JP7005907B2 - Curable composition and membrane - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Act August 24, 2016 Published in Proceedings Vol. 65, No. 2 of the Polymer Society of Japan, and the No. 1 of the Polymer Society of Japan held at Kanagawa University on September 16, 2016. Published at the 65th Polymer Discussion Meeting, and released at the 149th Lecture Meeting of the Radtech Study Group held at Tokyo University of Science on November 22, 2016.

The present invention uses a curable composition having excellent transparency and capable of forming a cured film expected to be used for an optical film such as an antireflection film, and a cured product formed from the curable composition. It relates to an optical film, a laminate, and a film having a phase-separated structure.

Living radical polymerization has been actively studied in recent years because it is possible to precisely control the molecular weight and structure of the obtained polymer.

The following have been reported as an example of using a polymer obtained by living radical polymerization.
In order to form a nanoporous structure, styrene / divinylbenzene is thermally cured by heat copolymerization in the presence of a polymer dormant species in which a specific chain transfer agent (RAFT agent) is introduced at the end of polylactic acid (PLA). It has been reported that after forming a co-continuous microphase-separated structure, PLA is hydrolyzed and removed to obtain a monolithic polymer having a nanoporous structure (Non-Patent Document 1). Further, Non-Patent Document 1 reports that when the PLA terminal does not have a RAFT site, it becomes a polymer blend and has a macrophase separated structure.
Further, although the technique of Non-Patent Document 1 is for performing living radical polymerization by heating, a technique for performing living radical polymerization by light irradiation is also proposed (Non-Patent Document 2).

M. Seo, M. A. Hillmyer, Science 2012, 336, 1422. J. Xu, K. Jung, A. Atme, S. Shanmugam, C. Boyer, J. Am. Chem. Soc. 2014, 136, 5508.

The above-mentioned Non-Patent Documents 1 and 2 disclose methods for producing polymers by various living radical polymerization methods, but the application of these polymers and the polymerization methods themselves to curable compositions for optical films is described. Not specifically examined.

The present invention is a curable composition utilizing living radical polymerization of a polymer in which terminal polymerization active groups are protected by a radically cleavable covalent bond, which has low reflectance and excellent transparency, and an antireflection film or the like. An object of the present invention is to provide a curable composition capable of forming a cured film expected to be used for an optical film.
Another object of the present invention is to provide a cured product and an optical film made of this curable composition, and a laminate using this curable composition.
Furthermore, it is an object of the present invention to provide a membrane having a specific phase separation structure.

As a result of diligent studies to solve the above problems, the present inventor has found that component (A): a polymer in which the terminal polymerization active group is protected by a radically cleavable covalent bond, and component (B): at least one in the molecule. A curable composition containing the above compound having a (meth) acryloyl group and the component (C): hollow silica fine particles in a predetermined ratio can solve the above-mentioned problems, and the curable composition provides transparency. Excellent, has a micro phase separation structure by spinodal decomposition, and has a structure in which hollow silica fine particles are selectively arranged in the domain of this phase separation structure, so that the reflectance becomes lower and an optical film such as an antireflection film is obtained. We have found that a cured film expected to be used in the above can be formed by a simple operation such as irradiation with active energy rays, and have reached the present invention.

That is, the aspects of the present invention are as follows [1] to [23].

[1] A curable composition containing the following components (A), component (B) and component (C), and containing 1 to 99 parts by weight of component (A) with respect to 100 parts by weight of component (B).
Component (A): Polymer component (B) in which the terminal polymerization active group is protected by a radically cleavable covalent bond: Compound component (C) having at least one (meth) acryloyl group in the molecule: Hollow silica Fine particles

[2] The curable composition according to [1], which contains the component (C) in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the component (B).

[3] The curable composition according to [1] or [2], wherein the component (A) is a polymer obtained by polymerizing a monomer having a radically polymerizable unsaturated double bond.

[4] The curability according to any one of [1] to [3], which is a polymer in which the terminal polymerization active group is protected by a covalent bond in which the component (A) can be radically cleaved by irradiation with active energy rays. Composition.

[5] The group that protects the terminal polymerization active group of the component (A) is an iodine atom, a bromine atom, an alkyldithioester group, a phenyldithioester group, an alkyltrithiocarbonate group, a phenyltrithiocarbonate group, or an alkyldithio. The curable composition according to any one of [1] to [4], which is at least one of the group consisting of a carbamate group, a phenyldithiocarbamate group, an alkylzantate group, a phenylzantate group, and a tellurium atom. ..

[6] The curable composition according to [5], wherein the group that protects the terminal polymerization active group of the component (A) is an iodine atom.

[7] The curable composition according to any one of [1] to [6], wherein the component (A) is a polymer obtained by living radical polymerization.

[8] The curable composition according to any one of [1] to [7], wherein the molecular weight distribution (Mw / Mn) of the component (A) is 2.0 or less.

[9] The curable composition according to any one of [1] to [8], wherein the component (A) is an iodine-terminated polymer having a structure in which an iodine atom is bonded to at least one terminal.

[10] The curable composition according to [9], wherein the component (A) is an iodine-terminated polymer having a structure in which an iodine atom is bonded to at least one terminal of the (meth) acrylic acid ester-based polymer.

[11] The component (A) is an iodine-terminated polymer having a structure in which an iodine atom is bonded to at least one terminal of the (meth) acrylic acid ester-based polymer via a structural unit derived from the acrylic acid ester-based monomer. The curable composition according to [10].

[12] The above-mentioned (10] or [11], wherein the (meth) acrylic acid ester-based polymer contains 1 to 100% by weight of a structural unit derived from a compound represented by the following formula (1) in the polymer. Curable composition.
CH ₂ = C (R ¹ ) -C (O) OR ² ... (1)
(In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² has an alkyl group having 1 to 22 carbon atoms or a polyalkylene glycol chain having 2 to 18 carbon atoms in the alkylene chain. The substituent representing the substituent and having the alkyl group or the polyalkylene glycol chain is a phenyl group, a benzyl group, an epoxy group, a hydroxyl group, a dialkylamino group, an alkoxy group having 1 to 18 carbon atoms, or 1 to 1 carbon atoms as the substituent. It may have a perfluoroalkyl group of 18, an alkylsulfanyl group having 1 to 18 carbon atoms, a trialkoxysilyl group, or a group having a polysiloxane structure.)

[13] The curable composition according to any one of [1] to [12], wherein the component (A) has a number average molecular weight of 800 to 150,000.

[14] The component (B) contains at least a compound having one (meth) acryloyl group in the molecule, and the content thereof is 1 to 99% by weight based on the total weight of the component (B). 1] The curable composition according to any one of [13].

[15] A cured product obtained by curing the curable composition according to any one of [1] to [14].

[16] A laminate having a base material and a cured film, wherein the cured film is obtained by curing the curable composition according to any one of [1] to [14] on the base material. Laminated body.

[17] The laminate according to [16], wherein the cured film is formed by irradiating the curable composition on a substrate with active energy rays to cure the film.

[18] Inside the cured film, the size of the domain formed by spinodal decomposition gradually decreases from the substrate side toward the side irradiated with the active energy rays, [16] or [ 17].

[19] An optical film having a layer made of the cured product according to [15].

[20] A film formed on the surface of a base material and satisfying the following formula (2).
0.1% ≤ [Silica volume fraction] _B <[Silica volume fraction] _T ... (2)
(In the above formula (2), [volume fraction of silica] _T and [volume fraction of silica] _B are measured by three-dimensional volume fraction, and [volume fraction of silica] _T is 0 μm or more in depth from the surface of the film. It is the ratio of the volume occupied by the silica fine particles in at least one region of 3 μm or less, and [volume fraction of silica] _B is the volume occupied by the silica fine particles in at least one region having a depth of 0 μm or more and 3 μm or less from the substrate interface of the film. The ratio of.)

[21] The film according to [20], which is formed from a cured product of a curable composition containing at least a compound having an ethylenically unsaturated double bond and silica particles.

[22] The membrane according to [21], which contains a compound having a (meth) acryloyl group as the compound having an ethylenically unsaturated double bond.

[23] The film according to any one of [20] to [22], wherein the film has a thickness of 2 to 1,000 μm.

According to the curable composition of the present invention, a cured film having low reflectance, excellent transparency, and expected to be used for an optical film such as an antireflection film can be formed by a simple operation. Further, a laminate and an optical film using this curable composition, and a film having a special phase separation structure are provided.

6 is a three-dimensional Tomography analysis image of the cured film obtained in Example 1.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example of embodiments of the present invention, and the present invention is limited to the following description as long as the gist thereof is not exceeded. is not it.
In addition, when the expression "-" is used in this specification, it shall be used as an expression including numerical values or physical property values before and after the expression. Further, in the present specification, the “structural unit derived from ………” is a repetition in which a monomer used as a raw material for producing a polymer constitutes a polymer in a polymer obtained by homopolymerization or copolymerization thereof. Represents one unit that exists as a unit. Further, in the present specification, the carbon number of various functional groups indicates the total carbon number including the substituent when the functional group has a substituent. Further, in the present specification, "(meth) acrylic" means one or both of "acrylic" and "methacrylic". "(Meta) acryloyl" and "(meth) acrylate" have the same meaning.

[Curable composition of the present invention]
The curable composition of the present invention contains the following components (A), component (B) and component (C), and contains 1 to 99 parts by weight of component (A) with respect to 100 parts by weight of component (B). ..
Component (A): Polymer component (B) in which the terminal polymerization active group is protected by a radically cleavable covalent bond: Compound component (C) having at least one (meth) acryloyl group in the molecule: Hollow silica Fine particles

[Ingredient (A)]
The component (A) is a polymer in which the terminal polymerization active group is protected by a radical-cleavable covalent bond, and preferably a polydialkylsiloxane, polyethylene oxide, or a monomer having a radically polymerizable unsaturated double bond is polymerized. A polymer in which at least one terminal polymerization active group is protected by a covalent bond that can be radically cleaved by irradiation with active energy rays and / or heating, and more preferably, a radically polymerizable unsaturated double. The terminal polymerization active group of the polymer obtained by polymerizing a monomer having a bond is a polymer protected by a covalent bond that can be radically cleaved by irradiation with active energy rays and / or heating, and is particularly preferably radically polymerizable unsaturated. It is a polymer in which a terminal polymerization active group obtained by polymerizing a monomer having a double bond is protected by a covalent bond that can radically cleave by irradiating with an active energy ray. That is, the polymer of the component (A) used in the present invention is obtained by covalently bonding a terminal polymerization active group (usually a carbon radical) with a group that protects the terminal polymerization active group, and the polymer is irradiated with active energy rays. And / or radical cleavage is possible by heating.

The group that protects the terminal polymerization active group of the component (A) may be any group as long as the terminal polymerization active group of the component (A) can be bonded by a radically cleavable covalent bond. For example, iodine atom, bromine atom, alkyldithioester group, phenyldithioester group, alkyltrithiocarbonate group, phenyltrithiocarbonate group, alkyldithiocarbamate group, phenyldithiocarbamate group, alkylzantate group, phenylzantate. Groups, ester atoms, etc. can be mentioned.
The component (A) may have only one kind of a group that protects these terminal polymerization active groups, or may have two or more kinds.

The method for producing a polymer having a group that protects the terminal polymerization active group as described above is not particularly limited. For example, it can be produced by the methods described in Non-Patent Documents 1 and 2 and Documents 1 to 7 below.
Reference 1: Chiefari, J .; Chong, YK; Ercole, Fo; Krstina, J .; Jeffery, J .; Le, TPT; Mayadunne, RTA; Meijs, GF; Moad, CL;
Load, G .; Rizzardo, E .; Thang, SH Macromolecules 1998, 31, 5559.
Reference 2: Mood, G .; Rizzardo, E .; Thang, SH Aust. J. Chem. 2005, 58, 379.
Reference 3: McCormick, CL; Lowe, AB Acc. Chem. Res. 2004, 37, 312.
Reference 4: Mayadunne, RTA; Rizzardo, E .; Chiefari, J .; Chong, YK;
Moad, G. Thang, SH; Macromolecules 1999, 32, 6977.
Reference 5: Destarac. M .; Charmot, D .; Franck, X .; Zard, SZ Macromol. Rapid.
Reference 6: Mayadunne, RTA; Rizzardo, E; Chiefari, J .; Kristina, J .; Moad, G .; Pastma, A .; Thang, SH Macromolecules 2000, 33, 243.
Reference 7: Francis, R .; Ajayaghosh, A. Macromolecules 2000, 33, 4699.

As a group that protects the terminal polymerization active group of the component (A), the group (A) has excellent bond stability to the terminal polymerization active group, and is irradiated with active energy rays and / or heated, particularly active energy rays. Iodine atoms are particularly preferred because they can be easily radically cleaved by irradiation.
Further, the component (A) is preferably a polymer obtained by living radical polymerization because the molecular weight and the polymer structure can be easily controlled to those of interest, and according to the living radical polymerization, the molecular weight distribution (Mw). / Mn) narrow component (A) can be easily produced.

As described above, the component (A) is preferably obtained by polymerizing a monomer having a radically polymerizable double bond, and the monomer having a radically polymerizable double bond used as a raw material thereof is a radically polymerizable carbon. The monomer is not particularly limited as long as it has a radical double bond. More specifically, a (meth) acrylic acid ester-based monomer as described later, particularly a compound represented by the following formula (1) can be mentioned.

The component (A) is preferably an iodine-terminated polymer having a structure in which an iodine atom is bonded to at least one terminal, and has a structure in which an iodine atom is bonded to at least one terminal of the (meth) acrylic acid ester-based polymer. It is more preferably an iodine-terminated polymer having an iodine terminal, and further preferably an iodine-terminated polymer having a structure in which an iodine atom is bonded via a structural unit derived from an acrylic acid ester-based monomer.

The (meth) acrylic acid ester-based polymer constituting this iodine-terminated polymer has a structural unit derived from a compound represented by the following formula (1) (hereinafter, may be referred to as “compound (1)”). Those containing 10 to 100% by weight are preferable. The content of the structural unit derived from the compound (1) in the polymer is more preferably 50 to 100% by weight, and particularly preferably 80 to 100% by weight. The content of the structural unit derived from the compound (1) referred to here is obtained from the charged weight of the raw material.
CH ₂ = C (R ¹ ) -C (O) OR ² (1)
(R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 22 carbon atoms or a substituent having a polyalkylene glycol chain having 2 to 18 carbon atoms in the alkylene chain. Substituents having a group or a polyalkylene glycol chain include a phenyl group, a benzyl group, an epoxy group, a hydroxyl group, a dialkylamino group, an alkoxy group having 1 to 18 carbon atoms, and a perfluoroalkyl group having 1 to 18 carbon atoms as substituents. It may have an alkylsulfanyl group having 1 to 18 carbon atoms, a trialkoxysilyl group, or a group having a polysiloxane structure.)

The "(meth) acrylic acid ester-based polymer" is a polymer composed of structural units derived from the (meth) acrylic acid ester-based monomer, and the "methacrylic acid ester-based monomer" is a general term for monomers having a methacryloyl group. Is. Further, the "acrylic acid ester-based monomer" is a general term for a monomer having an acryloyl group (excluding a monomer having an acryloyl group in which a carbon atom is bonded to a carbon atom of C = C of the acryloyl group).

As R ² in the above formula (1), an alkyl group having 1 to 18 carbon atoms and which may have an epoxy group, a hydroxyl group, a dialkylamino group and an alkoxy group having 1 to 4 carbon atoms as substituents is particularly preferable. preferable. In particular, an alkyl group having 1 to 6 carbon atoms and which may have an epoxy group, a hydroxyl group and an alkoxy group having 1 to 2 carbon atoms is preferable as a substituent, and an epoxy group having 1 to 6 carbon atoms is used as a substituent. Alkyl groups may be more preferred.

Specific examples of the compound (1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and hexyl (meth) acrylate. 2-Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, nonyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) Acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-Hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, diethylene glycol (meth) acrylate, 2- (Dimethylamino) ethyl (meth) acrylate, 2- (dimethylamino) propyl (meth) acrylate, 2- (dimethylamino) butyl (meth) acrylate, 2-isocyanoethyl (meth) acrylate, 2- (acetoacetoxy) ) Ethyl (meth) acrylate, perfluoroethyl (meth) acrylate having perfluoroalkyl having 1 to 18 carbon atoms, 2- (meth) ethyl (meth) acrylate (2-((meth) acryloyloxy) ethyl phosphate ), Trialkoxysilylpropyl (meth) acrylate, dialkoxymethylsilylpropyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate and the like.

Of these, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, in terms of being easily available industrially and having reactivity with other compounds after polymerization. Glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate and the like are preferable, and methyl (meth) acrylate is preferable. Acrylate, n-butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like are more preferable, and methyl (meth) acrylate and glycidyl (meth) acrylate are further preferable.

The (meth) acrylic acid ester-based polymer constituting the iodine-terminated polymer may contain a structural unit derived from one kind of compound (1), and a structural unit derived from two or more kinds of compounds (1). May be included. When a structural unit derived from two or more compounds (1) is contained, the (meth) acrylic acid ester-based polymer is usually a random copolymer.

The molecular weight of the component (A) is not particularly limited, but the number average molecular weight (Mn) is preferably 800 or more, preferably 1000 or more, from the viewpoint of being able to form a good microphase separation structure described later in the formed cured film. More preferably, 2000 or more is more preferable, and 2500 or more is most preferable. Further, 150,000 or less is preferable, 100,000 or less is more preferable, 50,000 or less is further preferable, and 10,000 or less is most preferable.

The molecular weight of the component (A) can be controlled, for example, by the conditions of living radical polymerization described later. Specifically, it can be controlled by the monomer, the polymerization initiator, the catalyst concentration, the reaction temperature, the reaction time, etc., and the monomer concentration is high, the initiator concentration is low, the catalyst concentration is high, the reaction temperature is high, and the reaction is carried out. The longer the time, the higher the molecular weight.

In particular, according to the living radical polymerization described later, such a molecular weight control is easy, and a polymer having a narrow molecular weight distribution (Mw / Mn) of the component (A) can be produced. The molecular weight distribution (Mw / Mn) of the component (A) is preferably 2.0 or less, more preferably 1.6 or less, further preferably 1.4 or less, particularly preferably 1.2 or less, and particularly preferably 1.1 or less. preferable. On the other hand, the molecular weight distribution of the component (A) is usually larger than 1.0.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer are measured by gel permeation chromatography (GPC) by the method described in Examples described later.

Hereinafter, among the above-mentioned iodine-terminated polymers suitable as the component (A), an iodine-terminated polymer having a structure in which an iodine atom is bonded to at least one terminal (hereinafter referred to as “iodine-terminated polymer (A)”). However, the component (A) is not limited to the following iodine-terminated polymers (A).

[Iodine-terminated polymer (A)]
The iodine-terminated polymer (A) used in the present invention is usually at least one end of a (meth) acrylic acid ester-based polymer (hereinafter, may be referred to as “main polymer in iodine-terminated polymer (A)”). It has a structure in which iodine atoms are bonded. The iodine-terminated polymer (A) is an example of a preferred embodiment of the present component (A).

The method for producing the iodine-terminal polymer (A) is not particularly limited, but the iodine-terminal polymer (A) is usually produced by living radical polymerization according to the production method described later, and polymerizes a (meth) acrylic acid ester-based monomer. It is sometimes manufactured by charging in bulk and then polymerizing. The (meth) acrylic acid ester-based monomer used for the polymerization may be a methacrylic acid ester-based monomer alone, an acrylic acid ester-based monomer alone, or both of them in combination.

When an acrylic acid ester-based monomer or a methacrylic acid ester-based monomer is used alone, the terminal has a structure in which an iodine atom is bonded to a structural unit derived from the monomer.

When an acrylic acid ester-based monomer and a methacrylic acid ester-based monomer are used in combination, the terminal structure differs depending on the polymerization temperature. Normally, if the polymerization temperature is controlled at 50 ° C. or higher and lower than 90 ° C., the methacrylic acid ester-based monomer and the iodine atom can be used. Although the bond between them is cleaved, the bond between the acrylic ester-based monomer and the iodine atom is not cleaved. , It has a structure in which iodine atoms are bonded via a structural unit derived from an acrylic acid ester monomer. On the other hand, usually, when the polymerization temperature is 90 ° C. or higher, both the bond between the methacrylic acid ester-based monomer and the iodine atom and the bond between the acrylic acid ester-based monomer and the iodine atom are cleaved. A state in which an iodine atom is bonded via a structural unit derived from a methacrylic acid ester-based monomer and an iodine atom is bonded via a structural unit derived from an acrylic acid ester-based monomer are randomly mixed. It becomes a thing. As the iodine-terminated polymer (A), it is preferable that the former terminal structure is a structural unit derived from an acrylic acid ester-based monomer-iodine atom, because it is more excellent in stability to light and heat. The term "cleavage" as used herein means radical cleavage.

The iodine-terminated polymer (A) can be produced by heating in the same manner as in a normal radical polymerization reaction, but it is also possible to irradiate light having a wavelength corresponding to a predetermined energy to cause a polymerization reaction. When the polymerization is carried out by irradiating with light, it is possible to carry out the polymerization at a temperature lower than the reaction temperature described later.

The (meth) acrylic acid ester-based polymer which is the main polymer in the iodine-terminated polymer (A) used in the present invention is the compound (1) represented by the above formula (1) (hereinafter, “(meth) acrylic acid ester (1)). It is preferable to include a structural unit derived from).

Specific examples of the (meth) acrylic acid ester (1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and hexyl. (Meta) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, nonyl (meth) acrylate, benzyl (meth) acrylate , Glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, diethylene glycol (Meta) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, 2- (dimethylamino) propyl (meth) acrylate, 2- (dimethylamino) butyl (meth) acrylate, 2-isocyanoethyl (meth) acrylate, 2- (Acetoacetoxy) ethyl (meth) acrylate, perfluoroethyl (meth) acrylate with perfluoroalkyl having 1-18 carbon atoms, 2- (phosphate) ethyl (meth) acrylate (2-((meth) acryloyl) Oxy) ethyl phosphate), trialkoxysilylpropyl (meth) acrylate, dialkoxymethylsilylpropyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, etc. Can be mentioned.

Of these, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, in terms of being easily available industrially and having reactivity with other compounds after polymerization. Glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate and the like are preferable, and methyl (meth) acrylate is preferable. Acrylate, n-butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like are more preferable, and methyl (meth) acrylate or glycidyl (meth) acrylate is further preferable.

The (meth) acrylic acid ester-based polymer of the main polymer in the iodine-terminated polymer (A) may contain structural units derived from one type of (meth) acrylic acid ester (1), and may contain two or more types of structural units. A structural unit derived from the (meth) acrylic acid ester (1) may be contained. When a structural unit derived from two or more (meth) acrylic acid esters (1) is contained, the (meth) acrylic acid ester-based polymer is usually a random copolymer.

[Manufacturing method of iodine-terminated polymer (A)]
The iodine-terminated polymer (A) used in the present invention is preferably produced by polymerizing a (meth) acrylic acid ester-based monomer in the presence of iodine, which is a protecting group for growth radicals at the polymer terminal of living radical polymerization. .. However, the iodine-terminated polymer (A) is not particularly limited as long as it is a method for obtaining the characteristic terminal structure of the iodine-terminated polymer (A) described above.

The iodine-terminated polymer (A) preferably contains iodine, a radical polymerization initiator (hereinafter, may be simply referred to as “initiator”), and a methacrylic acid ester-based monomer in a solvent in the presence of a catalyst. After polymerization, it is produced by mixing an acrylic acid ester-based monomer with a reaction system and reacting. In this case, the iodine-terminated polymer (A1) described later is produced as the iodine-terminated polymer (A).

<Iodine>
It is preferable to use 0.05 to 5 molar equivalents of iodine, particularly 0.3 to 1 molar equivalent, with respect to the polymerization initiator. If the amount of iodine used is more than the above lower limit, a large amount of unreacted polymerization initiator or polymerization initiator is dissociated and recombined by-reactants will not be produced, and if the amount of iodine used is less than the above upper limit, polymerization will occur. Since the rate does not slow down, it is preferable that the polymerization time is not excessively long in order to obtain a polymer having a desired molecular weight.

<Catalyst>
The catalyst has a function of extracting iodine or iodine at the end of the polymer to promote living radical polymerization, and is usually a quaternary ammonium iodide such as tetrabutylammonium iodide or ethylmethylimidazolium iodide, or tributylsulfonium. Sulfonium iodide such as iodide, iodonium iodide such as diphenyl iodonium iodide, phosphonium iodide such as tributylmethylphosphonium iodide, tetrakis (dimethylamino) ethylene, triethylamine, tributylamine, N, N, N', N' -Tetramethyldiaminomethane, N, N, N', N'-Tetramethylethylenediamine, 1,4,8,11-Tetramethyl-1,4,8,11-Tetraazacyclotetradecane, N, N'-dimethyl Amines such as ethylenediamine and ethylenediamine, and phosphines such as triphenylphosphine, tris (2-methylphenyl) phosphin, tris (3-methylphenyl) phosphin, and tris (4-methylphenyl) phosphine can be used. These catalysts may be used alone or in combination of two or more.

The ratio of the catalyst is not particularly limited as long as it is used according to the desired degree of polymerization and polymerization time, but it is usually used in an amount of 0.05 molar equivalent or more, preferably 0.3 molar equivalent or more with respect to the polymerization initiator. , More preferably 0.5 molar equivalents or more. In addition, it is usually used in an amount of 5 mol equivalents or less, preferably 3 mol equivalents or less, and more preferably 2 mol equivalents or less with respect to the polymerization initiator. When the amount of the catalyst used is more than the above lower limit, the polymerization rate does not become too low, so that the polymerization time does not become long, it becomes easy to obtain a polymer having a desired molecular weight in a predetermined polymerization time, and when it is less than the above upper limit. It is preferable because the polymerization rate does not become too fast, the molecular weight distribution can be narrowed, and the formation of a polymer in which iodine is not bonded to the terminal can be suppressed.

<Initiator of polymerization>
As the polymerization initiator used for the polymerization of the iodine-terminated polymer (A), known ones are used, and the polymerization initiator is not particularly limited, and commonly used organic peroxides and azo compounds can be used. Specific examples include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butylperoxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, and t-butylperoxy-2-ethylhexanoate. , T-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butyl) Peroxy) Hexil-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumylhydroperoxide, acetylperoxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, isobutyl peroxide, 3 , 3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) 3, 3,5-trimethylcyclohexane, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4) -Dimethylvaleronitrile), dimethyl-2,2'-azobis (isobutyrate) and the like. As the polymerization initiator, an azo compound is preferable from the viewpoint of stability after binding to iodine, and from the viewpoint of availability and dissociation temperature, 2,2'-azobis (isobutyronitrile), 2,2' -Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis (isobutyrate) are preferably used. Among these, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) or 2,2'-azobis (4-methoxy-2,4-dimethylvalero) Nitrile) is more preferably used.
These polymerization initiators may be used alone or in combination of two or more.

The proportion of the polymerization initiator is not particularly limited as long as it is used according to the desired molecular weight, but it is usually (meth) acrylic acid ester-based monomer (methacrylic acid ester-based monomer in the case of the iodine-terminated polymer (A1) described later) 100. It is used in an amount of 0.01 mol or more, preferably 0.05 mol or more, more preferably 0.1 mol or more, and most preferably 0.2 mol or more. Further, it is usually used in an amount of 5 mol or less, preferably 3 mol or less, more preferably 2 mol or less, and most preferably 1 mol or less.
If the amount of the polymerization initiator is at least the above lower limit, the molecular weight does not become too large, and it is easy to reduce the amount of unreacted monomers after polymerization. When the amount is small, the unreacted polymerization initiator and the polymerization initiator are dissociated and recombined, which is preferable because it is difficult to generate a large amount of by-reactants.

<Solvent>
If the reaction mixture containing the monomer used in the polymerization reaction is liquid at the reaction temperature, it is not always necessary to use a solvent, but in this case as well, a solvent may be used if necessary. As the solvent, a solvent used for general living radical polymerization can be used. For example, linear, branched, secondary or polyvalent alcohols such as water, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol, ethylene glycol; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones; ethers such as diethyl ether, dimethyl ether, dipropyl ether, methylcyclopropyl ether, tetrahydrofuran, dioxane, anisole; aromatic hydrocarbons such as toluene and xylene; Swazir series (manufactured by Maruzen Petrochemical Co., Ltd.), Petroleum-based aromatic mixed solvent such as Solbesso series (manufactured by Exxon Chemical Co., Ltd.); Cellosolves such as cellosolve and butyl cellosolve; Carbitols such as carbitol and butylcarbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether Classes; Polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; Acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate; Dialkyl glycol ethers and the like. Can be used.
These solvents may be used alone or in combination of two or more.

The solvent is usually 0.1 to 10 parts by weight, preferably 0, with respect to 1 part by weight of a (meth) acrylic acid ester-based monomer (in the case of the iodine-terminated polymer (A1) described later, a methacrylic acid ester-based monomer). It is used in a proportion of about 3 to 2 parts by weight, but in some cases, it is not necessary to use a solvent in particular.

<Living radical polymerization reaction>
The living radical polymerization of the (meth) acrylic acid ester-based monomer is preferably carried out in a reaction system containing the (meth) acrylic acid ester-based monomer, iodine, initiator, catalyst and solvent under an atmosphere of an inert gas such as nitrogen. It is carried out at ° C. or higher, more preferably at 60 ° C. or higher. Further, it is preferably carried out at 150 ° C. or lower, more preferably 130 ° C. or lower, further preferably 110 ° C. or lower, particularly preferably 90 ° C. or lower, and most preferably 80 ° C. or lower. ..
Here, when the reaction temperature is at least the above lower limit, the living radical polymerization reaction proceeds sufficiently, and when it is at least the above upper limit, the polymerization by heat of the (meth) acrylic acid ester-based monomer, which is not the desired living radical polymerization, is suppressed. can do.

The reaction time varies depending on the reaction temperature, the target (meth) acrylic acid ester-based polymer, and the molecular weight of the iodine-terminated polymer, but is usually about 10 minutes to 150 hours, preferably about 1 to 24 hours. ..
After the reaction, the iodine-terminated polymer (A) can be recovered by purification and solid-liquid separation in the same manner as in the method for producing the iodine-terminated polymer (A1) described later.

It should be noted that the terminal structure of the iodine terminal polymer (A) is that the iodine atom is bonded, for example, from the measurement result of the molecular weight by the MALDI-TOF method, as shown in the section of Examples described later. It can be confirmed by analyzing the structure and identifying it.

[Iodine-terminated polymer (A1)]
The iodine-terminated polymer (A) has, in particular, a structure in which an iodine atom is bonded to at least one end of a methacrylic acid ester-based polymer via a structural unit derived from an acrylic acid ester-based monomer (hereinafter, “iodine terminal”). The polymer (A1) may be referred to. Further, the methacrylic acid ester-based polymer in the iodine-terminated polymer (A1) may be referred to as the "main polymer in the iodine-terminated polymer (A1)"), which is excellent in photostability. It is preferable because it is a thing. This is because when the terminal structure is a structural unit-iodine atom derived from an acrylic acid ester-based monomer, the α-position carbon atom of the acrylic acid ester of the structural unit is more sterically damaged than the α-position carbon atom of the methacrylic acid ester. It is presumed that this is because the structural unit derived from the acrylic ester-based monomer-the terminal structure of the iodine atom is highly stable because of its small size.

The iodine-terminated polymer (A1) is preferably produced by living radical polymerization according to the above-mentioned method for producing an iodine-terminated polymer (A), and the method for producing the same is methacrylic acid that forms the main polymer in the iodine-terminated polymer (A1). The ester-based monomer and a small amount of acrylic acid ester-based monomer forming the terminal structure may be charged together at the time of polymerization and then polymerized. After the polymerization, an acrylic acid ester-based monomer may be further reacted with the methacrylic acid ester-based polymer which is the main polymer in the obtained iodine-terminated polymer (A1), but the latter is preferable from the viewpoint of molecular weight control. Manufactured by the method.

The methacrylic acid ester-based polymer that becomes the main polymer in the iodine-terminated polymer (A1) is a compound (1) represented by the above formula (1) in which R1 in the formula ( ¹ ) is a methyl group (hereinafter,). It may be referred to as "methacrylic acid ester (1')") and preferably contains structural units.

Specific examples of the methacrylic acid ester (1') include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate and tridecyl. Methacrylate, Octadecyl methacrylate, Nonyl methacrylate, benzyl methacrylate, Glycidyl methacrylate, Cyclohexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, Butoxyethyl methacrylate, methoxytetraethylene glycol methacrylate, 2-Hydroxyethyl methacrylate, 2-Hydroxypropyl methacrylate , 3-Chloro-2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, diethylene glycol methacrylate, 2- (dimethylamino) ethyl methacrylate, 2- (dimethylamino) propyl methacrylate, 2- ( Dimethylamino) butyl methacrylate, 2-isocyanoethyl methacrylate, 2- (acetoacetoxy) ethyl methacrylate, perfluoroethyl methacrylate having perfluoroalkyl having 1 to 18 carbon atoms, 2- (methacryloyl) ethyl methacrylate (2- (methacryloyl) Oxy) ethyl phosphate), trialkoxysilylpropylmethacrylate, dialkoxymethylsilylpropylmethacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, polytetramethylene glycol methacrylate and the like.

Of these, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 2-methoxyethyl methacrylate, in terms of being easily available industrially and having reactivity with other compounds after polymerization. 2-Hydroxyethyl methacrylate, polyethylene glycol methacrylate, 2- (dimethylamino) ethyl methacrylate and the like are preferable. Methyl methacrylate, n-butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate and the like are more preferable, and methyl methacrylate or glycidyl methacrylate is further preferable.

The methacrylic acid ester-based polymer of the main polymer in the iodine-terminated polymer (A1) may contain a structural unit derived from one type of methacrylic acid ester (1'), and two or more types of methacrylic acid esters (1') may be contained. ') Derived structural units may be included. When a structural unit derived from two or more kinds of methacrylic acid esters (1') is contained, the methacrylic acid ester-based polymer is usually a random copolymer.

Further, the iodine-terminated polymer (A1) can be produced by heating in the same manner as a normal radical polymerization reaction, but it is also possible to irradiate light having a wavelength corresponding to a predetermined energy to cause a polymerization reaction. When the polymerization is carried out by irradiating with light, it is possible to carry out the polymerization at a temperature lower than the reaction temperature described later.

The methacrylic acid ester-based polymer, which is the main polymer in the iodine-terminated polymer (A1) thus produced, usually has structural units derived from the acrylic acid ester-based monomer only at one end of both ends thereof. The iodine atom is bonded to the polymer, but the structure may be such that the iodine atom is bonded to both ends via a structural unit derived from an acrylic ester-based monomer. Further, at the end of the methacrylic acid ester polymer, the number of structural units derived from the acrylic acid ester monomer that is the connecting portion between the iodine atom and the methacrylic acid ester polymer is usually 1 unit, but 2 units or more. It may be via a structural unit derived from an acrylic acid ester-based monomer.

<Reaction of acrylic acid ester-based monomer>
Following the above-mentioned living radical polymerization, an acrylic acid ester-based monomer is mixed and reacted in the reaction system, whereby one end or both ends of the methacrylic acid ester-based polymer is mediated by a structural unit derived from the acrylic acid ester-based monomer. It is possible to obtain an iodine-terminated polymer (A1) to which an iodine atom is bonded.

Further, in the present invention, the structural unit derived from the methacrylic acid ester-based monomer of the main polymer in the iodine-terminated polymer (A1) and the acrylic acid ester-based monomer connecting the iodine atom is the compound represented by the above formula (1). Of the (1), it is preferable to include a structural unit derived from the one in which R ¹ in the formula (1) is a hydrogen atom (hereinafter, may be referred to as "acrylic acid ester (1')").

Specific examples of the acrylic acid ester (1') include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl acrylate, and tridecyl. Acrylate, octadecyl acrylate, nonyl acrylate, benzyl acrylate, glycidyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, butoxyethyl acrylate, methoxytetraethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate , 3-Chloro-2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, diethylene glycol acrylate, 2- (dimethylamino) ethyl acrylate, 2- (dimethylamino) propyl acrylate, 2- ( Dimethylamino) butyl acrylate, 2-isocyanoethyl acrylate, 2- (acetoacetoxy) ethyl acrylate, perfluoroethyl acrylate having perfluoroalkyl having 1 to 18 carbon atoms, 2- (phosphate) ethyl acrylate (2- (acryloyl) Oxy) ethyl phosphate), trialkoxysilylpropyl acrylate, dialkoxymethylsilylpropyl acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, polytetramethylene glycol acrylate and the like can be mentioned.

Of these, n-butyl acrylate, 2-ethylhexyl acrylate, n-octadecyl acrylate, 2-methoxyethyl acrylate, and 2-hydroxyethyl are easy to obtain industrially, easy to handle at the time of manufacture, and safe. Acrylate, N, N-dimethylaminoethyl acrylate and the like are preferable, n-butyl acrylate, 2-ethylhexyl acrylate, n-octadecyl acrylate, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate and the like are more preferable, and n-butyl acrylate, etc. 2-Ethylhexyl acrylate or n-octadecyl acrylate is more preferable.

The iodine-terminated polymer (A1) usually contains a structural unit derived from one acrylic acid ester-based monomer, but when it contains two or more structural units derived from an acrylic acid ester-based monomer, these are the same type of acrylic. It may be a structural unit derived from an acid ester-based monomer or a structural unit derived from a different acrylic acid ester-based monomer.

Here, the acrylic acid ester-based monomer is usually used in an amount of 0.1 mol or more, preferably 0.5 mol or more, more preferably 10 mol or more, with respect to 1 mol of iodine charged, which is the theoretical amount of the polymer terminal. , More preferably 20 mol or more. Further, it is usually used in a ratio of 400 mol equivalent or less, preferably 300 mol or less, more preferably 200 mol or less, still more preferably 100 mol or less.

The reaction temperature of the methacrylic acid ester polymer and the acrylic acid ester monomer at the time of reaction is preferably 50 ° C. or higher, more preferably 60 ° C. or higher. Further, it is preferably carried out at 90 ° C. or lower, and more preferably 80 ° C. or lower.
Here, when the reaction temperature is at least the above lower limit, the acrylic acid ester-based monomer can be sufficiently reacted, and when it is at least the above upper limit, the living radical polymerization reaction of the acrylic acid ester-based monomer can be controlled, and the methacrylic can be controlled. It is possible to obtain an iodine-terminated polymer (A1) in which an iodine atom is bonded to one end or both ends of the acid ester-based polymer via a structural unit derived from an acrylic acid ester-based monomer.

The present inventors have different temperatures at which the bonds between the methacrylic ester-based monomer and the iodine atom at the polymer terminal and between the acrylic acid ester-based monomer and the iodine atom are dissociated, preferably 50 to 90 ° C., more preferably 60 to 80 ° C. The bond between the methacrylic acid ester-based monomer and the iodine atom dissociates at a relatively low temperature of about ° C., but the bond between the acrylic acid ester-based monomer and the iodine atom does not easily dissociate at such a temperature. If an acrylic acid ester-based monomer is present in the system when the polymerization of the methacrylic acid ester-based polymer is produced, one acrylic acid ester-based monomer is usually incorporated into the polymer terminal by a reaction in such a temperature range. After that, it was found that the dissociation of the bond between the acrylic ester-based monomer and the iodine atom did not occur, and the reaction was stopped with the iodine atom bonded to the terminal end.
Therefore, the iodine-terminated polymer (A1) can be produced by selecting a temperature at which the living radical polymerization reaction of the acrylic acid ester-based monomer cannot proceed as described above and carrying out the reaction.

The reaction time of the acrylic acid ester-based monomer varies depending on the reaction temperature and the target reaction rate, but is usually about 10 minutes to 24 hours, preferably about 1 to 12 hours.

The iodine-terminated polymer (A1) used in the present invention is prepared by lowering the temperature of the reaction solution to about 0 to 40 ° C. after the reaction of the acrylic acid ester-based monomer as described above is completed, and then using water, methanol, as necessary. After removing impurities by precipitation and purification with a solvent having low solubility of the iodine-terminated polymer (A1) such as diethyl ether and heptane, the polymer is recovered by solid-liquid separation. At that time, it is preferable that the operations from the reaction to purification and solid-liquid separation are performed under light shielding. That is, the iodine-terminated polymer (A1) has excellent photostability as compared with the conventional polymer because the iodine atom is bonded to the terminal via a structural unit derived from an acrylic acid ester-based monomer. However, the color does not change at all under light irradiation, and it may be colored when exposed to light for a long time. Therefore, the iodine-terminated polymer (A1) may be manufactured, recovered, and then stored under light shielding. preferable.

The fact that the terminal structure of the iodine-terminal polymer (A1) thus obtained has iodine atoms bonded via a structural unit derived from an acrylic acid ester-based monomer is described in, for example, in the section of Examples described later. As shown, it can be confirmed by analyzing the terminal structure and identifying it from the measurement result of the molecular weight by the MALDI-TOF method.

[Component (B)]
The component (B) is a compound having at least one (meth) acryloyl group in the molecule (however, excluding those corresponding to the component (A)).
The compound having one or more (meth) acryloyl groups in the molecule may be a monomer, an oligomer, or a mixture of a monomer and an oligomer. Among the compounds having one or more (meth) acryloyl groups in the molecule, as the monomer, a monofunctional monomer, a polyfunctional monomer, for example, a dealcohol reaction product of a polyhydric alcohol and a (meth) acrylate may be used. Can be done. Examples of the oligomer include urethane (meth) acrylate oligomers and polyester (meth) acrylate oligomers.

The component (B) used in the present invention is a living radical polymerization of the component (A) to the terminal polymerization active group by irradiation with active energy rays and / or heating. From the viewpoint of being able to form a phase-separated structure, a compound having only one (meth) acryloyl group (monofunctional (meth) acrylate) and a compound having two or more (meth) acryloyl groups (bifunctional or more). It preferably contains a polyfunctional (meth) acrylate).

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acryloylmorpholine, tetrahydroflufreel (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) Acrylate, Isodecyl (meth) acrylate, Lauryl (meth) acrylate, Tridecyl (meth) acrylate, Cetyl (meth) acrylate, Stearyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxy Butyl (meth) acrylate, ethylcarbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, ethylene oxide-modified phenoxy (meth) acrylate, propylene oxide-modified phenoxy. (Meta) acrylate, nonylphenol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, propylene oxide-modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolytylene glycol (meth) acrylate, methoxypropylene glycol (meth) ) Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogenphthalate, 2- (meth) acryloyloxypropyl Hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogenphthalate, 2- (meth) acryloyloxypropyl tetrahydrohydrogenphthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) Acrylate, Hexafluoropropyl (meth) acrylate, Octafluoropropyl (meth) acrylate, Octafluoropropyl (meth) acrylate, 2-adamantan And adamantane derivative mono (meth) acrylate such as adamantyl (meth) acrylate having a monovalent mono (meth) acrylate derived from adamantane diol. These may be used alone or in admixture of two or more.

Of these, dimethylaminoethyl (meth) acrylate and n-butyl (meth) acrylate are difficult to volatilize because the molecular weight is not too small, and dimethylaminoethyl (meth) acrylate and n-butyl (meth) acrylate are easy to proceed with polymerization because the molecular weight is not too large. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydroflufreel (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or isobornyl (meth) acrylate. Is preferable. Of these, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydroflufreel (meth) acrylate, or isobornyl (meth) acrylate is more preferable.

Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate (= 1,4-bis ((meth) acryloyloxy) butane), and the like. Hexadiol di (meth) acrylate, nonanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate. , Tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalic acid Examples thereof include di (meth) acrylate such as neopentyl glycol di (meth) acrylate.

Examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethyl propanoltri (meth) acrylate, ethoxylated trimethylol propanetri (meth) acrylate, propoxylated trimethylol propanetri (meth) acrylate, and tris 2-hydroxy. Ethylisocyanurate tri (meth) acrylate, tri (meth) acrylate such as glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylol propanthry (meth) acrylate and the like. Trifunctional (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylol propanepenta (meth) Trifunctional or higher polyfunctional (meth) acrylates such as acrylates, dipentaerythritol hexa (meth) acrylates, and ditrimethylolpropane hexa (meth) acrylates, and some of these (meth) acrylates are replaced with alkyl groups or ε-caprolactone. Examples thereof include polyfunctional (meth) acrylate compounds.

As for these bifunctional or higher functional (meth) acrylates, one kind may be used alone, or two or more kinds may be mixed and used.

Of these, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, because the raw materials are industrially easily available and the molecular weight is not too large, the motility of the molecule is high and the polymerization is easy to proceed. 1,4-Bis ((meth) acryloyloxy) butane, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanthry (meth) acrylate, Tris 2 -Hydroxyethyl isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa. (Meta) acrylate is preferred. Among these, 1,4-bis ((meth) acryloyloxy) butane, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate is preferred.

The component (B) is usually 1 to 99% by weight of a monofunctional (meth) acrylate and 99 to 1% by weight of a polyfunctional (meth) acrylate having two or more functionalities (however, monofunctional (meth) acrylate and polyfunctional (however). Meta) Contains 100% by weight in total of acrylate.

Of these, the monofunctional (meth) acrylate is preferably contained in an amount of 5 to 95% by weight, more preferably 20 to 92% by weight, more preferably 50 to 90% by weight, and 60 to 85% by weight. Most preferably, it is contained in% by weight. As the amount of monofunctional (meth) acrylate increases within this range, the amount of bifunctional or higher polyfunctional (meth) acrylate decreases, and the polymer from the end of the component (A) can be sufficiently extended, so that the co-continuous phase can be sufficiently extended. A phase-separated structure having the above is formed, and a desired cured film can be obtained. On the contrary, the smaller the amount of monofunctional (meth) acrylate in this range, the larger the amount of polyfunctional (meth) acrylate having two or more functionalities, and the larger the number of crosslinked structures, so that the cured film is less likely to be fragile.

[Component (C)]
As the component (C), hollow silica fine particles in which the inside of the silica fine particles is hollow are used.

The average primary particle diameter of the hollow silica fine particles used as the component (C) is preferably 0.1 nm or more and 50 nm or less, more preferably 1 nm or more and 40 nm or less, and further preferably 2 nm or more and 30 nm or less. It is particularly preferably 3 nm or more and 20 nm or less, and most preferably 5 nm or more and 15 nm or less.
If the average primary particle size of the hollow silica fine particles is less than the above lower limit value, good steel wool resistance and antifouling property may not be obtained when low reflectance is realized. On the other hand, if the average primary particle size of the hollow silica fine particles exceeds the above upper limit value, the void ratio of the hollow silica fine particles becomes large, so that the desired hardness may not be obtained, and the film thickness of the formed cured film may not be obtained. When is about 100 nm, a part of the hollow silica fine particles may protrude from the film surface and the cured film may become cloudy, and during the steel wool resistance test, the steel wool may protrude from the cured film into the hollow silica fine particles. It may get caught or scratched.

The average primary particle size of the hollow silica fine particles is obtained from, for example, an image of a cross-sectional electron microscope (preferably a transmission electron microscope such as TEM or STEM having a magnification of 50,000 times or more) using image processing software. be able to. In addition, hollow silica fine particles are obtained by manually calculating the average value using an image of a cross-sectional electron microscope (preferably a transmission electron microscope such as TEM or STEM with a magnification of 50,000 times or more) in consideration of the scale. The average primary particle size of the above may be obtained. In this case, 10 hollow silica fine particles are selected from the larger one of the hollow silica fine particles in one image, this is performed for 5 images, and the average value is calculated from a total of 50 hollow silica fine particles. Further, if the hollow silica fine particles are present alone, that is, before the hollow silica fine particles are incorporated into the cured film or the curable composition, the average primary particle size of the hollow silica fine particles should be measured by a laser scattering method. Can be done. The measurement result by the laser scattering method and the calculation result from the image of the cross-section electron microscope are almost equal.

The hollow silica fine particles preferably have a photopolymerizable functional group on the surface. Such silica fine particles having a photopolymerizable functional group on the surface can be produced by surface-treating the silica fine particles with a silane coupling agent or the like. As a method of treating the surface of the silica fine particles with a silane coupling agent, a dry method of spraying the silane coupling agent on the silica fine particles or a wet method of dispersing the silica fine particles in a solvent and then adding the silane coupling agent to react. And so on.

As the hollow silica fine particles, the corresponding commercially available product may be used, and for example, acrylic-modified hollow silica fine particles “Thruria 4320” manufactured by JGC Catalysts and Chemicals Co., Ltd. can be used.

[Content ratio of component (A), component (B) and component (C)]
The curable composition of the present invention contains 1 to 99 parts by weight of the component (A) with respect to 100 parts by weight of the component (B). If the content of the component (A) in the curable composition is large, it is possible to cause a desired phase separation, and if it is small, the viscosity does not become too high and it is easy to handle during film formation and molding. Therefore, the curable composition of the present invention preferably contains 5 parts by weight or more of the component (A) with respect to 100 parts by weight of the component (B), more preferably 10 parts by weight or more, and 20 parts by weight. It is more preferably contained in an amount of 30 parts by weight or more, particularly preferably 40 parts by weight or more, and most preferably 40 parts by weight or more. Further, it is preferable to contain 90 parts by weight or less of the component (A), more preferably 80 parts by weight or less, still more preferably 70 parts by weight or less, and 60 parts by weight with respect to 100 parts by weight of the component (B). It is particularly preferable to include the following, and most preferably 50 parts by weight or less.

Further, the curable composition of the present invention contains 0.5 to 30 parts by weight of the component (C) with respect to 100 parts by weight of the component (B), that is, the component (C) is the component (A). It is preferable because it is uniformly dispersed in the mixture of the component (B) and transparency can be easily ensured. When the content of the component (C) with respect to the component (B) is at least the above lower limit, the effect of reducing the reflectance due to the inclusion of the component (C) can be obtained more reliably. On the other hand, when the content of the component (C) with respect to the component (B) is not more than the above upper limit, the reflectance is reduced and transparency can be sufficiently ensured. Therefore, the curable composition of the present invention preferably contains the component (C) in an amount of 1 part by weight or more, more preferably 1.5 parts by weight or more, based on 100 parts by weight of the component (B). It is particularly preferable to contain more than 3 parts by weight, and most preferably 3 parts by weight or more. Further, it is more preferably 25 parts by weight or less, further preferably 20 parts by weight or less, particularly preferably 15 parts by weight or less, and most preferably 10 parts by weight or more.

[catalyst]
The curable composition of the present invention preferably contains a catalyst in order to improve the reactivity of living radical polymerization.
As the catalyst, a known catalyst that can be used in the reaction of living radical polymerization can be used, and one or more of those exemplified as the catalyst used in the production of the iodine-terminated polymer (A) described above can be used.

The content of the catalyst is preferably 0.01 part by weight or more, more preferably 0.05 part by weight or more, based on 100 parts by weight of the total of the component (A) and the component (B) from the viewpoint of enhancing the reactivity. It is more preferably 0.1 parts by weight or more. The content of the catalyst is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 5 parts by weight or less from the viewpoint of suppressing the coloring of the coating film.

[Other ingredients]
The curable composition of the present invention may contain components other than the above-mentioned component (A), component (B), component (C), and catalyst as long as the effects of the present invention are not impaired. .. Other components that the curable composition may contain include solvents for uniformly mixing each component, and various commonly used components such as antistatic agents, plasticizers, surfactants, antioxidants, and UV absorbers. Additives and the like can be mentioned.

The solvent is not particularly limited, and is appropriately selected in consideration of the component (A), the component (B), the material of the base material (C), the material of the base material as a base, the coating method of the composition, and the like. Specific examples of the solvent include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and ethylene glycol diethyl ether. , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol and other ether solvents; ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate and other ester solvents; dimethylformamide, diethylformamide, N-methyl Examples thereof include amide-based solvents such as pyrrolidone; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; alcohol-based solvents such as methanol, ethanol, propanol, isopropanol and butanol; halogen-based solvents such as dichloromethane and chloroform; and the like.

One of these solvents may be used alone, or two or more of them may be used in combination. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.

The amount of the solvent used is not particularly limited, and is appropriately determined in consideration of the coatability of the prepared curable composition, the viscosity / surface tension of the liquid, the compatibility of the solid content, and the like. Usually, the curable composition of the present invention is prepared as a coating liquid having a solid content concentration of 20 to 100% by weight, preferably 30 to 100% by weight, using the above-mentioned solvent. Here, the solid content in the curable composition means the total amount of components other than the solvent contained in the curable composition. The curable composition of the present invention does not contain a solvent and may have a solid content of 100% by weight.

[Method for preparing curable composition]
The method for preparing the curable composition of the present invention is not particularly limited, and for example, the above-mentioned component (A), component (B) and component (C) are further mixed with the above-mentioned catalyst or the like as needed. Can be prepared by.

[Use]
The use of the curable composition of the present invention is not particularly limited, but it is particularly industrially useful for forming the cured film described below.

[Curing / laminated body]
A cured product can be obtained by irradiating the curable composition of the present invention with active energy rays and / or heating to cure the composition. In particular, a laminate (hereinafter, may be referred to as "laminate") formed by forming a cured film of the curable composition on the substrate by curing the curable composition on the substrate. can do. Further, a cured film can be obtained by curing the curable composition in the form of a film on a substrate. Further, by applying a curable composition on another resin film as a base material and curing it to form a cured film, a film laminate formed by laminating the cured film on the other resin film can be obtained.

As the base material used for obtaining the cured film, various resin films, resin plates, and the like can be used. Examples of the resin film include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, and polyester film. , Polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth) acrylic nitrile film, cycloolefin polymer (COP) film and the like can be used. Further, as the resin plate, for example, an acrylic plate, a triacetyl cellulose plate, a polyethylene terephthalate plate, a diacetylene cellulose plate, an acetate butyrate cellulose plate, a polyethersulfone plate, a polyurethane plate, a polyester plate, a polycarbonate plate, a polysulfone plate, a polyether plate. , Polymethylpentene plate, polyester ketone plate, (meth) acrylic nitrile plate and the like. In addition, glass or the like can be used if necessary. All of these base materials have excellent transparency and are also preferable for application to an optical film described later. The thickness of the base material can be selected in a timely manner according to the intended use, but generally, a material having a thickness of about 25 to 1000 μm is used.

When the curable composition is cured on the substrate, the method for applying the curable composition to the substrate is not particularly limited. For example, dip coating method, air knife coating method, curtain coating method, spin coating method, roller coating method, bar coating method, wire bar coating method, gravure coating method, extrusion coating method (US Pat. No. 2,681294), etc. It can be applied by the method of.

A cured film can be formed as a cured product by curing the coating film obtained by applying the curable composition or the coating film dried after application, if necessary. Curing can be performed by irradiating the coating film with light using a light source that emits active energy rays having a wavelength as required. The light irradiation for curing is preferably such that the integrated light amount is 100 mJ / cm ² to 20,000 mJ / cm ² . As the light source, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide, a xenon flash, an ultraviolet LED, an electron beam, or the like can be used.

As shown in Examples below, when the curable composition is applied to a substrate as described above and irradiated with active energy rays to form a cured film, the component (A) is componentd from the end. By polymerizing (B), the interface of the domain after phase separation takes a co-continuous structure, and as a result, the size of the domain becomes smaller, while the surface silanol residue of the component (C) having a low refractive index is high. It is considered that the coating film becomes transparent because it is mainly present in the domain of this phase-separated structure due to its polarity. On the other hand, when a polymer having no starting point for initiating polymerization is used instead of the component (A), when only the component (B) is polymerized, only the component (A) is aggregated by the excluded volume effect, and as a result, the domain It is considered that the coating film does not become transparent due to the increase in size.

Further, when the curable composition of the present invention is applied to a substrate as described above and irradiated with active energy rays to form a cured film, the active energy rays are applied to the opposite side of the substrate, that is, coated. By irradiating from the film side in the presence of oxygen near the surface of the coating film, the size of the domain formed by spinodal decomposition inside the cured film is increased from the substrate side to the side irradiated with the active energy ray. It is possible to form a cured film having a microphase-separated structure that gradually becomes smaller toward the surface and is inclined toward the surface side of the cured film.
This is because, at the air interface on the surface of the membrane, polymerization inhibition occurs due to oxygen in the air, whereas as it goes deeper into the membrane, the polymerization inhibition disappears, so that the polymerization becomes easier to proceed, and as the polymerization progresses, it becomes easier to proceed. It is considered that this is because a relatively large domain is formed by phase separation by spinodal decomposition, and a relatively small domain is formed by polymerization inhibition by oxygen from the deep part of the membrane toward the membrane surface side.
Here, the "phase-separated structure" means that the structure is distinguished as a phase image in the analysis by the atomic force microscope.

[Membrane of the present invention]
As another aspect of the present invention, the film of the present invention is a film formed on the surface of a base material, and is characterized by satisfying the following formula (2).
0.1% ≤ [Silica volume fraction] _B <[Silica volume fraction] _T ... (2)
(In the above formula (2), [volume fraction of silica] _T and [volume fraction of silica] _B are measured by three-dimensional volume fraction, and [volume fraction of silica] _T is 0 μm or more in depth from the surface of the film. It is the ratio of the volume occupied by the silica fine particles to the unit volume of at least one region of 3 μm or less, and [volume fraction of silica] _B is the unit of at least one region having a depth of 0 μm or more and 3 μm or less from the substrate interface of the film. It is the ratio of the volume occupied by the silica fine particles to the volume.)
The method for producing this film is not particularly limited, but it can be preferably obtained by using the above-mentioned curable composition of the present invention.

Here, the three-dimensional Tomography is carried out as follows.
<3D Tomography>
Using a transmission electron microscope (JEOL-2100 manufactured by JEOL Ltd., on-board electron gun: LaB6), a thin film section cut out to 100 nm was photographed while tilting from -50 ° to + 50 ° in 1 ° increments. The obtained two-dimensional data is imaged with reconstruction / analysis software (Composer Ver3.0, VISUALIZER-KAI manufactured by System Infrontia), and the silica content in the cured film is calculated.

The silica used for forming the film of another aspect of the present invention is silica particles whose surface is modified with the following compounds having an acryloyl group in addition to the hollow silica fine particles of the above component (C) (hereinafter, "silica of another aspect"). It may also be referred to as "particle").

The silica particles whose surface is modified with the compound having an acryloyl group can be produced, for example, by subjecting the silica particles dispersed in a solvent to a hydrolysis condensation reaction with the silane compound having an acryloyl group. Silica particles whose surface is modified with a compound having an acryloyl group can be produced, for example, by the method described in JP-A-2006-249322, and more specifically, a compound having an acryloyl group on its surface. First, a silane compound having an acryloyl group is added to the silica particles using an organic solvent as a dispersion medium, and then water and acetylacetone aluminum are added as a hydrolysis catalyst, and the particles are stirred under heating. It can be obtained by advancing the hydrolysis reaction.

Examples of the silica particles dispersed in the solvent include methanol, ethanol, propanol, butanol, isopropyl alcohol, ethylene glycol, xylene, dimethylacetamide, methylethylketone, methylisobutylketone, ethylene glycol monon-propyl ether, propylene glycol monomethyl ether, and the like. Examples thereof include silica particles dispersed in one or more kinds of solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, toluene and cyclohexanone. These are available as commercial products, and examples thereof include methanol silica sol MA-ST-M manufactured by Nissan Chemical Industry Co., Ltd., isopropyl alcohol silica sol IPA-ST, ethylene glycol silica sol EG-ST, and xylene /. Butanol silica sol XBA-ST, dimethyl acetamide silica sol DMAC-ST, methyl ethyl ketone silica sol MEK-ST, methyl isobutyl ketone silica sol MIBK-ST, ethylene glycol mono n-propyl ether silica sol NPC-ST-30, propylene glycol monomethyl ether silica sol PGM-ST, Ethylene acetate silica sol EAC-ST, propylene glycol monomethyl ether acetate PMA-ST, toluene silica sol TOR-ST, cyclohexanone silica sol CHO-ST-M and the like can be used. These may be used alone or in combination of two or more.

Further, the silica particles dispersed in the solvent preferably have an average primary particle diameter of 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, and 200 nm or less. It is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less. When the average primary particle diameter of the silica particles is at least the above lower limit value, the scratch resistance and the surface hardness tend to be improved, and when it is at least the above upper limit value, the transparency of the cured product tends to be good. .. The average primary particle diameter of the silica particles dispersed in the solvent in the present invention is a value obtained as a conversion value from the following formula by obtaining a specific surface area measurement value (based on JIS Z8830) by the BET adsorption method. Catalog values can be used for commercial products.
[Average primary particle size (nm)] =
6,000 / [[Specific surface area (m ² / g)] x [Density (g / cm ³ )]]

Examples of the silane compound having an acryloyl group include β- (meth) acryloyloxyethylmethyldimethoxysilane, β- (meth) acryloyloxyethylmethyldiethoxysilane, and β- (meth) acryloyloxyethyldimethylmethoxysilane. β- (meth) acryloyloxyethyldimethylethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxypropyldimethylmethoxysilane, γ- (Meta) acryloyloxypropyldimethylethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ-( Meta) Acryloyloxypropyltriethoxysilane or the like can be used. These may be used alone or in combination of two or more.
Amount of acryloyl group modified on the silica particle surface of silica particles whose surface is modified with a compound having an acryloyl group (Amount of double bond per 1 g of silica particles whose surface is modified with a compound having a (meth) acryloyl group ( mol)), the value calculated from the charged value is preferably 0.1 to 2.0 mmol / g, more preferably 0.2 to 1.5 mmol / g, and further preferably 0.3 to 1.0 mmol / g. preferable.
In addition, in another aspect of the present invention, it is still in the range of speculation and is not limited to the following speculation, but in another aspect of the present invention, the inclination is seen in a region having a thinner surface. Further, the component (A) has a higher polarity than the component (B), and an epoxy group having a good affinity with silica is introduced, so that the silica is more arranged on the surface. Therefore, it is presumed that the effect of the present invention can be obtained not only with hollow silica but also with colloidal silica as described above.

When the [volume fraction of silica] _B of the cured film of the present invention is 0.1% or more, silica is distributed over the entire film without being present only on the surface, so that the refractive index is inclined and low reflection is achieved. Become. [Volume fraction of silica] _B is preferably 1% or more, more preferably 3% or more, and most preferably 5% or more.
Further, the fact that [silica volume fraction] _T is larger than [silica volume fraction] _B indicates that silica particles having a low refractive index are distributed more on the surface side than on the base material side, and the reflectance. It contributes to the reduction of.
Further, the [volume fraction of silica] _T is preferably 7% or more, and more preferably 10% or more from the viewpoint of reducing the reflectance. On the other hand, from the viewpoint of suppressing aggregation of silica in the vicinity of the surface and ensuring transparency, the [volume fraction of silica] _T is preferably 70% or less, and more preferably 50% or less.
Further, the difference between [silica volume fraction] _T and [silica volume fraction] _B is preferably about 2 to 30%.

Hereinafter, the structure of the cured film of the present invention satisfying the above formula (2) may be referred to as "silica distribution structure of the present invention".

The thickness of the film of the present invention is not particularly limited, but is preferably 2 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, particularly preferably 15 μm or more, and most preferably 20 μm or more. be. The thickness of the film is preferably 1,000 μm or less, more preferably 700 μm or less, further preferably 400 μm or less, particularly preferably 150 μm or less, and most preferably 50 μm or less. It is preferable that the thickness of the film is within the above range from the viewpoint of fully utilizing the physical characteristics of the film of the present invention due to the inclined structure of phase separation in applications such as optical films.

[Membrane manufacturing method]
The method for producing the film of the present invention is not particularly limited, but is cured by containing at least a compound having an ethylenically unsaturated bond and silica particles such as hollow silica fine particles of the above-mentioned component (C) and / or silica particles of another embodiment. It is preferably formed from a cured product of the sex composition.
The type of the ethylenically unsaturated bond in the compound having an ethylenically unsaturated bond is not particularly limited, and examples thereof include a (meth) acryloyl group, a (meth) acrylamide group, a styryl group, and an allyl group. Among these, it is preferable to include a compound having a (meth) acryloyl group. The number of ethylenically unsaturated bonds in one molecule of a compound having an ethylenically unsaturated bond that can be used as a raw material for the film of the present invention is not particularly limited, but is usually 1 to 15. Further, two or more kinds of raw materials having different numbers of ethylenically unsaturated bonds may be mixed and used.

Among the compounds having an ethylenically unsaturated bond, the compound having a (meth) acryloyl group includes a monofunctional (meth) acrylate having one (meth) acryloyl group and a polyfunctional compound having two or more (meth) acryloyl groups. Examples include (meth) acrylate. These may be used alone or in combination of two or more, but preferably contain a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate , Isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (Meta) acrylate, ethylcarbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, ethylene oxide-modified phenoxy (meth) acrylate, propylene oxide-modified phenoxy ( Meta) acrylate, nonylphenol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, propylene oxide-modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolytylene glycol (meth) acrylate, methoxypropylene glycol (meth) Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropylhydrogen Phtalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyltetrahydrohydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate , Hexafluoropropyl (meth) acrylate, Octafluoropropyl (meth) acrylate, Octafluoropropyl (meth) acrylate, 2-adamantan And adamantane derivative mono (meth) acrylate such as adamantyl (meth) acrylate having a monovalent mono (meth) acrylate derived from adamantane diol. These may be used alone or in combination of two or more.

Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth) acrylate. Ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) Bifunctional (meth) acrylates such as acrylates, neopentyl glycol di (meth) acrylates, ethoxylated neopentyl glycol di (meth) acrylates, tripropylene glycol di (meth) acrylates, and hydroxypivalate neopentyl glycol di (meth) acrylates. Trimethylol propanetri (meth) acrylate, ethoxylated trimethylol propanetri (meth) acrylate, propoxylated trimethylol propanetri (meth) acrylate, tris2-hydroxyethylisocyanurate tri (meth) acrylate, glycerintri (meth) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylol propanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol tetra ( Trifunctional or higher polyfunctional (meth) acrylates such as meth) acrylates, dipentaerythritol penta (meth) acrylates, ditrimethylol propanepenta (meth) acrylates, dipentaerythritol hex (meth) acrylates, and ditrimethylol propanehexa (meth) acrylates. Acrylate; A modified product of a polyfunctional (meth) acrylate compound in which a part of these (meth) acrylates is replaced with an alkyl group or ε-caprolactone; a nitrogen atom-containing heterocycle such as a polyfunctional (meth) acrylate having an isocyanurate structure. Polyfunctional (meth) acrylate having a structure; Polyfunctional (meth) acrylate having a multi-branched dendritic structure such as polyfunctional (meth) acrylate having a dendrimer structure and polyfunctional (meth) acrylate having a hyperbranched polymer structure; Urethane (meth) acrylate obtained by adding a (meth) acrylate having a hydroxyl group to cyanate or triisocyanate, or (meth) acrylate having a hydroxyl group in a reaction product having an isocyanate group at the terminal obtained by reacting an isocyanate compound with a diol compound. Examples thereof include urethane (meth) acrylate such as urethane (meth) acrylate added with. These can be used alone or in combination of two or more.

Among the ethylenically unsaturated compounds listed above, the film of the present invention is preferably formed from at least a compound having a (meth) acryloyl group, and more preferably at least from a polyfunctional (meth) acrylate. It is preferable that it is formed of a polyfunctional (meth) acrylate and a monofunctional (meth) acrylate.

The number of ethylenically unsaturated bonds in the compound having an ethylenically unsaturated bond is not particularly limited, but is usually 15 or less, preferably 10 or less, more preferably 6 or less, and further. The number is preferably 4 or less, and most preferably 2 or less. The smaller the number of ethylenically unsaturated bonds, the smaller the domain size, which is preferable because transparency can be easily ensured. Further, when the number of ethylenically unsaturated bonds in the ethylenically unsaturated compound is two or more, the polymers are crosslinked with each other and the film becomes tough, which is preferable.

When obtaining the film of the present invention, a compound having an ethylenically unsaturated bond, preferably a compound having a (meth) acryloyl group, hollow silica fine particles of the above-mentioned component (C), and / or silica of another embodiment are usually obtained. The particles are mixed with an organic solvent to obtain a curable composition. Next, it is preferable to coat this on a substrate to form a coating film, which is then irradiated with active energy rays to form a cured film. As the organic solvent and the base material that can be used in the above-mentioned production method, silica particles of another embodiment may be used instead of the above-mentioned component (A), component (B) and component (C) (component (C)). The organic solvent used in the curable composition of the present invention containing (good) and the base material used in the laminate can be mentioned. Further, in the curable composition used for obtaining the film of the present invention, silica particles of another embodiment are used instead of the above-mentioned components (A), (B) and (C) (component (C)). A curable composition containing) is preferable.

The illuminance of the active energy ray when curing the coating film is not particularly limited, but is preferably 1,000 mW / cm ² or less, more preferably 600 mW / cm ² or less, and more preferably. It is 300 mW / cm ² or less, more preferably 200 mW / cm ² or less, and particularly preferably 150 mW / cm ² or less. The illuminance of the active energy rays when curing the coating film is preferably 1 mW / cm ² or more, more preferably 5 mW / cm ² or more, still more preferably 10 mW / cm ² or more, and particularly preferable. Is 20 mW / cm ² or more, and most preferably 50 mW / cm ² or more. When the illuminance is not more than the above upper limit, sufficient polymerization time is secured to form a phase-separated structure, which is preferable. Further, when the illuminance is equal to or higher than the above lower limit, the terminal active radical of the component (A) is generated in an amount required for polymerization by irradiation with active energy rays, which is preferable because a desired phase separation structure can be easily formed.

The irradiation time of the active energy rays when curing the coating film is not particularly limited, but is preferably 0.01 seconds or longer, more preferably 0.1 seconds or longer, and even more preferably 0. It is 3 seconds or more, particularly preferably 0.5 seconds or more, and most preferably 1 second or more. The irradiation time of the active energy ray when curing the coating film is preferably 10 hours or less, more preferably 1 hour or less, further preferably 10 minutes or less, and particularly preferably 1 minute or less. The most preferable is within 10 seconds. When the irradiation time of the active energy ray is not less than the above lower limit, the polyfunctional acrylate contained in the component (B) promotes cross-linking, which tends to increase the strength of the film, which is preferable. Further, when the irradiation time of the active energy rays is within the above upper limit, it is preferable that the time required for the phase separation to be formed is sufficiently secured.

The film of the present invention is particularly preferably the same as the above-mentioned curable composition of the present invention, and when the cured film is formed by irradiating the film with active energy rays, the active energy rays are placed on the opposite side of the substrate, that is, It is preferable to irradiate from the coating film side in the presence of oxygen in the vicinity of the surface of the coating film. By irradiating the activated energy rays in this way, the size of the domain inside the cured film gradually decreases from the substrate side toward the side irradiated with the active energy rays and is inclined toward the surface side of the cured film. Along with this, the hollow silica particles are selectively arranged in a more polar domain, so that the volume fraction of the hollow silica fine particles is increased toward the surface side of the cured film, that is, the film having a microphase-separated structure, that is, the silica distribution structure of the present invention. It is possible to form a film having. This is because, at the air interface on the membrane surface, polymerization inhibition occurs due to oxygen in the air, whereas as it goes deeper into the membrane, the polymerization inhibition disappears, so that the polymerization becomes easier to proceed, and as the polymerization progresses, it becomes easier to proceed. , A relatively large domain is formed by phase separation by spinodal decomposition, and a relatively small domain is formed by polymerization inhibition by oxygen from the deep part of the membrane toward the membrane surface side, and as a result, as described above. It is considered that this is because the hollow silica is selectively arranged in one domain, so that the body integration rate of the hollow silica fine particles is larger on the film surface side than in the deep part of the cured film. In addition, in the case of obtaining the film of the present invention, it can be carried out in the same manner as in the case of obtaining the cured product of the present invention except for the above-mentioned conditions.

When producing the film having the silica distribution structure of the present invention, the above-mentioned iodine-terminated polymer was used as the component (A) in the curable composition of the present invention, and the polyfunctional (meth) acrylate was used as the component (B). When monofunctional (meth) acrylate is used, each component is considered to contribute to the reaction of forming a film as follows.
That is, when the curable composition of the present invention is photopolymerized and crosslinked in the presence of oxygen, the iodine terminal of the component (A) becomes the photopolymerization starting point, and the living radical polymerization of the component (B) proceeds from the starting point. At this time, as the polymerization of the component (B) proceeds from the end of the component (A), the polymerized portions of the component (A) and the component (B) are phase-separated, but spinodal when two kinds of ordinary polymers are mixed. Unlike decomposition, it is considered that the domain size becomes smaller due to the co-continuous phase separation state. Furthermore, since oxygen is present in the vicinity of the film surface, the polymerization progress of the film surface is slower than that of the inside due to the polymerization inhibitory effect, and the phase separation structure formed by the polymer of the component (A) and the component (B) is the surface. It is thought that it will be closer to uniform in the vicinity.

The laminate formed by forming a cured film on the base film using the curable composition of the present invention and the film having the silica distribution structure of the present invention are applied to various uses. Because the cured product of the curable composition of the present invention and the film having the silica distribution structure of the present invention have a small domain size, excellent transparency, and low reflectance due to hollow silica fine particles can be obtained. In particular, it can be suitably used as an optical film used for various optical applications. In particular, by having an inclined structure in which the size of the domain gradually decreases from the substrate side to the surface side of the cured film, the body integral index of the hollow silica fine particles increases from the substrate side to the surface side of the cured film. The film having the silica distribution structure of the present invention, which gradually grows, is inside the cured film by selecting a raw material and localizing it to a domain formed by phase separation of a component having a high refractive index and / or a component having a low refractive index. The refractive index is inclined, and the reflection of light at the interface between air and the film is suppressed due to the inclination of the refractive index, resulting in low refractive index, and it is expected to be used as an antireflection film suitable for displays and the like. Further, the film having the silica distribution structure of the present invention is viscoelastic inside the cured film by selecting a raw material and localizing it to a domain formed by phase separation of a component having high viscoelasticity and / or a component having low viscoelasticity. It has an elastic slope and is expected to be used as a protective film suitable for flexible displays and the like.

In use as an optical film such as an antireflection film, the laminate using the curable composition of the present invention is subjected to special treatment as necessary to perform optical functions (light transmission, light diffusion, light collection, refraction). , Scattering, HAZE, and other functions) may be imparted. In the application as an optical film, the laminate of the present invention may be used alone or as a laminate for an optical element by laminating several kinds of optical films in multiple layers with a coating agent or an adhesive. Examples of the optical film to which the laminate of the present invention is applied include a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film, a retardation film, an elliptical polarizing film, an antireflection film, a light diffusing film, and brightness. Examples thereof include an improved film, a prism film (also referred to as a prism sheet), a light guide film (also referred to as a light guide plate), and the like. Such an optical film is used in a liquid crystal display device, a PDP module, a touch panel module, an organic EL module, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Further, the values of various manufacturing conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-mentioned upper limit or lower limit value. , The range specified by the combination of the values of the following examples or the values of the examples may be used.

The structure and physical properties of the polymers obtained in the following synthetic examples were evaluated by the following methods.
(1) Identification of the terminal structure of the polymer MALDI (Matrix Assisted Laser Desorption Ionization) -TOF (Time Of Flight: flight time type) method (using Bruker's "Autoflex III"), excitation The molecular weight of the polymer was measured with a laser intensity (output 60%), and the terminal structure was identified by whether or not a molecular weight conforming to the following formula was confirmed.
M _IN + (M _M 1 x N ₁ + M _{M 2} x N ₂ + ...) + M _A + M _I + M _H or M _IN + (M _M 1 x N ₁ + M _{M 2} x N ₂ + ...) + M _A + M _I + M _Na
In the above formula, each symbol has the following meaning.
_MIN : Molecular weight after initiator dissociation (= 1/2 of initiator molecular weight)
M _M1 , M M ₂ ...: Molecular weight of the monomers constituting the main polymer (M ₁ , M ₂ ...
・ ・ Represents a different monomer. )
N: Natural number MA: Molecular weight of acrylic acid ester on the terminal side MI: Atomic weight of iodine atom ( _{= 126.90} )
_MH : Atomic weight of hydrogen atom (= 1.01)
M _Na : Atomic weight of sodium atom (= 22.99)

For example, as in Synthesis Example 1, the initiator is 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd.) (molecular weight after dissociation =). 154.21) When the monomer constituting the main polymer is methyl methacrylate (molecular weight = 100.12) and the terminal acrylic acid ester is butyl acrylate (molecular weight = 142.20), the molecular weight is represented by the following formula. ..
154.21 + 100.12 x N + 142.20 + 126.90 + 1.01 or 154.21 + 100.12 x N + 142.20 + 126.90 + 22.99

Identification was performed based on the above measurement results of molecular weight, and evaluation was performed according to the following criteria. Here, the desired terminal structure means that the structure is (polymethylmethacrylate)-(structural unit derived from various acrylates) -I.
◯: A molecular weight conforming to the above formula has been confirmed, and a desired terminal structure is present.
X: The molecular weight conforming to the above formula has not been confirmed, and the desired terminal structure does not exist.

(2) Molecular Weight The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polymer were measured by the GPC measurement method under the following conditions.
Equipment: Shimadzu "RID-10A / CBM-20A / DGU-20A3,"
LC-20AD / DPD-M20A / CTO-20A "
Column: "TSKgel superHM-N" manufactured by Tosoh Corporation
Detector: Differential refractive index detector (RI detector / built-in)
Solvent: Chloroform, Temperature: 40 ° C, Flow rate: 0.3 mL / min,
Injection volume: 20 μL
Concentration: 0.1% by weight, Calibration sample: Monodisperse polystyrene, Calibration method: Polystyrene

[Synthesis Example 1: Synthesis of Iodine Terminal Polymer (PMMA-BA-I)]
2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd.) in a reactor equipped with a stirrer, a reflux condenser, and a thermometer: 2.8 parts by weight of iodine, 1.5 parts by weight of iodine, and 120 parts by weight of anisole were charged, and the mixture was stirred until the solution became uniform. After shading the inside of the system and replacing with nitrogen, the temperature was raised to 65 ° C., and the mixture was stirred for 0.5 hours. Subsequently, 120 parts by weight of methyl methacrylate (MMA) and 4.4 parts by weight of tetrabutylammonium iodide (Bu ₄ NI) were added, and the mixture was stirred at 70 ° C. for 2 hours. Further, 120 parts by weight of n-butyl acrylate (BA) was added, and the mixture was stirred at 70 ° C. for 3 hours. Then, after cooling to room temperature, an iodine-terminated polymer (PMMA-BA-I) was obtained as a white powder by precipitation purification to methanol under shading.
The terminal structure and molecular weight of the obtained polymer were evaluated as described in (1) and (2) above. The results are shown in Table 1.

From Table 1, by further reacting the main polymer obtained by the living radical polymerization of the methacrylic acid ester-based monomer with the acrylic acid ester-based monomer, the iodine atom is passed through the structural unit derived from the acrylic acid ester-based monomer at the terminal. It can be seen that an iodine-terminated polymer having a structure bound to the above was produced.

[Synthesis Example 2: Synthesis of Hollow Siene Particles (Hollow Si—A)]
A nonionic surfactant (“Pluronic F-127” manufactured by AnaSpec): 250 mg was dissolved in an aqueous solution of potassium chloride (2.0 mol / L): 60 mL, and further 1,3,5-trimethylbenzene (Tokyo Chemical Industry Co., Ltd.) was dissolved. (Manufactured): 250 mg, potassium chloride (manufactured by Kanto Chemical Co., Inc.): 875 mg was added, and the mixture was stirred at 40 ° C. for 2 hours. Then, 1.0 g of bis (triethoxysilyl) benzene (manufactured by SIGMA-ALDRICH) was added, and the mixture was further stirred at 40 ° C. for 1 hour, heated to 100 ° C., and reacted for 24 hours. After cooling, an aqueous potassium hydroxide solution (2.0 mol / L) was gradually added to adjust the pH to 9, and then the same amount of ethanol was added to this solution and stirred to dissolve the surfactant. After removing the supernatant by centrifugation (SIGMA "Tabletop Cooling Centrifuge 4-16K", SPEED: 10000, Temperature: 5 ° C, 15 minutes), add the same amount of ethanol, and centrifuge and remove the supernatant. The process was repeated 3 times to obtain a hollow silica ethanol wet product.

Separately, add 1.2 g of hexyltrimethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 8.0 g of methanol to 10.8 g of an aqueous solution prepared by mixing acetic acid and water to adjust the pH to 4, and 1 at room temperature. After stirring for a time, a solution further containing 30.0 g of methanol was prepared as a silane coupling agent solution.

To this silane coupling agent solution, 1.50 g of the above-mentioned hollow silica ethanol wet product is added, and ultrasonic waves are irradiated using an ultrasonic homogenizer (“BRANSON SONIFIER 250” manufactured by EMERSON, DutyCycle: 30% Output Control: 3). Then, the obtained solution was centrifuged to remove the supernatant, and then dispersed in 600 g of methyl isobutyl ketone (MIBK), and the MIBK dispersion of hollow silica nanoparticles (hollow Si—A) (hollow silica nanoparticles / MIBK = 5 /). 1000 weight ratio) was obtained. The average primary particle diameter of the hollow silica nanoparticles obtained from the TEM observation image was about 10 nm.

[Example 1]
Surface-modified hollow silica nanoparticles (hollow Si-A) dispersion: 5.60 g is centrifuged (SIGMA "Tabletop Cooling Centrifuge 4-16K", SPEED: 10000, temperature: 5 ° C, 15 minutes). After removing the supernatant, dimethylaminoethyl acrylate (DMAEA) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 373 mg was added to an ultrasonic homogenizer (EMERSON Co., Ltd. "BRANSON SONIFIER 250", DutyCycle: 20% Output Control: 2). ) Was irradiated with ultrasonic waves for 15 minutes to prepare a dispersion. Iodine-terminated polymer (PMMA-BA-I): 200 mg, triphenylphosphine (TPP) (manufactured by Kanto Kagaku Co., Ltd.): 7.5 mg, 1,4-bis (acryloyloxy) butane (DA) (Tokyo) in this dispersion. (Manufactured by Kasei Kogyo Co., Ltd.): 93.3 mg was dissolved to obtain a curable composition coating liquid.

After forming a bar coat on a triacetyl cellulose (TAC) film (thickness: 40 μm), the curable composition coating liquid is applied to an Hg lamp (“SP-9” manufactured by Ushio, Inc., 365 nm, 50 mW /) in the atmosphere. cm ² , i-bandpass filter (“365nm bandpass filter for SP-9” manufactured by Ushio, Inc.), heat ray cut filter (“heat ray cut filter 3 for SP-9” manufactured by Ushio, Inc.) for 30 minutes of UV light By irradiating, a transparent photocurable film (thickness 10 μm) was formed.

The reflectance of the obtained TAC film with a cured film was evaluated by the following method, and the results are shown in Table 2. Table 2 also shows the blending ratios of PMMA-BA-I, hollow Si-A, DMAEA, DA, and TPP in the curable composition.

<Evaluation method of reflectance>
Scratch the back side of the TAC film with a cured film vertically and horizontally using sandpaper (# 2000 manufactured by Sankyo Rikagaku Co., Ltd.), and paint the top with a black oil-based marker. Absolute reflectance was measured using a spectrophotometer (manufactured by JASCO Corporation, "V-670").
The reflectance was evaluated as follows.
⊚: Reflectance is less than 3.0% ○: Reflectance is 3.0% or more and less than 3.5% Δ: Reflectance is 3.5% or more and less than 4.0% ×: Reflectance is 4.0 Greater than%

In addition, the volume fraction of silica was evaluated for the obtained TAC film with a cured film by the following method.

<Evaluation method of silica volume fraction>
A TAC film with a cured film was cut into a size of 1 mm × 1 cm and placed in a flat plate embedding plate for an electron microscope (Dosaka EM Co., Ltd.). Furthermore, an embedding resin (Visible light curable embedding resin "Aronix LCR D-800" manufactured by Toagosei Co., Ltd.) is put in, and the cut out TAC film with a cured film is placed almost in the center of the embedding resin, and the embedding resin is completely completed. It was irradiated with ultraviolet rays (lamp: manufactured by USHIO, "SP-9 SPOT CURE") until it was cured. The embedded resin containing the sample is sliced with a room temperature cutting ultramicrotome (“EM UC7” manufactured by Leica) to prepare a sample piece of about 100 nm, and a grid (EM Japan “carbon 20 support film”) is used. I scooped it up. Using a transmission electron microscope (JEOL-2100 manufactured by JEOL Ltd., on-board electron gun: LaB6), a thin film section cut out to 100 nm was photographed while tilting from -50 ° to + 50 ° in 1 ° increments. The shooting procedure is described below.
1. 1. The acceleration voltage is gradually increased to 160 kV, 180 kV, and 200 kV.
2. 2. Set the sample grit on the sample rod for high inclination (manufactured by JEOL Ltd.) and introduce the sample rod.
3. 3. After evacuating, press the "BEAM" button to emit an electron beam. "STANDART FO
After pressing "COUS", move the sample to the center on the fluorescent plate. Align the Z-axis of the sample with the Z-axis adjustment button on the operation panel. "HT WOBBRE", "BRITE"
Press "TILT" and adjust the left and right "TILT" knobs to align the voltage axis with the observation location.
4. Observe the sample on a fluorescent screen at a magnification of "15K" and "FOC" so that the outline of the sample stands out.
Adjust the "OUS" knob.
5. Start up SightX Viewer (manufactured by JEOL Ltd.) and observe the sample with a CCD camera.
6. By adjusting the Z-axis adjustment button on the operation panel while tilting the X-axis by 5 °, the center of the rotation axis of the sample rod is aligned with the observation position.
7. Open Recorder (manufactured by System Infrontia). "Camera" on the tab
Open "Window", click "Live Start", and click "Exposur".
Adjust the amount of light with "e". Click "Live Stop" and click "Camer"
a Window ”is closed.
8. Click "Calibration" at an angle of 0 °. "OK" on the confirmation screen
Click.
9. After calibration, move the tilt angle to -50 °.
10. Enter 50 ° for the end tilt angle and click "Start" to perform automatic tilt shooting at each angle.

In 3D Tomography analysis, the obtained 2D image is imaged by the following procedure using reconstruction / analysis software (Composer Ver3.0, VISUALIZER-KAI manufactured by System Infrontia), and silica in the cured film. The content was calculated.
The analyzed image is shown in FIG. The analysis conditions are as follows.
1. 1. Open the measured tmg file with Composer Ver 3.0.
2. 2. Select 16 alignment areas and click "START".
3. 3. After the alignment is completed, check that all the tilted images are smoothly and continuously tilted.
Open the "Reconstruction" tab and select the reconstruction area.
4. First, select "Bing 2" and click "START" to start the rebuild.
5. Open the "Result" tab, select "XZ Plane" and "YZ Plane" respectively, and specify the reconstruction range and angle of each axis.
6. Open the "Reconstruction" tab again and select "Bing 1".
Click "START" to perform the reconfiguration.
7. Click "VISUALIZER-KAI" on the "Result" tab to launch the software. The operation in "VISUALIZER-KAI" is described below.
8. Click "Volume Data" in "Control", specify the sizes of the X, Y, and Z axes in the "Crop" tab, and determine the 3D data to be cut out.
9. Click "Color" of "Control" and select "Constant" in the "Opakue Map" tab. Similarly, click "Auto" on the tab, adjust the value of "Min", eliminate the noise, and then binarize it.
10. "Vol. Fraction" of "Decoration" on the main screen was clicked, and the volume fraction with high electron density in the selected three-dimensional data was calculated.
In FIG. 1, the uncolored portion is the portion occupied by silica, and the volume fraction of silica ([volume fraction of silica] _T ) on the surface side (T) and the portion on the substrate side (B). The volume fraction of silica ([volume fraction of silica] _B ) was as follows.
[Volume fraction of silica] _T : 11.5v / v%
[Volume fraction of silica] _B : 8.0v / v%

[Comparative Example 1]
In Example 1, the curable composition coating solution was prepared in the same manner except that DMAEA: 373 mg, PMMA-BA-I: 200 mg, TPP: 7.49 mg, and DA: 93.3 mg were dissolved. A TAC film with a cured film was manufactured, the reflectance was evaluated in the same manner, and the results are shown in Table 2.

[Comparative Example 2]
In Example 1, the hollow Si—A dispersion was replaced with colloidal silica (“MEK-ST” manufactured by Nissan Chemical Industries, Ltd., solid content = 30% by weight), and the weight was set to 93 mg. A TAC film was produced, the reflectance was evaluated in the same manner, and the results are shown in Table 2.

[Comparative Example 3]
In Example 1, the hollow Si—A dispersion was replaced with colloidal silica (“MEK-ST” manufactured by Nissan Chemical Industries, Ltd., solid content = 30% by weight), and the weight was 186 mg. A TAC film was produced, the reflectance was evaluated in the same manner, and the results are shown in Table 2.

[Comparative Example 4]
In Example 1, the curable composition coating solution was added to dipentaerythritol penta / hexaacrylate (DPHA): 466.3 mg as a low-molecular-weight polymerization initiator (BASF's "Irgacure (registered trademark) 184" (Irg). 184)): A TAC film with a cured film was produced in the same manner except that 4.7 mg was dissolved, and the reflectance was evaluated in the same manner, and the results are shown in Table 2.

[Comparative Example 5]
In Example 1, the reflectance was similarly evaluated only for the TAC film (without forming the photocurable film), and the results are shown in Table 2.

As shown in Table 2, by using a curable composition containing the component (A) and the component (B) as in Comparative Example 1, curing with a lower reflectance than that of Comparative Example 5 which is a base film. Although a film can be formed, in Example 1, a cured film having a lower reflectance can be obtained by containing the component (C) as compared with Comparative Example 1. The effect of this low reflectance is obtained by using hollow silica fine particles, and such an effect cannot be obtained in Comparative Examples 2 and 3 using non-hollow silica.
Even with the cured film of the polyfunctional acrylate of Comparative Example 4, sufficient low reflectivity cannot be obtained.
Both the cured films of Example 1 and Comparative Examples 1 to 4 were excellent in transparency.

[Synthesis Example 3: Synthesis of Iodine Terminal Polymer (PGMA-BA-I)]
2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd.) in a reactor equipped with a stirrer, a reflux condenser, and a thermometer: 1.8 parts by weight, iodine: 1.5 parts by weight, and anisole: 100 parts by weight were charged and stirred until the solution became uniform. After shading the inside of the system and substituting with nitrogen, the temperature was raised to 65 ° C., and the mixture was stirred for 0.5 hours. Subsequently, 110 parts by weight of glycidyl methacrylate (GMA) and 2.9 parts by weight of tetrabutylammonium iodide (Bu ₄ NI) were added, and the mixture was stirred at 65 ° C. for 2 hours. Further, 300 parts by weight of n-butyl acrylate (BA) was added, and the mixture was stirred at 65 ° C. for 3 hours. Then, after cooling to room temperature, an iodine-terminated polymer (PGMA-BA-I) was obtained as a white powder by precipitation purification to methanol under shading.

When the terminal structure of the obtained polymer was identified from the above (1), the main polymer obtained by the living radical polymerization of the methacrylic acid ester-based monomer was further reacted with the acrylic acid ester-based monomer to cause acrylic acid at the terminal. It was confirmed that an iodine-terminated polymer having a structure in which an iodine atom was bonded via a structural unit derived from an ester-based monomer was produced.

Moreover, when the molecular weight of the obtained polymer was measured from the above (2), it was found that Mn = 3,000 and Mw = 3,240 (Mw / Mn = 1.08).

[Example 2]
In Example 1, PGMA-BA-I was used instead of PMMA-BA-I, and methyl acrylate (MA) was used instead of dimethylaminoethyl acrylate (DMAEA) to reduce the weight of the hollow Si-A dispersion. A TAC film with a cured film was produced in the same manner as in Example 1 except that the weight was 2,000 g, the reflectance was evaluated and the volume fraction of silica was evaluated in the same manner as in Example 1, and the results are shown in the table. It is shown in -3.

[Example 3]
In Example 2, the hollow Si—A dispersion was changed to colloidal silica (“MEK-ST” manufactured by Nissan Chemical Industries, Ltd., solid content = 30% by weight) in the same manner as in Example 1 except that the weight was 200 mg. A TAC film with a cured film was produced, and the reflectance and the volume fraction of silica were evaluated in the same manner as in Example 1, and the results are shown in Table 3.

[Comparative Example 6]
In Example 3, a TAC film with a cured film was produced in the same manner except that the surface was covered with a slide glass at the time of curing, and the reflectance and the volume fraction of silica were evaluated in the same manner as in Example 3. The results are shown in Table 3. In this example, by covering the surface with a slide glass, sufficient oxygen is not supplied to the surface, oxygen inhibition on the surface does not occur, and it is difficult to form an inclined structure.

[Comparative Example 7]
In Example 2, a TAC film with a cured film was produced in the same manner as in Example 1 except that the hollow Si—A dispersion was not used, and the reflectance and the volume of silica were evaluated in the same manner as in Example 1. The fractions were evaluated and the results are shown in Table 3.

In Table 3, the reflectance was evaluated as follows.
◯: Reflectance is less than 3.7% Δ: Reflectance is 3.7% or more and 4.2% or less ×: Reflectance is larger than 4.2%

From Table 3, the following can be seen.

In Examples 2 and 3, a polymer composed of a hydrophobic methacrylic acid ester-based monomer-a highly polar iodine-terminated polymer (PGMA-BA-I) was carried out by changing the component (A) with respect to Example 1. The relationship is the opposite of Example 1.
In addition, it is presumed that the epoxy group, which has a higher affinity with silica, was introduced, and the inclination of silica became remarkable, and the effect of the present invention was achieved.

The laminate formed by forming a cured film on the base film using the curable composition of the present invention and the film having the silica distribution structure of the present invention are applied to various uses. The cured product of the curable composition of the present invention and the film having the silica distribution structure of the present invention are particularly used for various optical applications because a film having a small domain size and excellent transparency can be obtained. It can be suitably used as an optical film. In particular, the film having the silica distribution structure of the present invention, which has an inclined structure in which the volume fraction of silica gradually increases from the substrate side to the surface side of the cured film, has a higher refractive index by selecting a raw material. By localizing to the domain formed by the phase separation of the component and / or the low component, the refractive index is inclined inside the cured film, and it is expected to be used as an antireflection film suitable for displays and the like. Further, the film having the silica distribution structure of the present invention is viscoelastic inside the cured film by selecting a raw material and localizing it to a domain formed by phase separation of a component having high viscoelasticity and / or a component having low viscoelasticity. It has an elastic slope and is expected to be used as a protective film suitable for flexible displays and the like.

In use as an optical film such as an antireflection film, the laminate using the curable composition of the present invention is subjected to special treatment as necessary to perform optical functions (light transmission, light diffusion, light collection, refraction). , Scattering, HAZE, and other functions) may be imparted. In the application as an optical film, the laminate of the present invention may be used alone or as a laminate for an optical element by laminating several kinds of optical films in multiple layers with a coating agent or an adhesive. Examples of the optical film to which the laminate of the present invention is applied include a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film, a retardation film, an elliptical polarizing film, an antireflection film, a light diffusing film, and brightness. Examples thereof include an improved film, a prism film (also referred to as a prism sheet), a light guide film (also referred to as a light guide plate), and the like. Such an optical film is used in a liquid crystal display device, a PDP module, a touch panel module, an organic EL module, and the like.

Claims (12)

A curable composition containing the following component (A), component (B) and component (C), and containing 1 to 99 parts by weight of component (A) with respect to 100 parts by weight of component (B).
Component (A): Iodine-terminated polymer component (B): molecule having a structure in which an iodine atom is bonded to at least one terminal of the (meth) acrylic acid ester-based polymer via a structural unit derived from an acrylic acid ester-based monomer. Compound component (C) having at least one (meth) acryloyl group within: Hollow silica fine particles The curable composition according to claim 1, wherein the component (C) is contained in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the component (B). The curable composition according to claim 1 or 2, wherein the molecular weight distribution (Mw / Mn) of the component (A) is 2.0 or less. The invention according to any one of claims 1 to 3, wherein the (meth) acrylic acid ester-based polymer contains 1 to 100% by weight of a structural unit derived from a compound represented by the following formula (1) in the polymer. Curable composition.
CH ₂ = C (R ¹ ) -C (O) OR ² ... (1)
(In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² has an alkyl group having 1 to 22 carbon atoms or a polyalkylene glycol chain having 2 to 18 carbon atoms in the alkylene chain. The group representing a group and having an alkyl group or a polyalkylene glycol chain has a phenyl group, a benzyl group, an epoxy group, a hydroxyl group, a dialkylamino group, an alkoxy group having 1 to 18 carbon atoms, and a group having 1 to 18 carbon atoms as substituents. It may have a perfluoroalkyl group, an alkylsulfanyl group having 1 to 18 carbon atoms, a trialkoxysilyl group, or a group having a polysiloxane structure.) The curable composition according to any one of claims 1 to 4, wherein the component (A) has a number average molecular weight of 800 to 150,000. Claims 1 to 1, wherein the component (B) contains at least a compound having one (meth) acryloyl group in the molecule, and the content thereof is 1 to 99% by weight based on the total weight of the component (B). 5. The curable composition according to any one of 5. A cured product obtained by curing the curable composition according to any one of claims 1 to 6. A laminate having a base material and a cured film, wherein the cured film is obtained by curing the curable composition according to any one of claims 1 to 6 on the substrate. The laminate according to claim 8, wherein in the inside of the cured film, the size of the domain formed by spinodal decomposition gradually decreases from the substrate side toward the side irradiated with the active energy rays. .. An optical film having a layer made of the cured product according to claim 7. A film having a thickness of 10 μm or more formed on the surface of a substrate, which is formed from a cured product of a curable composition containing at least a compound having an ethylenically unsaturated double bond and silica particles, and has the curability. The composition contains a compound having a (meth) acryloyl group as the compound having an ethylenically unsaturated double bond, and is a film for an optical film satisfying the following formula (2).
0.1% ≤ [Silica volume fraction] _B ≤ [Silica volume fraction] _T -1.6 ... (2)
(In the above formula (2), [volume fraction of silica] _T and [volume fraction of silica] _B are measured by three-dimensional volume fraction, and [volume fraction of silica] _T is 0 μm or more in depth from the surface of the film. It is the ratio of the volume occupied by the silica fine particles in the region of 3 μm or less, and [volume fraction of silica] _B is the ratio of the volume occupied by the silica fine particles in the region of 0 μm or more and 3 μm or less in depth from the substrate interface of the film.) The film according to claim 11 , wherein the film has a thickness of 10 to 1,000 μm.

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