JPH10147739A - Composition for forming antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can give an antireflection film having a low refractive index, exhibiting good antireflective effect and having high hardness and excellent scratch resistance by using a modified fluoro copolymer obtained by reacting a reactive-group-containing fluoro copolymer with a silane coupling agent. SOLUTION: This composition contains a modified fluoro copolymer obtained by reacting 100 pts.wt. reactive-group-containing fluoro copolymer (A) obtained by polymerizing a mixture containing 20-70mol% hexafluoropropylene, 1-20mo% monomer having at least one reactive group selected from among hydroxyl groups, amino groups and carboxyl groups and 10-70mol% monomers copolymerizable therewith with 1-50 pts.wt. silane coupling agent (B) represented by the formula (wherein R<1> is an alkyl or the like, X is a functional group reactive with the reactive group of copolymer A, such as epoxy, amino or isocyanato).

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 an antireflection film, and more particularly to an antireflection film having a low refractive index and a high hardness and exhibiting a good antireflection effect required in the optical field. The present invention relates to a composition for forming an anti-reflection film capable of forming an antireflection film.

[0002]

2. Description of the Related Art With the development of multimedia today, various display devices (display devices) have been developed and widely used. Thus, in such a display device, improving the visibility is an important technical problem. Conventionally, as one means for improving visibility, coating the substrate surface with an antireflection film made of a low refractive index substance has been performed. Here, as a method of forming the antireflection film, for example, a method of forming a thin film of an inorganic compound containing fluorine by a vapor deposition method is known. However, with the recent demand for larger display devices and the spread of liquid crystal display devices, a technology that can efficiently form an antireflection film even on a large substrate has become necessary.

However, when a conventional vapor deposition method is employed as a method for forming an anti-reflection film, a large vapor deposition apparatus that can handle a large substrate is required, which results in a tremendous increase in cost and a practical increase. is not.

Under these circumstances, there has been proposed a method of forming a liquid composition by dissolving a fluorine-based polymer having a low refractive index in an organic solvent and applying the composition to the surface of a substrate to form an antireflection film. Considered, for example, in JP-A-61-40
No. 845 and Japanese Patent Publication No. 6-98703 disclose a technique in which a hydrolyzate of a fluorinated alkylsilane is applied on a hard coat layer formed on a substrate surface to form a coating layer having a two-layer structure. It has been disclosed.

[0005]

However, in the case of a conventionally known forming material based on a fluorine-based polymer, the formed antireflection film does not have a sufficient hardness and the surface is easily damaged. Have a problem.

The present invention has been made based on the above circumstances. An object of the present invention is to provide a composition for forming an anti-reflection film capable of forming an anti-reflection film having a low refractive index, capable of exhibiting a good anti-reflection effect, and having high hardness and excellent scratch resistance. To provide things.

[0007]

The composition for forming an antireflection film according to the present invention comprises [A] hexafluoropropylene 20 to 7
0 mol%, 1 to 20 mol% of a monomer containing at least one reactive group selected from a hydroxyl group, an epoxy group, an amino group and a carboxyl group (hereinafter also referred to as “reactive group-containing monomer”), And a fluorine content of at least 40% by weight obtained by polymerizing a monomer mixture containing 10 to 70 mol% of a monomer copolymerizable therewith (hereinafter also referred to as a “copolymerizable monomer”); The intrinsic viscosity measured at 25 ° C. in N, N-dimethylacetamide is 0.05 to
With respect to 100 parts by weight of a fluorine-containing copolymer having a reactive group (hereinafter also referred to as "reactive fluorine-containing copolymer [A]") of 2 dl / g, [B] in the following general formula (1) The silane coupling agent having a hydrolyzable silyl group shown below (hereinafter also referred to as “reactive silane coupling agent [B]”) is modified with a silane coupling agent obtained by reacting 1 to 50 parts by weight. (Hereinafter, also referred to as “modified fluorine-containing copolymer [I]”).

[0008]

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[Wherein R ¹ represents an alkyl group, an aryl group or an alkoxyalkyl group, and the three groups represented by (OR ¹ ) may be the same or different. X represents a functional group selected from an epoxy group, an amino group, an isocyanate group, a mercapto group and a (meth) acryloyl group, which can react with the reactive group of the reactive fluorine-containing copolymer [A]. ]

Further, the composition for forming an antireflection film of the present invention comprises an alkoxysilane represented by the following general formula (2) (hereinafter referred to as “alkoxysilanes”) per 100 parts by weight of the modified fluorine-containing copolymer [I]. 20 to 80 parts by weight of colloidal silica and 0 to 80 parts by weight of a colloidal silica, and water is added to the mixture to effect hydrolysis and condensation reaction. It is characterized by containing a copolymer (hereinafter also referred to as "modified fluorine-containing copolymer [II]").

[0011]

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[In the formula, R ² represents an alkyl group or an aryl group, and when there are a plurality of groups represented by R ^2, they may be the same or different. R
³ represents a hydrogen atom or an alkyl group, and when there are a plurality of groups represented by R ^3, they may be the same or different. Here, at least one group represented by R ³ is an alkyl group. m is an integer from 0 to 3. ]

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION

<Reactive Fluorine-Containing Copolymer [A]> The reactive fluorine-containing copolymer [A] used for producing the composition for forming an antireflection film of the present invention is hexafluoropropylene 20.
To 70 mol% and a reactive group-containing monomer 1 to 20 mol%
And a monomer mixture containing 10 to 70 mol% of a copolymerizable monomer.

<Reactive Group-Containing Monomer> The reactive group-containing monomer constituting the monomer mixture is used for introducing a reactive group into the obtained reactive fluorine-containing copolymer [A]. It is a monomer, and specific examples thereof include a hydroxyl group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer and a carboxyl group-containing monomer.

Specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl vinyl ether and 3-hydroxyethyl vinyl ether.
Hydroxyl group-containing vinyl ethers such as hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether; 2-hydroxyethyl allyl ether;
Examples include hydroxyl group-containing allyl ethers such as hydroxybutyl allyl ether and glycerol monoallyl ether; and allyl alcohol.

Specific examples of the epoxy group-containing monomer include:
For example, vinyl glycidyl ether, allyl glycidyl ether, glycidyl crotonate, glycidyl (meth) acrylate, glycidoxyalkylvinyl dialkoxysilanes and the like can be mentioned.

Examples of the amino group-containing monomer include diethylaminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, acrylamide,
Vinyl pyridine, vinyl caprolactam and the like can be mentioned.

Examples of the carboxyl group-containing monomer include crotonic acid, itaconic acid, α-vinyl acetic acid, (meth)
Unsaturated carboxylic acids such as acrylic acid; polyvalent vinyl esters such as vinyl fumarate, vinyl maleate, vinyl succinate and vinyl phthalate; monounsaturated carboxylic acids such as methyl fumarate and ethyl maleate Esters; carboxyalkyl vinyl dialkoxysilanes and the like can be mentioned.

These reactive group-containing monomers may be used alone or may have the same or different reactive groups.
A mixture of two or more monomers may be used.

<Copolymerizable Monomer> The copolymerizable monomer constituting the monomer mixture is not particularly limited as long as it is copolymerizable with hexafluoropropylene or a monomer containing a reactive group. It is not something to be done. Specific examples of such a copolymerizable monomer include, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl Vinyl ether, n-octyl vinyl ether, n-
Alkyl vinyl ethers such as dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether or cycloalkyl vinyl ethers; perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), and perfluoro (butyl vinyl ether) Fluoro (isobutyl vinyl ether),
Perfluoro (alkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether); general formula “CH ₂ ＣＨCH—O—R _f ” (where R _f is alkyl containing a fluorine atom) (Fluoroalkyl) vinyl ethers or (fluoroalkoxyalkyl) vinyl ethers represented by the following formulas or alkoxyalkyl groups: vinylidene fluoride, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, tetrafluoroethylene, etc. Fluoroolefins; vinyl acetate, vinyl propionate, vinyl butyrate,
Carboxylic acid vinyl esters such as vinyl pivalate, vinyl caproate, vinyl versatate and vinyl stearate; α such as ethylene, propylene and isobutene
-Olefins: 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2 -(Perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2
-Fluorine-containing (meth) acrylates such as (perfluorodecyl) ethyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2 -Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2
(Meth) acrylic acid esters such as-(n-propoxy) ethyl (meth) acrylate. These copolymerizable monomers may be used alone or 2
A mixture of two or more monomers may be used.

Among these copolymerizable monomers, alkyl vinyl ethers, cycloalkyl vinyl ethers, vinyl carboxylate and the like are used from the viewpoint of increasing the yield of the obtained reactive fluorine-containing copolymer [A]. It can be suitably used. Further, from the viewpoint of increasing the fluorine content in the obtained reactive fluorine-containing copolymer [A], methyl vinyl ether, ethyl vinyl ether,
n-propyl vinyl ether, isopropyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate,
Low molecular weight monomers such as vinyl pivalate can be suitably used. Further, when the proportion of hexafluoropropylene contained in the monomer mixture is small (for example,
(Less than 3% by weight), it is preferable to use a fluorine-containing copolymerizable monomer such as perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) as the copolymerizable monomer.

<Monomer Mixture> In the monomer mixture for obtaining the reactive fluorine-containing copolymer [A], hexafluoropropylene, a reactive group-containing monomer, and a copolymerizable monomer are used. The content ratio of “fluoropropylene:
Reactive group-containing monomer: copolymerizable monomer (molar ratio) "
Usually, it is 20 to 70: 1 to 20:10 to 70, preferably 25 to 55: 3 to 15:30 to 70.

When the content of hexafluoropropylene in the monomer mixture is less than 20% by mole, the fluorine content of the obtained reactive fluorine-containing copolymer [A] is at least 40% by weight. When the fluorine-containing copolymerizable monomer is used in excess to make the fluorine content 40% by weight or more, the resulting reactive fluorine-containing copolymer [A] may be converted into an organic solvent. The solubility is remarkably reduced, and the antireflection film formed by the prepared composition does not have sufficient hardness. On the other hand, the content ratio of hexafluoropropylene is 70 mol%.
Also when exceeding, the solubility of the reactive fluorine-containing copolymer [A] in the organic solvent is significantly reduced, and the antireflection film formed by the composition to be prepared has a transparency and Adhesion is poor.

When the content of the reactive group-containing monomer in the monomer mixture is less than 1 mol%, the antireflection film formed by the prepared composition has a sufficient hardness. Does not have On the other hand, when the content of the reactive group-containing monomer exceeds 20 mol%,
The prepared composition tends to gel and the storage stability is reduced, and the antireflection film formed by the composition becomes brittle.

<Polymerization of Monomer Mixture (Preparation of Reactive Fluorine-Containing Copolymer [A])> The polymerization of the monomer mixture can be carried out in the presence of a radical polymerization initiator. Any of a suspension polymerization method, a bulk polymerization method, and a solution polymerization method may be employed. In addition, the polymerization operation is also batch type,
It can be appropriately selected according to the purpose, such as a semi-continuous type or a continuous type.

Examples of the radical polymerization initiator used for polymerizing the monomer mixture include diacyl peroxides such as acetyl peroxide and benzoyl peroxide; methyl ethyl ketone peroxide;
Ketone peroxides such as cyclohexanone peroxide; hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide and cumene hydroperoxide; di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide and the like Dialkyl peroxides; tert
Peroxyesters such as -butylperoxyacetate and tert-butylperoxypivalate; azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile; ammonium persulfate, sodium persulfate and potassium persulfate; Persulfates and the like can be used, if necessary, sodium hydrogen sulfite, inorganic reducing agents such as sodium pyrosulfite, cobalt naphthenate,
An organic reducing agent such as dimethylaniline can also be used. Further, for example, perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, 2- (perfluorohexyl) ethyl iodide, perfluoroheptyl Iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2- (perfluorodecyl) ethyl iodide, heptafluoro-2
-Iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide, -(Perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide, 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyliod Dyed, 1H, H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-
An iodine-containing fluorine compound such as 1,2-diiodoethane, octafluoro-1,4-diiodobutane, dodecafluoro-1,6-diiodohexane, alone or as the organic peroxide, azo compound or persulfate; Can be used with

Among the reactive fluorine-containing copolymers [A] thus prepared, specific examples of those having a hydroxyl group as a reactive group include hexafluoropropylene / hydroxyalkyl vinyl ether / alkyl vinyl ether copolymer. Copolymer, hexafluoropropylene / hydroxyalkyl vinyl ether / perfluoro (alkyl vinyl ether) / alkyl vinyl ether copolymer, hexafluoropropylene / hydroxyalkyl vinyl ether / perfluoro (alkoxyalkyl) vinyl ether / alkyl vinyl ether copolymer, hexafluoropropylene / hydroxy Alkyl vinyl ether / (perfluoroalkyl) vinyl ether / alkyl vinyl ether copolymer, hexafluoropropylene / hydr Alkoxyalkyl vinyl ether / (perfluoroalkoxy alkyl) vinyl ether / alkyl vinyl ether copolymer, and the like.

The reactive fluorine-containing copolymer [A] prepared as described above contains a hydroxyl group, an epoxy group,
A fluorine-containing copolymer having at least one reactive group selected from an amino group and a carboxyl group. The reactive group contained in the reactive fluorine-containing copolymer [A] is usually one introduced by a reactive group-containing monomer.
In addition, a reactive fluorine-containing copolymer [A] was prepared using a carboxyl group-containing monomer as the reactive group-containing monomer, and the reactive fluorine-containing copolymer [A] and a diepoxy compound were prepared. , It is also possible to substitute a part or all of the reactive groups (carboxyl groups) of the reactive fluorine-containing copolymer [A] with epoxy groups. Further, a reactive fluorine-containing copolymer [A] was prepared using a hydroxyl group-containing monomer as the reactive group-containing monomer, and the reactive fluorine-containing copolymer [A] was prepared.
And a polyvalent carboxylic anhydride (eg, maleic anhydride, trimellitic anhydride) to react with a part of the reactive group (hydroxyl group) of the reactive fluorine-containing copolymer [A] or It is also possible to replace all with a carboxyl group.

<Fluorine Content of Reactive Fluorine-Containing Copolymer [A]> The reactive fluorine-containing copolymer [A] has a fluorine content of 40% by weight or more, preferably 45% by weight.
That is all. When the fluorine content is less than 40% by weight, the composition prepared has a high refractive index, and the antireflection film formed by the composition does not exhibit a sufficient antireflection effect. The fluorine content of the reactive fluorine-containing copolymer [A] can be controlled by adjusting the content of hexafluoropropylene or a fluorine-containing copolymerizable monomer in the monomer mixture.

<Intrinsic Viscosity of Reactive Fluorine-Containing Copolymer [A]> The reactive fluorine-containing copolymer [A] contains N, N
The intrinsic viscosity measured at 25 ° C. in dimethylacetamide is 0.05 to 2 dl / g, preferably 0.1 to 2 dl / g;
1.5 dl / g. This intrinsic viscosity is 0.05dl
If it is less than / g, the antireflection film formed by the composition to be prepared will not have sufficient mechanical strength. On the other hand, when the intrinsic viscosity exceeds 2 dl / g, the coatability of the composition to be prepared is reduced, and a thin film necessary for exhibiting an antireflection effect cannot be formed.

<Reactive silane coupling agent [B]> The reactive silane coupling agent [B] represented by the general formula (1) has a hydrolyzable silyl group and a reactive fluorine-containing copolymer. It is a silane coupling agent having a functional group X capable of reacting with the reactive group [A]. Here, the functional group X is an epoxy group, an amino group, an isocyanate group,
Among mercapto groups and (meth) acryloyl groups,
It is selected according to the type of the reactive group contained in the reactive fluorine-containing copolymer [A].

Preferred combinations of the reactive group of the reactive fluorine-containing copolymer [A] and the functional group X of the reactive silane coupling agent [B] are shown in Table 1 below. In addition, among the combinations shown in Table 1, [A] hydroxy group-
A combination with [B] an isocyanate group and a combination with [A] an epoxy group- [B] mercapto group are particularly preferable.

[0033]

[Table 1]

Specific examples of the reactive silane coupling agent [B] having an epoxy group as the functional group X include, for example, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, γ-
Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyldimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, γ- Glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) propyltriethoxysilane, β- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ-
(3,4-epoxycyclohexyl) propyltriethoxysilane, γ- (3,4-epoxycyclohexyl)
Propyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, glycidoxymethylmethyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxypropylphenyldimethoxysilane, γ-glycidoxy Propylmethyldiethoxysilane and the like can be mentioned. Also,
Commercial products of the reactive silane coupling agent [B] having an epoxy group include “SH6040” (manufactured by Dow Corning Toray Silicone Co., Ltd .: γ-glycidoxypropyltrimethoxysilane), and “AY43-026”. "
[Manufactured by the company: γ-glycidoxypropylmethyldimethoxysilane], “S-530” [manufactured by Chisso: β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane], "AZ-6137" [Nihon Unicar Co., Ltd.
Manufactured by: γ-glycidoxypropylmethyldimethoxysilane], “AZ-6165” [manufactured by the company: γ-glycidoxypropylmethyldiethoxysilane], “AZ-617”
3 "(manufactured by the company: γ-glycidoxypropyltriethoxysilane).

Specific examples of the reactive silane coupling agent [B] having an amino group as the functional group X include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyl Examples thereof include diethoxysilane and γ-aminopropylethyldimethoxysilane. Commercial products of the reactive silane coupling agent [B] having an amino group include "SH6020" and "SH6020P" [manufactured by Dow Corning Toray Silicone Co., Ltd .: γ- (2-
Aminoethyl) aminopropyltrimethoxysilane],
“SZ6023” [manufactured by the company: γ- (2-aminoethyl)
Aminopropylmethyldimethoxysilane], "SZ60
83 "(manufactured by the company: γ-anilinopropyltrimethoxysilane)," SH6026 "," SZ6050 "(manufactured by the company)," APS-E "(manufactured by Chisso Corporation: aminopropyltriethoxysilane)," A- 1102 "[manufactured by Nippon Unicar: Aminopropyltriethoxysilane],
“A-1170” (manufactured by the company: N, N-bis (γ-trimethoxysilylpropyl) amine), “Y-9669”
[Manufactured by the company: N- (γ-trimethoxysilylpropyl) aniline].

Specific examples of the reactive silane coupling agent [B] having an isocyanate group as the functional group X include γ-trimethoxysilylpropyl isocyanate.
γ-triethoxysilylpropyl isocyanate. Commercial products of the reactive silane coupling agent (B) having an isocyanate group include:
"Y-5187" (manufactured by Nippon Unicar: γ-trimethoxysilylpropyl isocyanate), "Y903
0 "(manufactured by the company: γ-triethoxysilylpropyl isocyanate).

Specific examples of the reactive silane coupling agent [B] having a mercapto group as the functional group X include:
γ-mercaptopropylmethyldimethoxysilane, γ-
Mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and the like can be mentioned.
Examples of commercially available products of the reactive silane coupling agent [B] having a mercapto group include “SH6062” (manufactured by Dow Corning Toray Silicone Co., Ltd .: γ-mercaptopropyltrimethoxysilane). it can.

Specific examples of the reactive silane coupling agent [B] having a (meth) acryloyl group as the functional group X include γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane,
γ-methacryloxypropylmethyldimethoxysilane,
γ-methacryloxypropyltriethoxysilane, γ-
Acryloxypropyltriethoxysilane and the like can be mentioned. As a commercially available product of the reactive silane coupling agent [B] having a (meth) acryloyl group, “SZ-6030” [manufactured by Dow Corning Toray Silicone Co., Ltd .: γ-methacryloxypropyltrimethoxysilane] ], “AY-43-060” [manufactured by the company: γ-
(Methacryloxypropylmethyldimethoxysilane),
“Y-9910” (manufactured by Nippon Unicar Co., Ltd .: γ-methacryloxypropylmethyldimethoxysilane), “Y-9”
936 "(manufactured by the company: γ-methacryloxypropyltriethoxysilane).

<Modified Fluorine-Containing Copolymer [I]> The modified fluorine-containing copolymer [I] contained in the antireflection film-forming composition of the present invention is a reactive fluorine-containing copolymer [A].
And a reactive silane coupling agent [B]. The types of the reactive fluorine-containing copolymer [A] and the reactive silane coupling agent [B] to be subjected to the reaction for obtaining the modified fluorine-containing copolymer [I] include a reactive group having the former, There is no particular limitation as long as the chemical reaction with the functional group X of the latter is possible, but it is preferable to select the combination so as to satisfy the combinations shown in Table 1 above.

When the reactive group of the reactive fluorine-containing copolymer [A] and the functional group X of the reactive silane coupling agent [B] are, for example, groups each having active hydrogen, Alternatively, the reactive group and the functional group X can be bonded via a diisocyanate compound. Such diisocyanate compounds include, for example, toluene diisocyanate, methylene bisphenylene diisocyanate, hydrogenated xylene diisocyanate,
Examples include isophorone diisocyanate and hexamethylene diisocyanate.

The reactive fluorine-containing copolymer [A] subjected to the reaction for obtaining the modified fluorine-containing copolymer [I]
And the ratio of the reactive silane coupling agent [B] is such that the reactive silane coupling agent [B] is 1 to 50 parts by weight based on 100 parts by weight of the reactive fluorine-containing copolymer [A], Preferably, it is 5 to 40 parts by weight. When the amount of the reactive silane coupling agent [B] is less than 1 part by weight, the antireflection film formed by the composition to be prepared does not have sufficient abrasion resistance, and If the amount exceeds 50 parts by weight, the refractive index of the formed anti-reflection film becomes high, so that a good anti-reflection effect cannot be exhibited.

The reactive fluorine-containing copolymer [A]
And the method of mixing the reactive silane coupling agent [B] with the reactive silane coupling agent [B], for example, a method of adding and mixing them in an organic solvent, a method of mixing with various mixers, rolls, kneaders and the like are particularly limited. Not something.

Further, the reactive fluorine-containing copolymer [A]
And the reactive silane coupling agent [B], for example, by adding them to an organic solvent, and then setting the temperature in the range of freezing point to boiling point of these components, preferably 0 to 100 ° C. Under the conditions, a method of stirring for 30 minutes to 72 hours can be mentioned. The reaction time can be shortened by adding a reaction accelerator to this reaction system. Here, examples of the reaction accelerator include organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and octyltin trilaurate, and Lewis acids represented by zinc compounds such as zinc dilaurate, triethylamine, tributylamine, and tricyclohexylamine. Lewis bases such as tertiary amines can be used. The addition amount of the reaction accelerator is usually 0.001 to 1.0 part by weight based on 100 parts by weight of the reactive fluorine-containing copolymer [A].

<Modified fluorine-containing copolymer [II]> The modified fluorine-containing copolymer [I] 10 obtained as described above
20 to 80 parts by weight of the alkoxysilane represented by the general formula (2) and 0 to 10 parts by weight of colloidal silica
80 parts by weight, and water was added to the mixture to effect hydrolysis (hydrolysis of alkoxy groups) and condensation reaction (formation of a siloxane bond), thereby obtaining a fluorine-containing copolymer modified with polysiloxane. As a result, a modified fluorine-containing copolymer [II], which is a union, is obtained.

<Alkoxysilanes> The general formula (2)
Alkoxysilanes represented in is at least one alkyl alkoxy silane substituent R ² is the alkyl, and the substituent R ² is a case of aryl groups arylalkoxy silane. Among the alkoxysilanes, specific examples of the alkylalkoxysilane include:
For example, tetramethoxysilane, tetraethoxysilane,
Tetraalkoxysilanes such as tetraisopropoxysilane, tetra-n-butoxysilane and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyl Alkyltrialkoxysilanes such as triethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane and dibutyldimethoxysilane; and arylalkoxysilanes among the alkoxysilanes. Specific examples include aryltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; and diaryldialkoxysilanes such as diphenyldimethoxysilane. And the like can be exemplified dialkoxy silanes. These can be used alone or in combination of two or more.

Commercially available alkoxysilanes include "SS-1900" (manufactured by Dow Corning Silicone Toray Co., Ltd .: tetraethoxysilane), and "SS-1900".
670 "(manufactured by the company: methyltrimethoxysilane)," S
“S-1650” (manufactured by the company: methyltriethoxysilane), “SS-1840” (manufactured by the company: phenyltrimethoxysilane), “SS-1830” (manufactured by the company: phenyltriethoxysilane), “SS-1130” ( Made by the company:
n-butyltrimethoxysilane), "SS-1260"
(Manufactured by the company: dimethyldimethoxysilane), "SS-12
50 "(manufactured by the company: dimethyldiethoxysilane)," SS
-1300 "(manufactured by the company: diphenyldimethoxysilane)
Can be mentioned.

The amount of the alkoxysilane to be used for obtaining the modified fluorine-containing copolymer [II] is 20 to 80 parts by weight per 100 parts by weight of the modified fluorine-containing copolymer [I]. When the amount is less than 20 parts by weight, sufficient coating film hardness cannot be obtained, while when the amount exceeds 80 parts by weight, the refractive index of the prepared composition is high, The antireflection film formed by the composition does not exhibit a sufficient antireflection effect.

<Colloidal Silica> Colloidal silica, which is optionally added to a reaction system for obtaining the modified fluorine-containing copolymer [II], has an average particle size of 0.001 to 0.001.
It is preferably 0.100 μm, more preferably 0.001 to 0.050 μm. When the average particle size of the colloidal silica exceeds 0.100 μm, the transparency of the antireflection film formed by the prepared composition tends to decrease.

The amount of the colloidal silica to be added is 0 to 80 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the modified fluorine-containing copolymer [I]. If the amount of the colloidal silica exceeds 80 parts by weight, the transparency of the antireflection film formed by the composition to be prepared tends to decrease.

The colloidal silica is usually used in a state of being dispersed in a dispersion medium. Here, examples of the dispersion medium include water and an organic solvent. 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;
Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; ethers such as tetrahydrofuran and 1,4-dioxane; Among them, alcohols and ketones are preferred. These organic solvents can be used alone or
More than one kind can be mixed and used as a dispersion medium.

Commercially available water-dispersed colloidal silica includes "ST-UP", "ST-O-UP", and "S-UP".
T-20 "," ST-40 "," ST-C "," ST-
N "," ST-O "," ST-50 "," ST-OL "
[The above is manufactured by Nissan Chemical Industries, Ltd.]. Commercially available colloidal silica of the organic solvent dispersion system includes “methanol silica sol” and “IPA-S”.
T "," MEK-ST "," NBA-ST "," XBA
-ST "and" DMAC-ST ".

<Composition for forming anti-reflective film> As a method for producing a composition containing the modified fluorine-containing copolymer [II] (the composition for forming an anti-reflective film of the present invention), a modified fluorine-containing copolymer is used. In a mixture containing [I], the alkoxysilanes represented by the general formula (2), and optionally colloidal silica, all the alkoxy groups 1 present in the mixture are added.
Usually, 0.3 to 1.0 mol, preferably 0.1 to 1.0 mol per mol.
The modified fluorine-containing copolymer [I] and the alkoxysilanes are hydrolyzed by adding 4 to 0.6 mol of water, and the resulting silanol is subjected to a condensation reaction to form a polysiloxane.

The procedure for the hydrolysis and condensation reaction is as follows: the reaction system is heated to a temperature ranging from 0 ° C. to the boiling point of the main solvent, preferably from 30 to 120 ° C., in dry air at normal pressure for 30 minutes to 30 minutes. A method of stirring for 72 hours can be mentioned. The reaction time can be shortened by adding a reaction accelerator consisting of an acid or a base to the reaction system. Here, examples of the acid that can be used as the reaction accelerator include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid, and toluenesulfonic acid. Further, as a base that can be used as a reaction accelerator, sodium hydroxide, potassium hydroxide,
Inorganic bases such as ammonia; tetramethylammonium hydroxides; ammonium hydroxides such as tetrabutylammonium hydroxide; amines such as triethylamine and tributylamine; triisopropoxyaluminum, tributoxyaluminum, tetrabutoxyzirconium and tetrabutoxy Metal alkoxides such as titanium; and complexes of the metal alkoxides with chelating reagents such as ethyl acetoacetate and acetylacetone. Among these,
Metal alkoxides and complexed products of metal alkoxides are preferred. The amount of the reaction accelerator to be added is generally 0.01 to 10 mol%, preferably 0.1 to 1 mol%, based on all the alkoxy groups present in the mixture. If the addition amount is less than 0.01 mol%, a sufficient reaction promoting effect cannot be obtained, while if it exceeds 10 mol%, the storage stability of the obtained composition may decrease.

In order to extend the pot life of the composition containing the reaction accelerator, the composition is neutralized by adding a base or an acid, or is stabilized by adding a chelating agent to form a complex. Can also. For example, when a metal alkoxide or a complex of a metal alkoxide is used as a reaction accelerator, acetylacetone, triethanolamine, and diethanolamine are preferably used as a stabilizer.

The composition for forming an antireflection film of the present invention may contain components other than the modified fluorine-containing copolymer [I], the modified fluorine-containing copolymer [II], and colloidal silica. Such components include organic solvents, antioxidants, ultraviolet absorbers, leveling agents, defoamers, slip agents, and ultraviolet absorbers.

Specific examples of the organic solvent constituting the composition of the present invention include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; methanol, ethanol, and the like.
Alcohols such as isopropyl alcohol and butanol; hydrocarbons such as toluene and xylene; and ethers such as tetrahydrofuran, 1,4-dioxane and carbitol. Examples of antioxidants include “Irganox-1010” and “-103.
5 "," -1076 "and" -1222 "(all manufactured by Ciba-Geigy Corporation). In addition, as a UV absorber, "TINUVIN-P234",
"-320", "-326", "-327",
"-328", "-213" and "-329" (all manufactured by Ciba-Geigy).

Examples of the substrate to which the composition of the present invention is applied include transparent substrates made of plastic, glass, ceramics, etc. Among them, polycarbonate, poly (meth) acrylate, polyarylate, polyolefin And a transparent resin such as polyester. The refractive index of such a transparent substrate is preferably 1.40 or more, more preferably 1.50 or more, from the viewpoint of exhibiting a sufficient antireflection effect.

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

The coating film of the composition of the present invention coated on the substrate surface is dried at a temperature not higher than the deformation temperature of the substrate. Here, the drying temperature is usually 0 to 300
° 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, as a specific example of the curing accelerator,
For example, organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and octyltin trislaurate; metal alkoxides such as triisoproxyaluminum and tetrabutoxyzirconium; partially complexed ethyl acetoacetate or acetylacetone of the metal alkoxide Aminosilanes such as aminopropyltriethoxysilane and aminoethylaminopropyltrimethoxysilane.

The thickness of the cured film (anti-reflection film) formed on the surface of the substrate by the composition of the present invention is set in consideration of the refractive index of the substrate so as to obtain a good reaction prevention effect. The thickness is usually 0.02 to 1 μm, and preferably 0.05 to 0.50 μm.

The refractive index of the antireflection 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 transparent resin substrate. , More preferably 1.40 or less. In this specification, the “refractive index”
It refers to the value (measuring temperature 20 ° C.) measured by Abbe refractometer using sodium D line as a light source.

[0062]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following, “parts” indicates “parts by weight”.

[Preparation Example 1] After a stainless steel autoclave (1.5 liter internal volume) equipped with an electromagnetic stirrer was sufficiently replaced with nitrogen gas, 500 g of ethyl acetate (solvent) and ethyl vinyl ether (Ethyl vinyl ether) were placed in the autoclave. 57.2 g of a copolymerizable monomer), 10.2 g of hydroxybutyl vinyl ether (a monomer containing a reactive group), and 3.0 g of lauroyl peroxide (a radical polymerization initiator) were charged, and the solution in the autoclave was charged. After cooling to −50 ° C. with dry ice-methanol, oxygen in the system was removed again with nitrogen gas. Next, 146.0 g of hexafluoropropylene was added to the solution in the autoclave to prepare a monomer solution, and the temperature of the monomer solution was started to rise. The temperature of the monomer solution in the autoclave is 60 ° C
When the pressure in the autoclave reaches 5.3
kgf / cm ² . By stirring while maintaining the temperature of the reaction system at 60 ° C., the polymerization reaction was continued for 20 hours. After 20 hours, when the pressure in the autoclave dropped to 1.5 kgf / cm ² , the autoclave was cooled with water to stop the polymerization reaction. After cooling the reaction product solution to room temperature, the unreacted monomer is removed,
The autoclave was opened, and a polymer solution having a solid concentration of 28.1% was taken out. The obtained polymer solution was poured into a large amount of methanol to precipitate a polymer, and the precipitate was washed with methanol and dried at 50 ° C. under vacuum. As a result, 193 g of a reactive fluorine-containing copolymer [A] having a hydroxyl group (hereinafter referred to as “copolymer [A-1]”) was obtained.

The copolymer [A-
1), 2 in N, N-dimethylacetamide
Intrinsic viscosity (η) at 5 ° C, DSC glass
Transition temperature (Tg) for alizarin complexon method
Acetylation method using acetic anhydride
The hydroxyl value and the refractive index were measured. Also,
¹H-NMR and¹³NMR analysis by C-NMR
Results, elemental analysis results, fluorine content, hydroxyl value
Of the monomer constituting the reactive fluorine-containing copolymer [A]
The ratio (molar fraction) was determined. Table 2 shows these results.
You.

[Preparation Examples 2 to 4] In the same manner as in Preparation Example 1 except that the composition of the monomer solution (the type and amount of the monomer) was changed in accordance with the formulation shown in Table 2, the reactive fluorine-containing solution was used. A copolymer [A] (copolymer [A-2] to copolymer [A-4]) was obtained. For each of the obtained copolymers [A-2] to [A-4], the intrinsic viscosity (η), the glass transition temperature (Tg), the fluorine content, and the hydroxyl value were obtained in the same manner as in Preparation Example 1. And the refractive index were measured to determine the composition ratio (molar fraction) of the constituent monomers. Table 2 also shows these results.

[0066]

[Table 2]

Example 1 According to the formulation shown in Table 3, the copolymer having a hydroxy group [A-
1] 100 parts and γ-triethoxysilylpropyl isocyanate (reactive silane coupling agent [B]) 10
Parts, 440 parts of methyl ethyl ketone, and 0.01 part of dibutyltin dilaurate at 20 ° C. in a nitrogen gas atmosphere.
And the mixture is stirred for 12 hours to obtain the copolymer [A-1].
And γ-triethoxysilylpropyl isocyanate. By adding excess dibutylamine to a part of the reaction product solution thus obtained and titrating unreacted dibutylamine with 0.1N hydrochloric acid, the concentration of the isocyanate groups remaining in the reaction product solution is reduced. The measurement confirmed that the isocyanate groups had been consumed. Further, a part of the reaction solution was coated on a NaCl plate, and dried under a nitrogen atmosphere to form a film. When the film was subjected to infrared spectrum analysis, characteristic peaks derived from isocyanate groups were detected. Did not. As a result, the copolymer [A-1]
And γ-triethoxysilylpropyl isocyanate were completely reacted to form a modified fluorine-containing copolymer [I]. To 100 parts of the reaction product solution obtained as described above, 5 parts of an octyltin trislaurate xylene solution (concentration: 10% by weight) was added to prepare a composition (1) of the present invention.

Example 2 According to the formulation shown in Table 3, the copolymer having a hydroxy group [A-
2] 100 parts, 20 parts of γ-triethoxysilylpropyl isocyanate, 480 parts of methyl ethyl ketone,
By stirring 0.01 part of dibutyltin dilaurate at 20 ° C. for 12 hours under a nitrogen gas atmosphere, the copolymer [A-2] is reacted with γ-triethoxysilylpropyl isocyanate to contain modified fluorine. A reaction product solution containing the copolymer [I] was prepared. Next, to 100 parts of the reaction product solution, 5 parts of a xylene solution of octyltin trislaurate (concentration: 10% by weight) was added,
Composition (2) of the present invention was prepared.

Example 3 According to the formulation shown in Table 3, a copolymer having a hydroxy group prepared in Preparation Example 2 [A-
2] 100 parts, 20 parts of γ-triethoxysilylpropyl isocyanate, 750 parts of methyl ethyl ketone,
By stirring 0.01 part of dibutyltin dilaurate at 20 ° C. for 12 hours under a nitrogen gas atmosphere, the copolymer [A-2] is reacted with γ-triethoxysilylpropyl isocyanate to contain modified fluorine. A reaction product solution containing the copolymer [I] was prepared. To the solution thus obtained is added methyltrimethoxysilane 240
, 48 parts of ion-exchanged water and 0.5 parts of 0.1N hydrochloric acid, and the system is stirred at 60 ° C. for 6 hours to cause a hydrolysis and condensation reaction, thereby obtaining a modified fluorine-containing copolymer. A reaction product solution containing [II] was prepared. Next, 5 parts of an octyltin trislaurate xylene solution (concentration: 10% by weight) was added to 100 parts of the reaction product solution to prepare a composition (3) of the present invention.

Example 4 According to the formulation shown in Table 3, the copolymer having an epoxy group prepared in Preparation Example 3 [A-
3] 100 parts, 33 parts of γ-mercaptopropyltrimethoxysilane, 500 parts of methyl ethyl ketone, and 0.1 part of triethylamine were placed in a nitrogen gas atmosphere at 60 ° C.
And the mixture was stirred for 12 hours to obtain a copolymer [A-3].
And γ-mercaptopropyltrimethoxysilane were reacted to prepare a reaction product solution containing the modified fluorine-containing copolymer [I]. In the solution thus obtained,
133 parts of methyltrimethoxysilane, 67 parts of colloidal silica “MEK-ST” dispersed in methyl ethyl ketone (manufactured by Nissan Chemical Co., Ltd., solid content 30%), 24 parts of ion-exchanged water, 0.1N Hydrochloric acid and 0.2 part of hydrochloric acid were added, and the system was stirred at 60 ° C. for 6 hours to cause a hydrolysis and condensation reaction to prepare a reaction product solution containing the modified fluorine-containing copolymer [II]. Next, to 100 parts of the reaction product solution, 5 parts of a octyltin trislaurate xylene solution (concentration: 10% by weight) was added to prepare a composition (4) of the present invention.

Example 5 According to the formulation shown in Table 3, 100 parts of the copolymer [A-4] having a hydroxy group and a carboxyl group prepared in Preparation Example 4, 17 parts of γ-aminopropyltriethoxysilane , Methyl ethyl ketone 1
200 parts of the modified fluorine-containing copolymer [I] by reacting the copolymer [A-4] with γ-aminopropyltriethoxysilane by stirring for 12 hours at 60 ° C. in a nitrogen gas atmosphere. ] Was prepared. To the solution thus obtained, 554 parts of methyltrimethoxysilane, 110 parts of ion-exchanged water, and 18 parts of aluminum tris (ethyl acetoacetate) (manufactured by Kawaken Fine Chemical Co., Ltd.) were added. At 60 ° C for 6
The mixture was stirred for a period of time to carry out hydrolysis and condensation reactions, and further, 16 parts of acetylacetone was added to prepare a reaction product solution containing the modified fluorine-containing copolymer [II]. Next, 100 parts of the reaction product solution was added to a xylene solution of octyltin trislaurate (concentration: 10% by weight).
5 parts were added to prepare a composition (5) of the present invention.

Comparative Example 1 According to the formulation shown in Table 3, the copolymer having a hydroxy group [A-
1] 100 parts and 400 parts of methyl ethyl ketone were mixed, and to 100 parts of the obtained mixture, 5 parts of a octyltin trislaurate xylene solution (concentration: 10% by weight) was added, and a composition for comparison (C -1) was prepared.

Comparative Example 2 According to the formulation shown in Table 3, the copolymer having a hydroxy group prepared in Preparation Example 2 [A-
2] 100 parts, 750 parts of methyl ethyl ketone, 240 parts of methyltrimethoxysilane, 48 parts of ion-exchanged water, and 0.5 part of 0.1N hydrochloric acid in a nitrogen gas atmosphere for 6 hours.
Stirred at 0 ° C. for 12 hours. Next, 5 parts of an octyltin trislaurate xylene solution (concentration: 10% by weight) was added to 100 parts of the obtained reaction product solution to prepare a comparative composition (C-2).

[0074]

[Table 3]

[Formation of Reaction Prevention Film] The compositions (1) to (5) of the present invention obtained in Examples 1 to 5 and the comparative composition (C- 1) to (C
Each of -2) was applied to the surface of a transparent substrate (2 mm thick) made of polycarbonate by a dipping method, and the coating film was dried at 100 ° C. for 30 minutes using a hot-air circulation oven to obtain a film thickness of 0.1 mm. A cured film (antireflection film) of 1 μm was formed.

[Evaluation of Anti-Reaction Film] For each of the anti-reflection films formed on the transparent substrate surface as described above, the pencil hardness, the reflectance and the refractive index were measured, and the transparency and adhesion to the substrate were measured. , Weather resistance and antireflection properties were evaluated. The results are shown in Table 4 below. In addition, the measuring method and the evaluation method are as follows.

(1) Pencil hardness: Measured according to JIS K5400. (2) Reflectivity: A black paint is applied to the back surface of the transparent substrate (the surface opposite to the surface on which the antireflection film is formed) to prepare a test piece, and the test piece is subjected to visible light (400 to 700 nm).
The reflectance was measured with a spectrophotometer using a 60 mmφ integrating sphere. The reflectance of the transparent substrate (polycarbonate) on which the antireflection film was not formed was 6.2%. (3) Refractive index: A film having a thickness of 30 to 50 μm was prepared, and this film was measured with an Abbe refractometer (measuring temperature: 20 ° C.). (4) Transparency: "O" indicates that the entire surface of the antireflection film has uniform transparency, and "X" indicates that a portion having poor transparency is observed. (5) Adhesion: 100 squares were made with a cross cut of 1 mm width, the number of film pieces remaining on the substrate was measured by a peeling test using an adhesive tape, and all the film pieces remained. Is “○”, the number of remaining film pieces is 50 to 99, “△”, and the number of remaining film pieces is less than 50, “x”. (6) Weather resistance: Each of the substrates on which the antireflection film was formed was subjected to a weather resistance acceleration test using a fade meter (manufactured by Suga Test Instruments Co., Ltd.). The gloss retention rate (%) after 1000 hours was measured, and the case where the gloss was 100 to 80% was “○”, the case where it was 79 to 40% was “△”, and the case where it was 39% or less was “X”. did. (7) Anti-reflective property: polycarbonate plate (2 mm thick)
An anti-reflection film (0.12 μm thick) is formed on a part of the surface of, and the anti-reflection effect is visually determined while comparing with a part where the anti-reflection film is not formed. The case where it was recognized that sufficient antireflection properties were exhibited was rated as “○”, and the case where no remarkable difference was observed between the portion where the antireflection film was formed and the portion where the antireflection film was not formed was rated “x”.

[0078]

[Table 4]

[0079]

The antireflection film formed by the composition of the present invention has a low refractive index, can exhibit an excellent antireflection effect, and has high hardness and excellent scratch resistance. Further, the antireflection film is excellent in transparency, adhesion to a substrate, and weather resistance.

Claims (2)

[Claims] [A] hexafluoropropylene 20 to
70 mol%, 1 to 20 mol% of a monomer containing at least one reactive group selected from a hydroxyl group, an epoxy group, an amino group and a carboxyl group, and 10 to 70 mol of a monomer copolymerizable therewith % By polymerization of a monomer mixture having a fluorine content of 40%.
% By weight or more based on 100 parts by weight of a reactive group-containing fluorine-containing copolymer having an intrinsic viscosity of 0.05 to 2 dl / g measured in N, N-dimethylacetamide at 25 ° C. It contains a fluorine-containing copolymer modified by a silane coupling agent, obtained by reacting 1 to 50 parts by weight of a silane coupling agent having a hydrolyzable silyl group represented by the following general formula (1). A composition for forming an antireflection film, comprising: Embedded image [In the formula, R ¹ represents an alkyl group, an aryl group or an alkoxyalkyl group, and the three groups represented by (OR ¹ ) may be the same or different. X
Is selected from an epoxy group, an amino group, an isocyanate group, a mercapto group and a (meth) acryloyl group,
[A] A functional group capable of reacting with the reactive group of the fluorine-containing copolymer having a reactive group. ] 2. An alkoxysilane represented by the following general formula (2) based on 100 parts by weight of the fluorine-containing copolymer modified with the silane coupling agent according to claim 1.
0 parts by weight and 0 to 80 parts by weight of colloidal silica are added and mixed, and the mixture contains a fluorine-containing copolymer modified with polysiloxane, which is obtained by adding water to the mixture and subjecting it to hydrolysis and condensation. A composition for forming an antireflection film, comprising: Embedded image [Wherein, R ² represents an alkyl group or an aryl group;
When there are a plurality of groups represented by R ² ,
They may be the same or different. R ³ represents a hydrogen atom or an alkyl group, and when there are a plurality of groups represented by R ^3, they may be the same or different. Here, at least one group represented by R ³ is an alkyl group. m is an integer from 0 to 3. ]