatives, fats and oils In addition, other conventional natural and synthetic polymer compounds, ionic compounds such as inorganic fillers and antistatic agents of condensates of alkoxylanes can also be added.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.

"Synthesis Example 1" Preparation of urethane acrylate (A-1) having a structure derived from polysiloxane In a four-necked flask with a capacity of 2 liters equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, Polysiloxane having a hydroxyl group (trade name: FZ-2191, hydroxyl value: 45.9, manufactured by Toray Dow Corning) was charged in 24 parts by mass (0.02 mol), and isophorone diisocyanate was 144.3 parts by mass (0.65 mol). In addition, the reaction was carried out at 80 ° C. for 2 hours while suppressing the exotherm.

After confirming that the equivalent of the isocyanate group was 131.5, which was almost the same as the theoretical value when all the hydroxyl groups of the polysiloxane reacted with the isocyanate group, the mixture was cooled to 50 ° C. and dipentaerythritol pentaacrylate (product) Name: SR-399E (manufactured by Sartomer) 1600 parts by mass (3.1 mol) was added, 0.02 part by mass of tin catalyst was added as a reaction promoting catalyst, and the mixture was reacted at 90 ° C. for 7 hours in an air atmosphere.
And after an unreacted isocyanate group became 0.3 mass% or less, the urethane acrylate (A-1) of the number average molecular weight 1968 which has a structure derived from polysiloxane is added by adding 0.1 mass part of hydroquinone. Obtained.

“Synthesis Example 2” Preparation of urethane acrylate (A-2) having a structure derived from polysiloxane In a four-necked flask with a capacity of 1 liter equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 37 parts by mass (0.03 mol) of a polysiloxane having a hydroxyl group (trade name: FZ-2191, hydroxyl value: 45.9, manufactured by Toray Dow Corning) was added, and 206 parts by mass (1 mol) of norbornene diisocyanate was added to generate heat. The reaction was allowed to proceed at 80 ° C. for 2 hours.

After confirming that the equivalent of the isocyanate group was 123, which was almost the same as the theoretical value when all the hydroxyl groups of the polysiloxane reacted with the isocyanate group, it was cooled to 50 ° C. and 375 parts by mass of pentaerythritol triacrylate ( 1.26 mol) and 122 parts by mass (1.05 mol) of 2-hydroxyethyl acrylate were added, 0.02 parts by mass of tin catalyst was added as a reaction promoting catalyst, and the mixture was reacted at 90 ° C. for 7 hours in an air atmosphere.
And after an unreacted isocyanate group became 0.3 mass% or less, the urethane acrylate (A-2) of the number average molecular weight 1842 which has a structure derived from polysiloxane is added by adding 0.1 mass part of hydroquinone. Obtained.

“Synthesis Example 3” Preparation of Urethane Acrylate (A-3) Having Structure Derived from Polysiloxane A hydroxyl group was added to a two-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. Dimethylpolysiloxane (trade name: X22-160A, number average molecular weight: 935, manufactured by Shin-Etsu Chemical Co., Ltd.) is charged in 468 parts by mass (0.5 mol), and isophorone diisocyanate (IPDI) is added in 222 parts by mass (1 mol). The reaction was carried out at 80 ° C. for 5 hours while suppressing the exotherm.

Since the equivalent of the isocyanate group was 690, which was almost the same as the theoretical value when all the hydroxyl groups of the polysiloxane reacted with the isocyanate group, and stabilized, the mixture was cooled to 40 ° C. and 188 parts by mass (0.63 mol) of pentaerythritol triacrylate. Then, 61 parts by mass (0.53 mol) of 2-hydroxyethyl acrylate was added, 0.02 part by mass of tin catalyst was added as a reaction promoting catalyst, and the reaction was carried out at 90 ° C. for 7 hours in an air atmosphere.
And after an unreacted isocyanate group became 0.3 mass% or less, the urethane acrylate (A-3) of the number average molecular weight 1793 which has a structure derived from polysiloxane is added by adding 0.05 mass part of hydroquinone. Obtained.

Synthesis Example 4 Preparation of Epoxy Acrylate (A-4) Having Structure Derived from Polysiloxane Epoxy was added to a two-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. 980 parts by weight (1 mol) of dimethylpolysiloxane having a group (trade name: KF-105, number average molecular weight: 980, manufactured by Shin-Etsu Chemical Co., Ltd.), 144 parts by weight (2 mol) of acrylic acid, and 110 ° C. For 8 hours.
Since the acid value became 4 and stabilized, an epoxy acrylate (A-4) having a number average molecular weight of 1124 having a polysiloxane-derived structure was obtained by adding 0.05 part by mass of hydroquinone.

“Synthesis Example 5” Preparation of Urethane Acrylate (A-5) Having Polysiloxane-Derived Structure A hydroxyl group was added to a 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. 1275 parts by mass (0.25 mol) of dimethylpolysiloxane (trade name: KF-6003, number average molecular weight: 5100, manufactured by Shin-Etsu Chemical Co., Ltd.) and 111 parts by mass (0.5 mol) of isophorone diisocyanate (IPDI) In addition, the reaction was allowed to proceed at 80 ° C. for 5 hours while suppressing heat generation.

Since the equivalent of the isocyanate group was 2772, which was almost the same as the theoretical value when all the hydroxyl groups of the polysiloxane reacted with the isocyanate group, and stabilized, the mixture was cooled to 40 ° C. and 61 parts by mass (0.52 mol of 2-hydroxyethyl acrylate). In addition, 0.02 part by mass of tin catalyst was added as a reaction promoting catalyst, and the reaction was carried out at 90 ° C. for 7 hours in an air atmosphere.
And after an unreacted isocyanate group became 0.3 mass% or less, by adding 0.05 mass part of hydroquinone, the urethane acrylate (A-5) of the number average molecular weight 5776 which has a structure derived from polysiloxane is added. Obtained.

"Synthesis Example 6" Preparation of urethane acrylate (A-6) having no polysiloxane-derived structure A two-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser In addition, 536 parts by mass (1 mol) of hexamethylene isocyanate (trade name: Duranate 24A-100, manufactured by Asahi Kasei Co., Ltd.) and 365 parts by mass (3.15 mol) of 2-hydroxyethyl acrylate were added, and a tin catalyst was added as a reaction promoting catalyst. 0.02 part by mass was added and reacted at 90 ° C. for 7 hours in an air atmosphere.
And after an unreacted isocyanate group will be 0.3 mass% or less, 0.1 mass part of hydroquinone is added, By this, the urethane acrylate (A-6 of number average molecular weight 1956 which does not have a structure derived from polysiloxane) )

“Synthesis Example 7” Preparation of urethane acrylate (A-7) having a structure derived from polysiloxane Hydroxyl group in a four-liter flask having a capacity of 2 liters equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser Dimethylpolysiloxane (trade name: X22-160A, number average molecular weight: 935, manufactured by Shin-Etsu Chemical Co., Ltd.) is charged in an amount of 242 parts by mass (0.25 mol), and isophorone diisocyanate (IPDI) is added in an amount of 111 parts by mass (0.5 mol). In addition, the reaction was allowed to proceed at 80 ° C. for 5 hours while suppressing heat generation.

Since the equivalent of the isocyanate group was 722, which was almost the same as the theoretical value when all the hydroxyl groups of the dimethylpolysiloxane reacted with the isocyanate group, and stabilized, it was cooled to 40 ° C. and dipentaerythritol pentaacrylate (trade name: SR-399E). , Manufactured by Sartomer Co., Ltd.), 625 parts by mass (1.2 mol) was added, 0.02 part by mass of tin catalyst was added as a reaction promoting catalyst, and the mixture was reacted at 90 ° C. for 7 hours in an air atmosphere.
And after an unreacted isocyanate group will be 0.3 mass% or less, by adding 0.05 mass part of hydroquinone, the urethane acrylate (A-7) of the number average molecular weight 2427 which has a structure derived from polysiloxane is added. Obtained.

"Example 1"
At 60 ° C., 9 parts by mass of urethane acrylate (A-1), 91 parts by mass of 2,2,2-trifluoroethyl methacrylate, and 14 parts by mass of dihexaerythritol hexaacrylate are stirred and mixed. By preparing a uniform solution, the film-forming radical polymerizable resin composition of Example 1 was prepared.

"Examples 2-7, Comparative Examples 1-2"
Except for the urethane acrylates (A-1 to A-6), fluorine atom-containing polymerizable unsaturated monomers, and crosslinking agents obtained in Synthesis Examples 1 to 6 having the compositions shown in Table 1 or Table 2. In the same manner as in Example 1, the radically polymerizable resin compositions for film formation of Examples 2 to 7 and Comparative Examples 1 and 2 were prepared.

[Measurement method of refractive index]
A release film prepared by dissolving 3% by mass of Irgacure 184 (manufactured by Ciba Japan) in each of the radical-forming resin compositions for film formation prepared in Examples 1 to 7 and Comparative Examples 1 and 2 (Product name: PHT, thickness: 35 μm, manufactured by Futamura Chemical Co., Ltd.) The coating was applied to a thickness of about 0.1 mm, and in an air atmosphere, one UV lamp 120W metal halide (UV irradiation) was applied to the coated surface. A film was formed by irradiating ultraviolet rays using a quantity of 1000 mJ / cm ^{2 (1} pass) to cure the radical-polymerizable resin composition for film formation.
The refractive index of the obtained film was measured using a measuring instrument (Universal Abbe refractometer, manufactured by ERMA Inc.) in an environment of 25 ° C.
If this refractive index is approximately 1.45 or less, it can be said that the refractive index is sufficiently low for practical use.

[Measurement method of haze, total light transmittance and hardness]
Polyethylene terephthalate (in which 3% by mass of Irgacure 184 (manufactured by Ciba Japan) was dissolved in each of the film-forming radical polymerizable resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 and 2 was used. A PET film (trade name: A4100, thickness: 100 μm, manufactured by Toyobo Co., Ltd.) was applied to an easily adhesive-treated surface to a thickness of about 5 μm, and one UV lamp 120W metal halide lamp (UV irradiation amount 1000 mJ / cm) was applied to the coated surface. ^The film was formed by irradiating ultraviolet rays using ^{2 1} pass) to cure the radically polymerizable resin composition for film formation.
The hardness of the obtained film was measured in accordance with JIS K5600 “Scratch hardness (pencil method)”.
Moreover, the haze and total light transmittance of the obtained film were measured using a haze meter (trade name: NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

"Example 8"
At 60 ° C., 29 parts by mass of urethane acrylate (A-7), 71 parts by mass of 2,2,2-trifluoroethyl acrylate, methacryloyl group-containing polybutyl acrylate (trade name: Macromonomer AB-6, A radically polymerizable resin composition for film formation of Example 8 was prepared by stirring and mixing 14 parts by mass with Toagosei Co., Ltd. to obtain a uniform solution.

"Examples 9 to 11 and Comparative Examples 3 to 4"
Except having set the compounding composition as described in Table 3, it carried out similarly to Example 8, and prepared the radically polymerizable resin composition for film formation of Examples 9-11 and Comparative Examples 3-4.

[Measurement method of refractive index]
The refractive indexes of the cured products (films) of the respective radical-forming resin compositions for film formation prepared in Examples 8-11 and Comparative Examples 3-4 were prepared in Examples 1-7 and Comparative Examples 1-2. It measured similarly to the case of the hardened | cured material (film) of each radically polymerizable resin composition for film formation.

[Measurement of haze and total light transmittance]
The haze and total light transmittance of the cured products (coating films) of the respective radical-forming resin compositions for film formation prepared in Examples 8 to 11 and Comparative Examples 3 to 4 are as in Examples 1 to 7 and Comparative Examples 1 to 1. The measurement was carried out in the same manner as in the case of the cured product (coating) of each radical-forming resin composition for film formation prepared in 2.

[Flexibility evaluation method]
A release film in which 3% by mass of Irgacure 184 (manufactured by Ciba Japan) was dissolved in each of the film-forming radical polymerizable resin compositions prepared in Examples 8 to 11 and Comparative Examples 3 to 4 was used. (Product name: PHT, thickness: 35 μm, manufactured by Futamura Chemical Co., Ltd.) The coating was applied to a thickness of about 0.1 mm, and in an air atmosphere, one UV lamp 120W metal halide (UV irradiation) was applied to the coated surface. A film was formed by irradiating ultraviolet rays using a quantity of 1000 mJ / cm ^{2 (1} pass) to cure the radical-polymerizable resin composition for film formation.
Subsequently, the obtained coating film was peeled from the release film.
The obtained coating was cut into a strip shape having a width of 10 mm and a length of 70 mm to obtain a test piece.
The tensile modulus, breaking elongation, and tensile strength of the obtained test piece were measured using an autograph with a video extensometer (trade name: AG-I, manufactured by Shimadzu Corporation) at a test speed of 4.0 mm / The measurement was performed under the conditions of min and a gap between marked lines of 20 mm. The calculation method conformed to JIS K 7113 “Plastic Tensile Test Method”.

Claims (7)

Resin (A) having a polysiloxane structure and two or more polymerizable unsaturated double bonds in the molecule, and a fluorine atom-containing polymerizable unsaturated monomer (B) represented by the following general formula (I) )
The resin (A) is one or more selected from the group consisting of urethane (meth) acrylate (a1) and epoxy (meth) acrylate (a2),
Radical polymerizable resin for film formation, wherein the blending mass ratio of the resin (A) and the fluorine atom-containing polymerizable unsaturated monomer (B) is in the range of 2/98 to 50/50 Composition.

(However, in the above general formula (I), R ₁ represents H or CH ₃ , R ₂ represents H or F, n = 1 to 3 and m = 1 to 4)  The radically polymerizable resin composition for film formation according to claim 1, wherein the resin (A) has a number average molecular weight of 1000 to 5000. The urethane (meth) acrylate (a1) has an isocyanate group-containing polyurethane produced by reacting a polysiloxane having an active hydrogen atom-containing group at both molecular terminals and a polyisocyanate, and an active hydrogen atom-containing group (meth). The radically polymerizable resin composition for film formation according to claim 1 , which is produced by reacting with acrylate. Further, Ri Na contain three or more polymerizable unsaturated crosslinking agent having a double bond, the crosslinking agent is selected from the group consisting of di-hexa hexa (meth) acrylate and pentaerythritol tri (meth) acrylate film-forming radical-polymerizable resin composition according to der Ru claim 1 1 or more.  And a monomer having one radical polymerizable unsaturated double bond capable of forming a homopolymer having a glass transition temperature of −30 ° C. or lower, and one polymerizable unsaturated double bond; The radical curable resin composition for film formation of Claim 1 containing the 1 type (s) or 2 or more types chosen from the group which consists of a polymer which has a glass transition temperature of degrees C or less.  The radically polymerizable resin composition for film formation according to claim 1, which is ultraviolet curable. The film formed by hardening | curing the radically polymerizable resin composition for film formation of any one of Claim 1 thru | or 6 .