JP2015078339A - Organic-inorganic composite production method, curable composition, curable composition production method, curable composition cured product, hard coat material, and hard coat film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that can be used to form a hard coat film having excellent pencil hardness, low curing shrinkage and transparency, as well as also having excellent flexing resistance and scratch resistance.SOLUTION: A curable composition can be produced by: dehydration-condensation reacting or dealcoholization-condensation reacting a silane coupling agent, and an inorganic oxide fine particle dispersed in protonic solvent to obtain a protonic solvent liquid dispersion in which an organic-inorganic composite (A) is dispersed in protonic solvent; while removing the water or alcohol produced by the dehydration-condensation reaction or dealcoholization-condensation reaction, and the protonic solvent, from the protonic solvent liquid dispersion, an aprotic solvent (S1) having a polarity is added to carry out solvent substitution, to obtain a liquid dispersion in which the organic-inorganic composite (A) is dispersed in the aprotic solvent (S1) having a polarity; and into this liquid dispersion, a poly-functional (meth) acrylate monomer (B) having at least 2 (meth)acryloyl groups, and a polymerization initiator (C) to obtain the curable composition.

Description

  The present invention relates to a method for producing an organic-inorganic composite in which a silane coupling agent is covalently bonded to inorganic oxide fine particles. The present invention also relates to a curable composition that can be cured, a method for producing the curable composition, and a cured product obtained by curing the curable composition. Furthermore, the present invention relates to the application of the curable composition as a hard coat material and a hard coat film formed using the hard coat material.

  Surfaces such as plastic sheets and plastic films are relatively soft, have poor scratch resistance and low pencil hardness, so improving the performance by providing a hard coat film on the surface of these articles to increase the surface hardness Is planned. Similar treatments have been widely performed for resin base materials made of polycarbonate, ABS resin (acrylonitrile-butadiene-styrene resin) or the like for the purpose of preventing scratches on the surface.

  Conventionally, organic materials such as polyfunctional acrylates have been used as the main material of the composition for forming such a hard coat film. However, since the curing shrinkage rate at the time of curing the coating film is large, it is suitable for plastic sheets and plastic films. When a hard coat film is provided, the end of the plastic sheet or plastic film tends to roll up (curl phenomenon), and when a hard coat film is provided on the surface of the base material, There was a problem that cracks and the like were likely to occur in the hard coat film.

In addition, the deterioration, deformation, and shrinkage due to humidity and heat are large, making it unsuitable for applications that require precise coating properties, or for applications that require environmental resistance such as light resistance and wet heat resistance. there were.
On the other hand, in order to increase the pencil hardness of the hard coat film, the influence of the resin base material, the thickness, hardness, and plasticity of the hard coat film must be taken into account. It was necessary to construct an optimal composition of the composition for forming the film.

Under such circumstances, as a composition for forming a hard coat film, Patent Document 1 contains a urethane acrylic monomer having a (meth) acryloyl group, an acrylic monomer having a hydroxyl group and an ether bond, and colloidal silica. An ultraviolet curable resin raw material composition is disclosed.
Patent Document 2 includes hexafunctional urethane acrylate, tetrafunctional or higher (meth) acrylic monomer, and colloidal silica surface-treated with a silane coupling agent having a monofunctional reactive (meth) acrylate group. A hard coat composition is disclosed.

Further, Patent Document 3 discloses an organic-inorganic composite in which polyfunctional (meth) acrylate is covalently bonded to inorganic oxide fine particles by surface treatment using a silane coupling agent, and 1-4 molecules in one molecule. An active energy ray-curable resin composition containing (meth) acrylate having a (meth) acryloyl group is disclosed.
Furthermore, Patent Document 4 discloses a protective film having a layer obtained by irradiating a composition containing polyfunctional (meth) acrylate, surface-modified inorganic fine particles, and an active energy ray-sensitive radical polymerization initiator with active energy rays. Has been. The surface-modified inorganic fine particles are a condensation reaction product of colloidal silica fine particles and a hydrolysis product of an organic silane compound, and the surface of hydrophilic colloidal silica fine particles is coated with silicone to be hydrophobized.

JP-A-9-157315 JP 2008-150484 A JP 2010-121013 A JP 2012-116173 A

  However, in the ultraviolet curable resin raw material composition disclosed in Patent Document 1, colloidal silica is dispersed but not bonded to a reactive unsaturated group, so the composition was cured to form a hard coat film. In this case, colloidal silica is not incorporated into the crosslinking system. Therefore, there is a possibility that a hard coat film having a predetermined hardness and elastic modulus cannot be obtained. In addition, colloidal silica may fall off from the hard coat film.

  In addition, in the hard coat composition disclosed in Patent Document 2, colloidal silica is incorporated into the cross-linking system when the composition is cured to form a hard coat film. It is possible to suppress omission. However, since the (meth) acrylate group of the silane coupling agent surface-treated on colloidal silica is monofunctional, the crosslinking density is lowered and the scratch resistance cannot be sufficiently obtained.

Furthermore, since the active energy ray-curable resin composition disclosed in Patent Document 3 has an insufficient surface modification amount of the inorganic oxide fine particles by the silane coupling agent, the composition was cured to form a hard coat film. In particular, it is difficult to obtain a high degree of uniform crosslinking. Therefore, the hard coat film is likely to warp, and the flex resistance and scratch resistance are insufficient.
Furthermore, the composition disclosed in Patent Document 4 has a monofunctional (meth) acrylate group in the hydrolysis product of the organosilane compound surface-treated on colloidal silica fine particles, so that the crosslinking density is reduced, and the scratch resistance is reduced. Sex cannot be obtained sufficiently.

  Therefore, the present invention solves the problems of the prior art as described above, and forms a hard coat film having excellent pencil hardness, low curing shrinkage, transparency, and excellent bending resistance and scratch resistance. It is an object to provide a curable composition and a hard coat material that can be used. Moreover, this invention makes it a subject to also provide the manufacturing method of the curable composition which can manufacture the said curable composition. Furthermore, this invention makes it a subject to provide the hard coat film | membrane and hardened | cured material which are excellent in pencil hardness, low hardening shrinkage | contraction property, transparency, and also excellent in bending resistance and scratch resistance. Furthermore, the present invention can produce a curable composition and a hard coat material capable of forming a hard coat film having excellent pencil hardness, low curing shrinkage, transparency, and excellent flex resistance and scratch resistance. Another object is to provide a method for producing a simple organic-inorganic composite.

In order to solve the above problems, the embodiments of the present invention are as described in [1] to [12] below.
[1] An organic-inorganic composite in which inorganic oxide fine particles are surface-treated with a silane coupling agent having at least two (meth) acryloyl groups and the silane coupling agent is covalently bonded to the inorganic oxide fine particles ( A) production method comprising:
The silane coupling agent and the inorganic oxide fine particles dispersed in the protic solvent are subjected to a dehydration condensation reaction or a dealcoholization condensation reaction, whereby the organic-inorganic composite (A) is dispersed in the protic solvent. A surface treatment step for obtaining a protic solvent dispersion,
While removing water or alcohol produced by the dehydration condensation reaction or the dealcoholization condensation reaction and the protic solvent from the protic solvent dispersion, a polar aprotic solvent (S1) and a boiling point of 110 ° C. or higher The aprotic solvent (S1) having the above polarity and the protic solvent (S2) having a boiling point of 110 ° C. or more are added by adding at least one kind (D) selected from the protic solvent (S2). A solvent replacement step for obtaining a dispersion in which the organic-inorganic composite (A) is dispersed in at least one selected from (D);
A method for producing an organic-inorganic composite, comprising:

[2] An organic-inorganic composite in which inorganic oxide fine particles are surface-treated with a silane coupling agent having at least two (meth) acryloyl groups, and the silane coupling agent is covalently bonded to the inorganic oxide fine particles ( A), a polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups, a polymerization initiator (C), a polar aprotic solvent (S1), and a boiling point of 110 ° C. or more A protic solvent (S2) of at least one selected from (D), and a method for producing a curable composition comprising:
The silane coupling agent and the inorganic oxide fine particles dispersed in the protic solvent are subjected to a dehydration condensation reaction or a dealcoholization condensation reaction, whereby the organic-inorganic composite (A) is dispersed in the protic solvent. A surface treatment step for obtaining a protic solvent dispersion,
While removing water or alcohol produced by the dehydration condensation reaction or the dealcoholization condensation reaction and the protic solvent from the protic solvent dispersion, the aprotic solvent having the polarity (S1) and the boiling point of 110 At least one kind (D) selected from a protic solvent (S2) having a temperature of not lower than ° C. is added to perform solvent substitution, and the aprotic solvent (S1) having the polarity and the protic solvent having a boiling point of 110 ° C. or higher ( A solvent replacement step of obtaining a dispersion in which the organic-inorganic composite (A) is dispersed in at least one (D) selected from S2);
A method for producing a curable composition comprising:

[3] In the solvent substitution step, the solvent substitution is performed in the presence of the polyfunctional (meth) acrylate monomer (B) having the at least two (meth) acryloyl groups, and the at least two (meth) acryloyl groups are changed. The polyfunctional (meth) acrylate monomer (B), the organic-inorganic composite (A), the aprotic solvent (S1) having the polarity, and the protic solvent (S2) having a boiling point of 110 ° C. or higher are selected. A method for producing a curable composition according to [2], wherein a dispersion containing at least one (D) is obtained.

[4] The curability according to [2] or [3], wherein in the solvent replacement step, the catalyst for the dehydration condensation reaction or the dealcoholization condensation reaction is removed together with water or alcohol and the protic solvent. A method for producing the composition.

[5] An organic-inorganic composite in which inorganic oxide fine particles are surface-treated with a silane coupling agent having at least two (meth) acryloyl groups and the silane coupling agent is covalently bonded to the inorganic oxide fine particles ( A) and
A polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups;
A polymerization initiator (C);
At least one (D) selected from a polar aprotic solvent (S1) and a protic solvent (S2) having a boiling point of 110 ° C. or higher;
Containing
When the content of the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups is 100 parts by mass, the content of the organic-inorganic composite (A) is 10 parts by mass or more and 2000 parts by mass. Less than or equal to
The polymerization initiator (C) when the total content of the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups is 100 parts by mass. The curable composition characterized by having a content of 0.1 to 10 parts by mass.

[6] The curable composition according to [5], wherein the silane coupling agent is a compound represented by the following chemical formula (I).
However, M in the following chemical formula (I) represents a hydroxyl group residue of a compound having at least two (meth) acryloyl groups and at least one hydroxyl group. X represents an oxygen atom or a sulfur atom. Further, R ¹ and R ² are each a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group optionally having an alkyl group having 1 to 3 carbon atoms. R ¹ and R ² may be the same or different. R ³ represents a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, or a phenylene group that may have an alkyl group having 1 to 3 carbon atoms. The alkylene group may contain an oxygen atom in the chain. Further, l represents an integer from 0 to 2, m represents an integer from 1 to 3, the sum of l and m is 3, and n represents an integer from 1 to 3.

[7] X in the chemical formula (I) is an oxygen atom, l is 0, m is 3, R ² is a methyl group or an ethyl group, and R ³ is a linear propylene group. The curable composition according to [6], which is characterized in that it exists.
[8] The silane coupling agent is obtained by a condensation reaction between a compound having an alkoxysilyl group and an isocyanato group and a compound having at least two (meth) acryloyl groups and at least one hydroxyl group, The curable composition according to [6] or [7], wherein the condensation reaction is a condensation reaction in which the isocyanate group and the hydroxyl group react to generate a urethane bond.

[9] The inorganic oxide fine particles are at least one fine particle selected from the group consisting of silica, titania, zirconia, and alumina, according to any one of [5] to [8]. Curable composition.
[10] A cured product obtained by curing the curable composition according to any one of [5] to [9].
[11] A hard coat material comprising the curable composition according to any one of [5] to [9].
[12] A hard coat film formed by placing the hard coat material according to [11] on a surface of a base material in a film shape and curing it.

  The curable composition and the hard coat material of the present invention can form a hard coat film having excellent pencil hardness, low curing shrinkage, transparency, and excellent flex resistance and scratch resistance. Moreover, the manufacturing method of the curable composition of this invention can manufacture the said curable composition. Furthermore, the hard coat film and the cured product of the present invention are excellent in pencil hardness, low curing shrinkage and transparency, and excellent in flex resistance and scratch resistance. Furthermore, the manufacturing method of the organic inorganic composite of this invention can manufacture the organic inorganic composite which can manufacture the said curable composition and the said hard-coat material.

It is a figure which shows an example of a silane coupling agent. It is a figure explaining reaction which manufactures an organic inorganic composite (A). It is a figure which shows the condensation reaction which synthesize | combines a silane coupling agent. It is a figure which shows the Michel addition reaction which synthesize | combines a silane coupling agent. It is a figure which shows the nucleophilic addition reaction which synthesize | combines a silane coupling agent. It is a figure which shows the condensation reaction which synthesize | combines a silane coupling agent. It is a figure explaining the example of the perfluoropolyether structure of a fluorine-containing compound. It is a figure explaining the example of the linear polysiloxane structure of a fluorine-containing compound. It is a figure explaining the example of the cyclic polysiloxane structure of a fluorine-containing compound. It is a figure which shows the example of the fluorine-containing compound which the perfluoro polyether structure and the cyclic polysiloxane structure have couple | bonded directly. It is a figure which shows the example of the fluorine-containing compound which has a perfluoro polyether structure and a cyclic polysiloxane structure directly couple | bonded, and has a carbon-carbon double bond.

Embodiments of the present invention will be described in detail with reference to the drawings. In the present invention, “(meth) acrylate” means methacrylate and / or acrylate.
As a result of intensive studies to solve the various problems of the above-described conventional technology, the present inventors have conducted organic treatment in which inorganic oxide fine particles are surface-treated with a silane coupling agent having at least two (meth) acryloyl groups. An inorganic composite and a polyfunctional (meth) acrylate monomer having at least two (meth) acryloyl groups are combined, and these and a polymerization initiator are combined with a polar aprotic solvent and a proton having a boiling point of 110 ° C. or higher. It has been found that the above-mentioned problems can be solved by dispersing in at least one selected from curable solvents to obtain a curable composition (hard coat material), and the present invention has been completed.

  That is, the curable composition of the present invention is obtained by surface-treating inorganic oxide fine particles with a silane coupling agent having at least two (meth) acryloyl groups and covalently bonding the silane coupling agent to the inorganic oxide fine particles. Combined organic-inorganic composite (A), polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups, polymerization initiator (C), polar aprotic solvent ( And a polyfunctional (meth) acrylate monomer (B) containing at least one (D) selected from S1) and a protic solvent (S2) having a boiling point of 110 ° C. or higher and having at least two (meth) acryloyl groups ) Content is 100 parts by mass, the content of the organic-inorganic composite (A) is 10 parts by mass or more and 2000 parts by mass or less. Content of the polymerization initiator (C) when the total content of the inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups is 100 parts by mass The amount is from 0.1 to 10 parts by mass.

  By the surface treatment, an organic-inorganic composite (A) in which the surface of the inorganic oxide fine particles is uniformly combined with a polyfunctional silane coupling agent can be obtained. A cured product obtained by copolymerizing such an organic-inorganic composite (A) and a polyfunctional (meth) acrylate monomer (B) and curing (for example, ultraviolet curing) is a cross-linked surface of the organic-inorganic composite (A). In addition to the high degree of elasticity, the elastic modulus is high due to the construction of a uniform cross-linking system, so the bending resistance characteristic of curable organic materials and the high hardness and low shrinkage characteristic of curable inorganic material composites And both. In addition, the inorganic oxide fine particles are coated with a sufficient amount of organic groups, and the modifier of the inorganic oxide fine particles is polyfunctionalized to improve the degree of crosslinking. Dropping is prevented, and the cured product of the curable composition also has high scratch resistance.

  And such a curable composition can be manufactured as follows. First, when producing the organic-inorganic composite (A), the silane coupling agent and the inorganic oxide fine particles are subjected to a dehydration condensation reaction or a dealcoholization condensation reaction in the presence of a protic solvent to obtain the protic solvent. A protic solvent dispersion in which the organic-inorganic composite (A) is dispersed is obtained (surface treatment step).

  Next, while removing water or alcohol produced by the dehydration condensation reaction or the dealcoholization condensation reaction and the protic solvent from the protic solvent dispersion, the polar aprotic solvent (S1) and the boiling point are The aprotic solvent (S1) having the above polarity and the protic solvent having a boiling point of 110 ° C. or more are added by adding at least one (D) selected from 110 ° C. or more of the protic solvent (S2). A dispersion in which the organic-inorganic composite (A) is dispersed in at least one (D) selected from (S2) is obtained (solvent replacement step).

When the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups and the polymerization initiator (C) are mixed in this dispersion, the curable composition (hard coat material) ) Can be manufactured.
Since the dehydration condensation reaction or dealcoholization condensation reaction between the inorganic oxide fine particles and the silane coupling agent is an equilibrium reaction, a reverse reaction (decomposition reaction) may also occur. When the reverse reaction occurs, the performances of the cured product (hard coat film) obtained by curing the curable composition (hard coat material) may be insufficient.

  In the curable composition (hard coat material) of this embodiment, the water or alcohol produced by the dehydration condensation reaction or the dealcoholization condensation reaction and the protic solvent are removed by the solvent substitution, and water or alcohol Since the content and the content of the protic solvent are reduced, the equilibrium shifts in the direction in which a dehydration condensation reaction or a dealcoholization condensation reaction occurs, and the reverse reaction hardly occurs. Therefore, the various performances of the cured product (hard coat film) obtained by curing the curable composition (hard coat material), that is, pencil hardness, low curing shrinkage, flex resistance, and scratch resistance are excellent.

In addition, since protic solvents are harder to vaporize than aprotic solvents, it takes a long time to remove the solvent when producing a cured product (hard coat film) by curing a curable composition (hard coat material). Or a high temperature, the manufacturing cost may increase.
The organic solvent contained in the curable composition (hard coat material) is mainly at least one (D) selected from a polar aprotic solvent (S1) and a protic solvent (S2) having a boiling point of 110 ° C. or higher. The content of the protic solvent which is a component and has a boiling point of less than 100 ° C. is preferably as small as possible.

Moreover, it is preferable that the content of water or alcohol produced by the dehydration condensation reaction or the dealcoholization condensation reaction contained in the curable composition (hard coat material) is as small as possible.
In addition, the polyfunctional (meth) acrylate monomer (B) is added to the protic solvent dispersion obtained in the surface treatment step by adding at least two polyfunctional (meth) acrylate monomers (B) having (meth) acryloyl groups. ) -Containing protic solvent dispersion may be subjected to a solvent replacement step to perform solvent replacement. Accordingly, the polyfunctional (meth) acrylate monomer (B), the organic / inorganic composite (A), the polar aprotic solvent (S1), and the protic solvent (S2) having a boiling point of 110 ° C. or more are selected. Since a dispersion liquid containing at least one kind (D) is obtained, the curable composition (hard coat material) can be produced by mixing the polymerization initiator (C) here.

  In addition, when a catalyst for the dehydration condensation reaction or the dealcoholization condensation reaction (for example, an acid or a basic compound) is used in the surface treatment step, this catalyst is used together with water or alcohol and a protic solvent in the solvent replacement step. It is preferable to remove the catalyst and reduce the content of the catalyst. The content of the catalyst in the curable composition (hard coat material) is preferably as small as possible.

Below, each component of the curable composition of this embodiment and the material for manufacturing this component are demonstrated.
<(1) Organic-inorganic composite (A)>
In the curable composition of this embodiment, the inorganic oxide fine particles are surface-treated with a silane coupling agent having at least two (meth) acryloyl groups, and the silane coupling agent is bonded to the inorganic oxide fine particles by a covalent bond. Contains an organic-inorganic composite (A). An example of the silane coupling agent is shown in FIG.

This organic-inorganic composite (A) is composed of a polyfunctional (meth) acrylic silane coupling agent (A-1) having at least two (meth) acryloyl groups and an alkoxysilyl group, and inorganic oxide fine particles (A-2). ) With a dehydration condensation reaction or a dealcoholization condensation reaction (see FIG. 2).
Since the inorganic oxide fine particles (A-2) have a large number of OH groups on the surface thereof, this OH group and the alkoxysilyl group of the silane coupling agent (A-1) undergo a condensation reaction. The silane coupling agent (A-1) and the inorganic oxide fine particles (A-2) can be bonded by a covalent bond.

<(1-1) Multifunctional (meth) acrylic silane coupling agent (A-1)>
The type of polyfunctional (meth) acrylic silane coupling agent (A-1) has at least two (meth) acryloyl groups (more preferably at least three (meth) acryloyl groups) and an alkoxysilyl group. For example, the compound represented by the following chemical formula (I) may be used.

ただし、前記化学式（Ｉ）中のＭは、少なくとも２つの（メタ）アクリロイル基と少なくとも１つのヒドロキシル基を有する化合物のヒドロキシル基残基を示す。また、Ｘは酸素原子又は硫黄原子を示す。さらに、Ｒ¹ 及びＲ² は炭素数１以上１０以下の直鎖状、分岐鎖状、若しくは環状のアルキル基又はフェニル基（炭素数が１以上３以下のアルキル基を有していてもよい）を示し、Ｒ¹ とＲ² は同一であってもよいし異なっていてもよい。さらに、Ｒ³ は炭素数１以上１０以下の直鎖状、分岐鎖状、若しくは環状のアルキレン基又はフェニレン基（炭素数が１以上３以下のアルキル基を有していてもよい）を示し、このアルキレン基は鎖中に酸素原子を含んでいてもよい。さらに、ｌは０以上２以下の整数を示し、ｍは１以上３以下の整数を示し、ｌとｍの和は３であり、ｎは１以上３以下の整数を示す。

However, M in the chemical formula (I) represents a hydroxyl group residue of a compound having at least two (meth) acryloyl groups and at least one hydroxyl group. X represents an oxygen atom or a sulfur atom. Further, R ¹ and R ² are linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms or phenyl groups (which may have an alkyl group having 1 to 3 carbon atoms). R ¹ and R ² may be the same or different. R ³ represents a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms or a phenylene group (which may have an alkyl group having 1 to 3 carbon atoms); This alkylene group may contain an oxygen atom in the chain. Further, l represents an integer from 0 to 2, m represents an integer from 1 to 3, the sum of l and m is 3, and n represents an integer from 1 to 3.

The compound represented by the chemical formula (I) can be obtained by a condensation reaction between a compound having an alkoxysilyl group and an isocyanato group and a compound having at least two (meth) acryloyl groups and at least one hydroxyl group. it can. This condensation reaction is a condensation reaction in which an isocyanato group and a hydroxyl group react to form a urethane bond.
Hereinafter, the polyfunctional (meth) acrylic silane coupling agent (A-1) will be described in more detail.

The polyfunctional (meth) acrylic silane coupling agent (A-1) can be synthesized by, for example, the following three examples (a) to (c).
(A) Compound (a-1) having an alkoxysilyl group and an isocyanato group, an organic group (hydroxyl group, mercapto group, amino group, carboxyl group, etc.) that can be condensed with the isocyanato group, and at least two (meth) acryloyl groups And a condensation reaction with the compound (a-2) having the formula (see FIG. 3).
(B) A method using a compound (b-1) having a mercapto group as a starting material, for example, a compound (b-1) having an alkoxysilyl group and a mercapto group, and a polyfunctional (meth) acrylic compound ( Michel addition reaction with b-2) (see FIG. 4), or compound (b-1) with compound (b-3) having at least one isocyanato group and two or more (meth) acryloyl groups Condensation reaction.
(C) a compound (c-1) having an alkoxysilyl group and an epoxy group, and a compound having at least two (meth) acryloyl groups and at least one phenolic hydroxyl group, mercapto group, amino group, or carboxyl group (c) -2) with nucleophilic addition reaction (see FIG. 5).

First, the method (a) will be described. Examples of the compound (a-1) include, but are not limited to, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. Moreover, these can also be used individually by 1 type and can also use 2 or more types together.
Examples of the compound (a-2) include glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, and 3-hydroxy-2- (meth) acrylic. Leuoxypropyl (meth) acrylate, bis ((meth) acryloyloxyethyl) -2-hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, Examples thereof include dipentaerythritol penta (meth) acrylate and dipentaerythritol tetra (meth) acrylate.

Furthermore, a cyclic acid is formed by a (meth) acrylic copolymer having an active hydrogen group and a (meth) acryloyl group in the side chain such as a hydroxyl group, an amino group, a mercapto group, and a carboxyl group, or a polyfunctional acrylate having a hydroxyl group. Examples include compounds formed by ring opening of anhydrides.
However, a compound (a-2) is not restricted to these, These can also use 1 type individually and can also use 2 or more types together.

  Furthermore, as the compound (a-2), a compound having a hydroxyl group is preferable because it has no reactivity with an unsaturated group and can be easily controlled, and has a moderate reactivity with an isocyanato group. . In particular, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth) acrylate are preferable.

In the condensation reaction (a), the following can be used as a catalyst for the reaction. Examples of the catalyst include tin, zirconia, titania, zinc, iron, nickel, bismuth, chromium, cobalt, amine, and phosphorus. The reaction temperature is preferably 20 ° C or higher and 60 ° C or lower, and more preferably 30 ° C or higher and 55 ° C or lower.
The reaction solvent is not particularly limited, but in order to promote the condensation reaction, it is preferable to use a solvent with little solvation. For example, nonpolar solvents such as cyclohexane, methylcyclohexane, benzene, toluene, xylene, and dichloromethane can be used. Of these, toluene is most preferable from the viewpoints of compatibility with organic substances, low water absorption, and relatively easy distillation.

Next, the method (b) will be described. Examples of the compound (b-1) include, but are not limited to, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like. Moreover, these compounds can also be used individually by 1 type, and can also use 2 or more types together.
Examples of the compound (b-2) include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tri ( (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 3 or more in the side chain A (meth) acrylic copolymer having an unsaturated group, a urethane acrylate compound obtained by condensation reaction of the compound (a-2) and a compound having two or more isocyanato groups in the molecule. It can gel, but not limited thereto. Moreover, these compounds can also be used individually by 1 type, and can also use 2 or more types together.

  Examples of the compound (b-3) include the following compounds. For example, 1,3-bis ((meth) acryloyloxy) propyl-2-methyl-2-isocyanate (trade name: Karenz BEI, manufactured by Showa Denko KK), compound (a-2) and at least two isocyanato groups A compound in which an isocyanato group remains in the molecule by condensing with a compound having an isocyanate (see FIG. 6), a (meth) acrylate copolymer having an isocyanato group and at least two unsaturated groups in the side chain, etc. However, it is not limited to these. Moreover, these compounds can also be used individually by 1 type, and can also use 2 or more types together.

  Next, the method (c) will be described. Examples of the compound (c-1) include, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Examples thereof include glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, but are not limited thereto. Moreover, these compounds can also be used individually by 1 type, and can also use 2 or more types together.

Examples of the compound (c-2) include, but are not limited to, compounds obtained by opening a cyclic acid anhydride with a polyfunctional acrylate having a hydroxyl group.
Among the methods for obtaining the polyfunctional (meth) acrylic silane coupling agent (A-1) described above, from the viewpoint of easy handling, reaction selectivity, and reaction controllability, (a) to (c) The method (a) is more preferable because the range of compound selection is wide and the handling property is high.

<(1-2) Inorganic oxide fine particles (A-2)>
Next, regarding the inorganic oxide fine particles (A-2), the following substances can be used. For example, silica, hollow silica, alumina, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, antimony tin oxide (ATO), cerium oxide, potassium oxide, Among these, an alloy in which two or more kinds are combined can be used. In particular, silica is preferred from the viewpoint of specific gravity and hardness when obtaining a hardened product, and zirconia and titania are preferred from the viewpoint of particle refractive index, handling, and transparency when obtaining a cured product having a high refractive index. Antimony tin oxide is preferable, and hollow silica is preferable from the same viewpoint when it is desired to obtain a cured product having a low refractive index.

  The inorganic oxide fine particles (A-2) are used as an organic solvent-dispersed sol in which the inorganic oxide fine particles (A-2) are dispersed in an organic solvent. The organic solvent used as the dispersion medium is a protic solvent. For example, alcohols such as methanol, ethanol, isopropanol, butanol and octanol, ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether, phenol, cresol, o- Phenols such as cresol, m-cresol, p-cresol, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, valeric acid, isovaleric acid, caproic acid, 2-ethylbutyric acid, caprylic acid, 2- Examples thereof include carboxylic acids such as ethylhexanoic acid and oleic acid. Among these, since the reactivity between the polyfunctional (meth) acrylic silane coupling agent (A-1) and the inorganic oxide fine particles (A-2) is good, the protonicity has a boiling point of less than 100 ° C. A solvent is preferable, and methanol and isopropanol are particularly preferable.

  Furthermore, the average primary particle size of the inorganic oxide fine particles (A-2) is preferably 1 nm or more and 200 nm or less, particularly preferably 5 nm or more and 100 nm or less, from the viewpoint of handling and transparency. If the average primary particle diameter is smaller than 1 nm, it is difficult to maintain a dispersed state due to the activity of the particle surface, which may cause aggregation and gelation. On the other hand, when the average primary particle diameter exceeds 200 nm, haze due to Rayleigh scattering is observed. Rayleigh scattering is proportional to the square of the particle volume, that is, the sixth power of the particle diameter, and in a particle having an average primary particle diameter of 1/4 or more of the wavelength of visible light, the scattering rapidly increases. There are high barriers to use.

The average primary particle diameter is, for example, an inorganic oxide fine particle observed with a high-resolution transmission electron microscope (H-9000 type, manufactured by Hitachi, Ltd.), and arbitrarily 100 inorganic oxide particle images from the observed fine particle image. The number average particle diameter can be obtained by a known image data statistical processing method.
As a product marketed as an organic solvent-dispersed sol of silica fine particles, for example, colloidal silica includes OSCAL-1132, OSCAL-1432M, OSCAL-1432, OSCAL-1632 manufactured by JGC Catalysts & Chemicals, and Nissan Chemical Industries, Ltd. Methanol silica sol, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, PGM-ST, PMA-ST, EAC-ST, Fuso Chemical Co., Ltd. PL-1-IPA, PL-2L-PGME, PL-2L-MEK, etc. can be mentioned.

  Moreover, as a product marketed as an organic solvent dispersion sol of zirconia fine particles, for example, Nanouse OZ-30M and Nanouse OZ-S30K manufactured by Nissan Chemical Industries, Ltd. can be mentioned. Furthermore, examples of products that are commercially available as organic solvent-dispersed sols of titania fine particles include OPTOLAKE 1130Z and OPTPLAKE 6320Z manufactured by JGC Catalysts & Chemicals.

  Examples of the shape of the inorganic oxide fine particles (A-2) include a spherical shape, a hollow spherical shape, a bead shape, a flat plate shape, and a fibrous shape. Is preferable, and a spherical shape is particularly preferable. Examples of beaded silica include IPA-ST-UP (trade name) manufactured by Nissan Chemical Industries, Ltd., and examples of hollow silica include sulria (trade name) manufactured by JGC Catalysts & Chemicals. Can be mentioned.

<(1-3) Synthesis of organic-inorganic composite (A)>
<Surface modification (surface treatment)>
For the synthesis of the organic-inorganic composite (A), a polyfunctional (meth) acrylic silane coupling agent (A-1) and a small amount of water are added in a solvent in which inorganic oxide fine particles (A-2) are dispersed. In addition, a method of advancing the dehydration condensation reaction or the dealcoholization condensation reaction by mixing and stirring can be used. Thereby, the solvent dispersion liquid in which the organic-inorganic composite (A) is dispersed in the solvent can be obtained.

Furthermore, if necessary, an acid or a basic compound may be added as a catalyst, and examples thereof include acetic acid, hydrochloric acid, nitric acid, sulfuric acid, and aqueous ammonia. Although the addition amount of a catalyst is not specifically limited, It is 0.01-1 mass part normally with respect to 100 mass parts of inorganic oxide microparticles | fine-particles (A-2), such as a silica microparticle which performs surface treatment, Preferably it is 0.01-0. .5 parts by mass.
The temperature of the dehydration condensation reaction or dealcoholization condensation reaction is preferably 10 ° C. or higher and 80 ° C. or lower, more preferably 20 ° C. or higher and 60 ° C. or lower, and further preferably 35 ° C. or higher and 55 ° C. or lower. If the reaction temperature is too low, the condensation reaction between the inorganic oxide fine particles (A-2) and the polyfunctional (meth) acrylic silane coupling agent (A-1) hardly proceeds, and the target compound cannot be obtained sufficiently. There is a fear. On the other hand, when the temperature exceeds 80 ° C., unsaturated groups in the system may be polymerized by radicals generated by heat to cause gelation.

  As the condensation reaction solvent (A-3), the dispersion medium of the above-mentioned inorganic oxide fine particles (A-2) can be used, but from the viewpoint of compatibility with the surface of the inorganic oxide fine particles (A-2), water is used. Protonic solvents such as methanol, ethanol, isopropanol, butanol, octanol, and propylene glycol monomethyl ether are preferable, and in view of both the strength of solvation and the reactivity of the surface of the inorganic oxide fine particles (A-2), Protic solvents having a boiling point of less than 100 ° C. are preferred, with methanol and isopropanol being most preferred.

  The amount of the polyfunctional (meth) acrylic silane coupling agent (A-1) used for the surface treatment of the inorganic oxide fine particles (A-2) is the same as that of the inorganic oxide fine particles (A-2) that are not surface-treated. 20 mass parts or more and 100 mass parts or less are preferable with respect to 100 mass parts, 30 mass parts or more and 95 mass parts or less are more preferable, and 40 mass parts or more and 90 mass parts or less are more preferable. When the amount of the polyfunctional (meth) acrylic silane coupling agent (A-1) used is less than 20 parts by mass, sufficient condensation reaction is not performed on the surface of the inorganic oxide fine particles (A-2). The dispersibility of the product fine particles (A-2) may be reduced. On the other hand, if it is used in excess of 100 parts by mass, the crosslink density becomes too high, which may cause warping or cracking of the hard coat film.

  In addition, in addition to the polyfunctional (meth) acrylic silane coupling agent (A-1), other silane coupling agents (A-4) are used in combination for the surface treatment of the inorganic oxide fine particles (A-2). You can also. Although the example of the silane coupling agent which can be used together is not specifically limited, 3- (meth) acryloyloxyethyltrimethoxysilane, 3- (meth) acryloyloxyethylmethyldimethoxysilane, 3- (meth) acryl Unsaturated group-containing products such as yloxyethyltriethoxysilane, 3- (meth) acryloyloxyethylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, and methyltrimethoxysilane Dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysila , Decyl trimethoxysilane, decyl triethoxysilane, trifluoromethyl trimethoxysilane, alkoxysilane compounds having a par full polyether groups and the like having a repeating unit in the molecule.

<Solvent replacement>
After the synthesis of the organic-inorganic composite (A) is completed, the solvent (dispersion medium) such as a protic solvent in the solvent dispersion in which the organic-inorganic composite (A) is dispersed is replaced with another type of solvent. The solvent replacement can be performed by adding another type of solvent to the solvent dispersion while removing the solvent (dispersion medium) from the solvent dispersion, whereby the organic-inorganic composite (A) is made of the other type of solvent. A solvent dispersion dispersed in the solvent can be obtained.

  The other type of solvent, that is, the type of the solvent (A-5) used for solvent substitution is preferably higher in boiling point than the condensation reaction solvent (A-3), and further has no hydroxyl group, or Even if it has a hydroxyl group, the electron donating property of the protic group residue is high, and it is difficult to hydrolyze the covalent bond between the silicon atom of the silane coupling agent and the inorganic oxide fine particles (A-2). is there. That is, the solvent (A-5) used for the solvent substitution is at least one selected from a polar aprotic solvent (S1) and a protic solvent (S2) having a boiling point of 110 ° C. or higher. Here, “having polarity” means having a polar group such as a ketone structure, an ester structure, an ether structure, an amide structure, or a sulfoxide structure.

  Specifically, polar aprotic solvents (S1) include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; dimethylformamide, dimethyl Amides such as acetamide and N-methylpyrrolidone can be exemplified, and examples of the protic solvent (S2) having a boiling point of 110 ° C. or higher include hydroxyl group-containing ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether. be able to. In particular, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like are preferable from the viewpoints of ease of handling, transparency, environmental load, and the like.

  By replacing the solvent, properties suitable for the use can be obtained, as well as water used in the condensation reaction, acid added as a catalyst, basic compound, and water or alcohol produced by the condensation reaction. It is possible to remove unnecessary components for the purpose. Since the content of these unnecessary components is reduced by solvent replacement, the equilibrium shifts in the direction in which a dehydration condensation reaction or a dealcoholization condensation reaction occurs, and the reverse reaction (decomposition reaction) hardly occurs.

In addition, by performing solvent substitution with a polar solvent such as a polar aprotic solvent (S1) or a protic solvent (S2) having a boiling point of 110 ° C. or higher, a polyfunctional (meta-functional) in the curable composition is obtained. ) The solubility of the acrylate monomer (B) is improved.
Furthermore, the content of the protic solvent having a boiling point of less than 100 ° C. is preferably 5% by mass or less, more preferably 1% by mass or less, and more preferably 0.25% by mass or less at the end of the solvent replacement step. Is most preferred. Since the protic solvent having a boiling point of less than 100 ° C. functions as a hydrolysis material for the surface modification of the inorganic oxide fine particles, if the content is 5% by mass or more, the surface treatment of the inorganic oxide fine particles is impaired and the physical properties are deteriorated. And may cause aggregation of inorganic oxide fine particles.

Moreover, the protic solvent used in the condensation reaction between the polyfunctional (meth) acrylic silane coupling agent (A-1) and the inorganic oxide fine particles (A-2) is replaced with a polar aprotic solvent ( The reason why it is preferable to substitute at least one (D) selected from S1) and a protic solvent (S2) having a boiling point of 110 ° C. or higher is as follows.
A compound having a hydroxyl group, such as a protic solvent having a boiling point of less than 100 ° C., causes a hydrolysis or a nucleophilic substitution reaction of alcohol depending on conditions, so that a covalent bond is formed on the surface of the inorganic oxide fine particles (A-2). The amount of silane coupling agent to be reduced may decrease. The condensation reaction occurring on the surface of the inorganic oxide fine particles (A-2) is an equilibrium reaction, but by removing the solvent having a hydroxyl group in the system (protic solvent having a boiling point of less than 100 ° C.) The condensation reaction on the surface of the oxide fine particles (A-2) is promoted, and the decomposition of the covalent bond due to hydrolysis or alcohol nucleophilic substitution reaction hardly occurs. Therefore, the amount of the silane coupling agent covalently bonded to the surface of the inorganic oxide fine particles (A-2) can be increased.

  As a result, the surface treatment amount of the inorganic oxide fine particles (A-2) increases, so that the dispersibility of the inorganic oxide fine particles (A-2) is improved and the silane coupling agent and the inorganic oxide fine particles (A-) are improved. Since the reaction 2) is an equilibrium reaction, the amount of the unmodified silane coupling agent can be reduced. Therefore, the stability over time of the curable composition is improved, and the physical properties of the cured product are improved due to an increase in the number of crosslinking points.

  The method for solvent replacement is not particularly limited. For example, the protic solvent is removed from a protic solvent dispersion in which the organic-inorganic composite (A) is dispersed in a protic solvent having a boiling point of less than 100 ° C. While leaving, at least one (D) selected from a polar aprotic solvent (S1) and a protic solvent (S2) having a boiling point of 110 ° C. or higher is added, and the solvent (dispersion medium) of the dispersion is added. By substituting at least one solvent (D) selected from a protic solvent having a boiling point of less than 100 ° C. with a polar aprotic solvent (S1) and a protic solvent having a boiling point of 110 ° C. or higher (S2), The organic / inorganic composite (A) is dispersed in at least one solvent (D) selected from a polar aprotic solvent (S1) and a protic solvent (S2) having a boiling point of 110 ° C. or higher. A method of obtaining a liquid, and the like.

The amount of the at least one solvent (D) selected from the polar aprotic solvent (S1) and the protic solvent (S2) having a boiling point of 110 ° C. or higher is the kind of the protic solvent having a boiling point of less than 100 ° C. For example, the boiling point is preferably 10 parts by mass or more and less than 600 parts by mass with respect to 100 parts by mass of the protic solvent having a boiling point of less than 100 ° C.
Further, the heating temperature of the protic solvent dispersion for distilling off the protic solvent having a boiling point of less than 100 ° C. varies depending on the type of the protic solvent having a boiling point of less than 100 ° C. and the solvent used for solvent replacement. It is preferable to set it as 70 degreeC or more. At this time, for example, a gas containing oxygen element such as nitrogen monoxide or air may be introduced into the protic solvent dispersion and bubbled. Moreover, when distilling off the protic solvent having a boiling point of less than 100 ° C., it is preferable to add a polymerization inhibitor to the protic solvent dispersion. The addition amount of the polymerization inhibitor is preferably 100 ppm or more and 1000 ppm with respect to the nonvolatile content in the protic solvent dispersion.

<(2) Polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups>
Examples of the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups include (meth) acrylic acid esters (B-1), epoxy (meth) acrylates (B-2), Urethane (meth) acrylates (B-3) are mentioned.

<(2-1) (Meth) acrylic acid esters (B-1)>
As (meth) acrylic acid esters (B-1), specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, tricyclodecane di (meth) acrylate, diacrylates such as bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Intererythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (2- (meth) Examples thereof include, but are not limited to, polyfunctional (meth) acrylates such as (acryloyloxyethyl) isocyanurate, and ethylene oxide modified products and propylene oxide modified products thereof. Among these, a trifunctional or higher functional (meth) acrylate monomer is preferable from the viewpoint of improving the hardness and scratch resistance of the cured product. Moreover, these compounds can also be used individually by 1 type, and can also use 2 or more types together.

<(2-2) Epoxy (meth) acrylates (B-2)>
Epoxy (meth) acrylates (B-2) can be obtained by reacting an epoxy compound with a carboxylic acid having a (meth) acryloyl group. Specific examples of the epoxy compound include glycidyl (meth) acrylate, glycidyl ethers having both ends of a linear alcohol having 1 to 12 carbon atoms, diethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and bisphenol A diglycidyl. Examples include ether, ethylene oxide-modified bisphenol A diglycidyl ether, propylene oxide-modified bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and glycerin diglycidyl ether. Examples of the carboxylic acid having a (meth) acryloyl group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and the like.

<(2-3) Urethane (meth) acrylates (B-3)>
Urethane (meth) acrylates (B-3) are based on alcohol compound (B-3-1), polyfunctional thiol compound (B-3-2), or polyfunctional amine compound (B-3-3). , (Meth) acryloyl group-containing isocyanate compound (B-3-4). Alternatively, the alcohol compound (B-3-1) and the isocyanate compound (B-3-5) are subjected to a condensation reaction under the condition that the isocyanate group is excessive to synthesize a polyurethane compound having an isocyanate group at the terminal, and then the terminal isocyanate group. It can also be obtained by subjecting an alcohol compound (B-3-6) having a (meth) acryloyl group to a condensation reaction.

  Specific examples of the alcohol compound (B-3-1) include (meth) acryloyloxy group-containing alcohols such as 2-hydroxyethyl acrylate, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, polyglycerin, tris (2-hydroxyethyl) isocyanurate, 1,3,5-trihydroxypentane, 1,4-dithian-2,5-dimethanol tricyclodecanediol, tri Methylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, norbornane dimethanol, polycarbonate diols, polysiloxane diols, bisphenol A, hydrogenated bisphenol A, perfluoroalcohols, perfluoropolyether Le alcohols, and their EO (ethylene oxide) modified products, PO (propylene oxide) modified products, caprolactone-modified products thereof.

  Moreover, as a polyfunctional thiol compound (B-3-2), it is C2-C20 linear, branched, or cyclic alkylthiols (It may have a thioether structure in a molecule | numerator). And thiirane adducts of the alkyl thiols. Or the ester compound which made the compound which has at least 2 hydroxyl group among the said alcohol compounds (B-3-1) and the compound of following Chemical formula (II) react is mentioned.

なお、上記化学式（II）中のＲ⁴ 及びＲ⁵ は各々独立して水素原子又は炭素数１〜１０のアルキル基若しくは芳香環であり、中でもメチル基又はエチル基が好ましい。また、Ｒ⁴ 及びＲ⁵ の一方が水素原子で、他方が炭素数１〜１０のアルキル基（特にメチル基又はエチル基）であることがさらに好ましい。ｍは０以上２以下の整数であり、好ましくは０又は１である。ｎは０又は１であり、好ましくは０である。

In addition, R ⁴ and R ⁵ in the chemical formula (II) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic ring, and among them, a methyl group or an ethyl group is preferable. More preferably, one of R ⁴ and R ⁵ is a hydrogen atom, and the other is an alkyl group having 1 to 10 carbon atoms (particularly a methyl group or an ethyl group). m is an integer of 0 or more and 2 or less, preferably 0 or 1. n is 0 or 1, preferably 0.

  Specific examples of the compound of the chemical formula (II) include 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptobutanoic acid, 3-mercaptobutanoic acid, 4-mercaptobutanoic acid, 2-mercaptoisobutanoic acid, 2- Examples include mercaptoisopentanoic acid, 3-mercaptoisopentanoic acid, and 3-mercaptoisohexanoic acid, with 3-mercaptopropionic acid and 3-mercaptobutanoic acid being preferred.

  Examples of the polyfunctional amine compound (B-3-3) include isophorone diamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminocyclohexyl) propane, hexamethylene diamine, melamine, and melamine. Derivatives and the like. From the viewpoint of the weather resistance and hardness of the cured product, isophoronediamine, 2,2-bis (4-aminocyclohexyl) propane, and melamine are preferable.

  Examples of the (meth) acryloyl group-containing isocyanate compound (B-3-4) include 2- (meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, 5- (Meth) acryloyloxypentyl isocyanate, 6- (meth) acryloyloxyhexyl isocyanate, 2- (2- (meth) acryloyloxyethyl) oxyethyl isocyanate, 3- (meth) acryloyloxyphenyl isocyanate, 4- (meth) acryloyl Oxyphenyl isocyanate, 1,3-bis ((meth) acryloyloxy) propyl-2-methyl-2-isocyanate, 1,3-bis ((meth) acryloyloxy) propyl-2-isocyanate Doors and the like.

  As the isocyanate compound (B-3-5), in addition to the aforementioned (meth) acryloyl group-containing isocyanate compound (B-3-4), hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate and its Examples thereof include hydrogenated products, xylylene diisocyanate and hydrogenated products thereof, norbornane diisocyanate, and allophanate, dimer (uretdione) and trimer (isocyanurate).

  As the alcohol compound (B-3-6) having a (meth) acryloyl group, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3- (Meth) acryloyloxypropyl (meth) acrylate, 3-hydroxy-2- (meth) acryloyloxypropyl (meth) acrylate, bis ((meth) acryloyloxyethyl) -2-hydroxyethyl isocyanurate, pentaerythritol tri (Meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, the aforementioned epoxy (meth) acrylates (B-2), and the like. It is.

<(3) Polymerization initiator (C)>
The polymerization initiator (C) used in the present invention reacts with the (meth) acryloyl group of the organic-inorganic composite (A) and the (meth) acryloyl group of the polyfunctional (meth) acrylate monomer (B) to form an organic inorganic A copolymer of the composite (A) and the polyfunctional (meth) acrylate monomer (B) can be obtained, and the following polymerization initiators can be exemplified.

  Examples thereof include a photopolymerization initiator that generates radicals by light (ultraviolet light, visible light, etc.) and a thermal polymerization initiator that generates radicals by heat. In addition, when the curing reaction is performed by ionic polymerization, an ionic polymerization initiator (for example, a photoacid generator or a photobase generator) can be used. These polymerization initiators can be used alone or in combination of two or more.

  Examples of the photopolymerization initiator include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxy-phenylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4. , 6-trimethylbenzoyldiphenylphosphine oxide and diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide. These photopolymerization initiators can be used alone or in combination of two or more.

  The content of the photopolymerization initiator in the curable composition of the present embodiment is not particularly limited as long as it is an amount capable of appropriately curing the curable composition, and at least 2 with the organic-inorganic composite (A). Preferably, 0.1 part by weight or more and 10 parts by weight or less are blended with respect to 100 parts by weight of the total of the polyfunctional (meth) acrylate monomer (B) having two (meth) acryloyl groups. More preferably, the content is 8 parts by mass or less.

  When the blending amount of the photopolymerization initiator is less than 0.1 parts by mass, curing may be insufficient. On the other hand, if it exceeds 10 parts by mass, the storage stability of the curable composition may be lowered or colored. In addition, there is a risk of cross-linking when obtaining a cured product by cross-linking, causing problems such as cracking during curing, and increasing the outgas component during high-temperature processing, which may contaminate the equipment. is there.

  Examples of the thermal polymerization initiator include peroxide-based and azo-based thermal polymerization initiators. For example, benzoyl oxide, tertiary butyl peroxypivalate, tertiary butyl peroxy-2-ethylhexanoate, 2,2-bisazoisobutyronitrile, dimethyl-2-2′-azobis (2-methylpropyl) (Pionate) etc. are mentioned, but it is not limited to these. Moreover, these thermal polymerization initiators can also be used individually by 1 type, and can also use 2 or more types together.

Content of the thermal polymerization initiator in the curable composition of this embodiment is the same as that of the case of the above-mentioned photoinitiator. Moreover, you may use together a photoinitiator and a thermal-polymerization initiator.
As described above, the curable composition of this embodiment may contain the organic-inorganic composite (A), the polyfunctional (meth) acrylate monomer (B), and the polymerization initiator (C). The mass ratio of the components is preferably as follows. That is, for 100 parts by mass of the polyfunctional (meth) acrylate monomer (B), the organic-inorganic composite (A) needs to be 10 parts by mass or more and 2000 parts by mass or less, and 20 parts by mass or more and 1500 parts by mass or less. It is preferable to make it 20 parts by mass or more and 1200 parts by mass or less.

Further, the polymerization initiator (C) needs to be 0.1 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyfunctional (meth) acrylate monomer (B), and 0.3 parts by mass or more and 150 parts by mass. It is preferable to set it as mass parts or less, and it is more preferable to set it as 0.5 mass parts or more and 100 mass parts or less.
In a mixture of these three components (organic-inorganic composite (A), polyfunctional (meth) acrylate monomer (B), polymerization initiator (C)), when the organic-inorganic composite (A) is less than 10 parts by mass, A cured product with a predetermined pencil hardness may not be obtained due to the low content of the inorganic component, and the curing shrinkage increases, so that it is described as a film-like cured product (hereinafter referred to as “cured film” or “hard coat film”). In some cases, warping may increase. On the other hand, when it exceeds 2000 parts by mass, the influence of the properties of the inorganic oxide fine particles is so strong that the flex resistance of the film-like cured product may be lowered.

  On the other hand, if the ratio of the polyfunctional (meth) acrylate monomer (B) is too high, in the case of a film-like cured product, the film may be greatly warped or cracked due to curing shrinkage. On the other hand, if the ratio of the polyfunctional (meth) acrylate monomer (B) is too low, a cured product having sufficient hardness cannot be obtained due to a decrease in the crosslinking density, and there is a risk of causing a decrease in scratch resistance.

  Moreover, when there are few polymerization initiators (C) than 0.1 mass part, performances, such as pencil hardness and scratch resistance, may become inadequate by insufficient hardening. On the other hand, when the amount is more than 200 parts by mass, the cured film may be warped due to the progress of crosslinking more than necessary, or the unreacted polymerization initiator (C) may remain as a residual component, resulting in outgassing during heating. There is a risk of going out. On the other hand, when the ratio of the polymerization initiator (C) is too low, there is a possibility that sufficient hardness of the cured product cannot be obtained with a decrease in the crosslinking density.

In the curable composition of the present embodiment, an antifouling property imparting agent (E) that imparts excellent antifouling property and slipperiness to the cured product of the curable composition within a range that does not impair the purpose and effect of the present invention. Or you may mix | blend the additive (F) which provides a desired characteristic to a curable composition or hardened | cured material.
The antifouling agent (E) used in the curable composition of the present embodiment is composed of a fluorine-containing compound, and this fluorine-containing compound is a compound having a perfluoropolyether structure and a carbon-carbon double bond. Moreover, this fluorine-containing compound may further have a linear or cyclic polysiloxane structure. The molecular weight is not particularly limited, but the polystyrene-equivalent weight average molecular weight as measured by GPC (gel permeation chromatography) is preferably 1,000 or more and 100,000 or less.

  Although the kind of perfluoropolyether structure is not specifically limited, As a preferable example, there are three perfluoropolyether structures shown in FIG. The type of polysiloxane structure is not particularly limited, but a preferred example is the polysiloxane structure shown in FIG. 8, and a more preferred example is the cyclic polysiloxane structure shown in FIG.

  In the fluorine-containing compound, the perfluoropolyether structure and the polysiloxane structure may be directly bonded or may be bonded via a linking group. Examples of the fluorine-containing compound in which the perfluoropolyether structure and the polysiloxane structure are directly bonded include those shown in FIG. 10 (perfluoropolyether structure types are limited to those shown in FIG. 10). Instead, the other two types shown in FIG. 7 may be used). The type of the linking group is not particularly limited, and examples thereof include an ester group, an ether group, a sulfide group, a urethane group, and a sulfone group.

  The fluorine-containing compound has a carbon-carbon double bond. Then, when this cures the curable composition, the carbon-carbon double bond of the fluorine-containing compound is converted into the (meth) acryloyl group of the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer ( Since it is copolymerized with the (meth) acryloyl group of B), the antifouling property-imparting agent (E) will be covalently bonded to the cured product of the curable composition. As a result, the antifouling property of the cured product is particularly excellent.

  An example of the fluorine-containing compound having a carbon-carbon double bond is shown in FIG. In the fluorine-containing compound shown in FIG. 11, a group having a carbon-carbon double bond is linked to silicon having a cyclic polysiloxane structure via a urethane group. As the group having a carbon-carbon double bond, a (meth) acryloyl group, a (meth) acryloyloxy group and the like are preferable.

  Furthermore, when adding an antifouling property imparting agent (E) to the curable composition of this embodiment, the antifouling property imparting agent (E) is added to 100 parts by mass of the polyfunctional (meth) acrylate monomer (B). On the other hand, it is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 40 parts by mass, and 0.4 to 30 parts by mass. Further preferred.

When the antifouling property imparting agent (E) is less than 0.1 parts by mass, the effect of the antifouling property imparting agent (E) cannot be sufficiently obtained, and the performance such as antifouling property, dynamic friction coefficient, contact angle, etc. is not good. May be sufficient. On the other hand, when it exceeds 50 parts by mass, the pencil density, scratch resistance and the like may be insufficient due to a decrease in the crosslink density on the surface of the cured product.
Furthermore, examples of the additive (F) include a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a defoaming agent, a plasticizer, an ultraviolet absorber, an antioxidant, and a charge. Examples thereof include an inhibitor, a silane coupling agent, a pigment, a dye, a slip agent, and a chain transfer agent.

  Furthermore, an organic solvent can be mix | blended with the curable composition of this embodiment. If the solvent dispersion obtained by solvent substitution, the polyfunctional (meth) acrylate monomer (B), and the polymerization initiator (C) are mixed to produce a curable composition, the solvent dispersion ( A curable composition containing the solvent (A-5) used for solvent replacement is obtained. Of course, you may add another kind of organic solvent to the curable composition containing the said solvent (A-5) obtained in this way.

Further, the solvent (solvent (A-5) used for solvent replacement) is removed from the solvent dispersion obtained by solvent replacement to separate the organic-inorganic composite (A), and the separated organic-inorganic composite (A ), A polyfunctional (meth) acrylate monomer (B), a polymerization initiator (C), and an organic solvent may be mixed to produce a curable composition.
The type of the organic solvent is not particularly limited. For example, ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; , Aromatic compounds such as toluene and xylene. In addition, aliphatic hydrocarbons such as cyclohexane and methylcyclohexane, ethers such as diethyl ether, tetrahydrofuran, and propylene glycol monomethyl ether, and alcohols such as methanol, ethanol, isopropanol, and butanol can be used. Among these organic solvents, propylene glycol monomethyl ether, or aprotic solvents such as methyl ethyl ketone and methyl isobutyl ketone are preferable.

The ratio of the organic solvent in the curable composition is not particularly limited, depending on the type of organic solvent, the nature of the curable composition, the type of the target substrate using the curable composition, the shape, etc. What is necessary is just to set suitably.
In the present invention, a material that improves the surface performance such as scratch resistance and antifouling properties by coating the surface of an article made of various materials such as resin and glass is called a hard coat material. The curable composition of this embodiment containing an organic solvent can be used as a hard coat material.

The liquid hard coat material of the present invention is arranged in the form of a film on the surface of a base material of various materials (resin, glass, etc.) by a conventional method such as coating, spraying, or dipping, and the hard coat material is heated or lighted. When the organic solvent is removed by drying or the like, the hard coat film can be coated on the surface of the substrate.
If the curable composition of this embodiment is processed into a film by a conventional method and the curable composition is cured and the organic solvent is removed, a film-like cured product of the curable composition can be obtained. . When the curable composition is a hard coat material, the film-like cured product becomes a hard coat film.

For example, in the case of forming a hard coat film on the surface of the base material, a hard coat material is applied to the surface of the base material, and volatile components such as an organic solvent are dried at 10 ° C. or higher and 150 ° C. or lower. If the hard coat material is cured by radiation, heat or the like, a molded body coated with the hard coat film can be obtained.
In the case of performing polymerization by heat, for example, an electric heater, an infrared lamp, hot air, or the like can be used as the heat source. The preferable curing conditions when the polymerization is performed by heat are a temperature of 40 ° C. or higher and 150 ° C. or lower and a time of 10 seconds or longer and 24 hours or shorter.

When performing polymerization by radiation (light), the type of radiation (light) is particularly limited as long as the hard coat material can be cured in a short time after coating the hard coat material. However, for example, visible light, ultraviolet light, electron beam, and the like can be given.
Examples of the visible light source include sunlight, a visible light lamp, a fluorescent lamp, and a laser. Furthermore, examples of the ultraviolet ray source include a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, and a laser. Furthermore, as a source of electron beam, a method using thermoelectrons generated from a commercially available tungsten filament, a cold cathode method in which metal is generated through a high voltage pulse, and collision between ionized gaseous molecules and metal electrode The secondary electron system using the secondary electrons generated by the above can be mentioned.

Next, uses of the curable composition, the hard coat material, and the hard coat film of the present embodiment will be described.
The curable composition of the present embodiment is suitable as a hard coat material for use in hard coat films such as coating materials for surface protection (hard coat, clear hard coat) and antireflection films. Examples of the base material to be applied include plastics (polyethylene terephthalate, polycarbonate, polyacrylate, polymethacrylate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS resin (acrylonitrile-butadiene-styrene). Resin), AS resin (acrylonitrile-styrene resin), norbornene resin, cycloolefin polymer (COP resin, etc.), metal, wood, paper, glass, slate, and the like.

  The shape of these base materials is not particularly limited, and examples thereof include a plate shape, a film shape, and a three-dimensional molded body. Examples of the hard coating material coating method include ordinary coating methods such as gravure printing, micro gravure printing, inkjet coating, dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, and brush coating. be able to. The thickness of the coating film in these coatings is the thickness after drying and curing, and is usually 0.1 μm or more and 400 μm or less, preferably 1 μm or more and 200 μm or less.

  The hard coat substrate (for example, a hard coat film for decorative molding) obtained by forming the hard coat film of the present embodiment on the substrate surface is excellent in pencil hardness, low curing shrinkage, transparency, and is flex-resistant. Excellent surface properties and scratch resistance, surface coverings for optical disks, automobile headlamps, automobile bodies, mobile phone terminals, solar cells, touch panels, display panels, television receivers, flexible display devices, personal computers, etc. Can be applied to.

  The hard coat film of this embodiment has high pencil hardness, excellent scratch resistance, workability, and low warpage, and particularly excellent low warpage, so that it is a plastic optical component, touch panel, display panel, film type liquid crystal In addition to elements and plastic containers, it is particularly suitable as a protective coating material for preventing damage (scratching) and contamination of floor materials, wall materials, artificial marble and the like as building interior materials.

  In addition, the hard coat film of the present embodiment is a recording disk such as a CD (compact disk), DVD (digital versatile disk), MO (magneto-optical disk), BD (Blu-ray disk), a film type liquid crystal element, a touch panel. It is particularly suitable as an antireflection film for display panels and plastic optical parts.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
(1) Synthesis of silane coupling agent (inorganic oxide fine particle modifier) having at least three acryloyl groups [Synthesis Example 1]: Synthesis of inorganic oxide fine particle modifier (D-1) In a separable flask, a reaction solvent 129.2 g of toluene and a polyfunctional acrylate having a hydroxyl group, a reaction product of dipentaerythritol and acrylic acid (46.7% by mass of dipentaerythritol pentaacrylate, 23.1% by mass of dipentaerythritol tetraacrylate, 100 g of a mixture of 27.9% by mass of dipentaerythritol hexaacrylate and 2.3% by mass of other unknowns; DPPA mixture) is heated with stirring so that the internal temperature of the separable flask becomes 50 ° C. A homogeneous solution was obtained.

  Next, 29.2 g of 3-isocyanatopropyltriethoxysilane (trade name KBE-9007; manufactured by Shin-Etsu Chemical Co., Ltd.) as an isocyanate compound having an alkoxysilyl group, and zirconium tetraacetylacetonate (trade name ZC as a reaction catalyst). -700: Matsumoto Fine Chemical Co., Ltd., non-volatile content 20% by mass toluene solution) 0.58 g was added, stirred for 6 hours with heating, and further stirred for 10 hours at room temperature.

As a result of analyzing the peak derived from the isocyanate group of 2250 cm ⁻¹ with FT-IR (Avatar 360 manufactured by Thermo-Nicolet) for the obtained reaction solution, the peak disappeared, and the progress of the reaction was confirmed. As a result, 256 g of a toluene solution of 49.7% by mass (including 10.9% by mass of dipentaerythritol hexaacrylate) of the inorganic oxide fine particle modifier (D-1) was obtained.

[Synthesis Example 2]: Synthesis of inorganic oxide fine particle modifier (D-2) The same procedure as in Synthesis Example 1 was conducted except that the amount of each compound used was changed as shown in Table 1, and inorganic oxidation was performed. As a result, 562 g of a toluene solution of 50.6% by mass (including 9.9% by mass of dipentaerythritol hexaacrylate) of the organic fine particle modifier (D-2) was obtained.

(2) Synthesis of organic-inorganic composite dispersion [Production Example 1]: Synthesis of organic-inorganic composite dispersion (C-1) Isopropyl alcohol-dispersed colloidal silica (silica content of 30% by mass, silica average particle size of 10 to 10%) 200 nm of 20 nm, trade name Snowtech IPA-ST; manufactured by Nissan Chemical Co., Ltd.) was put in a separable flask, and further a toluene solution of inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 107. 0 g (non-volatile content: 49.7% by mass) was added and mixed by stirring to obtain a uniform solution.

Furthermore, 4.4 g of 0.18% by mass HCl aqueous solution as a reaction catalyst was added to this mixed solution, and the silica fine particles were surface-treated by heating and stirring for 6 hours at an internal temperature of 40 ° C. 304.3 g of (C′-1) was obtained.
Next, 150.0 g of the obtained intermediate reaction liquid (C′-1) was put into a flask equipped with a gas blowing port, and further 481.5 g of methyl isobutyl ketone and 2,6-ditertiary as a polymerization inhibitor were used. 0.027 g of butyl-para-cresol was added to make a uniform solution.

  Next, the temperature inside the flask was heated to 40 ° C., and the system was depressurized while bubbling nitrogen gas containing 5% oxygen into the solution at a rate of 100 mL / min, and a solvent (isopropyl alcohol and methyl isobutyl ketone) Was distilled off. Solvent replacement was performed by distilling off the solvent (isopropyl alcohol and methyl isobutyl ketone) so that the nonvolatile content would be 45% by mass, and an organic-inorganic composite dispersion liquid (C- 1) 119 g was obtained. In addition, by this solvent substitution, the alcohol produced | generated by the condensation reaction in the synthesis | combination of inorganic oxide fine particle modifier (D-1), HCl added as a reaction catalyst, and the content of water were also reduced.

[Production Example 2]: Synthesis of organic-inorganic composite dispersion liquid (C-2) Synthesis example in place of inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 as an inorganic oxide fine particle modifier The same procedure as in Production Example 1 was performed except that the inorganic oxide fine particle modifier (D-2) synthesized in 2 was used (see Table 2 for the amount of each compound used, etc.). 119 g of complex dispersion (C-2) was obtained.

［製造例３］：有機無機複合体分散液（Ｃ−３）の合成
無機酸化物微粒子修飾剤として、合成例１にて合成した無機酸化物微粒子修飾剤（Ｄ−１）に換えて合成例２にて合成した無機酸化物微粒子修飾剤（Ｄ−２）を使用し、溶剤置換において用いる溶剤（Ａ−５）をメチルイソブチルケトン（ＭＩＢＫ）に換えてプロピレングリコールモノメチルエーテル（ＰＧＭＥ）とする点以外は、製造例１と同様の操作を行って（各化合物等の使用量については表２を参照）、有機無機複合体分散液（Ｃ−３）１１９ｇを得た。

[Production Example 3]: Synthesis of organic-inorganic composite dispersion liquid (C-3) Synthesis example in place of inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 as an inorganic oxide fine particle modifier The inorganic oxide fine particle modifier (D-2) synthesized in Step 2 is used, and the solvent (A-5) used in solvent replacement is changed to methyl isobutyl ketone (MIBK) to be propylene glycol monomethyl ether (PGME). Except for the above, the same operation as in Production Example 1 was carried out (see Table 2 for the amount of each compound used) to obtain 119 g of an organic-inorganic composite dispersion (C-3).

[Production Example 4]: Synthesis of organic-inorganic composite dispersion liquid (C-4) Synthesis example in place of inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 as an inorganic oxide fine particle modifier Inorganic oxide fine particle modifier (D-2) synthesized in Step 2 is used, and colloidal silica is replaced with isopropyl alcohol-dispersed colloidal silica and methyl isobutyl ketone-dispersed colloidal silica (silica content 30% by mass, average of silica The same operation as in Production Example 1 was carried out except that the particle diameter was 10 to 20 nm, and the trade name Snow Tech MIBK-ST (manufactured by Nissan Chemical Co., Ltd.) was used. ), 119 g of an organic-inorganic composite dispersion (C-4) was obtained.

[Production Example 5]: Synthesis of organic-inorganic composite dispersion liquid (C-5) Synthesis example in place of inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 as an inorganic oxide fine particle modifier Except for using the inorganic oxide fine particle modifier (D-2) synthesized in Step 2 and not performing solvent substitution, the same operation as in Production Example 1 was carried out (about the amount of each compound used, etc.) 148 g of an organic-inorganic composite dispersion (C-5) was obtained. Since solvent replacement is not performed in this production example, the intermediate reaction liquid in production example 1 corresponds to the organic-inorganic composite dispersion liquid (C-5).

[Production Example 6]: Synthesis of organic-inorganic composite dispersion liquid (C-6) Synthesis example in place of inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 as an inorganic oxide fine particle modifier Production Example 1 except that the inorganic oxide fine particle modifier (D-2) synthesized in 2 is used and that the solvent (A-5) used in solvent replacement is replaced with methyl isobutyl ketone to form toluene. The same operation was performed (see Table 2 for the amount of each compound used) to obtain 119 g of an organic-inorganic composite dispersion (C-6).

[Production Example 7]: Synthesis of organic-inorganic composite dispersion liquid (C-7) As the inorganic oxide fine particle modifier, instead of the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, ) Use of 3-acryloyloxypropyltrimethoxysilane (trade name KBM-5103; manufactured by Shin-Etsu Chemical Co., Ltd.) having only one acryloyl group, and methyl isobutyl ketone and a polymerization inhibitor in the intermediate reaction solution The same operation as in Production Example 1 was carried out except that dipentaerythritol hexaacrylate DPHA (trade name SARTOMER DPHA; manufactured by SARTOMER) was further added as a polyfunctional acrylate when charged into a uniform solution (each For the amount of the compound used, etc., see Table 2), 157 g of an organic-inorganic composite dispersion (C-7) was obtained.

(3) Preparation of curable composition [Preparation Example 1]: Preparation of curable composition (M-1) 209.6 parts by mass of the organic-inorganic composite dispersion liquid (C-1) obtained in Production Example 1. 3. 14.7 parts by mass of trisacryloyloxyethyl isocyanurate (trade name Aronix M-315; manufactured by Toagosei Co., Ltd.) as a polyfunctional acrylate, 2-hydroxycyclohexylacetophenone (trade name: IRG184; manufactured by BASF) as a polymerization initiator 4 mass parts was mixed and the curable composition (M-1) was obtained by adding 69.8 mass parts of methyl isobutyl ketone so that components other than a non-volatile content, ie, a solvent, may be 38 mass%.

[Preparation Example 2]: Preparation of Curable Composition (M-2) Organic-inorganic composite dispersion obtained in Production Example 2 instead of Organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except using liquid (C-2), operation similar to the preparation example 1 was performed (refer Table 3 about the usage-amounts of each compound etc.), and the curable composition (M-2) was obtained.

[Preparation Example 3]: Preparation of Curable Composition (M-3) Organic-inorganic composite dispersion obtained in Production Example 3 instead of Organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except the point which uses liquid (C-3), operation similar to preparation example 1 was performed (refer Table 3 about the usage-amounts of each compound etc.), and the curable composition (M-3) was obtained. .
[Preparation Example 4]: Preparation of Curable Composition (M-4) Organic-inorganic composite dispersion obtained in Production Example 4 instead of Organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except the point which uses liquid (C-4), operation similar to preparation example 1 was performed (refer Table 3 about the usage-amounts of each compound etc.), and the curable composition (M-4) was obtained. .

[Preparation Example 5]: Preparation of Curable Composition (M-5) Organic-inorganic composite dispersion obtained in Production Example 5 instead of organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except the point which uses liquid (C-5), operation similar to preparation example 1 was performed (refer Table 3 about the usage-amounts of each compound etc.), and the curable composition (M-5) was obtained. .
[Preparation Example 6]: Preparation of Curable Composition (M-6) Organic-inorganic composite dispersion obtained in Production Example 6 instead of organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except the point which uses liquid (C-6), operation similar to preparation example 1 was performed (refer Table 3 about the usage-amounts of each compound etc.), and the curable composition (M-6) was obtained. .

[Preparation Example 7]: Preparation of Curable Composition (M-7) Organic-inorganic composite dispersion obtained in Production Example 7 instead of the organic-inorganic composite dispersion (C-1) obtained in Production Example 1. Preparation Example, except that liquid (C-7) is used and dipentaerythritol hexaacrylate DPHA (trade name SARTOMER DPHA; manufactured by SARTOMER) is used in addition to trisacryloyloxyethyl isocyanurate as a polyfunctional acrylate The same operation as in No. 1 was performed (see Table 3 for the amount of each compound used) to obtain a curable composition (M-7).

(4) Production and evaluation of coating film [Example 1]
The curable composition (M-1) is made of a polyethylene terephthalate (PET) film (trade name: Cosmo Shine (trademark) A-4100; trade name: Toyobo Co., Ltd.) having a thickness of 125 μm so that the thickness of the dried coating film becomes 5 μm ) And dried at 100 ° C. for 1 minute. Next, using a conveyor exposure machine, UV light (200 mJ / cm ² ) is irradiated with a UV lamp (high pressure mercury) with a UV lamp (high pressure mercury) under a nitrogen atmosphere to cure the curable composition (M-1), and curable. A PET film (hereinafter referred to as “coating film”) coated with a cured product (hard coat film) of the composition (M-1) was obtained. The obtained coating film was subjected to various tests according to the evaluation method described later.

[Example 2, Example 3, Comparative Examples 1-4]
A coating film was obtained in the same manner as in Example 1 except that the curable composition (M-1) of Example 1 was changed to curable compositions (M-2) to (M-7), respectively. These were subjected to various tests in the same manner as in Example 1.

(5) Coating film evaluation method [Evaluation of pencil hardness]
Using a surface property measuring instrument (Tribogear 14FW manufactured by Shinto Kagaku Co., Ltd.) and a pencil hardness measuring pencil (Mitsubishi UNI manufactured by Mitsubishi Pencil Co., Ltd.), the pencil hardness based on the method specified in JIS K5600-5-4 Was measured. The measurement load was 750 g, the measurement speed was 30 mm / min, and the measurement distance was 5 mm. The measurement was performed 5 times, and the hardness of the pencil having a pass number exceeding 4/5 was used as the evaluation result.

[Evaluation of optical properties]
Regarding optical characteristics, three items of total light transmittance, haze, and b * were evaluated. The total light transmittance and Haze were measured using a haze meter / haze meter (NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.). The total light transmittance was evaluated based on the method defined in JIS K7361, and Haze was defined in JIS K7136. b * was evaluated based on the method specified in JIS K8729 using a color difference meter (SD-6000 manufactured by Nippon Denshoku Industries Co., Ltd.).

[Evaluation of warpage]
The coating film was cut to prepare a 10 cm square test piece. This test piece was allowed to stand under conditions of a temperature of 23 ° C. and a relative humidity of 50%. Then, the test piece was arrange | positioned on a desk, the height of the test piece four corners which are separated from the desk upper surface by curvature was measured, and the average value of the height of four corners was made into the evaluation result.

[Mandrel flexibility]
Evaluation was performed based on the method specified in JIS K5600-5-1 using a cylindrical mandrel bending tester (TQCBD-2000 manufactured by Cortec Co., Ltd.). The measurement was performed three times, and the average value of the obtained results was used as the evaluation result.

[Evaluation of scratch resistance]
Scratch resistance was measured using a surface property measuring instrument (Tribogear 14FW manufactured by Shinto Kagaku Co., Ltd.) and steel wool (Steel Wool Grade (count) # 0000 manufactured by Bonstar Sales Co., Ltd.). The presence or absence of scratches was visually observed and evaluated according to the following criteria.
A: No scratch B: Partially scratched C: Full scratched

That is, steel wool was placed on the coating film, moved linearly while applying a load of 175 g / cm ^2, and reciprocated 100 times to rub the surface of the coating film with steel wool. And the presence or absence of a damage | wound (by visual observation) and Haze change ((DELTA) Haze) before and behind rubbing were evaluated. In addition, about Haze, it evaluated by the above-mentioned method. The results are shown in Table 4.

  Since Examples 1-3 are excellent in curvature compared with Comparative Examples 1-4, it turns out that the cure shrinkage of a curable composition is low. Moreover, since Examples 1-3 are excellent in mandrel flexibility compared with Comparative Examples 1-4, it turns out that it is excellent in the bending resistance of hardened | cured material. Further, Examples 1 to 3 are superior in scratch resistance of the cured product because there are few scratches due to rubbing compared to Comparative Examples 1 to 4 and the change in Haze before and after rubbing is small. I understand.

Claims (12)

An organic-inorganic composite (A) in which inorganic oxide fine particles are surface-treated with a silane coupling agent having at least two (meth) acryloyl groups and the silane coupling agent is covalently bonded to the inorganic oxide fine particles. A manufacturing method comprising:
The silane coupling agent and the inorganic oxide fine particles dispersed in the protic solvent are subjected to a dehydration condensation reaction or a dealcoholization condensation reaction, whereby the organic-inorganic composite (A) is dispersed in the protic solvent. A surface treatment step for obtaining a protic solvent dispersion,
While removing water or alcohol produced by the dehydration condensation reaction or the dealcoholization condensation reaction and the protic solvent from the protic solvent dispersion, a polar aprotic solvent (S1) and a boiling point of 110 ° C. or higher The aprotic solvent (S1) having the above polarity and the protic solvent (S2) having a boiling point of 110 ° C. or more are added by adding at least one kind (D) selected from the protic solvent (S2). A solvent replacement step for obtaining a dispersion in which the organic-inorganic composite (A) is dispersed in at least one selected from (D);
A method for producing an organic-inorganic composite, comprising: An organic-inorganic composite (A) in which inorganic oxide fine particles are surface-treated with a silane coupling agent having at least two (meth) acryloyl groups, and the silane coupling agent is covalently bonded to the inorganic oxide fine particles; , A polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups, a polymerization initiator (C), a polar aprotic solvent (S1), and a proton having a boiling point of 110 ° C. or higher A method for producing a curable composition containing at least one kind (D) selected from a solvent (S2),
The silane coupling agent and the inorganic oxide fine particles dispersed in the protic solvent are subjected to a dehydration condensation reaction or a dealcoholization condensation reaction, whereby the organic-inorganic composite (A) is dispersed in the protic solvent. A surface treatment step for obtaining a protic solvent dispersion,
While removing water or alcohol produced by the dehydration condensation reaction or the dealcoholization condensation reaction and the protic solvent from the protic solvent dispersion, the aprotic solvent having the polarity (S1) and the boiling point of 110 At least one kind (D) selected from a protic solvent (S2) having a temperature of not lower than ° C. is added to perform solvent substitution, and the aprotic solvent (S1) having the polarity and the protic solvent having a boiling point of 110 ° C. or higher ( A solvent replacement step of obtaining a dispersion in which the organic-inorganic composite (A) is dispersed in at least one (D) selected from S2);
A method for producing a curable composition comprising:   In the solvent replacement step, the solvent replacement is performed in the presence of the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups, and the polyfunctional having at least two (meth) acryloyl groups. At least one selected from the (meth) acrylate monomer (B), the organic-inorganic composite (A), the polar aprotic solvent (S1), and the protic solvent (S2) having a boiling point of 110 ° C. or higher. The method for producing a curable composition according to claim 2, wherein a dispersion containing (D) is obtained.   The curable composition according to claim 2 or 3, wherein, in the solvent replacement step, the catalyst for the dehydration condensation reaction or the dealcoholization condensation reaction is removed together with water or alcohol and the protic solvent. Production method. An organic-inorganic composite (A) in which inorganic oxide fine particles are surface-treated with a silane coupling agent having at least two (meth) acryloyl groups, and the silane coupling agent is covalently bonded to the inorganic oxide fine particles; ,
A polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups;
A polymerization initiator (C);
At least one (D) selected from a polar aprotic solvent (S1) and a protic solvent (S2) having a boiling point of 110 ° C. or higher;
Containing
When the content of the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups is 100 parts by mass, the content of the organic-inorganic composite (A) is 10 parts by mass or more and 2000 parts by mass. Less than or equal to
The polymerization initiator (C) when the total content of the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups is 100 parts by mass. The curable composition characterized by having a content of 0.1 to 10 parts by mass. 6. The curable composition according to claim 5, wherein the silane coupling agent is a compound represented by the following chemical formula (I).
However, M in the following chemical formula (I) represents a hydroxyl group residue of a compound having at least two (meth) acryloyl groups and at least one hydroxyl group. X represents an oxygen atom or a sulfur atom. Further, R ¹ and R ² are each a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group optionally having an alkyl group having 1 to 3 carbon atoms. R ¹ and R ² may be the same or different. R ³ represents a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, or a phenylene group that may have an alkyl group having 1 to 3 carbon atoms. The alkylene group may contain an oxygen atom in the chain. Further, l represents an integer from 0 to 2, m represents an integer from 1 to 3, the sum of l and m is 3, and n represents an integer from 1 to 3.

X in the chemical formula (I) is an oxygen atom, l is 0, m is 3, R ² is a methyl group or an ethyl group, and R ³ is a linear propylene group. The curable composition according to claim 6.   The silane coupling agent is obtained by a condensation reaction between a compound having an alkoxysilyl group and an isocyanato group and a compound having at least two (meth) acryloyl groups and at least one hydroxyl group. The curable composition according to claim 6 or 7, wherein is a condensation reaction in which the isocyanate group and the hydroxyl group react to form a urethane bond.   The curable composition according to any one of claims 5 to 8, wherein the inorganic oxide fine particles are at least one fine particle selected from the group consisting of silica, titania, zirconia, and alumina.   Hardened | cured material which hardened the curable composition as described in any one of Claims 5-9.   The hard-coat material which consists of a curable composition as described in any one of Claims 5-9.   A hard coat film formed by arranging the hard coat material according to claim 11 on the surface of a base material in a film shape and curing it.

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