JP2017171726A - Curable composition, cured product thereof, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition capable of forming a cured product excellent in pencil hardness, scratch resistance, water repellency, and optical characteristics and also excellent in adhesion to a substrate.SOLUTION: The curable composition contains: at least either an organic-inorganic composite (A) in which a silane coupling agent having at least one (meth)acryloyl group is covalently bonded to the surface of inorganic oxide fine particles, or a polyfunctional (meth)acrylate monomer (B) having at least two (meth)acryloyl groups; a polymerization initiator (C); and a silane coupling agent (D) having at least two (meth)acryloyl groups.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition that can be cured, and a cured product obtained by curing the curable composition. Moreover, this invention relates to the laminated body formed using the said curable composition.

  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.

  On the other hand, even a relatively high-hardness substrate such as glass is intended to provide functionality, particularly pencil hardness, scratch resistance, water repellency, and fingerprint resistance, for reasons of use and structure. The coating process has come to be performed. And also in the coating process applied to a glass base material, the hardening of the coating material by active energy rays, such as an ultraviolet-ray, an electron beam, and a visible ray, is examined as an effective method from a viewpoint of energy saving or manufacturing efficiency. .

  However, for a high-hardness substrate such as glass, as a method for improving the adhesion between the substrate and the coating film, for example, a method of eroding the surface of the substrate with a component of the coating material, It is difficult to apply a technique that utilizes an anchor effect or the like that provides adhesion by surface irregularities. For this reason, there are certain restrictions on what can be used as a coating material for a substrate with high hardness such as glass.

  Patent Document 1 discloses a plastic base material. The hard coat composition of Patent Document 1 contains colloidal silica surface-treated with a silane coupling agent having one (meth) acrylate group in the molecule. Patent Document 2 discloses a curable resin composition for hard coat intended for plastic substrates, glass substrates and the like. The hard coat curable resin composition of Patent Document 2 contains a compound having an alkoxysilyl group, for example, a compound having an alkoxysilyl group and one (meth) acryloyl group.

JP 2008-150484 A JP 2015-187205 A

  However, the hard coat composition of Patent Document 1 may have insufficient adhesion to the glass substrate, and the hard coat curable resin composition of Patent Document 2 has insufficient hardness and adhesion. There was a case.

  Therefore, the present invention solves the above-mentioned problems of the prior art, a cured product excellent in pencil hardness, scratch resistance, water repellency, optical properties and adhesion to a substrate, and the cured product It is an object of the present invention to provide a curable composition capable of forming a film. Another object of the present invention is to provide a laminate in which a cured product excellent in pencil hardness, scratch resistance, water repellency, and optical properties and a glass substrate are adhered with excellent adhesion.

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 (A) in which a silane coupling agent having at least one (meth) acryloyl group is covalently bonded to the surface of the inorganic oxide fine particle, and a polyfunctional having at least two (meth) acryloyl groups At least one of the (meth) acrylate monomer (B);
A polymerization initiator (C);
A silane coupling agent (D) having at least two (meth) acryloyl groups;
Containing
When the organic / inorganic composite (A) is contained, the content of the organic / inorganic composite (A) is 100 masses of the silane coupling agent (D) having at least two (meth) acryloyl groups. 0 parts by mass and 800 parts by mass or less as a part,
When the polyfunctional (meth) acrylate monomer (B) is contained, the content of the polyfunctional (meth) acrylate monomer (B) is the silane coupling agent (D) having the at least two (meth) acryloyl groups. The curable composition which is 0 mass part excess 500 mass parts or less by making 100 content into 100 mass parts.

[2] The curable composition according to [1], wherein the silane coupling agent (D) having at least two (meth) acryloyl groups is a compound represented by the following chemical formula (I).
However, M in the following chemical formula (I) represents a hydroxy 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 ¹ and R ² may be 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. Represents a group, and 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.

[3] X in the chemical formula (I) is an oxygen atom, l is 0, m is 3, R ² is a methyl group or an ethyl group, and R ³ is a linear propylene group. The curable composition according to [2].

[4] The silane coupling agent (D) having at least two (meth) acryloyl groups includes an isocyanate group of a compound having an alkoxysilyl group and an isocyanato group, at least two (meth) acryloyl groups, and at least one hydroxy group. The curable composition according to [2] or [3], which is a urethane compound that is a condensation reaction product with a hydroxy group of a compound having a group.

[5] The curable composition according to [4], wherein the compound having at least two (meth) acryloyl groups and at least one hydroxy group has a hydroxyl value of 75 mgKOH / g or more.
[6] The antifouling property-imparting agent (E) comprising a fluorine-containing compound having a fluoropolyether structure and an ethylenic carbon-carbon double bond, as described in any one of [1] to [5] Curable composition.

[7] The curable composition according to any one of [1] to [6], wherein the inorganic oxide fine particles are at least one fine particle selected from the group consisting of silica, titania, zirconia, and alumina.
[8] A cured product of the curable composition according to any one of [1] to [7].
[9] A laminate in which the cured product according to [8] is arranged in a film shape on the surface of a glass substrate.

The curable composition of the present invention can form a cured product having excellent pencil hardness, scratch resistance, water repellency, and optical properties, and particularly excellent adhesion to a glass substrate.
In addition, the cured product of the present invention is excellent in pencil hardness, scratch resistance, water repellency, optical properties, and particularly in adhesion to a glass substrate.
Furthermore, as for the laminated body of this invention, hardened | cured material and the glass base material are closely_contact | adhered with the outstanding adhesiveness.

It is a figure which shows an example of a silane coupling agent. It is a figure explaining reaction which manufactures an organic inorganic composite (A). It is a figure which shows the condensation reaction which synthesize | combines a silane coupling agent. It is a figure which shows the Michel addition reaction which synthesize | combines a silane coupling agent. It is a figure which shows the nucleophilic addition reaction which synthesize | combines a silane coupling agent. It is a figure which shows the condensation reaction which synthesize | combines a silane coupling agent. It is a figure explaining the example of the perfluoropolyether structure of a fluorine-containing compound. It is a figure explaining the example of the linear polysiloxane structure of a fluorine-containing compound. It is a figure explaining the example of the cyclic polysiloxane structure of a fluorine-containing compound.

  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, “(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 techniques, the present inventors have used the silane coupling agent having at least two (meth) acryloyl groups as an adhesion-imparting component. The present inventors have found that the problem 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 at least one (meth) acryloyl group-containing silane coupling agent is covalently bonded to the surface of the inorganic oxide fine particles, and at least two ( Contains at least one of a polyfunctional (meth) acrylate monomer (B) having a (meth) acryloyl group, a polymerization initiator (C), and a silane coupling agent (D) having at least two (meth) acryloyl groups To do.

  And content of the organic inorganic composite (A) in the whole curable composition in case the curable composition of this invention contains an organic inorganic composite (A) has at least 2 (meth) acryloyl group. The content of the silane coupling agent (D) is 100 parts by mass and exceeds 0 parts by mass and is 800 parts by mass or less. Moreover, content of the polyfunctional (meth) acrylate monomer (B) in the whole curable composition in case the curable composition of this invention contains a polyfunctional (meth) acrylate monomer (B) is at least 2 ( The content of the silane coupling agent (D) having a (meth) acryloyl group is 100 parts by mass and is 0 part by mass or more and 500 parts by mass or less.

  The cured product obtained by curing (for example, ultraviolet curing) of the curable composition of the present invention is such that the alkoxysilyl group of the silane coupling agent (D) having at least two (meth) acryloyl groups is chemically formed on the surface of the substrate. By bonding, not only the resin base material and the like, but also the glass base material that has been difficult to obtain in the past has good adhesiveness. Further, the curable composition of the present invention achieves crosslinking at a high crosslinking density at the time of curing as compared with a conventional monofunctional (meth) acrylic silane coupling agent, and at least two Since the silane coupling agent (D) having a (meth) acryloyl group and other composition components are highly crosslinked by a plurality of (meth) acryloyl groups, the silane coupling having at least two (meth) acryloyl groups The agent (D) and other composition components are integrated with each other and are not easily destroyed. Thereby, the adhesiveness with respect to a base material becomes more favorable.

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 curable composition of this embodiment may contain the organic-inorganic composite (A) in which a silane coupling agent having at least one (meth) acryloyl group is covalently bonded to the surface of the inorganic oxide fine particles. . If inorganic oxide fine particles are surface-treated with a silane coupling agent having at least one (meth) acryloyl group, and the silane coupling agent is covalently bonded to the inorganic oxide fine particles, at least one (meth) acryloyl group An organic-inorganic composite (A) in which the surface of the inorganic oxide fine particles is uniformly combined with the silane coupling agent having the above can be obtained.
Here, the silane coupling agent having at least one (meth) acryloyl group includes a silane coupling agent having at least one (meth) acryloyloxy group.

  A cured product obtained by copolymerizing such an organic-inorganic composite (A) and, for example, a polyfunctional (meth) acrylate monomer (B) and curing (for example, ultraviolet curing) is formed on the surface of the organic-inorganic composite (A). In addition to a high degree of crosslinking, it has a high modulus of elasticity due to the construction of a uniform cross-linking system, so that it has the bending resistance characteristic of curable organic materials and the high hardness and low shrinkage characteristic of curable inorganic material composites. Has both sex and. In addition, since the inorganic oxide fine particles are prevented from falling off due to surface abrasion, the cured product of the curable composition also has high scratch resistance.

  An example of the silane coupling agent is shown in FIG. As the silane coupling agent to be covalently bonded to the surface of the inorganic oxide fine particles, a silane coupling agent having at least one (meth) acryloyl group can be used, but at least two (meth) acryloyl groups can be used. It is preferable to use a silane coupling agent having a silane coupling agent, and it is more preferable to use a silane coupling agent having at least three (meth) acryloyl groups.

This organic-inorganic composite (A) is a dehydration condensation of a (meth) acrylic silane coupling agent (A-1) having a (meth) acryloyl group and an alkoxysilyl group and inorganic oxide fine particles (A-2). It can be obtained by reaction or dealcohol condensation reaction (see FIG. 2).
Since the inorganic oxide fine particles (A-2) have a large number of OH groups on their surfaces, the OH groups and the alkoxysilyl groups of the (meth) acrylic silane coupling agent (A-1) are condensed. By reacting, the (meth) acrylic silane coupling agent (A-1) and the inorganic oxide fine particles (A-2) can be bonded by a covalent bond.

<(1-1) (Meth) acrylic silane coupling agent (A-1)>
As long as the type of the (meth) acrylic silane coupling agent (A-1) has at least one (meth) acryloyl group (more preferably at least three (meth) acryloyl groups) and an alkoxysilyl group. Although not particularly limited, for example, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and a compound represented by the following chemical formula (I) can be given.

However, M in the chemical formula (I) represents a hydroxy 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. Furthermore, R ¹ and R ² may have a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms or a phenyl group (an alkyl group having 1 to 3 carbon atoms). ) And R ¹ and R ² may be the same or different. Further, R ³ represents a linear, branched, or cyclic alkylene group or phenylene group having 1 to 10 carbon atoms (which 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.

Among the compounds represented by the chemical formula (I), X is an oxygen atom, l is 0, m is 3, R ² is a methyl group or an ethyl group, and R ³ is a straight chain. A compound which is a propylene group is more preferable.
The compound represented by the chemical formula (I) can be obtained by a condensation reaction between a compound having an alkoxysilyl group and an isocyanato group and a compound having at least two (meth) acryloyl groups and at least one hydroxy group. it can. 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 (A-1) will be described in more detail.
The (meth) acrylic silane coupling agent (A-1) 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 (hydroxy group, mercapto group, amino group, carboxy group, etc.) that can be condensed with the isocyanato group, and at least two (meth) acryloyl groups And a condensation reaction with the compound (a-2) having the formula (see FIG. 3).

(B) A method using a compound (b-1) having a mercapto group as a starting material, for example, a compound (b-1) having an alkoxysilyl group and a mercapto group, and a polyfunctional (meth) acrylic compound ( Michel addition reaction with b-2) (see FIG. 4), or compound (b-1) with compound (b-3) having at least one isocyanato group and two or more (meth) acryloyl groups Condensation reaction.

(C) a compound (c-1) having an alkoxysilyl group and an epoxy group, and a compound having at least two (meth) acryloyl groups and at least one phenolic hydroxy group, mercapto group, amino group, or carboxy group (c -2) with nucleophilic addition reaction (see FIG. 5).

  First, the method (a) will be described. Examples of the compound (a-1) include, but are not limited to, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. Moreover, these can also be used individually by 1 type and can also use 2 or more types together.

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

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 carboxy 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 with little solvation. For example, nonpolar solvents such as cyclohexane, methylcyclohexane, benzene, toluene, xylene, and dichloromethane can be used. Of these, toluene is most preferable from the viewpoints of compatibility with organic substances, low water absorption, and relatively easy distillation.

  Next, the method (b) will be described. Examples of the compound (b-1) include, but are not limited to, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like. Moreover, these compounds can also be used individually by 1 type, and can also use 2 or more types together.

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

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

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

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

<(1-2) Inorganic oxide fine particles (A-2)>
Next, regarding the inorganic oxide fine particles (A-2), the following substances can be used. For example, silica, hollow silica, alumina, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, antimony tin oxide (ATO), cerium oxide, potassium oxide, Among these, an alloy in which two or more kinds are combined can be used. In particular, silica is preferred from the viewpoint of specific gravity and hardness when obtaining a hardened product, and zirconia and titania are preferred from the viewpoint of particle refractive index, handling, and transparency when obtaining a cured product having a high refractive index. Antimony tin oxide is preferred, and hollow silica is preferred 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, observed with inorganic oxide fine particles with a high-resolution transmission electron microscope (H-9000 type, manufactured by Hitachi, Ltd.), and optionally 100 inorganic oxide particle images 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.

  Moreover, as a product marketed as an organic solvent-dispersed 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 marketed 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 (meth) acrylic silane coupling agent (A-1) and a small amount of water are added and mixed in a solvent in which inorganic oxide fine particles (A-2) are dispersed. A method of advancing a dehydration condensation reaction or a dealcoholization condensation reaction by 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 amount of the catalyst to be added is not particularly limited, but is usually 0.01 parts by mass or more and 1 part by mass or less, preferably 0. 01 parts by mass or more and 0.5 parts by mass or less.

  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 too low, the condensation reaction between the inorganic oxide fine particles (A-2) and the (meth) acrylic silane coupling agent (A-1) hardly proceeds, and the target compound may not be sufficiently obtained. is there. 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 (meth) acrylic silane coupling agent (A-1) used for the surface treatment of the inorganic oxide fine particles (A-2) is 100 parts by mass of the inorganic oxide fine particles (A-2) used for the surface treatment. Is preferably 20 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more and 95 parts by mass or less, and still more preferably 40 parts by mass or more and 90 parts by mass or less. When the amount of the (meth) acrylic silane coupling agent (A-1) used is less than 20 parts by mass, the surface of the inorganic oxide fine particles (A-2) is not sufficiently condensed, and the inorganic oxide fine particles The dispersibility of (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, 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. 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. Here, the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups includes a polyfunctional (meth) acrylate monomer having at least two (meth) acryloyloxy groups.

<(2-1) (Meth) acrylic acid esters (B-1)>
(Meth) acrylic acid esters (B-1) are, for example, compounds having a (meth) acryloyloxy group, specifically 1,3-bis ((meth) acryloyloxy) propyl-2-methyl. -2-isocyanate, 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, tricyclo Diacrylates such as candi (meth) acrylate and bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyfunctional (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) isocyanurate, and their ethylene oxide modification Body, propylene oxide modified body, caprolactone modified body and the like, but are not limited thereto. 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) acryloyloxy 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) acryloyloxy 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)>
In the present invention, the urethane (meth) acrylates (B-3) include a compound having a urethane bond, a thiourethane bond, or a urea bond and having a (meth) acrylate structure.
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 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 Ether 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 hydroxy 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). 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 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, for example, those having a (meth) acryloyloxy group, 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) acryloyloxyphenyl isocyanate, 1,3-bis ((meth) acryloyloxy) propyl-2-methyl-2-isocyanate, 1,3-bis (Meth) acryloyloxy) propyl-2 isocyanate.

  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).

  Examples of the alcohol compound (B-3-6) having a (meth) acryloyl group include those having a (meth) acryloyloxy group, such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 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, Mentioned epoxy (meth) acrylates (B-2), and the like.

<(3) Polymerization initiator (C)>
The polymerization initiator (C) used in the present embodiment reacts with the (meth) acryloyl group of the organic-inorganic composite (A) or the (meth) acryloyl group of the polyfunctional (meth) acrylate monomer (B) to produce an organic inorganic A homopolymer of the composite (A) or the polyfunctional (meth) acrylate monomer (B) can be obtained. Moreover, the polymerization initiator (C) used in the present embodiment reacts the (meth) acryloyl group of the organic-inorganic composite (A) with the (meth) acryloyl group of the polyfunctional (meth) acrylate monomer (B). A copolymer of the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B) can be obtained. The following can be illustrated as a polymerization initiator.

  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.

  Although content of the photoinitiator (C) in the curable composition of this embodiment will not be specifically limited if it is the quantity which can harden a curable composition moderately, At least 2 (meta) It is preferable to mix 1 part by mass or more and 50 parts by mass or less, and more preferably 3 parts by mass or more and 45 parts by mass or less, with respect to 100 parts by mass of the silane coupling agent (D) having an acryloyl group. Most preferably, the blending amount is not less than 40 parts by mass.

  If the blending amount of the photopolymerization initiator is 1 part by mass or more, sufficient curing is performed. On the other hand, if it is 50 parts by mass or less, the storage stability of the curable composition is excellent, and coloring is unlikely to occur. In addition, since the crosslinking reaction at the time of crosslinking to obtain a cured product proceeds at an appropriate rate, problems such as cracking during curing are less likely to occur, and outgas components during high-temperature processing are suppressed, thus contaminating the apparatus. Low risk.

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) Silane coupling agent (D) having at least two (meth) acryloyl groups>
The curable composition of the present embodiment contains a silane coupling agent (D) having at least two (meth) acryloyl groups. Therefore, the hardened | cured material of the curable composition of this embodiment has favorable adhesiveness with respect to the glass base material with which it was difficult to acquire adhesiveness conventionally. Here, the silane coupling agent (D) having at least two (meth) acryloyl groups includes a silane coupling agent having at least two (meth) acryloyloxy groups.

  The type of the silane coupling agent (D) having at least two (meth) acryloyl groups is not particularly limited as long as it is a silane coupling agent having two or more (meth) acryloyl groups. Among the silane coupling agents described in the section “1) Organic-inorganic composite (A)”, a silane coupling agent having two or more (meth) acryloyl groups can be used. And the silane coupling agent (D) which has an at least 2 (meth) acryloyl group can also be used individually by 1 type, and can also use 2 or more types together.

  The details of the silane coupling agent are the same as those described in the section “(1) Organic-inorganic composite (A)”, and thus detailed description thereof is omitted. However, the silane coupling agent (D) having at least two (meth) acryloyl groups is an isocyanate group of a compound having an alkoxysilyl group and an isocyanato group (hereinafter also referred to as “isocyanato group compound”), and at least It may be a urethane compound which is a condensation reaction product with a hydroxy group of a compound having two (meth) acryloyl groups and at least one hydroxy group (hereinafter also referred to as “hydroxy-containing compound”). At this time, a hydroxy-containing compound having a hydroxyl value of 75 mgKOH / g or more may be used. The hydroxyl value is measured by a method according to JIS K1557-1.

  When a silane coupling agent (D) having at least two (meth) acryloyl groups is synthesized by a condensation reaction of an isocyanato group compound and a hydroxy group compound, a hydroxy group having a hydroxyl value of 75 mgKOH / g or more is synthesized. You may synthesize | combine as follows using a base compound. That is, the hydroxyl value of the hydroxy group compound used for the condensation reaction is X (unit is mg KOH / g), the mass of the hydroxy group compound used for the condensation reaction is Y (unit is g), and the isocyanato group compound used for the condensation reaction is You may synthesize | combine so that the value of Z / (XY / 56.1) may be 0.6 or more and 1.2 or less, when the number of moles of the derived isocyanato group is Z (unit is mmol).

  By synthesizing the silane coupling agent (D) having at least two (meth) acryloyl groups in this way, the reactivity with the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B) is improved. This increases the scratch resistance and hardness of the cured product of the curable composition. In addition, the presence of such a silane coupling agent (D) particularly increases the adhesion between glass and a cured product.

<(5) Antifouling agent (E) comprising a fluorine-containing compound having a fluoropolyether structure and an ethylenic carbon-carbon double bond>
In the curable composition of this embodiment, an antifouling agent (E) composed of a fluorine-containing compound having a fluoropolyether structure and an ethylenic carbon-carbon double bond may be blended. If the antifouling property imparting agent (E) is contained in the curable composition, the cured product of the curable composition has excellent water repellency and scratch resistance.

  The antifouling property imparting agent (E) used in the curable composition of this embodiment comprises a fluorine-containing compound, and this fluorine-containing compound is a compound having a fluoropolyether structure and an ethylenic 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 the fluoropolyether structure is not particularly limited, but preferred examples include three perfluoropolyether structures shown in FIG. The type of polysiloxane structure is not particularly limited, but a preferred example is the polysiloxane structure shown in FIG. 8, and a more preferred example is the cyclic polysiloxane structure shown in FIG.

  The fluorine-containing compound has an ethylenic carbon-carbon double bond. Then, when this cures the curable composition, the ethylenic carbon-carbon double bond of the fluorine-containing compound is the (meth) acryloyl group or polyfunctional (meth) acrylate of the organic-inorganic composite (A). Since copolymerization is performed together with the (meth) acryloyl group of the monomer (B), the antifouling agent (E) is bonded to the cured product of the curable composition by a covalent bond. As a result, the antifouling property of the cured product is particularly excellent.

Examples of the fluorine-containing compound having an ethylenic carbon-carbon double bond include the compounds described in JP 2010-95695 A and JP 2010-53114 A, but are not limited thereto. It is not a thing.
As described above, the curable composition of the present embodiment includes at least one of the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B), the polymerization initiator (C), and at least two ( A silane coupling agent (D) having a (meth) acryloyl group, and the mass ratio of these components needs to be as follows.

  That is, as described above, when the curable composition of the present embodiment contains the organic-inorganic composite (A), the content of the organic-inorganic composite (A) is at least two (meth) acryloyl groups. It is necessary to make the content of the silane coupling agent (D) having a content of 100 parts by mass more than 0 parts by mass and 800 parts by mass or less. Moreover, when the curable composition of this embodiment contains a polyfunctional (meth) acrylate monomer (B), the content of the polyfunctional (meth) acrylate monomer (B) is at least two (meth) acryloyl. The content of the silane coupling agent (D) having a group needs to be 0 part by mass and 500 parts by mass or more based on 100 parts by mass.

  If the content of the organic-inorganic composite (A) is 800 parts by mass or less, the influence of the properties of the inorganic oxide fine particles is favorably reflected, so that the toughness of the film-like cured product is reduced or the self-supporting film is formed. There is no risk of difficulty. Moreover, since the relative quantitative ratio of the silane coupling agent (D) having at least two (meth) acryloyl groups is sufficient, the silane coupling agent (D) having at least two (meth) acryloyl groups and glass Is sufficiently formed, and the adhesiveness between the cured product and the glass substrate is excellent.

In addition, when the content of the polyfunctional (meth) acrylate monomer (B) is 500 parts by mass or less, in the case of a film-like cured product, there is no possibility that the film is greatly warped or cracked due to curing shrinkage. .
Furthermore, the mass ratio of the above components in the curable composition of the present embodiment may be as follows.

  That is, the sum of the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B) when the content of the silane coupling agent (D) having at least two (meth) acryloyl groups is 100 parts by mass. The content of is preferably 100 parts by mass or more and 1000 parts by mass or less, more preferably 150 parts by mass or more and 850 parts by mass or less, and further preferably 200 parts by mass or more and 700 parts by mass or less.

  Moreover, it is preferable that content of a polymerization initiator (C) shall be 1 to 50 mass parts with respect to 100 mass parts of silane coupling agents (D) which have at least two (meth) acryloyl groups. It is more preferably 3 parts by mass or more and 45 parts by mass or less, and further preferably 5 parts by mass or more and 40 parts by mass or less.

  Furthermore, content of antifouling property imparting agent (E) shall be 0 mass part excess 5 mass parts or less with respect to 100 mass parts of silane coupling agents (D) which have at least 2 (meth) acryloyl group. Is preferable, more preferably 0 part by mass and 4 parts by mass or less, and still more preferably 0 part by mass and 3 parts by mass or less.

  When the content of the polymerization initiator (C) is 1 part by mass or more, it is easy to obtain a cured product having a high crosslinking density and excellent performance such as pencil hardness and scratch resistance. Moreover, if content of a polymerization initiator (C) is 50 mass parts or less, the problem that the curvature of a cured film will be induced by progress of crosslinking more than necessary, and unreacted polymerization initiator (C) remain. It becomes a component and outgas is generated during heating, or the problem of bleeding out hardly occurs.

  Furthermore, if content of antifouling property imparting agent (E) is 5 mass parts or less, the effect by antifouling property imparting agent (E) will be fully acquired, and performance, such as antifouling property, a dynamic friction coefficient, and a contact angle. However, it is easy to obtain a cured product having a high cross-linking density on the surface of the cured product and excellent performances such as pencil hardness and scratch resistance.

  In the curable composition of the present embodiment, an additive (F) that imparts desired characteristics to the curable composition or the cured product may be blended 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. Pigments, dyes, slip agents, and chain transfer agents.

  Similarly, the curable composition of this embodiment may be blended with a monofunctional monomer (G) that is a compound having one double bond for the purpose of imparting flexibility and controlling adhesion. Good. The monofunctional monomer (G) is preferably a compound having one (meth) acryloyloxy group, one (meth) acryloyl group, or one vinyl group. For example, a monofunctional (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) having an alkyl group which may contain a linear or branched ether bond having 1 to 20 carbon atoms. ) Acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) Acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate quaternized product (chlorine ion), diethylaminoethyl (meth) acrylate quaternized product (salt) Ion), (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate , Glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, trifluoroethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, propylene glycol monomethyl ether (meth) acrylate, ethoxylated-o- Phenylphenol (meth) acrylate, p-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, 2- (meth) acryloyloxyethyl isocyanate, N, N-dimethyl (meth) Acrylamide, N- (meth) acryloylmorpholine, N-hydroxyethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide methyl chloride quaternary salt, N-isopropyl (meth) acrylamide, diethyl ( Acrylic) amide, vinyloxazoline, N-vinylcaprolactam, N-vinylpyrrolidone, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl ( (Meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, nonylphenol ethylene oxide (EO) modified (meth) acrylate, 2- (meth) acryloyl ester Tyloxazolidone is mentioned.

Organic solvent (H) 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 (H) 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 substrate of various materials (resin, glass, etc.) by conventional methods such as coating, spraying, and dipping, and the hard coat material is heated or activated. If the organic solvent is removed by drying or the like while being cured with energy rays, the surface of the substrate can be coated with a hard coat film.

  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 (H) is removed, a film-shaped cured product of the curable composition is obtained. be able to. When the curable composition is a hard coat material, the film-like cured product becomes a hard coat film.

  For example, if a hard coat film is to be formed on the surface of a glass substrate, a hard coat material is applied to the surface of the glass substrate, and volatile components such as an organic solvent (H) are dried at 10 ° C. to 180 ° C. Then, if the hard coat material is cured by active energy rays, heat or the like, a laminate in which the hard coat film is coated on the surface of the glass substrate can be obtained.

When curing 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 10 ° C. or higher and 180 ° C. or lower and a time of 10 seconds or longer and 24 hours or shorter.
When curing with an active energy ray, the type of the active energy ray is not particularly limited as long as the hard coat material can be cured in a short time after coating the hard coat material. For example, visible light, ultraviolet light, electron beam, infrared light, γ-ray, X-ray and the like can be mentioned.

  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, sapphire glass, slate, and the like. And the curable composition of this embodiment has the adhesiveness especially excellent with respect to glass.

  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, brush coating, and the like. it can. 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.

  Since the hard coat substrate obtained by forming the hard coat film of the present embodiment on the substrate surface is excellent in pencil hardness, scratch resistance, water repellency, and optical properties, for example, optical disks, automobile headlamps, The present invention can be applied to the surface coating of automobile bodies such as automobiles, mobile phone terminals, solar cells, touch panels, television receivers, display devices (for example, flexible display devices), personal computers, and the like. In particular, since the hard coat film of the present embodiment has excellent adhesion to a glass substrate, for example, a liquid crystal cover glass, a touch panel front plate glass, protective glass, outdoor glass, building glass, kitchen glass, etc. It can be applied to the surface coating.

  Since the hard coat film of this embodiment is excellent in pencil hardness, scratch resistance, water repellency, and optical characteristics, it is a flooring material as a building interior material in addition to plastic optical parts, touch panels, film-type liquid crystal elements, and plastic containers. It is particularly suitable as a protective coating material for preventing damage (scratching) and contamination of wall materials, artificial marble and the like.

  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 a protective film for plastic optical parts.

The present invention will be described in more detail with reference to the following examples and comparative examples.
(1) Synthesis of a silane coupling agent (inorganic oxide fine particle modifier) having at least two acryloyl groups

[Synthesis Example 1]: Synthesis of Silane Coupling Agent (K-1) In a separable flask, 285.6 g of toluene as a reaction solvent, and dipentaerythritol pentaacrylate and dipentaerythritol as polyfunctional acrylates having a hydroxy group. Mixture of tetraacrylate (mixture of 46.7% by mass of dipentaerythritol pentaacrylate, 23.1% by mass of dipentaerythritol tetraacrylate, 27.9% by mass of dipentaerythritol hexaacrylate, 2.3% by mass of other unknowns; DPPA 200 g of the mixture having a hydroxyl value of 101 mgKOH / g) was added, and the mixture was heated with stirring so that the internal temperature of the separable flask was 50 ° C., to obtain a uniform 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., non-volatile content 20% by mass toluene solution) 0.3 g was added, and after 6 hours of heating and stirring, the mixture was further stirred at room temperature for 10 hours.

As a result of analyzing the peak derived from the isocyanate group of 2250 cm ⁻¹ by 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 50.0% by mass of the silane coupling agent (K-1) was obtained.

(2) Synthesis of organic-inorganic composite dispersion [Production Example 1]: Synthesis of organic-inorganic composite dispersion (L-1) Isopropyl alcohol-dispersed colloidal silica (silica content 30% by mass, silica average particle diameter 10 to 10) 200 nm of 20 nm, trade name Snowtech IPA-ST; manufactured by Nissan Chemical Co., Ltd.) was placed in a separable flask, and further, 106.3 g of a toluene solution of the silane coupling agent (K-1) synthesized in Synthesis Example 1 ( (Non-volatile content: 50.0% by mass) was added and mixed by stirring to obtain a uniform solution.

Further, 5.0 g of a 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. 310.0 g of (L′-1) was obtained.
Next, 200.0 g of the obtained intermediate reaction liquid (L′-1) was put into a flask equipped with a gas blowing port, and further, 514.1 g of methyl isobutyl ketone and 2,6-ditertiary as a polymerization inhibitor. 0.036 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. By distilling off the solvent so that the non-volatile content was 45% by mass, 159 g of an organic-inorganic composite dispersion (L-1) was obtained.

[Production Example 2]: Synthesis of organic-inorganic composite dispersion liquid (L-2) Isopropyl alcohol-dispersed colloidal silica (silica content 30% by mass, silica average particle diameter 10-20 nm, trade name Snowtech IPA-ST; Nissan Chemical Co., Ltd.) 500 g is put into a separable flask, and 45 g of 3-acryloyloxypropyltrimethoxysilane (trade name KBM-5103; manufactured by Shin-Etsu Chemical Co., Ltd.) is added as a silane coupling agent, followed by stirring and mixing. A homogeneous solution was obtained.

Further, 8.3 g of a 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. 553.0 g of (L′-2) was obtained.
Next, 200.0 g of the obtained intermediate reaction liquid (L′-2) was put in a flask equipped with a gas blowing port, and further 394.0 g of methyl isobutyl ketone and 2,6-ditertiary as a polymerization inhibitor. 0.034 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. 168 g of organic-inorganic composite dispersion liquid (L-2) was obtained by distilling off the solvent so that the nonvolatile content was 45% by mass.

(3) Preparation of curable composition [Preparation Example 1]: Preparation of curable composition (M-1) Dipentaerythritol as polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryloyl groups 42 parts by mass of hexaacrylate DPHA (trade name SARTOMER DPHA; manufactured by SARTOMER) and 33.6 parts by mass of trisacryloyloxyethyl isocyanurate (trade name Aronix M-315; manufactured by Toagosei Co., Ltd.) and a polymerization initiator (C) The silane coupling agent synthesized in Synthesis Example 1 as a silane coupling agent (D) having 4 parts by mass of 2-hydroxycyclohexylacetophenone (trade name IRG184; manufactured by BASF) and at least two (meth) acryloyl groups K-1) in toluene solution (nonvolatile content 50.0) 48.8 parts by mass), and by adding 145.3 parts by mass of methyl isobutyl ketone so that the components other than the non-volatile content, that is, the solvent is 38% by mass, the curable composition (M-1) Got.

[Preparation Example 2]: Preparation of curable composition (M-2) As antifouling agent (E), a fluoropolyether antifouling agent having an acryloyl group and a siloxane unit (trade name: KY-1203; Except for further adding 1 part by mass of Shin-Etsu Chemical Co., Ltd., the same procedure as in Preparation Example 1 was performed (see Table 2 for the amount of each compound used), and the curable composition (M- 2) was obtained.

[Preparation Example 3]: Preparation of Curable Composition (M-3) The same operation as in Preparation Example 2 was performed except that the amount of each compound used was different (Table 2 shows the amount of each compound used). And a curable composition (M-3) was obtained.
[Preparation Example 4]: Preparation of Curable Composition (M-4) As the organic-inorganic composite (A), 41.9 parts by mass of the organic-inorganic composite dispersion (L-1) obtained in Production Example 1 was used. Furthermore, except the point added, operation similar to the preparation example 2 was performed (refer Table 2 about the usage-amounts of each compound etc.), and the curable composition (M-4) was obtained.

[Preparation Example 5]: Preparation of curable composition (M-5) The same operation as in Preparation Example 4 was performed except that dipentaerythritol hexaacrylate DPHA was not used (for the amounts used of each compound, etc.) 2) and a curable composition (M-5) was obtained.
[Preparation Example 6]: Preparation of curable composition (M-6) Table 2 shows the points of not using dipentaerythritol hexaacrylate DPHA and trisacryloyloxyethyl isocyanurate, and the amount of organic-inorganic composite (A). A curable composition (M-6) was obtained in the same manner as in Preparation Example 4 (see Table 2 for the amount of each compound used, etc.) except that the procedure was as described above.

[Preparation Example 7]: Preparation of curable composition (M-7) The same procedure as in Preparation Example 4 was performed except that dipentaerythritol hexaacrylate DPHA and trisacryloyloxyethyl isocyanurate were not used (each compound) For the amount used, etc., see Table 2), a curable composition (M-7) was obtained.

[Preparation Example 8]: Preparation of Curable Composition (M-8) Production Example 2 as the organic-inorganic composite (A) instead of the organic-inorganic composite dispersion (L-1) obtained in Production Example 1. The same procedure as in Preparation Example 5 was performed except that the organic-inorganic composite dispersion liquid (L-2) obtained in (1) was used (see Table 2 for the amount of each compound used), and the curable composition A product (M-8) was obtained.

[Preparation Example 9]: Preparation of curable composition (M-9) The same operations as in Preparation Example 2 were performed except that the silane coupling agent (D) having at least two (meth) acryloyl groups was not used. (See Table 2 for the amount of each compound used) to obtain a curable composition (M-9).

[Preparation Example 10]: Preparation of Curable Composition (M-10) The same operation as in Preparation Example 2 was performed except that the amount of each compound used was different (Table 2 shows the amount of each compound used). And a curable composition (M-10) was obtained. This Preparation Example 10 is an example where the amount of the silane coupling agent (D) having at least two (meth) acryloyl groups is too small.

[Preparation Example 11]: Preparation of Curable Composition (M-11) The same operation as in Preparation Example 4 was performed except that the amount of each compound used was different (Table 2 shows the amount of each compound used). And a curable composition (M-11) was obtained. This Preparation Example 11 is an example where the amount of the silane coupling agent (D) having at least two (meth) acryloyl groups is too small.

[Preparation Example 12]: Preparation of curable composition (M-12) Silane coupling having one (meth) acryloyl group instead of silane coupling agent (D) having at least two (meth) acryloyl groups The same procedure as in Preparation Example 2 except that the agent (3-acryloyloxypropyltrimethoxysilane (trade name KBM-5103; manufactured by Shin-Etsu Chemical Co., Ltd.)) is used (about the amount of each compound used) See Table 2) to obtain a curable composition (M-12).

[Preparation Example 13]: Preparation of curable composition (M-13) Silane coupling having one (meth) acryloyl group instead of silane coupling agent (D) having at least two (meth) acryloyl groups The same procedure as in Preparation Example 5 except that the agent (3-acryloyloxypropyltrimethoxysilane (trade name KBM-5103; manufactured by Shin-Etsu Chemical Co., Ltd.)) is used (about the amount of each compound used) See Table 2) to obtain a curable composition (M-13).

[Preparation Example 14]: Preparation of curable composition (M-14) The same operation as in Preparation Example 5 was performed except that the silane coupling agent (D) having at least two (meth) acryloyl groups was not used. (See Table 2 for the amount of each compound used) to obtain a curable composition (M-14).

(4) Production and evaluation of coating film [Example 1]
The curable composition (M-1) was applied on a plate-like glass substrate (trade name Gorilla Glass 2; manufactured by Corning) with a thickness of 700 μm so that the thickness of the dried coating film was 5 μm. Dry at 150 ° C. for 30 minutes. Next, using a conveyor exposure machine, UV light (200 mJ / cm ² ) is irradiated with a UV lamp (high pressure mercury) under a nitrogen gas atmosphere to cure the curable composition (M-1) and cure. The glass base material (henceforth "coating glass") by which the hardened | cured material (hard coat film) of the property composition (M-1) was coated was obtained. The obtained coating glass was subjected to various tests according to the evaluation method described later, and the hard coat film of the coating glass was evaluated.

[Examples 2 to 8, Comparative Examples 1 to 6]
A coating glass was obtained in the same manner as in Example 1 except that the curable composition (M-1) of Example 1 was changed to curable compositions (M-2) to (M-14), respectively. These were subjected to various tests in the same manner as in Example 1.

(5) Evaluation method of coating glass [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 Pencil Co., Ltd. manufactured by Mitsubishi Pencil Co., Ltd.), a coating glass based on the method specified in JIS K5600-5-4 The pencil hardness of the hard coat film 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. The results are shown in Table 3.

[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.). The results are shown in Table 3.

[Evaluation of scratch resistance]
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 scratch resistance of the hard coat film of the coated glass is measured. did. 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

More specifically, steel wool is placed on the hard coat film of the coating glass, moved linearly while applying a load of 175 g / cm ^2, and moved back and forth 1000 times to thereby change the surface of the hard coat film to steel wool. Rubbed with. Then, the presence or absence of scratches (by visual observation) was evaluated. The results are shown in Table 3.

[Water repellency (water contact angle)]
3 μL of the measurement liquid was dropped on the hard coat film of the coating glass, and the water contact angle after 5 seconds from the dropping was measured using an automatic contact angle meter (DM-501 manufactured by Kyowa Interface Science Co., Ltd.). The θ / 2 method was applied to calculate the angle. The results are shown in Table 3.

[Adhesion]
A cross-cut guide (manufactured by Cortec Co., Ltd.) was placed on the coating glass, and the hard coat film of the coating glass was cut into grids using a cutter knife. 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 glass base material of a hard-coat film | membrane was observed visually, and adhesiveness was determined with the following evaluation criteria from the ratio of the mass which did not peel from a glass base material among a total of 100 masses.

5B: no peeling 4B: peeling is less than 5 squares 3B: peeling is 5 squares or more and less than 15 squares 2B: peeling is 15 squares or more and less than 35 squares 1B: peeling is 35 squares or more

  Since Examples 1-8 contain the silane coupling agent (D) which has at least 2 (meth) acryloyl group in the curable composition, the adhesiveness with respect to glass was excellent. On the other hand, in Comparative Examples 1 and 6, since the curable composition did not contain the silane coupling agent (D) having at least two (meth) acryloyl groups, the adhesion to glass was insufficient. It was.

In Comparative Examples 4 and 5, the curable composition contains a silane coupling agent, but is a silane coupling agent having only one (meth) acryloyl group in the molecule. Adhesion was insufficient.
Furthermore, although the comparative examples 2 and 3 contain the silane coupling agent (D) which has a curable composition which has at least 2 (meth) acryloyl group, since the content is too little, it is adhesiveness with respect to glass. Was insufficient.

Claims (9)

Organic / inorganic composite (A) in which a silane coupling agent having at least one (meth) acryloyl group is covalently bonded to the surface of the inorganic oxide fine particle, and polyfunctional (meth) having at least two (meth) acryloyl groups At least one of the acrylate monomers (B);
A polymerization initiator (C);
A silane coupling agent (D) having at least two (meth) acryloyl groups;
Containing
When the organic / inorganic composite (A) is contained, the content of the organic / inorganic composite (A) is 100 masses of the silane coupling agent (D) having at least two (meth) acryloyl groups. 0 parts by mass and 800 parts by mass or less as a part,
When the polyfunctional (meth) acrylate monomer (B) is contained, the content of the polyfunctional (meth) acrylate monomer (B) is the silane coupling agent (D) having the at least two (meth) acryloyl groups. The curable composition which is 0 mass part excess 500 mass parts or less by making 100 content into 100 mass parts. The curable composition according to claim 1, wherein the silane coupling agent (D) having at least two (meth) acryloyl groups is a compound represented by the following chemical formula (I).
However, M in the following chemical formula (I) represents a hydroxy 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 ¹ and R ² may be 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. Represents a group, and R ¹ and R ² may be the same or different. R ³ represents a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, or a phenylene group that may have an alkyl group having 1 to 3 carbon atoms. The alkylene group may contain an oxygen atom in the chain. Further, l represents an integer from 0 to 2, m represents an integer from 1 to 3, the sum of l and m is 3, and n represents an integer from 1 to 3.

X in the chemical formula (I) is an oxygen atom, l is 0, m is 3, R ² is a methyl group or an ethyl group, and R ³ is a linear propylene group. 2. The curable composition according to 2.   The silane coupling agent (D) having at least two (meth) acryloyl groups has an isocyanate group of a compound having an alkoxysilyl group and an isocyanato group, at least two (meth) acryloyl groups, and at least one hydroxy group. The curable composition according to claim 2 or 3, which is a urethane compound that is a condensation reaction product with a hydroxy group of the compound.   The curable composition according to claim 4, wherein the compound having at least two (meth) acryloyl groups and at least one hydroxy group has a hydroxyl value of 75 mgKOH / g or more.   The curable composition as described in any one of Claims 1-5 which further contains the antifouling property imparting agent (E) which consists of a fluorine-containing compound which has a fluoro polyether structure and an ethylenic carbon-carbon double bond.   The curable composition according to any one of claims 1 to 6, 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 of the curable composition as described in any one of Claims 1-7.   The laminated body by which the hardened | cured material of Claim 8 was distribute | arranged to the surface of the glass base material at the film form.

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