TW201927941A - Composition for forming hard coating layer, hard coating layer and substrate - Google Patents

Abstract

The present invention provides a composition for forming a hard coating layer, a hard coating layer and a substrate. The composition for forming the hard coating layer includes a hydrolysis condensate (A), a phenolic epoxy resin (B) and a solvent (C). The hydrolysis condensate (A) is reacted from a mixture of an alkoxysilane compound (a1) and an alkoxymetal compound (a2). A hard coating layer with high refractive index having yellowing resistance and high hardness can be formed from the composition.

Description

Hard coating film composition, hard coating film and substrate

The present invention relates to a composition for a hard coat film, and particularly to a high refractive index hard coat film having yellowing resistance and high hardness formed by hardening a composition for a hard coat film.

In recent years, in the technical field of optical lenses, particularly ophthalmic lens materials, in order to replace the substrate of the conventional inorganic glass, the plastic substrate is mainly used as a center. The plastic substrate has the advantages of light weight, excellent impact resistance, processability, and dyeability, so the plastic substrate is developed and improved as a second generation, in order to develop lighter and achieve high refraction. The effect of the rate. However, such a plastic substrate has a technical problem of being easily damaged compared to conventional inorganic glass.

In order to solve the above-mentioned technical problems, the prior art generally provides a hardenable coating film containing a siloxane (hereinafter referred to as a hard coating film) on the surface of an optical lens (hereinafter simply referred to as a plastic lens) using a plastic substrate. Further, in the case of using a plastic lens having a high refractive index, in order to prevent a light interference phenomenon (generating light interference fringes) generated between the lens substrate and the hard coat film, the prior art makes the hard coat film The metal oxide fine particles are contained, and the refractive index of the hard coat film is adjusted in accordance with the refractive index of the lens. For example, Patent Document 1 discloses a hard coat film comprising fine particles of a composite oxide such as titanium oxide, zirconium oxide or tantalum pentoxide.

The light-interference phenomenon can be improved by including the composite oxide fine particles in the hard coat film. However, the composition containing the composite oxide fine particles is liable to cause yellowing during heat hardening treatment, and cannot satisfy the industry. demand.

Therefore, in order to meet the requirements of the current industry, how to improve the light interference phenomenon, and at the same time, the composition for the hard coating film can form a high refractive index hard coating film having yellowing resistance and high hardness, and is an effort for those skilled in the art to study One of the goals.

[Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. Hei 5-264806

In view of the above, the present invention provides a composition for a hard coat film which is capable of improving the above-mentioned problem of easy yellowing and insufficient hardness.

The present invention provides a composition for a hard coat film comprising: a hydrolysis condensate (A), a novolac type epoxy resin (B), and a solvent (C), and the hydrolysis condensate (A) comprises an alkoxydecane compound (a1) And a mixture of a metal alkoxide compounds (a2) is obtained by reacting a mixture.

In one embodiment of the present invention, the alkoxydecane-containing compound (a1) includes a tetraalkoxydecane compound (a1-1) and an epoxy group-containing decane compound (a1-2).

In one embodiment of the invention, the alkoxy metal compound (a2) is a tetraalkoxy metal compound selected from at least one of the compounds represented by the following formula (a2-1), M(OR _a ) ₄ (a2-1) In the formula (a2-1), M represents titanium or zirconium; and R _a represents an alkyl group having 1 to 5 carbon atoms.

In one embodiment of the present invention, the phenolic epoxy resin (B) includes at least one selected from the group consisting of compounds represented by the following formula (B-1) to (B-3). Formula (B-1) Formula (B-2) In the formula (B-1) to the formula (B-3), R ₁ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each independently represent a monovalent organic group having 1 to 18 carbon atoms. R ₂ each independently represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms; m1, m2, and m6 each independently represent an integer of 0 to 3; m3 and m5 each independently represent an integer of 0 to 4; m4 is independently An integer representing 0 to 2; n1 and n2 are averages, representing a number between 0 and 10; n3 and n4 are averages, representing a number between 0 and 11, and the value of (n3+n4) is 1 to The number between 11; n5 is the average, representing the number between 0 and 1.

In an embodiment of the invention, the surface-modified inorganic oxide particles (D) are further included. The surface of the surface-modified inorganic oxide particles (D) is modified with an organic ruthenium compound containing at least one selected from the group consisting of a decane compound, a decazane compound, and a siloxane compound.

In one embodiment of the present invention, the above organic ruthenium compound has at least one functional group selected from the group consisting of the following formula (D-1) to formula (D-5): In the formula (D-1), A represents a hydrogen atom or a methyl group, and a represents an integer of 1 to 3; In the formula (D-2), b represents an integer of 0 or 1; In the formula (D-3), B represents an oxygen atom or a single bond, c represents an integer of 1 to 3, and d represents an integer of 0 to 6, wherein when d represents 0, B is a single bond; In the formula (D-4), e represents an integer of 0 to 6; In the formula (D-5), D represents an alkylene group having 2 to 6 carbon atoms, and E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In one embodiment of the present invention, the amount of the phenolic epoxy resin (B) used is from 2 parts by weight to 18 parts by weight based on 100 parts by weight of the hydrolysis condensate (A); use of the solvent (C) The amount is from 150 parts by weight to 1000 parts by weight.

In one embodiment of the present invention, the surface-modified inorganic oxide particles (D) are used in an amount of from 3 parts by weight to 30 parts by weight based on 100 parts by weight of the hydrolysis-condensation product (A).

In an embodiment of the invention, the alkoxydecane compound (a1) is used in an amount of from 1 mol, and the alkoxy metal compound (a2) is used in an amount of from 0.1 mol to 0.5 mol.

In an embodiment of the present invention, the total amount of the alkoxydecane compound (a1) is 1 mol, and the tetraalkoxydecane compound (a1-1) is used in an amount of 0.1 mol to 0.8 mol; The epoxy group-containing decane compound (a1-2) is used in an amount of from 0.2 mol to 0.9 mol.

In an embodiment of the invention, the surface-modified inorganic oxide particles (D) have an average particle diameter of from 3 nm to 1000 nm.

The present invention further provides a hard coat film formed by hardening a composition for a hard coat film as described above.

In an embodiment of the invention, the hard coat film has a refractive index of 1.5 to 1.8.

The present invention further provides a substrate comprising the above-described hard coat film.

In an embodiment of the invention, the substrate has a refractive index of from 1.5 to 2.0.

Based on the above, the composition for a hard coat film of the present invention contains a hydrolysis condensate (A) having a specific structure and a novolac type epoxy resin (B), and therefore, the composition for a hard coat film can be subjected to a hardening treatment. The formation of a high refractive index hard coating film having yellowing resistance and high hardness can improve the technical problems of yellowing and insufficient hardness in the prior art.

The above described features and advantages of the invention will be apparent from the following description.

< Composition for Hard Coating Film > The present invention provides a composition for a hard coating film comprising a hydrolysis-condensation product (A), a novolac type epoxy resin (B), and a solvent (C), and optionally includes a surface modification. The inorganic inorganic oxide particles (D) and the additive (E). The hydrolysis condensate (A) is obtained by reacting a mixture comprising an alkoxydecane compound (a1) and an alkoxy metal compound (a2), and the composition for a hard coat film used in the present invention will be described in detail below. The individual components of the object. Hydrolyzed condensate ( A )

The hydrolysis-condensation product (A) contained in the composition for a hard coat film of the present invention is obtained by a mixture reaction comprising an alkoxydecane compound (a1) and an alkoxy metal compound (a2). For example, the hydrolysis-condensation product (A) of the present invention is obtained by adding water to a solvent containing alkoxydecane compound (a1) and a metal alkoxide compound (a2), followed by hydrolysis, followed by polycondensation. However, the present invention is not limited thereto, and the hydrolysis-condensation product (A) of the present invention may be added to water in a solvent to which the alkoxydecane compound (a1) and the metal alkoxide compound (a2) are added, and optionally other After hydrolysis of the compound and/or the catalyst, it is obtained by polycondensation. The components used in the production of the hydrolysis condensate (A) will be described in detail below. Alkoxydecane compound ( a1 )

The type of the alkoxydecane compound (a1) is not particularly limited, but from the viewpoint of enhancing yellowing resistance, a tetraalkoxydecane compound (a1-1) and an epoxy group-containing decane compound (a1) are used. 2) Preferably, other alkoxydecane-containing compounds (a1-3) may be added as appropriate. Tetraalkoxydecane compound ( a1-1 )

The tetraalkoxydecane compound (a1-1) is selected from the group consisting of tetramethoxynonane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, tetra-n-butoxydecane, and tetrad. At least one of the group consisting of dibutoxydecane, or a combination of the above compounds.

The total amount of the alkoxydecane compound (a1) used is 1 mol, and the tetraalkoxydecane compound (a1-1) is used in an amount of 0.1 mol to 0.8 mol, preferably 0.2 mol to 0.7 mol. Ears are preferably from 0.3 moles to 0.6 moles. Epoxy group-containing decane compound ( a1-2 )

The epoxy group-containing group contained in the epoxy group-containing decane compound (a1-2) is, for example, a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group or An oxetanyl group.

Specifically, the epoxy group-containing group may include a group represented by the above formula (D-3), a group represented by the above formula (D-4), and a group represented by the above formula (D-5). At least one.

More specifically, the epoxy group-containing group may include a group represented by the following formula (a1-2-1), a group represented by the formula (a1-2-2), and a formula (a1-2-3). At least one of the indicated bases: Formula (a1-2-1) Formula (a1-2-2) Formula (a1-2-3).

Specific examples of the epoxy group-containing decane compound (a1-2) include 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, 3-(N-allyl-N-glycidol) Aminopropyltrimethoxydecane, 3-glycidyl ether propyl trimethoxy decane, 3-glycidyl ether propyl triethoxy decane, 3-glycidyl ether propyl methyl dimethyl Oxydecane, 3-glycidyl ether propyl methyl diethoxy decane, 3-glycidyl ether propyl dimethyl methoxy decane, 3-glycidyl ether propyl dimethyl ethoxy Decane, 2-glycidyl ether ethyltrimethoxydecane, 2-glycidyl ether ethyltriethoxydecane, 2-glycidyl ether ethylmethyldimethoxydecane, 2-glycidyl ether Ethylethyldiethoxy decane, 2-glycidyl ether ethyl dimethyl methoxy decane, 2-glycidyl ether ethyl dimethyl ethoxy decane, 4-glycidyl ether butyl Trimethoxy decane, 4-glycidyl ether butyl triethoxy decane, 4-glycidyl ether butyl methyl dimethoxy decane, 4-glycidyl ether butyl methyl diethoxy decane, 4- Shrink Glycidyl ether butyl dimethyl methoxy decane, 4-glycidyl ether butyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane, 2 -(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl) Propyltriethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propyltrimethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy Propyltriethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propylmethyldimethoxydecane or ((3-ethyl-3-epoxypropane) a methoxy) propane dimethyl methoxy decane, or a combination of the above compounds.

Specific examples of the epoxy group-containing decane compound (a1-2) preferably include 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, 3-(N-allyl-N - glycidyl) aminopropyl trimethoxy decane, 3-glycidyl ether propyl trimethoxy decane, 2-glycidyl ether ethyl trimethoxy decane, 4-glycidyl ether butyl trimethoxy Baseline, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-ring Oxycyclohexyl)propyltriethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propyltrimethoxydecane, ((3-ethyl-3-epoxypropane) Methoxy)propyltriethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propylmethyldimethoxydecane or a combination of the above.

The total amount of the alkoxydecane compound (a1) used is 1 mol, and the epoxy group-containing decane compound (a1-2) is used in an amount of 0.2 mol to 0.9 mol, preferably 0.3 mol to 0.8. Moor, more preferably 0.4 to 0.7 m.

When the composition for a hard coat film is simultaneously used with a tetraalkoxydecane compound (a1-1) and an epoxy group-containing decane compound (a1-2), the yellowing resistance of the hard coat film formed thereof can be further improved. . Other alkoxydecane -containing compounds ( a1-3 )

The kind of the other alkoxydecane-containing compound (a1-3) is not limited, and specific examples thereof include trimethoxydecane, triethoxydecane, fluorotrimethoxydecane, fluorotriethoxydecane, and methyltrimethoxy. Basear, methyltriethoxydecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-(trifluoromethyl)ethyltriethoxydecane, hydroxymethyltrimethoxydecane, Hydroxyethyltrimethoxydecane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane,phenyltrimethoxy Base decane, phenyltriethoxy decane, methyl dimethoxy decane, methyl diethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, methyl [2- (perfluoro-n-octyl)ethyl]dimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, methoxydimethylsilane, methoxytrimethylnonane, methoxymethyl Diphenyl decane or a diaryl dialkoxy decane compound represented by the following formula (a1-3-1). In the formula (a1-3-1), R ¹ and R ² are each independently an alkyl group having a carbon number of 1 to 3, and R ³ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. .

The above other alkoxydecane-containing compound (a1-3) may be used alone or in combination of two or more.

The other alkoxydecane-containing compound (a1-3) is preferably methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane or 3-mercaptopropyl. Trimethoxydecane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane a diaryl dialkoxy decane compound represented by the formula (a1-3-1), or a combination of the above compounds, more preferably a diaryl dialkoxy group represented by the formula (a1-3-1) A quinone compound.

The total amount used based on the alkoxydecane compound (a1) is 1 mole, and the other alkoxydecane-containing compound (a1-3) is used in an amount of from 0 moles to 0.5 moles, preferably from 0.05 moles to 0.4. Moore, more preferably from 0.1 mol to 0.3 mol.

Further, an alkoxy group-free decane compound may be further added as long as it does not affect the synthesis of the hydrolysis condensate (A), and specifically, for example, tetrachloromethane, trichlorodecane, fluorotrichloromethane, methyltrichloromethane, 2-(Trifluoromethyl)ethyltrichlorodecane, methylol trichloromethane, decylmethyltrichloromethane, 3-mercaptopropyltrichloromethane, phenyltrichlorodecane, methyldichlorodecane, two Methyl dichloromethane, methyl [2-(perfluoro-n-octyl)ethyl]dichlorodecane, 3-mercaptopropylmethyldichlorodecane, diphenyldichlorodecane, chlorodimethylsilane, chlorine Trimethyldecane, bromotrimethylnonane, iodotrimethyldecane, chloromethyldiphenylnonane, or a combination of the above compounds.

The total amount of the alkoxydecane compound (a1) used is 1 mole, and the alkoxy group-free decane compound is used in an amount of from 0 moles to 0.3 moles, preferably from 0.05 moles to 0.25 moles, more preferably Good for 0.1 moles to 0.2 moles. Alkoxy metal compound ( a2 )

The alkoxy metal compound (a2) is a tetraalkoxy metal compound selected from at least one of the compounds represented by the following formula (a2-1), M(OR _a ) ₄ (a2-1) Formula (a2- In 1), M represents titanium or zirconium; and R _a represents an alkyl group having 1 to 5 carbon atoms.

When M is titanium, the tetraalkoxy metal may, for example, be tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, or tetra. Titanium isobutoxide, titanium tetrabutoxide, titanium tetrapentoxide, and the like. Preferred is titanium tetraethoxide, titanium tetraisopropoxide or titanium tetra-n-butoxide.

When M is zirconium, the tetraalkoxy metal may, for example, be tetramethoxy zirconium, tetraethoxy zirconium, tetrapropoxy zirconium, tetrabutoxy zirconium, tetrapentyl zirconium or tetrahexyloxy group. Zirconium, trimethoxyethoxy zirconium, dimethoxydiethoxyzirconium, dimethoxydipropoxyzirconium, diethoxydipropoxyzirconium, triethoxybutoxyzirconium, two Zirconium dibutoxide.

The alkoxy decane compound (a1) is used in an amount of 1 mol, and the alkoxy metal compound (a2) is used in an amount of 0.1 mol to 0.5 mol, preferably 0.15 mol to 0.4 mol, more preferably It is 0.2 moles to 0.3 moles.

When the alkoxide metal compound (a2) is not used for the composition for a hard coat film, the hard coat film formed has a problem that the yellowing resistance is lowered. Method for producing hydrolysis condensate ( A )

The method for producing the hydrolysis-condensation product (A) of the present invention is not particularly limited, and any method capable of polycondensing the alkoxydecane compound (a1) and the alkoxy metal compound (a2) can be applied. For example, an alkoxydecane compound is added to a solvent to which the alkoxydecane compound (a1) and the alkoxy metal compound (a2) are added, by adding water and, if necessary, other compounds and/or catalysts. A1) and the alkoxy metal compound (a2) are hydrolyzed in a solvent, and then subjected to polycondensation to obtain a hydrolysis condensate (A). The hydrolysis may be partial hydrolysis or complete hydrolysis.

The solvent to be used in the production of the hydrolyzed condensate (A) is not particularly limited as long as it can dissolve the alkoxydecane compound (a1) and the alkoxy metal compound (a2). Further, it is also possible to use a solvent which does not dissolve the alkoxydecane compound (a1) and the alkoxy metal compound (a2) at first, but dissolves the alkoxydecane compound (a1) simultaneously with the progress of the hydrolysis polycondensation reaction. And a solvent of the alkoxy metal compound (a2). Since the alkoxydecane compound (a1) and the alkoxy metal compound (a2) are subjected to a hydrolysis polycondensation reaction to produce an alcohol, it is preferred to use an organic compound having good compatibility with an alcohol, a glycol or a glycol ether. Solvent.

Specific examples of the solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, and 1,3-propanediol; , 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1 , glycols such as 4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol; ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether Glycol ethers such as diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butane , Dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide acyl, m-cresol and the like. The above solvents may be used singly or in combination of two or more.

The amount of water used in the hydrolysis polycondensation reaction in the present invention can be appropriately selected, and is usually 0.5 to 2.5 times the total alkoxy group in the alkoxydecane compound (a1) and the alkoxy metal compound (a2). The ear is preferably 0.75 times to 1.5 times moles.

The catalyst may be added to promote the hydrolysis polycondensation reaction, and the catalyst is not particularly limited, and examples thereof include acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, and fumaric acid or metal salts thereof; and amines; Alkali such as water, methylamine, ethylamine, ethanolamine or triethylamine. The above catalysts may be used alone or in combination of two or more. The catalyst is used in an amount of from 0.2 mol to 2 mol based on the total alkoxy group 1 mol of the alkoxydecane compound (a1) and the alkoxy metal compound (a2).

Further, in addition to the addition of a catalyst to enhance the hydrolysis polycondensation reaction, the hydrolysis polycondensation reaction may be promoted by heating. At this time, the heating temperature and the heating time can be appropriately selected. Generally, the heating temperature is 30 to 180 ° C, and the heating time is 0.5 to 120 hours.

In the process of producing the hydrolysis condensate (A), the alkoxydecane compound (a1) and the alkoxide metal compound (a2) may be mixed and simultaneously hydrolyzed, or the alkoxydecane compound (a1) or alkoxylate may be used. The base metal compound (a2) is hydrolyzed and then added to the other to be hydrolyzed, or may be further mixed after hydrolysis. Phenolic epoxy resin ( B )

The novolac type epoxy resin (B) includes at least one selected from the group consisting of compounds represented by the following formula (B-1) to formula (B-3), Formula (B-1) Formula (B-2) In the formula (B-1) to the formula (B-3), R ₁ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each independently represent a monovalent organic group having 1 to 18 carbon atoms. R ₂ each independently represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms; m1, m2, and m6 each independently represent an integer of 0 to 3; m3 and m5 each independently represent an integer of 0 to 4; m4 is independently An integer representing 0 to 2; n1 and n2 are averages, representing a number between 0 and 10; n3 and n4 are averages, representing a number between 0 and 11, and the value of (n3+n4) is 1 to The number between 11; n5 is the average, representing the number between 0 and 1.

Specifically, the compound represented by the formula (B-1) is, for example, an epoxy resin obtained by reacting a novolac type phenol resin with epichlorohydrin, and is not particularly limited.

In the formula (B-1), the monovalent organic group having 1 to 18 carbon atoms represented by R ₁ or R ₂ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group or a second group. An alkyl group such as a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopentyl group or a cyclohexyl group; an aryl group such as a phenyl group, a tolyl group, a benzyl group or a 1-phenylethyl group; and a methoxy group; An alkoxy group such as an oxy group, a propoxy group or a butoxy group. R _{1 is} preferably a methyl group, a phenyl group, a benzyl group or a 1-phenylethyl group. R _{2 is} preferably a hydrogen atom. M1 is preferably 1. N1 is preferably an integer of 0 to 3.

Specifically, the compound represented by the formula (B-2) is, for example, an epoxy resin obtained by reacting a novolac type phenol resin having a salicylaldehyde skeleton with epichlorohydrin, and is not particularly limited.

In the formula (B-2), the monovalent organic group having 1 to 18 carbon atoms represented by R ₃ or R ₄ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group or a second group. An alkyl group such as a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopentyl group or a cyclohexyl group; an aryl group such as a phenyl group, a tolyl group, a benzyl group or a 1-phenylethyl group; and a methoxy group; An alkoxy group such as an oxy group, a propoxy group or a butoxy group. R _{3 is} preferably a methyl group, a cyclohexyl group or a phenyl group. M2 is preferably 0 or 1. M3 is preferably 0.

Specifically, the compound represented by the formula (B-3) is, for example, an epoxy resin obtained by reacting a novolac type phenol resin having a naphthol skeleton with epichlorohydrin, and is not particularly limited.

In the formula (B-3), the monovalent organic group having 1 to 18 carbon atoms represented by R ₅ , R ₆ or R ₇ may, for example, be methyl, ethyl, propyl, isopropyl or n-butyl. An alkyl group such as a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopentyl group or a cyclohexyl group; an aryl group such as a phenyl group, a tolyl group, a benzyl group or a 1-phenylethyl group; and a methoxy group; An alkoxy group such as a ethoxy group, a propoxy group or a butoxy group. R ₅ , R ₆ or R _{7 is} preferably a methyl group or a phenyl group. M4, m5, m6 are preferably 0 or 1.

The phenolic epoxy resin (B) is used in an amount of 2 parts by weight to 18 parts by weight, preferably 2.5 parts by weight to 16 parts by weight, more preferably 3, based on 100 parts by weight of the hydrolysis condensate (A). Parts by weight to 14 parts by weight.

When the phenolic epoxy resin (B) is not contained in the composition for a hard coat film, the hard coat film formed thereon has a problem that the refractive index and hardness are lowered. Solvent ( C )

The type of the solvent (C) is not limited, and is preferably an alcohol such as methanol, ethanol, isopropanol or butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether or polyethylene glycol. Alcohol monomethyl ether, polyethylene glycol monomethyl ether acetate, dimethylformamide, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, tetrahydrofuran, dioxane, Toluene, etc.

The solvent (C) is used in an amount of from 150 parts by weight to 1000 parts by weight, based on the amount of the hydrolysis condensate (A), preferably from 160 parts by weight to 900 parts by weight, more preferably from 180 parts by weight to 800 parts by weight. Parts by weight. Surface modified inorganic oxide particles ( D )

The inorganic oxide particles used for the surface-modified inorganic oxide particles (D) and the method for modifying the surface thereof are not particularly limited, and as long as the effects of the present invention can be achieved, it is preferred to use an organic hydrazine compound for modification. . Inorganic oxide particles

The type of the inorganic oxide particles is not particularly limited, and examples thereof include at least one element selected from the group consisting of ruthenium, aluminum, zirconium, titanium, zinc, bismuth, indium, tin, antimony, magnesium, and strontium. The oxide as a main component of the particles. Specific examples of such particles include ceria, alumina, zirconia, titania, zinc oxide, cerium oxide, indium oxide, tin oxide, cerium oxide, magnesium oxide, cerium oxide, and the like. Further, the inorganic oxide particles may be used alone or in combination of two or more. Examples of the composite oxide containing two or more kinds thereof include indium tin oxide, barium titanate (BaTiO ₃ ), barium titanate (SrTiO ₃ ), barium zirconate (BaZrO ₃ ), and cobalt tetraoxide dihydrate (CoFe ₂ O). ₄ ), nickel tetraoxide dihydrate (NiFe ₂ O ₄ ), manganese tetraoxydicarboxylate (MnFe ₂ O ₄ ), and the like. Among them, the inorganic oxide particles are preferably at least one selected from the group consisting of cerium oxide, aluminum oxide, zirconium oxide and cerium oxide, and particularly preferably cerium oxide and aluminum oxide.

The shape of the inorganic oxide particles is not particularly limited, and is, for example, a powder selected from the group consisting of a granular shape, a spherical shape, a needle shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fibrous shape, or an indefinite shape. The choice is granular or spherical. Further, the inorganic oxide particles have an average particle diameter of from 3 nm to 1000 nm, preferably from 5 nm to 500 nm, more preferably from 10 nm to 300 nm, and further, the average particle diameter of the inorganic oxide particles is by dynamic light scattering. The value measured by the law. The specific surface area of the inorganic oxide particles measured by the BET method using nitrogen oxide adsorption is 0.1 m ² /g to 3,000 m ² /g, preferably 10 m ² /g to 1,500 m ² /g, more preferably 50 m ² /g to 1,000 m ² /g.

When the cerium oxide particles are used as the inorganic oxide particles, the use form of the cerium oxide particles may be a dry state powder or a state of being dispersed by water or an organic solvent. In the latter case, a dispersion of a conventional fine particle-shaped cerium oxide particle can be directly used as a colloidal silica or by solvent replacement. In order to achieve transparency, it is preferred to use a cerium oxide sol.

Commercially available products of cerium oxide particles, such as cerium oxide sol, may be exemplified by IPA-ST, IPA-ST-L, MA-ST-M, MA-ST-L, MEK-ST, NBA-ST, XBA. -ST, DMAC-ST, EG-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, STN, ST-O, ST-50, ST-OL (above is Nissan Chemical Manufacturing) ), PL-2L-PGME, PL-2L-BL, PL-2L-DAA, PL-2L, GP-2L (above made by Fuso Chemical), Oscar (OSCAR) 101, Oscar 105, Oscar 106, CATALOID-S (The above is the production of the Japanese wave catalyst). In addition, powdered cerium oxide can be exemplified by: AEROSIL 130, Ai Rossir 300, Ai Luosil 380, Ai Rossir TT600, Ai Rossir OX50 (above is Japan's Irothy (AEROSIL)), Sildex H31, Sydext H32, Sydext H51, Sydext H52, Sydex H12l, Sydges H122 (above is manufactured by Asahi Glass), E220A, E220 (above is manufactured by Nippon Silica Industrial), SYLYSIA 470 (manufactured by FUJI SYLYSIA), SG Flake (made in Japan plate glass), etc.

Other commercially available products include, for example, OPTOLAKE TR-505 (the above is manufactured by Nikko Co., Ltd.), MT-05, MT-100W, MT-100SA, MT-100HD, MT-300HD, MT-150A, ND138, ND139, Titanium oxide particles such as ND140, ND154, ND165, ND177, TS-063, TS-103, and TS-159 (above, manufactured by TAYCA); OPTOLAKE TR-554 (above, manufactured by Nikko Catalyst), HXU-110JC, HXU- 210C, NZD-3101 (above for Sumitomo Osaka Cement), ZR-40BL, ZR-30BFN, ZR-30AL, ZR-20AS, ZR-30AH (above produced by chemical production) and other zirconia particles; AS-200, AS -520-A (above Nissan Chemical) alumina particles; OPTOLAKE TR-502, OPTOLAKE TR-503, OPTOLAKE TR-504, OPTOLAKE TR-513, OPTOLAKE TR-520, OPTOLAKE TR-521, OPTOLAKE TR-527 , OPTOLAKE TR-528, OPTOLAKE TR-529 (above is manufactured by Nikko Catalyst), Admafine SO-E1, SO-E2, SO-E3, SO-E4, SO-E5, SE3200-SEJ (above, manufactured by Admatechs) And other composite oxide particles.

The organic ruthenium compound for modifying the surface of the inorganic oxide particles is not particularly limited, and it is preferred to use an organic ruthenium compound containing at least one selected from the group consisting of a decane compound, a guanidinium compound, and a decane compound. Revamped.

Specifically, the organic ruthenium compound has at least one functional group selected from the following formula (D-1) to formula (D-5); In the formula (D-1), A represents a hydrogen atom or a methyl group, and a represents an integer of 1 to 3; In the formula (D-2), b represents an integer of 0 or 1; In the formula (D-3), B represents an oxygen atom or a single bond, c represents an integer of 1 to 3, and d represents an integer of 0 to 6, wherein when d represents 0, B is a single bond; In the formula (D-4), e represents an integer of 0 to 6; In the formula (D-5), D represents an alkylene group having 2 to 6 carbon atoms, and E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

When the surface-modified inorganic oxide particles (D) in the composition for a hard coat film have at least one functional group selected from the above formula (D-1) to formula (D-5), Then, the yellowing resistance of the hard coating film formed by the film can be improved. Decane compound

Specific examples of the decane compound include 3-(meth)acryloxypropyltrichlorodecane, 3-(meth)acryloxypropyltrimethoxydecane, and 8-propenyloxyoctyldimethyl Methoxymethoxydecane, 8-propenyloxyoctylmethyldimethoxydecane, 8-propenyloxyoctyldimethoxymethoxydecane, 8-propenyloxyoctylethyldimethacrylate Oxydecane, 8-propenyloxyoctyltrimethoxydecane, 8-propenyloxyoctyldimethylethoxydecane, 8-propenyloxyoctylmethyldiethoxydecane, 8 - propylene decyloxy octyl diethyl ethoxy decane, 8-propenyl methoxy octyl ethyl diethoxy decane, 8- propylene decyl octyl triethoxy decane, 8-methyl propylene醯oxyoctyl dimethyl methoxy decane, 8-methylpropenyl octyl methoxymethyl dimethoxy decane, 8-methyl propylene octyl octyl methoxy decane, 8-methyl Propylene oxime octyl ethyl dimethoxy decane, 8-methyl propylene oxy octyl trimethoxy decane, 8-methyl propylene oxy oxy dimethyl ethoxy decane, 8- Methyl propylene methoxy octyl methyl diethoxy decane 8-Methyl propylene decyloxy octyl diethyl ethoxy decane, 8-methyl propylene methoxy octyl ethyl diethoxy decane, 8-methyl propylene oxy octyl triethoxy Decane, 10-propenyloxydecyltrimethoxydecane, 10-methylpropenyldecyltrimethoxydecane, 10-propenyloxydecyltriethoxydecane, 10-methylpropenyloxyl Mercapto triethoxy decane, 12 propylene decyloxy dodecyl trimethoxy decane, 12-methyl propylene oxy oxy dodecyl trimethoxy decane, 12-propylene decyloxy dodecyl Triethoxy decane, 12-methacryloxydecyl triethoxy decane, vinyl trichlorodecane, vinyl trimethoxy decane, allyl trimethoxy decane, 3-(N, N-diglycidyl)aminopropyltrimethoxydecane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane, 3-glycidyl ether propyltrimethoxy Basear, 3-glycidyl ether propyl triethoxy decane, 3-glycidyl ether propyl methyl dimethoxy decane, 3-glycidyl ether propyl methyl diethoxy decane, 3 - glycidyl ether Dimethyl methoxy decane, 3-glycidyl ether propyl dimethyl ethoxy decane, 2-glycidyl ether ethyl trimethoxy decane, 2-glycidyl ether ethyl triethoxy Decane, 2-glycidyl ether ethyl methyl dimethoxy decane, 2-glycidyl ether ethyl methyl diethoxy decane, 2-glycidyl ether ethyl dimethyl methoxy decane, 2-glycidyl ether ethyl dimethyl ethoxy decane, 4-glycidyl ether butyl trimethoxy decane, 4-glycidyl ether butyl triethoxy decane, 4-glycidyl ether butyl group Dimethoxy decane, 4-glycidyl ether butyl methyl diethoxy decane, 4-glycidyl ether butyl dimethyl methoxy decane, 4-glycidyl ether butyl dimethyl ethoxy Baseline, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-ring Oxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltriethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propane Trimethoxy decane, ((3-ethyl-3-epoxypropenyl) methoxy) Propyltriethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propylmethyldimethoxydecane or ((3-ethyl-3-epoxypropane) Methoxy)propane dimethyl methoxy decane, tetrachloro decane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, Four second butoxy decane, trichlorodecane, trimethoxy decane, triethoxy decane, fluorotrichloro decane, fluorotrimethoxy decane, fluorotriethoxy decane, methyl trichloro decane, methyl trimethyl Oxydecane, methyltriethoxydecane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-(trifluoromethyl)B Triethoxy decane, hydroxymethyl trichloro decane, hydroxymethyl trimethoxy decane, hydroxyethyl trimethoxy decane, hydrazine methyl trichloro decane, 3-mercaptopropyl trichloro decane, hydrazine methyl trimethyl Oxydecane, decylmethyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane,phenyltrichlorodecane,phenyltrimethoxydecane,phenyltriphenyl Ethoxy decane, methyl dichloro decane Methyldimethoxydecane, methyldiethoxydecane, dimethyldichlorodecane, dimethyldimethoxydecane, dimethyldiethoxydecane, methyl[2-(perfluoro-positive Octyl)ethyl]dichlorodecane, methyl[2-(perfluoro-n-octyl)ethyl]dimethoxydecane, 3-mercaptopropylmethyldichlorodecane, 3-mercaptopropylmethyldi Methoxy decane, diphenyl dichlorodecane, diphenyl dimethoxy decane, chlorodimethyl decane, methoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl Alkane, methoxytrimethylnonane, chloromethyldiphenylnonane, methoxymethyldiphenylnonane, or a combination of the above compounds.

Specific examples of the decane compound preferably include tetramethoxydecane, tetraethoxydecane, tetra-n-butoxydecane, methyltrimethoxydecane, methyltriethoxydecane, and 2-glycidyl ether. Trimethoxy decane, 3-glycidyl ether propyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxycyclohexyl Ethyltriethoxydecane, [(3-ethyl-3-epoxypropenyl)methoxy]propyltrimethoxydecane, [(3-ethyl-3-epoxypropenyl)methoxy Propyltriethoxydecane, phenyltrimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, trichlorodecane, fluorotrichlorodecane, 3-(methyl) Propylene methoxypropyltrichloromethane, 3-(meth)acryloxypropyltrimethoxydecane, 8-propenyloxyoctyldimethylmethoxydecane, 8-propenyloxyoctane Ethyl ethyl ethoxy decane, vinyl trichloro decane, vinyl trimethoxy decane, allyl trimethoxy decane, 3- glycidyl ether propyl trimethoxy decane, 4-glycidyl ether butyl Trimethoxy decane, 2-(3,4-epoxy ring Hexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propyltrimethyl Oxydecane, ((3-ethyl-3-epoxypropenyl)methoxy)propyltriethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3- Mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, or a combination of the above compounds. Aziridine compound

Specific examples of the decane compound include hexamethyldiazepine and hexaethyldioxane. Oxane compound

Specific examples of the oxirane compound include hexamethyl disiloxane, 1,3-dibutyl tetramethyl disiloxane, and 1,3-diphenyl. 1,3-diphenyl tetramethyl disiloxane, 1,3-divinyl tetramethyl disiloxane, hexaethyldioxane Hexaethyldisiloxane), 3-glycidoxypropylpentamethyl disiloxane, and the like. Surface modification method

The method of surface-modifying the inorganic oxide particles is not particularly limited, and it is preferred to use an amount of 0.1 to 5 organic ruthenium compound molecules per 1 nm ² of the surface area of the inorganic oxide particles. The method of surface-modifying inorganic oxide particles using an organic cerium compound can be suitably used by a known method, for example, a wet method or a dry method. The wet method may be, for example, dispersing an organic cerium compound in a solvent and simultaneously modifying the surface of the inorganic oxide particles; the dry method may be, for example, mixing inorganic oxide particles with an organic cerium compound by a device such as a kneader. At the same time, the surface is modified.

In the wet method, specifically, in the presence of a solvent, the inorganic oxide particles and the organic cerium compound may be allowed to stand at room temperature for a specific period of time or heat-treated at a specific time.

More specifically, after the sol of the inorganic oxide particles or the inorganic oxide particles is mixed in the solution of the organic ruthenium compound (such as water or ethanol), the energy is added from the outside using stirring or bead media. , react at a temperature of 5 to 150 ° C for 1 to 40 hours. Further, the unreacted components in the mixed solution may be removed by ultrafiltration, centrifugation or the like as the case may be.

Among them, in order to promote the surface modification of the inorganic cerium compound to the inorganic acid hydride fine particles, an appropriate amount of a catalyst may be added. The above catalyst can be exemplified by the use of an acid, a base or a salt. Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and organic acids such as methanesulfonic acid, phthalic acid, formic acid, acetic acid, and oxalic acid; and the above-mentioned bases may be inorganic salts such as sodium hydroxide or potassium hydroxide. a base, an aliphatic amine such as diethylamine or triethylamine, an aromatic amine such as pyridine, a quaternary ammonium salt compound such as tetramethylammonium hydroxide or tetrabutylammonium hydroxide; and the above salt may be exemplified by tetramethylammonium hydrochloride. Salt and so on.

The method for producing the above inorganic oxide particle solution is not particularly limited, and preferably, the starting material of the above sol is subjected to heat treatment at 200 ° C to 350 ° C, more preferably 230 ° C to 300 ° C, and the heat treatment is performed. It can be carried out in a pressure vessel (autoclave).

The starting material for the inorganic oxide particle sol is exemplified by cerium oxide, and the active citric acid obtained by subjecting the alkaline ceric acid aqueous solution to the alkali removal reaction. Among them, specific examples of the aqueous alkaline citrate solution include an aqueous solution of sodium citrate and an aqueous solution of potassium citrate, and the de-alkali reaction is preferably an ion exchange method using a cation exchange resin. Further, active citric acid can also be obtained by washing and removing the acid-neutralized and formed alkali metal salt.

More preferably, a strong acid is added to the active citric acid obtained above, and after the above ion exchange step, high purity active citric acid is obtained. Among them, examples of the strong acid to be used include hydrochloric acid, sulfuric acid, and nitric acid.

The dispersion medium of the above cerium oxide sol is not particularly limited, and includes water or an organic solvent. The organic solvent may, for example, be an alcohol, a ketone, an ether, an ester or a hydrocarbon, and one organic solvent may be used. Or you can mix 2 or more types. Further, in a conventional method such as a water-dispersed cerium oxide sol by distillation, an organic solvent-dispersed cerium oxide sol can be obtained by replacing a solvent in the process with an organic solvent.

Specific examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, and 1-hexyl alcohol. Alcohol, 1-octanol, 2-ethyl-1-hexanol, allyl alcohol, benzyl alcohol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, 2-methoxyethanol, 2 - ethoxyethanol, 2-propoxyethanol, 2-(methoxyethoxy)ethanol, 1-methoxy-2-propanol, dipropylene glycol monomethyl ether, diacetone alcohol, ethyl carbene Alcohol, butyl carbitol, and the like.

Specific examples of the ketones include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, and Isobutyl ketone, cyclohexanone, and the like.

Specific examples of the ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dioxane, tetrahydrofuran, and 1,2-diethoxyethane.

Specific examples of the esters include ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol. Butyl ether acetate, hydroxyethyl methacrylate, hydroxyethyl acrylate, γ-butyrolactone, methyl methacrylate, isobutyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, acrylic acid Trifluoroethyl ester, glycidyl methacrylate, and the like.

Specific examples of the hydrocarbons include n-hexane, cyclohexane, benzene, toluene, xylene, solvent naphtha, styrene, or a halogenated hydrocarbon group such as dichloromethane or trichloroethylene.

The surface-modified inorganic oxide particles (D) are used in an amount of 3 parts by weight to 30 parts by weight, preferably 4 parts by weight to 27 parts by weight, based on 100 parts by weight of the hydrolysis condensate (A), More preferably, it is 5 parts by weight to 24 parts by weight.

When the composition for a hard coat film contains surface-modified inorganic oxide particles (D), the refractive index, hardness, and yellowing resistance of the hard coat film formed can be further improved. Additive ( E )

In order to further increase the coatability of the composition for a hard coat film of the present invention and to improve the properties of the coating film formed after the composition is cured, the additive (E) may be further used. Specific examples thereof include an antistatic agent, a smoothing agent, an antioxidant, a dye, a pigment, a photochromic compound, an ultraviolet absorber, a hindered amine compound, or a hindered phenol compound; and the viewpoint of imparting excellent weather resistance to a coating film In view of the above, it is preferably one selected from the group consisting of an antioxidant, a hindered amine compound, and a hindered phenol compound, and two or more of them. From the viewpoint of imparting excellent scratch resistance to the coating film, a smoothing agent is preferably used, and among them, the compound of the following formula (E-1) is most effective. In the formula (E-1), R ₈ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cationically polymerizable group. Or an ethylenically unsaturated group, h1 and h2 are integers of 1 to 5, h3 is an integer of 1 to 30, h4 is an integer of 1 to 70, and h3/h4 is 1 or less.

For the commercially available product of the compound of the above formula (E-1), for example, BYK-306, BYK-307, BYK-333, BYK-375 (manufactured by BYK-Chemie), OX-SQSI20 (manufactured by Toagosei Co., Ltd.), and the like can be given. .

The content of the additive (E) is not particularly limited, and the content of the additive (E) is preferably 5 parts by weight or less based on 100 parts by weight of the composition for a hard coat film.

In addition, as long as it does not affect the performance of the composition for a hard coat film, other resin components may be used as the additive (E), and specific examples thereof include polyurethane, polyester, polyether, polystyrene, acrylic resin and the like. The amount of the resin to be used is not particularly limited, and the amount of the resin used is preferably 5 parts by weight or less based on 100 parts by weight of the composition for a hard coat film. < Method for Producing Composition for Hard Coating Film >

The method for producing the composition for a hard coat film of the present invention is not particularly limited, and a known production method can be used, for example, a hydrolysis condensate (A), a novolac type epoxy resin (B), and a solvent (C) are stirred. The mixture is stirred, uniformly mixed into a solution state, and a surface-modified inorganic oxide particle (D) and an additive (E) are added as needed. < Method of Forming Hard Coating Film >

The method for forming the hard coat film of the present invention is not particularly limited, and specific examples thereof include a dip coating method, a flow coating method, a cast coating method, a spin coating method, a spray method, a wire bar coating method, and a roll. Coating a hard coating film composition on a substrate by a coating method, a knife coating method, an air knife coating method, a letterpress printing method, a gravure printing method, or an inkjet method, and then promoting by heating or irradiating ultraviolet rays. It is hardened to form a hard coat film on the substrate. If necessary, it can also be hardened by both.

The temperature conditions required for the above heating are generally 50 ° C or higher, preferably 80 ° C or higher, more preferably 100 ° C to 200 ° C for several hours to harden the environment, wherein the heating time is 0.5 to 5 hours, It is preferably 1 to 4 hours, more preferably 1.5 to 3 hours.

The above-mentioned ultraviolet light source for irradiating ultraviolet rays may be selected from various mercury lamps, chemical lamps, metal halide lamps, ultraviolet lasers, etc. of low pressure, high pressure and ultra high pressure. The illumination time is preferably from 1 second to 10 minutes. Less than 1 second does not sufficiently promote hardening, and if it exceeds 10 minutes, it is liable to cause coloration or cracking due to deterioration of the coating film or the substrate.

The thickness of the hard coat film is 0.01 to 100 μm, preferably 0.1 to 20 μm, more preferably 1 to 5 μm.

Further, the refractive index of the hard coat film is 1.5 to 1.8, and in order to prevent generation of interference fringes, the refractive index of the hard coat film must be adjusted to a range of ±0.05 with respect to the refractive index of the substrate, preferably adjusted to Range of ±0.02. < Substrate >

The type of the substrate of the present invention is not particularly limited, and preferred substrates are glass substrates, cellulose triacetate (TAC), polyethylene terephthalate (PET), diethyl cellulose, and acetic acid. a film formed of various resins such as acid cellulose, polyether fluorene, (meth)acrylic resin, polyurethane resin, ester resin, polycarbonate, polyfluorene, polyether, polyether ketone, and the like, and the substrate of the present invention The shape is not particularly limited, and may be exemplified by a flat shape (such as a film or a plate), a curved shape (such as a CRT surface, etc.), a spherical or aspherical lens shape (such as a microlens, etc.); wherein, the refractive index of the substrate It is preferably 1.5 to 2.8, more preferably 1.6 or more. < Use >

The composition for a hard coat film of the present invention can be applied to, for example, a microlens array (such as a spectacle lens, a Fresnel lens, a convex lens or a CCD), and various optical lenses (for example). A coating film formed of the composition may also be used as an antireflection film in the above-mentioned fields, in addition to a glass lens, a liquid crystal display, an EL display, a plasma display, a CRT display, a filter, or the like. Further, in order to protect the surface of a printed matter such as a notice board, a logo, or a poster, the hard coat film of the present invention can be applied to the surface of a printed matter as a protective film.

The invention is further described in the following examples, but it should be understood that these examples are merely illustrative and are not to be construed as limiting. < Examples > Synthesis examples of hydrolysis condensate ( A )

Synthesis Example A1 A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed in a four-necked flask of 500 ml in volume, and nitrogen gas was introduced, followed by addition of 0.8 mol of tetramethoxy decane (TMOS for short), 0.2 m of a nail. Base trimethoxy decane (MTMS for short), 0.2 mol of titanium tetrabutoxide (TBT) and methanol (abbreviated as MeOH) 80 g, and add oxalic acid aqueous solution (1.0 g) over 30 minutes while stirring at room temperature. Oxalic acid / 10 grams of water). The four-necked flask was immersed in an oil bath at 30 ° C and stirred for 30 minutes, and then the oil bath was heated to 80 ° C in 30 minutes. When the internal temperature of the solution reached 65 ° C, heating and stirring were continued for polycondensation for 5.5 hours. The solution was allowed to stand for 1 day to obtain a hydrolysis condensate (A1).

Synthesis Examples A2 to A10 The hydrolysis condensate of Synthesis Example A2 to Synthesis Example A10 was prepared in the same manner as in Synthesis Example A1, and was distinguished by changing the alkoxydecane compound (a1) and the alkoxy metal compound ( A2), the type of the solvent and the amount thereof, the type of the catalyst, the amount thereof, the reaction temperature, and the polycondensation time (as shown in Table 1), the hydrolysis condensate (A2) to (A10) can be obtained.

[Table 1]

Comparative Synthesis Example A'1 A nitrogen inlet, a stirrer, a condenser and a thermometer were placed in a four-necked flask of 500 ml volume, and nitrogen was introduced, followed by 0.8 mol of TMOS, 0.2 mol of MTMS and 80 g of MeOH. An aqueous oxalic acid solution (1.0 g of oxalic acid/10 g of water) was added over 30 minutes while stirring at room temperature. The four-necked flask was immersed in an oil bath at 30 ° C and stirred for 30 minutes, and then the oil bath was heated to 75 ° C in 30 minutes. When the internal temperature of the solution reached 65 ° C, heating and stirring were continued for polycondensation for 5.5 hours. The solution was allowed to stand for 1 day to obtain a hydrolysis condensate (A'1).

Comparative Synthesis Examples A'2 to A'5 The hydrolysis condensate of Comparative Synthesis Example A'2 to Comparative Synthesis Example A'5 was prepared in the same manner as Comparative Synthesis Example A'1, and the difference was that the alkane was changed. The oxydecane compound (a1), the metal alkoxide compound (a2), the type of the solvent, the amount thereof, the type of the catalyst, the amount thereof, the reaction temperature, and the polycondensation time (as shown in Table 2), A hydrolysis condensate (A'2)~(A'5) can be obtained.

[Table 2]

The compounds corresponding to the labels in Tables 1 to 2 are as follows: Synthesis example of surface-modified inorganic oxide particles ( D )

Synthesis Example D1 A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed in a four-necked flask of 500 ml in volume, and a nitrogen gas was introduced, followed by the addition of 180 g of cerium oxide particles IPA-ST (particle size 10 to 15 nm, Nissan Chemical Co., Ltd.) And 100 g of 3-glycidyl ether propyl trimethoxy decane were stirred and mixed at 35 ° C for 3 hours, and then 15 g of hydrochloric acid was added. After further stirring at the same temperature for 5 hours, surface-modified inorganic oxide particles (D1) were obtained.

Synthesis Example D2 A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed in a four-necked flask of 500 ml in volume, and nitrogen gas was introduced, followed by the addition of 190 g of cerium oxide-titania composite particles OPTOLAKE TR-521 (particle diameter: 15 nm, 5% by weight of 3-methylpropenyloxypropyltrimethoxydecane and 50 g of phenyltrimethoxydecane, and stirred and mixed at 40 ° C for 1 hour, then added 18 g hydrochloric acid. After further stirring at the same temperature for 6 hours, surface-modified inorganic oxide particles (D2) were obtained.

Synthesis Example D3 A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed in a four-necked flask of 500 ml in volume, and nitrogen gas was introduced, followed by the addition of 200 g of zirconium oxide particles ZR-30AH (particle size: 98 nm, manufactured by Nissan Chemical Co., Ltd.) 50 g of allyltrimethoxydecane and 60 g of hexamethyldioxane were stirred and mixed at 60 ° C for 3 hours, and then 15 g of acetic acid was added. After further stirring at the same temperature for 6 hours, surface-modified inorganic oxide particles (D3) were obtained.

Synthesis Example D4 A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed in a 500-mL four-necked flask, and nitrogen gas was introduced, followed by the addition of 180 g of alumina particles AS-520-A (particle size 15 to 30 nm, Nissan Chemical Co., Ltd., 60 g of [(3-ethyl-3-epoxypropenyl)methoxy]propyltriethoxydecane, 30 g of 8-propenyloxyoctyldimethylmethoxy After hydrazine and 5 g of dimethyldiethoxymethane were stirred and mixed at 40 ° C for 2 hours, 10 g of triethylamine was added. After further stirring at the same temperature for 4 hours, surface-modified inorganic oxide particles (D4) were obtained.

Synthesis Example D5 A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed in a 500-mL four-necked flask, and nitrogen gas was introduced, followed by the addition of 220 g of cerium oxide particles PL-7 (particle size 75 nm, manufactured by Fuso Chemical Co., Ltd. ) 30 g of 3-glycidoxypropyl pentamethyldioxane, 30 g of 3-propenyloxypropyltrimethoxydecane and 30 g of methyltrimethoxydecane at room temperature After stirring for 5 hours, 12 g of oxalic acid was added. After further stirring at the same temperature for 5 hours, surface-modified inorganic oxide particles (D5) were obtained.

Synthesis Example D6 A nitrogen inlet, a stirrer, a condenser and a thermometer were placed in a 500-mL four-necked flask, and nitrogen was introduced, followed by the addition of 240 g of cerium oxide particles MA-ST-L (particle size 40 to 50 nm). , Nissan Chemical Co., Ltd., 80 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 10 g of vinyltrimethoxydecane, 15 g of 4-glycidyl ether butyltrimethyl Oxydecane and 3 g of hexamethyldioxane were stirred and mixed at 70 ° C for 1 hour, and then 20 g of tetramethylammonium hydroxide was added. After further stirring at the same temperature for 3 hours, surface-modified inorganic oxide particles (D6) were obtained. Example of composition for hard coating film

Hereinafter, Examples 1 to 16 and Comparative Examples 1 to 7 of the photosensitive resin composition will be described:

Example 1 100 parts by weight of the hydrolysis-condensation product (A1) of Synthesis Example A1, 2 parts by weight of the novolac type epoxy resin (B1), and 10 parts by weight of the surface-modified inorganic oxide particles of Synthesis Example D1 ( D1), a composition for a hard coat film of Example 1 was obtained by adding 250 parts by weight of ethylene glycol monoethyl ether (C1) and stirring at room temperature with a shaking stirrer.

Examples 2-16 and Comparative Example 1-7 Examples 2 to Example 16 and Comparative Example 1 to the photosensitive resin composition prepared in Comparative Example 7 is the same as in Example 1, step, and it is different in that: Changing the composition of the hydrolysis condensate (A), the novolac type epoxy resin (B), the solvent (C), the surface-modified inorganic oxide particles (D) and the additive (E), and the amount thereof (Table 3) - Table 5). Evaluation method

The refractive index coatings of the hard coating film compositions of the examples and the comparative examples were applied to a glass substrate by spin coating, and then dried on a hot plate at a temperature of 80 ° C for 3 minutes, and then dried. In the circulating oven, after hardening treatment at a temperature of 130 ° C for 60 minutes, a hard coat film was formed. Then, the refractive index (Refractive Index, hereinafter referred to as RI) of the hard coat film was measured by a reflection type optical thick film machine (Model FE-3000; manufactured by Otsuka Electronics Co., Ltd.), and evaluated according to the following criteria: ◎: RI>1.65 ○: 1.60<RI≦1.65 △:1.58<RI≦1.60 ╳:Y≦1.58 -: film formation is impossible

Yellowness using a colorimeter (Model MCPD; Otsuka Electronics Ltd.) measured above the hard coat film yellowness (Yellow Index, referred to as YI), and evaluated based on the following criteria: ※: YI <2.0 ◎: 2.0 ≦ YI <2.5 ○: 2.5≦YI<2.8 △: 2.8≦YI<3 ╳:Y≧3 -: film formation is impossible

Hardness The hard coat film formed of the composition for a hard coat film of the examples and the comparative examples was analyzed by a pencil hardness meter (manufactured by Mitsubishi Co., Ltd. / model: P-247). The weight is measured using a weight of 500g, and pencils of different hardnesses such as 4H, 3H, 2H, H, HB, and B are used, respectively, at 60 degrees, 120 degrees, 180 degrees, 240 degrees, 300 degrees, and 360 degrees of the film. The six angles are 1 cm long at a moving speed of 0.5 mm/s. When two or more of the six lines (including two) are drawn, the judgement is unqualified and evaluated according to the following criteria: ◎: The pencil of 2H or more is qualified. ○: The pencil of H is qualified. △: The pencil of HB is qualified. 铅笔: The pencil of HB or less (including HB, B, etc.) is unacceptable -: Film cannot be formed.

The compounds corresponding to the labels in Table 3 - Table 5 are as follows:

[table 3]

[Table 4]

[table 5] Evaluation results

It is understood from Tables 3 to 5 that the composition for a hard coat film of the present invention (Examples 1 to 16) contains a hydrolysis condensate (A) having a specific structure and a novolac type epoxy resin (B). The hard coating film composition is subjected to a hardening treatment to form a high refractive index hard coat film having yellowing resistance and high hardness.

On the other hand, the composition for a hard coat film which does not contain the hydrolysis-condensation product (A) of a specific structure (Comparative Examples 1-5 and 7) or the phenolic-type epoxy resin (B) (Comparative Example 6-7) was not contained. The hard coating film formed cannot simultaneously obtain three properties of yellowing resistance, hardness and high refractive index.

Further, the tetraalkoxydecane compound (a1-1) and the epoxy group-containing decane compound (a1-2) are simultaneously used in the preparation of the hydrolysis condensate (A) of the composition for a hard coat film (Examples) When 2-5, 7, 9, 10, 12-14), the yellowing resistance of the hard coat film formed by the film can be further improved.

Further, when the composition for a hard coat film further contains surface-modified inorganic oxide particles (D) (Examples 1-6), the refractive index and hardness of the hard coat film formed thereon can be further improved. And yellowing resistance.

As described above, since the composition for a hard coat film of the present invention contains a hydrolysis condensate (A) having a specific structure and a novolac type epoxy resin (B), the composition for a hard coat film is hardened. The treatment can form a high refractive index hard coat film having yellowing resistance and high hardness, which can improve the technical problems existing in the prior art.

Further, when the tetraalkoxydecane compound (a1-1) and the epoxy group-containing decane compound (a1-2) are used in combination in the preparation of the hydrolysis condensate (A) for the composition for a hard coat film, Further improve the yellowing resistance of the hard coating film.

In addition, when the surface-modified inorganic oxide particles (D) are further contained in the composition for a hard coat film, the refractive index, hardness, and yellowing resistance of the composition for a hard coat film can be further improved.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

no.

no.

Claims (15)

A composition for a hard coating film comprising: a hydrolysis condensate (A) obtained by reacting a mixture comprising an alkoxydecane compound (a1) and an alkoxy metal compound (a2); a phenolic ring Oxygen resin (B); and solvent (C). The composition for a hard coat film according to the above aspect of the invention, wherein the alkoxydecane compound (a1) comprises a tetraalkoxydecane compound (a1-1) and an epoxy group-containing decane compound ( A1-2). The composition for a hard coat film according to the first aspect of the invention, wherein the alkoxy metal compound (a2) is at least one selected from the group consisting of compounds represented by the following formula (a2-1). Oxymetal compound, M(OR _a ) ₄ Formula (a2-1) In the formula (a2-1), M represents titanium or zirconium; and R _a represents an alkyl group having 1 to 5 carbon atoms. The composition for a hard coat film according to the first aspect of the invention, wherein the phenolic epoxy resin (B) comprises a compound selected from the group consisting of the following formula (B-1) to (B-3); At least one of the compounds, Formula (B-1) Formula (B-2) In the formula (B-1) to the formula (B-3), R ₁ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each independently represent a monovalent organic group having 1 to 18 carbon atoms. R ₂ each independently represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms; m1, m2, and m6 each independently represent an integer of 0 to 3; m3 and m5 each independently represent an integer of 0 to 4; m4 is independently An integer representing 0 to 2; n1 and n2 are averages, representing a number between 0 and 10; n3 and n4 are averages, representing a number between 0 and 11, and the value of (n3+n4) is 1 to The number between 11; n5 is the average, representing the number between 0 and 1. The composition for a hard coat film according to claim 1, further comprising surface-modified inorganic oxide particles (D), a surface of the surface-modified inorganic oxide particles (D) The modification is carried out with an organic ruthenium compound containing at least one selected from the group consisting of a decane compound, a guanidinium compound, and a decane compound. The composition for a hard coat film according to claim 5, wherein the organic bismuth compound has at least one functional group selected from the group consisting of the following formula (D-1) to formula (D-5). : In the formula (D-1), A represents a hydrogen atom or a methyl group, and a represents an integer of 1 to 3; In the formula (D-2), b represents an integer of 0 or 1; In the formula (D-3), B represents an oxygen atom or a single bond, c represents an integer of 1 to 3, and d represents an integer of 0 to 6, wherein when d represents 0, B is a single bond; In the formula (D-4), e represents an integer of 0 to 6; In the formula (D-5), D represents an alkylene group having 2 to 6 carbon atoms, and E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The composition for a hard coat film according to the first aspect of the invention, wherein the amount of the phenolic epoxy resin (B) used is 100 parts by weight based on the amount of the hydrolysis condensate (A). 2 parts by weight to 18 parts by weight; the solvent (C) is used in an amount of from 150 parts by weight to 1000 parts by weight. The composition for a hard coat film according to claim 5, wherein the surface-modified inorganic oxide particles (D) are used based on 100 parts by weight of the hydrolysis condensate (A). The amount used is from 3 parts by weight to 30 parts by weight. The composition for a hard coat film according to claim 1, wherein the alkoxy metal compound (a2) is used in an amount of 1 mol based on the alkoxydecane compound (a1). The amount is from 0.1 mol to 0.5 mol. The composition for a hard coat film according to the second aspect of the invention, wherein the total amount of the alkoxydecane compound (a1) used is 1 mol, and the tetraalkoxydecane compound (a1) 1) is used in an amount of from 0.1 mol to 0.8 mol; and the epoxy group-containing decane compound (a1-2) is used in an amount of from 0.2 mol to 0.9 mol. The composition for a hard coat film according to claim 5, wherein the surface-modified inorganic oxide particles (D) have an average particle diameter of from 3 nm to 1000 nm. A hard coat film formed by hardening a composition for a hard coat film according to any one of claims 1 to 11. The hard coat film according to claim 12, which has a refractive index of 1.5 to 1.8. A substrate comprising a hard coat film as described in claim 12 or claim 13. The substrate of claim 14, which has a refractive index of from 1.5 to 2.0.