JP6819034B2 - Curable Compositions for Optical Films and Optical Films - Google Patents

Description

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 has been reported as an example of using a polymer obtained by living radical polymerization.
In order to form a nanoporous structure, styrene / divinylbenzene is heat-copolymerized 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) to thermoset it. 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, a polymer blend is formed and a macrophase separated structure is formed.
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 has also been proposed (Non-Patent Document 2).

M. Seo, M. A. Hillmyer, Science 2012, 336, 1422. J. Am. Chem. Soc. 2014, 136, 5508-5519

The above 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 excellent transparency and can be applied to an optical film such as an antireflection film. An object of the present invention is to provide a curable composition capable of forming a cured film that is expected to be used.
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 in a predetermined ratio can solve the above-mentioned problems, and the curable composition has excellent transparency and a microphase-separated structure by spinodal decomposition. We have found that a cured film which is expected to be used for an optical film such as an antireflection film can be formed by a simple operation such as irradiation with active energy rays, and has 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 component (A) and component (B), and containing 1 to 99% by weight of component (A) with respect to the total amount thereof.
Component (A): Polymer component in which the terminal polymerization active group is protected by a radically cleaving covalent bond (B): Compound having at least one (meth) acryloyl group in the molecule.

[2] The curable composition according to [1], wherein the component (A) is a polymer obtained by polymerizing a monomer having a radically polymerizable unsaturated double bond.
[3] The curable composition according to [1] or [2], wherein the component (A) is a polymer in which a terminal polymerization active group is protected by a covalent bond capable of radical cleavage when irradiated with active energy rays.
[4] The group that protects the terminal polymerization active group of the component (A) is iodine, an alkyldithioester group, a phenyldithioester group, an alkyltrithiocarbonate group, a phenyltrithiocarbonate group, an alkyldithiocarbamate group, or a phenyl. The curable composition according to any one of [1] to [3], which is at least one of the group consisting of a dithiocarbamate group, an alkylzantate group, a phenylzantate group, and a tellurium atom.

[5] The curable composition according to [4], wherein the group that protects the terminal polymerization active group of the component (A) is an iodine atom.
[6] The curable composition according to any one of [1] to [5], wherein the component (A) is a polymer obtained by living radical polymerization.
[7] The curable composition according to any one of [1] to [6], wherein the molecular weight distribution (Mw / Mn) of the component (A) is 2.0 or less.

[8] The curable composition according to any one of [1] to [7], wherein the component (A) is an iodine-terminated polymer having a structure in which an iodine atom is bonded to at least one terminal.
[9] The curable composition according 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 of the (meth) acrylic acid ester-based polymer.
[10] 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 [9].

[11] The method according to [9] or [10], wherein the (meth) acrylic acid ester-based polymer contains 1 to 99% by weight of a structural unit derived from the 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 (I), 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 having an alkyl group or a polyalkylene glycol chain represents a substituent, and the substituent includes 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 1 to 1 carbon atoms. It may have a perfluoroalkyl group of 18, an alkylsulfanyl group having 1 to 18 carbon atoms, a trialcocyxysilyl group, or a group having a polysiloxane structure.)

[12] The curable composition according to any one of [1] to [11], wherein the number average molecular weight of the component (A) is 800 to 150,000.
[13] 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 [12].
[14] A cured product obtained by curing the curable composition according to any one of [1] to [13].

[15] 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 [13] on the base material. Laminated body.
[16] The laminate according to [15], wherein the cured film is formed by irradiating the curable composition on the substrate with active energy rays from the side opposite to the substrate. ..
[17] 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, [15] or [ 16].
[18] An optical film having a layer made of the cured product according to [14].

[19] A film having a phase-separated structure that satisfies the following formulas (2) and (3).
40 μm ^-1 ≤ [specific surface area] _B <[specific surface area] _T ... (2)
[Specific surface area] _T − [Specific surface area] _B ≧ 10 μm ^-1 … (3)
(In the above formulas (2) and (3), [specific surface area] _T and [specific surface area] _B are measured by an interatomic force microscope (AFM), and [specific surface area] _T is 0 μm or more and 2 μm in depth from the surface of the film. It is the specific surface area of at least one region below, and [specific surface area] _B is the specific surface area of at least one region having a depth of 5 μm or more and 50 μm or less from the surface of the film (specific surface area [μm ^-1 ] = boundary line). Length [μm] / Area [μm ² ]).)

[20] The film according to [19], which further satisfies the following formula (4).
[Specific surface area] _B <[Specific surface area] _M <[Specific surface area] _T ... (4)
(In the above formula (4), [specific surface area] _M is the specific surface area of an arbitrary region having a depth of more than 2 μm and less than 5 μm measured by an atomic force microscope (AFM) (specific surface area [μm ^-1 ]). = Boundary length [μm] / area [μm ² ]).)
[21] The film according to [19] or [20], which is formed from a cured product of a curable composition containing a compound having at least an ethylenically unsaturated double bond.
[22] The membrane according to [21], which comprises a compound having a (meth) acryloyl group as the compound having an ethylenically unsaturated double bond.
[23] The film according to any one of [19] to [23], wherein the film has a thickness of 5 to 1,000 μm.

According to the curable composition of the present invention, a cured film having 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-separated structure are provided.

6 is an AFM image of a cross section of the cured film obtained in Example 2-1.

The embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is limited to the following description as long as the gist of the present invention 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" shall mean one or both of "acrylic" and "methacryl". "(Meta) acryloyl" and "(meth) acrylate" have the same meaning.

[Curable composition]
The curable composition of the present invention contains the following components (A) and (B), and contains 1 to 99% by weight of the component (A) with respect to the total amount thereof.
Component (A): Polymer component in which the terminal polymerization active group is protected by a radically cleaving covalent bond (B): Compound having at least one (meth) acryloyl group in the molecule.

[Component (A)]
The component (A) is a polymer in which the terminal polymerization active group is protected by a radically cleavable covalent bond, and preferably a monomer having a radically polymerizable unsaturated double bond is polymerized and irradiated with active energy rays. And / or a polymer in which the terminal polymerization active group is protected by a covalent bond that can be radically cleaved by heating. The component (A) is particularly preferably a polymer in which the terminal polymerization active group is protected by a covalent bond that can be radically cleaved by irradiation with active energy rays. 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. Radical cleavage is possible by heating and / or 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 radical-cleavable covalent bond. For example, iodine atom, alkyldithioester group, phenyldithioester group, alkyltrithiocarbonate group, phenyltrithiocarbonate group, alkyldithiocarbamate group, phenyldithiocarbamate group, alkylzantate group, phenylzantate group, tellurium. Examples include atoms.
The component (A) may have only one type of a group that protects these terminal polymerization active groups, or may have two or more types.

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 Nacromolecules 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 binding stability of these component (A) to the terminal polymerization active group is excellent, and activation energy ray irradiation and / or heating, particularly active energy ray. 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 polymer structure can be easily controlled to those of interest. According to living radical polymerization, the molecular weight distribution (Mw) The narrow component (A) of / Mn) 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 an interdouble 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 a structure in which an iodine atom is bonded to at least one terminal of the (meth) acrylic acid ester polymer. It is more preferably an iodine-terminal polymer having an iodine terminal, and further preferably an iodine-terminal polymer having a structure in which iodine atoms are 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 1 to 99% by weight are preferable. The content of the structural unit derived from compound (1) in the polymer is more preferably 2 to 98% by weight, and particularly preferably 3 to 97% 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 polyalkylene glycol chain include phenyl group, benzyl group, epoxy group, hydroxyl group, dialkylamino group, alkoxy group having 1 to 18 carbon atoms, perfluoroalkyl group having 1 to 18 carbon atoms, and the like. 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 a structural unit 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 and the like 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 or an alkoxy group having 1 to 2 carbon atoms is preferable, and an epoxy group having 1 to 6 carbon atoms is used as the 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 structural units derived from one kind of compound (1), and structural units 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 2,000, from the viewpoint of being able to form a good microphase-separated structure described later in the formed cured film. The above is more preferable, 3,000 or more is further preferable, and 4,000 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 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, and particularly preferably 1.6 or less. 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 attached to 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 this component (A).

The method for producing the iodine-terminated polymer (A) is not particularly limited, but the iodine-terminated 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. Sometimes it is 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 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 Although the bond between them is cleaved, the bond between the acrylic ester monomer and the iodine atom is not cleaved. Therefore, the terminal structure of the polymer is the same regardless of whether the acrylic ester monomer is charged at once during polymerization, during polymerization or at the time of termination of polymerization. , It has a structure in which iodine atoms are bonded via a structural unit derived from an acrylic 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, so that the terminal structure of the polymer is changed. A state in which iodine atoms are bonded via a structural unit derived from a methacrylic acid ester-based monomer and those in which iodine atoms are bonded via a structural unit derived from an acrylic 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-iodine atom derived from an acrylic acid ester-based monomer, 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 cause a polymerization reaction by irradiating light having a wavelength corresponding to a predetermined energy. When the polymerization is carried out by irradiating light, the polymerization can be carried out at a temperature lower than the reaction temperature described later.

The (meth) acrylic acid ester-based polymer serving as 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 to 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 structural units derived from two or more (meth) acrylic acid esters (1) are contained, the (meth) acrylic acid ester-based polymer is usually a random copolymer.

[Method for producing 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 method for producing the iodine-terminated polymer (A) is not particularly limited as long as the method can obtain 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 methacrylate-based monomer in a solvent in the presence of a catalyst. After the polymerization, it is produced by mixing an acrylic acid ester-based monomer with the reaction system and reacting the reaction system. 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 is not generated, and if the amount of iodine used is less than the above upper limit, polymerization Since the rate is not slowed 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) phosphine, tris (3-methylphenyl) phosphine, and tris (4-methylphenyl) phosphine can be used. One of these catalysts may be used alone, or two or more of these catalysts may be used in combination.

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 molar equivalents or less, preferably 3 molar equivalents or less, and more preferably 2 molar equivalents or less with respect to the polymerization initiator. If 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 if it is less than the above upper limit. It is preferable because the polymerization rate does not become too high, 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.

<Polymerization initiator>
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) hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumylhydroperoxide, acetylperoxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, isobutylperoxide, 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 (isobutylate) 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) and 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.
One of these polymerization initiators may be used alone, or two or more thereof may be used in combination.

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 with respect to the molar. 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.
When 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 below the above upper limit, the molecular weight does not become too small, and iodine is relatively 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 side 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 butylcellosolve; Calbitols such as carbitol and butylcarbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether Kind: 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.
One of these solvents may be used alone, or two or more of these solvents may be used in combination.

The solvent is usually 0.1 to 10 parts by weight, preferably 0, based on 1 part by weight of a (meth) acrylic acid ester-based monomer (a methacrylic acid ester-based monomer in the case of the iodine-terminated polymer (A1) described later). 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>
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 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, the terminal 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-terminated polymer)”. 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-carbon atom of the acrylic acid ester of the structural unit is more sterically damaged than the α-carbon atom of the methacrylic acid ester. It is presumed that this is because the structural unit derived from the acrylic acid ester-based monomer-the terminal structure of the iodine atom is highly stable because of its small size.

The iodine-terminal polymer (A1) is preferably produced by living radical polymerization according to the above-mentioned production method of the iodine-terminal polymer (A), and the production method is methacrylic acid forming the main polymer in the iodine-terminal 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, and the methacrylic acid ester-based monomer forming the main polymer in the iodine-terminated polymer (A1) in advance may be prepared. 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 serves as the main polymer in the iodine-terminated polymer (A1) is a compound (1) represented by the above formula (1) in which R ¹ in the formula (1) is a methyl group (hereinafter, It may be referred to as "methacrylic acid ester (1')"), preferably containing 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 may contain two or more types of methacrylic acid esters (1). A structural unit derived from') 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-terminal polymer (A1) can be produced by heating in the same manner as a normal radical polymerization reaction, but it is also possible to cause a polymerization reaction by irradiating light having a wavelength corresponding to a predetermined energy. When the polymerization is carried out by irradiating light, the polymerization can be carried out 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) produced in this manner, usually has a structural unit derived from an 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 acid ester-based monomer. Further, at the terminal of the methacrylic acid ester-based polymer, the number of structural units derived from the acrylic acid ester-based monomer that is the connecting portion between the iodine atom and the methacrylic acid ester-based 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, so that a structural unit derived from the acrylic acid ester-based monomer is interposed at one end or both ends of the methacrylic acid ester-based polymer. The iodine-terminated polymer (A1) to which the iodine atom is bonded can be obtained.

Further, in the present invention, the structural unit derived from the acrylic acid ester-based monomer that connects the methacrylic acid ester-based polymer of the main polymer and the iodine atom in the iodine-terminated polymer (A1) is the compound represented by the above formula (1). Among (1), it is preferable to include a structural unit derived from a compound 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.

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, 2-Ethylhexyl acrylate or n-octadecyl acrylate is more preferable.

The iodine-terminated polymer (A1) usually contains structural units derived from one acrylic acid ester-based monomer, but when it contains structural units derived from two or more acrylic acid ester-based monomers, 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, based on 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 during the reaction of the methacrylic acid ester polymer and the acrylic acid ester monomer 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. It is possible to obtain an iodine-terminal 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 bond 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 acid 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 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 completion of the reaction of the acrylic ester-based monomer as described above, and then using water, methanol, etc. as necessary. Impurities are removed by precipitation purification with a solvent having low solubility of the iodine-terminated polymer (A1) such as diethyl ether and methanol, and then solid-liquid separation is performed for recovery. 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 production, recovery, and subsequent storage of the iodine-terminated polymer (A1) may be performed under light shielding. preferable.

The fact that the terminal structure of the iodine terminal polymer (A1) thus obtained has iodine atoms bonded via structural units 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 and identifying the terminal structure 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 (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 or the like is 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, and in the cured film obtained, good microscopic results by spinodal decomposition described later. 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 higher). 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. Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfreel (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, methoxypolythylene 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) acryloyloxypropyl Hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrohydrogen 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. One of these may be used alone, or two or more thereof may be mixed and used.

Of these, dimethylaminoethyl (meth) acrylate and n-butyl (meth) acrylate are difficult to volatilize because the molecular weight is not too small, and are easy to proceed with polymerization because the molecular weight is not too large. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfreel (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or isobornyl (meth) acrylate. Is preferable. Of these, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfreel (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 functional polyfunctional (meth) acrylate include trimethyl propantri (meth) acrylate, ethoxylated trimethylol propanthry (meth) acrylate, propoxylated trimethylol propanthry (meth) acrylate, and tris 2-hydroxy. Ethyl isocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate and other 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 type may be used alone, or two or more types 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, trimethylpropantri (meth) acrylate, Tris 2 -Hydroxyethyl isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropanetetra (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 preferable.

The component (B) is usually 1 to 99% by weight of monofunctional (meth) acrylate and 99 to 1% by weight of bifunctional or higher polyfunctional (meth) acrylate (however, monofunctional (meth) acrylate and polyfunctional (but). Meta) Contains 100% by weight of acrylate in total.

Of these, the monofunctional (meth) acrylate is preferably contained in an amount of 5 to 98% by weight, more preferably 20 to 97% by weight, more preferably 50 to 96% by weight, and 60 to 90% 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 cocontinuous phase 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 bifunctional or higher polyfunctional (meth) acrylate, and the larger the number of crosslinked structures, so that the cured film is less likely to become brittle.

[Content ratio of component (A) and component (B)]
The curable composition of the present invention contains 1 to 99% by weight of the component (A) with respect to the total amount of the component (A) and 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 the component (A) in an amount of 5% by weight or more, preferably 10% by weight or more, based on the total amount of the component (A) and the component (B). preferable. Further, it is preferable that the component (A) is contained in an amount of 60% by weight or less, and more preferably 40% by weight or less, based on the total amount of the component (A) and the component (B).

[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 parts by weight or more, more preferably 0.05 parts 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), 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 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 Amido-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 these solvents 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, it is prepared by mixing the above-mentioned components (A) and (B) together with the above-mentioned catalyst and the like, if necessary. Can be done.

[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.

[Cured product / laminate]
A cured product can be obtained by irradiating the curable composition of the present invention with active energy rays and / or heating and curing the composition. In particular, a laminate obtained by forming a cured film of the curable composition on the substrate by curing the curable composition on the substrate (hereinafter, may be referred to as "laminate"). can do. Further, a cured film can be obtained by curing the curable composition on a substrate in the form of a film. 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 polyether sulfone plate, a polyurethane plate, a polyester plate, a polycarbonate plate, a polysulfone plate, a polyether plate. , Polymethylpentene plate, polyetherketone 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 base material having a thickness of about 25 to 1000 μm is used.

When the curable composition is cured on the substrate, the method of 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, it is preferred that the cumulative amount of light is irradiated so as to be ^{100mJ / cm 2 ~20,000mJ / 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 the examples below, when the curable composition is applied to the above-mentioned substrate and irradiated with active energy rays to form a cured film, the component (A) is componentd from the end. It is considered that the polymerization of (B) causes the interface of the domain after phase separation to have a co-continuous structure, and as a result, the size of the domain is reduced and the coating film becomes transparent. On the other hand, when a polymer having no starting point for starting polymerization is used instead of the component (A) as in the comparative example described later, when only the component (B) is polymerized, only the component (A) is excluded volume. It is considered that the coating film does not become transparent due to the aggregation due to the effect and the resulting increase in the size of the domain.

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 base material 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 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.

[Membrane having a phase-separated structure]
The film of the present invention has a phase-separated structure satisfying the following formulas (2) and (3). The method for producing this film is not particularly limited, but it can be preferably obtained by using the curable composition of the present invention described above.
40 μm ^-1 ≤ [specific surface area] _B <[specific surface area] _T ... (2)
[Specific surface area] _T − [Specific surface area] _B ≧ 10 μm ^-1 … (3)

In the above formulas (2) and (3), [specific surface area] _T is the specific surface area of at least one region having a depth of 0 μm or more and 2 μm or less from the surface of the film, and [specific surface area] _B is the depth from the surface of the film. The specific surface area of at least one region of 5 μm or more and 50 μm or less. These specific surface areas have been measured by an atomic force microscope (AFM). Specifically, these specific surface areas are measured by the following methods. Here, the "phase-separated structure" means having a structure that can be distinguished as a phase image in the following analysis by an atomic force microscope.

<Specific surface area analysis method>
The specific surface area is calculated according to the following procedure using image analysis software (Asylum Research MFP3D 120804 manufactured by Oxford Instruments).
1. 1. Open the measured phase image.
2. 2. The baseline is zero-point corrected (fitting at 0th order) to smooth the image.
Operation: Set "Flatten order" on the "Flatten" tab of the "Modify panel" to "0" and click "Flatten". Set "Planefit order" on the "Planefit" tab to "3" and click "X".
3. 3. Set the mask to 0 or higher at the zero point.
Operation: Set "Threshold" on the "Mask" tab of "Modify panel" to 0, uncheck "inverse", and click "Calc Mask".
The area of 4.0 or less is recognized as a particle.
Operation: Click "Set particle" on the "Particle analysis" tab of the "Analyze panel", and then click "Analysis Particles".
5. Divide the perimeter of the particles (corresponding to the "boundary length" below in the present invention) by the area.
Operation: After the analysis is completed, open "Detailed Stats" and divide the value of "Perimeter" by "Area" to calculate the specific surface area.
(Specific surface area [μm ^-1 ] = length of boundary line [μm] / area [μm ² ])

The specific surface area of the membrane of the present invention is an index of the domain size of the phase-separated structure formed inside the membrane, and the larger the value of the specific surface area, the smaller the domain size. That is, here, the formula (2) shows that the average domain size is smaller than the size that affects the transparency, and the formula (3) exists inside the membrane rather than the domain near the surface. It shows that the domain is smaller.

Conventionally, a phase-separated structure is also formed in the membrane described in Non-Patent Document 1 (M. Seo, M. A. Hillmyer, Science 2012, 336, 1422.), But the domain size thereof is the domain size of the present invention. It is larger than the membrane. Further, since the curing process is thermosetting, the polymerization cross-linking reaction proceeds uniformly in the membrane, and the domain size of the phase-separated structure is uniform in the membrane, and the present invention has further differences. It has a characteristic phase separation structure that was not known.

From the viewpoint of film transparency, the film of the present invention preferably further satisfies the following formula (2-1), more preferably satisfies the formula (2-2), and further satisfies the formula (2-3). Is more preferable.
60 μm ^-1 ≤ [specific surface area] _B <[specific surface area] _T ... (2-1)
75 μm ^-1 ≤ [Specific surface area] _B <[Specific surface area] _T ... (2-2)
90 μm ^-1 ≤ [specific surface area] _B <[specific surface area] _T ... (2-3)

Further, in the film of the present invention, the larger the difference in domain size between the film surface and the inside, the larger the difference in physical properties between the film surface and the inside. From the viewpoint of utilizing this property, it is preferable to satisfy the following formula (3-1), and it is more preferable to satisfy the formula (3-2).
[Specific surface area] _T- [Specific surface area] _B ≥ 100 μm ^-1 ... (3-1)
[Specific surface area] _T − [Specific surface area] _B ≧ 250 μm ^-1 … (3-2)

The film of the present invention preferably further satisfies the following formula (4).
[Specific surface area] _B <[Specific surface area] _M <[Specific surface area] _T ... (4)
In the above formula (4), [specific surface area] _M is the specific surface area of an arbitrary region having a depth of more than 2 μm and less than 5 μm from the surface, and the specific surface area is measured by an atomic force microscope (AFM). Equation (4) indicates that the domain size of the phase-separated structure gradually increases from the surface to the inside of the membrane, that is, the domain size has a slanted structure.

The thickness of the film of the present invention is usually 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, still more preferably 20 μm or more. 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 properties 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 it is preferably formed from a cured product of a curable composition containing at least a compound having an ethylenically unsaturated bond.
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 membrane 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. 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, methoxypolythylene 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) acryloyloxypropyl tetrahydrohydrogen 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. Only one of these may be used, or two or more thereof may be used in combination.

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. Hexanylated 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 neopentyl glycol di (meth) acrylates of hydroxypivalate. Trimethylol propanetri (meth) acrylate, ethoxylated trimethylol propanetri (meth) acrylate, propoxylated trimethylol propanetri (meth) acrylate, tris2-hydroxyethyl isocyanurate tri (meth) acrylate, glycerin tri (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 meta) acrylates, dipentaerythritol penta (meth) acrylates, ditrimethylolpropanpenta (meth) acrylates, dipentaerythritol hexa (meth) acrylates, and ditrimethylolpropanehexa (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 dendrimer structure, Polyfunctional (meth) acrylate having a hyperbranched polymer structure, etc. Polyfunctional (meth) acrylate having a multi-branched dendritic structure; Diiso 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. Preferably, it is more preferably formed from 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 membrane of the present invention, a curable composition is usually obtained by mixing a compound having an ethylenically unsaturated bond, preferably a compound having a (meth) acryloyl group, with an organic solvent. 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. The organic solvent and the base material that can be used in the above-mentioned production method are used for the organic solvent and the laminate used in the curable composition of the present invention containing the above-mentioned components (A) and (B). Each of the base materials to be used is mentioned. Further, the curable composition used for obtaining the film of the present invention is preferably a curable composition containing the above-mentioned component (A) and component (B).

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 ray 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-separated structure can be easily formed.

The irradiation time of the active energy ray 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 curable composition of the present invention described above, and when the cured film is formed by irradiating the film with active energy rays, the active energy rays are directed to the opposite side of the substrate, that is, It is preferable to irradiate from the coating film side in the presence of oxygen near the surface of the coating film. By irradiating the active 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. A film having a microphase-separated structure, that is, a film having the phase-separated structure of the present invention can be formed. 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 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. 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 conditions.

When producing a film having a phase-separated structure of the present invention, the above-mentioned iodine-terminated polymer is used as the component (A) in the curable composition of the present invention, and the polyfunctional (meth) acrylate is 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 a photopolymerization starting point, and the living radical polymerization of the component (B) proceeds from that 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-separated structure formed by the polymer of the component (A) and the component (B) is the surface. It is thought that it will be more uniform in the vicinity.

A laminate formed by forming a cured film on a base film using the curable composition of the present invention and a film having a phase-separated 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 phase-separated structure of the present invention are particularly used in various optical applications because they have a small domain size and can be obtained with excellent transparency. It can be suitably used as an optical film. In particular, the film having the phase-separated structure of the present invention having an inclined structure in which the size of the domain gradually decreases from the base material side to the surface side of the cured film is a component having a higher refractive index by selecting a raw material. By localizing to the domain formed by phase separation of the and / or low components, 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 phase-separated 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 higher 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 added. 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), and a light guide film (also referred to as a light guide plate). 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.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to the following Examples. Further, the values of various production 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 polymer terminal structure MALDI (Matrix Assisted Laser Desorption Ionization) -TOF (Time Of Flight) 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 checking whether or not a molecular weight conforming to the following formula was confirmed.
M _IN + (M _M1 x N ₁ + M _M2 x N ₂ + ...) + M _A + M _I + M _H or
M _IN + (M _M1 x N ₁ + M _M2 x N ₂ + ...) + M _A + M _I + M _Na
In the above formula, each symbol has the following meaning.
M _IN : Molecular weight after dissociation of initiator (= 1/2 of the molecular weight of initiator)
_{M M1,} M M2 ···: the molecular weight of the monomer constituting the trunk polymer _(M 1, M ₂ ·
・ ・ Represents a different monomer. )
N: natural number M _A: molecular weight of terminal acrylate M _I: 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.) 2 in a reactor equipped with a stirrer, a reflux condenser, and a thermometer. 8.8 parts by weight, 1.5 parts by weight of iodine, and 120 parts by weight of anisole were charged and 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 with 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.

[Synthesis Example 2: Synthesis of Polymer (PMMA)]
2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) ("V-70" manufactured by Wako Pure Chemical Industries, Ltd.) 2 in a reactor equipped with a stirrer, a reflux condenser, and a thermometer. 8.8 parts by weight, 1.5 parts by weight of iodine, and 120 parts by weight of anisole were charged and 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. Then, after cooling to room temperature, a polymer (PMMA) was obtained as a white powder by precipitation purification with 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 living radical polymerization of the methacrylic acid ester-based monomer with the acrylic acid ester-based monomer, an iodine atom is present at the terminal via a structural unit derived from the acrylic acid ester-based monomer. It can be seen that an iodine-terminated polymer having a structure in which is bonded is produced.

[Synthesis Example 3: Synthesis of Low Molecular Initiator (CP-I, the same applies hereinafter)]
76.14 mg (3.00 × 10 ^-1 mmol) of iodine and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (“V-70” manufactured by Wako Pure Chemical Industries, Ltd.) 277.5 mg (9.00 × 10 ^-1 mmol) was dissolved in 1 mL of ethanol, bubbling with nitrogen gas for 15 minutes, and then heated at 60 ° C. for 2 hours to prepare a low molecular weight initiator (CP-I) solution.

[Example 1-1]
Iodine-terminated polymer (PMMA-BA-I) 300mg (6.00 × 10 -2 mmol), _catalyst: and (triphenylphosphine ^{PPh 3) 15.7mg (6.00 × 10} -2 mmol), dimethylamino A curable composition was prepared by dissolving in a mixed solution (DMAEA / DA = 4/1) of 560 mg of ethyl acrylate (DMAEA) and 140 mg of 1,4-bis (acryloyloxy) butane (DA). This curable composition was bar-coated on a PET substrate, and the film-formed surface was covered with a slide glass. From this slide glass side, Hg lamp (USHIO, "SP-9") (365 nm, 1.0 mW / cm ² , i-bandpass filter (365 nm bandpass filter for SP9, Ushio, Inc.), heat ray cut filter ( A photocurable film (thickness 10 μm) was formed by living radical copolymerization by UV irradiation for 4 hours with a heat ray cut filter for SP9 manufactured by Ushio, Inc. 3)).
The transparency of the obtained PET substrate with a cured film was evaluated by the following method, and the results are shown in Table 2. The Table 2 shows the iodine-terminated polymer in the curable composition (PMMA-BA-I), DMAEA, DA, and the mixing ratio of PPh ₃ the accumulated amount of light.

<Transparency evaluation method>
A PET substrate with a cured film was placed on a paper on which 8-point yellow letters were printed in a size of 100% on a red background, and the transparency was visually observed and evaluated as follows.
◯: The cured film is transparent.
Δ: The cured film is slightly white and hazy.
X: The cured film is white and hazy.

<Evaluation method of specific surface area>
The obtained PET substrate with a film is cut into a size of 1 mm × 1 cm, placed in a flat plate embedding plate for an electron microscope (Dosaka EM Co., Ltd.), and further embedded resin (visible light curable embedding resin manufactured by Toa Synthetic Co., Ltd.” Aronix LCR D-800 ”) was added to half and irradiated with ultraviolet rays for 10 seconds (lamp: USHIO,“ SP-9 SPOT CURE ”). The PET substrate with a cured film cut out in the above-mentioned embedding resin whose fluidity became low due to curing was placed in the center, and the embedding resin was further added and irradiated with ultraviolet rays until the embedding resin was completely cured. A smooth cross section is cut out from the embedded resin containing the sample by cutting at room temperature with an ultramicrotome (“EM UC7” manufactured by Leica), and the cross section is cut using an operating probe microscope (“MFP-3D” manufactured by Oxford Instruments). Atomic force microscope (AFM) observation (tapping mode) was performed.

The measurement conditions for AFM observation (tapping mode) are as follows.
Using "OMCL-AC160TS-R3 Target" manufactured by OLYMPUS as a probe, the amplitude value (Amplitude) at free amplitude is 1 V and the amplitude value (Set Point) of the probe at the time of measurement is 800 mV in the voltage signal applied to the piezo element. Measurement was started as the initial value. The two parameters were changed so that the phase was 90 degrees or less at all measurement points (measured in repulsive mode). The speed of adjusting the change in amplitude to 0 (Gain, the speed of response to an error) was increased to just before oscillation.
Set value Scan Size: 1 μm
Scan Rate: 1.0Hz
Scan Point, Scan Line (resolution): 256
Scan Angle: 90 degrees The specific surface area was determined by analysis by the method described above.

[Examples 1-2 to 1-4]
In Example 1, a PET substrate with a cured film was produced in the same manner except that the DMAEA / DA ratio was changed to the ratio shown in Table 2 and the UV output was 0.6 mW / cm ² , and the same was transparent. The sex was evaluated and the results are shown in Table-2.

[Example 1-5]
In Example 2, a PET substrate with a cured film was produced in the same manner as in Example 2 except that dipentaerythritol hexaacrylate (DPHA) was used instead of DA, and the transparency was evaluated in the same manner. The results are shown in Table-2.

[Comparative Example 1-1]
Polymer (PMMA) 300 mg (6.00 x 10 ^-2 mmol), Small Initiator (CP-I) 7.59 mg (6.00 x 10 ^-2 mmol), PPh ₃ 15.7 mg (6.00 x 10) ^-2 mmol) was dissolved in a mixed solution of 560 mg of DMAEA and 140 mg of DA to prepare a curable composition. A PET substrate with a cured film was produced using this curable composition in the same manner as in Example 1, and the results of evaluating the transparency in the same manner are shown in Table 2.

[Evaluation result (1)]
From Table 2, it can be seen that according to the curable composition of the present invention, a cured film having a large specific surface area (small domain size) and excellent transparency can be formed.

[Examples 2-1 to 2-3]
The cured film was prepared in the same manner as in Example 1-1, except that the coating film was not coated with the slide glass at the time of curing, and the film thickness, the illuminance and time of ultraviolet irradiation were changed to the conditions shown in Table 3. Formed. The specific surface area inside the cured film was measured by the following method. The results obtained are shown in Table 3.

<Method of evaluating specific surface area and method of AFM observation>
Samples for specific surface area analysis were prepared by the same methods as in Examples 1-1 to 1-5 and Comparative Example 1-1. Moreover, the specific surface area was analyzed and obtained by the above-mentioned method. The measurement points of the specific surface area are as follows.
[Specific surface area] _B : Depth of (20 ± 1) μm from the outermost surface [Specific surface area] _M : Depth of (10 ± 1) μm from the outermost surface [Specific surface area] _T : Depth of (1 ± 1) from the outermost surface μm depth

AFM observation (tapping mode) was carried out as follows. A PET substrate with a cured film produced by the above method is cut into a size of 1 mm × 1 cm, placed in a flat plate embedding plate for an electron microscope (Dosaka EM Co., Ltd.), and further embedded resin (visible light curable by Toa Synthetic Co., Ltd.). The embedding resin "Aronix LCR D-800") was put in half and irradiated with ultraviolet rays for 10 seconds (lamp: manufactured by USHIO, "SP-9 SPOT CURE"). The PET substrate with a cured film cut out in the above-mentioned embedding resin whose fluidity became low due to curing was placed in the center, the embedding resin was further added, and ultraviolet rays were irradiated until the embedding resin was completely cured. A smooth cross section is cut out from the embedded resin containing the sample by cutting at room temperature with an ultramicrotome (“EM UC7” manufactured by Leica), and the cross section is cut using an operating probe microscope (“MFP-3D” manufactured by Oxford Instruments). Atomic force microscope (AFM) observation (tapping mode) was performed.

The measurement conditions for AFM observation (tapping mode) are as follows.
Using "OMCL-AC160TS-R3Target" manufactured by OLYMPUS as a probe, the amplitude value (Amplitude) at free amplitude is 1V and the amplitude value (Set Point) of the probe at the time of measurement is 800mV in the voltage signal applied to the piezo element. Measurement was started as the initial value. The two parameters were changed so that the phase was 90 degrees or less at all measurement points (measured in repulsive mode). The speed of adjusting the change in amplitude to 0 (Gain, the speed of response to an error) was increased to just before oscillation.
Set value Scan Size: 1 μm
Scan Rate: 1.0Hz
Scan Point, Scan Line (resolution): 256
Scan Angle: 90 degrees Further, AFM photographs of the deep part (PET substrate side), the middle part, and the surface side of the film during AFM observation are shown in FIGS. 1 (a), (b), (c), and (d). ..

[Comparative Example 2-1]
The same procedure as in Example 2-3 was carried out except that the coating film was coated with a slide glass at the time of curing and the illuminance and time of ultraviolet rays were changed. Moreover, the specific surface area was measured in the same manner as the method described in Example 2-1. Table 3 shows the results of the measured positions (depth from the film surface) and their specific surface areas.

[Comparative Example 2-2]
Instead of the iodine-terminated polymer of component (A), a polymer (PMMA) having no site for generating radicals by active energy rays at the terminal is used, and a low-molecular-weight polymerization initiator (BASF's "Irgacare (registered trademark) 184") is used. (Irg 184)) was used, and the same procedure as in Example 2-2 was carried out except that the film thickness was changed. Moreover, the specific surface area was measured in the same manner as the method described in Example 2-1. Table 3 shows the results of the measured positions (depth from the film surface) and their specific surface areas.

[Evaluation result (2)]
First, regarding Example 2-1 in FIGS. 1 (a), (b), (c), and (d), the light-colored portion has a slower amplitude phase (soft) when the AFM probe comes into contact with it. In addition, the dark part indicates that the phase of the amplitude becomes faster (harder) when the AFM probe comes into contact with the probe, and each represents a phase separation domain formed by spinodal decomposition. A polymerization-induced and block copolymer-derived microphase-separated structure was formed inside the film, and in particular, inclined structures having different domain sizes in the film thickness direction were observed. It was confirmed that this domain size was larger toward the PET substrate side ((d) side) of the cured film and smaller toward the film surface side ((a) side). It is considered that this is because the polymerization is inhibited by oxygen at the air interface on the surface of the film, whereas a clear domain is formed in the deep part of the film by microphase separation by spinodal decomposition as the polymerization progresses.

Further, as shown in Table 3, in Examples 2-1 to 2-3, the value of the specific surface area becomes smaller as the position becomes deeper in the depth direction from the film surface, and the phase separation structure of the present invention can be obtained. It can be seen that the film to have is formed.

A laminate formed by forming a cured film on a base film using the curable composition of the present invention and a film having a phase-separated 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 phase-separated structure of the present invention are particularly used in various optical applications because they have a small domain size and can be obtained with excellent transparency. It can be suitably used as an optical film. In particular, the film having the phase-separated structure of the present invention having an inclined structure in which the size of the domain gradually decreases from the base material side to the surface side of the cured film is a component having a higher refractive index by selecting a raw material. By localizing to the domain formed by phase separation of the and / or low components, 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 phase-separated 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 higher 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 added. 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), and a light guide film (also referred to as a light guide plate). 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 (13)

A curable composition for an optical film containing the following component (A) and component (B) and containing 1 to 99% by weight of component (A) with respect to the total content of component (A) and component (B).
Component (A): 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. Component (B): Molecule Compounds having at least one (meth) acryloyl group within The curable composition for an optical film according to claim 1, wherein the molecular weight distribution (Mw / Mn) of the component (A) is 2.0 or less. The curability for an optical film according to claim 1 or 2, wherein the (meth) acrylic acid ester-based polymer contains 1 to 99% by weight of a structural unit derived from a compound represented by the following formula (1) in the polymer. Composition.
CH ₂ = C (R ¹ ) -C (O) OR ² (1)
(In the above formula (I), 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 having an alkyl group having 1 to 22 carbon atoms or a polyalkylene glycol chain having 2 to 18 carbon atoms in the alkylene chain is a substituent such as a phenyl group, a benzyl group or an epoxy group. , A hydroxyl group, a dialkylamino group, an alkoxy group having 1 to 18 carbon atoms, a perfluoroalkyl group having 1 to 18 carbon atoms, an alkylsulfanyl group having 1 to 18 carbon atoms, a trialkoxysilyl group, or a group having a polysiloxane structure. May have.) The curable composition for an optical film according to any one of claims 1 to 3, wherein the number average molecular weight of the component (A) is 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). 4. The curable composition for an optical film according to any one of 4. An optical film obtained by curing the curable composition for an optical film according to any one of claims 1 to 5. An optical film having a base material and a cured film, wherein the cured film is obtained by curing the curable composition for an optical film according to any one of claims 1 to 5 on the base material. Optical film. In the interior of the cured film, the size of domains of phase-separated structure toward earlier than Kimoto material side to the surface of the cured film side is gradually decreased, the optical film of claim 7. An optical film having a film having a phase-separated structure satisfying the following formulas (2) and (3).
40 μm ^-1 ≤ [specific surface area] _B <[specific surface area] _T ... (2)
[Specific surface area] _T − [Specific surface area] _B ≧ 10 μm ^-1 … (3)
(In the above formulas (2) and (3), [specific surface area] _T and [specific surface area] _B are measured by an interatomic force microscope (AFM), and [specific surface area] _T is 0 μm or more and 2 μm in depth from the surface of the film. It is the specific surface area of the following regions, and [specific surface area] _B is the specific surface area of the region having a depth of 5 μm or more and 50 μm or less from the surface of the film (specific surface area [μm ^-1 ] = boundary line length [μm] / Area [μm ² ]).) The optical film according to claim 9 , wherein the film having a phase-separated structure further satisfies the following formula (4).
[Specific surface area] _B <[Specific surface area] _M <[Specific surface area] _T ... (4)
(In the above formula (4), [specific surface area] _M is the specific surface area of a region having a depth of more than 2 μm and less than 5 μm as measured by an atomic force microscope (AFM).) The optical film according to claim 9 or 10 , wherein the film having a phase-separated structure is formed from a cured product of a curable composition containing at least a compound having an ethylenically unsaturated double bond. The optical film according to claim 11 , wherein the curable composition contains a compound having a (meth) acryloyl group as the compound having an ethylenically unsaturated double bond. The optical film according to any one of claims 9 to 12 , wherein the film having the phase-separated structure has a thickness of 5 to 1,000 μm.

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