JP2002053806A - Coating film forming composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating film forming composition excellent in adhesiveness to various substrates such as glass, ceramics, metals, plastics and the like, scratch resistance, weatherability, antifouling properties, water repellency and reflection-preventing properties, capable of effectively forming a transparent hardened coating film having a low refractive index, suitably used as an outer paint requiring weatherability, a hard coating material, a moisture-protecting coating material and a reflection-preventing coating material and especially useful as a coating material for constituting optical parts by coating a transparent base such as glass, plastics and the likes. SOLUTION: This coating film-forming composition contains a condensate obtained by condensing a partly or completely hydrolyzed fluorinated alkyl group-containing alkoxysilane compound with a silane compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming a film, and more particularly, to a composition having excellent adhesion to various substrates, abrasion resistance, weather resistance, water repellency, stain resistance and fingerprint adhesion prevention, and refraction. The present invention relates to a film-forming composition capable of efficiently forming a transparent cured film having a low ratio, and an article on which a cured film of this composition is formed.

[0002]

2. Description of the Related Art In recent years,
For example, polymer coatings such as coatings for exterior coatings, hard coatings, moisture-proof coatings, and anti-reflection coatings include adhesion to substrates, scratch resistance, weather resistance, water repellency, stain resistance, and low refractive index. Various characteristics such as sex are required.

[0003] Recently, in various fields such as paints for building exterior and the like, a polymer material containing a fluorine atom has attracted attention because of good weather resistance and the like. Further, in such a polymer material, studies have been made to reduce the refractive index of the material by increasing the content ratio of fluorine atoms.

[0004] However, a polymer containing a fluorine atom has characteristics that its solubility parameter is significantly different from that of other organic materials and that the intermolecular cohesion is small. For this reason, the types of solvents that can be used when preparing the polymer material are limited, and when a film is formed on the surface of the substrate, the adhesion to the substrate and the hardness of the film are low, and the transparency is sufficient. Have problems such as the inability to secure In order to solve these problems, the following techniques have been proposed. (1) JP-A-61-258852 A method of obtaining a fluorine-based polymer having good adhesiveness by copolymerizing a fluoroolefin, vinyl ether, and vinylalkoxysilane. (2) Japanese Patent Application Laid-Open No. Sho 62-185740 A fluoroolefin copolymer having an amino group and a carboxyl group, an epoxy-functional alkoxysilane,
A method for obtaining a composition having good weather resistance and curability by using a silanol group-containing compound. (3) Japanese Unexamined Patent Publication (Kokai) No. 4-275379 A top coat for automobiles having good weather resistance, scratch resistance and acid resistance by using a fluorine-containing polymer having a hydroxy group and a carboxy group and a hydrolysis condensate of a metal alkoxide. How to get. (4) JP-A-61-40845, JP-A-64-1
No. 527 A method for producing an antireflection product using a hydrolyzate of a fluorinated alkoxysilane. (5) JP-A-2-19801, JP-A-4-226
No. 177, a method using a composition in which a polymer having a fluorinated aliphatic ring structure is dissolved in a solvent, as a low-reflection processing agent. (6) JP-A-10-147740 A method of producing a low refractive index coating using a functional group-containing fluoropolymer, a silane compound and a metal catalyst. (7) JP-A-2000-119634 A method in which a fluorine silane compound and a polyfunctional organic silicon compound or a hydrolyzate thereof are blended and used as an antifouling composition.

Although various methods as described above have been proposed, JP-A-61-258852 and JP-A-62-1
In the method disclosed in Japanese Patent Application No. 85740 and Japanese Patent Application Laid-Open No. 64-1527, it is necessary to dry the formed coating film for a long time, which is problematic from the viewpoint of production efficiency.
Further, JP-A-61-40845 and JP-A-4-24-2
The technique disclosed in Japanese Patent No. 75379 has a problem that the type of the applicable base material is limited because the drying treatment is performed under a high temperature condition. In the technique disclosed in JP-A-2-19801, the type of solvent constituting the composition is limited,
There is also a problem that the formed film does not have sufficient abrasion resistance. JP-A-10-14774
In the method disclosed in Japanese Patent Publication No. 0, the manufacturing process is complicated and the cost is high. In addition, there is a problem that the refractive index does not decrease one more time. In JP-A-2000-119634, since a fluorine silane compound and a polyfunctional organic silicon compound or a hydrolyzate thereof are merely blended, it is difficult to obtain hardness, abrasion resistance, weather resistance and water repellency, and The rate has also been reduced, and there have been problems such as the inability to increase the film thickness.

As described above, conventionally, adhesion to a substrate, abrasion resistance, weather resistance, water repellency, stain resistance,
There is no known film-forming composition capable of efficiently forming a cured film having good low refractive index and transparency.

The present invention has been made in view of the above circumstances, and forms a protective film having excellent adhesion to a substrate, scratch resistance, weather resistance, water repellency, stain resistance, low refractive index, and transparency. It is an object of the present invention to provide a film-forming composition capable of being formed and an article having a cured film of the composition.

[0008]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, as a film forming composition, (1) a silane compound containing a fluorinated alkyl group was used. It has been found that it is effective to use a reaction product obtained by performing a condensation reaction between a partially hydrolyzed product or a completely hydrolyzed product and (2) a silane compound.

That is, the inventor of the present invention is to efficiently form a cured film excellent in all of adhesion to a substrate, scratch resistance, weather resistance, water repellency, stain resistance, low refractive index and transparency. As a result of various studies on a film-forming composition capable of forming a film, a reaction obtained by a condensation reaction between (1) a partially hydrolyzed product or a completely hydrolyzed product of a fluorinated alkyl group-containing silane compound and (2) a silane compound. When the product is used, it is possible to obtain a good cured film with respect to all of the adhesion to the substrate, abrasion resistance, weather resistance, water repellency, stain resistance, low refractive index and transparency. I found it.

Usually, a reaction product of two different silane compounds is usually produced by a hydrolysis-condensation reaction with a small amount of water using an alkoxide compound. However, the fluorinated alkyl group-containing alkoxysilane compound has a lower hydrolysis rate than other alkoxysilane compounds,
Simply by hydrolyzing the two, a co-hydrolyzate could not be successfully obtained, and the alkyl fluoride group could not be successfully incorporated into the siloxane. Therefore, the reaction solution caused layer separation, did not dissolve in the solvent, had poor film properties, and could not have a refractive index of 1.42 or less.

Therefore, the present inventor attempted a condensation reaction with a silane compound using a hydrolyzate (silanol compound) containing an alkyl fluoride group as a starting material. It was found that the film produced thereby had good film-forming properties and a low refractive index, and was studied in further detail to complete the present invention.

[0012] Accordingly, the present invention provides a film-forming method characterized by containing a partially or completely hydrolyzed product of a fluorinated alkyl group-containing silane compound and a condensate obtained by condensing the silane compound. A composition and an article having a cured coating of the composition are provided.

Hereinafter, the present invention will be described in more detail.
The film-forming composition of the present invention contains a condensate obtained by condensing (1) a partially hydrolyzed product or a completely hydrolyzed product of a fluorinated alkyl group-containing silane compound with (2) a silane compound. It can form a cured film having excellent adhesion to a substrate, abrasion resistance, weather resistance, water repellency, stain resistance, low refractive index, and transparency.

The partially or completely hydrolyzed product of the component (1) fluorinated alkyl group-containing silane compound and the component (2) constituting the composition of the present invention are described below. Partial hydrolyzate of fluorinated alkyl group-containing silane compound or
As the partially hydrolyzed product or the completely hydrolyzed product of the fluorinated alkyl group-containing silane compound, those represented by the following general formula (1) are preferable.

[0015]

Embedded image (Where Rf is

Embedded image (N is an integer of 1 to 20, m is 1 or more, preferably 1 to 2
0, especially an integer of 1 to 10)
Include FOB indicates which may polyfluoroalkyl group, X is _{-CH 2 -, - CH 2 O} -, - NR 2 -, - CO
^{O -, - CONR 2 -,} - S -, - SO 3 - or SO ₂ N
R ^2- (R ² is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms)
Represents one or more bonding groups, and R ¹ has 1 to ¹ carbon atoms.
4 represents an alkyl group, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. a is an integer of 0 to 3, b is an integer of 1 to 3, and c is an integer of 0 to 2. )

Rf is C _n F _{2n + 1} or CF ₃ CF ₂ CF ₂ O
(CFCF ₃ CF ₂ O) _m CFCF ₃ − (n and m are as described above), and as C _n F _{2n + 1} , CF ₃ −, C ₂ F ₅ −,
_{C 3 F 7 -, C 4} F 9 -, C 6 F 13 -, C 8 F 17 -, C 10 F 21
_{-, C 12 F 25 -,} C 14 F 29 -, C 16 F 33 -, C 18 F
₃₇ -, C ₂₀ F ₄₁ -, and the like.

Examples of the silane compound of the general formula (1) include the following. Rf (CH ₂ ) ₂ Si (OH) ₃ Rf (CH ₂ ) ₂ SiCH ₃ (OH) ₂ Rf (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂ Rf (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) (OH) ₂ Rf (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OH) Rf (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH) Rf (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₂ ( OH) Rf (CH ₂ ) ₃ Si (OH) ₃ Rf (CH ₂ ) ₃ SiCH ₃ (OH) ₂ Rf (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂ Rf (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) (OH) ₂ Rf (CH ₂ ) ₃ Si (CH ₃ ) ₂ (OH) Rf (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH) Rf (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) _{2 (OH) RfNH (CH 2} ) 2 Si (OH) 3 RfNH (CH 2) 2 SiCH 3 (OH) 2 RfNH (CH 2 _{2 Si (OCH 3) (OH} ) 2 RfNH (CH 2) 2 Si (OCH 2 CH 3) (OH) 2 RfNH (CH 2) 2 Si (CH 3) 2 (OH) RfNH (CH 2) 2 Si ( OCH ₃ ) ₂ (OH) RfNH (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₂ (OH) RfNH (CH ₂ ) ₂ NH (CH ₂ ) ₂ Si (OH) ₃ RfNH (CH ₂ ) ₂ NH (CH ₂ ) ₂ SiCH ₃ (OH) ₂ RfNH (CH ₂ ) ₂ NH (CH ₂ ) ₂ Si (OCH ₃ )
(OH) ₂ RfNH (CH ₂ ) ₂ NH (CH ₂ ) ₂ Si (OCH ₂ C
_{H 3) (OH) 2 RfNH} (CH 2) 2 NH (CH 2) 2 Si (CH 3) 2 (O
H) RfNH (CH ₂ ) ₂ NH (CH ₂ ) ₂ Si (OCH ₃ )
_{2 (OH) RfNH (CH 2} ) 2 NH (CH 2) 2 Si (OCH 2 C
_{H 3) 2 (OH) RfCONH} (CH 2) 2 Si (OH) 3 RfCONH (CH 2) 2 SiCH 3 (OH) 2 RfCONH (CH 2) 2 Si (OCH 3) (OH) 2 RfCONH (CH 2) _{2 Si (OCH 2 CH 3)} (OH)
₂ RfCONH (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OH) RfCONH (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH) RfCONH (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₂ (O
H)

Preferred examples include the following. _{CF 3 (CH 2) 2 Si} (OH) 3 CF 3 (CH 2) 2 SiCH 3 (OH) 2 CF 3 (CH 2) 2 Si (OCH 3) (OH) 2 CF 3 (CH 2) 2 Si ( _{CH 3) 2 (OH) CF} 3 (CH 2) 2 Si (OCH 3) 2 (OH) C 8 F 17 (CH 2) 2 Si (OH) 3 C 8 F 17 (CH 2) 2 SiCH 3 (OH ) ₂ C ₈ F ₁₇ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂ C ₈ F ₁₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OH) C ₈ F ₁₇ (CH ₂ ) ₂ Si (OCH) _{3) 2 (OH) C 3} F 7 (CF (CF 3) CF 2 O) 3 CF (CF 3) CH 2
O (CH ₂ ) ₃ Si (OH) ₃ C ₃ F ₇ (CF (CF ₃ ) CF ₂ O) ₃ CF (CF ₃ ) CH ₂
O (CH ₂ ) ₃ SiCH ₃ (OH) ₂ C ₃ F ₇ (CF (CF ₃ ) CF ₂ O) ₃ CF (CF ₃ ) CH ₂
O (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂ C ₃ F ₇ (CF (CF ₃ ) CF ₂ O) ₃ CF (CF ₃ ) CH ₂
O (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)

These compounds are obtained by adding a substantial amount of water to a fluoroalkyl group-containing halogenosilane compound or a fluoroalkyl group-containing alkoxysilane compound, hydrolyzing and silanolizing the compound.

When a silanol is formed by hydrolyzing a halogenated silane compound containing an alkyl fluoride group, the ratio of the halogenated silane compound containing the alkyl fluoride group to the hydrolysis water is based on 100 parts by weight of the halogenated silane compound containing the alkyl fluoride group. Preferably 50 to 1,000 parts by weight of water, particularly preferably 300 to 600 parts by weight. If the amount of water is less than 50 parts by weight, condensation of the generated silanol compound proceeds, and gelation may occur. If the amount is more than 1,000 parts by weight, the pot yield is reduced.

In carrying out this reaction, the reaction may be carried out by adding an organic solvent. Specific examples of the organic solvent used include methyl isobutyl ketone, ethyl acetate, butyl acetate, xylene, toluene, diethyl ether, tetrahydrofuran and the like.

When the halogenated silane compound containing a fluorinated alkyl group is hydrolyzed and silanolized, it is preferable to include a conventionally known dehalogenating agent that captures hydrogen halide produced as a by-product. Specific examples include lithium carbonate, sodium carbonate, potassium carbonate, sodium potassium carbonate, calcium carbonate, magnesium carbonate, magnesium calcium carbonate, cerium carbonate, sodium acetate,
Potassium acetate, copper acetate, urea, ion exchange resins and the like can be mentioned.

This hydrolysis reaction is preferably carried out in a temperature range of 0 to 20 ° C. for 1 to 10 hours. More preferably, the reaction is carried out at 0 to 5 ° C for 1 to 3 hours.

After the reaction, the resulting silanol solution containing a fluoroalkyl group can be obtained by separating it from the aqueous layer, drying the water and evaporating the solvent.

When the alkoxysilane compound containing a fluorinated alkyl group is (partially) hydrolyzed to form a silanol,
For example, water is added to a lower alcohol solution of the silane compound in the presence of an acid catalyst. As a lower alcohol,
Methanol, ethanol, isopropanol, butanol and the like are exemplified. Examples of the solvent that can be used in combination with the alcohol include ketones such as acetone and acetylacetone, esters such as ethyl acetate and isobutyl acetate, and ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and diisopropyl ether. .

The ratio of the amount of hydrolysis water is equivalent to the amount of hydrolysis of the alkoxysilane compound containing a fluorinated alkyl group.
A conventionally known acid catalyst can be used at this time. Specific examples include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and maleic acid.

This hydrolysis reaction is preferably carried out in a temperature range of 0 to 60 ° C. for 1 to 20 hours. The reaction is more preferably performed at 0 to 30 ° C for 1 to 10 hours.

After the reaction, it is more preferable to carry out the condensation reaction of the present invention in a solution state without taking out the produced silanol solution containing a fluoroalkyl group from the solution. Silane compound The silane compound is represented by the following general formula (2). R ³ _d Si (OR ⁴ ) _4-d (2) (wherein, R ³ is an organic group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or an alkyl, alkenyl, or aryl group having 1 to 10 carbon atoms) , An alkoxyalkyl group or an acyl group. D is an integer of 0 to 3, preferably 0 to 2.)

Here, R ³ is an alkyl group having 1 to 10 carbon atoms, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, an epoxy group, a (meth) acryloxy group, a mercapto group, an amino group. , A cyano-substituted alkyl group, an aryl group, an epoxy group such as an alkenyl group, a (meth) acryloxy group, a mercapto group,
Represents an organic group having an amino group, a cyano group, or the like. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a decyl group and a cyclohexyl group; an aryl group such as a phenyl group and a phenethyl group; a 3-chloropropyl group; Alkyl groups such as 3,3,3-trifluoropropyl group, halogenated aryl groups such as p-chlorophenyl group, alkenyl groups such as vinyl group, allyl group, 9-decenyl group and p-vinylbenzyl group; Glycidoxypropyl group, β
-(3,4-epoxycyclohexyl) ethyl group, 9,
An epoxy group-containing organic group such as a 10-epoxydecyl group,
(meth) acryloxy group-containing organic groups such as γ-methacryloxypropyl group and γ-acryloxypropyl group; mercapto-containing organic groups such as γ-mercaptopropyl group and p-mercaptomethylphenylethyl group; γ-aminopropyl group And an amino group-containing organic group such as (β-aminoethyl) -γ-aminopropyl group, and a cyano group-containing organic group such as β-cyanoethyl group.

R ⁴ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, an alkoxyalkyl group or an acyl group, and specifically, methyl, ethyl, propyl, isopropyl Butyl, hexyl, phenyl, isopropenyl, methoxyethyl, acetyl and the like.

Specific examples of these silane compounds include:
Methyltrimethoxysilane, methyltriethoxysilane, methyltris (2-methoxyethoxy) silane, methyltriacetoxysilane, methyltripropoxysilane, methyltriisopropenoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloro Propyltrimethoxysilane,
γ-chloropropyltriethoxysilane, γ-chloropropyltripropoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycid Xypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltri Methoxysilane, γ-
Mercaptopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ- Trialkoxy or triacyloxysilanes such as acryloxypropyltrimethoxysilane and γ-acryloxypropyltriethoxysilane; dimethyldimethoxysilane,
Dimethyldiethoxysilane, dimethyldi (2-methoxyethoxy) silane, dimethyldiacetoxysilane, dimethyldipropoxysilane, dimethyldiisopropenoxysilane, dimethyldibutoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi Acetoxysilane, vinylmethyldi (2-methoxyethoxy) silane, vinylmethyldiisopropenoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldiacetoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-gly Sidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acrylo Xypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ
-Aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane,
dialkoxysilanes or diacyloxysilanes such as β-cyanoethylmethyldimethoxysilane; methyl silicate, ethyl silicate, n-propyl silicate, n
-Butyl silicate, sec-butyl silicate and t
And tetraalkoxysilanes such as -butyl silicate.

In particular, when a film is to be formed by curing with an ultraviolet ray, an electron beam or the like, a silane compound having an organic group having an acryloyl group or a methacryloyl group is preferable, and γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane,
γ-acryloxypropyltriethoxysilane and the like.

Further, these silane compounds may be used alone or as a mixture of two or more.

The conditions for the condensation reaction between component (1) and component (2) in the present invention are described below. Ingredient (1)
The ratio of the component (2) to 100 parts by weight is 10 to 500.
Parts by weight are preferred. Particularly preferred is 30 to 200 parts by weight. When the amount is more than 500 parts by weight, the refractive index of the obtained film does not become 1.42 or less, which is economically disadvantageous.
If the amount is less than 0 parts by weight, adhesion to a substrate and abrasion resistance may be deteriorated.

In carrying out the condensation reaction of the above components (1) and (2) by dealcoholization, it is preferable to use a condensation reaction accelerator in order to promote the reaction more effectively.

Examples of the condensation reaction accelerator include metal salts of organic carboxylic acids such as iron-2-ethylhexoate, titanium naphthate, zinc stearate, dibutyltin diacetate, tetrabutoxytitanium, tetra-i-propoxy and the like. Organic titanium esters such as titanium, dibutoxy- (bis-2,4-pentanedionate) titanium and di-i-propoxy (bis-2,4-pentanedionate) titanium;
Organic zirconium esters such as tetrabutoxy zirconium, tetra-i-propoxy zirconium, dibutoxy- (bis-2,4-pentanedionate) zirconium, and di-i-propoxy (bis-2,4-pentanedionate) zirconium , An alkoxyaluminum compound, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-
Aminoalkyl-substituted alkoxysilanes such as (β-aminoethyl) -γ-aminopropyltriethoxysilane,
Hexylamine, octylamine, dibutylamine and salts thereof, quaternary ammonium salts such as benzyltriethylammonium chloride and tetramethylammonium hydroxide, fluoride salts such as potassium fluoride and sodium fluoride, solid acidic catalyst or solid base Examples thereof include an acidic catalyst (for example, an ion exchange resin catalyst), which may be used alone or in combination.

The amount of the catalyst added depends on the components (1) and (2)
Is preferably from 0.01 to 10 parts by weight based on 100 parts by weight of
Parts by weight, particularly preferably 0.1 to 1 part by weight. If this amount is less than 0.01 parts by weight, it may take too long to complete the reaction or the reaction may not proceed. 1
If the amount is more than 0 parts by weight, it is disadvantageous in terms of cost, and the resulting composition may be colored or side reactions may be increased.

This reaction can be carried out without a solvent or with an organic solvent, but is more preferably carried out with an organic solvent. Specific examples of the organic solvent used include diacetone alcohol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, isobutyl alcohol, isopropyl alcohol, n-butyl alcohol, and n-propyl alcohol. , Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, ethyl acetate,
Butyl acetate, xylene, toluene, 1,3-bis (trifluoromethyl) benzene, 1,4-bis (trifluoromethyl) benzene, perfluoro (2-butyltetrahydrofuran), perfluorohexane, perfluorooctane, (CF ₃ ) ₂ CHOH, F (CF ₂ ) _f (C
H ₂ ) _g OH [f = 1 to 12, g = 1 to 5], (CF ₃ ) ₂
CF (CF ₂ ) _h (CH ₂ ) _i OH [h = 1 to 10, i = 1
~5], F (CF (CF 3) CF 2 O) j CF (CF 3) C
H ₂ OH [j = 1 to 4] and the like.

The condensation reaction between the components (1) and (2) is 2
The reaction is preferably performed in a temperature range of 0 to 120 ° C for 1 to 10 hours.

The obtained condensate may be used as it is as the film-forming composition of the present invention, or after the condensation reaction,
Subsequently, the hydrolysis reaction may be performed alone, or a component hydrolyzed by further adding the component (2) may be used. In this case, the addition amount of the component (2) is preferably 1.0 to 300 parts by weight, particularly preferably 10 to 100 parts by weight, based on 100 parts by weight of the solid content of the condensate. If the amount is more than 300 parts by weight, the fluorine content of the total composition may decrease, and as a result, the refractive index may increase.

At this time, the condensate or the mixture with the component (2) is preferably 0.1 to 0.1 in terms of a silane compound.
Add 6.0 molar equivalents of water and hydrolyze. More preferably, the molar equivalent is 0.5 to 3.0 times. If this amount is more than 6.0 molar equivalents, gelation may occur.

The reaction at the time of hydrolysis / condensation is from 20 to 12
The reaction is preferably performed in a temperature range of 0 ° C. for 1 to 10 hours. More preferably, the reaction is carried out at 20 to 60 ° C for 5 to 20 hours.

Further, at this time, hydrolysis and condensation may be carried out under acidic or alkaline conditions in the system. For that purpose, a conventionally known acidic catalyst or basic catalyst can be used. As the acidic catalyst, acidic hydrogen halide, carboxylic acid, sulfonic acid and the like are preferable. Specific examples include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and maleic acid.
Further, the basic catalyst is preferably an amine catalyst.
Specific examples include ammonia, dimethylamine, diethylamine and the like.

The film-forming composition of the present invention contains, in addition to the above essential components, (a) inorganic fine particles, (b) an organic solvent,
(C) Optional components such as an ultraviolet absorber and a leveling agent may be contained. Hereinafter, these components will be described.

(A) Inorganic fine particles: As the inorganic fine particles added to the composition of the present invention, metal oxide fine particles such as silica fine particles and alumina fine particles are preferable, and colloidal silica is particularly preferable. By including the inorganic fine particles in the composition of the present invention, the scratch resistance of the formed cured film can be further improved. Colloidal silica suitable as inorganic fine particles has an average particle diameter of 0.001 to 0.001.
It is preferably 0.1 μm, more preferably 0.1 μm.
001 to 0.05 μm. When the average particle size of the colloidal silica exceeds 0.1 μm, the transparency of the cured film formed by the prepared composition tends to decrease. The amount of colloidal silica to be added is 5 to 80 parts by weight, preferably 10 to 50 parts by weight, in terms of solid content, based on 100 parts by weight of the condensate or the hydrolyzate thereof. When the amount of the colloidal silica exceeds 80 parts by weight, the transparency of a cured film formed by the prepared composition tends to decrease.

Colloidal silica is usually used in a state of being dispersed in a dispersion medium. Here, as the dispersion medium,
Water and organic solvents can be mentioned. When water is used as the dispersion medium of colloidal silica, the pH of the dispersion medium is preferably adjusted to 2 to 10, preferably 3 to 7.

Organic solvents suitable as a dispersion medium for colloidal silica include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; toluene and xylene. Aromatic hydrocarbons, dimethylformamide, dimethylacetamide, amides such as N-methylpyrrolidone, ethyl acetate, butyl acetate,
Esters such as γ-butyrolactone and ethers such as tetrahydrofuran and 1,4-dioxane can be exemplified, and among these, alcohols and ketones are preferable. These organic solvents can be used alone or in combination of two or more as a dispersion medium.

It is preferable to add a buffer solution and a curing catalyst to the film-forming composition containing the colloidal silica so as to obtain optimum abrasion resistance.

Examples of the curing catalyst include acid catalysts such as hydrochloric acid, sulfuric acid, phosphoric acid and methanesulfonic acid, sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, ammonia, dimethylamine, ethylamine, triethylamine, DBU, 3-aminopropyltrimethoxysilane, ethanolamine acetate, dimethylaniline formate, benzoic acid, tetraethylammonium salt, sodium acetate, sodium propionate, sodium formate,
Alkaline catalysts such as benzoyltrimethylammonium acetate, tetra-i-propoxytitanium, tetra-n-
Butoxytitanium, tetrabutoxyzirconium, dibutoxy- (bis-2,4-pentanedionate) titanium,
Di-i-propoxy (bis-2,4-pentanedionate) titanium tetra-i-propoxyzirconium, dibutoxy- (bis-2,4-pentanedionate) zirconium, di-i-propoxy (bis-2,4) -Pentanedionate) zirconium, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, cobalt octylate, cobalt acetylacetonate, zinc octylate, zinc acetylacetonate, iron acetyl Examples include acetonate, tin acetylacetonate, dibutyltin octylate, dibutyltin laurate and the like. The amount of the curing catalyst to be added is preferably 0.02 to 0.4 parts by weight based on 100 parts by weight of the solid content of the film forming composition containing colloidal silica.

From the viewpoint of ensuring stability, it is preferable to control the pH in the system to pH 2 to 7, particularly preferably pH 3 to 6, in which silanol groups can be stably present. p
A combination of an acid and a basic compound serving as a buffer for adjusting H, for example, acetic acid-sodium acetate, disodium hydrogen phosphate-citric acid, and the like may be added.

(B) Organic solvent: The organic solvent constituting the composition of the present invention includes acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone, ethyl acetate,
Esters such as butyl acetate, alcohols such as methanol, ethanol, isopropyl alcohol, butanol, diacetone alcohol, hydrocarbons such as toluene and xylene, ethers such as tetrahydrofuran, 1,4-dioxane and carbitol, propylene glycol Glycols such as monomethyl ether and polyethylene glycol monomethyl ether acetate can be exemplified.

(C) Ultraviolet absorber: An ordinary ultraviolet absorber may be added to the film-forming composition of the present invention within a range that does not adversely affect the composition. An inorganic oxide sol or an organic compound such as a compound derivative whose main skeleton is hydroxybenzophenone-based, benzotriazole-based, cyanoacrylate-based, or triazine-based is preferable. Further, a polymer such as a vinyl polymer containing these ultraviolet absorbers in the side chain may be used.
Specifically, titanium oxide, zinc oxide, an inorganic ultraviolet absorber composed of an inorganic oxide sol such as cerium oxide, or
2,4′-dihydroxybenzophenone, 2,2 ′,
4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-
Hydroxy-4-n-octoxybenzophenone, 2-
Hydroxy-4-n-dodecyloxybenzophenone, 2
-Hydroxy-4-n-benzyloxybenzophenone,
2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-diethoxybenzophenone, 2,2′-dihydroxy-4,
4′-dipropoxybenzophenone, 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, 2,
2'-dihydroxy-4-methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2- (2-hydroxy-5
-T-methylphenyl) benzotriazole, 2- (2
-Hydroxy-5-t-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl -2-cyano-3,3-diphenyl acrylate,
2- (2-hydroxy-4-hexyloxyphenyl)
Polymer of -4,6-diphenyltriazine, 4- (2-acryloxyethoxy) -2-hydroxybenzophenone, polymer of 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole And other organic UV absorbers. In addition, two or more of these ultraviolet absorbers may be used in combination.

The composition of the present invention can be coated on a substrate surface by dipping, spin coating, or the like.
Flow coating method, roll coating method, spray coating method,
Although not particularly limited, such as a screen printing method,
The spray method and the roll coating method are preferable because the film thickness can be easily controlled.

The coating film of the composition of the present invention coated on the surface of the substrate is formed by (1) a method of curing at a temperature lower than the deformation temperature of the substrate to form a film, and (2) a film being cured by ultraviolet rays. Formed by the method.

Method (1): The drying temperature is usually from 0 to 3
00 ° C., preferably 50 to 150 ° C., and the drying time is usually 10 seconds to 24 hours, preferably 30 seconds to 1 hour.
Time. The drying time (curing time) can be reduced by adding a curing accelerator to the composition of the present invention. Here, specific examples of the curing accelerator include dimethylamine, ethanolamine acetate, dimethylaniline formate, benzoic acid, tetraethylammonium salt, sodium acetate, sodium propionate, sodium formate, benzoyltrimethylammonium acetate,
Tetra-i-propoxytitanium, tetra-n-butoxytitanium, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, cobalt octylate, cobalt acetylacetonate,
Examples include zinc octylate, zinc acetylacetonate, iron acetylacetonate, tin acetylacetonate, dibutyltin octylate, dibutyltin laurate, aminosilanes such as aminopropyltriethoxysilane and 2-aminoethylaminopropyltrimethoxysilane.

Method (2): In order to use this method, it is essential that the condensate of the present invention or its hydrolyzate contains a (meth) acryloyl group. Compounds having an acryloyl group or a methacryloyl group alone or for the purpose of adjusting physical properties such as hardness, adhesion to a substrate, and scratch resistance, or adjusting the viscosity, curability, etc. of the composition ( Hereinafter, (meth) acrylate compound) may be further added. Specific examples of the (meth) acrylate compound include (meth) acrylate of ethylene oxide-modified phenol, (meth) acrylate of propylene oxide-modified phenol, (meth) acrylate of ethylene oxide-modified nonylphenol, and (meth) acrylate of propylene oxide-modified nonylphenol. -Ethylhexyl carbitol (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate , Diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, triethylene Monofunctional (meth) acrylates such as glycol mono (meth) acrylate and tripropylene glycol mono (meth) acrylate; diethylene glycol di (meth) acrylate; triethylene glycol di (meth) acrylate; tetraethylene glycol di (meth) acrylate; Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, ethylene oxide-modified neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, ethylene oxide-modified water Bisphenol A di (meth) acrylate, trimethylolpropane di (meth)
Acrylate, trimethylolpropane allyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth)
Polyfunctional (meth) acrylates such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate, Aronix M-64
00 (Polyester acrylate manufactured by Toagosei Co., Ltd.)
Polyester acrylate, Aronix M-12
Urethane acrylate such as 00 (urethane acrylate manufactured by Toagosei Co., Ltd.), 2,2,6,6-tetramethyl-4-piperidinyl methacrylate having a cyclic hindered amine structure, 1,2,2,6,6-pentamethyl-
4-piperidinyl methacrylate and the like.

For the purpose of further lowering the refractive index, a fluoroalkyl group-containing monofunctional or polyfunctional (meth) acrylate compound may be used. _{Specifically, CF 3 (CH 2) 2} COOCH = CH 2 C 3 F 7 (CH 2) 2 COOCH = CH 2 C 6 F 13 (CH 2) 2 COOCH = CH 2 C 8 F 17 (CH 2) ₂ COOCH = CH ₂ CF ₃ (CH ₂ ) ₂ COOC (CH ₃ ) = CH ₂ C ₃ F ₇ (CH ₂ ) ₂ COO (CH ₃ ) = CH ₂ C ₆ F ₁₃ (CH ₂ ) ₂ COO (CH _{3 ) = CH 2 C 8 F 17} (CH 2) 2 COO (CH 3) = CH 2 CH 2 = CHCOO (CH 2) 2 C 6 F 12 (CH 2) 2 COO
_{CH = CH 2 CH 2 = CHCOO} (CH 2) 2 C 8 F 16 (CH 2) 2 COO
CH = CH _{2 and the} like.

The mixing ratio varies depending on the purpose of use.
Although not particularly limited, the mixing ratio of the (meth) acrylate compound to 100 parts by weight of the condensate or hydrolyzate thereof of the present invention is preferably 5 to 1,000 parts by weight, more preferably 10 to 300 parts by weight. Parts by weight.

It is preferable to add a photopolymerization initiator to this system to cause photopolymerization. Examples of the photopolymerization initiator include arylketone-based photopolymerization initiators (eg, acetophenones, benzophenones, alkylaminobenzophenones). , Benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoyl benzoates, α-acyloxime esters, etc.), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acylphosphines Oxide-based photopolymerization initiator,
There are other photopolymerization initiators. Further, the photopolymerization initiator can be used in combination with a photosensitizer such as an amine.

Specific examples of the photopolymerization initiator include the following compounds. 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone,
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-methylpropan-1-one, 1- {4 (2-hydroxyethoxy) phenyl} -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-} 4- (methylthio) phenyl {-2-morpholinopropan-1-one, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin isobutyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone,
3,3′-dimethyl-4-methoxybenzophenone,
3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ′, 4 ″ -diethylisophthalophenone , Α-acyloxime ester, methyl phenylglyoxylate, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4
-Dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide,
2,6-dimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,
4,4-trimethylpentylphosphine oxide and the like.

The addition amount of the photopolymerization initiator is 0.01 to 20 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the condensate or the hydrolyzate thereof and the (meth) acrylate compound. Parts are preferred.

The thickness of the cured film formed on the substrate surface by the composition of the present invention is usually 0.02 to 1 μm,
Preferably it is 0.05 to 0.5 μm. Further, the refractive index of the cured film of the composition of the present invention is preferably 1.42 or less from the viewpoint of exhibiting a good antireflection effect when formed on the surface of a substrate made of a transparent resin, More preferably, it is 1.40 or less, especially 1.35 to
1.040.

In order to further enhance the antireflection property by using this cured film, it is more preferable to laminate a high refractive index layer having a refractive index of 1.65 or more below the cured film of the present invention. In order to increase the refractive index of this layer, it is preferable to include an additive made of a substance having a higher refractive index. As such an additive, there is a high refractive index ultrafine particle made of a metal oxide sol having a refractive index of 1.5 or more. The high refractive index metal oxide sol has an average particle size of 1 to 100.
A high refractive index metal oxide sol having a thickness of 1 nm to 50 nm is particularly preferable. When blending the high refractive index metal oxide sol, the blending amount is not particularly limited, but in order to sufficiently achieve the purpose of blending, in order to achieve the blending purpose, 100 parts by weight of the curable component of the composition forming the high refractive index layer. Preferably 5 to 500 parts by weight.
Particularly preferred is 100 to 250 parts by weight. If the amount is more than 500 parts by weight, problems such as generation of haze in the cured film are likely to occur. On the other hand, if the amount is less than 5 parts by weight, the refractive index may not be increased.

The high refractive index metal oxide sol is preferably higher than the cured product refractive index of the cured layer and 1.5 or more in view of increasing the refractive index of the high refractive index cured product layer. . Specific examples include ZnO (n = 1.90),
TiO ₂ (n = 2.3 to 2.7), Sb ₂ O ₅ (n = 1.
71), Y ₂ O ₃ (n = 1.87), La ₂ O ₃ (n = 1.
95), ZrO ₂ (n = 2.05), Al ₂ O ₃ (n =
1.63), ITO (n which is a mixed oxide of In and Sn
= 1.95), and a high refractive index metal oxide sol made of a metal oxide is preferred. Other In ₂ O ₃ , SnO ₂ , Ce
A metal oxide sol such as O ₂ can also be used. These high refractive index metal oxide sols may be those whose surfaces are modified with a silane coupling agent or the like from the viewpoint of improving the dispersion stability.

As the curable resin forming the high refractive index cured layer, a conventionally known organic resin or silicone resin such as a thermosetting acrylic resin, a moisture curable acrylic resin, a thermoplastic acrylic resin, or a silane or siloxane modified resin is used. Acrylic resin, urethane resin and the like can be used, and particularly preferred is an acrylic and / or vinyl monomer having an alkoxysilyl group and another monomer copolymerizable with these monomers. It is a composition containing an organic copolymer. By introducing the alkoxysilyl group, the adhesiveness with the substrate, the adhesion with the low refractive index layer (the cured film layer formed by the film-forming composition) is improved, and the alkoxysilyl groups are cross-linked. Thereby, heat resistance is improved and durability can be imparted.

In this case, if the content of the monomer containing an alkoxysilyl group is less than 0.1% by weight, heat resistance and durability may not be improved, and 50% by weight.
If the amount is more than 100%, it may be too hard, and the adhesiveness may be reduced.

The acrylic monomers containing an alkoxysilyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyl. Methyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane,
3-acryloxypropylmethyldimethoxysilane, 3
-Acryloxypropylmethyldiethoxysilane, 3-
Methacryloxymethyltrimethoxysilane, 3-methacryloxymethyltriethoxysilane, 3-methacryloxymethylmethyldimethoxysilane, 3-methacryloxymethylmethyldiethoxysilane, 3-acryloxymethyltrimethoxysilane, 3-acryloxymethyltri Ethoxysilane, 3-acryloxymethylmethyldimethoxysilane, 3-acryloxymethylmethyldiethoxysilane and the like are exemplified. , 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane are preferred.

Examples of the vinyl monomer containing an alkoxysilyl group include vinyltrimethoxysilane and
Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane,
Vinylmethyldiethoxysilane, vinylmethylbis (2
-Methoxyethoxy) silane, 3-vinyloxypropyltrimethoxysilane, 3-vinyloxypropyltriethoxysilane, 3-vinyloxypropylmethyldimethoxysilane, 3-vinyloxypropylmethyldiethoxysilane, styryltrimethoxysilane, styryltri Ethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane and the like are exemplified. Among these, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-vinyloxypropyltrimethoxysilane are used from the viewpoint of handleability and reactivity. preferable.

Next, other monomers copolymerizable with these alkoxysilanes (monomers containing an alkoxysilyl group) include alkyl methacrylates such as methyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate; Methyl acrylate, ethyl acrylate, alkyl acrylates such as butyl acrylate, glycidyl methacrylate, acrylamide, acrylonitrile, vinyl acetate, ethyl vinyl ether,
Vinyl ethers such as butyl vinyl ether and hexyl vinyl ether, styrene, ethylene glycol dimethacrylate, and benzotriazoles which are ultraviolet absorbers containing a methacryl group, for example, 2- (2 '
-Hydroxy-5'-methacryloxyethylphenyl)
Hindered amines such as -2H-benzotriazole and the like, which contain a methacryl group in hindered amines, for example, 2,2,6,6-tetramethyl-4-piperidinyl-methacrylate, 1,2,2,6,6 -Pentamethyl-4-piperidinyl-methacrylate and the like. In addition, it can react with an alkoxysilyl group, for example,
2-Hydroxyethyl methacrylate is not preferred because the composition for a high refractive index cured coating causes a change with time such as thickening and gelling.

This organic copolymer is a copolymer of the above-mentioned monomer containing an alkoxysilyl group and another monomer copolymerizable therewith. A radical polymerization initiator selected from peroxides such as dicumyl peroxide and benzoyl peroxide or azo compounds such as azobisisobutyronitrile is added to the contained solution and easily obtained by reacting under heating. Can be

The composition ratio of the organic copolymer in the coating composition (the composition for a high refractive index cured film) is 10%.
If it is less than 80% by weight, it may become thermoplastic and the heat resistance may be reduced. If it is more than 80% by weight, the adhesiveness may be poor.

When the viscosity of the composition for a high refractive index cured coating is too low to make it difficult to apply the coating and the coating becomes thin, the flexibility is imparted without lowering the adhesiveness. An acrylic copolymer may be added as a component. Acrylic copolymers include poly (methyl methacrylate),
Examples thereof include poly (alkyl methacrylate) such as poly (butyl methacrylate) and poly (butyl acrylate), poly (alkyl acrylate), and a copolymer thereof. These are intended to impart flexibility to the high refractive index cured coating composition without deteriorating the adhesiveness. When this is added, if it is added in an amount of more than 30% by weight based on the composition for a high refractive index cured coating, the thermosetting property of the composition may be deteriorated.
% By weight or less is desirable.

Further, in order to impart good water resistance to the composition for a high refractive index cured coating, or to crosslink with the alkoxysilyl group in the organic copolymer, a nitrogen atom and an alkoxysilyl group are contained in one molecule. Compounds containing groups may be added. More specifically, it has one nitrogen atom in one molecule.
Those having at least two and at least two alkoxysilyl groups are more preferred.

As this component, amino group-containing alkoxysilane, amino group-containing di (alkoxysilane), amide group-containing alkoxysilane, reaction product of amino group-containing alkoxysilane with epoxy group-containing alkoxysilane and silylating agent are used. Amidated, reaction product of amino group-containing alkoxysilane and polyfunctional (meth) acrylic compound, reaction product of amino group-containing alkoxysilane and (meth) acrylic compound, amino group-containing alkoxysilane and (meth) Reaction products of acrylic group-containing alkoxysilanes, reaction products of polyamine compounds and (meth) acrylic group-containing alkoxysilanes, amidated reaction products of amino group-containing alkoxysilanes and polyfunctional isocyanate compounds, amino Group-containing alkoxysilanes and isocyanates Amidation of the reaction product with the containing alkoxysilane, a reaction product of the thiol group-containing alkoxysilane and the isocyanate group-containing alkoxysilane are preferably used, and more preferably the amino group-containing alkoxysilane and the epoxy group Amidation of the reaction product with the contained alkoxysilane and the silylating agent is desirable.

Specific examples of the components used as these components are shown below. Examples of the amino group-containing alkoxysilane include 3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane.
Aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3 -Aminopropyltriethoxysilane, N-
(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3- (trimethoxysilylpropyl) aminopropyltrimethoxysilane,
3- (triethoxysilylpropyl) aminopropyltriethoxysilane, 2- (trimethoxysilylpropyl) aminoethyl-3-aminopropyltrimethoxysilane, 2- (triethoxysilylpropyl) aminoethyl-3-aminopropyltriethoxy Examples include silane.

The amide group-containing alkoxysilane includes:
Examples thereof include ureidopropyltrimethoxysilane, ureidopropyltriethoxysilane, ureidopropylmethyldimethoxysilane, and ureidopropylmethyldiethoxysilane.

Amidation of the reaction product of an amino group-containing alkoxysilane, an epoxy group-containing alkoxysilane and a silylating agent is produced by the following method. Examples of the amino group-containing alkoxysilane include those described above. From the viewpoint of adhesiveness and operability, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl ) -3-Aminopropylmethyldimethoxysilane and the like are preferred. Further, the epoxy group-containing alkoxysilane used here includes γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane and β-
(3,4-epoxycyclohexyl) ethylmethyldiethoxysilane and the like are exemplified. Reactivity in these,
From the viewpoint of operability, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane are preferred.

Examples of the silylating agent used here include hexamethyldisilazane, N, N'-bis (trimethylsilyl) formamide, N, N'-bis (trimethylsilyl) urea and the like. What protects the OH group generated by the reaction between the amino group-containing alkoxysilane and the epoxy group-containing alkoxysilane to form OH
This is for preventing the reaction between the group and the alkoxysilyl group and for preventing the reaction product from changing with time.

The reaction of the amino group-containing alkoxysilane with the epoxy group-containing alkoxysilane and the silylating agent is carried out by dropping the epoxy group-containing alkoxysilane into a mixture of the amino group-containing alkoxysilane and the silylating agent, followed by a heating reaction. The amino group-containing alkoxysilane and the epoxy group-containing alkoxysilane may be reacted, and the reaction product may be reacted by adding a silylating agent.

In this reaction, the mixing ratio of the amino group-containing alkoxysilane and the epoxy group-containing alkoxysilane is such that if the molar ratio of epoxy group / amino group (= NH) is less than 0.3, crosslinking in one molecule may occur. If the number of participating alkoxy groups is too small, the curability is weakened, the entire molecule is not spread, the surface adhesiveness may be weakened and the adhesiveness may be poor, and if it exceeds 1.2 or more, it will be described later. It can be amidated in amidation = N—H groups are almost eliminated, and there is a possibility that water-resistant adhesiveness may be deteriorated.
It is preferable to set the range of 1.2.

Further, this component is considered to be amidated from the reaction product, and the amidation is performed by acetic chloride,
The reaction may be carried out with an acid halide, acid anhydride, or acid isopropenyl ester compound of a carboxylic acid exemplified by bromide acetate, propionyl chloride, acetic anhydride, isopropenyl acetate, benzoyl chloride, and the like.

The amount of this component in the high refractive index cured coating composition is preferably 0.5 to 20 parts by weight based on 100 parts by weight of the above-mentioned organic copolymer. If it is added in excess of 20 parts by weight, the crosslink density becomes too high, and the hardness of the resulting coating increases, which may result in poor adhesion.

An ordinary ultraviolet absorber may be added to the composition for a high refractive index cured coating as long as it does not adversely affect the composition. In this case, an organic ultraviolet absorber having good compatibility with the above organic copolymer is preferable. In particular, a compound derivative whose main skeleton is a hydroxybenzophenone-based, benzotriazole-based, cyanoacrylate-based, or triazine-based is preferable. Further, a polymer such as a vinyl polymer containing these ultraviolet absorbers in the side chain may be used. Specifically, 2,4'-
Dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-
4-n-octoxybenzophenone, 2-hydroxy-
4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone,
2,2′-dihydroxy-4,4′-diethoxybenzophenone, 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, 2,2′-dihydroxy-4,
4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone 2- (2-hydroxy-5-t-methylphenyl) benzotriazole, 2- (2-hydroxy-5-t-oxytylphenyl) benzotriazole, 2
-(2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, ethyl-2-cyano-3,3
-Diphenyl acrylate, 2-ethylhexyl-2-
Cyano-3,3-diphenyl acrylate, 2- (2-
(Hydroxy-4-hexyloxyphenyl) -4,6-
Diphenyltriazine, polymer of 4- (2-acryloxyethoxy) -2-hydroxybenzophenone, 2-
A polymer of (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole is exemplified. In addition, two or more of these organic ultraviolet absorbers may be used in combination.

The composition for a high refractive index cured film may be used after being diluted with a solvent. Examples of the solvent include diacetone alcohol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, isobutyl alcohol, isopropyl alcohol, n-butyl alcohol, n-propyl alcohol, acetone, methyl ethyl ketone , Methyl isobutyl ketone, acetylacetone, ethyl acetate,
Examples thereof include butyl acetate, xylene, and toluene. The composition for a high refractive index cured coating is usually diluted with the above-mentioned solvent and used as a 5 to 10% by weight solution of the above-mentioned organic copolymer.

If necessary, known additives used in conventional coating agents, such as a leveling agent, may be added. Further, a fluorine-based or silicone-based surfactant may be added to smooth the coating film. Further, a cross-linking curing catalyst may be added to accelerate the curing of the coating film.

A solution obtained by adding a metal oxide sol to the composition for a high refractive index cured coating film is applied to the surface of a substrate such as a previously cleaned plastic film, and the above-mentioned diluting solvent is evaporated at room temperature or under heating. What is necessary is just to form a coating film having a thickness of 0.01 to 1 μm, preferably 0.05 to 0.5 μm.

Means for applying this composition to form this high refractive index cured coating layer is not particularly limited, and a known or well-known method can be employed. For example, methods such as a dip method, a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, and an air knife coating method can be employed.

Examples of the film-forming composition of the present invention or a substrate coated with the above-mentioned composition for a high refractive index cured film include transparent substrates made of plastic, glass, ceramics and the like. In particular, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate,
(Meth) acrylonitrile, triacetyl cellulose,
A substrate made of a transparent resin such as diacetyl cellulose and acetate butyrate cellulose is preferred. The transparent substrate preferably has a refractive index of 1.40 or more. In addition,
In this specification, the value of the “refractive index” refers to sodium D
Using a line as a light source, it refers to a value measured by an Abbe refractometer (measuring temperature: 20 ° C.).

[0089]

EXAMPLES The following shows synthesis examples, examples and comparative examples,
The present invention will be specifically described, but the present invention is not limited to the following examples. In the following examples,% is% by weight, part is part by weight, and the average molecular weight in the present specification is expressed by gel permeation chromatography (hereinafter referred to as G
PC) and the number average molecular weight in terms of polystyrene.

<Synthesis of Reaction Condensate> [Synthesis Example 1] 230 g of ion-exchanged water was placed in a 0.5-liter flask equipped with a stirrer, a condenser and a thermometer.
0.2 g of 5% hydrochloric acid was charged and the mixture was stirred.
_{8 F 1 7 (CH 2)} 2 SiCH 3 (OH) heptadecafluorooctyl ethyl methyl dihydroxysilane 3 represented by ₂
0 g (0.056 mol), 12 g (0.056 mol) of γ-acryloxypropyltrimethoxysilane, 168 g of methyl isobutyl ketone and dibutoxy- (bis-
0.42 g (2,4-pentadionate) titanium (0.0
01 mol), the internal temperature was increased by heating to 80 ° C., and the reaction was allowed to proceed for 2 hours to obtain a pale yellow transparent solution. This had a solid content of 18.0%. Its molecular weight by GPC is about 2,000.
It was 0.

[0091] [Synthesis Example 2] a stirrer, 0.5 liter flask equipped with a condenser and a thermometer was charged with ion-exchanged water 230 g, 35% hydrochloric acid 0.2 g, were added. While stirring, C ₈ F ₁ 30 g (0.056 mol) of heptadecafluorooctylethylmethyldihydroxysilane represented by ₇ (CH ₂ ) ₂ SiCH ₃ (OH) ₂ , 36 g (0.168 mol) of γ-acryloxypropyltrimethoxysilane, methyl isobutyl ketone 215 g and dibutoxy- (bis-2,4-pentadionate) titanium 0.42
g (0.001 mol), the internal temperature was increased by heating to 80 ° C., and the mixture was allowed to react for 2 hours to obtain a pale yellow transparent solution. Its solids concentration is 17.0.
%Met. The molecular weight of this product by GPC was about 2,500.

[Synthesis Example 3] In a 0.5 liter flask equipped with a stirrer, a condenser and a thermometer, 230 g of ion-exchanged water and 0.2 g of 35% hydrochloric acid were charged, and C ₈ F ₁ was stirred. 30 g (0.056 mol) of heptadecafluorooctylethylmethyldihydroxysilane represented by ₇ (CH ₂ ) ₂ SiCH ₃ (OH) ₂ , 12 g (0.056 mol) of γ-acryloxypropyltrimethoxysilane, tetraethoxysilane 11.7 g (0.056 mol), 215 g of methyl isobutyl ketone and 0.42 of dibutoxy- (bis-2,4-pentadionate) titanium
g (0.001 mol), the internal temperature was increased by heating to 80 ° C., and the mixture was allowed to react for 2 hours to obtain a pale yellow transparent solution. Its solids concentration is 18.0.
%Met. Further, the molecular weight of this product by GPC was about 2,600.

Synthesis Example 4 Dibutoxy- (bis-2,4
-Pentadionate) titanium 0.42 g (0.001 mol) was added to benzyltriethylammonium chloride 0.42 g
After that, the mixture was charged and reacted in the same manner as in Synthesis Example 1 to obtain a transparent solution. Its solids concentration is 1
It was 8.0%. Further, the molecular weight of this product by GPC was about 2,200.

[0094] [Synthesis Example 5] a stirrer, 0.5 liter flask equipped with a condenser and thermometer, C ₈ F _{1 7} (C
30 g of heptadecafluorooctylethylmethyldihydroxysilane represented by H ₂ ) ₂ SiCH ₃ (OH) ₂ (0.
056 mol), 19.6 g of methyltrimethoxysilane
(0.056 mol), 11.7 g of tetraethoxysilane
(0.056 mol), 245 g of methyl isobutyl ketone
And dibutoxy- (bis-2,4-pentadionate)
0.42 g (0.001 mol) of titanium is charged, and the temperature is 80 ° C.
When the internal temperature was raised by heating until the reaction was continued for 2 hours, a pale yellow transparent solution was obtained. This had a solid content of 17.0%. Further, the molecular weight of this product by GPC was about 2,300.

[Synthesis Example 6] To 100 g of the condensate solution synthesized in Synthesis Example 1, 1.4 g of an aqueous solution of 0.25N acetic acid was added, and the mixture was stirred at room temperature for 3 hours to carry out a hydrolysis reaction to give a pale yellow transparent solution. Obtained. Its molecular weight by GPC was about 5,000.

[Synthesis Example 7] To 100 g of the condensate solution synthesized in Synthesis Example 5, 7.6 g (0.03 g) of tetraethoxysilane was added.
6 mol) and 2.1 g of a 0.25N acetic acid aqueous solution were added, and the mixture was stirred at room temperature for 3 hours to carry out a hydrolysis reaction to obtain a pale yellow transparent solution. Its molecular weight by GPC was about 5,200.

[Synthesis Example 8] To 100 g of the condensate solution synthesized in Synthesis Example 1, 7.6 g (0.03 g) of tetraethoxysilane was added.
6 mol) and 2.1 g of a 0.25N acetic acid aqueous solution were added, and the mixture was stirred at room temperature for 3 hours to carry out a hydrolysis reaction to obtain a pale yellow transparent solution. Its molecular weight by GPC was about 5,500.

[0098] [Synthesis Example 9] (Comparative Example) stirrer, 0.5 liter flask equipped with a condenser and _{thermometer, C 8 F 1 7 (CH} 2) 2 SiCH 3 (OC
Heptadecafluorooctylethylmethyldimethoxysilane 32 g (0.056 mol) represented by H ₃ ) ₂ and γ-acryloxypropyltrimethoxysilane 12 g (0.
056 mol), 176 g of methyl isobutyl ketone and 3.0 g of a 0.25 N acetic acid aqueous solution were charged, the internal temperature was raised to 80 ° C. by heating, and the mixture was reacted as it was for 2 hours to obtain a finely turbid solution. Its solids concentration is 1
7.0%. When GPC was observed, both unreacted raw materials were observed.

[0099] [Synthesis Example 10] (comparative example) stirrer, indicated A 0.5-liter flask equipped with a condenser and thermometer, with _{C 8 F 1 7 (CH 2} ) 2 Si (OCH 3) 3 -heptadec 32 g (0.056 mol) of fluorooctylethylmethyltrimethoxysilane, 12 g of γ-acryloxypropyltrimethoxysilane (0.056 mol)
Mol), 176 g of methyl isobutyl ketone and 0.25
When 3.0 g of an aqueous acetic acid solution of N was charged, the internal temperature was increased by heating to 80 ° C., and the mixture was reacted for 2 hours.
A turbid solution was obtained. This had a solid content of 16.5%. When GPC was observed, both unreacted raw materials were observed.

[0100] [Synthesis Example 11] (comparative example) stirrer, indicated A 0.5-liter flask equipped with a condenser and thermometer, with _{C 8 F 1 7 (CH 2} ) 2 Si (OCH 3) 3 -heptadec 32 g (0.056 mol) of fluorooctylethyltrimethoxysilane, 19.6 g (0.056 mol) of methyltrimethoxysilane, 11.7 g (0.056 mol) of tetraethoxysilane, 176 g of methyl isobutyl ketone and 0.25N 4.5 g of acetic acid aqueous solution
Was charged, and the internal temperature was raised to 80 ° C. by heating, and the mixture was reacted for 2 hours to obtain a slightly turbid solution. This had a solid content of 17.0%. When GPC was observed, unreacted raw materials were observed.

<Synthesis of Organic Copolymer Containing Alkoxysilyl Group> [Synthesis Example 12] 20 g of γ-methacryloxypropyltrimethoxysilane and methyl methacrylate 6 were placed in a 0.5 liter flask equipped with a stirrer, a condenser and a thermometer.
0 g, 5 g of ethyl acrylate, 5 g of vinyl acetate, 10 g of glycidyl methacrylate, 0.2 g of ethylene glycol dimethacrylate, 0.5 g of azobisisobutyronitrile as a polymerization initiator, 20 g of diacetone alcohol as a solvent, and 80 g of ethylene glycol monomethyl ether were charged. At 80-90 ° C under nitrogen stream
Stirred for hours. The viscosity of the obtained organic copolymer solution containing an alkoxysilyl group was 43,600 cst, and the alkoxyl group content in the copolymer was 20%.

Synthesis Example 13 20 g of γ-methacryloxypropyltrimethoxysilane of Synthesis Example 12 was added to 10 g.
An organic copolymer solution containing an alkoxysilyl group was prepared in the same manner as in Synthesis Example 12 except that 60 g of methyl methacrylate was replaced with 70 g. The viscosity of the obtained organic copolymer solution containing an alkoxysilyl group is 40,60.
0 cst, and the content of alkoxyl group in the copolymer was 10%.

[Synthesis Example 14] An organic copolymer containing an alkoxysilyl group was synthesized in the same manner as in Synthesis Example 12 except that 20 g of γ-methacryloxypropyltrimethoxysilane in Synthesis Example 12 was replaced with 20 g of vinyltrimethoxysilane. A coalescence solution was prepared. The viscosity of the obtained organic copolymer solution containing an alkoxysilyl group was 39,700 cst, and the content of the alkoxyl group in the copolymer was 20%.

<Synthesis of Compound Containing Nitrogen Atom and Alkoxysilyl Group in Molecule> [Synthesis Example 15] N-2- (aminoethyl) was placed in a 2.0-liter flask equipped with a stirrer, a condenser and a thermometer.
222 g of -3-aminopropyltrimethoxysilane and 242 g of hexamethyldisilazane as a silylating agent were charged and heated to 120 ° C. under a nitrogen stream, and 496 g of γ-glycidoxypropylmethyldiethoxysilane was added dropwise thereto. After reacting and stirring for 5 hours at 120 ° C,
When the low boiling point components were removed at 100 ° C. under reduced pressure, a viscosity of 1,
862 g of a viscous compound having 387 cst, a refractive index of 1.4618, and a specific gravity of 1.048 was obtained.

Next, 862 g of this reaction product and 862 g of toluene were charged into a 2.0 liter flask equipped with a stirrer, a condenser and a thermometer, and 141 g of acetic anhydride was added dropwise thereto at room temperature under a nitrogen stream to cause a reaction. 110 ° C
And stirred at 50 ° C for 2 hours.
1 g was added dropwise, and the mixture was stirred with heating at 50 ° C. for 1 hour, and then the low-boiling components were removed at 100 ° C. under reduced pressure to obtain a highly viscous compound. When an infrared absorption spectrum of this compound was measured, no absorption due to an OH group or NH group was observed in a region of 3,000 cm ⁻¹ or more, and a strong absorption due to an amide group was observed at 1,650 cm ^−1. Admitted.

Next, examples and comparative examples will be described. The abbreviations of the condensate, the hydrolyzate thereof, the organic copolymer, and the like of the present invention used in Examples and Comparative Examples are as follows. <Condensate and Hydrolyzate> FS-1: Reaction Product of Synthesis Example 1 FS-2: Reaction Product of Synthesis Example 2 FS-3: Reaction Product of Synthesis Example 3 FS-4: Synthesis Product of Synthesis Example 4 Reaction Product FS-5: Reaction Product of Synthesis Example 5 FS-6: Reaction Product of Synthesis Example 6 FS-7: Reaction Product of Synthesis Example 7 FS-8: Reaction Product of Synthesis Example 8 FS-9 : Reaction product of Synthesis Example 9 FS-10: Reaction product of Synthesis Example 10 FS-11: Reaction product of Synthesis Example 11 <Alkoxysilyl group-containing organic copolymer> Pol-1: Reaction of Synthesis Example 12 Product Pol-2: Reaction product of Synthesis Example 13 Pol-3: Reaction product of Synthesis Example 14 <Compound containing a nitrogen atom and an alkoxysilyl group in the molecule> NSi-1: Ureidopropyltriethoxysilane NSi- 2: Reaction product of Synthesis Example 15

The measurement and evaluation of various physical properties in the examples were performed by the following methods. (1) Pencil hardness Measured according to JIS K5400. (2) Weather resistance test For each of the base materials on which the coatings were formed, a weather resistance acceleration test was performed using a fade meter [manufactured by Suga Test Instruments Co., Ltd.]
The gloss retention (%) after 1,000 hours was measured. The evaluation was “「 ”when the gloss retention was 90% or more,“ △ ”when it was 89 to 60%, and“ X ”when it was 59% or less. (3) Scratch resistance test Abrasion wheels CS-10F were mounted on a Taber abrasion tester in accordance with ASTM 1044, and the test was performed under a load of 500 g for 1,000 hours.
The haze value after 0 rotation was measured. Taber abrasion (%) was represented by (haze after test)-(haze before test). (4) Adhesion of the cured film According to JIS K5400, the sample was cut in 11 vertical and horizontal directions at 1 mm intervals with a razor blade to make 100 grids, and a commercial cellotape (registered trademark) was adhered well. Thereafter, when the film was suddenly peeled 90 degrees toward the front, the number of squares (X) remaining without peeling off the coating was indicated by X / 100. (5) Transparency "○" indicates that the entire surface of the coating has uniform transparency.
The case where a part where transparency was impaired was recognized was evaluated as "x". (6) Refractive index A film having a film thickness of 30 to 50 μm was prepared, and this film was measured with an Abbe refractometer (measurement temperature: 20).
° C). (7) Reflectance Average luminous reflectance of the surface of the cured film substrate measured by a spectrophotometer. (8) Water repellency Using a contact angle measuring device, a water drop was dropped on the film, and the contact angle of water was measured. (9) Stain resistance A straight line was drawn on the film with red magic ink (registered trademark),
It was wiped off with a dry cloth, and the stain resistance was evaluated according to the situation. ：: Even if a line is drawn and wiping is repeated 10 times or more, it can be wiped off by gently rubbing. ○: Can be wiped out by drawing a line and repeating wiping,
A faint trace remains. Δ: Wipe off if not strongly rubbed; X: It cannot be wiped off at all.

[Examples and Comparative Examples] (1) Preparation of Film Forming Composition Condensates prepared in Synthesis Examples 1 to 11, methyl ethyl ketone dispersed colloidal silica (solid content: 30%), polyfunctional acrylate: trimethylolpropanetri Acrylate, fluorinated alkyl group-containing acrylate: C ₈ F ₁₇ (CH ₂ ) ₂
COOCH = CH ₂ , photopolymerization initiator: 2-hydroxy-
2-Methyl-1-phenylpropan-1-one, curing catalyst: sodium formate and the like were mixed, and the mixture was adjusted with diacetone alcohol so that the solid content became 15%.
~ L were prepared as shown in Table 1.

(2) Preparation of Composition for High-Refractive-Index Cured Coating Compositions prepared in Synthesis Examples 12 to 15, polymethyl methacrylate having an average molecular weight of 150,000, and a metal oxide sol having a high refractive index having a refractive index of 2.70 Methyl ethyl ketone sol (average particle diameter: 50 nm) of TiO ₂ was mixed and adjusted with diacetone alcohol so that the solid content of the organic copolymer became 10%. Compositions A to E are shown in Table 1. Was prepared as follows.

(3) Preparation of Surface Coating Formed Product When the composition for a high refractive index cured film of (2) is applied,
It is applied to a transparent resin plate (or film) having a cleaned surface by a flow coating method so as to have a thickness of 1 to 3 μm as a cured coating film, and is cured at about 120 ° C. for about 30 minutes. When the film-forming composition (1) is applied thereon, it is applied by a bar coater coating method so as to have a cured film thickness of 0.1 to 0.5 μm.

Thereafter, in the case of curing with ultraviolet rays, curing is performed by repeating 200 mJ / cm ² three times using a high-pressure mercury lamp. In the case of heat curing, the film is held and cured in a hot air circulating oven at 80 ° C. for 5 minutes. Or (2)
When the high refractive index cured coating composition is not applied, a bar coater coating is applied as a cured coating on a transparent resin plate (or film) having a cleaned surface so as to have a cured coating thickness of 0.1 to 0.5 μm. Apply by method. Thereafter, when curing with ultraviolet light, 200 mJ /
cm ² to 3 times repeatedly cured. In the case of heat curing, the film is held and cured in a hot air circulating oven at 80 ° C. for 5 minutes.

The transparent resin plate used was a 0.5 mm PC resin, and the film was a 50 μm PET film. Table 4 shows the evaluation results of the physical properties of the coating films thus obtained.
It was shown to.

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

[Table 3]

[0116]

[Table 4]

[0117]

According to the composition of the present invention, it has excellent adhesion to various substrates such as glass, ceramics, metals and plastics, excellent abrasion resistance, weather resistance, stain resistance, water repellency, antireflection performance and refraction. A transparent cured film having a low rate can be efficiently formed. The composition of the present invention can be suitably used as an exterior coating material that requires weather resistance, a hard coat material, a moisture-proof coat material, and an anti-reflective coat material, and covers a transparent substrate such as glass and plastic. It is particularly useful as a coating material constituting an optical component.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 77/24 C08G 77/24 77/26 77/26 77/28 77/28 C09D 5/16 C09D 5 / 16 143/04 143/04 183/02 183/02 183/04 183/04 (72) Inventor: Mitsuo Asai 1-chome, Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture 10 72) Inventor Kazuharu Sato 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture F-term (reference) 4F100 AA17C AB00 AD00 AG00 AH03C AH05B AK01 AK02C AK17B AK17J AK25C AK52B AK52J AL06B AR00C AT00A BA02 BA03 BA07 BA10A BA10C GB07 JB06 JL06 JM01C JN06B JN18B JN18C 4J027 AB01 AC03 AC04 AC06 AF03 AF05 AF06 AG01 BA07 BA08 BA13 BA19 BA26 CB10 CC05 CD08 4J035 A A01 BA01 BA11 CA051 CA061 CA131 CA141 CA161 CA181 CA26N CA261 EB02 LA03 LB01 LB07 4J038 CG141 CG142 CH031 CH032 DG321 DG322 DL021 DL022 DL031 DL032 DL051 DL052 FA071 DL081 FA0812 FA271 FA272 FA281 FA282 GA01 GA12 GA16 HA166 HA216 HA446 KA03 KA04 KA06 KA08 KA12 MA09 NA03 NA05 NA07 NA11 NA12 NA19 PA17 PA18 PA19 PB05 PB08 PC03 PC08

Claims (12)

[Claims] 1. A film-forming composition comprising a partially hydrolyzed product or a completely hydrolyzed product of a fluorinated alkyl group-containing silane compound and a condensate obtained by condensing the silane compound. 2. A partially hydrolyzed product or a completely hydrolyzed product of a fluorinated alkyl group-containing silane compound is represented by the following general formula (1), and the silane compound is represented by the following general formula (2)
The composition for forming a film according to claim 1, which is represented by: Embedded image (Wherein, Rf is (N is an integer from 1 to 20, m is an integer of 1 or more) indicates at least one which may contain polyfluoroalkyl group an ether bond represented, X is -CH ₂ -, - CH ₂ O- , -N
R ^2- , -COO-, -CONR ^2- , -S-, -SO ₃
— Or SO ₂ NR ² — (R ² is a hydrogen atom or a C 1-8
One or more types of linking groups)
¹ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. a is an integer of 0 to 3, b is 1 to
An integer of 3 and c is an integer of 0 to 2. R ³ _d Si (OR ⁴ ) _4-d (2) (wherein, R ³ is an organic group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or an alkyl group, alkenyl group, or aryl group having 1 to 10 carbon atoms) A d, an alkoxyalkyl group or an acyl group, and d is an integer of 0 to 3.) 3. The composition according to claim 2, wherein at least one of R ^{3 represented by} the general formula (2) is an organic group having an acryloyl group or a methacryloyl group. 4. The composition for forming a film according to claim 2, wherein the composition comprises a product obtained by co-hydrolyzing the obtained condensate and a silane compound represented by the general formula (2). . 5. The film-forming composition according to claim 1, further comprising a product obtained by further hydrolyzing the obtained condensate. 6. The coating composition according to claim 1, wherein the cured coating has a refractive index of 1.42 or less. 7. An article having a protective film excellent in stain resistance and water repellency, comprising a cured film of the composition for forming a film according to any one of claims 1 to 6. 8. An antireflection article having excellent antireflection properties, comprising a cured film of the composition for forming a film according to any one of claims 1 to 6. 9. A high-refractive-index layer having a refractive index of 1.65 or more, and a cured film of the composition for forming a film according to claim 1 laminated on the surface. An antireflection article excellent in antireflection properties according to claim 8. 10. The antireflection article having excellent antireflection properties according to claim 9, wherein the high refractive index layer contains a metal oxide sol. 11. The high refractive index layer contains an organic copolymer of an acrylic and / or vinyl monomer containing an alkoxysilyl group and another monomer copolymerizable with the acrylic and / or vinyl monomer. 11. The reflection having excellent antireflection properties according to claim 9 or 10, wherein the ratio of the acrylic and / or vinyl monomer containing an alkoxysilyl group in the combination is 0.1 to 50% by weight. Articles for prevention. 12. The antireflection article according to claim 11, wherein the high refractive index layer further contains a compound having a nitrogen atom and an alkoxysilyl group in one molecule.