JP2015078340A - Organic-inorganic composite production method, curable composition, curable composition cured product, hard coat material, hard coat film, and silane coupling agent - 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: Provided is an organic-inorganic composite production method by surface treating an inorganic oxide fine particle with a silane coupling agent having at least 2 (meth)acryloyl groups to obtain an organic-inorganic composite to which the silane coupling agent is covalently bonded, and the method has a step of condensation reacting an alkoxy silyl group-and-isocyanato group-containing isocyanato-group compound, and a hydroxyl group-containing compound having at least 2 (meth)acryloyl groups and at least 1 hydroxyl group and having a hydroxyl value of 75 mgKOH/g or more, to obtain the silane coupling agent, and in which setting the hydroxyl value of the hydroxyl group compound as X(mgKOH/g), the mass of the hydroxyl group compound as Y(g), and the mole number of the isocyanato group as Z(mmol), the value of Z/(XY/56.1) is 0.6 or more and 1.2 or less.

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 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. Furthermore, the present invention relates to a silane coupling agent.

  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 silane coupling agent obtained by reacting an acrylic resin, an isocyanato group-containing compound, a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and an acryloyl group, and a polysilane having three or more acryloyl groups. An abrasion resistant UV curable coating composition containing a functional acrylate and silica sol is disclosed.

JP-A-9-157315 JP 2008-150484 A JP 2010-121013 A Japanese Patent Application Laid-Open No. 6-100799

  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, the active energy ray-curable resin composition disclosed in Patent Document 3 and the abrasion-resistant UV-curable coating composition disclosed in Patent Document 4 have a small amount of surface modification of inorganic oxide fine particles by a silane coupling agent. Therefore, when the composition is cured to form a hard coat film, 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.

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.
Another object of the present invention is to provide a hard coat film and a cured product which are excellent in pencil hardness, low curing shrinkage and transparency, and excellent in flex 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 simple silane coupling agent. 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-mentioned problems, aspects of the present invention are as described in [1] to [9] 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 manufacturing method comprising:
By a condensation reaction between an isocyanato group compound having an alkoxysilyl group and an isocyanato group and a hydroxyl group compound having at least two (meth) acryloyl groups and at least one hydroxyl group and having a hydroxyl value of 75 mgKOH / g or more, Having a step of obtaining the silane coupling agent,
The condensation reaction is a condensation reaction in which a urethane bond is formed by a reaction between the isocyanato group of the isocyanato group compound and the hydroxyl group of the hydroxyl group compound,
Derived from the hydroxyl group value of the hydroxyl group compound to be subjected to the condensation reaction as X (mg KOH / g), the mass of the hydroxyl group compound to be subjected to the condensation reaction as Y (g), from the isocyanato group compound to be subjected to the condensation reaction A method for producing an organic-inorganic composite, wherein the value of Z / (XY / 56.1) is 0.6 or more and 1.2 or less when the number of moles of the isocyanato group is Z (mmol) .

[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) and
A polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups;
A polymerization initiator (C);
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 content of is 0.1 parts by mass or more and 10 parts by mass or less,
The silane coupling agent includes an isocyanato group compound having an alkoxysilyl group and an isocyanato group, a hydroxyl group having at least two (meth) acryloyl groups and at least one hydroxyl group, and a hydroxyl value of 75 mgKOH / g or more. Obtained by a condensation reaction with a compound, and this condensation reaction is a condensation reaction in which the isocyanate group of the isocyanate-containing compound and the hydroxyl group of the hydroxyl-containing compound react to form a urethane bond,
The hydroxyl group compound subjected to the condensation reaction has a hydroxyl value of X (mg KOH / g), the hydroxyl group compound to be subjected to the condensation reaction has a mass of Y (g), and is subjected to the condensation reaction. Curing characterized in that the value of Z / (XY / 56.1) is 0.6 or more and 1.2 or less when the number of moles of the isocyanate group derived from the isocyanato group compound is Z (mmol). Sex composition.

[3] The curable composition according to [2], 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 the hydroxyl group-containing compound. R ¹ and R ² are each a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group that 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 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.

[4] In the chemical formula (I), l is 0, m is 3, R ² is a methyl group or an ethyl group, and R ³ is a linear propylene group. 3].
[5] 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 [2] to [4], Curable composition.

[6] A cured product obtained by curing the curable composition according to any one of [2] to [5].
[7] A hard coat material comprising the curable composition according to any one of [2] to [5].
[8] A hard coat film formed by arranging the hard coat material according to [7] on the surface of a base material in a film shape and curing it.

[9] A silane coupling agent having at least two (meth) acryloyl groups, comprising an isocyanato group compound having an alkoxysilyl group and an isocyanato group, at least two (meth) acryloyl groups and at least one hydroxyl group. And having a hydroxyl value of 75 mgKOH / g or more, obtained by a condensation reaction with a hydroxyl group compound, and this condensation reaction involves the isocyanato group of the isocyanate group compound and the hydroxyl group of the hydroxyl group compound. It is a condensation reaction that causes a urethane bond by reaction,
Derived from the hydroxyl group value of the hydroxyl group compound to be subjected to the condensation reaction as X (mg KOH / g), the mass of the hydroxyl group compound to be subjected to the condensation reaction as Y (g), from the isocyanato group compound to be subjected to the condensation reaction A silane coupling agent, wherein the value of Z / (XY / 56.1) is 0.6 or more and 1.2 or less when the number of moles of the isocyanato group is Z (mmol).

  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. In addition, 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 silane coupling agent of the present invention has a curable composition and a hard composition that can form a hard coat film that is excellent in pencil hardness, low curing shrinkage, transparency, and also excellent in flex resistance and scratch resistance. A coating material can be manufactured. 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 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 techniques, the present inventors have found that an isocyanato group compound having an alkoxysilyl group and an isocyanato group, at least two (meth) acryloyl groups, and at least The present inventors have found that the above problems can be solved by using a silane coupling agent obtained by a condensation reaction with a hydroxyl group-containing compound having a high hydroxyl value having one hydroxyl group, and have completed the present invention.

  That is, the curable composition of the present invention has a surface treatment of inorganic oxide fine particles with a silane coupling agent having at least two (meth) acryloyl groups, and binds the silane coupling agent to the inorganic oxide fine particles by a covalent bond. The organic-inorganic composite (A), the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups, and the polymerization initiator (C), and at least two (meth) When the content of the polyfunctional (meth) acrylate monomer (B) having an acryloyl group 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, and the organic-inorganic composite The total content of the body (A) and the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups is 100 parts by mass. The content of the polymerization initiator (C) is not more than 10 parts by mass or more 0.1 part by mass of the case.

  The silane coupling agent contains an isocyanato group compound having an alkoxysilyl group and an isocyanato group, an at least two (meth) acryloyl groups and at least one hydroxyl group, and a hydroxyl value of 75 mgKOH / g or more. The condensation reaction is obtained by a condensation reaction with a hydroxyl group compound, and this condensation reaction is a condensation reaction in which the isocyanate group of the isocyanate-containing compound and the hydroxyl group of the hydroxyl-containing compound react to generate a urethane bond.

  By the surface treatment using the silane coupling agent, an organic-inorganic composite (A) in which the surface of the inorganic oxide fine particles is uniformly combined with the polyfunctional silane coupling agent can be obtained. Moreover, since the silane coupling agent is produced from a hydroxyl group compound having a high hydroxyl value, a large amount of the silane coupling agent is bonded to the surface of the inorganic oxide fine particles ( Large amount of surface modification).

  Therefore, 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 surface of the organic-inorganic composite (A). In addition to the extremely high degree of cross-linking, the elastic modulus is high due to the construction of a very uniform cross-linking system, so the bending resistance characteristic of curable organic materials and the high characteristic characteristic of curable inorganic material composites are high. It has both hardness and low shrinkage. 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.

If the hydroxyl value of the hydroxyl-containing compound is less than 75 mgKOH / g, the pencil hardness, low cure shrinkage, flex resistance, and scratch resistance of the cured product of the curable composition may be insufficient.
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）アクリロイル基及び少なくとも１つのヒドロキシル基を有し水酸基価が７５ｍｇＫＯＨ／ｇ以上である含ヒドロキシル基化合物のヒドロキシル基残基を示す。また、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 hydroxyl-containing compound having at least two (meth) acryloyl groups and at least one hydroxyl group and having a hydroxyl value of 75 mgKOH / g or more. R ¹ and R ² are each a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group (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) includes an isocyanato group compound having an alkoxysilyl group and an isocyanato group, at least two (meth) acryloyl groups and at least one hydroxyl group, and a hydroxyl value of 75 mgKOH / It can be obtained by a condensation reaction with a hydroxyl group-containing compound that is g or more. This condensation reaction is a condensation reaction in which a urethane bond is formed by a reaction between the isocyanato group of the isocyanato-containing compound and the hydroxyl group of the hydroxyl-containing compound.

Hereinafter, the polyfunctional (meth) acrylic silane coupling agent (A-1) will be described in more detail.
For example, as shown in FIG. 3, the polyfunctional (meth) acrylic silane coupling agent (A-1) includes an isocyanato group compound (a-1) having an alkoxysilyl group and an isocyanato group, and at least two (meta) ) It can be synthesized by a condensation reaction with a hydroxyl-containing compound (a-2) having an acryloyl group and at least one hydroxyl group.

This condensation reaction is suitable as a method for obtaining the above-mentioned polyfunctional (meth) acrylic silane coupling agent (A-1) from the viewpoint of easy handling, reaction selectivity, and reaction controllability. It can be said that it is preferable because the selection range is wide and the handling property is high.
Examples of the isocyanato-containing compound (a-1) include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane, but are not limited thereto. Moreover, these can also be used individually by 1 type and can also use 2 or more types together.

  Examples of the hydroxyl-containing compound (a-2) include glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, and 3-hydroxy-2- ( (Meth) acryloyloxypropyl (meth) acrylate, bis ((meth) acryloyloxyethyl) -2-hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, ditrimethylolpropane tri (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth) acrylate.

Among these, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth) acrylate are particularly preferable.
Furthermore, a (meth) acrylic copolymer having a hydroxyl group and a (meth) acryloyl group in the side chain, a compound obtained by opening a cyclic acid anhydride with a polyfunctional acrylate having a hydroxyl group, and the like can be exemplified. .

However, the hydroxyl group compound (a-2) is not limited thereto, and these can be used alone or in combination of two or more.
Here, the hydroxyl value of the hydroxyl-containing compound (a-2) needs to be 75 mgKOH / g or more, preferably 82 mgKOH / g or more, more preferably 90 mgKOH / g or more.

  When the hydroxyl value is less than 75 mgKOH / g, the number of reaction points with the isocyanato group compound (a-1) decreases, so that the resulting polyfunctional (meth) acrylic silane coupling agent (A-1) The active ingredient (alkoxysilyl group) is reduced. As a result, the polyfunctional (meth) acrylic silane coupling agent (A-1) may not sufficiently function as a silane coupling agent.

However, when the hydroxyl value of the hydroxyl-containing compound (a-2) is 200 mgKOH / g or more, the unsaturated group ((meth) acryloyl) of the resulting polyfunctional (meth) acrylic silane coupling agent (A-1) Group) may be reduced. Therefore, when the curable composition is cured, a sufficient crosslinking density cannot be obtained, and the performance of the cured product may be insufficient.
The hydroxyl value of the hydroxyl-containing compound (a-2) is defined by the following formula and can be measured by the hydroxyl value measuring method specified in JIS K0070.

HV = {(V ₀ −V ₁ ) × C × 56.1} / m + TAV
HV: hydroxyl value V ₀ : volume of methanol solution of potassium hydroxide used for measurement (ml)
V ₁ : Volume of methanol solution of potassium hydroxide used in the blank test (ml)
C: Accurate concentration of methanol solution of potassium hydroxide (mol / ml)
m: Mass of the sample (g)
TAV: Total acid value

  The hydroxyl value of the hydroxyl group compound (a-2) used when synthesizing the polyfunctional (meth) acrylic silane coupling agent (A-1) by the condensation reaction is X (mg KOH / g), hydroxyl group. When the amount of the compound (a-2) used is Y (g) and the number of moles of the isocyanate group derived from the isocyanato group compound used is Z (mmol), the value of Z / (XY / 56.1) is It is 0.6 or more and 1.2 or less, more preferably 0.7 or more and less than 1.15, and further preferably 0.8 or more and less than 1.1.

If the value of Z / (XY / 56.1) is less than 0.6, the performance of the cured product of the curable composition may be insufficient, and the value of Z / (XY / 56.1) is If it exceeds 1.2, the unreacted isocyanato group may undergo intramolecular condensation, resulting in the formation of a solvent-insoluble urea or the like.
In the condensation reaction of FIG. 3, 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 having a small 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.

<(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 preferably 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 not particularly limited. For example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and ethyl acetate , Esters such as butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether, benzene, toluene, xylene, etc. Aromatic hydrocarbons and amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone can be mentioned. Of these, methanol and isopropanol are preferred.

  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, MEK-ST, MEK-ST-L, MEK-ST- ZL, MIBK-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.

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. The addition amount of the catalyst is not particularly limited, but is usually 0.01 to 1 part by mass, preferably 0.01 to 0 part per 100 parts by mass of inorganic oxide fine particles (A-2) such as silica fine particles to be subjected to surface treatment. .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), Most preferred are methanol and isopropanol.

  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.

<(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.

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 (D) 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 property imparting agent (D) used in the curable composition of this embodiment comprises 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.

  The type of perfluoropolyether structure is not particularly limited, but preferred examples include the 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. 5, 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. 7 (perfluoropolyether structure types are limited to those shown in FIG. 7). Not the other two types shown in FIG. 4). 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 copolymerizes with the (meth) acryloyl group of B), antifouling property imparting agent (D) will couple | bond together by the covalent bond with the hardened | cured material of a curable composition. As a result, the antifouling property of the cured product is particularly excellent.

  Examples of the fluorine-containing compound having a carbon-carbon double bond include those shown in FIG. In the fluorine-containing compound shown in FIG. 8, 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 (D) to the curable composition of this embodiment, the antifouling property imparting agent (D) 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.

If the antifouling property imparting agent (D) is less than 0.1 parts by mass, the effect of the antifouling property imparting agent (D) 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.
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, methyl ethyl ketone, and methyl isobutyl ketone are preferable.

The ratio of the organic solvent (E) is not particularly limited, and is appropriately set according to the type of the organic solvent, the property of the curable composition, the type and shape of the target substrate on which the curable composition is used. do it.
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 substrate, a hard coat material was applied to the surface of the substrate, and volatile components such as an organic solvent (E) were dried at 10 ° C. or higher and 150 ° C. or lower. Thereafter, if the hard coat material is cured by light, 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 from 0.03 μm to 400 μm, preferably from 1 μm to 200 μm.

  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 two 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 reaction product of dipentaerythritol and acrylic acid, which is a polyfunctional acrylate (hydroxyl group-containing compound) having a hydroxyl group (46.7% by mass of dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate 23) A mixture of 1 mass%, dipentaerythritol hexaacrylate 27.9 mass%, and other unknown substances 2.3 mass%; DPPA mixture a, hydroxyl value 101) 100 g was added, and the internal temperature of the separable flask was stirred. Was heated to 50 ° C. to obtain a uniform solution.

  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 (containing isocyanato group compound) and zirconium tetraacetyl as a reaction catalyst 0.58 g of acetonate (trade name ZC-700: manufactured by Matsumoto Fine Chemical Co., Ltd., non-volatile content 20% by mass toluene solution) was added, and after 6 hours of heating and stirring, stirring was further performed at room temperature for 10 hours. .

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 49.7 mass% toluene solution of the inorganic oxide fine particle modifier (D-1) was obtained.

[Synthesis Example 2]: Synthesis of Inorganic Oxide Fine Particle Modifier (D-2) Inorganic oxide microparticles were prepared in the same manner as in Synthesis Example 1 except that the amount of each compound used was changed as shown in Table 1. 571 g of a toluene solution with a nonvolatile content of 50.6% by mass of the modifier (D-2) was obtained.

[Synthesis Example 3]: Synthesis of inorganic oxide fine particle modifier (D-2-2) DPPA mixture a which is a polyfunctional acrylate having a hydroxyl group is converted to dipentaerythritol and acrylic which are polyfunctional acrylates having a hydroxyl group. Reaction product of acid (mixture of 43.6% by mass of dipentaerythritol pentaacrylate, 19.2% by mass of dipentaerythritol tetraacrylate, 33.1% by mass of dipentaerythritol hexaacrylate, 4.1% by mass of other unknowns; DPPA The same procedure as in Synthesis Example 1 was performed except that the mixture was replaced with the mixture a-2 (hydroxyl value 90) (see Table 1 for the amount of each compound used), and the inorganic oxide fine particle modifier (D-2- As a result, 551 g of a toluene solution having a nonvolatile content of 50.1% by mass of 2) was obtained.

[Synthesis Example 4]: Synthesis of inorganic oxide fine particle modifier (D-2-3) DPPA mixture a, which is a polyfunctional acrylate having a hydroxyl group, is converted to dipentaerythritol, which is a polyfunctional acrylate having a hydroxyl group, and acrylic. Reaction product of acid (mixture of 41.5% by mass of dipentaerythritol pentaacrylate, 16.5% by mass of dipentaerythritol tetraacrylate, 36.8% by mass of dipentaerythritol hexaacrylate, 5.3% by mass of other unknowns; DPPA The same procedure as in Synthesis Example 1 was performed except that the mixture was replaced with the mixture a-3 (hydroxyl value 82) (see Table 1 for the amount of each compound used), and the inorganic oxide fine particle modifier (D-2- 3) Non-volatile content 50.0 mass% toluene solution 538g was obtained.

[Synthesis Example 5]: Synthesis of inorganic oxide fine particle modifier (D-2-4) DPPA mixture a which is a polyfunctional acrylate having a hydroxyl group is converted to dipentaerythritol and acrylic which are polyfunctional acrylates having a hydroxyl group. Reaction product of acid (mixture of 39.6% by mass of dipentaerythritol pentaacrylate, 14.1% by mass of dipentaerythritol tetraacrylate, 39.9% by mass of dipentaerythritol hexaacrylate, 6.4% by mass of other unknowns; DPPA The same procedure as in Synthesis Example 1 was performed except that the mixture was replaced with the mixture a-4 (hydroxyl value 75) (see Table 1 for the amount of each compound used), and the inorganic oxide fine particle modifier (D-2- As a result, 541 g of a toluene solution having a nonvolatile content of 50.1% by mass of 4) was obtained.

[Synthesis Example 6]: Synthesis of inorganic oxide fine particle modifier (D-2-5) DPPA mixture a, which is a polyfunctional acrylate having a hydroxyl group, is converted to pentaerythritol, which is a polyfunctional acrylate having a hydroxyl group, and acrylic acid. Reaction product (pentaerythritol triacrylate 59.7% by mass, pentaerythritol diacrylate 9.6% by mass, pentaerythritol tetraacrylate 21.8% by mass, other unknown 8.9% by mass; PETA mixture, hydroxyl value 159) and the point that zirconium tetraacetylacetonate was replaced with dibutyltin dilaurate was the same as in Synthesis Example 1 (see Table 1 for the amount of each compound used), and inorganic Non-volatile content of oxide fine particle modifier (D-2-5) 48.4 mass 324 g of a% toluene solution was obtained.

[Synthesis Example 7]: Synthesis of inorganic oxide fine particle modifier (D-2-6) 3-isocyanatopropyltriethoxysilane was changed to 3-isocyanatopropyltrimethoxysilane (trade name Sylquest A-Link35; Momentive Performance) -The same operation as in Synthesis Example 1 was performed (see Table 1 for the amount of each compound used) except that the material was replaced with (Materials), and the inorganic oxide fine particle modifier (D-2-6) As a result, 543 g of a toluene solution having a nonvolatile content of 49.9 mass% was obtained.

[Synthesis Example 8]: Synthesis of inorganic oxide fine particle modifier (D-3) DPPA mixture a, which is a polyfunctional acrylate having a hydroxyl group, is mixed with dipentaerythritol, which is a polyfunctional acrylate having a hydroxyl group, and acrylic acid. Reaction product (mixture of 35.8% by mass of dipentaerythritol pentaacrylate, 9.3% by mass of dipentaerythritol tetraacrylate, 46.4% by mass of dipentaerythritol hexaacrylate, 8.6% by mass of other unknowns; DPPA mixture b Except for the hydroxyl value 61), the same operation as in Synthesis Example 1 was performed (see Table 1 for the amount of each compound used), and the nonvolatile content of the inorganic oxide fine particle modifier (D-3) was 50. 514 g of a 1% by weight toluene solution was obtained.

[Synthesis Example 9]: Synthesis of inorganic oxide fine particle modifier (D-4) DPPA mixture a, which is a polyfunctional acrylate having a hydroxyl group, is mixed with dipentaerythritol, which is a polyfunctional acrylate having a hydroxyl group, and acrylic acid. Reaction product (mixture of 38.2% by mass of dipentaerythritol pentaacrylate, 12.3% by mass of dipentaerythritol tetraacrylate, 42.3% by mass of dipentaerythritol hexaacrylate, and 7.2% by mass of other unknowns; DPHA mixture a Except that the hydroxyl value is 70), the same operation as in Synthesis Example 1 is performed (see Table 1 for the amount of each compound used), and the inorganic oxide fine particle modifier (D-4) has a nonvolatile content of 50. 531 g of a 1% by weight toluene solution was obtained.

[Synthesis Example 10]: Synthesis of inorganic oxide fine particle modifier (D-5) DPPA mixture a, which is a polyfunctional acrylate having a hydroxyl group, was converted into dipentaerythritol pentaacrylate and dipenta, which are polyfunctional acrylates having a hydroxyl group. Synthesis Example 1 except that the mixture was replaced with a mixture of erythritol hexaacrylate (a mixture of 64.8% by mass of dipentaerythritol pentaacrylate, 35.2% by mass of dipentaerythritol hexaacrylate; DPHA mixture a-2, hydroxyl value 70). The same operation was performed (see Table 1 for the amount of each compound used) to obtain 531 g of a 50.1 mass% toluene solution of the inorganic oxide fine particle modifier (D-5) in a nonvolatile content.

[Synthesis Example 11]: Synthesis of Inorganic Oxide Fine Particle Modifier (D-6) Inorganic oxide microparticles were prepared in the same manner as in Synthesis Example 1 except that the amount of each compound used was changed as shown in Table 1. 490 g of a toluene solution with a nonvolatile content of 50.0% by mass of the modifier (D-6) was obtained.
[Synthesis Example 12]: Synthesis of Inorganic Oxide Fine Particle Modifier (D-7) Inorganic oxide microparticles were prepared in the same manner as in Synthesis Example 1 except that the amount of each compound used was changed as shown in Table 1. 635 g of a toluene solution with a nonvolatile content of 50.0% by mass of the modifier (D-7) 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 the solvent was distilled off. 119 g of organic-inorganic composite dispersion liquid (C-1) was obtained by distilling off the solvent so that the nonvolatile content was 45% by mass.

[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 Step 2 was used (see Table 2 for the amount of each compound used). 159 g of body dispersion liquid (C-2) was obtained.

[Production Example 3]: Synthesis of organic-inorganic composite dispersion liquid (C-2-2) Instead of the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 as the inorganic oxide fine particle modifier The same operation as in Production Example 1 was performed except that the inorganic oxide fine particle modifier (D-2-2) synthesized in Synthesis Example 3 was used (see Table 2 for the amount of each compound used). Then, 160 g of an organic-inorganic composite dispersion (C-2-2) was obtained.

[Production Example 4]: Synthesis of organic-inorganic composite dispersion liquid (C-2-3) Instead of the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 as the inorganic oxide fine particle modifier The same operation as in Production Example 1 was performed except that the inorganic oxide fine particle modifier (D-2-3) synthesized in Synthesis Example 4 was used (see Table 2 for the amount of each compound used). Then, 161 g of an organic-inorganic composite dispersion (C-2-3) was obtained.

[Production Example 5]: Synthesis of organic-inorganic composite dispersion liquid (C-2-4) Inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 was used as the inorganic oxide fine particle modifier. The same operation as in Production Example 1 was performed except that the inorganic oxide fine particle modifier (D-2-4) synthesized in Synthesis Example 3 was used (see Table 2 for the amount of each compound used). Then, 161 g of an organic-inorganic composite dispersion (C-2-4) was obtained.

[Production Example 6]: Synthesis of organic-inorganic composite dispersion liquid (C-2-5) As the inorganic oxide fine particle modifier, the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 was used instead. The same operation as in Production Example 1 was performed except that the inorganic oxide fine particle modifier (D-2-5) synthesized in Synthesis Example 3 was used (see Table 2 for the amount of each compound used). Then, 117 g of an organic-inorganic composite dispersion (C-2-5) was obtained.

[Production Example 7]: Synthesis of organic-inorganic composite dispersion liquid (C-2-6) In place of the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1 as the inorganic oxide fine particle modifier. The same operation as in Production Example 1 was performed except that the inorganic oxide fine particle modifier (D-2-6) synthesized in Synthesis Example 3 was used (see Table 2 for the amount of each compound used). , 162 g of an organic-inorganic composite dispersion (C-2-6) was obtained.

[Production Example 8]: 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 same procedure as in Production Example 1 was performed except that the inorganic oxide fine particle modifier (D-3) synthesized in 3 was used (see Table 2 for the amount of each compound used, etc.). 163 g of body dispersion liquid (C-3) was obtained.

[Production Example 9]: Synthesis of organic-inorganic composite dispersion (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 The same procedure as in Production Example 1 was carried out except that the inorganic oxide fine particle modifier (D-4) synthesized in Step 4 was used (see Table 2 for the amount of each compound used). 163 g of body dispersion liquid (C-4) was obtained.

[Production Example 10]: 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 The same procedure as in Production Example 1 was performed except that the inorganic oxide fine particle modifier (D-5) synthesized in 3 was used (see Table 2 for the amount of each compound used, etc.). 162 g of body dispersion liquid (C-5) was obtained.

[Production Example 11]: 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 The same procedure as in Production Example 1 was performed except that the inorganic oxide fine particle modifier (D-6) synthesized in 3 was used (see Table 2 for the amount of each compound used, etc.). 161 g of body dispersion liquid (C-6) was obtained.

[Production Example 12]: Synthesis of organic-inorganic composite dispersion liquid (C-7) 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-7) synthesized in Step 3 was used (see Table 2 for the amount of each compound used). 162 g of body dispersion liquid (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-2-2) Organic-inorganic composite obtained in Production Example 3 in place of the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except for using the body dispersion liquid (C-2-2), the same operation as in Preparation Example 1 was carried out (see Table 3 for the amount of each compound used), and the curable composition (M-2 -2) was obtained.
[Preparation Example 4]: Preparation of Curable Composition (M-2-3) Organic-inorganic composite obtained in Production Example 3 in place of the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except for using the body dispersion liquid (C-2-3), the same operation as in Preparation Example 1 was carried out (see Table 3 for the amount of each compound used), and the curable composition (M-2 -3) was obtained.

[Preparation Example 5]: Preparation of Curable Composition (M-2-4) Organic-inorganic composite obtained in Production Example 3 in place of the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except for using the body dispersion liquid (C-2-4), the same operation as in Preparation Example 1 was carried out (see Table 3 for the amount of each compound used), and the curable composition (M-2 -4) was obtained.
[Preparation Example 6]: Preparation of Curable Composition (M-2-5) Organic-inorganic composite obtained in Production Example 3 instead of the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except for using the body dispersion liquid (C-2-5), the same operation as in Preparation Example 1 was performed (see Table 3 for the amount of each compound used), and the curable composition (M-2 -5) was obtained.

[Preparation Example 7]: Preparation of Curable Composition (M-2-6) Organic-inorganic composite obtained in Production Example 3 in place of the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except for using the body dispersion liquid (C-2-6), the same operation as in Preparation Example 1 was carried out (see Table 3 for the amount of each compound used), and the curable composition (M-2 -6) was obtained.
[Preparation Example 8]: Preparation of Curable Composition (M-3) Organic-inorganic composite dispersion obtained in Production Example 3 in place 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 9]: 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 10]: Preparation of Curable Composition (M-5) 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-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 11]: Preparation of Curable Composition (M-6) 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-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 12]: Preparation of Curable Composition (M-7) Organic-inorganic composite dispersion obtained in Production Example 3 in place of Organic-inorganic composite dispersion (C-1) obtained in Production Example 1 Except for using the liquid (C-7), the same operation as in Preparation Example 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, Examples 2-2 to 2-6, Comparative Examples 1 to 5]
The curable composition (M-1) of Example 1 was changed to curable compositions (M-2), (M-2-2) to (M-2-6), and (M-3) to (M-), respectively. A coating film was obtained in the same manner as in Example 1 except that it was changed to 7), and 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, 2 and Examples 2-2 to 2-6 are superior in warpage as compared with Comparative Examples 1 to 5, it can be seen that the curing shrinkage of the curable composition is low. Moreover, since the mandrel flexibility is excellent compared with Comparative Examples 1-5, it turns out that it is excellent in the bending resistance of hardened | cured material. Furthermore, since the change in Haze before and after rubbing is small in addition to the few scratches due to rubbing compared to Comparative Examples 1 to 5, it can be seen that the cured product is excellent in scratch resistance.

Claims (9)

A method for producing 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. There,
By a condensation reaction between an isocyanato group compound having an alkoxysilyl group and an isocyanato group and a hydroxyl group compound having at least two (meth) acryloyl groups and at least one hydroxyl group and having a hydroxyl value of 75 mgKOH / g or more, Having a step of obtaining the silane coupling agent,
The condensation reaction is a condensation reaction in which a urethane bond is formed by a reaction between the isocyanato group of the isocyanato group compound and the hydroxyl group of the hydroxyl group compound,
Derived from the hydroxyl group value of the hydroxyl group compound to be subjected to the condensation reaction as X (mg KOH / g), the mass of the hydroxyl group compound to be subjected to the condensation reaction as Y (g), from the isocyanato group compound to be subjected to the condensation reaction A method for producing an organic-inorganic composite, wherein the value of Z / (XY / 56.1) is 0.6 or more and 1.2 or less when the number of moles of the isocyanato group is Z (mmol) . 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);
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 content of is 0.1 parts by mass or more and 10 parts by mass or less,
The silane coupling agent includes an isocyanato group compound having an alkoxysilyl group and an isocyanato group, a hydroxyl group having at least two (meth) acryloyl groups and at least one hydroxyl group, and a hydroxyl value of 75 mgKOH / g or more. Obtained by a condensation reaction with a compound, and this condensation reaction is a condensation reaction in which the isocyanate group of the isocyanate-containing compound and the hydroxyl group of the hydroxyl-containing compound react to form a urethane bond,
The hydroxyl group compound subjected to the condensation reaction has a hydroxyl value of X (mg KOH / g), the hydroxyl group compound to be subjected to the condensation reaction has a mass of Y (g), and is subjected to the condensation reaction. Curing characterized in that the value of Z / (XY / 56.1) is 0.6 or more and 1.2 or less when the number of moles of the isocyanate group derived from the isocyanato group compound is Z (mmol). Sex composition. The curable composition according to claim 2, 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 the hydroxyl group-containing compound. R ¹ and R ² are each a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group that 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 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.

4 in the chemical formula (I), wherein 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 as described.   The curable composition according to any one of claims 2 to 4, 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 2-5.   The hard-coat material which consists of a curable composition as described in any one of Claims 2-5.   A hard coat film formed by arranging and curing the hard coat material according to claim 7 on the surface of a substrate. A silane coupling agent having at least two (meth) acryloyl groups, an isocyanato group compound having an alkoxysilyl group and an isocyanato group, a hydroxyl group having at least two (meth) acryloyl groups and at least one hydroxyl group It was obtained by a condensation reaction with a hydroxyl-containing compound having a valency of 75 mgKOH / g or more, and this condensation reaction was caused by the reaction of the isocyanate group of the isocyanate-containing compound with the hydroxyl group of the hydroxyl-containing compound. A condensation reaction in which a urethane bond occurs,
Derived from the hydroxyl group value of the hydroxyl group compound to be subjected to the condensation reaction as X (mg KOH / g), the mass of the hydroxyl group compound to be subjected to the condensation reaction as Y (g), from the isocyanato group compound to be subjected to the condensation reaction A silane coupling agent, wherein the value of Z / (XY / 56.1) is 0.6 or more and 1.2 or less when the number of moles of the isocyanato group is Z (mmol).

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