TWI523922B - A method for producing an organic-inorganic composite, a hardened composition, a hardened product of a hardened composition, a hard coat material, a hard coat film and a silane coupling agent - Google Patents

Description

Method for producing organic-inorganic composite, curable composition, cured product of curable composition, hard coating material, hard coating film, and decane coupling agent

The present invention relates to a method for producing an organic-inorganic composite in which a decane coupling agent is covalently bonded to inorganic oxide fine particles. Further, the present invention relates to a hardenable curable composition and a cured product obtained by curing the curable composition. Further, the present invention relates to the use of the curable composition as a hard coat material and a hard coat film formed using the hard coat material. Further, the present invention relates to a decane coupling agent.

Since the surface of the plastic sheet or the plastic film is relatively soft, the scratch resistance is insufficient, and the pencil hardness is low, the surface hardness is increased by providing a hard coating film on the surface of the article, in an attempt to improve the aforementioned performance. Further, the resin substrate composed of polycarbonate or ABS resin (acrylonitrile-butadiene-styrene resin) or the like is widely treated for the purpose of preventing surface damage.

In the past, an organic material such as a polyfunctional acrylate has been used as a main material for forming a composition for such a hard coating film. However, when the coating film is cured, the curing shrinkage rate is large, and when a hard coating film is provided on a plastic sheet or a plastic film, It is easy to roll up (curl phenomenon) at the end of a plastic sheet or a plastic film. Further, when a hard coat film is provided on the surface of the substrate, the hard coat film on the substrate is liable to cause cracks or the like.

Further, since deterioration, deformation, and shrinkage due to humidity or heat are large, there is a problem in that it is not suitable for applications requiring precise coating properties, or for applications requiring environmental resistance such as light resistance or moist heat resistance.

On the other hand, in order to increase the pencil hardness of the hard coat film, it is necessary to consider the influence of the resin base material, or the thickness, hardness, and plasticity of the hard coat film, so it is necessary to find a composition for forming a hard coat film in accordance with the use thereof. The best composition.

Here, as a composition for forming a hard coat film, Patent Document 1 discloses an acrylic monomer having a (meth)acryl oxime group, an acrylic monomer having a hydroxyl group and an ether bond, and A UV curable resin raw material composition of colloidal cerium oxide.

Further, Patent Document 2 discloses that a hexafunctional urethane acrylate, a tetrafunctional or higher (meth)acrylic monomer, and a decane coupling agent having a monofunctional reactive (meth) acrylate group are disclosed. A hard coating composition of a surface treated colloidal ceria.

Further, Patent Document 3 discloses an organic-inorganic composite containing a polyfunctional (meth) acrylate covalently bonded to inorganic oxide fine particles by surface treatment using a decane coupling agent, and has 1 to 4 in one molecule. An active energy ray-curable resin composition of (meth) acrylonitrile-based (meth) acrylate.

Further, Patent Document 4 discloses a decane coupling agent containing an acrylic resin and reacting an isocyanato group-containing compound with a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and an acrylonitrile group, and having three or more propylene oximes. A wear-resistant ultraviolet curable coating composition of a polyfunctional acrylate and a cerium oxide sol.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 9-157315

[Patent Document 2] JP-A-2008-150484

[Patent Document 3] JP-A-2010-121013

[Patent Document 4] Japanese Patent Publication No. 6-100799

However, in the ultraviolet curable resin raw material composition disclosed in Patent Document 1, colloidal cerium oxide is dispersed, but is not bonded to a reactive unsaturated group, and the composition is hardened to form a hard coating film, colloidal cerium oxide. Do not combine incoming contacts. Therefore, there is a possibility that a hard coat film having a specified hardness or modulus of elasticity cannot be obtained. Further, there is a phenomenon in which the colloidal cerium oxide is detached from the hard coating film.

Further, in the composition for hard coating disclosed in Patent Document 2, when the composition is cured to form a hard coat film, the colloidal cerium oxide is combined and crosslinked, whereby high pencil hardness can be exhibited and the colloidal cerium oxide can be prevented from falling off. However, since the (meth) acrylate group which is subjected to surface treatment of colloidal cerium oxide is monofunctional, the crosslinking density is lowered and scratch resistance cannot be sufficiently obtained.

Furthermore, the active energy ray-curable resin composition disclosed in Patent Document 3 and the abrasion-resistant ultraviolet curable coating composition disclosed in Patent Document 4 have insufficient surface modification amount of the inorganic oxide fine particles due to the decane coupling agent. When the material hardens to form a hard coat film, it is difficult to obtain a highly uniform crosslink. Therefore, the hard coating film is liable to be bent, and the bending resistance and scratch resistance are insufficient.

In order to solve the problems of the above-described conventional techniques, the present invention can form a hardenable composition of a hard coat film which is excellent in pencil hardness, low heat shrinkage, and transparency, and excellent in bending resistance and scratch resistance. Coating materials are the subject.

Moreover, the present invention has been made to provide a hard coat film and a cured product which are excellent in pencil hardness, low heat shrinkage shrinkage, and transparency, and which are excellent in bending resistance and scratch resistance. Further, the present invention provides a decane coupling agent capable of producing a hardenable composition and a hard coating material which are excellent in pencil hardness, low heat shrinkage, and transparency, and excellent in bending resistance and scratch resistance. Question. Further, the present invention provides an organic-inorganic composite capable of producing a hardenable composition and a hard coating material which are excellent in pencil hardness, low heat shrinkage, and transparency, and excellent in bending resistance and scratch resistance. The manufacturing method is a problem.

In order to solve the above problems, the aspects of the present invention are as follows [1] to [9].

[1] A method for producing an organic-inorganic composite, which is a system The inorganic oxide fine particles are surface-treated with a decane coupling agent having at least two (meth) acrylonitrile groups, and the decane coupling agent is covalently bonded to the organic-inorganic composite of the inorganic oxide fine particles. A manufacturing method characterized by having an isocyanato-containing compound having an alkoxyalkyl group and an isocyanato group, and having at least two (meth)acrylonyl groups and at least one hydroxyl group and having a hydroxyl group a condensation reaction of a hydroxy group-containing compound having a hydroxy group-containing compound of 75 mgKOH/g or more, wherein the condensation reaction is carried out by reacting an isocyanato group-containing isocyanato group with a hydroxyl group of the hydroxyl group-containing compound to produce an aminocarboxylic acid a condensation reaction of an ethyl ester bond, a hydroxyl group of the hydroxyl group-containing compound supplied to the condensation reaction having a valence of X (mgKOH/g), a mass of the hydroxyl group-containing compound supplied to the condensation reaction of Y (g), and a supply of the condensation reaction When the number of moles of the isocyanato group containing the isocyanato compound is Z (mmol), the value of Z/(XY/56.1) is 0.6 or more and 1.2 or less.

[2] A curable composition characterized in that the inorganic oxide fine particles are surface-treated with a decane coupling agent having at least two (meth) acrylonitrile groups, and the decane coupling agent is covalently bonded. An organic-inorganic composite (A) having the above inorganic oxide fine particles, a polyfunctional (meth) acrylate monomer (B) having at least two (meth) acrylonitrile groups, and a polymerization initiator (C) ), When the content of the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acrylonitrile groups is 100 parts by mass, the content of the organic-inorganic composite (A) is 10 parts by mass or more. 2,000 parts by mass or less, when the total content of the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acrylonitrile groups is 100 parts by mass, The content of the polymerization initiator (C) is 0.1 parts by mass or more and 10 parts by mass or less, and the decane coupling agent is an isocyanato group-containing compound having an alkoxyalkyl group and an isocyanato group, and has at least 2 A condensation reaction of a (meth)acrylonyl group and at least one hydroxyl group and a hydroxyl group-containing compound having a hydroxyl group value of 75 mgKOH/g or more, and the condensation reaction is the isocyanato group-containing isocyanato group a condensation reaction with a hydroxyl group of the hydroxyl group-containing compound to produce a urethane bond, and a hydroxyl group having a hydroxyl group value of X (mgKOH/g) supplied to the condensation reaction and supplying the hydroxyl group-containing compound to the condensation reaction The mass is Y (g), and the aforementioned condensation reaction is supplied. When the number of moles of the isocyanate group from the compound containing the isocyanate group is Z (mmol), Z / (XY / 56.1) value of 0.6 or more and 1.2 or less.

[3] The curable composition according to [2], wherein the decane coupling agent is a compound represented by the following chemical formula (I).

However, in the following chemical formula (I), M is a hydroxyl group residue of the hydroxyl group-containing compound, and R ¹ and R ² are a linear, branched or cyclic alkyl group having 1 or more and 10 or less carbon atoms. Or a phenyl group having an alkyl group having 1 or more and 3 or less carbon atoms, and R ¹ and R ² may be the same or different, and further R ³ is a linear or branched chain having a carbon number of 1 or more and 10 or less; a cyclic alkyl group or a phenyl group having an alkyl group having 1 or more and 3 or less carbon atoms, and the alkyl group may contain an oxygen atom in the chain, and 1 is an integer of 0 or more and 2 or less, and m is 1 For an integer of 3 or more, the sum of 1 and m is 3, and n is an integer of 1 or more and 3 or less.

[4] The curable composition according to [3], wherein, in the chemical formula (I), 1 is 0, m is 3, R ² is a methyl group or an ethyl group, and R ³ is a linear propyl group. .

[5] The curable composition according to any one of [2], wherein the inorganic oxide fine particles are selected from the group consisting of ceria, titania, zirconia, and alumina. At least one type of microparticles.

[6] A cured product characterized in that the curable composition according to any one of [2] to [5] is cured.

[7] A hard coating material comprising the curable composition according to any one of [2] to [5].

[8] A hard coat film characterized in that the hard coat material described in [7] is formed in a film form and hardened on the surface of the substrate.

[9] A decane coupling agent which is a decane coupling agent having at least two (meth) acrylonitrile groups, which has an isocyanato group-containing compound having an alkoxyalkyl group and an isocyanato group, and has At least 2 (meth) propyl a condensation reaction of an olefin group having at least one hydroxyl group and a hydroxyl group having a hydroxyl group value of 75 mgKOH/g or more, wherein the condensation reaction is an isocyanato group-containing isocyanato group and the aforementioned hydroxyl group-containing compound The hydroxyl group is reacted to produce a condensation reaction of a urethane bond, The hydroxy group of the hydroxyl group-containing compound supplied to the condensation reaction is X (mgKOH/g), the mass of the hydroxyl group-containing compound supplied to the condensation reaction is Y (g), and the isocyanate-containing compound supplied from the condensation reaction is supplied. When the number of moles of the isocyanato group is Z (mmol), the value of Z/(XY/56.1) is 0.6 or more and 1.2 or less.

The curable composition and the hard coating material of the present invention can form a hard coat film which is excellent in pencil hardness, low heat shrinkage shrinkage, and transparency, and which is excellent in bending resistance and scratch resistance. Further, the hard coat film and the cured product of the present invention are excellent in pencil hardness, low heat shrinkage shrinkage, and transparency, and are excellent in bending resistance and scratch resistance. Further, the decane coupling agent of the present invention can produce a hardenable composition and a hard coat material which can form a hard coat film which is excellent in pencil hardness, low heat shrinkage shrinkage, and transparency, and which is excellent in bending resistance and scratch resistance. Further, in the method for producing an organic-inorganic composite of the present invention, the curable composition and the organic-inorganic composite which can produce the hard-coated material can be produced.

Fig. 1 is a view showing an example of a decane coupling agent.

Fig. 2 is a view for explaining a reaction for producing an organic-inorganic composite (A).

Fig. 3 is a view showing a condensation reaction of a synthetic decane coupling agent.

Fig. 4 is a view showing an example of a structure of a perfluoropolyether of a fluorine-containing compound.

Fig. 5 is a view showing an example of a linear polyoxyalkylene structure of a fluorine-containing compound.

Fig. 6 is a view showing an example of a structure of a cyclic polysiloxane of a fluorine-containing compound.

Fig. 7 is a view showing an example of a fluorine-containing compound directly bonded to a perfluoropolyether structure and a cyclic polyoxyalkylene structure.

Fig. 8 is a view showing an example of a fluorine-containing compound having a perfluoropolyether structure directly bonded to a cyclic polyoxyalkylene structure and having a carbon-carbon double bond.

[Best Mode for Carrying Out the Invention]

The form of the embodiment of the present invention will be described in detail with reference to the drawings. Further, in the present invention, the "(meth) acrylate" is a methacrylate and/or an acrylate.

In order to solve various problems of the prior art, the inventors of the present invention have tried to review the results and found that by using an isocyanato-containing compound having an alkoxyalkyl group and an isocyanato group, and having at least two (A) The decane coupling agent obtained by the condensation reaction of a hydroxy group-containing hydroxy group-containing hydroxy group-containing hydroxy group and at least one hydroxyl group can solve the above problems and complete the present invention.

That is, the curable composition of the present invention contains inorganic oxide fine particles by a decane coupling agent having at least two (meth) acrylonitrile groups. Surface treatment, the organic-inorganic composite (A) in which the decane coupling agent is covalently bonded to the inorganic oxide fine particles, and the polyfunctional (meth) acrylate single having at least two (meth) acrylonitrile groups Organic-inorganic substance when the content of the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acryl fluorenyl groups is 100 parts by mass, and the polymerization initiator (C) The content of the composite (A) is 10 parts by mass or more and 2000 parts by mass or less, and the organic-inorganic composite (A) and a polyfunctional (meth) acrylate monomer having at least two (meth) acrylonitrile groups (B) The content of the polymerization initiator (C) when the total content is 100 parts by mass is 0.1 part by mass or more and 10 parts by mass or less.

Further, the decane coupling agent is an isocyanato group-containing compound having an alkoxyalkyl group and an isocyanato group, and having at least two (meth)acrylonyl groups and at least one hydroxyl group and having a hydroxyl group It is obtained by a condensation reaction of a hydroxyl group-containing compound of 75 mgKOH/g or more, and the condensation reaction is a condensation reaction of an isocyanato group-containing isocyanato group with a hydroxyl group-containing compound hydroxyl group to produce a urethane bond. .

By using the surface treatment of the above-described decane coupling agent, an organic-inorganic composite (A) in which the surface of the inorganic oxide fine particles is uniformly composited with a polyfunctional decane coupling agent can be obtained. Further, since the decane coupling agent is produced by using a hydroxyl group-containing compound having a high hydroxyl value as a raw material, a large amount of the above-described decane coupling agent is bonded to the surface of the inorganic oxide fine particles (the amount of surface modification is large).

Therefore, the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B) are copolymerized to be cured (for example, ultraviolet-cured), except for the surface of the organic-inorganic composite (A). Very high degree of crosslinking Since the elastic modulus is high due to the formation of a very uniform cross-linking structure, both the bending resistance of the characteristics of the curable organic material and the high hardness and low shrinkage of the characteristics of the curable inorganic material composite are combined. Further, since the inorganic oxide fine particles and the modifier of the inorganic oxide fine particles are multi-functionalized by a sufficient amount of the organic group to increase the degree of crosslinking, the inorganic oxide fine particles due to surface abrasion are prevented from falling off and the curability is improved. The cured product of the composition also has high scratch resistance.

When the hydroxyl value of the hydroxyl group-containing compound is less than 75 mgKOH/g, the pencil hardness, low hardening shrinkage, bending resistance, and scratch resistance of the cured product having the curable composition are insufficient.

The components used to produce the curable composition of the present embodiment and the materials of the components will be described below.

<(1) Organic-inorganic composite (A)>

The curable composition of the present embodiment contains a surface treatment of the inorganic oxide fine particles with a decane coupling agent having at least two (meth) acrylonitrile groups, and the decane coupling agent is covalently bonded to the inorganic oxide fine particles. Organic-inorganic composite (A). One of the decane coupling agents is shown in Fig. 1.

The organic-inorganic composite (A) can be oxidized by a polyfunctional (meth)acrylic decane coupling agent (A-1) having at least two (meth)acryl fluorenyl groups and alkoxyalkylene groups. The dehydration condensation reaction or the dealcoholization condensation reaction of the fine particles (A-2) is obtained (Fig. 2 as a reference).

The inorganic oxide fine particles (A-2) have a plurality of OH groups on the surface thereof, and are carried out by the OH group and the alkoxyalkyl group of the decane coupling agent (A-1). In the condensation reaction, the decane coupling agent (A-1) and the inorganic oxide fine particles (A-2) may be covalently bonded.

<(1-1) Polyfunctional (meth)acrylic decane coupling agent (A-1)>

a type of polyfunctional (meth)acrylic decane coupling agent (A-1) having at least two (meth) acrylonitrile groups (more preferably at least three (meth) acryl fluorenyl groups) and alkoxy groups The base group is not particularly limited, and examples thereof include compounds represented by the following formula (I).

However, M in the above chemical formula (I) is a hydroxyl group-containing hydroxyl group-containing compound having at least two (meth)acryl fluorenyl groups and at least one hydroxyl group and having a hydroxyl group value of 75 mgKOH/g or more. Further, R ¹ and R ² are a linear, branched or cyclic alkyl group or a phenyl group having 1 or more and 10 or less carbon atoms (may also have an alkyl group having 1 or more and 3 or less carbon atoms), and R ¹ It may be the same as or different from R ² . Further, R ³ is a linear, branched or cyclic alkyl group or a phenyl group (which may have an alkyl group having a carbon number of 1 or more and 3 or less) having a carbon number of 1 or more and 10 or less. The chain may contain oxygen atoms. Further, 1 is an integer of 0 or more and 2 or less, m is an integer of 1 or more and 3 or less, a sum of 1 and m is 3, and n is an integer of 1 or more and 3 or less.

Further, the compound represented by the above formula (I) may be an isocyanato-containing compound having an alkoxyalkyl group and an isocyanato group, and It is obtained by a condensation reaction of a hydroxyl group-containing compound having at least two (meth)acrylonyl groups and at least one hydroxyl group and having a hydroxyl group value of 75 mgKOH/g or more. The condensation reaction is a condensation reaction of an isocyanato group-containing isocyanato group with a hydroxyl group-containing compound hydroxyl group to produce a urethane bond.

Hereinafter, the polyfunctional (meth)acrylic acid decane coupling agent (A-1) will be described in detail.

The polyfunctional (meth)acrylic acid decane coupling agent (A-1), for example, as shown in FIG. 3, may be an isocyanato-containing compound (a-1) having an alkoxyalkyl group and an isocyanato group, It is synthesized by a condensation reaction with a hydroxyl group-containing compound (a-2) having at least two (meth)acrylinyl groups and at least one hydroxyl group.

The condensation reaction is preferably used as a method for obtaining the polyfunctional (meth)acrylic acid decane coupling agent (A-1) from the viewpoints of ease of handling, reaction selectivity, and reaction controllability, particularly because of a wide selection of compounds and operability. Also high and good.

Examples of the isocyanato group-containing compound (a-1) include, for example, 3-isocyanopropyltrimethoxydecane, 3-isocyanoxypropyltriethoxydecane, and the like, but are not limited thereto. In addition, these may be used alone or in combination of two or more.

Further, examples of the hydroxyl group-containing compound (a-2), for example, glycerol di(meth)acrylate, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, 3-hydroxy- 2-(Methyl)acryloxypropyl (meth) acrylate, bis((meth)acryloyloxyethyl)-2-hydroxyethyl isocyanurate, pentaerythritol tris(methyl) ) acrylate, pentaerythritol di(meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate.

Among these, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate is preferable.

Further, for example, a (meth)acrylic copolymer having a hydroxyl group and a (meth)acrylonitrile group in a side chain, or a compound obtained by ring-opening a cyclic acid anhydride with a polyfunctional acrylate having a hydroxyl group may, for example, be mentioned.

However, the hydroxyl group-containing compound (a-2) is not limited thereto, and these may be used alone or in combination of two or more.

Here, the hydroxyl group-containing compound (a-2) has a hydroxyl group content of 75 mgKOH/g or more, preferably 82 mgKOH/g or more, more preferably 90 mgKOH/g or more.

When the valence of the hydroxyl group is less than 75 mgKOH/g, the number of reaction points with the isocyanato group-containing compound (a-1) is small, and the obtained polyfunctional (meth)acrylic acid decane coupling agent (A-1) is effective. The component (alkoxyalkylene group) becomes less. As a result, the polyfunctional (meth)acrylic decane coupling agent (A-1) was not able to function as a decane coupling agent.

However, when the hydroxyl group content of the hydroxyl group-containing compound (a-2) is 200 mgKOH/g or more, the unsaturated group of the obtained polyfunctional (meth)acrylic type decane coupling agent (A-1) ((meth)acryl oxime) The case where the amount of base is reduced. Therefore, when the curable composition is cured, sufficient crosslink density cannot be obtained, and the performance of the cured product becomes insufficient.

The hydroxyl value of the hydroxyl group-containing compound (a-2) is defined by the following formula and can be measured by a hydroxyl value measuring method specified in JIS K0070.

HV={(V ₀ -V ₁ )×C×56.1}/m+TAV

HV: hydroxyl price

V ₀ : measuring the volume of methanol solution used in potassium hydroxide (ml)

V ₁ : volume of methanol solution of potassium hydroxide used in the empty test (ml)

C: correct concentration of potassium hydroxide in methanol solution (mol/ml)

m: mass of sample (g)

TAV: full acid price

The hydroxyl group-containing compound (a-2) used in the condensation reaction of the polyfunctional (meth)acrylic acid-type decane coupling agent (A-1) has a hydroxyl group value of X (mgKOH/g) and a hydroxyl group-containing compound (a-). 2) When the amount of use is Y (g) and the number of moles of the isocyanato group containing the isocyanato compound is Z (mmol), the value of Z/(XY/56.1) is 0.6 or more and 1.2 or less. It is better if it is 0.7 or more, it is not 1.15, and it is more than 0.8.

When the value of Z/(XY/56.1) is less than 0.6, the performance of the cured product of the curable composition becomes insufficient. When the value of Z/(XY/56.1) exceeds 1.2, there is unreacted isocyanine. The group causes intramolecular condensation to form a solvent such as urea which is poorly soluble in a solvent.

In the condensation reaction of Fig. 3, the following can be used as the reaction catalyst. For example, a catalyst such as a tin-based, zirconia-based, titanium dioxide-based, zinc-based, iron-based, nickel-based, lanthanide-based, chromium-based, cobalt-based, amine-based, or phosphorus-based catalyst. The reaction temperature is preferably 20 ° C or more and 60 ° C or less, more preferably 30 ° C or more and 55 ° C or less.

The reaction solvent is not particularly limited, and in order to promote the condensation reaction, it is preferred to use a solvent having a small solvent mixture. For example, a non-polar solvent such as cyclohexane, methylcyclohexane, benzene, toluene, xylene or dichloromethane, wherein the compatibility with an organic substance, low water absorption, and ease of distillation are Benzene is the best.

<(1-2) Inorganic oxide fine particles (A-2)>

Next, as the inorganic oxide fine particles (A-2), the following may be used. For example, cerium oxide, hollow cerium oxide, aluminum oxide, zirconium oxide, titanium dioxide, zinc oxide, cerium oxide, indium oxide, tin oxide, indium tin oxide (ITO), cerium oxide, antimony tin oxide (ATO), oxidation铈, potassium oxide, an alloy in which two or more of these are combined. In particular, in the case of obtaining a cured product having a high hardness, cerium oxide is preferred from the viewpoint of specific gravity and hardness, and in the case of obtaining a cured product having a high refractive index, from the viewpoints of particle refractive index, handleability, and transparency, Zirconium oxide, titanium oxide, and antimony tin oxide are preferred. When a cured product having a low refractive index is desired, hollow cerium oxide is preferred from the same viewpoint.

Further, the inorganic oxide fine particles (A-2) are preferably used as an organic solvent-dispersed sol dispersed as an inorganic oxide fine particle (A-2) in an organic solvent. The organic solvent used as the dispersion medium is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol, or acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. And other ketones, or ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc., or An ether such as ethylene glycol monomethyl ether or diethylene glycol monobutyl ether; or an aromatic hydrocarbon such as benzene, toluene or xylene; or dimethylformamide or dimethylacetamide. Amidoxis such as N-methylpyrrolidone. Among these, methanol and isopropyl alcohol are preferred.

Further, the average primary particle diameter of the inorganic oxide fine particles (A-2) is preferably 1 nm or more and 200 nm or less, and particularly preferably 5 nm or more and 100 nm or less from the viewpoint of handleability and transparency. When the average primary particle diameter is smaller than 1 nm, it is difficult to maintain the dispersed state for the activity of the particle surface, and there is a possibility of causing aggregation and colloid formation. On the other hand, when the average primary particle diameter exceeds 200 nm, the haze value of Rayleigh scattering is observed. Rayleigh scattering is a particle which is proportional to the second power of the particle volume, that is, the sixth order of the particle diameter, and has an average primary particle diameter of 1/4 or more of the wavelength of visible light. The barrier of the transparent material is high.

For the average primary particle diameter, for example, the inorganic oxide fine particles are observed by a transmission electron microscope (H-9000 type manufactured by Hitachi, Ltd.), and an arbitrary number of inorganic oxide particle images are selected from the observed fine particle image. Knowing the image data statistical processing method can be determined by the number average particle size.

As a commercially available product of the organic solvent-dispersing sol of the cerium oxide microparticles, for example, colloidal cerium oxide, for example, OSCAL-1132, OSCAL-1432M, OSCAL-1432, OSCAL-1632, or Nissan, manufactured by Nikko Kasei Co., Ltd. Chemical Industry Co., Ltd. produces methanol cerium oxide 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, or PL-1-IPA, PL-2L-PGME, PL-2L-MEK, etc. manufactured by Fuso Chemical Co., Ltd.

Further, as a commercially available product of an organic solvent dispersion sol of zirconia fine particles, for example, Nanouse OZ-30M manufactured by Nissan Chemical Industries Co., Ltd. NanouseOZ-S30K. Further, as a commercially available product of the organic solvent-dispersed sol of the titanium dioxide fine particles, for example, OPTOLAKE 1130Z, OPTPLAKE 6320Z, and the like manufactured by Nikko Kasei Kasei Kogyo Co., Ltd.

The shape of the inorganic oxide fine particles (A-2) is, for example, a spherical shape, a hollow spherical shape, a beaded shape, a flat plate shape, or a fibrous shape. However, in terms of workability and dispersibility, it is spherical, hollow, and rosary. The shape is good and the ball is particularly good. For example, the example of the hollow beryllium dioxide, such as the IPA-ST-UP (trade name) manufactured by Nissan Chemical Industries Co., Ltd., may be, for example, Sururia (made by Nikko Kasei Co., Ltd.). Product name).

<(1-3) Synthesis of organic-inorganic composite (A)> <surface modification (surface treatment)>

The synthesis of the organic-inorganic composite (A) can be carried out by adding a polyfunctional (meth)acrylic-type decane coupling agent (A-1) and a small amount of water to a solvent for dispersing the inorganic oxide fine particles (A-2). A method of performing a dehydration condensation reaction or a dealcoholization condensation reaction by mixing and stirring.

Further, an acid or a basic compound may be added as a catalyst, such as acetic acid, hydrochloric acid, nitric acid, sulfuric acid, ammonia water or the like, as necessary. The amount of the catalyst added is not particularly limited, and is usually 0.01 to 1 part by mass, preferably 0.01 to 0.5 part by mass, per 100 parts by mass of the inorganic oxide fine particles (A-2) such as ceria particles to be surface-treated. .

The temperature of the dehydration condensation reaction or the dealcoholization condensation reaction is preferably 10° C. or higher and 80° C. or lower, more preferably 20° C. or higher and 60° C. or lower, and 35° C. or higher and 55° C. The following is even better. When the reaction temperature is too low, the condensation reaction between the inorganic oxide fine particles (A-2) and the polyfunctional (meth)acrylic acid decane coupling agent (A-1) is difficult to proceed, and it is difficult to sufficiently obtain the target compound. On the other hand, when it exceeds 80 ° C, the unsaturated group in the system is polymerized by the radical generated by heat, and gelation occurs.

In the condensation reaction solvent (A-3), the dispersion medium of the inorganic oxide fine particles (A-2) can be used, but water and methanol are used from the viewpoint of compatibility with the surface of the inorganic oxide fine particles (A-2). A protic solvent such as ethanol, isopropanol, butanol, octanol or propylene glycol monomethyl ether is preferred, and further, in view of the reactivity of the solvent and the surface of the inorganic oxide fine particles (A-2) It is best with methanol and isopropanol.

The amount of the polyfunctional (meth)acrylic decane coupling agent (A-1) used for surface treatment of the inorganic oxide fine particles (A-2) relative to the inorganic oxide fine particles (A-2) which have not been surface-treated 100 parts by mass 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, more preferably 40 parts by mass or more and 90 parts by mass or less. When the polyfunctional (meth)acrylic decane coupling agent (A-1) is used in an amount of less than 20 parts by mass, there is no sufficient condensation reaction on the surface of the inorganic oxide fine particles (A-2), and inorganic oxide fine particles are present ( A-2) The reduction in dispersibility. On the other hand, when the amount is more than 100 parts by mass, the crosslinking density becomes too high, which may cause warpage or cracking of the hard coat film.

Further, the surface treatment of the inorganic oxide fine particles (A-2) may be carried out in combination with a polyfunctional (meth)acrylic acid decane coupling agent (A-1) and a decane coupling agent (A-4) other than the above. Examples of decane coupling agents that can be used together are not particularly limited The formula may, for example, be 3-(meth)acryloxyethyltrimethoxydecane, 3-(meth)acryloxyethylethyldimethoxydecane, or 3-(methyl)propene oxime. Oxyethyl triethoxy decane, 3-(methyl) propylene methoxyethyl methyl diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, p-styryl An unsaturated group containing trimethoxydecane or the like, or methyltrimethoxydecane, dimethyldimethoxydecane, phenyltrimethoxydecane, tetraethoxydecane, methyltriethoxydecane, Dimethyldiethoxydecane, n-propyltrimethoxydecane, n-propyltriethoxydecane, hexyltrimethoxydecane, hexyltriethoxydecane,decyltrimethoxydecane,decyl Triethoxy decane, trifluorotrimethoxy decane, an alkoxy decane compound having a perfluoropolyether group having a repeating unit in the molecule, and the like.

<(2) Polyfunctional (meth) acrylate monomer (B) having at least two (meth) acrylonitrile groups>

A polyfunctional (meth) acrylate monomer (B) having at least 2 (meth) acrylonitrile groups, such as (meth) acrylate (B-1), epoxy (meth) acrylate Class (B-2), ethyl urethane (meth) acrylate (B-3).

<(2-1)(Meth)acrylate (B-1)>

Specific examples of the (meth) acrylate (B-1) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(methyl). Acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene Alcohol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate , dicyclodecane di(meth)acrylate, diacrylate such as bisphenol A di(meth)acrylate, or trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylic acid Ester, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ginseng (2-( But not limited to polyfunctional (meth) acrylates such as methyl)acrylenyloxyethyl)isocyanurate, and their ethylene oxide modified and propylene oxide modified products. This is the case. Among these, a (meth)acrylate monomer having three or more functional groups is preferred because the hardness and scratch resistance of the cured product are good. Further, these compounds may be used alone or in combination of two or more.

<(2-2) Epoxy (meth) acrylate (B-2)>

The epoxy group (meth) acrylate (B-2) can be obtained by reacting an epoxy compound with a carboxylic acid having a (meth) acrylonitrile group. Specific examples of the epoxy compound include glycidyl (meth) acrylate, a terminal glycidyl ether of a linear alcohol having 1 to 12 carbon atoms, diethylene glycol diglycidyl ether, and tripropylene glycol. Diglycidyl ether, bisphenol A diglycidyl ether, ethylene oxide modified bisphenol A diglycidyl ether, propylene oxide modified bisphenol A diglycidyl ether, trimethylolpropane three Glycidyl ether, pentaerythritol tetraglycidyl ether, hydrogenated bisphenol A diglycidyl ether, glycerol diglycidyl ether, and the like. The carboxylic acid having a (meth) acrylonitrile group may, for example, be (meth)acrylic acid, 2-(meth)acryloxyethyl succinic acid, 2-(A) Base) acryloxyethyl hexahydrophthalic acid and the like.

<(2-3) ethyl urethane (meth) acrylate (B-3)>

Ethyl urethane (meth) acrylate (B-3), which may be obtained by an alcohol compound (B-3-1), a polyfunctional thiol compound (B-3-2), or a polyfunctional amine compound ( B-3-3) is obtained by reacting with a (meth)acrylonitrile-containing isocyanate compound (B-3-4). Alternatively, a polyaminocarboxylic acid having an isocyanato group at the end may be synthesized by subjecting the alcohol compound (B-3-1) to an isocyanate compound (B-3-5) in an excess reaction of isocyanato group. After the ethyl ester compound, a terminal isocyanato group is obtained by subjecting an alcohol compound (B-3-6) having a (meth)acryl fluorenyl group to a condensation reaction.

Specific examples of the alcohol compound (B-3-1) include a (meth)acrylonitrile-based alcohol such as 2-hydroxyethyl acrylate, ethylene glycol, and 1,3-propanediol. 1,4-butanediol, 1,6-hexanediol, glycerin, polyglycerol, ginseng (2-hydroxyethyl) isocyanurate, 1,3,5-trihydroxypentane, 1,4- Dithiane-2,5-dimethanol tricyclodecanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, norbornane dimethanol, polycarbonate diol, polyfluorene Oxyalkyl glycols, bisphenol A, hydrogenated bisphenol A, perfluoroalcohols, perfluoropolyether alcohols, and EO (ethylene oxide) modified, PO (propylene oxide) modified Body, caprolactone modified body.

Further, the polyfunctional thiol compound (B-3-2) may, for example, be a linear, branched or cyclic alkylthiol having 2 to 20 carbon atoms (the thioether structure may be contained in the molecule). Or an alkylthioethane adduct of the alkyl mercaptan. Or, for example, at least two of the aforementioned alcohol compounds (B-3-1) may be mentioned An ester compound of a compound of a hydroxy group which is reacted with a compound of the following formula (II).

Further, R ⁴ and R ⁵ in the above formula (II) are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or an aromatic ring, and a methyl group or an ethyl group is preferred. Further, one of R ⁴ and R ⁵ is a hydrogen atom, and the other is preferably an alkyl group having 1 to 10 carbon atoms (especially a methyl group or an ethyl group). m is an integer of 0 or more and 2 or less, preferably 0 or 1. n is 0 or 1, preferably 0.

Specific examples of the compound of the formula (II) include 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptobutanoic acid, 3-mercaptobutanoic acid, 4-mercaptobutanoic acid, and 2-mercaptoisoyl. Butanoic acid, 2-mercaptoisopentanoic acid, 3-mercaptoisopentanoic acid, 3-mercaptoisohexane acid, preferably 3-mercaptopropionic acid or 3-mercaptobutanoic acid.

The polyfunctional amine compound (B-3-3) may, for example, be isophorone diamine, 2,2-bis(4-aminophenyl)propane or 2,2-bis(4-aminocyclohexyl). Propane, hexamethylenediamine, melamine, melamine derivatives, and the like. From the viewpoint of weather resistance and hardness of the cured product, isophorone diamine, 2,2-bis(4-aminocyclohexyl)propane, and melamine are preferred.

The (meth)acrylonitrile-containing isocyanate compound (B-3-4) may, for example, be 2-(meth)acryloyloxyethyl isocyanate or 3-(methyl)propenyloxypropyl group. Isocyanate, 4-(methyl) propylene decyloxy Isocyanate, 5-(meth)acryloyloxypentyl isocyanate, 6-(methyl)propenyloxyhexyl isocyanate, 2-(2-(methyl)propenyloxyethyl)oxy Ethyl ethyl isocyanate, 3-(methyl) propylene decyloxy phenyl isocyanate, 4-(methyl) propylene decyl oxy phenyl isocyanate, 1,3-bis((meth) propylene decyloxy Propyl-2-methyl-2-isocyanate, 1,3-bis((meth)acrylenyloxy)propyl-2-isocyanate, and the like.

The isocyanate compound (B-3-5) may, for example, be hexamethylene diisocyanate, isophorone diisocyanate or toluene, in addition to the (meth)acrylonitrile-containing isocyanate compound (B-3-4). Diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate and its hydride, decyl diisocyanate and its hydride, norbornane diisocyanate, and further urea carboxylate, 2 polymer ( Uretdione), 3-mer (isocyanurate).

The alcohol compound (B-3-6) having a (meth) acrylonitrile group may, for example, be 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate or glycerol (a) Acrylate, 2-hydroxy-3-(meth)acryloxypropyl (meth) acrylate, 3-hydroxy-2-(meth) propylene methoxy propyl (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 above epoxy (meth) acrylate (B-2), and the like.

<(3) Polymerization initiator (C)>

The polymerization initiator (C) which can be used in the present invention is a (meth) propylene oxime group of the organic-inorganic composite (A) and a (meth) acryl oxime of the polyfunctional (meth) acrylate monomer (B). The base reaction can obtain a copolymer of the organic-inorganic composite (A) and the polyfunctional (meth) acrylate monomer (B), and the following polymerization initiators can be exemplified.

For example, a photopolymerization initiator which generates a radical due to light (ultraviolet rays, visible light, etc.) or a thermal polymerization initiator which generates a radical due to heat. Further, in the case where the curing reaction is carried out by ionic polymerization, an ionic polymerization initiator (for example, a photoacid generator or a photobase generator) can be used. These polymerization initiators may be used alone or in combination of two or more.

Photopolymerization initiators such as benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxy-phenyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2 ,6-dimethylbenzimidyldiphenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and diphenyl-(2,4,6-trimethyl Benzobenzyl)phosphine oxide. These photopolymerization initiators may 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 the amount of the curable composition is moderately cured, and the total amount of the organic-inorganic composite (A) and at least two (methyl) 100 parts by mass of the polyfunctional (meth) acrylate monomer (B) of the acrylonitrile group is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less.

When the amount of the photopolymerization initiator is less than 0.1 part by mass, the hardening becomes insufficient. On the other hand, if it exceeds 10 parts by mass, it is hard. The storage stability of the chemical composition is lowered and the coloration is reduced. Further, in the case where the cross-linking at the time of obtaining a cured product is progressed violently, and the problem of cracking at the time of hardening occurs, there is a problem that the gas-steaming component at the time of high-temperature treatment increases and the device is contaminated.

Further, examples of the thermal polymerization initiator include a thermal polymerization initiator such as a peroxide system or an azo system. For example, benzamidine oxide, tert-butyl peroxypivalate, tert-butylperoxy-2-ethylhexanoate, 2,2-bisazoisobutyronitrile, dimethyl-2 -2'-azobis(2-methylpropionate) or the like, but is not limited thereto. Further, these thermal polymerization initiators may be used alone or in combination of two or more.

The content of the thermal polymerization initiator in the curable composition of the present embodiment is the same as that of the above photopolymerization initiator. Further, a photopolymerization initiator and a thermal polymerization initiator may be used in combination.

As described above, the curable composition of the present embodiment may contain the organic-inorganic composite (A), the polyfunctional (meth) acrylate monomer (B), and the polymerization initiator (C), but the quality of these components For example, the following is better. In other words, the organic-inorganic composite (A) must be 10 parts by mass or more and 2,000 parts by mass or less, and preferably 20 parts by mass or more and 1500 parts by mass or less, based on 100 parts by mass of the polyfunctional (meth) acrylate monomer (B). More preferably, 20 parts by mass or more and 1200 parts by mass or less.

In addition, the polymerization initiator (C) must be 0.1 parts by mass or more and 200 parts by mass or less based on 100 parts by mass of the polyfunctional (meth) acrylate monomer (B), and preferably 0.3 parts by mass or more and 150 parts by mass or less. It is more preferably 0.5 parts by mass or more and 100 parts by mass or less.

In the mixture of the three components (organic-inorganic composite (A), polyfunctional (meth) acrylate monomer (B), polymerization initiator (C)), the organic-inorganic composite (A) is 10 parts by mass. When there is a small amount of the inorganic component, the cured product of the pencil hardness is not obtained, and the cured product is cured in a film form (hereinafter referred to as "cured film" or "hard coated film"). In the case of a case where there is an increase in warpage. On the other hand, when the amount is more than 2,000 parts by mass, the influence of the properties of the inorganic oxide fine particles is too strong, and the warpage resistance of the cured film is lowered.

Further, the ratio of the polyfunctional (meth) acrylate monomer (B) is too high, and in the case of a film-like cured product, the film is warped and cracked due to hardening and shrinkage. On the other hand, when the ratio of the polyfunctional (meth) acrylate monomer (B) is too low, a cured product having a sufficient hardness cannot be obtained due to a decrease in the crosslinking density, and the scratch resistance is lowered.

In addition, when the polymerization initiator (C) is less than 0.1 part by mass, the performance such as pencil hardness and scratch resistance may be insufficient due to insufficient curing. On the other hand, if it is more than 200 parts by mass, the warpage of the cured film may be caused by crosslinking or more, or the unreacted polymerization initiator (C) may be a residual component, and the gas is released upon heating. Even the overflow. On the other hand, when the ratio of the polymerization initiator (C) is too low, the hardness of the cured product cannot be obtained with a decrease in the crosslinking density.

In the curable composition of the present embodiment, the antifouling property imparting agent (D) excellent in antifouling property and slidability which imparts excellent properties to the cured product of the curable composition can be used without impairing the object or effect of the present invention. Or an additive (F) which imparts desired properties to the curable composition or cured product.

The antifouling agent (D) which can be used in the curable composition of the present embodiment is composed of a fluorine-containing compound, and the fluorine-containing compound is a compound having a perfluoropolyether structure and a carbon-carbon double bond. Further, the fluorine-containing compound may have a linear or cyclic polyoxyalkylene structure. The molecular weight is not particularly limited, and the polystyrene-equivalent weight average molecular weight measured by GPC (colloidal permeation chromatography) is preferably 1,000 or more and 100,000 or less.

The type of the perfluoropolyether structure is not particularly limited, and preferred examples thereof include three kinds of perfluoropolyether structures shown in Fig. 4 . Further, the type of the polyoxymethane structure is not particularly limited, and a preferred example thereof is a polyoxyalkylene structure as shown in Fig. 5. Further preferred examples thereof include a cyclic polyoxane structure as shown in Fig. 6.

The perfluoropolyether structure and the polyoxymethane structure in the fluorine-containing compound may be directly bonded or bonded through a linking group. The perfluoropolyether structure and the polyfluorinated alkane structure directly bonded to the fluorine-containing compound can be exemplified as shown in FIG. 7 (the type of the perfluoropolyether structure is not limited to that shown in FIG. 7 or may be as shown in FIG. The other two). Further, the type of the linking group is not particularly limited, and examples thereof include an ester group, an ether group, a sulfide group, a urethane group, and a sulfo group.

Further, the fluorine-containing compound has a carbon-carbon double bond. In this way, when the hardenable composition is cured, the carbon-carbon double bond of the fluorine-containing compound and the (meth)acryloyl group and the polyfunctional (meth)acrylic acid of the organic-inorganic composite (A) are obtained. The (meth) acrylonitrile group of the ester monomer (B) is copolymerized together, and the cured product of the curable composition and the antifouling property imparting agent (D) are bonded by a covalent bond. As a result, the antifouling property of the cured product becomes particularly excellent.

a fluorine-containing compound having a carbon-carbon double bond, as shown in FIG. By. In the fluorine-containing compound shown in Fig. 8, a group having a carbon-carbon double bond is transmitted through a urethane group and bonded to a cyclic polyoxyalkylene structure. The group having a carbon-carbon double bond is preferably a (meth) acrylonitrile group or a (meth) acryl decyloxy group.

When the antifouling property imparting agent (D) is added to the curable composition of the present embodiment, the antifouling property imparting agent (D) is used in an amount of 100 parts by mass based on 100 parts by mass of the polyfunctional (meth)acrylate monomer (B). It is preferably 0.1 parts by mass or more and 50 parts by mass or less, more preferably 0.2 parts by mass or more and 40 parts by mass or less, more preferably 0.4 parts by mass or more and 30 parts by mass or less.

When the antifouling agent (D) is less than 0.1 part by mass, the effect of the antifouling agent (D) may not be obtained, and the properties such as the antifouling property, the dynamic friction coefficient, and the contact angle may be insufficient. On the other hand, when the amount is more than 50 parts by mass, the crosslink density of the surface of the cured product is lowered, and the pencil hardness, the scratch resistance, and the like are insufficient.

Further, the additive (F), for example, a photosensitizer, a polymerization blocker, a polymerization initiator, a flat agent, a wettability improver, an antifoaming agent, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, Decane coupling agents, pigments, dyes, slip agents, chain transfer agents.

Further, the curable composition of the present embodiment can be blended with an organic solvent.

The type of the organic solvent is not particularly limited, and examples thereof include ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone, or methyl acetate, ethyl acetate, butyl acetate, and propylene glycol. An ester such as monomethyl ether acetate or an aromatic compound such as toluene or xylene. Also, for example, a ring An aliphatic hydrocarbon such as hexane or methylcyclohexane; or an ether such as diethyl ether, tetrahydrofuran or propylene glycol monomethyl ether; or an alcohol such as methanol, ethanol, isopropanol or butanol. Among these organic solvents, propylene glycol monomethyl ether, methyl ethyl ketone, and methyl isobutyl ketone are preferred.

The ratio of the organic solvent (E) is not particularly limited, and may be appropriately set depending on the type of the organic solvent, the properties of the curable composition, the type and shape of the target substrate on which the curable composition is used, and the like.

In the present invention, a material applied to the surface of an article made of various materials such as resin or glass to improve the surface properties such as scratch resistance or antifouling property is referred to as a hard coating material. The curable composition of this embodiment in combination with an organic solvent can be used as a hard coating material.

The liquid hard coating material of the present invention is placed in a film form on the surface of a substrate of various materials (resin, glass, etc.) by a conventional method such as coating, spraying, dipping, etc., and the hard coating material is hardened by heat or light. At the same time, the organic solvent is removed by drying or the like, and the surface of the substrate can be coated with a hard coat film.

By the conventional method, the curable composition of the present embodiment is processed into a film shape, and the curable composition is cured and the organic solvent is removed, whereby a film-like cured product of the curable composition can be obtained. When the curable composition is a hard coating material, the film-like cured product becomes a hard coating film.

For example, when a hard coating film is formed on the surface of the substrate, a hard coating material is applied to the surface of the substrate, and the volatile component such as the organic solvent (E) is dried at 10° C. or higher and 150° C. or lower, and then light, radiation, heat, or the like is used. When the hard coating material is hardened, a molded body coated with a hard coating film can be obtained.

In the case of heat-induced polymerization, the heat source can be used, for example, electric heating. , infrared light, hot air, etc. The preferable curing conditions in the case of performing polymerization by heat are 40 ° C or more and 150 ° C or less, and the time is 10 seconds or more and 24 hours or less.

When the polymerization is carried out by radiation (light), the hard coating material can be cured in a short time after the hard coating material is applied. The type of the radiation (light) is not particularly limited, and for example, visible light, ultraviolet light, or electron beam.

The line source of the visible light may, for example, be a daylight, a visible light lamp, a fluorescent lamp, a laser or the like. Further, as a line source of ultraviolet rays, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a laser or the like can be mentioned. Further, the line source of the electron beam may be, for example, a method using a hot electron generated from a commercially available tungsten fiber, a cold cathode method in which a metal is generated by a high voltage pulse, and a collision between a gas-like molecule and a metal electrode due to ionization. 2 times electronic 2 times electronic method.

Next, the use 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 for use as a hard coat material, a hard coat film such as a surface protective material (hard coat, transparent hard coat) or an antireflection film, and is used as a base for antireflection or coating. Materials such as plastic (polyethylene terephthalate, polycarbonate, polyacrylate, polymethacrylate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy, Melamine, cellulose triacetate, ABS resin (acrylonitrile-butadiene-styrene resin), AS resin (acrylonitrile-styrene resin), norbornene-based resin, cycloolefin polymer (COP resin), etc. Metal, wood, paper, glass, slate, etc.

The shape of these base materials is not particularly limited, and is, for example, a plate shape, a film shape, or a ternary molded body. The coating method of the hard coating material may, for example, be a usual coating method such as gravure printing, micro gravure printing, ink jet printing coating, dip coating, spray coating, flow coating, shower coating, roll coating, spin coating. , brush coating, etc. The thickness of the coating film to be applied is usually from 0.03 μm to 400 μm, preferably from 1 μm to 200 μm, after drying and curing.

The hard coat substrate (for example, a hard coat film for decorative molding) obtained by forming the hard coat film of the present embodiment on the surface of the substrate has excellent pencil hardness, low heat shrinkage shrinkage, and transparency, and is resistant to bending and scratching. Excellent in performance, so it can be applied to the surface of bodies such as optical discs, car headlights, automobiles, mobile phone terminal bodies, solar cells, touch panels, display panels, television receivers, flexible display devices, personal computers, etc. Covered.

The hard coat film of the present embodiment is excellent in pencil hardness, scratch resistance, workability, and low bendability, and is particularly excellent in low warpage, so it is particularly suitable for use in plastic optical parts, touch panels, display panels, and films. In addition to liquid crystal components and plastic containers, it can be used as a protective coating material for damage prevention (scratch) or anti-pollution of floor boards, wall materials, artificial marbles, etc.

Further, the hard coat film of the present embodiment is preferably used as a recording disc such as a CD (Compact Disc), a DVD (digital video disc), an MO (magneto-optical disc), or a BD (Blu-ray Disc), or a film type. Antireflection films such as liquid crystal elements, touch panels, display panels, and plastic optical components.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples.

(1) Synthesis of a decane coupling agent (inorganic oxide fine particle modifier) having at least two acrylonitrile groups [Synthesis Example 1]: Synthesis of inorganic oxide fine particle modifier (D-1)

In a separable flask, 129.2 g of toluene in a reaction solvent, a reaction of dipentaerythritol with a polyfunctional acrylate (hydroxyl group-containing compound) having a hydroxyl group and acrylic acid (dipentaerythritol pentaacrylate 46.7 mass%, dipentaerythritol tetraacrylate) 23.1% by mass, 27.9% by mass of dipentaerythritol hexaacrylate, and 2.3% by mass of other unidentified substances; DPPA mixture a, hydroxyl group 101) 100 g, heated to a temperature of 50 ° C in a separable flask while stirring, and made uniform Solution.

Next, 3-isocyanoxypropyltriethoxydecane (trade name KBE-9007; manufactured by Shin-Etsu Chemical Co., Ltd.) as an isocyanate compound having an alkoxyalkylene group (containing an isocyanato compound) was added. g, and 0.58 g of ethyl acetonide zirconium (trade name: ZC-700: manufactured by Matsumoto Fine Chemical Co., Ltd., nonvolatile matter, toluene solution) as a reaction catalyst, heated and stirred for 6 hours, and further at room temperature Stir for 10 hours.

The peak of the obtained isocyanoxy group of 2250 cm ^{-1 was} analyzed by FT-IR (Avatar 360 manufactured by Thermo-Nicolet Co., Ltd.), and the peak disappeared, and it was confirmed that the reaction progressed to obtain an inorganic oxide fine particle modifier ( D-1) 256 g of a nonvolatile matter 49.7 mass% toluene solution.

[Synthesis Example 2]: Synthesis of inorganic oxide fine particle modifier (D-2)

The amount of each compound used was changed to that shown in Table 1, and the same operation as in Synthesis Example 1 was carried out to obtain 571 g of a nonvolatile content of 50.6 mass% of a toluene solution of the inorganic oxide fine particle modifier (D-2).

[Synthesis Example 3]: Synthesis of inorganic oxide fine particle modifier (D-2-2)

In addition to changing the DPPA mixture a having a polyfunctional acrylate having a hydroxyl group to a reaction of dipentaerythritol and acrylic acid having a polyfunctional acrylate having a hydroxyl group (dipentaerythritol pentaacrylate 43.6 mass%, dipentaerythritol tetraacrylate 19.2 mass%, two The mixture was subjected to the same operation as in Synthesis Example 1 except that the mixture of the pentaerythritol hexaacrylate (33.1% by mass) and the other unidentified substance: 4.1% by mass; the DPPA mixture a-2 and the hydroxy group 90) (the amount of each compound used is referred to in Table 1). The inorganic oxide fine particle modifier (D-2-2) had a nonvolatile content of 551 g of a 50.1% by mass toluene solution.

[Synthesis Example 4]: Synthesis of inorganic oxide fine particle modifier (D-2-3)

A reaction product of dipentaerythritol and acrylic acid (dipentaerythritol pentaacrylate 41.5 mass%, dipentaerythritol tetraacrylate 16.5 mass%, two in addition to a DPPA mixture a having a polyfunctional acrylate having a hydroxyl group changed to a polyfunctional acrylate having a hydroxyl group The same operation as in Synthesis Example 1 was carried out except that the mixture of pentaerythritol hexaacrylate (36.8 mass%) and other unidentified substances was 5.3% by mass; the DPPA mixture a-3 and the hydroxyl group price 82) (the amount of each compound used is referred to in Table 1). The inorganic oxide fine particle modifier (D-2-3) had a nonvolatile content of 538 g of a 50.0 mass% toluene solution.

[Synthesis Example 5]: Synthesis of inorganic oxide fine particle modifier (D-2-4)

In addition to changing the DPPA mixture a of a polyfunctional acrylate having a hydroxyl group to dipentaerythritol and acrylic acid of a polyfunctional acrylate having a hydroxyl group The reactant (mixture of dipentaerythritol pentaacrylate 39.6% by mass, dipentaerythritol tetraacrylate 14.1% by mass, dipentaerythritol hexaacrylate 39.9% by mass, other unidentified material 6.4% by mass; DPPA mixture a-4, hydroxyl group 75) The same operation as in Synthesis Example 1 was carried out (the amount of each compound used is referred to in Table 1), and 541 g of a nonvolatile matter 50.1% by mass toluene solution of the inorganic oxide fine particle modifier (D-2-4) was obtained.

[Synthesis Example 6]: Synthesis of inorganic oxide fine particle modifier (D-2-5)

A reaction of pentaerythritol and acrylic acid in which a DPPA mixture a having a polyfunctional acrylate having a hydroxyl group is changed to a polyfunctional acrylate having a hydroxyl group (pentaerythritol triacrylate 59.7 mass%, pentaerythritol diacrylate 9.6% by mass, pentaerythritol tetraacrylate) a mixture of 21.8 mass% and other unidentified substances of 8.9% by mass; a PETA mixture, a hydroxyl group of 159), and the same operation as in Synthesis Example 1 except that the zirconium acetonate was changed to dibutyltin dilaurate (the use of each compound) The amount of the inorganic oxide fine particle modifier (D-2-5) was 324 g of a 48.4% by mass toluene solution of the inorganic oxide fine particle modifier (D-2-5).

[Synthesis Example 7]: Synthesis of inorganic oxide fine particle modifier (D-2-6)

Except that 3-isocyanooxypropyltriethoxydecane was changed to 3-isocyanoxypropyltrimethoxydecane (trade name: Silquest A-Link 35; manufactured by Momentive Performance Materials Inc.), Synthesis Example 1 was carried out. The same operation (the amount of each compound used is as shown in Table 1), and a nonvolatile matter of 49.9% by mass of a toluene solution of the inorganic oxide fine particle modifier (D-2-6) was obtained. 543g.

[Synthesis Example 8]: Synthesis of inorganic oxide fine particle modifier (D-3)

In addition to changing the DPPA mixture a having a polyfunctional acrylate having a hydroxyl group to a reaction of dipentaerythritol and acrylic acid having a polyfunctional acrylate having a hydroxyl group (dipentaerythritol pentaacrylate 33.8% by mass, dipentaerythritol tetraacrylate 9.3% by mass, two A mixture of 46.4% by mass of pentaerythritol hexaacrylate and 8.6% by mass of other unidentified substances; a mixture of DPPA mixture b and a hydroxyl group of 61) was subjected to the same operation as in Synthesis Example 1 (the amount of each compound used is referred to in Table 1) to obtain inorganic oxidation. The non-volatile fraction of the fine particle modifier (D-3) was 514 g of a 50.1% by mass toluene solution.

[Synthesis Example 9]: Synthesis of inorganic oxide fine particle modifier (D-4)

A reaction product of dipentaerythritol and acrylic acid having a DPPA mixture a having a polyfunctional acrylate having a hydroxyl group changed to a polyfunctional acrylate having a hydroxyl group (dipentaerythritol pentaacrylate 38.2% by mass, dipentaerythritol tetraacrylate 12.3% by mass, two The mixture was subjected to the same operation as in Synthesis Example 1 except that the mixture of 42.3 mass% of pentaerythritol hexaacrylate and 7.2 mass% of other unidentified substances; the DPHA mixture a and the hydroxyl group value 70) (the amount of each compound used is referred to in Table 1) to obtain inorganic oxidation. The nonvolatile matter of the fine particle modifier (D-4) was 531 g of a 50.1% by mass toluene solution.

[Synthesis Example 10]: Synthesis of inorganic oxide fine particle modifier (D-5)

In addition to changing the DPPA mixture a of a polyfunctional acrylate having a hydroxyl group a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate having a hydroxyl group-containing polyfunctional acrylate (mixture of dipentaerythritol pentaacrylate 66.8% by mass, dipentaerythritol hexaacrylate 35.2% by mass; DPHA mixture a-2, The same operation as in Synthesis Example 1 was carried out except for the hydroxyl group of 70) (the amount of each compound used was referred to in Table 1), and 531 g of a nonvolatile content of 50.1% by mass of a toluene solution of the inorganic oxide fine particle modifier (D-5) was obtained.

[Synthesis Example 11]: Synthesis of inorganic oxide fine particle modifier (D-6)

The amount of each compound used was changed to the same as in Synthesis Example 1, except that the amount of the compound used was changed to 490 g of a nonvolatile content of 50.0% by mass of a toluene solution of the inorganic oxide fine particle modifier (D-6).

[Synthesis Example 12]: Synthesis of inorganic oxide fine particle modifier (D-7)

The amount of each compound used was changed to the same as in Synthesis Example 1, except that the amount of the compound used was changed to 635 g of a nonvolatile content of 50.0% by mass of a toluene solution of the inorganic oxide fine particle modifier (D-7).

(2) Synthesis of organic-inorganic composite dispersion [Production Example 1] Synthesis of Organic-Inorganic Composite Dispersion (C-1)

The isopropyl alcohol-dispersed colloidal cerium oxide (cerium oxide content: 30% by mass, cerium oxide average particle diameter: 10 to 20 nm, trade name: Snowtex IPA-ST; manufactured by Nissan Chemical Co., Ltd.), 200 g, was placed in a separable flask. Further, the inorganic oxide fine particle modifier (D-1) synthesized in the above Synthesis Example 1 was added. The toluene solution was 107.0 g (nonvolatile content: 49.7 mass%), and stirred and mixed to prepare a homogeneous solution.

Further, 4.4 g of a 0.18 mass% HCl aqueous solution as a reaction catalyst was added to the mixture, and the mixture was heated and stirred at an internal temperature of 40 ° C for 6 hours to carry out surface treatment of cerium oxide fine particles to obtain an intermediate reaction liquid ( C'-1) 304.3 g.

Next, 150.0 g of the obtained intermediate reaction liquid (C'-1) was placed in a flask equipped with a gas inlet, and further, 481.5 g of methyl isobutyl ketone was introduced, and 2,6-di third butyl as a polymerization blocker was added. 0.027 g of ki-p-cresol was prepared as a homogeneous solution.

Next, the inner temperature of the flask was heated to 40 ° C, and a nitrogen gas containing 5% of oxygen was depressurized while being aerated at a rate of 100 mL/min in the solution, and a solvent was distilled off. The solvent was distilled off to a nonvolatile content of 45% by mass to obtain 119 g of an organic-inorganic composite dispersion (C-1).

[Production Example 2]: Synthesis of organic-inorganic composite dispersion (C-2)

In addition to the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 2 was used as the inorganic oxide fine particle modifier (D-2). In the same manner as in Production Example 1, the amount of each compound used was referred to in Table 2, and 159 g of an organic-inorganic composite dispersion (C-2) was obtained.

[Production Example 3]: Synthesis of organic-inorganic composite dispersion (C-2-2)

In addition to the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, the inorganic oxide fine particle modifier (D-2-2) synthesized in Synthesis Example 3 was used as the inorganic oxide fine particle modifier. The same operation as in Production Example 1 was carried out (the amount of each compound used was referred to in Table 2), and 160 g of an organic-inorganic composite dispersion (C-2-2) was obtained.

[Production Example 4]: Synthesis of organic-inorganic composite dispersion (C-2-3)

In addition to the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 4 was used as the inorganic oxide fine particle modifier. The same operation as in Production Example 1 was carried out (the amount of each compound used was referred to in Table 2), and 161 g of an organic-inorganic composite dispersion (C-2-3) was obtained.

[Production Example 5]: Synthesis of organic-inorganic composite dispersion (C-2-4)

In addition to the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, the inorganic oxide fine particle modifier (D-2-4) synthesized in Synthesis Example 3 was used as the inorganic oxide fine particle modifier. The same operation as in Production Example 1 was carried out (the amount of each compound used was referred to in Table 2), and 161 g of an organic-inorganic composite dispersion (C-2-4) was obtained.

[Production Example 6] Synthesis of organic-inorganic composite dispersion (C-2-5)

In addition to the inorganic oxide fine particle modifier, the substitution synthesis example 1 The inorganic oxide fine particle modifier (D-1) was used in the same manner as in Production Example 1 except for the inorganic oxide fine particle modifier (D-2-5) synthesized in Synthesis Example 3 (the amount of each compound used) Taking Table 2 as a reference), 117 g of an organic-inorganic composite dispersion (C-2-5) was obtained.

[Production Example 7] Synthesis of Organic-Inorganic Composite Dispersion (C-2-6)

In addition to the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, the inorganic oxide fine particle modifier (D-2-6) synthesized in Synthesis Example 3 was used as the inorganic oxide fine particle modifier. The same operation as in Production Example 1 was carried out (the amount of each compound used was referred to in Table 2), and 162 g of an organic-inorganic composite dispersion (C-2-6) was obtained.

[Production Example 8]: Synthesis of organic-inorganic composite dispersion (C-3)

In addition to the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 3 was used as the inorganic oxide fine particle modifier (D-3). In the same manner as in Production Example 1, the amount of each compound used was referred to in Table 2, and 163 g of an organic-inorganic composite dispersion (C-3) was obtained.

[Production Example 9] Synthesis of organic-inorganic composite dispersion (C-4)

In addition to the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 4 was used as the inorganic oxide fine particle modifier. The same operation as in Production Example 1 (the amount of use of each compound or the like is referred to in Table 2), and Machine inorganic composite dispersion (C-4) 163g.

[Production Example 10]: Synthesis of organic-inorganic composite dispersion (C-5)

In addition to the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 3 was used as the inorganic oxide fine particle modifier (D-5). In the same manner as in Production Example 1, (the amount of each compound used was referred to in Table 2), 162 g of an organic-inorganic composite dispersion (C-5) was obtained.

[Production Example 11]: Synthesis of organic-inorganic composite dispersion (C-6)

In addition to the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 3 was used as the inorganic oxide fine particle modifier (D-6). In the same manner as in Production Example 1, the amount of each compound used was referred to in Table 2, and 161 g of an organic-inorganic composite dispersion (C-6) was obtained.

[Production Example 12]: Synthesis of organic-inorganic composite dispersion (C-7)

In addition to the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 1, the inorganic oxide fine particle modifier (D-1) synthesized in Synthesis Example 3 was used as the inorganic oxide fine particle modifier. In the same manner as in Production Example 1, the amount of each compound used was referred to in Table 2, and 162 g of an organic-inorganic composite dispersion (C-7) was obtained.

(3) Modulation of hardenable composition [Modulation Example 1] Modulation of Curable Composition (M-1)

209.6 parts by mass of the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 and triacryloyloxyethyl isocyanurate as a polyfunctional acrylate (trade name: ARONIX M-315; East Asia 14.7 parts by mass of 2-hydroxycyclohexylacetophenone (trade name: IRG184; manufactured by BASF Corporation) as a polymerization initiator, 4.4 parts by mass of a component other than a solvent, which is a non-volatile matter, is 38 mass. In a manner of %, 69.8 parts by mass of methyl isobutyl ketone was added to obtain a curable composition (M-1).

[Preparation Example 2]: Modulation of the curable composition (M-2)

The same operation as in Preparation Example 1 was carried out except that the organic-inorganic composite dispersion liquid (C-1) obtained in Production Example 1 was used, except for the organic-inorganic composite dispersion liquid (C-2) obtained in Production Example 2 (each compound) The amount of use is referred to in Table 3 as a reference to obtain a curable composition (M-2).

[Preparation Example 3]: Modulation of the curable composition (M-2-2)

The same procedure as in Preparation Example 1 except that the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 was used instead of the organic-inorganic composite dispersion (C-2-2) obtained in Production Example 3. The operation (the amount of each compound or the like used is referred to in Table 3) to obtain a curable composition (M-2-2).

[Preparation Example 4]: Modulation of the curable composition (M-2-3)

The same procedure as in Preparation Example 1 except that the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 was used instead of the organic-inorganic composite dispersion (C-2-3) obtained in Production Example 3. The operation (the amount of each compound or the like used is referred to in Table 3) to obtain a curable composition (M-2-3).

[Modulation Example 5] Modulation of Curable Composition (M-2-4)

The same procedure as in Preparation Example 1 except that the organic-inorganic composite dispersion liquid (C-1) obtained in Production Example 1 was used instead of the organic-inorganic composite dispersion liquid (C-2-4) obtained in Production Example 3. The operation (the amount of each compound or the like used is referred to in Table 3) to obtain a curable composition (M-2-4).

[Preparation Example 6] Modulation of Curable Composition (M-2-5)

The same procedure as in Preparation Example 1 except that the organic-inorganic composite dispersion liquid (C-1) obtained in Production Example 1 was used instead of the organic-inorganic composite dispersion liquid (C-2-5) obtained in Production Example 3. The operation (the amount of each compound or the like used is referred to in Table 3) to obtain a curable composition (M-2-5).

[Preparation Example 7] Modulation of a hardenable composition (M-2-6)

The same procedure as in Preparation Example 1 except that the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 was used instead of the organic-inorganic composite dispersion (C-2-6) obtained in Production Example 3. The operation (the amount of each compound or the like used is referred to in Table 3) to obtain a curable composition (M-2-6).

[Preparation Example 8]: Modulation of the curable composition (M-3)

The same operation as in Preparation Example 1 was carried out except that the organic-inorganic composite dispersion liquid (C-1) obtained in Production Example 1 was used, except that the organic-inorganic composite dispersion liquid (C-3) obtained in Production Example 3 was used. The amount of each compound or the like used is referred to in Table 3 to obtain a curable composition (M-3).

[Modulation Example 9] Modulation of hardenable composition (M-4)

The same operation as in Preparation Example 1 was carried out except that the organic-inorganic composite dispersion liquid (C-1) obtained in Production Example 1 was used, except that the organic-inorganic composite dispersion liquid (C-4) obtained in Production Example 4 was used. The amount of each compound or the like used is referred to in Table 3 to obtain a curable composition (M-4).

[Preparation Example 10] Modulation of Curable Composition (M-5)

The same operation as in Preparation Example 1 was carried out except that the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 was used instead of the organic-inorganic composite dispersion (C-5) obtained in Production Example 3 ( The amount of each compound or the like used is referred to in Table 3 to obtain a curable composition (M-5).

[Preparation Example 11]: Modulation of the curable composition (M-6)

The same operation as in Preparation Example 1 was carried out except that the organic-inorganic composite dispersion liquid (C-1) obtained in Production Example 1 was used, except that the organic-inorganic composite dispersion liquid (C-6) obtained in Production Example 3 was used. The amount of each compound or the like used is referred to in Table 3 to obtain a curable composition (M-6).

[Preparation Example 12] Modulation of Curable Composition (M-7)

The same operation as in Preparation Example 1 was carried out except that the organic-inorganic composite dispersion (C-1) obtained in Production Example 1 was used instead of the organic-inorganic composite dispersion (C-7) obtained in Production Example 3 ( The amount of each compound or the like used is referred to in Table 3 to obtain a curable composition (M-7).

(4) Fabrication and evaluation of coated film [Example 1]

The curable composition (M-1) was applied to a polyethylene terephthalate (PET) film having a thickness of 125 μm so that the thickness of the dried coating film was 5 μm (trade name Cosmoshine (trademark) A-4100; It was dried at 100 ° C for 1 minute on a Toyobo Co., Ltd. product. Then, using a conveyor belt exposure machine, ultraviolet rays having a cumulative exposure amount of 200 mJ/cm ^{2 were} irradiated with a UV lamp (high-pressure mercury) under a nitrogen atmosphere to cure the curable composition (M-1) to obtain a curable composition (M- 1) A cured film (hard coat film) of a PET film coated with a film (hereinafter referred to as "coated film"). The obtained coating film was provided to various tests in the following evaluation methods.

[Example 2, Examples 2-2 to 2-6, Comparative Examples 1 to 5]

The curable composition (M-1) of Example 1 was changed to each of the curable compositions (M-2), (M-2-2) to (M-2-6), and (M-3). A coating film was obtained in the same manner as in Example 1 except for (M-7), and various tests were carried out in the same manner as in Example 1.

(5) Evaluation method of coated film [Evaluation of pencil hardness]

The pencil hardness was measured in accordance with the method specified in JIS K5600-5-4 using a surface measuring instrument (TriboGear 14FW manufactured by Shinto Scientific Co., Ltd.) and a pencil for pencil hardness measurement (Mitsubishi UNI, manufactured by Mitsubishi Pencil Co., Ltd.). The measurement load was 750 g, the measurement speed was 30 mm/min, and the measurement distance was 5 mm. The measurement was carried out 5 times, and the hardness of the pencil having a pass number exceeding 4/5 was used as the evaluation result.

[Evaluation of optical characteristics]

In terms of optical characteristics, the total light transmittance, Haze, and b* items were evaluated. The total light transmittance was measured by Haze using Turbidity (Haze) meters (NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.). The total light transmittance is based on JIS K7361, and Haze is evaluated according to the method specified in JIS K7136. b* was evaluated using a color difference meter (SD-6000 manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with the method specified in JIS K8729.

[evaluation of warping]

The coated film was cut to prepare a square test piece of 10 cm square. The test piece was allowed to stand under the conditions of a temperature of 23 ° C and a relative humidity of 50%. Thereafter, the test piece was placed on a table, and the heights of the four corners of the test piece which were separated from the table top by the warpage were measured, and the average value of the heights of the four corners was used as the evaluation result.

[mandrel bending]

The evaluation was carried out in accordance with the method specified in JIS K5600-5-1 using a cylindrical mandrel warpage tester (TQCBD-2000 manufactured by COTEC Co., Ltd.). The measurement was carried out 3 times, and the average value of the obtained results was used as the evaluation result.

[Evaluation of scratch resistance]

The scratch resistance was measured using a surface measuring instrument (TriboGear 14FW manufactured by Shinto Scientific Co., Ltd.) and steel wool (steel wool grade (calculated) #0000 manufactured by BONSTAR SALES Co., Ltd.). The presence or absence of damage was visually observed and evaluated by the following criteria.

A: no damage

B: Partial damage

C: Comprehensive damage

Namely, steel wool was placed on the coated film, and a load of 175 g/cm ^{2 was applied} while moving straight, and the back and forth were repeated 100 times to rub the surface of the coated film with steel wool. However, the presence or absence of damage (visual observation) and Haze change (ΔHaze) before and after the friction were evaluated. Further, Haze was evaluated by the aforementioned method. The results are shown in Table 4.

In Examples 1 and 2 and Examples 2-2 to 2-6, the warpage was excellent as compared with Comparative Examples 1 to 5, and it was found that the curable composition had low hardenability. Moreover, compared with the comparative examples 1-5, since the mandrel bendability is excellent, it turns out that the hardened object is excellent in the bending resistance. Further, compared with Comparative Examples 1 to 5, the damage due to friction was small, and the Haze change before and after the rubbing was small, and it was found that the cured product was excellent in scratch resistance.

Claims (9)

A method for producing an organic-inorganic composite by surface-treating inorganic oxide fine particles with a decane coupling agent having at least two (meth) acrylonitrile groups, wherein the decane coupling agent is covalently bonded to The method for producing an organic-inorganic composite of the inorganic oxide fine particles characterized by having an isocyanato-containing compound having an alkoxyalkyl group and an isocyanato group, and having at least two (meth) propylene groups a condensation reaction of a hydrazine-containing compound having at least one hydroxyl group and having a hydroxyl group value of 75 mgKOH/g or more to obtain the above-described decane coupling agent, wherein the condensation reaction is the isocyanato group-containing isocyanato group and the aforementioned The hydroxyl group-containing compound hydroxy group reacts to generate a urethane bond condensation reaction, and the hydroxyl group-containing compound supplied to the condensation reaction has a hydroxyl group value of X (mgKOH/g), and the mass of the hydroxyl group-containing compound supplied to the condensation reaction is When Y (g) and the number of moles of the isocyanato group derived from the above-mentioned isocyanato compound are Z (mmol), the value of Z/(XY/56.1) is 0.6 or more and 1.2 or less. A curable composition characterized in that the inorganic oxide fine particles are surface-treated with a decane coupling agent having at least two (meth) acrylonitrile groups, and the decane coupling agent is covalently bonded to the aforementioned Organic-inorganic composite of inorganic oxide microparticles (A), polyfunctional (meth) propylene having at least two (meth) acrylonitrile groups The acid ester monomer (B) and the polymerization initiator (C), the content of the polyfunctional (meth) acrylate monomer (B) having at least two (meth) acrylonitrile groups described above is 100 parts by mass. In the case where the content of the organic-inorganic composite (A) is 10 parts by mass or more and 2,000 parts by mass or less, the organic-inorganic composite (A) and the above-mentioned polyfunctional (methyl) having at least two (meth)acryl fluorenyl groups (methyl group) When the total content of the acrylate monomer (B) is 100 parts by mass, the content of the polymerization initiator (C) is 0.1 parts by mass or more and 10 parts by mass or less, and the decane coupling agent is an alkoxy fluorenyl group. And an isocyanooxy group-containing isocyanato compound, and a condensation reaction with a hydroxyl group-containing compound having at least two (meth)acrylonyl groups and at least one hydroxyl group and having a hydroxyl group value of 75 mgKOH/g or more The condensation reaction is a condensation reaction of the isocyanato group-containing isocyanato group with a hydroxyl group of the hydroxyl group-containing compound to produce a urethane bond, and the hydroxyl group of the hydroxyl group-containing compound supplied to the condensation reaction is X (mgKOH/g), the aforementioned hydroxyl group-containing compound supplied to the condensation reaction When the mass is Y (g) and the number of moles of the isocyanato group derived from the isocyanato group-containing compound is Z (mmol), the value of Z/(XY/56.1) is 0.6 or more and 1.2 or less. . The curable composition according to claim 2, wherein the decane coupling agent is a compound represented by the following chemical formula (I), wherein M in the following chemical formula (I) is a hydroxyl group residue of the hydroxyl group-containing compound, Further, R ¹ and R ² are a linear, branched or cyclic alkyl group having 1 or more and 10 or less carbon atoms, or a phenyl group which may have an alkyl group having 1 or more and 3 or less carbon atoms, and R ¹ and R ² may be the same or different, and further R ³ is a linear, branched or cyclic alkyl group having 1 or more and 10 or less carbon atoms, or may have an alkyl group having 1 or more and 3 or less carbon atoms. The phenyl group may have an oxygen atom in the chain, and further 1 is an integer of 0 or more and 2 or less, m is an integer of 1 or more and 3 or less, a sum of 1 and m is 3, and n is 1 or more and 3 or less. Integer, The curable composition according to claim 3, wherein one of the chemical formula (I) is 0, m is 3, R ² is a methyl group or an ethyl group, and R ³ is a linear stretch propyl group. The curable composition according to any one of claims 2 to 4, wherein the inorganic oxide fine particles are at least one type of fine particles selected from the group consisting of ceria, titania, zirconia, and alumina. A cured product characterized in that the curable composition according to any one of claims 2 to 4 is cured. A hard coating material comprising the curable composition according to any one of claims 2 to 4. A hard coat film characterized in that the hard coat material described in claim 7 is formed into a film shape and hardened on the surface of the substrate. A decane coupling agent having at least two (meth) acrylonitrile-based decane coupling agents having an alkoxyalkyl group and an isocyanato group a condensation reaction involving an isocyanato compound and a hydroxyl group-containing compound having at least two (meth)acrylonium groups and at least one hydroxyl group and having a hydroxyl group value of 75 mgKOH/g or more. The condensation reaction is as described above. The isocyanato group-containing isocyanato group reacts with the hydroxyl group of the hydroxyl group-containing compound to form a condensation reaction of the urethane bond, and the hydroxyl group of the hydroxyl group-containing compound supplied to the condensation reaction has a valence of X (mgKOH/g). When the mass of the hydroxyl group-containing compound supplied to the condensation reaction is Y (g), and the number of moles of the isocyanato group derived from the isocyanato compound to be supplied to the condensation reaction is Z (mmol), Z/( The value of XY/56.1) is 0.6 or more and 1.2 or less.