JPH07126552A - Fluorine-containing curable liquid coating composition and fluorine-containing cured coating film - Google Patents

Abstract

PURPOSE:To obtain a fluorine-containing curable liquid coating compsn. which gives a transparent, thin coating film having excellent weatherability and heat resistance, a high hardness, and a low refractive index by compounding a specific fluorocopolymer with a fluorine-contg. solvent. CONSTITUTION:The coating compsn. contains a fluorocopolymer and a fluorine- contg. solvent. The copolymer comprises structural units of which at least 50wt.% consists of fluorinated di(meth)acrylic ester units of formula I (wherein X<1> and X<2> are each H or methyl; and Y<1> is an at least trifluroinated 1-14C alkyl group, etc.) and fluorinated (meth)acrylic acid units of formula II (wherein X<3> is H or methyl; and Y<2> is an at least trifluorinated 2-14C alkyl group, etc.) and/or fumaric diester units of formula III (wherein Z is a 3C higher branched alkyl group; and Y<3> is an at least trifluorinated 2-14C alkyl).

Description

Detailed Description of the Invention

[0001]

The present invention has a high surface hardness,
The present invention relates to a fluorine-containing cured coating that can be used on the surface of various base materials and a fluorine-containing curable coating liquid that can be used as a raw material for the cured coating.

[0002]

2. Description of the Related Art Fluorocarbons have a very strong C—F bond due to the strong electron-withdrawing property of a fluorine atom and are chemically stable, and do not have an interaction force (van der Waals force) like a hydrogen atom. , Shows properties different from hydrocarbon-based substances, such as low viscosity and high volatility. These properties due to the fluorine atom are similarly expressed not only in the low molecular weight substance but also in the high molecular weight substance, that is, the resin having a large number of fluorine atoms (fluorine resin). In particular, a fluororesin is used as a low-refractive-index resin because of its low refractive index, chemical stability, heat resistance and the like.

However, polymers having a fluorine atom introduced into the polymer main chain such as trifluoroethylene, vinylidene fluoride, and perfluoroethylene polymers are excellent in heat resistance and chemical stability, When it is used for treating a material such as a thermoplastic resin that needs to be heat-processed, it has a problem in processability and poor solubility in an organic solvent. Furthermore, metal, plastic, glass,
When the surface of a material such as wood is coated with the fluororesin for surface treatment, it is necessary to heat and melt the fluororesin once and then mechanically press-bond it to the base material having a complicated shape. Cannot be coated and is not suitable for a mechanically brittle substrate such as glass, which poses a problem that the materials that can be coated are limited. Further, since these polymers are opaque or have a refractive index higher than 1.44, they are unsuitable as low refractive index coating resins which require transparency.

Therefore, for the purpose of improving the thermal processability and the solubility in organic solvents, it has been proposed to copolymerize a perfluoroethylene monomer with another monomer. Therefore, the heat resistance is poor, the solubility in an organic solvent is insufficient, and a sufficiently low refractive index is not obtained.

Further, a polymerizable monomer having a perfluoroalkyl group in its side chain, for example, a polymer containing an acrylic acid fluorine-containing alkyl ester or a methacrylic acid fluorine-containing alkyl ester or a polymer containing a fluorine-containing alkylstyrene has been proposed. There is.

However, although the polymer containing a fluorine-containing alkylstyrene or the like has improved solubility in an organic solvent, it has long-term stability (weather resistance) because the aromatic group absorbs ultraviolet rays and a deterioration reaction proceeds. In addition, since the aromatic group exhibits a high refractive index, it is unsuitable as a resin having a low refractive index. On the other hand, although the fluorine-containing alkyl ester has a low refractive index, it has a drawback that it has poor wear resistance because of its low surface hardness.

Further, even if these fluorine-containing monomers are applied to a substrate to a film thickness of 10 μm or less, they are repelled by the substrate due to the low surface energy and low viscosity peculiar to the fluorine compound, and a uniform film is obtained. Is very difficult. Therefore, like an antireflection film, the film thickness is 1/4 of visible light, that is, 0.0
It is very difficult to form a thin film that requires a film thickness of 9 to 0.2 μm.

[0008]

An object of the present invention is to provide excellent weather resistance and heat resistance, a high surface hardness, a film thickness of 10 μm or less, and a light-transmitting low refractive index. A fluorine-containing cured coating and a fluorine-containing curable coating material that can be used as a raw material for the cured coating.

[0009]

According to the present invention, the following general formula 4 (wherein X ¹ and X ² are the same or different groups and represent a hydrogen atom or a methyl group, and Y ¹ is Fluorine-containing di (meth) acrylic acid ester represented by a C1-C14 fluoroalkyl group having three or more fluorine atoms or a C3-C14 fluorocycloalkyl group having four or more fluorine atoms. (Hereinafter referred to as di (meth) acrylic acid ester 1) and the following general formula 5 (in the formula, X ³ represents a hydrogen atom or a methyl group, and Y ² represents ² to 3 carbon atoms having 2 or more fluorine atoms). Fluorine-containing (meth) acrylic acid ester (hereinafter referred to as (meth) acrylic acid ester 2) represented by 14 fluoroalkyl group or C 4-14 fluorocycloalkyl group having 4 or more fluorine atoms. And / or the following general formula 6 (wherein Z is a branched alkyl group having 3 or more carbon atoms, a cycloalkyl group having 4 or more carbon atoms, or a fluoroalkyl group having 3 or more fluorine atoms as a substituent) A branched alkyl group having 3 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms is shown, and Y ³ is a C 2-14 fluoroalkyl group having 3 or more fluorine atoms or a carbon number having 4 or more fluorine atoms. A fluoropolymer (hereinafter referred to as polymer 4) containing 50 wt% or more of a fumaric acid diester (hereinafter referred to as fumaric acid diester 3) represented by 4 to 14 as a constituent unit. ,
A fluorine-containing curable coating liquid containing a fluorine-containing solvent is provided.

[0010]

[Chemical 4]

[0011]

[Chemical 5]

[0012]

[Chemical 6]

Further, according to the present invention, the pencil hardness obtained by polymerizing and curing the above fluorine-containing curable coating liquid has a surface hardness of H or more and a refractive index of 1.44 or less. A fluorine cured coating is provided.

The present invention will be described in more detail below.

The fluorine-containing curable coating liquid of the present invention comprises a di (meth) acrylic acid ester 1 represented by the above general formula 4.
And a polymer 4 containing a specific amount of the (meth) acrylic acid ester 2 represented by the general formula 5 and / or the fumaric acid diester 3 represented by the general formula 6 as a constitutional unit, and a fluorine-containing solvent. When it is a coating liquid containing it, when it is cured, it exhibits a three-dimensional network structure, has a high glass transition temperature, and is excellent in heat resistance, weather resistance and the like. In the general formulas 4, 5, and 6, when Y has 15 or more carbon atoms, the production is difficult.

Examples of the di (meth) acrylic acid ester 1 include di (meth) acrylic acid-2,2,2-trifluoroethylethylene glycol, di (meth) acrylic acid-2,2,3,3,3. 3-pentafluoropropyl ethylene glycol, di (meth) acrylic acid-2,2
3,3,4,4,4-heptafluorobutyl ethylene glycol, di (meth) acrylic acid-2,2,3,3,3
4,4,5,5,5-nonafluoropentylethylene glycol, di (meth) acrylic acid-2,2,3,3,3
4,4,5,5,6,6,6-undecafluorohexyl ethylene glycol, di (meth) acrylic acid-2,
2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,4 5, 5,
6,6,7,7,8,8,8-pentadecafluorooctylethylene glycol, di (meth) acrylic acid-3,
3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,4 5, 5,
6,6,7,7,8,8,9,9,10,10,10-
Nonadecafluorodecyl ethylene glycol, di (meth) acrylic acid-3,3,4,4,5,5,6,6,6
7,7,8,8,9,9,10,10,10-heptadecafluorodecylethylene glycol, di (meth) acrylic acid-2-trifluoromethyl-3,3,3-trifluoropropylethylene glycol, Di (meth) acrylic acid-3-trifluoromethyl-4,4,4-trifluorobutylethylene glycol, di (meth) acrylic acid-1-methyl-2,2,3,3,3-pentafluoropropylethylene Glycol, di (meth) acrylic acid-1
-Methyl-2,2,3,3,4,4,4-heptafluorobutylethylene glycol and the like can be preferably mentioned, and when used, they can be used alone or as a mixture. To prepare such a di (meth) acrylic acid ester 1, for example, a hydroxy (meth) acrylic acid that can be easily obtained by a usual ring-opening reaction between a corresponding fluorine-containing epoxy and (meth) acrylic acid. It can be easily obtained by a usual esterification reaction of an ester with (meth) acrylic acid.

The polymer 4 is a polymer containing 50% by weight or more, preferably 70% by weight or more of a structural unit constituted by the (meth) acrylic acid ester 2 and / or the fumaric acid diester 3 and 50% by weight or less of the structural unit composed of the copolymerizable monomer may be contained, and each structural unit may be random or block.
At this time, when the constitutional unit composed of the (meth) acrylic acid ester 2 and / or the fumaric acid diester 3 is less than 50% by weight, the compatibility with the di (meth) acrylic acid ester 1 becomes poor and a uniform coating is obtained. No film can be obtained. When the constituent units of both the (meth) acrylic acid ester 2 and the fumaric acid diester 3 are contained, the mixing ratio of each constituent unit is
There is no particular limitation as long as the total is 50% by weight or more.

Examples of the (meth) acrylic acid ester 2 which can be a constitutional unit of the polymer 4 include, for example, (meth) acrylic acid-2,2,2-trifluoroethyl,
(Meth) acrylic acid-2,2,3,3,3-pentafluoropropyl, (meth) acrylic acid-2,2,3,3,3
4,4,4-heptafluorobutyl, (meth) acrylic acid-2,2,3,3,4,4,5,5,5-nonafluoropentyl, (meth) acrylic acid-2,2,3 Three
4,4,5,5,6,6,6-undecafluorohexyl, (meth) acrylic acid-2,2,3,3,4,4
5,5,6,6,7,7,7-tridecafluoroheptyl, (meth) acrylic acid-2,2,3,3,4,4,4
5,5,6,6,7,7,8,8,8-pentadecafluorooctyl, (meth) acrylic acid-3,3,4,4,4
5,5,6,6,7,7,8,8,8-tridecafluorooctyl, (meth) acrylic acid-2,2,3,3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,10-nonadecafluorodecyl, (meth) acrylic acid-3,3,4,4,5,5,6,6,7,7,
8,8,9,9,10,10,10-heptadecafluorodecyl, (meth) acrylic acid-2-trifluoromethyl-3,3,3-trifluoropropyl, (meth) acrylic acid-3-tri Fluoromethyl-4,4,4-trifluorobutyl, (meth) acrylic acid-1-methyl-2,
2,3,3,3-pentafluoropropyl, (meth) acrylic acid-1-methyl-2,2,3,3,4,4,4-
Preferred examples include heptafluorobutyl,
When used, they can be used alone or as a mixture.

Examples of the fumaric acid diester 3 which can be a constituent unit of the polymer 4 include, for example, isopropyl-2,2,2-trifluoroethyl fumarate and isopropyl-2,2,3,3,3-fumarate. Pentafluoropropyl, isopropyl fumarate-2,2,3,3,4
4,4-heptafluorobutyl, isopropyl fumarate-2,2,3,3,4,4,5,5,5-nonafluoropentyl, isopropyl fumarate-2,2,3,3,3
4,4,5,5,6,6,6-undecafluorohexyl, isopropyl fumarate-2,2,3,3,4,4
5,5,6,6,7,7,7-tridecafluoroheptyl, isopropyl fumarate-2,2,3,3,4,4,4
5,5,6,6,7,7,8,8,8-pentadecafluorooctyl, isopropyl fumarate-3,3,4,4
4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl, isopropyl fumarate-2,2,3,3
3,4,4,5,5,6,6,7,7,8,8,9,
9,10,10,10-nonadecafluorodecyl, isopropyl fumarate-3,3,4,4,5,5,6,6
7,7,8,8,9,9,10,10,10-heptadecafluorodecyl, isopropyl-2-trifluoromethyl-3,3,3-trifluoropropyl fumarate, isopropyl-3-trifumarate Fluoromethyl-4,
4,4-trifluorobutyl, isopropyl fumarate-
1-methyl-2,2,3,3,3-pentafluoropropyl, isopropyl fumarate-1-methyl-2,2,2
3,3,4,4,4-heptafluorobutyl, fumarate-tert-butyl-2,2,2-trifluoroethyl, fumarate-tert-butyl-2,2,3,3,3
-Pentafluoropropyl, -tert-butyl fumarate-2,2,3,3,4,4,4-heptafluorobutyl, -tert-butyl fumarate-2,2,3,3,3
4,4,5,5,5-nonafluoropentyl, tert-butyl fumarate-2,2,3,3,4,4,5
5,6,6,6-undecafluorohexyl, f-tert-butyl fumarate-2,2,3,4,4,5,5
5,6,6,7,7,7-tridecafluoroheptyl,
Fumarate-tert-butyl-2,2,3,3,4
4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl, fumarate-tert-butyl-3,
3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl, tert-butyl fumarate-2,2,3,3,4,4,5 5, 6, 6, 7, 7,
8,8,9,9,10,10,10-nonadecafluorodecyl, -tert-butyl fumarate-3,3,4,4
4,5,5,6,6,7,7,8,8,9,9,10,
10,10-Heptadecafluorodecyl, fumaric acid-t
ert-Butyl-2-trifluoromethyl-3,3,3
-Trifluoropropyl, fumarate-tert-butyl-3-trifluoromethyl-4,4,4-trifluorobutyl, fumarate-tert-butyl-1-methyl-
2,2,3,3,3-pentafluoropropyl, -tert-butyl-1-methyl fumarate-2,2,3,3,3
Preferred are 4,4,4-heptafluorobutyl and the like, and when used, they can be used alone or as a mixture.

Further, in the polymer 4, as the other copolymerizable monomer which can be a constituent unit if necessary, olefin, (meth) acrylic acid and their alkyl esters; fumaric acid, maleic acid, citraconic acid , Unsaturated polybasic acids such as mesaconic acid, itaconic acid, tetrahydrophthalic acid and their alkyl esters, vinyl esters of fatty acids, styrenes, vinyl halides,
Preferable examples thereof include vinylidene halide, vinyl alkyl ether, vinyl alkyl ketone, butadiene, and the like. Specific examples include ethylene, propylene, methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, acrylonitrile, and methacrylic acid. Ronitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl pivalate, styrene, α-methylstyrene, vinyl chloride, vinylidene chloride, aryl acetate, vinyl butyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl carbazole, 1, Preferable examples include 3-butadiene and isobrene.

The polymer 4 can be easily prepared by a generally used radical polymerization method or the like. Specifically, for example, azo radical polymerization initiators such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile and azobisvaleronitrile; benzoyl peroxide,
Organic peroxide radical polymerization initiators such as tert-butyl hiddle peroxide, cumene peroxide, diacyl peroxide; inorganic radical polymerization initiators such as ammonium persulfate and potassium persulfate; hydrogen peroxide-sodium hydroxide system It can be obtained by a known radical polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or radiation polymerization using various radical polymerization initiators such as the redox type initiator. At this time, the reaction temperature is 10 to 100.
The temperature and reaction time are preferably 1 to 100 hours. The polymer 4 thus obtained has an average molecular weight of 10
It is preferably from 00 to 300,000.

Specific examples of the fluorine-containing solvent include trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene, hexafluorobenzene,
Hexafluorocyclohexane, perfluorodimethylcyclohexane, perfluoromethylcyclohexane,
Octafluorodecalin, 1,1,2-trichloro-
1,2,2-trifluoromethylethane and the like can be mentioned, and the trade name is "ASAHIKLIN (AK225)".
Commercial products such as (manufactured by Asahi Glass Co., Ltd.) can also be used.

In the fluorine-containing curable coating liquid of the present invention, the mixing ratio of the di (meth) acrylic acid ester 1 and the polymer 4 is such that the di (meth) acrylic acid ester 1 100
Polymer 4 is preferably 0.001 to 5 with respect to parts by weight.
0 parts by weight, particularly 0.01 to 25 parts by weight is desirable. When the compounding ratio of the polymer 4 is less than 0.001 part by weight, thin film coatability cannot be improved, and when it exceeds 50 parts by weight, the surface hardness of the cured film is lowered, which is not preferable. The mixing ratio of the fluorinated solvent is not particularly limited, but is preferably 2 to 50 times by weight based on the total amount of the curable components in the fluorinated curable coating liquid.

In the fluorine-containing curable coating liquid of the present invention,
If necessary, a thermosetting resin, an energy ray curable resin or the like which is usually used as another curable component may be added. For example, a polyfunctional monomer having two or more polymerizable unsaturated groups, specifically, di (meth) acrylic acid hexanediol, di (meth) acrylic acid nonanediol, di (meth) acrylic acid neopentyl glycol, di (meth) acrylic acid Preferable examples include (meth) acrylic acid tricyclodecane dimethanol, tri (meth) acrylic acid pentaerythritol, tris (acryloxyethyl) isocyanate, divinylben, and diethylene glycol di (meth) acrylate. The mixing ratio of other curable components is
It is preferably 100 parts by weight or less, and particularly preferably 50 parts by weight or less with respect to 100 parts by weight of the di (meth) acrylic acid ester 1. When the blending ratio of the curing component exceeds 100 parts by weight, the refractive index increases when polymerized and cured, and a desired cured film cannot be obtained, which is not preferable.

The fluorine-containing cured coating film of the present invention is obtained by polymerizing and curing the above-mentioned fluorine-containing curable coating liquid, and has a surface hardness of pencil hardness H or more and a refractive index of 1.44 or less. . The film thickness obtained is preferably 0.05 to 2000 μm.

To prepare the fluorine-containing cured coating film of the present invention, for example, a curing initiator and the like are optionally added to the fluorine-containing curable coating solution and mixed, and then a commonly used coating method, for example, a roll coating method, Apply to the substrate by methods such as gravure coating method, dip coating method and spin coating method,
After drying, it can be obtained by a method such as heat curing or polymerization curing by irradiation with active energy rays such as ultraviolet rays, electron beams and radiation.

As the curing initiator, for example, azo radical polymerization initiators such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile and azobisvaleronitrile; benzoyl peroxide, tert-butyl hiddle peroxide, cumene per Organic peroxide-based radical polymerization initiators such as oxides and diacyl peroxides, benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; carbonyl compounds such as benzyl, benzophenone, acetophenone and Michler's ketone; Azo compounds such as azobisisobutyronitrile and azodibenzoyl; and photopolymerization initiators such as a mixture of α-diketone and a tertiary amine can be used. The amount of the curing initiator used is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the curing component in the fluorine-containing curable coating liquid.

The base material is not particularly limited, but examples thereof include inorganic materials such as glass, stone, concrete and tile; vinyl chloride resin, polyethylene terephthalate, polyolefin resin, (meth) acrylic resin,
Synthesis of (meth) acrylic acid ester resin, phenol resin, xylene resin, urea resin, melamine resin, epoxy resin, silicone resin diallyl phthalate resin, furan resin, amino resin, alkyd resin, urethane resin, vinyl ester resin, polyimide resin, etc. Resin: Metals such as iron, aluminum and copper, wood, paper and the like can be mentioned.

Furthermore, the drying and heating conditions are from room temperature to 2
It is preferably carried out at 00 ° C. for 0.5 to 100 hours.

[0030]

Since the fluorine-containing curable coating liquid of the present invention contains the di (meth) acrylic acid ester 1 and the polymer 4 as the curing components, the fluorine-containing cured coating obtained by curing has a weather resistance. Excellent in heat resistance, water repellency and oil repellency, and also has high surface hardness and thus excellent abrasion resistance, and has a low refractive index. Therefore, it is particularly useful as an antireflection film material having light transmittance. Further, since the polymer 4 is contained, a cured coating having a film thickness of 0.05 to 2000 μm can be obtained without being repelled by the base material. In addition, this fluorine-containing cured coating,
Glass, metal used in buildings, automobiles, electrical appliances, etc.
In addition to being widely applicable to synthetic resins, it has low surface energy peculiar to fluoropolymers and has excellent stain resistance, so it is a biocompatible material with low protein absorption, medical instruments, clinical examinations. It can also be applied to instruments and the like.

[0031]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0032]

Example 1 Diacrylic acid-2,2,3,3,4,4
5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene glycol (hereinafter F ₁₇ EG
DA (abbreviated as DA) 10 parts by weight, poly (acrylic acid-3,3,3)
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,10-heptadecafluorodecyl) (hereinafter P
1 part by weight of F ₁₄ A) and 100 parts by weight of trifluoromethylbenzene were mixed to prepare a fluorine-containing curable coating liquid.
Then, using a dipping type thin film forming apparatus (manufactured by Sugiyama Gen-Igiki Co., Ltd.), it was applied on a polyethylene terephthalate film (hereinafter abbreviated as PET film) so that the film thickness after drying would be 0.15 μm, and a fluorine-containing coating film was applied. Formed. After drying, accelerator voltage 174k by electron beam irradiator (Iwasaki Electric Co., Ltd.)
A fluorine-containing cured coating was prepared by irradiating an electron beam with an absorbed dose of 30 Mard at V and a beam current of 5 mA to cure. The pencil hardness of the obtained fluorine-containing cured film (hereinafter referred to as a thin film) having a film thickness of 0.15 μm on PET was measured according to JIS K54.
00 was measured. Further, the contact angle to pure water was measured using a contact angle meter (manufactured by Kyowa Kagaku Co., Ltd.). Separately, a fluorine-containing coating film was formed by the same method so that the film thickness after drying of the prepared fluorine-containing curable coating liquid was 500 μm, and an electron beam irradiator (manufactured by Iwasaki Electric Co., Ltd.)
Was irradiated with an electron beam having an absorbed dose of 10 Mard at an accelerator voltage of 174 kV and a beam current of 5 mA to be cured to obtain a fluorine-containing cured film (hereinafter referred to as a thick film). The obtained thick film is P
After peeling from the ET film, the refractive index was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.). The results are shown in Table 1.

[0033]

Examples 2 to 9 Diester 1 and polymer 4 shown in Table 1
A fluorine-containing curable coating liquid was prepared in the same manner as in Example 1 except that the other copolymer components shown in Table 1 were used. A thin film and a thick film were prepared in the same manner as in Example 1 using the obtained fluorine-containing curing coating solution, and the refractive index, pencil hardness and contact angle were measured. The results are shown in Table 1.

[0034]

Example 10 Diester 1 shown in Table 1, polymer 4 and trade name "DAROCUR 1116" as a curing initiator
A fluorinated curing coating solution was prepared in the same manner as in Example 1 except that (Acetophenone compound manufactured by Merck & Co., Inc.) was used. A thin film and a thick film were prepared in the same manner as in Example 1 using the obtained fluorine-containing curing coating liquid. Incidentally, the curing of the coating film is performed by a UV irradiator (manufactured by ORC, trade name "U" instead of the electron beam irradiator.
V-330AP1 "), and the ultraviolet ray of 330 nm is 1
Irradiation was performed at 000 mJ / cm ² . Each measurement was performed on the obtained thin film and thick film in the same manner as in Example 1. The results are shown in Table 1.

[0035]

Example 11 A fluorine-containing curable coating liquid was prepared in the same manner as in Example 1 except that the diester 1, polymer 4 and curable initiator shown in Table 1 were used. A thin film and a thick film were prepared in the same manner as in Example 1 using the obtained fluorine-containing curing coating liquid.
The thin film was cured by heating at 100 ° C. for 2 hours, and the thick film was formed in the same manner as in Example 1. Each measurement was performed on the obtained thin film and thick film in the same manner as in Example 1. The results are shown in Table 1.
Shown in.

[0036]

Comparative Example 1 A fluorinated curable coating liquid was prepared in the same manner as in Example 1 except that the diester 1 and the polymer 4 shown in Table 1 were used. Example 1 using the obtained fluorine-containing curing coating liquid
A thin film and a thick film were prepared in the same manner as in, and the refractive index, pencil hardness, and contact angle were measured. The results are shown in Table 1.

[0037]

[Table 1]

The abbreviations in Table 1 indicate the following compounds, respectively.

F ₁₇ EGDA; diacrylic acid-2,2
3,3,4,4,5,5,6,6,7,7,8,8,
9,9,9-Heptadecafluorononylethylene glycol F ₁₉ EGDA; diacrylic acid-perfluoro-7-methyloctylmethylethylene glycol F ₂₁ EGDA; diacrylic acid-2,2,3,3,4.
4,5,5,6,6,7,7,8,8,9,9,10,
10,11,11,11- Heng eicosa fluoro nonyl ethylene glycol F ₂₃ EGDA; diacrylate - perfluoro-9-methyl-decyl methyl ethylene glycol F ₁₇ EGDMA; dimethacrylate 2,2,3,3,
4,4,5,5,6,6,7,7,8,8,9,9,9
-Heptadecafluorononyl ethylene glycol NMO
DA; nonanediol diacrylate F ₁₇ A; acrylic acid-3,3,4,4,5,5,6
6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl PF ₁₇ A; poly (acrylic acid-3,3,4,4,5,5
5,6,6,7,7,8,8,9,9,10,10,1
0-heptadecafluorodecyl) PF ₁₇ F; poly (fumaric acid-iso-3,3,4,4,4)
5,5,6,6,7,7,8,8,9,9,10,1
0,10-heptadecafluorodecyl) P (F ₁₇ AB); (acrylic acid-3,3,4,4,4)
5,5,6,6,7,7,8,8,9,9,10,1
0,10-Heptadecafluorodecyl-acrylic acid-n
-Butyl) copolymer (weight ratio 4: 1) BPO; benzoyl peroxide DAR. 1116; Product name "DAROCUR 1116" (manufactured by Merck)

[0040]

Comparative Example 2 Diacrylic acid-2,2,3,3,4,4
5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene glycol (hereinafter F ₁₇ EG
10 parts by weight (referred to as DA) and 100 parts by weight of trifluoromethylbenzene were mixed to prepare a fluorine-containing curable coating liquid. Then, coating was attempted to form a thin film on the PET film in the same manner as in Example 1, but after the coating, evaporation of the solvent immediately caused F ₁₇ EGDA to be repelled, and the thin film could not be formed.

Claims (2)

[Claims] 1. The following general formula 1 (wherein X ¹ and X ² are the same or different groups and represent a hydrogen atom or a methyl group, and Y ¹ is a carbon atom having 3 or more fluorine atoms. ~
14 shows a fluoroalkyl group having 14 or more, or a fluorocycloalkyl group having 3 to 14 carbon atoms and having 4 or more fluorine atoms. ) And a fluorine-containing di (meth) acrylic acid ester represented by the following general formula 2 (in the formula, X ³ represents a hydrogen atom or a methyl group, and Y ² represents ² to 3 carbon atoms having 2 or more fluorine atoms). 14 fluoroalkyl groups or 4 fluorine atoms
It shows a C4-C14 fluorocycloalkyl group having one or more. ) And / or the following general formula 3 (wherein Z is a branched alkyl group having 3 or more carbon atoms, a cycloalkyl group having 4 or more carbon atoms, or 3 or more fluorine atoms) A branched alkyl group having 3 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms, which has a fluoroalkyl group as a substituent, Y
³ represents a C 2-14 fluoroalkyl group having 3 or more fluorine atoms or a C 4-14 fluorocycloalkyl group having 4 or more fluorine atoms. ) A fluorine-containing curable coating liquid containing a fluorine-containing polymer containing 50% by weight or more of a fumaric acid diester represented by the formula (1) as a constitutional unit, and a fluorine-containing solvent. [Chemical 1] [Chemical 2] [Chemical 3] 2. A surface hardness having a pencil height of H or more, which is obtained by polymerizing and curing the fluorine-containing curable coating liquid according to claim 1.
A fluorine-containing cured coating having a refractive index of 1.44 or less.