JP2016003319A - Curable composition, cured product thereof, hard coat material, and hard coat film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition and a hard coat material which are capable of forming a hard coat film simultaneously having a high refractive index, scratch resistance, pencil hardness, adhesion to a substrate, and weather resistance.SOLUTION: The curable composition contains an organic-inorganic composite (A) in which a silane coupling agent having a (meth)acryloyl group and an alkoxysilyl group is bonded to inorganic oxide fine particles, a polyfunctional (meth)acrylate monomer (B) having at least two (meth)acryloyl groups, a polymerization initiator (C), and an adhesion-imparting agent (D) being a compound having an ethylenic double bond and a polar group, at a predetermined ratio. The hard coat material comprises the curable composition.

Description

  The present invention relates to a curable composition that can be cured, and a cured product obtained by curing the curable composition. The present invention also relates to the application of the curable composition as a hard coat material and a hard coat film formed using the hard coat material.

Surfaces such as plastic sheets and plastic films are relatively soft, have poor scratch resistance and low pencil hardness, so improving the performance by providing a hard coat film on the surface of these articles to increase the surface hardness Is planned.
Further, by providing a hard coat film on these articles, various performances can be imparted in addition to scratch resistance and pencil hardness. For example, the refractive index can be improved by providing a hard coat film.

  In the field of touch panels, which have been developed in recent years, an ITO (Indium Tin Oxide) layer as a transparent conductive electrode is formed on a hard-coated film, but the refractive index difference between the ITO layer and the hard-coated film is large. Since the reflectance increases and the total light transmittance decreases and the visibility decreases, the smaller the refractive index difference between the ITO layer and the hard coat treatment film, the better.

  As a method for improving the refractive index of the hard coat film, there is a method of blending metal oxide particles such as titanium, zirconium, zinc, indium tin, antimony tin, and aluminum into the hard coat film. The method of blending the metal oxide fine particles can obtain a hard coat film having a high refractive index while maintaining high hardness and scratch resistance. For example, Patent Documents 1 and 2 describe coating compositions containing metal oxide fine particles such as titania.

In the technique disclosed in Patent Document 1, a coating composition containing a titania fine particle and an organosilicon compound is coated on a substrate by a dipping method, and then heated and thermally cured to obtain a transparent high refractive index. A coating is obtained.
In the technique disclosed in Patent Document 2, a coating film having excellent pencil hardness and scratch resistance is obtained by treating the surface of titania fine particles with a polysiloxane compound having an unsaturated group.

JP 2002-129102 A JP 2012-220556 A

  However, with regard to the adhesion between the coating composition and the substrate, the technique disclosed in Patent Document 1 only supplements the adhesion by applying an alkali treatment or the like to the plastic molded body as the substrate. There is no disclosure of improving the adhesion of the composition for use. Moreover, the technique disclosed in Patent Document 2 does not disclose that the base material is glass and the adhesion to a plastic base material is improved.

  Therefore, the present invention solves the problems of the prior art as described above, and can form a hard coat film having high refractive index, scratch resistance, pencil hardness, substrate adhesion, and weather resistance at the same time. It is an object to provide a curable composition and a hard coat material. Another object of the present invention is to provide a hard coat film and a cured product having high refractive index, scratch resistance, pencil hardness, substrate adhesion, and weather resistance at the same time.

In order to solve the above-mentioned problems, aspects of the present invention are as described in [1] to [6] below.
[1] An organic-inorganic composite (A) in which a silane coupling agent having a (meth) acryloyl group and an alkoxysilyl group and inorganic oxide fine particles are bonded;
A polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups;
A polymerization initiator (C);
An adhesion-imparting agent (D) which is a compound having an ethylenic double bond and a polar group;
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. And the content of the polymerization initiator (C) is 0.1 parts by mass or more and 100 parts by mass or less,
The total content of the organic-inorganic composite (A), the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups, and the polymerization initiator (C) was 100 parts by mass. Content of the said adhesion imparting agent (D) in case is 0.01 mass part or more and 10 mass parts or less, The curable composition characterized by the above-mentioned.

[2] The curable composition according to [1], wherein the adhesion-imparting agent (D) is a compound represented by the following chemical formula (I).
However, R ¹ in the following chemical formula (I) represents a linear or branched alkylene group having 1 to 10 carbon atoms or a divalent aromatic group, R ² represents a hydrogen atom or a methyl group, n represents an integer of 1 to 5.

[3] The inorganic oxide fine particles are at least one fine particle selected from the group consisting of silica, titania, zirconia, alumina, indium tin oxide, antimony tin oxide, and zinc oxide [1] ] Or the curable composition as described in [2].
[4] A cured product obtained by curing the curable composition according to any one of [1] to [3].
[5] A hard coat material comprising the curable composition according to any one of [1] to [3].
[6] A hard coat film formed by arranging the hard coat material according to [5] on the surface of a base material in a film shape and curing it.

The curable composition and hard coat material of the present invention can form a hard coat film having high refractive index, scratch resistance, pencil hardness, substrate adhesion, and weather resistance at the same time.
Further, the hard coat film and the cured product of the present invention have a high refractive index, scratch resistance, pencil hardness, substrate adhesion, and weather resistance at the same time.

Embodiments of the present invention will be described in detail. In the present invention, “(meth) acrylate” means methacrylate and / or acrylate, “(meth) acryloyl” means methacryloyl and / or acryloyl, and “(meth) acryl” means methacryl and / or Means acrylic.
As a result of intensive studies to solve the various problems of the above-described conventional technology, the present inventors have found that a silane coupling agent having a (meth) acryloyl group and an alkoxysilyl group is bonded to inorganic oxide fine particles. By combining the organic-inorganic composite, a polyfunctional (meth) acrylate monomer having at least two (meth) acryloyl groups, and an adhesion-imparting agent that is a compound having an ethylenic double bond and a polar group, The present inventors have found that the above problems can be solved and have completed the present invention.

  That is, the curable composition of the present invention comprises an organic-inorganic composite (A) in which a silane coupling agent having a (meth) acryloyl group and an alkoxysilyl group and inorganic oxide fine particles are bonded, and at least two ( Contains a polyfunctional (meth) acrylate monomer (B) having a (meth) acryloyl group, a polymerization initiator (C), and an adhesion promoter (D) which is a compound having an ethylenic double bond and a polar group. The content of the organic-inorganic composite (A) when the content of the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups is 100 parts by mass is 10 parts by mass or more and 2000 parts by mass. And the content of the polymerization initiator (C) is 0.1 parts by mass or more and 100 parts by mass or less, and the organic-inorganic composite (A) and at least two (meth) acryloids When the total content of the polyfunctional (meth) acrylate monomer (B) having a group and the polymerization initiator (C) is 100 parts by mass, the content of the adhesion promoter (D) is 0.01 parts by mass. The content is 10 parts by mass or less.

  The organic-inorganic composite (A) is prepared by, for example, surface-treating inorganic oxide fine particles with a silane coupling agent having a (meth) acryloyl group and an alkoxysilyl group, and covalently bonding the silane coupling agent to the inorganic oxide fine particles. Can be obtained by bonding. A cured product and hard coat film of such a curable composition obtained by copolymerizing and curing (for example, ultraviolet curing) the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B) are organic and inorganic. In addition to the high degree of cross-linking of the surface of the composite (A), it has a high pencil hardness because of its high elastic modulus due to the construction of a uniform cross-linking system. In addition, since the falling off of the inorganic oxide fine particles caused by surface abrasion is prevented by crosslinking, the cured product of the curable composition and the hard coat film also have high scratch resistance. Furthermore, since the adhesiveness-imparting agent (D) is contained in the curable composition, the adhesiveness of the hard coat film to the substrate is high.

Below, each component of the curable composition of this embodiment and the material for manufacturing this component are demonstrated.
<(1) Organic-inorganic composite (A)>
The organic-inorganic composite (A) includes a silane coupling agent having a (meth) acryloyl group and an alkoxysilyl group (hereinafter referred to as “(meth) acrylic silane coupling agent (A-1)”) and inorganic oxide fine particles. It can be obtained by dehydration condensation reaction or dealcoholization condensation reaction with (A-2).
Since the inorganic oxide fine particles (A-2) have a large number of hydroxy groups (OH groups) on their surfaces, these hydroxy groups and alkoxysilyls of the (meth) acrylic silane coupling agent (A-1) When the group undergoes a condensation reaction, the (meth) acrylic silane coupling agent (A-1) and the inorganic oxide fine particles (A-2) can be covalently bonded.

<(1-1) (Meth) acrylic silane coupling agent (A-1)>
The (meth) acrylic silane coupling agent (A-1) is not particularly limited as long as it has a (meth) acryloyl group and an alkoxysilyl group. For example, (meth) acryloyloxypropyltri Examples thereof include methoxysilane, (meth) acryloyloxypropyltriethoxysilane, (meth) acryloyloxypropylmethyldimethoxysilane, (meth) acryloyloxypropylmethyldiethoxysilane, and a compound represented by the following chemical formula (II).

However, M in the chemical formula (II) represents a hydroxyl group residue of a compound having at least two (meth) acryloyl groups and at least one hydroxy group. X represents an oxygen atom or a sulfur atom. Further, R ⁴ and R ⁵ are linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms or phenyl groups (which may have an alkyl group having 1 to 3 carbon atoms). R ⁴ and R ⁵ may be the same or different. Further, 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 k represents an integer from 1 to 3.
The compound represented by the chemical formula (II) can be obtained by a condensation reaction between a compound having an alkoxysilyl group and an isocyanato group and a compound having at least two (meth) acryloyl groups and at least one hydroxy group. . This condensation reaction is a condensation reaction in which an isocyanato group and a hydroxy group react to form a urethane bond.

Hereinafter, the (meth) acrylic silane coupling agent will be described in more detail.
The (meth) acrylic silane coupling agent can be synthesized, for example, by the following three examples (a) to (c).
(A) Compound (a-1) having an alkoxysilyl group and an isocyanato group, an organic group that can be condensed with the isocyanato group (hydroxy group, mercapto group, amino group, carboxyl group, etc.) and at least two (meth) acryloyl groups A condensation reaction with the compound (a-2).
(B) A method of using a compound having a mercapto group as a starting material, for example, a Michel addition reaction between a compound having an alkoxysilyl group and a mercapto group and a polyfunctional (meth) acryl compound, or an alkoxysilyl group And a compound having a mercapto group, a compound having at least one isocyanato group and two or more (meth) acryloyl groups.
(C) Nucleophilic addition reaction between a compound having an alkoxysilyl group and an epoxy group and a compound having at least two (meth) acryloyl groups and at least one phenolic hydroxy group, mercapto group, amino group, or carboxyl group.

Among these, since the method (a) is preferable from the viewpoints of stability of the resulting compound, ease of reaction control, and the like, the method (a) will be described in detail here.
Examples of the compound (a-1) include, but are not limited to, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. Moreover, these can also be used individually by 1 type and can also use 2 or more types together.

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

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

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

In the condensation reaction (a), the following can be used as a catalyst for the reaction. Examples of the catalyst include tin, zirconia, titania, zinc, iron, nickel, bismuth, chromium, cobalt, amine, and phosphorus. The reaction temperature is preferably 20 ° C or higher and 60 ° C or lower, and more preferably 30 ° C or higher and 55 ° C or lower.
The reaction solvent is not particularly limited, but in order to promote the condensation reaction, it is preferable to use a solvent 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, a composite oxide in which two or more kinds are combined can be given. In particular, when a cured product having a high refractive index is desired, zirconia, titania, and antimony tin oxide are preferable from the viewpoint of particle refractive index, handling, and transparency.

  The inorganic oxide fine particles (A-2) are preferably used as an organic solvent-dispersed sol 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, octanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, acetic acid Esters such as butyl, 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, and aromatic hydrocarbons such as benzene, toluene and xylene And amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Among these, methanol and isopropanol are preferable because the dispersion stability of the inorganic oxide fine particles (A-2) is good.

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 1 nm or more, the particle surface has low activity, and thus it is easy to maintain a dispersed state, and aggregation and gelation are unlikely to occur. On the other hand, if the average primary particle diameter is 200 nm or less, haze due to Rayleigh scattering is difficult to observe. Since Rayleigh scattering is proportional to the square of the particle volume, that is, the sixth power of the particle diameter, scattering is small for particles having an average primary particle diameter of ¼ or less of the wavelength of visible light, and is suitable for a transparent material. Can be used.
The average primary particle size is, for example, observed with a high-resolution transmission electron microscope (H-9000 type, manufactured by Hitachi, Ltd.), and the inorganic oxide fine particles are arbitrarily selected from the observed fine particle images. 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.

  Examples of products that are commercially available as organic solvent-dispersed sols of zirconia fine particles include Nanouse (trademark) OZ-30M and Nanouse (trademark) OZ-S30K manufactured by Nissan Chemical Industries, Ltd. 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. However, the spherical shape, the hollow shape, and the bead shape are favorable in terms of handling properties and dispersibility. 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)>
The organic-inorganic composite (A) is mixed and stirred by adding a polyfunctional (meth) acrylic silane coupling agent (A-1) and a small amount of water to a solvent in which inorganic oxide fine particles (A-2) are dispersed. Thus, it can be obtained by advancing a dehydration condensation reaction or a dealcoholization condensation reaction.
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 temperature of the 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 10 ° C. or higher, the condensation reaction between the inorganic oxide fine particles (A-2) and the polyfunctional (meth) acrylic silane coupling agent (A-1) is likely to proceed, and the target compound is sufficient. Easy to obtain. On the other hand, if it is 80 ° C. or lower, radical generation due to heat hardly occurs, and therefore gelation due to polymerization of unsaturated groups in the system hardly occurs.

  As the condensation reaction solvent, the dispersion medium of the inorganic oxide fine particles (A-2) can be used. From the viewpoint of compatibility with the surface of the inorganic oxide fine particles (A-2), water, methanol, ethanol, Protic solvents such as isopropanol, butanol, octanol, and propylene glycol monomethyl ether are preferable. In view of both the strength of solvation and the reactivity of the surface of the inorganic oxide fine particles (A-2), methanol and isopropanol are the most preferred. preferable.

  The amount of the (meth) acrylic silane coupling agent (A-1) used for the surface treatment of the inorganic oxide fine particles (A-2) is 100 mass of the inorganic oxide fine particles (A-2) that are not surface-treated. 10 parts by mass or more and 100 parts by mass or less are preferable, 15 parts by mass or more and 95 parts by mass or less are more preferable, and 20 parts by mass or more and 90 parts by mass or less are more preferable. If the amount of the (meth) acrylic silane coupling agent (A-1) used is 10 parts by mass or more, a sufficient condensation reaction is performed on the surface of the inorganic oxide fine particles (A-2). There is no possibility of reducing the dispersibility of the fine particles (A-2). On the other hand, if it is 100 parts by mass or less, the crosslink density does not become too high, so that the hard coat film is hardly warped or cracked.

  In addition, for the surface treatment of the inorganic oxide fine particles (A-2), in addition to the (meth) acrylic silane coupling agent (A-1), other silane coupling agents (A-4) may be used in combination. it can. Examples of silane coupling agents that can be used in combination are not particularly limited, but include unsaturated group-containing products such as vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane, methyltrimethoxysilane, and dimethyldimethoxy. Silane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, Examples include decyltriethoxysilane, trifluorotrimethoxysilane, and alkoxysilane compounds having a perfluoropolyether group having a repeating unit in the molecule.

Next, while removing water or alcohol produced by the dehydration condensation reaction or the dealcoholization condensation reaction and the condensation reaction solvent from the condensation reaction solution, a substitution solvent is added to perform solvent substitution, A solvent dispersion in which the organic-inorganic composite (A) is dispersed may be obtained (solvent replacement step).
The kind of the substitution solvent is not particularly limited, and solvents such as ketone, ester, aromatic hydrocarbon, aliphatic hydrocarbon, alcohol, amide, and ether can be used. The addition of the polymerization inhibitor is preferably performed in this solvent replacement step.

In the solvent dispersion, a polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups, a polymerization initiator (C), a compound having an ethylenic double bond and a polar group The curable composition (hard coat material) can be produced by mixing with a certain adhesion-imparting agent (D).
Since the dehydration condensation reaction or dealcoholization condensation reaction between the inorganic oxide fine particles (A-2) and the silane coupling agent is an equilibrium reaction, a reverse reaction (decomposition reaction) may also occur. When the reverse reaction occurs, the performances of the cured product (hard coat film) obtained by curing the curable composition (hard coat material) may be insufficient.

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

  The polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups in the dispersion of the organic-inorganic composite (A) obtained by the surface treatment of the inorganic oxide fine particles (A-2). And a substitution solvent and a polymerization inhibitor may be added and subjected to a solvent substitution step to perform solvent substitution. As a result, a dispersion containing the polyfunctional (meth) acrylate monomer (B), the organic-inorganic composite (A), and the substitution solvent is obtained, and therefore the polymerization initiator (C) and the adhesion-imparting agent (D ) Can be mixed to produce the curable composition (hard coat material).

<(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 ester (B-1), epoxy (meth) acrylate (B-2), urethane ( And (meth) acrylate (B-3).

<(2-1) (Meth) acrylic acid ester (B-1)>
Specific examples of the (meth) acrylic acid ester (B-1) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 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, Diacrylates such as 6-hexanediol di (meth) acrylate, tricyclodecane di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Taerythritol 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) acrylate (B-2)>
The epoxy (meth) acrylate (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) acrylate (B-3)>
Urethane (meth) acrylate (B-3) is an alcohol compound (B-3-1), a polyfunctional thiol compound (B-3-2), or a polyfunctional amine compound (B-3-3). It can be obtained by reacting a (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 conditions where the isocyanate group is excessive to synthesize a polyurethane compound having an isocyanate group at the terminal, and then a terminal isocyanate group. It can 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 diol, polysiloxane diol, bisphenol A, hydrogenated bisphenol A, perfluoroalcohol, perfluoropolyether Alcohol, 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), a C2-C20 linear, branched or cyclic alkylthiol (which may have a thioether structure in the molecule), And thiirane adducts of the alkyl thiols. Or the ester compound which made the compound which has at least 2 hydroxy group among the said alcohol compounds (B-3-1) and the compound of following Chemical formula (III) react is mentioned.

Incidentally, R ⁶ and R ⁷ in the chemical formula (III) are each independently hydrogen atom or an alkyl group or an aromatic group having 1 to 10 carbon atoms, methyl group or ethyl group is preferred. More preferably, one of R ⁶ and R ⁷ 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). p is an integer of 0 or more and 2 or less, preferably 0 or 1. q is 0 or 1, preferably 0.

  Specific examples of the compound of the formula (III) 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) acrylate (B-2), etc. That.

<(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-phenyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone (product of BASF; trade name Irgacure 184, etc.), 2, 2-dimethoxy-1,2-diphenylethane-1-one (product of BASF; trade name Irgacure 651, etc.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product of BASF; trade name Darocur) 1173), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (product of BASF; trade name Irgacure 2959, etc.), 2-hydroxy- 1- {4- [4- (2-hydroxy -2-methylpropionyl) -benzyl] -phenyl} -2-methylpropan-1-one (BASF product; trade name Irgacure 127, etc.), phenylglyoxylic acid methyl ester (BASF product; trade name Darocur MBF, etc.) ), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (product of BASF; trade name Irgacure 907, etc.), 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1-one (product of BASF; trade name Irgacure 369, etc.), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl -Phenyl) -butan-1-one (product of BASF; trade name Irgacure 379 etc.), bis (2, , 6-Trimethylbenzoyl) -phenylphosphine oxide (product of BASF; trade name Irgacure 819 etc.), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (product of BASF; trade name Lucilin TPO etc.), bis (η5-2 , 4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (product of BASF; trade name Irgacure 784, etc.), 1,2- Octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (BASF product; trade name Irgacure OXE01, etc.), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -1,1- (0-acetyloxime) (BA F's products; such as Irgacure OXE02), and the like. 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). 100 parts by mass of the total of the polyfunctional (meth) acrylate monomer (B) having two (meth) acryloyl groups and the adhesion-imparting agent (D) is blended in an amount of 0.1 to 10 parts by mass. It is preferable to blend 1 part by mass or more and 8 parts by mass or less.
If the compounding quantity of a photoinitiator is 0.1 mass part or more, hardening of a curable composition will become enough. On the other hand, if it is 10 parts by mass or less, the storage stability of the curable composition is not easily lowered or colored. In addition, problems such as rapid cross-linking during cross-linking to obtain a cured product and cracks during curing are less likely to occur, and there are few outgas components during high-temperature processing, and there is no possibility of contaminating the apparatus.

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.

<(4) Adhesion imparting agent (D)>
The adhesion-imparting agent (D) used in the curable composition of the present embodiment is blended in order to improve adhesion to a resin surface such as a polyethylene terephthalate (PET) film or a glass surface, and is ethylenic. It is a compound having a double bond and a polar group. Examples of polar groups include isocyanato groups, amino groups, carboxyl groups, and hydroxy groups.
A preferred adhesion-imparting agent (D) is a compound represented by the following chemical formula (I). However, R ¹ in the following chemical formula (I) represents a linear or branched alkylene group having 1 to 10 carbon atoms or a divalent aromatic group, and R ² represents a hydrogen atom or a methyl group. N is an integer of 1 or more and 5 or less, preferably 1 or 2.

A preferred specific example of the adhesion-imparting agent (D) is the aforementioned (meth) acryloyl group-containing isocyanate compound (B-3-4). By adding a small amount of the (meth) acryloyl group-containing isocyanate compound, a hard coat film having high adhesion can be obtained without significantly impairing mechanical properties and high refractive index.
As mentioned above, the curable composition of this embodiment contains an organic-inorganic composite (A), a polyfunctional (meth) acrylate monomer (B), a polymerization initiator (C), and an adhesion-imparting agent (D). However, the mass ratio of these 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.

  In the mixture of these four components, if the content of the organic-inorganic composite (A) is 10 parts by mass or more with respect to 100 parts by mass of the polyfunctional (meth) acrylate monomer (B), the inorganic content is sufficient. Therefore, a cured product having a predetermined pencil hardness and refractive index is obtained, and the curing shrinkage is small. Even in the case of a film-like cured product (sometimes referred to as “cured film” or “hard coat film”), warpage increases. Hateful. On the other hand, when the amount is 2000 parts by mass or less, since the influence of the properties of the inorganic oxide fine particles does not appear strongly, the film-like cured product has excellent bending resistance, and a self-supporting film can be formed.

The content of the polymerization initiator (C) needs to be 0.1 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polyfunctional (meth) acrylate monomer (B). It is preferably 90 parts by mass or less, and more preferably 2 parts by mass or more and 80 parts by mass or less.
When the content of the polymerization initiator (C) is 0.1 parts by mass or more with respect to 100 parts by mass of the polyfunctional (meth) acrylate monomer (B), performance such as pencil hardness and scratch resistance is obtained by sufficient curing. It will be enough. On the other hand, if it is 100 parts by mass or less, the cured film is hardly warped by the progress of appropriate crosslinking, and the unreacted polymerization initiator (C) hardly remains, so that bleed out or outgas occurs during heating. There is no fear.

Furthermore, the content of the adhesion-imparting agent (D) is based on 100 parts by mass of the total of the organic-inorganic composite (A), the polyfunctional (meth) acrylate monomer (B), and the polymerization initiator (C). 0.01 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass or more and 7 parts by mass or less, more preferably 1 parts by mass or more and 5 parts by mass or less.
The content of the adhesion-imparting agent (D) relative to 100 parts by mass of the total of the organic-inorganic composite (A), the polyfunctional (meth) acrylate monomer (B), and the polymerization initiator (C) is 0. If it is 01 mass part or more, the adhesiveness with respect to the base material of a hard-coat film | membrane will fully express. On the other hand, if the amount is 10 parts by mass or less, the strength of the hard coat film is not impaired due to the flexibility of the compound (adhesion imparting agent (D)), and thus high pencil hardness and scratch resistance are expressed. . Moreover, although the refractive index of a compound (adhesion imparting agent (D)) is not so high, a high refractive index is expressed without lowering the refractive index of the hard coat film.
Moreover, if the ratio of a polyfunctional (meth) acrylate monomer (B) is suitable, a hardened | cured material with a high refractive index will be obtained. Further, a cured product having sufficient hardness can be obtained due to a high crosslinking density, high scratch resistance can be obtained, and a self-supporting film can be formed.

  An organic solvent (E) 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, cyclohexanone, esters such as methyl acetate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, toluene And aromatic compounds such as 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) in the curable composition is not particularly limited, and the type of the organic solvent, the property of the curable composition, the type and shape of the target substrate using the curable composition, and the like. Accordingly, it may be set appropriately.
In the present invention, a material that coats the surface of an article (base material) made of various materials such as resin and glass and improves surface performance such as scratch resistance and adhesion is called a hard coat material. The curable composition of this embodiment containing an organic solvent can be used as a hard coat material.

  In addition, the curable composition of the present embodiment may be blended with an additive (F) that imparts desired characteristics to the curable composition or the cured product within a range that does not impair the object and effect of the present invention. . Examples of the additive (F) include photosensitizers, polymerization inhibitors, polymerization initiation assistants, leveling agents, wettability improvers, antifoaming agents, plasticizers, ultraviolet absorbers, antioxidants, and antistatic agents. , Silane coupling agents, pigments, dyes, slip agents, chain transfer agents.

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 0.1 μm or more and 400 μm or less, preferably 1 μm or more and 200 μm or less.

  The hard coat substrate obtained by forming the hard coat film of the present embodiment on the substrate surface has excellent adhesion between the hard coat film and the substrate surface, has a high surface refractive index, and is a pencil. Excellent hardness, weather resistance, transparency, and scratch resistance. Therefore, index matching film, antireflection film, optical disc, light emitting diode (LED) lighting device, automobile headlamp, automobile body, mobile phone terminal body, solar cell, touch panel, TV receiver, flexible display device, personal computer, etc. Can be applied to.

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 (meth) acryloyl group and alkoxysilyl group [Synthesis Example 1]: Synthesis of inorganic oxide fine particle modifier (K-1) Separable flask In addition, 285.6 g of toluene as a reaction solvent and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate which are polyfunctional acrylates having a hydroxy group (46.7% by mass of dipentaerythritol pentaacrylate, dipentaerythritol tetra 200 g of acrylate 23.1% by mass, dipentaerythritol hexaacrylate 27.9% by mass, and other unknowns 2.3% by mass), and the internal temperature of the separable flask becomes 50 ° C. while stirring. To a homogeneous solution.

Next, 83.8 g of 3-isocyanatopropyltriethoxysilane (trade name KBE-9007; manufactured by Shin-Etsu Chemical Co., Ltd.) as an isocyanate compound having an alkoxysilyl group, and zirconium tetraacetylacetonate (trade name ZC as a reaction catalyst). -700; Matsumoto Fine Chemical Co., Ltd., 20 mass% non-volatile content toluene solution) 1.8 g was added, and the mixture was stirred for 6 hours with heating, and further stirred for 10 hours at room temperature.
As a result of analyzing the peak derived from the isocyanate group of 2250 cm ⁻¹ with FT-IR (Avatar 360 manufactured by Thermo-Nicolet) for the obtained reaction solution, the peak disappeared, and the progress of the reaction was confirmed. As a result, 571 g of a toluene solution having a nonvolatile content of 50.6% by mass of the inorganic oxide fine particle modifier (K-1) was obtained.

(2) Synthesis of organic-inorganic composite [Production Example 1]: Preparation of organic-inorganic composite dispersion (L-1) Methanol-dispersed zirconia fine particles (zirconia content 31 mass%, average particle diameter of zirconia 40 nm, trade name Nanouse 193.5 g of OZ-30M (manufactured by Nissan Chemical Industries, Ltd.) was placed in a separable flask, and further 18.0 g of 3-methacryloyloxypropyltrimethoxysilane (trade name KBM-503; manufactured by Shin-Etsu Chemical Co., Ltd.) In addition, the mixture was stirred and mixed to obtain a uniform solution.
Further, 3.1 g of a 0.18% by mass HCl aqueous solution as a reaction catalyst was added to this mixed solution, and the zirconia fine particles were surface-treated by heating and stirring for 6 hours under the condition of an internal temperature of 40 ° C. 214.6 g of (L′-1) was obtained.

Next, 200 g of the obtained intermediate reaction liquid (L′-1) was put into a flask equipped with a gas blowing port, and dipentaerythritol hexaacrylate (trade name SARTOMER DPHA; manufactured by SARTOMER) 7.8 g, 254.6 g of methyl isobutyl ketone and 0.024 g of 2,6-di-t-butyl-p-cresol as a polymerization inhibitor were added to obtain 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. The solvent was distilled off so that the non-volatile content was 30% by mass to obtain 268.4 g of an organic-inorganic composite dispersion (L-1).

[Production Example 2]: Preparation of organic-inorganic composite dispersion (L-2) Methanol-dispersed titania fine particles (titania content 30% by mass, titania average particle size 13 nm, trade name OPTOLAKE 1130Z instead of methanol-dispersed zirconia fine particles ; Except that JGC Catalysts & Chemicals Co., Ltd. is used, the same operation as in Production Example 1 is performed (see Table 1 for the amount of each raw material, etc.), and the organic-inorganic composite dispersion (L-2) 261.2 g was obtained.

[Production Example 3] Preparation of organic-inorganic composite dispersion (L-3) 3-acryloyloxypropyltrimethoxysilane (trade name KBM-5103; Shin-Etsu Chemical Co., Ltd.) instead of 3-methacryloyloxypropyltrimethoxysilane Except for the point of using Co., Ltd., the same operation as in Production Example 1 was performed (see Table 1 for the amount of each raw material, etc.), and 268.1 g of the organic-inorganic composite dispersion (L-3) was added. Obtained.

[Production Example 4]: Preparation of organic-inorganic composite dispersion (L-4) Methanol-dispersed titania fine particles (titania content 30% by mass, titania average particle diameter 13 nm, trade name OPTOLAKE 1130Z instead of methanol-dispersed zirconia fine particles And using 3-acryloyloxypropyltrimethoxysilane (trade name KBM-5103; manufactured by Shin-Etsu Chemical Co., Ltd.) instead of using 3-methacryloyloxypropyltrimethoxysilane; Except for the point of use, the same operation as in Production Example 1 was performed (see Table 1 for the amount of each raw material, etc.) to obtain 261.0 g of an organic-inorganic composite dispersion (L-4).

[Production Example 5]: Preparation of organic-inorganic composite dispersion (L-5) Inorganic oxide fine particle modifier (K-1) synthesized in Synthesis Example 1 instead of 3-methacryloyloxypropyltrimethoxysilane The organic-inorganic composite dispersion liquid was subjected to the same operation as in Production Example 1 except that dipentaerythritol hexaacrylate (DPHA) was not used (see Table 1 for the amount of each raw material). 231.8 g of (L-5) was obtained.

[Production Example 6] Preparation of organic-inorganic composite dispersion (L-6) Methanol-dispersed titania fine particles (titania content 30% by mass, titania average particle size 13 nm, trade name OPTOLAKE 1130Z instead of methanol-dispersed zirconia fine particles Using JGC Catalysts & Chemicals Co., Ltd.), using the inorganic oxide fine particle modifier (K-1) synthesized in Synthesis Example 1 instead of 3-methacryloyloxypropyltrimethoxysilane, and Except not using dipentaerythritol hexaacrylate (DPHA), the same operation as in Production Example 1 was performed (see Table 1 for the amount of each raw material, etc.), and an organic-inorganic composite dispersion (L-6) 225.8 g was obtained.

(3) Preparation of curable composition [Preparation Example 1]: Preparation of curable composition (M-1) 243.1 parts by mass of the organic-inorganic composite dispersion liquid (L-1) obtained in Production Example 1. 27.1 parts by mass of dipentaerythritol hexaacrylate (trade name SARTOMER DPHA; manufactured by SARTOMER) as a polyfunctional acrylate, 4.0 parts by mass of 2-hydroxycyclohexylacetophenone (trade name IRG184; manufactured by BASF) as a polymerization initiator As a property-imparting agent, 1.0 part by mass of 2-acryloyloxyethyl isocyanate (trade name Karenz AOI (trademark); manufactured by Showa Denko KK) is mixed and methylated so that components other than non-volatile components, ie, solvent, are 25% by mass. The curable composition (M-1) was obtained by adding 96.2 mass parts of isobutyl ketone.

[Preparation Examples 2 to 19]: Preparation of curable compositions (M-2) to (M-19) Same as Preparation Example 1 except that the types and amounts used of the respective raw materials were changed as shown in Table 2. Then, curable compositions (M-2) to (M-19) were obtained.
In addition, the trade name Karenz MOI (trademark) which is an adhesion imparting agent shown in Table 2 is 2-methacryloyloxyethyl isocyanate manufactured by Showa Denko KK, and the trade name Karenz BEI (trademark) is Showa Denko KK 1,1- (bisacryloyloxymethyl) ethyl isocyanate manufactured under the trade name Laromar 9000 (trademark) is an acryloyloxy group-containing diisocyanate compound manufactured by BASF.

(4) Production and evaluation of coating film [Example 1]
Easy adhesion of curable composition (M-1) to PET film (trade name Cosmo Shine (trademark) A-4100; manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm so that the thickness of the dried coating film becomes 3 μm. It was applied on the surface 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) under a nitrogen atmosphere, and the curable composition (M-1) is cured to cure. 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 a test of pencil hardness, optical properties, adhesion, and scratch resistance according to the evaluation method described later.

In addition, the curable composition (M-1) of a PET film (trade name Cosmo Shine (trademark) A-4100; manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm is used so that the thickness of the dry coating film becomes 30 μm. It apply | coated on the easily bonding surface and was dried at 100 degreeC for 1 minute. Next, using a conveyor exposure machine, UV light (200 mJ / cm ² ) is irradiated with a UV lamp (high pressure mercury) under a nitrogen atmosphere, and the curable composition (M-1) is cured to cure. A coating film coated with a cured product (hard coat film) of the composition (M-1) was obtained. The obtained coating film was subjected to a refractive index test according to the evaluation method described later.
[Examples 2 to 13 and Comparative Examples 1 to 6]
A coating film was obtained in the same manner as in Example 1 except that the curable composition (M-1) was changed to curable compositions (M-2) to (M-19), respectively. In the same manner as in Example 1, it was subjected to various tests.

(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 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: Fully whitened or completely scratched That is, steel wool was placed on the coating film and moved linearly while applying a load of 250 g / cm ^2. By reciprocating twice, the surface of the coating film was rubbed 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.

[Evaluation of adhesion]
A cross-cut guide (manufactured by Cortec Co., Ltd.) was placed on the coating film, and the hard coat film of the coating film was cut into squares using a cutter knife or the like. One square was 2 mm square in length and width, and was cut so that a total of 100 squares were formed by 10 squares and 10 squares.
An adhesive tape (Cellotape (registered trademark) manufactured by Nichiban Co., Ltd.) was applied to the cut hard coat film, and after sufficiently adhering, the adhesive tape was peeled off from the hard coat film. And the peeling condition from the base material (PET film) of a hard-coat film | membrane was observed visually, and the following reference | standard evaluated.
A: No peeling from the substrate B: Not all peeling, but some peeling is observed.
C: The whole surface peeled from the substrate

[Evaluation of refractive index]
The refractive index of the hard coat film of the coating film was measured using an Abbe refractometer (DR-M4 manufactured by Atago Co., Ltd.).
[Evaluation of weather resistance]
Using a compact black light blue fluorescent lamp (FPL27BLB manufactured by Sankyo Electric Co., Ltd.), the coating film was irradiated with ultraviolet rays for 1000 hours. And the adhesiveness evaluation was performed by the method similar to the above with respect to the coating film after irradiation. The superiority or inferiority of the weather resistance was judged good if the adhesion did not change before and after UV irradiation, and judged poor if it decreased.

  The results of these various tests are shown in Tables 3 and 4. Examples 1 to 13 and Comparative Examples 1 to 6 were excellent in pencil hardness, optical properties, and scratch resistance, and had a high refractive index. On the other hand, in Examples 1 to 13, the adhesion that was not obtained in Comparative Examples 1 to 6 was obtained, and good adhesion to the base material was obtained by the effect of adding the adhesion imparting agent. I understand. Moreover, Examples 1-13 differ from Comparative Examples 1-6, and it turns out that favorable adhesiveness is maintained after ultraviolet irradiation, and it has the outstanding weather resistance.

Claims (6)

An organic-inorganic composite (A) in which a silane coupling agent having a (meth) acryloyl group and an alkoxysilyl group and inorganic oxide fine particles are bonded;
A polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups;
A polymerization initiator (C);
An adhesion-imparting agent (D) which is a compound having an ethylenic double bond and a polar group;
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. And the content of the polymerization initiator (C) is 0.1 parts by mass or more and 100 parts by mass or less,
The total content of the organic-inorganic composite (A), the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups, and the polymerization initiator (C) was 100 parts by mass. Content of the said adhesion imparting agent (D) in case is 0.01 mass part or more and 10 mass parts or less, The curable composition characterized by the above-mentioned. The curable composition according to claim 1, wherein the adhesion-imparting agent (D) is a compound represented by the following chemical formula (I).
However, R ¹ in the following chemical formula (I) represents a linear or branched alkylene group having 1 to 10 carbon atoms or a divalent aromatic group, R ² represents a hydrogen atom or a methyl group, n represents an integer of 1 to 5.

  The inorganic oxide fine particles are at least one fine particle selected from the group consisting of silica, titania, zirconia, alumina, indium tin oxide, antimony tin oxide, and zinc oxide. Item 3. The curable composition according to Item 2.   Hardened | cured material which hardened the curable composition as described in any one of Claims 1-3.   The hard-coat material which consists of a curable composition as described in any one of Claims 1-3.   A hard coat film formed by arranging the hard coat material according to claim 5 on the surface of a base material in a film shape and curing it.