JPH08100136A - Fluorine-based coating material - Google Patents

Abstract

PURPOSE: To obtain the subject coating material, containing a specific copolymer containing fluorine and a polymerizable compound in a specified proportion, excellent in adhesion to a substrate, transparency, scuff resistance, etc., and useful for coating capable of forming an antireflection film. CONSTITUTION: This coating material is obtained by dissolving (A) 100 pts.wt. copolymer, containing fluorine and prepared by copolymerizing a monomer composition containing (i) 30-90wt.% vinylidene fluoride and (ii) 5-50wt.% hexafluoropropylene and having 60-70wt.% fluorine content and (B) 30-150 pts.wt., preferably 35-100 pts.wt. polymerizable compound containing an ethylenically unsaturated group [dipentaerythritol hexa(meth)acrylate is especially preferred] in (C) a solvent (e.g. acetone or methyl formate) and is curable by irradiation of active energy rays or heating. Furthermore, the component (C) is preferably used in an amount of 200-10000 pts.wt. based on 100 pts.wt. total amount of the components (A) and (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-based paint, and more particularly to a fluorine-based paint which is cured by irradiation with active energy rays or heating.

[0002]

2. Description of the Related Art At present, with respect to optical elements such as optical lenses and optical films, in order to prevent reflection of light on the surface, the optical element is used as a base material and lithium fluoride or fluoride is applied to the surface. It is known that a thin film made of an inorganic compound having a low refractive index such as magnesium is provided as an antireflection film, and it has been put to practical use. However, the antireflection film made of these inorganic compounds has low mechanical properties such as strength and abrasion resistance, and is easily scratched by an external physical stimulus or easily peeled from the base material. There is a drawback that. Further, the formation of the antireflection film needs to be performed by a vacuum vapor deposition method, but the vacuum vapor deposition method has a drawback that a uniform thin film cannot be formed in a wide area of a large base material. .

In order to solve these drawbacks, an antireflection film made of an organic polymer compound having a refractive index lower than that of the optical element serving as a base material is formed to impart an antireflection effect to the optical element. Attempts are being made. But,
Organic polymer compounds conventionally known for forming a useful antireflection film have insufficient adhesion to a substrate, low transparency of the formed thin film, and mechanical properties of the formed thin film. Since the strength is low, the mechanical properties such as scratch resistance of the surface of the base material cannot be made sufficiently good.

[0004]

The present invention, when applied to the surface of a substrate, has excellent adhesion to the substrate,
It is possible to form a thin film that has high transparency and low refractive index, and also has high mechanical strength and sufficiently improves mechanical properties such as scratch resistance of the surface of the substrate, and thus forms an antireflection film. It is an object of the present invention to provide a fluorine-based coating material which is suitable as a material for the above and which is cured by irradiation with active energy rays or heating.

[0005]

The fluorine-based coating composition of the present invention comprises (A) a monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene. Fluorine content is 60
100 parts by weight of a fluorine-containing copolymer of 70 to 70% by weight and (B) a polymerizable compound 3 having an ethylenically unsaturated group
It is characterized in that 0 to 150 parts by weight is dissolved in the solvent (C) and is cured by irradiation with active energy rays or heating.

[0006]

The fluorine-containing coating material of the present invention contains a specific fluorine-containing copolymer (A) and a specific polymerizable compound (B) in a specific ratio, so that it can be used as a base material even though it is an organic polymer compound. To form a thin film that has excellent adhesion to, has high transparency and a low refractive index, and has a large mechanical strength that sufficiently improves mechanical properties such as scratch resistance of the surface of the base material. By containing fluorine,
It is suitable as a paint for forming an antireflection film.

The present invention will be specifically described below.
The fluorine-based coating material of the present invention comprises at least a specific fluorine-containing copolymer (A) and a polymerizable compound (B) having an ethylenically unsaturated group, dissolved in a common solvent in a specific ratio. It has a property of being cured by irradiation with active energy rays or heating.

The fluorine-containing copolymer (A) used in the present invention is a copolymer obtained by copolymerizing a monomer composition containing vinylidene fluoride and hexafluoropropylene. The ratio of each component in is 30 to 90 for vinylidene fluoride.
%, Preferably 40 to 80% by weight, particularly preferably 40 to 70% by weight, and hexafluoropropylene at 5 to 50% by weight, preferably 10 to 50% by weight, particularly preferably 15 to 45% by weight. is there. This monomer composition further contains tetrafluoroethylene in an amount of 0 to 40% by weight, preferably 0 to 35% by weight, particularly preferably 10 to
It may contain 30% by weight.

Further, the monomer composition for obtaining the fluorine-containing copolymer (A) contains, for example, 2 or more other copolymerization components within a range not impairing the objects and effects of the present invention.
It may be contained in an amount of 0% by weight or less, preferably 10% by weight or less. Here, specific examples of the other copolymerization component include, for example, fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, and 1,2.
-Dichloro-1,2-difluoroethylene, 2-bromo-3,3,3-trifluoroethylene, 3-bromo-
3,3-difluoropropylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3
Examples thereof include polymerizable monomers containing a fluorine atom, such as trifluoropropylene and α-trifluoromethacrylic acid.

The fluorine-containing copolymer (A) obtained from such a monomer composition has a fluorine content of 60.
It is necessary to be 70 to 70% by weight, and the preferable fluorine content is 62 to 70% by weight, particularly preferably 64 to 6%.
8% by weight.

The fluorine-containing copolymer (A) has good solubility in the below-mentioned solvent (C) particularly when the fluorine-containing ratio is within the above specified range. Also,
By containing such a fluorine-containing copolymer (A) as a component, the fluorine-based coating material of the present invention has excellent adhesion to various base materials, high transparency and low refractive index. Since it forms a thin film having sufficient mechanical strength, it can have sufficiently high mechanical properties such as scratch resistance of the surface of the base material, and is very suitable as a coating for forming an antireflection film. is there.

The fluorine-containing copolymer (A) has a molecular weight of 5,000 to 20 in terms of polystyrene equivalent number average molecular weight.
It is preferably 0000, and particularly preferably 10,000 to 100,000. By using the fluorine-containing copolymer (A) having a molecular weight of such a size, the viscosity of the resulting fluorine-based coating material becomes a suitable size, and therefore a fluorine-based coating material having surely suitable coating properties is obtained. Obtainable.
Further, the fluorine-containing copolymer (A) itself has a refractive index of 1.45 or less, particularly 1.42 or less, and further 1.40.
The following are preferable. When the fluorine-containing copolymer (A) having a refractive index of more than 1.45 is used, the thin film formed by the obtained fluorine-based paint has a small antireflection effect, and a sufficiently good antireflection film is obtained. There are cases where it cannot be formed.

The polymerizable compound (B) used in the present invention is heated by irradiation with an active energy ray in the presence or absence of a photopolymerization initiator or in the presence of a thermal polymerization initiator. As a result, it is a compound having an ethylenically unsaturated group which causes addition polymerization. Specific examples of such a polymerizable compound (B) include the following.

(A) Styrene, α-methylstyrene, o
-Methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, divinylbenzene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1
-Diphenylstyrene, p-methoxystyrene, N, N
-Dimethyl-p-aminostyrene, N, N-diethyl-
Aromatic vinyl compounds such as p-aminostyrene and vinylpyridine; (b) (meth) acrylonitrile, α-chloro (meth)
Acrylonitrile, α-chloromethyl (meth) acrylonitrile, α-methoxy (meth) acrylonitrile, α
Unsaturated nitriles such as ethoxy (meth) acrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumaric acid dinitrile;

(C) Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, sec-butyl (meth) acrylate, tert
-Butyl (meth) acrylate, n-amyl (meth) acrylate, n-octyl (meth) acrylate, 2-
Ethylhexyl- (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate,
(Meth) acrylic acid esters such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and 2- (n-propoxy) ethyl (meth) acrylate;

(D) 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-
Fluorine-containing (meth) acrylic acid esters such as (perfluorooctyl) ethyl (meth) acrylate and 2- (perfluorodecyl) ethyl (meth) acrylate; (e) Methyl crotonate, ethyl crotonate, propyl crotonate, Butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, etc. Saturated carboxylic acid esters;

(F) Hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate; (g) polyethylene glycol, (Meth) acrylic acid monoesters of polyalkylene glycol such as polypropylene glycol; (h) Cyano group-containing (meth) such as cyanoethyl (meth) acrylate and cyanopropyl (meth) acrylate
Acrylic esters;

(I) Aryloxyalkyl esters of (meth) acrylic acid such as 2-phenoxyethyl (meth) acrylate, 2-phenoxypropyl (meth) acrylate and 3-phenoxypropyl (meth) acrylate; (j) Methoxypolyethylene (Meth) acrylic acid monoesters of alkoxy polyalkylene glycols such as glycol, ethoxy polyethylene glycol, methoxy polypropylene glycol and ethoxy polypropylene glycol; (k) aryloxy polyalkylene glycol (meth) such as phenoxy polyethylene glycol and phenoxy polypropylene glycol Acrylic acid monoesters;

(L) (Meth) acrylic acid diesters of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol; (m) polyethylene glycol A (meth) acrylic acid diester of polyalkylene glycol such as polypropylene glycol (having 2 to 23 alkylene glycol units), hydroxypolybutadiene having both terminals,
(Meth) acrylic acid diesters of polymers having hydroxyl groups at both terminals such as hydroxypolyisoprene at both terminals, hydroxybutadiene-acrylonitrile copolymer at both terminals, and hydroxypolycaprolactone at both terminals;

(N) Glycerin, 1,2,4-butanetriol, trimethylolalkane (alkane has 1 to 3 carbon atoms), tetramethylolalkane (alkane has 1 to 3 carbon atoms, for example). (), And (meth) acrylic acid oligoesters such as (meth) acrylic acid diesters, (meth) acrylic acid triesters or (meth) acrylic acid tetraesters of polyhydric alcohols having 3 or more valences such as pentaerythritol; ) (Meth) acrylic acid oligoesters such as (meth) acrylic acid triesters or (meth) acrylic acid tetraesters of polyalkylene glycol adducts of trihydric or higher polyhydric alcohols;

(P) 1,4-cyclohexanediol,
(Meth) acrylic acid oligoesters of cyclic polyhydric alcohols such as 1,4-benzenediol and 1,4-dihydroxyethylbenzene; (q) polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate , (Meth) acrylic acid oligoester prepolymers such as alkyd resin (meth) acrylate, silicone resin (meth) acrylate, spirane resin (meth) acrylate;

(R) (meth) acrylic acid, crotonic acid,
Cinnamic acid, itaconic acid, itaconic anhydride, maleic acid,
Unsaturated carboxylic acids such as maleic anhydride, fumaric acid, citraconic acid and mesaconic acid; (s) monomethyl esters of unsaturated polycarboxylic acids such as itaconic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid, monoethyl Free carboxyl group-containing esters such as esters, monopropyl esters, monobutyl esters, monohexyl esters, monooctyl esters; (t) unsaturated polycarboxylic acids such as itaconic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid Polyvalent esters of acid such as dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihexyl ester, dioctyl ester;

(U) (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide,
N, N'-methylenebis (meth) acrylamide, N,
N'-ethylenebis (meth) acrylamide, N, N '
-Unsaturated amides such as hexamethylenebis (meth) acrylamide, crotonic acid amide, cinnamic acid amide; (v) vinyl acetate, vinyl propionate, vinyl butyrate,
Vinyl carboxylic acid esters such as vinyl pivalate, vinyl caproate, vinyl versatate and vinyl stearate.

Of the above, preferred polymerizable compound (B)
Is one containing 3 or more, particularly 4 or more, and further 4 to 15 ethylenically unsaturated groups in one molecule. Specific examples of such a polymerizable compound (B) include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dierythritol tetra (meth) acrylate. Pentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified Dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, "U-15HA" (trade name, Shin-Nakamura Chemical Co., Ltd. ), And the like. Further, among these compounds, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate are particularly preferable.

When the polymerizable compound (B) used is one containing 3 or more ethylenically unsaturated groups in one molecule, the resulting fluorine-based coating composition is particularly excellent in adhesiveness to a substrate and in the substrate. A thin film having extremely good mechanical properties such as scratch resistance on the surface of is formed.

The amount of the polymerizable compound (B) used is 30 to 150 parts by weight, preferably 35 to 100 parts by weight, particularly preferably 40 to 70 parts by weight, based on 100 parts by weight of the fluorine-containing copolymer (A). Is. If the proportion of the polymerizable compound (B) used is too small, the thin film formed by the obtained coating material has low adhesion to the substrate, while if the proportion used is too large, the thin film formed is Since the refractive index is high, it is difficult to obtain a good antireflection effect.

In the fluorine-based coating material of the present invention, the fluorine content in the total amount of the polymer-forming components including the fluorine-containing copolymer (A) and the polymerizable compound (B) is 30 to 30.
It is preferably 55% by weight, especially 35 to 50% by weight. A coating material satisfying such conditions can surely form a thin film that achieves the objects and effects of the present invention more sufficiently. A thin film formed by a fluorine-based paint having an excessive fluorine content tends to have low adhesion to the base material, and mechanical properties such as scratch resistance of the surface of the base material slightly deteriorate. On the other hand, a thin film formed of a fluorine-based paint having an excessively low fluorine content has a large refractive index, and the antireflection effect tends to decrease.

The solvent (C) used in the present invention is
From the viewpoint of the coatability of the fluorine-based coating material and the adhesion of the thin film to be formed to the substrate, it is preferable that the boiling point be within the range of 50 to 200 ° C. under a pressure of 760 hectopascals. Specific examples of such a solvent (C) include acetone, diethyl ketone, dipropyl ketone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, methyl formate, ethyl formate,
Propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate,
Solvents consisting of ketones or carboxylic acid esters such as butyl acetate, isobutyl acetate, butyl acetate, amyl acetate, isoamyl acetate, diamyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, etc. Can be mentioned. These solvents may be used alone or as a mixture of two or more components, and solvents other than those exemplified above may be added within a range not impairing the performance of the coating material.

The solvent (C) is used in an amount of usually 200 to 10,000 parts by weight, preferably 1 to 100 parts by weight of the total amount of the fluorine-containing copolymer (A) and the polymerizable compound (B).
000 to 10000 parts by weight, particularly preferably 1200
4000 parts by weight. By adjusting the amount of the solvent (C) to be used in this range, the viscosity of the fluorine-based paint can be adjusted to 0.5 to 5 cps so that a preferable coating property as a paint can be obtained.
(25 ° C.), particularly in the range of 0.7 to 3 cps (25 ° C.), and as a result, the fluorine-based coating material is applied in a uniform and practically suitable manner as an antireflection film for visible light. A thin film having a uniform thickness of 0.1 to 0.2 μm can be easily formed, and a thin film having particularly excellent adhesion to a substrate can be formed.

The fluorine-based coating composition of the present invention is cured by the polymerization reaction of the ethylenically unsaturated group of the polymerizable compound (B) contained therein, and therefore the coating composition formed by coating the coating composition. The film is subjected to a curing treatment for polymerizing the polymerizable compound (B) to form a solid thin film. As means for such a curing treatment, means for irradiating the coating film of the fluorine-based paint with active energy rays or means for heating the coating film is utilized, whereby
It is practically extremely advantageous because it is possible to surely and easily form a desired thin film in a suitable cured state, and it is convenient in terms of a thin film forming operation.

When the fluorine-based coating material of the present invention is cured by irradiation with an active energy ray, when an electron beam is used as the active energy ray, the fluorine-based coating material is not particularly added with a polymerization initiator, The desired hardening process can be performed. Further, when a light ray such as an ultraviolet ray or a visible light ray is used as the active energy ray for the curing treatment, it is decomposed upon irradiation with the active energy ray to generate, for example, a radical, whereby a polymerizable compound ( A photopolymerization initiator for initiating the polymerization reaction of B) is added to the fluorine-based paint.

Specific examples of such a photopolymerization initiator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole and xanthone. , 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4
-Methoxybenzophenone, thioxanthone, 2,2-
Dimethoxy-2-phenylacetophenone, 1- (4-
Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2,4 6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2
-Methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 3-methylacetophenone,
3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone (BTTB), 2-
(Dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, 4-
Examples thereof include benzoyl-4′-methyldiphenyl sulfide, benzyl, or BTTB in combination with xanthene, thioxanthene, coumarin, ketocoumarin, and other dye sensitizers.

Among these photopolymerization initiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1
-Hydroxycyclohexyl phenyl ketone, 2,4
6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] 2-Phenylmethyl) -1-butanone and the like are preferable, and more preferably 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone and the like can be mentioned.

Further, when a heating means is used for the curing treatment, a thermal polymerization initiator for generating radicals by heating to initiate the polymerization of the polymerizable compound (B) is added to the fluorine-based coating material. It Specific examples of the thermal polymerization initiator include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert-butyl. Peroxide, tert-
Butyl hydroperoxide, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like can be mentioned.

The amount of the photopolymerization initiator or the thermal polymerization initiator added to the fluorine-based coating material of the present invention is usually 100 parts by weight based on 100 parts by weight of the fluorine-containing copolymer (A) and the polymerizable compound (B). 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, particularly preferably 2 to 7 parts by weight. If the amount added exceeds 10 parts by weight, the handling of the coating and the mechanical strength of the thin film formed may be adversely affected.
On the other hand, if the amount added is less than 0.5 parts by weight, the curing rate will be low.

The fluorine-based paint of the present invention may contain various additives such as triethanolamine, methyldiethanolamine, triethylamine, diethylamine, and other amine-based compounds, if necessary, within a range that does not impair the objects and effects of the present invention. Sensitizers or polymerization accelerators; epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, silicone oligomer Polymers or oligomers such as polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-tert-butyl-4-methylphenol; other leveling agents, wettability improvers, surface active agents It can be blended plasticizers, UV absorbers, silane coupling agents, inorganic fillers, resin particles, pigments, dyes and the like.

The fluorine-based coating composition of the present invention is prepared by uniformly mixing the fluorine-containing copolymer (A), the polymerizable compound (B) and the solvent (C), and optionally a polymerization initiator and additives. Can be prepared by This fluorine-based paint is evenly applied to the surface of the substrate, the solvent is removed from the coating film formed by this, and then the coating film is irradiated with active energy rays such as electron rays, ultraviolet rays, and visible rays. The coating film is cured by being subjected to a curing treatment or a curing treatment by heating, whereby the fluorine-containing copolymer (A) and the polymerizable compound (B).
A thin film containing the above-mentioned polymer as a constituent is formed on the surface of the substrate.

The substrate to which the fluorine-based coating material of the present invention is applied is not particularly limited, and various objects can be used as the substrate. Especially, optical lenses, optical films, and optical glasses. By using an optical disk substrate or other optical element as a base material, an antireflection film having excellent properties can be formed extremely well on the surface thereof. Further, the fluorine-based coating material of the present invention can be suitably used as a coating material for building materials, exterior coating material for automobiles, and other various applications.

A thin film formed by applying the fluorine-based coating material of the present invention to the surface of a base material and further curing it has a specific constituent component, that is, a fluorine-containing copolymer (A) and a polymer. By containing the specific compound (B) in a specific ratio, it is an organic polymer compound, but has excellent adhesion to a substrate, high transparency and low refractive index, and high mechanical strength. It is a thin film that sufficiently improves mechanical properties such as scratch resistance of the surface of the material.
Further, particularly by containing fluorine, it is suitable as a coating material for forming an antireflection film, and particularly when the fluorine content in the thin film is 30 to 55% by weight, it is suitable as an antireflection film. Is demonstrated.

[0040]

Hereinafter, embodiments of the present invention will be described.
The invention is not limited to these examples. The fluorine-containing copolymer (A) used in each Example or Comparative Example is a copolymer obtained by copolymerizing a monomer composition having the composition shown in Table 1, and its fluorine content ratio and molecular weight (polystyrene). The converted number average molecular weight) is as shown in Table 1.

[0041]

[Table 1]

Examples 1-5 and Comparative Examples 1-4 Each of the fluorine-containing copolymers 1-5 shown in Table 1 is shown in Table 2
The mixture was mixed with the polymerizable compound according to the composition ratio shown in 1 and stirred with methyl isobutyl ketone as a solvent for about 1 hour to prepare a solution having a concentration of 4% by weight to obtain a fluorine-based coating material. Using each of the obtained fluorine-based paint as a sample, while observing the appearance state of the solution, a thin film is formed on the surface of the base material according to the procedure shown below, and the refractive index, reflectance, and Various properties such as adhesion, pencil hardness, scratch resistance and steel wool resistance were tested. Table 2 shows the results.

[Refractive Index] A sample was applied onto the surface of a substrate made of a glass plate to form a coating film, which was heated to 60 ° C. to sufficiently evaporate the solvent, and an electron beam irradiation apparatus was used for this. 3M
The film was cured by irradiating it with an electron beam so as to give a dose of rad to form a thin film having a film thickness of about 10 to 20 μm, and the refractive index of this thin film at a temperature of 25 ° C. was measured using an Abbe refractometer. [Reflectance] The sample is polyethylene terephthalate (PE
T) A coating film is formed by coating on the surface of a base material made of a film, heated to 60 ° C. to evaporate the solvent sufficiently, and an electron beam irradiation device is used to obtain a dose of 3 Mrad. It is cured by irradiating it with a beam and the film thickness is about 0.1
A thin film having a thickness of ˜0.2 μm is formed, and the reflectance of light in the visible region of this thin film is measured using an ultraviolet-visible spectrophotometer equipped with a reflection measurement function.
The average value of the reflectance of light of 0 to 750 nm was obtained.

[Adhesiveness] A thin film was formed by the same operation as in the measurement of reflectance except that a flat plate-like polymethylmethacrylate was used as the base material. It was evaluated by an eye peel test. That is, in accordance with the conditions specified in JIS D0202, cut lines are formed in the thin film in the vertical and horizontal directions to form a group of 100 small pieces in which 10 square pieces are arranged in each of the vertical and horizontal directions, and then an adhesive tape is attached thereto. The peeling operation was performed, and the number n of the small pieces remaining on the substrate without peeling together with the adhesive tape was determined. The results are shown as "n / 100". [Pencil hardness] A thin film was formed by the same operation as in the case of the above adhesion test, and the pencil hardness of this thin film was determined.

[Scratch resistance] A thin film was formed by the same operation as in the case of the above adhesion test, the surface of this thin film was scratched with a nail, and the degree of scratches caused by this was evaluated. The evaluation criteria are as follows. ◎ No scratches, very good condition ○ Slight scratches, good condition × Clearly defective condition [Steel wool scratch resistance] In the case of the above adhesion test A thin film was formed by the same operation, and 200 g of steel wool (000) was rubbed so that the surface of this thin film was rubbed.
No. 0) was reciprocated 10 times and the degree of scratches caused by this was evaluated. The evaluation criteria are the same as those for scratch resistance.

Example 6 To the fluorine-based coating material prepared in Example 1, 1-hydroxycyclohexyl phenyl ketone, which is a photopolymerization initiator, was further added in a proportion of 3 parts by weight and dissolved to prepare a fluorine-containing photopolymerization initiator. A system paint was prepared. This fluorine-based paint,
It is applied on the surface of a substrate made of polyethylene terephthalate (PET) film to form a coating film, which is heated to 60 ° C. to evaporate the solvent sufficiently, and an ultraviolet irradiation device is used to
The film was cured by irradiation with ultraviolet rays having an energy of J / cm ² to form a thin film having a film thickness of about 0.1 to 0.2 μm. Then, with respect to this thin film, evaluation tests of various characteristics were conducted in the same manner as in Example 1. Table 2 shows the results.

[0047]

[Table 2]

[0048]

EFFECTS OF THE INVENTION According to the fluorine-based coating material of the present invention, it is an organic polymer compound but has excellent adhesion to a substrate,
It is possible to form a thin film having high transparency and a low refractive index, and having a large mechanical strength, which can sufficiently improve mechanical properties such as scratch resistance of the surface of a substrate, and particularly an antireflection film. It is suitable as a coating material for forming a composition, and is cured by irradiation with an active energy ray or heating, so that its treatment operation is easy.

Claims (1)

[Claims] 1. Fluorine having a fluorine content of 60 to 70% by weight, which is obtained by copolymerizing (A) a monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene. Containing Copolymer 10
0 parts by weight and (B) 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group are dissolved in a solvent (C), which is cured by irradiation with active energy rays or heating. Fluorine based paint.