JP2000178469A - Scratch resistant coating composition and base material coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition excellent in resistance to scratch and suitable as an antireflection film on a base material. SOLUTION: This composition is obtained by compounding a coating composition consisting of a fluorine-containing coating material with a silicone oil in an amount of 0.1-15.0 wt.% based on the solid component of the composition. The fluorine-containing coating material is prepared by dissolving (A) 100 pts.wt. of a fluorine-containing copolymer obtained by copolymerizing a monomer composition consisting of 20-90 wt.% of vinylidene fluoride and 5-75 wt.% of hexafluoropropylene and (B) 20-200 pts.wt. of a polymerizable compound having ethylenic unsaturated group in (C) a solvent, and curable by irradiating with actinic ray or heating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has a low reflection performance,
The present invention also relates to a coating composition excellent in scratch resistance, fingerprint adhesion prevention property and fingerprint adhesion stain removal property, and a substrate coated with the coating composition.

[0002]

2. Description of the Related Art It is known that, when a coating having a lower refractive index than a substrate is formed on the surface of the substrate, the reflectance of light reflected from the surface of the coating is reduced, and a so-called low reflection performance is exhibited. ing. Coatings exhibiting such low reflection performance are applied to various substrate surfaces as a light reflection preventing film, for example,
It is used to prevent reflection of external light on display materials such as displays.

[0003] In general, the thickness of a film exhibiting low reflection performance is:
Since it must be a thin film of about 0.1 μm, even if it has excellent low reflection performance, a film having sufficient scratch resistance cannot be obtained. When rubbing with a cloth or the like, there is a problem that the coating exhibiting the low reflection performance is scratched or peeled off, thereby lowering the low reflection performance or deteriorating the appearance. Specifically, in a Bencott abrasion test, which is one of the evaluation tests of the abrasion resistance performance, the coating showing low reflection performance is scratched within 30 reciprocations, making it difficult for practical use.

For this reason, a coating having low reflection performance and scratch resistance has been developed. For example, transparent fluorinated copolymers such as acrylic acid fluorinated alkyl ester polymers and methacrylic acid fluorinated alkyl ester polymers, and other fluorinated amorphous copolymers have been synthesized and attempted to be applied to low reflection coatings and the like. (Japanese Patent Laid-Open No. 64-1)
8573, JP-A-1-149808, JP-A-6-115023, etc.). However, all of these fluorine-containing copolymers have low hardness, and the coating is damaged within 30 reciprocations by a Bencott abrasion test.
This is a situation where it is practically difficult to use it as a low reflection coating layer.

[0005]

In view of such circumstances,
The present inventors have intensively studied to develop a coating composition which exhibits a low refractive index and can provide a film having excellent scratch resistance, and as a result, when a specific amount of silicone oil is added to the coating composition, Have found that a film made of the coating composition has improved surface slipperiness and improved abrasion resistance, leading to the present invention.

[0006]

That is, the present invention provides:
(A) 100 parts by weight of a fluorine-containing copolymer obtained by copolymerizing a monomer composition containing 20 to 90% by weight of vinylidene fluoride and 5 to 75% by weight of hexafluoropropylene, and (B) ethylenically unsaturated 20 to 200 parts by weight of a polymerizable compound having a group are dissolved in the solvent (C), and the solid content of the coating composition is 0.1 to 1 based on the solid content of the coating composition which is cured by irradiation with active energy rays or heating.
The present invention provides a scratch-resistant coating composition containing 5.0% by weight of silicone oil. Furthermore, the present invention provides a substrate characterized by being coated with a scratch-resistant coating composition containing 0.1 to 15.0% by weight of silicone oil based on the solid content of the coating composition. It is.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The coating composition of the present invention is obtained by copolymerizing (A) a monomer composition containing 20 to 90% by weight of vinylidene fluoride and 5 to 75% by weight of hexafluoropropylene. Fluorine content ratio is 60
100 parts by weight of a fluorine-containing copolymer in an amount of from 75 to 75% by weight, and (B) a polymerizable compound 2 having an ethylenically unsaturated group.
0 to 200 parts by weight is dissolved in the solvent (C), and a fluorine-based paint which is cured by irradiation with active energy rays or heated is used. The coating composition comprising the fluorine-based paint has excellent adhesion to a substrate, has high transparency and a low refractive index, and is most suitable as a paint for forming an antireflection film.

The fluorine-based paint is prepared by dissolving a specific fluorine-containing copolymer (A) and an ethylenically unsaturated group-containing (B) at a specific ratio in a common solvent. It has the property of being cured by heating.

The fluorine-containing copolymer (A) used in the present invention is obtained by copolymerizing a monomer composition containing 20 to 90% by weight of vinylidene fluoride and 5 to 75% by weight of hexafluoropropylene. The preferred range of vinylidene fluoride in the monomer composition is 30 to 90% by weight, the more preferred range is 40 to 80% by weight, and the preferred range of hexafluoropropylene is 5%. -50% by weight, more preferably 10-50% by weight. The monomer composition may further contain about 0 to 50% by weight, preferably 0 to 40% by weight of tetrafluoroethylene.

[0010] The monomer composition for obtaining the fluorine-containing copolymer (A) comprises, for example, 3
It may be contained in a range of 0% by weight or less.
Specific examples of other copolymer components include, for example, fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 2-bromo-3,3,3-trifluoroethylene,
3-bromo-3,3-difluoropropylene, 3,3
Polymerizable monomers containing a fluorine atom such as 3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene and α-trifluoromethacrylic acid can be exemplified.

The fluorine-containing copolymer (A) obtained from such a monomer composition has a fluorine content of 60%.
７５75% by weight, the preferred fluorine content is 62-70% by weight. When the fluorine content is in the above range, good solubility in the solvent (C) is exhibited.

The molecular weight of the fluorine-containing copolymer (A) is 5,000 to 200,000, preferably 10,000 to 10
0000, refractive index 1.45 or less, preferably 1.42
Below, more preferably, 1.40 or less are used. When the fluorine-containing copolymer (A) having such physical properties is used, it is excellent in coatability, and a thin film formed by the obtained fluorine-based paint has an excellent antireflection effect.

The polymerizable compound (B) used in the present invention is irradiated with an active energy ray in the presence or absence of a photopolymerization initiator, or heated in the presence of a thermal polymerization initiator. Is a compound having an ethylenically unsaturated group which causes addition polymerization, and is contained in an amount of 20 to 200 parts by weight, preferably 30 to 150 parts by weight based on 100 parts by weight of the fluorine-containing copolymer (A). Used. When the amount used is small, the thin film formed by the obtained paint has low adhesion to the substrate. On the other hand, if the amount is too large, the formed thin film has a high refractive index, and it is difficult to obtain a good antireflection effect.

Specific examples of the polymerizable compound (B) include, for example, 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-p-
Aromatic vinyl compounds such as aminostyrene and vinylpyridine:

(Meth) acrylonitrile, α-chloro (meth) acrylonitrile, α-chloromethyl (meth)
Unsaturated nitriles such as acrylonitrile, α-methoxy (meth) acrylonitrile, α-ethoxy (meth) acrylonitrile, nitrile crotonate, nitrile cinnamate, dinitrile itaconic acid, dinitrile maleate, dinitrile fumarate:

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) acrylates such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and 2- (n-propoxy) ethyl (meth) acrylate;

2,2,2-trifluoroethyl (meth)
Acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexylethyl (meth) acrylate, 2- (perfluoro Fluorine-containing (meth) acrylates such as octylethyl (meth) acrylate and 2- (perfluorodecyl) ethyl (meth) acrylate;

Methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethyl itaconate, diethyl itaconate, dimethyl maleate Unsaturated carboxylic acid esters such as, diethyl maleate, dimethyl fumarate, diethyl fumarate;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
-Hydroxy group-containing (meth) acrylates such as hydroxypropyl (meth) acrylate:

(Meth) of polyalkylene glycol such as polyethylene glycol and polypropylene glycol
Acrylic acid monoesters;

Cyano group-containing (meth) acrylates such as cyanoethyl (meth) acrylate and cyanopropyl (meth) acrylate;

2-phenoxydiethyl (meth) acrylate, 2-phenoxypropyl (meth) acrylate, 3
-(Meth) acrylic acid aryloxyalkyl esters such as phenoxydipropyl (meth) acrylate;

(Meth) acrylic acid monoesters of alkoxypolyalkylene glycols such as methoxypolyethylene glycol, ethoxypolyethylene glycol, methoxypolypropyleneglycol and ethoxypolypropyleneglycol;

(Meth) acrylic acid monoesters of aryloxy polyalkylene glycols such as phenoxy polyethylene glycol and phenoxy polypropylene glycol;

(Meth) acrylic acid diesters of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol;

(Meth) acrylic acid diesters of polyalkylene glycols (having, for example, 2 to 23 alkylene glycol units) such as polyethylene glycol and polypropylene glycol, hydroxypolybutadiene at both ends, hydroxypolyisoprene at both ends, and hydroxybutadiene at both ends (Meth) acrylic acid diesters of polymers having hydroxyl groups at both ends such as acrylonitrile copolymers and hydroxypolycaprolactone at both ends;

Glycerin, 1,2,4-butanetriol, trimethylolalkane (alkane has, for example, 1 to 3 carbon atoms), tetramethylolalkane (alkane has 1 to 3 carbon atoms, for example), (Meth) acrylic acid oligoesters such as (meth) acrylic acid diester, (meth) acrylic acid triester or (meth) acrylic acid tetraester of a trihydric or higher hydric alcohol such as pentaerythritol;

(Meth) acrylic acid oligoesters such as (meth) acrylic acid triester or (meth) acrylic acid tetraester of a polyalkylene glycol adduct of a trihydric or higher polyhydric alcohol:

1,4-cyclohexanediol, 1,4
-(Meth) acrylic acid oligoesters of cyclic polyhydric alcohols such as benzenediol and 1,4-dihydroxyethylbenzene;

(Meth) acrylic acid oligoesters such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate Prepolymers;

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, citraconic acid and mesaconic acid;

Monomethyl esters, monoethyl esters, monopropyl esters, monobutyl esters, monohexyl esters, monooctyl esters, etc. of unsaturated polycarboxylic acids such as itaconic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid Esters containing free carboxyl groups;

Polyhydric esters such as dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihexyl ester and dioctyl ester of unsaturated polycarboxylic acids such as itaconic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid ;

(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'-hexamethylenebis (meth) acrylamide, crotonic amide,
Unsaturated amides such as cinnamamide:

Vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate and vinyl stearate can be used.

The solvent (C) used in the present invention includes:
Any solvent may be used as long as it can dissolve the fluorine-containing copolymer (A) and the polymerizable compound (B) having an ethylenically unsaturated group. From aromatic compounds such as benzene, toluene, ethylbenzene, propylbenzene and xylene, acetone, methyl ethyl ketone, diethyl ketone, 2-heptanone, diisopropyl ketone, methyl propyl ketone, ethyl propyl ketone, 2-hexanone, methyl isobutyl ketone, -Heptanone, ethyl isobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone, methyl acetoacetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate,
Ethyl acetoacetate, propyl acetoacetate, acetonylacetone, mesityl oxide, carbonyl compounds such as acetophenone, methanol, ethanol, propanol,
Isopropanol, butanol, isobutanol, diacetone alcohol, ethylene glycol, diethylene glycol, triethylene glycol, cyclohexanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 2- (methoxymethoxy) ethanol, 2- (isopentyloxy) ethanol Alcohol compounds such as, 2-phenoxyethanol,
Esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ether compounds such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetamido, methylacetamide, ethylacetamide, dimethylacetamide, diethylacetamide, amide compounds such as methylethylacetamide, chloroform, Examples thereof include halogen-containing compounds such as dichloromethane, dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene, and 2-chloroethanol.

The amount of the solvent (C) used is usually from 300 to 1 based on 100 parts by weight of the total of the fluorine-containing copolymer (A) and the polymerizable compound (B) having an ethylenically unsaturated group.
It may be in the range of 10,000 parts by weight, preferably 1,000 to 10,000 parts by weight.

In the present invention, the fluorine-based paint (coating composition) is used in an amount of 0.1% based on the solid content of the paint.
It is essential that the silicone oil be contained in an amount of 1 to 15.0% by weight, preferably 0.5 to 10.0% by weight.
If the silicone oil content is less than the above range, the effect of improving the scratch resistance is not sufficient, while if it is too large, the scratch resistance is improved, but the coating composition has a uniform film thickness on the substrate. May not be coated, or the appearance may be poor.

The silicone oil used in the present invention is represented by the following general formula (1): R ¹ R ² R ³ SiO— [R ⁴ R ⁵ SiO] _m [R ⁶ R ⁷ SiO] _n —SiR ⁸ R ⁹ R ¹⁰ (1) (wherein, R ^{1 to} R ¹⁰ each independently represent an alkyl group, an aryl group, or another organic group; m and n each represent an integer.) Compounds in which the substituents R ^{1 to} R ¹⁰ in the above-mentioned compound having a straight-chain siloxane structure are substituted with other substituents are exemplified. The alkyl group in the substituents R ^{1 to} R ¹⁰ is usually an alkyl group having 1 to 12 carbon atoms, more specifically, a methyl group, an ethyl group and the like, and the aryl group is a phenyl group and the like.

[0040] Such silicone oils usually have a substituent R
¹ depending on the type of to R ¹⁰ is classified into a non-reactive silicone oil and reactive silicone oil, dimethyl silicone oil as a non-reactive silicone oil, phenylmethyl silicone oil, alkyl-aralkyl-modified Ricoh oil, fluorosilicone oil , Polyether-modified silicone oils, fatty acid ester-modified silicone oils, and the like. Reactive silicone oils include methyl hydrogen silicone oil, silanol group-containing silicone oil, alkoxy group-containing silicone oil, phenol group-containing silicone oil, methacryl-modified silicone oil, amino Modified silicone oil, carboxylic acid modified silicone oil, carbinol modified silicone oil, epoxy modified silicone oil, mercapto modified silicone oil Fluorine-modified silicone oil, polyether-modified silicone oil is exemplified, respectively. These silicone oils may be used by incorporating only one of them in the paint, or two or more thereof may be used in combination. The reactive silicone oil may have other functional groups introduced as necessary. The viscosity of silicone oil (measured at 25 ° C.) is usually about 1 to 1,000,000 mm ² / s.

Among the above silicone oils, dimethyl silicone oil and methacryl-modified silicone oil are particularly preferably used. Among them, the higher the viscosity of dimethyl silicone oil is, the more preferable it is, and the viscosity is about 1000 mm ² / s or more, especially about 10,000 mm ² / s
The above are preferred. By using these silicone oils, it is possible to obtain a film having satisfactory scratch resistance as well as good film appearance when coated on a substrate and sufficient durability. In consideration of the abrasion resistance, the film appearance and the durability, in the case of dimethyl silicone oil, the addition amount of the silicone oil to the coating solid content is particularly preferably in the range of about 0.5% by weight to about 9% by weight. Is particularly preferably used in an amount of about 1% to about 9%.

The method of adding silicone oil to the coating composition is to add an appropriate amount of silicone oil to the coating composition and then adjust the solid content of the coating to about 0.1 to about 33.3% by weight with a solvent or the like. Dilution, a method of diluting the coating composition with a solvent or the like to a solid concentration of about 0.1 to about 33.3% by weight, and then adding silicone oil, or a combination of both methods. Any of the methods may be used. After the silicone oil has been added to the coating composition, it can be used as a scratch-resistant coating composition in a solution state or a dispersion state by an operation such as ordinary stirring.

The abrasion-resistant coating composition of the present invention comprises:
It is cured by the polymerization effect of the ethylenically unsaturated group of the polymerizable compound (B) contained. As such a curing means, a means for irradiating an active energy ray to a film of the scratch-resistant coating composition or a means for heating is used. As the active energy ray, an electron beam, an ultraviolet ray, and a visible ray can be usually used. In particular, in the case of a film for antireflection use, a film having sufficient scratch resistance can be obtained even when cured in the air, an inert gas, or a mixed gas thereof. Performance is improved. As the inert gas, a nitrogen gas, an argon gas or the like is used.

When the curing treatment is performed by irradiation with active energy rays, when an electron beam is used, the curing treatment can be performed without adding a polymerization initiator to the abrasion-resistant coating composition. When an ultraviolet ray or a visible ray is used as the active energy ray, it is decomposed by irradiation of the active energy ray to generate, for example, a radical, thereby initiating a polymerization reaction of the polymerizable compound (B). A photopolymerization initiator is added to the abrasion resistant coating composition.

Specific examples of such a photopolymerization initiator include, for example, acetophenone, acetophenone benzyl ketone, anthraquinone, 1- (4-isopropylphenyl-2-hydroxy-21-methylpropan-1-one). , Carbazole, 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-morpholinopropane -1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2
-Methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoisopropyl ether, benzophenone, Michler's ketone, 3-methylacetophenone,
3,3 ', 4,4'-tetratert-butylperoxycarbonylbenzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1- Butanone, 4-benzoyl-4'-methyldiphenylsulfide, benzyl, or a combination of BTTB with xanthene, thioxanthene, coumarin, ketocoumarin, and other dye sensitizers can be used.

Of these photopolymerization initiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
-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, 11-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, -(Dimethylamino) -1- [4-1 (morpholinylphenyl) -2-phenylmethyl-1-butanone and the like can be used.

Further, when a heating means is used for the curing treatment, a thermal polymerization initiator which generates, for example, a radical by heating to start the polymerization of the polymerizable compound (B) is used as the scratch-resistant coating composition. Is added to Specific examples of the thermal polymerization initiator include, for example, 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) can be used.

The amount of the photopolymerization initiator or the thermal polymerization initiator to be added to the scratch-resistant coating composition of the present invention is usually about 0.1 to about 100 parts by weight based on 100 parts by weight of the solids contained in the scratch-resistant coating composition. 50 parts by weight. If the amount exceeds about 50 parts by weight, the handling of the coating agent and the mechanical strength and appearance of the formed thin film, particularly the color tone, may be adversely affected.
If the amount is less than parts by weight, the curing speed is low.

The method of coating the scratch-resistant coating composition is not particularly limited, and the coating is performed by any known method such as spraying, dipping, roll coating, flow coating, gravure coating, and spin coating. be able to. Drying after coating can be performed by any method such as air drying or heat drying. In addition, as a method for curing the coating film, a method for curing by irradiation with active energy rays or heating can be appropriately used as needed.

The coating composition of the present invention is applied by coating on a substrate. The substrate used for coating preferably has high transparency. Specifically, polymethyl methacrylate, a copolymer having polymethyl methacrylate as a main structural unit, polystyrene, styrene-methyl methacrylate copolymer, styrene acrylonitrile copolymer, polycarbonate, triacetyl cellulose resin, polyethylene terephthalate resin Preferred examples thereof include cellulose acetate butyrate resin, glass, and the like. Further, additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, and a coloring agent may be contained in the resin forming the base material. The shape of the substrate is not particularly limited, but a specific example is a plate-like product having a thickness of about 0.1 to about 50 mm.

Since the low refractive index layer is characterized in that it is formed on the surface of the base material, a film that imparts another function may be formed between the base material and the low refractive index layer. For example, a hard coat film or the like can be used. The hard coat film is not particularly limited, and an ordinary hard coat resin can be used. The thickness of the hard coat film is about 1 to about 10
μm, preferably about 3 to about 7 μm. In addition, a hard coat film with antistatic or antistatic properties to prevent dust adhesion, etc., and a hard coat film with a higher refractive index than the substrate to further improve low reflection performance, or their functions May be used as a hard coat film.

Examples of the component imparting antistatic properties or antistatic properties include ordinary antistatic agents, inorganic oxide particles, and mixtures thereof. Examples of the component that imparts a high refractive index include an organic component containing bromo, sulfur, and benzene rings, inorganic oxide fine particles, and a mixture thereof. The inorganic oxide is appropriately used for antistatic or antistatic properties, or for the purpose of increasing the refractive index, and examples thereof include tin oxide, antimony oxide, titanium oxide, zirconium oxide, and zinc oxide. In order to ensure the transparency of the film, the size of the inorganic oxide particles is preferably sufficiently smaller than the wavelength of visible light, and specifically, 100 nm.
The thickness is particularly preferably 50 nm or less. The method for forming these hard coat films is not particularly limited, and is usually performed on a substrate such as a transparent substrate by a coating method such as a spray method, a dipping method, a roll coating method, a flow coating method, a gravure coating method, and a spin coating method. After coating, air-drying or heat-drying, a method of forming by a usual curing method by irradiation of active energy rays or heating is used.

When the abrasion-resistant coating composition of the present invention is applied as an antireflection layer, when coated on a substrate, the coating has a refractive index of 1.49 or less and a thickness of 0.01.
It is recommended to apply in the range of μm to 1 μm.

The scratch-resistant coating composition of the present invention, for example, a front plate for a projection television, a front plate for a plasma display, a front plate for a liquid crystal display, and a display device such as a polarizing film disposed on the outermost surface of the liquid crystal display. Used as components, optical lenses, optical films, glasses lenses, optical fiber cladding materials, optical parts such as light guide plates, building materials such as soundproofing boards, signs and signs, water tanks, automobile instrument covers, solar cell covers, show window glasses, etc. can do.

[0055]

According to the present invention described in detail above, (A) vinylidene fluoride 20 to 90 is used as a coating composition.
% By weight and 5-75% by weight of hexafluoropropylene
Is obtained by dissolving in a solvent (C) 100 parts by weight of a fluorine-containing copolymer obtained by copolymerizing a monomer composition containing (B) and 20 to 200 parts by weight of a polymerizable compound having an ethylenically unsaturated group (B). By using a very simple method of using a fluorine-based paint that is cured by irradiation with active energy rays or heating and adding a specific amount of silicone oil to the paint, it has low reflection performance as well as conventionally known coating compositions. They have been found to exhibit an extremely excellent effect of improving scratch resistance as compared with products, and have extremely large industrial utility value. In addition, the film obtained by this method also has the effect of improving the anti-fingerprint property and the ability to remove fingerprint-fouling stains, and is of great industrial value.

[0056]

The present invention will be described in more detail with reference to the following examples. In the present invention, the scratch resistance was determined by the following method.

[Bencott Scratch Resistance Test] Using a surface property test device (manufactured by HEIDON), a Bencott cloth BEMC was used.
OT M-3 (made by ASAHI CHEMICAL)
Attached in a stack, contacted horizontally to the surface of the coating plate, load 500g / cm ² , stroke 5c
m, the reciprocating speed was 600 cm / min, and the number of reciprocations was 300, and the abrasion resistance test was performed. For the evaluation of scratch resistance, the presence or absence of scratches was visually observed as shown below. ：: no change, △: some scratches (up to about 10), ×: countless scratches, peeling of coating

[Cheesecloth Scratch Resistance Test] A US Summers O was tested with an eraser abrasion tester (manufactured by Motomitsu Seisakusho).
5 kg / cm using cheesecloth manufactured by Ptical
Reciprocate with the load applied under the load of ² until the coating layer is scratched, and measure the number of reciprocations.

[Fingerprint Adhesion Test] An index finger was pressed against the surface of the coated plate, and the state of adhesion of the fingerprint was visually observed. ：: no fingerprint attached, ：: fingerprint attached but not noticeable, Δ: fingerprint attached and noticeable, ×: fingerprint attached and quite noticeable.

[Fingerprint Adhesion Removal Test] The fingerprint adhesion stains on the surface of the coating plate were measured using a BEMCOT cloth BEMCOT.
The state after wiping with M-3 (manufactured by ASAHI CHEMICAL) by hand wiping was visually observed and determined as follows. ◎: Fingerprint stains can be easily removed, ○: Fingerprint stains can be removed, Δ: Fingerprint stains are difficult to remove, ×:
Fingerprint stains cannot be removed.

Example 1 Vinylidene fluoride / hexafluoroethylene / tetrafluoroethylene = 60/20/20 in monomer composition ratio
(Parts by weight) 70 parts by weight of a fluorine-containing copolymer and 30 parts by weight of dipentaerythritol hexaacrylate were diluted to 3% by weight in methyl isobutyl ketone to obtain a coating composition (A). Based on the solid content of the coating composition (A), 4% by weight of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone, dimethyl silicone oil KF96H-100,000 cs (viscosity 100,000 m
m ² / s, a refractive index of 1.403, manufactured by Shin-Etsu Silicone Co., Ltd.) in an amount of 2% by weight to obtain a scratch-resistant coating composition. The prepared scratch-resistant coating composition was coated on a 150 × 50 × 2 mm Sumielec FT plate (permanently antistatic hard-coated plate, manufactured by Sumitomo Chemical Co., Ltd.) by a dipping method at a pulling rate of 25 cm / min, and dried at room temperature. Thereafter, using an ultraviolet irradiation device (manufactured by Eye Graphic Co., Ltd.) in the atmosphere, the irradiation energy is about 400.
The coating is cured under the condition of mJ / cm ^{2 and} the thickness is about 0.1 μm.
m were prepared. Note that a small film thickness measuring device OP-50S (manufactured by Toray Industries, Inc.) was used for film thickness measurement. Using the prepared coated plate, the scratch resistance was evaluated by a Bencott abrasion test. In addition, fingerprint adhesion and fingerprint adhesion dirt removal were evaluated. Table 1 shows the results.

Example 2 Based on the solid content of the coating composition (A) shown in Example 1, 4% by weight of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone and a methacryl-modified silicone oil X-22-164B ( A viscosity of 58 mm ² / s, a refractive index of 1.410, manufactured by Shin-Etsu Silicone Co., Ltd.) was added to 3 wt% to obtain a scratch-resistant coating composition. The prepared scratch-resistant coating composition was subjected to a pulling speed of 40 c.
150 × 50 by dipping under the condition of m / min
X2mm Smielec FT plate (Permanent antistatic hard-coated plate, manufactured by Sumitomo Chemical Co., Ltd.), and after drying at room temperature, using an ultraviolet irradiation device (manufactured by Eye Graphic Co., Ltd.) in the atmosphere, irradiation energy of about 400 mJ / cm. ^The coating was cured under the conditions of ² to prepare a coating plate having a thickness of about 0.1 μm. In addition, a small film thickness measuring device O is used for film thickness measurement.
P-50S (manufactured by Toray Industries, Inc.) was used. Using the prepared coated plate, the scratch resistance was evaluated by a Bencott abrasion test. In addition, fingerprint adhesion and fingerprint adhesion dirt removal were evaluated. Table 1 shows the results.

Example 3 Based on the solid content of the coating composition (A) shown in Example 1, 4% by weight of a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone, a fluorine-modified silicone oil FL-100 (viscosity 100 mm) ² / s, refractive index 1.37
9, Shin-Etsu Silicone Co., Ltd.) in an amount of 3% by weight to obtain a scratch-resistant coating composition. The prepared scratch-resistant coating composition was subjected to a pulling speed of 40 cm / mi.
150 × 50 × 2mm by dipping under the condition of n
Sumielec FT board (permanent antistatic hard coat board,
(Sumitomo Chemical Co., Ltd.), dried at room temperature, and cured in air using an ultraviolet irradiation apparatus (manufactured by Eye Graphic Co., Ltd.) under the conditions of irradiation energy of about 400 mJ / cm ² to obtain a film thickness of about 0.1 μm. A 1 μm low reflection coated plate was prepared. In addition, a small film thickness measuring device OP-50S was used for film thickness measurement.
(Manufactured by Toray Industries, Inc.). Using the prepared low-reflection coated plate, abrasion resistance was evaluated by a Bencott abrasion test.
In addition, fingerprint adhesion and fingerprint adhesion dirt removal were evaluated.
Table 1 shows the results.

Comparative Example 1 A photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone was added at 4% by weight based on the solid content of the solid content (A) of the coating composition shown in Example 1 to prepare a coating composition. . The prepared coating composition was dipped at a pulling rate of 45 cm / min by dipping.
50 × 50 × 2 mm Sumielec FT board (Permanent antistatic hard coat board, manufactured by Sumitomo Chemical Co., Ltd.)
After drying at room temperature, an irradiation energy of about 400 mJ /
The coating was cured under the condition of cm ² to form a coating having a thickness of about 0.1 μm. Note that a small film thickness measuring device OP-50S (manufactured by Toray Industries, Inc.) was used for film thickness measurement. Using the prepared coated plate, the scratch resistance was evaluated by a Bencott abrasion test. In addition, fingerprint adhesion and fingerprint adhesion dirt removal were evaluated. Table 1 shows the results.

Comparative Example 2 The photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone was 4% by weight based on the solid content of the solid content (A) of the coating composition shown in Example 1, and liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) Was added so as to be 4% by weight to prepare a coating composition. By dipping the prepared coating composition under conditions of a pulling speed of 40 cm / min,
After coating on a Sumielec FT plate (permanently antistatic hard coat plate, manufactured by Sumitomo Chemical Co., Ltd.) of 150 × 50 × 2 mm, drying at room temperature, using an ultraviolet irradiation device (manufactured by Eye Graphic Co., Ltd.) in the atmosphere, the irradiation energy 400m
The film is cured under the condition of J / cm ^{2 and} the thickness is about 0.1 μm.
Was prepared. Note that a small film thickness measuring device OP-50S (manufactured by Toray Industries, Inc.) was used for film thickness measurement. Using the created coating plate, by Bencott wear test,
The abrasion resistance was evaluated. In addition, fingerprint adhesion and fingerprint adhesion dirt removal were evaluated. Table 1 shows the results.

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[Table 1] The numbers in the table represent the number of round trips. In addition, the adhesion indicates the fingerprint adhesion and the removal indicates the fingerprint adhesion removal.

Example 4 A coating having a thickness of 0.1 μm was formed in the same manner as in Example 1 except that the coating composition shown in Example 1 was cured under a nitrogen atmosphere (oxygen concentration: 0.2% or less). A board was created. In addition, a small film thickness measuring device OP-5 was used for film thickness measurement.
OS (manufactured by Toray Industries, Inc.) was used. Using the prepared coating plate, the scratch resistance was evaluated by a cheese cloth scratch resistance test. The coating plate prepared in Example 1 was used for comparison. Table 2 shows the results.

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[Table 2]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kiyoshi Muto 2-10-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Shinsuke Ochiai 2- 10-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Kagaku Kogyo Co., Ltd. WA02 4J038 CD111 CD112 CD131 CD132 DL032 FA041 FA042 FA061 FA062 FA091 FA092 FA101 FA102 FA121 FA122 FA151 FA152 FA271 FA272 KA03 KA06 NA05 NA11 NA19 PA17 PA19 PB02 PB05 PB08

Claims (3)

[Claims] (1) 20-90% by weight of vinylidene fluoride (A)
And 100 parts by weight of a fluorine-containing copolymer obtained by copolymerizing a monomer composition containing 5 to 75% by weight of hexafluoropropylene, and 20 to 200 parts by weight of (B) a polymerizable compound having an ethylenically unsaturated group. Is dissolved in the solvent (C), and the solid content of the coating composition which is cured by irradiation with active energy rays or by heating,
An abrasion-resistant coating composition comprising 0.1 to 15.0% by weight of silicone oil. 2. The composition according to claim 1, wherein the solid content of the coating composition is
A substrate coated with a scratch-resistant coating composition containing 0.1 to 15.0% by weight of silicone oil. 3. A coating film having a refractive index of 1.
3. The substrate according to claim 2, wherein the substrate has a thickness of not more than 49 and a thickness in a range of 0.01 μm to 1 μm.