JP2003089759A - Kit for coating and method for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a kit for coating, concealing the colors of a material to be coated such as a metal, a metal alloy, a resin, a ceramics, an earthenware material, a composite resin cured material, a hard tissue, capable of forming a coating layer having an excellent durability in adhesivity to a material to be covered even being exposed under an environment of always making a contact with water, and a method for coating. SOLUTION: The kit for coating consists of (A) an adhesive composition containing (a) an adhesive polymerizable monomer and (b) a solvent and (B) a coating composition containing (c) a fluorocarbon group-containing polymerizable monomer, (d) a polymerizable monomer, (e) a polymerization initiator and (f) an inorganic filler having >=1.9 birefringence, and the method for coating comprises applying the adhesive composition (A) on the surface of the material to be coated, applying the coating composition (B) on the same composition by laminating and further polymerizing and curing the coating layers to form a coating layer on the surface of the material to be coated.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to medical, electronic industry,
The present invention relates to a coating kit and a coating method capable of forming a coating layer having excellent adhesiveness in various fields such as precision machinery industry and jewelry. The coating kit and the coating method of the present invention can be applied in the various fields described above, but the color of adherends such as metals, metal alloys, resins, ceramics, porcelain, cured composite resin and hard tissues It is particularly suitable for the dental field, since it has excellent adhesive strength and durability against these adherends. Hereinafter, the present invention will be described by taking a dental application as an example.

[0002]

2. Description of the Related Art In dental treatment and preparation of dental restorative materials, metal castings such as metal alloys are often coated with organic materials from the viewpoint of aesthetics. As a method for coating such a metal casting with an organic material, for example, Japanese Patent Application Laid-Open No. 2-4
Japanese Patent No. 0322 discloses a coating in which a solvent containing an oxidant is applied to a metal surface, and then a polymerizable monomer, a photoinitiator, a reducing agent and an inorganic filler having a refractive index of 1.9 or more are contained on the metal surface. A method is described in which the composition is laminated and applied and cured.

[0003]

However, when the coating is carried out using the polymerizable monomer specifically described in the publication (there is no description of the fluorocarbon group-containing polymerizable monomer), it is sure that Although it is useful as a method for coating a metal cast body, there is a problem that the adhesive strength between the coating layer and the metal cast body is reduced in an environment where it is constantly in contact with water for a long period of time.

The objects of the present invention are metals, metal alloys, resins,
A coating that shields the color of adherends such as ceramics, porcelain, hardened composite resins and hard tissues, and has excellent adhesive strength and durability even when exposed to an environment that is in constant contact with water for a long period of time. It is to provide a coating kit and a coating method capable of forming a layer.

[0005]

Means for Solving the Problems The present inventor has paid attention to a fluorocarbon group-containing polymerizable monomer excellent in water repellency, and as a result of earnest studies, surprisingly, as a result, an adhesive polymerizable monomer and a solvent have been surprisingly obtained. After applying an adhesive composition containing a to a surface of an adherend, a fluorocarbon group-containing polymerizable monomer, a polymerizable monomer, a polymerization initiator and an inorganic filler having a refractive index of 1.9 or more are applied thereon. It was found that by coating the coating composition containing it in layers and polymerizing and curing it to form a coating layer, it is possible to shield the color of the adherend and to obtain a very excellent adhesive strength durability. The present invention has been completed.

That is, the present invention provides an adhesive composition (A) containing an adhesive polymerizable monomer (a) and a solvent (b).
And a fluorocarbon group-containing polymerizable monomer (c), a polymerizable monomer (d), a polymerization initiator (e) and a refractive index of 1.9.
A coating kit comprising the coating composition (B) containing the above inorganic filler (f).

Further, in the present invention, after the adhesive composition (A) containing the adhesive polymerizable monomer (a) and the solvent (b) is applied to the surface of the adherend, the fluorocarbon group-containing polymerization is applied thereon. Coating composition (B) containing a polymerizable monomer (c), a polymerizable monomer (d), a polymerization initiator (e) and an inorganic filler (f) having a refractive index of 1.9 or more is laminated and applied. The coating method further comprises forming a coating layer on the surface of the adherend by polymerizing and curing the coating layer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the adhesive polymerizable monomer (a) used in the adhesive composition (A) of the present invention include sulfur group-containing polymerizable monomer (a1) and phosphate group. Containing polymerizable monomer (a2), carboxylic acid group-containing polymerizable monomer (a
3), sulfonic acid group-containing polymerizable monomer (a4), polymerizable group-containing silane coupling agent (a5), and the like, metals, metal alloys, hard structures, resins, cured composite resins, ceramics and ceramics. Examples thereof include a polymerizable monomer having adhesiveness to materials and the like. In the present invention, (meth) acrylic is used to comprehensively represent both methacrylic and acrylic.

Examples of the sulfur group-containing polymerizable monomer (a1) include, for example, a mercapto group, a hydropolysulfide group, a sulfide group, a polysulfide group, a thioaldehyde group, a thioketone group, a thioacetal group, a thiocarboxylic acid group in the molecule. Thiocarboxylic acid ester group, thiocarboxylic acid anhydride group, thiophenecarboxylic acid group, thiirane group, mercaptothiadiazole group, thiouracil group, triazinedithione group, triazinemonothione group, thiophosphoric acid group, thiophosphoric acid ester group, thiopyrophosphoric acid group, thiopyrophosphoric acid group Examples thereof include a polymerizable monomer having an ester group and a thiophosphoric acid halide group. More specifically, the following compounds can be mentioned, for example. It should be noted that alkali metal salts, alkaline earth metal salts, ammonium salts and the like of these sulfur group-containing polymerizable monomers exhibit adhesiveness and are therefore preferably used.

[0010]

[Chemical 1]

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical 12]

[0022]

[Chemical 13]

[0023]

[Chemical 14]

[0024]

[Chemical 15]

[0025]

[Chemical 16]

The phosphoric acid group-containing polymerizable monomer (a2) may be, for example, a phosphoric acid group [phosphinico group;
(= O) OH, phosphono group; -P (= O) (OH) ₂ ]
Or pyrophosphate group [-P (= O) (OH) -OP (=
The polymerizable monomer etc. which have O) (OH)-] can be mentioned. More specifically, for example, 2- (meth) acryloyloxyethyl dihydrogen phosphate,
3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen Phosphate, 7- (meth) acryloyloxyheptyldihydrogenphosphate, 8- (meth) acryloyloxyoctyldihydrogenphosphate, 9- (meth) acryloyloxynonyldihydrogenphosphate, 10- (meth) acryloyloxydecyldiphosphate Hydrogen phosphate, 11-
(Meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth)
Acryloyloxyhexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, di [2- (meth) acryloyloxyethyl] hydrogen phosphate, di [4- (meth) acryloyloxybutyl] hydro Gen phosphate, di [6- (meth) acryloyloxyhexyl] hydrogen phosphate, di [8- (meth) acryloyloxyoctyl] hydrogen phosphate, di [9- (meth) acryloyloxynonyl] hydrogen phosphate, di [ 10-
(Meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenylhydrogen phosphate, 2- (meth) acryloyloxy Ethyl 2-bromoethyl hydrogen phosphate, 2-
(Meth) acryloyloxyethyl phenylphosphonate, 10- (meth) acryloyloxydecylphosphonic acid, etc .; (5-methacryloxy) pentyl-3-phosphonopropionate, (6) described in JP-A-3-294286. -Methacryloxy) hexyl-3-phosphonopropionate, (10-methacryloxy) decyl-3-phosphonopropionate, (6-methacryloxy) hexyl-3-phosphonoacetate, (10-methacryloxy) decyl-3- Phosphonoacetate and the like; 2-methacryloyloxyethyl (4-methoxyphenyl) hydrogen phosphate, 2-methacryloyloxypropyl (4-methoxyphenyl) hydrogen phosphate, and pyrophosphoric acid described in JP-A-62-182885. Di [2- (meth) acryloyloxyethyl], pyrophosphate di [4- (meth) acryloyloxybutyl], pyrophosphate di [6- (meth) acryloyloxyhexyl], pyrophosphate di [8- (meth) acryloyl] Oxyoctyl], pyrophosphate di [10-
(Meth) acryloyloxydecyl] and the like; and further, JP-A-52-113089 and JP-A-53-67740.
JP-A-53-69494, JP-A-53-69494
Examples include phosphoric acid group-containing polymerizable monomers exemplified in JP-A-144939, JP-A-58-128393 and JP-A-58-192891, and further, acid chlorides and alkalis thereof. Metal salts, alkaline earth metal salts, ammonium salts and the like are also included.

The carboxylic acid group-containing polymerizable monomer (a3) is, for example, a carboxylic acid group [carboxyl group; -C (= O) OH, acid anhydride group; -C (= O)-in the molecule. O
Examples thereof include a polymerizable monomer having —C (═O) —. More specifically, for example, maleic acid, methacrylic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalate. Acid, 4-
(Meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid, and their acid anhydrides; 5-
(Meth) acryloylaminopentylcarboxylic acid, 6-
(Meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decanedicarboxylic acid, 11- (meth ) Acryloyloxy-1,1-undecanedicarboxylic acid and the like, and further include acid chlorides, alkali metal salts, alkaline earth metal salts and ammonium salts thereof.

The sulfonic acid group-containing polymerizable monomer (a4) is, for example, a sulfonic acid group [sulfo group;
SO ₃ H, —OSO ₃ H] and other polymerizable monomers. More specifically, for example, 2-
(Meth) acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, 2-sulfoethyl (meth) acrylate, 10-sulfodecyl (meth) acrylate, 6-sulfohexyl (meth) acrylate and the like can be mentioned. Acid chlorides, alkali metal salts, alkaline earth metal salts, ammonium salts and the like.

As the silane coupling agent (a5) having a polymerizable group, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-
Methoxyethoxy) silane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane,
6- (meth) acryloyloxyhexyltriethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 10- (meth) acryloyloxydecyltriethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, 11 -(Meta)
Acryloyloxyundecyltriethoxysilane, 3
-(Meth) acryloyloxypropyl pentamethyldisiloxane etc. are mentioned.

These adhesive polymerizable monomers have different adhesive strengths depending on the type of adherend. For example, when adhered to gold, platinum, palladium, or alloys containing a large amount of these metals. Is a sulfur group-containing polymerizable monomer (a
When 1) is used, excellent adhesiveness can be obtained. In the case of adhering to nickel, chromium, cobalt, iron, titanium, aluminum, silver, copper, tin, or alloys containing a large amount of these metals, the phosphoric acid group-containing polymerizable monomer (a2). , A carboxylic acid group-containing polymerizable monomer (a
When 3) is used, excellent adhesiveness can be obtained. Further, in the case of adhering to hard tissues such as teeth, bones and nails, a phosphoric acid group-containing polymerizable monomer (a2), a carboxylic acid group-containing polymerizable monomer (a3), a sulfonic acid group-containing Excellent adhesiveness can be obtained by using the polymerizable monomer (a4). In the case of adhering to porcelain, ceramics, or cured composite resin, phosphoric acid group-containing polymerizable monomer (a2), carboxylic acid group-containing polymerizable monomer (a3), and silane having a polymerizable group. Excellent adhesiveness can be obtained by using the coupling agent (a5). Therefore, it is preferable to use these various adhesive polymerizable monomers in combination because excellent adhesiveness can be obtained for all adherends.

These adhesive polymerizable monomers (a) are used alone or in combination of plural kinds. If the content of these adhesive polymerizable monomers (a) is too large or too small, the adhesive strength may decrease, so that the content of the adhesive composition (A) of the present invention relative to the total weight. And preferably in the range of 0.00001 to 90% by weight,
The content is more preferably 0.001 to 50% by weight, further preferably 0.1 to 30% by weight.

The solvent (b) used in the adhesive composition (A) of the present invention is not limited as long as it can dissolve or uniformly disperse the adhesive polymerizable monomer (a). For example, the volatile solvent (b1) and the polymerizable monomer (b2) other than the adhesive polymerizable monomer described above are preferably used. As such a volatile solvent (b1), a volatile solvent having a boiling point of 150 ° C. or lower at atmospheric pressure, particularly 110 ° C. or lower is preferable, and examples thereof include alcohols such as water, ethanol, methanol, 1-propanol, and isopropyl alcohol. , Acetone, ketones such as methyl ethyl ketone, ethyl acetate, methyl acetate, ethyl propionate,
Esters such as methyl methacrylate, ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane and tetrahydrofuran, hydrocarbons such as heptane, hexane and toluene, and halogenated hydrocarbons such as chloroform and dichloromethane. Is preferably used. Above all,
Ethanol, isopropyl alcohol, acetone, methyl methacrylate, water and the like are preferably used. It is usually desirable that these volatile solvents are evaporated as much as possible by a dental air syringe or the like when used.

Specific examples of the polymerizable monomer (b2) are shown below. A monomer having one olefinic double bond is used as a monofunctional monomer, and the number of olefinic double bonds is changed according to the number of olefinic double bonds. And expressed as a bifunctional monomer or a trifunctional monomer.

Monofunctional monomer: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2, 3-dihydroxypropyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate , Lauryl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate,
(Meth) acrylamide, 2-hydroxyethyl (meth) acrylamide and the like can be mentioned.

Bifunctional monomer: ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipentaerythritol di (meth)
Acrylate, polyethylene glycol di (meth) acrylate (the number of oxyethylene groups is 9, 14 and 2
3), propylene glycol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, 1,1
0-decanediol di (meth) acrylate, bisphenol A diglycidyl methacrylate, 2,2-bis [4- (meth) acryloyloxyethoxyphenyl]
Propane, 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane, 1,2 -Bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, [2,2,4 −
Trimethylhexamethylene bis (2-carbamoyloxyethyl)] dimethacrylate, 1,3-di (meth) acryloryloxy-2-hydroxypropane and the like can be mentioned.

Monofunctional or higher functional monomers: trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, N, N '-(2,2,4-Trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-
Tetraacryloyloxymethyl-4-oxyheptane and the like can be mentioned.

These solvents (b) are used alone or in combination of plural kinds. The content of these solvents (b) is not particularly limited, but if it is too small or too large, the adhesive strength may decrease, so that it is relative to the total weight of the adhesive composition (A) of the present invention. ,
It is preferably used in the range of 10 to 99.99999% by weight, more preferably in the range of 50 to 99.999% by weight, and further preferably in the range of 70 to 99.9% by weight.

The fluorocarbon group-containing polymerizable monomer (c) used in the coating composition (B) of the present invention has a fluorocarbon group represented by the following formula (I) in the molecule, and is methacryloyl. It is a polymerizable monomer containing an olefinic double bond such as a group, an acryloyl group, a vinyl group and a vinylbenzyl group.

[0039]

[Chemical 17]

Examples of the fluorocarbon group-containing polymerizable monomer (c) include the following general formulas (1) to (2).
The polymerizable monomer represented by 6) can be mentioned.

[0041]

[Chemical 18]

[0042]

[Chemical 19]

[0043]

[Chemical 20]

[0044]

[Chemical 21]

Among these, general formulas (11) to (2)
The polyfunctional fluorocarbon group-containing polymerizable monomer having two or more olefinic double bonds in the molecule such as 0) is excellent in curability and can be polymerized and cured in a short time, which is very suitable. Is. These fluorocarbon group-containing polymerizable monomers (c) are used alone or in combination of two or more. The content of the fluorocarbon group-containing polymerizable monomer (c) is not particularly limited,
If it is too much or too little, the adhesiveness may decrease, so it is preferably 1 to 90% by weight, relative to the total weight of the polymerizable monomers constituting the coating composition (B) of the present invention. It is more preferably used in the range of 5 to 80% by weight, further preferably 10 to 70% by weight.

The polymerizable monomer (d) used in the coating composition (B) of the present invention is a polymerizable monomer other than the fluorocarbon group-containing polymerizable monomer (c),
For example, the polymerizable monomer (b2) exemplified as the constituent component of the adhesive composition can be used. Among these, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Dipentaerythritol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, Bisphenol A diglycidyl methacrylate, 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane,
2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2-bis [4- [3-
(Meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane, 1,2-bis [3- (meth)]
Acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol di (meth) acrylate,
1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, [2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl)]
Dimethacrylate, 1,3-di (meth) acryloyloxy-2-hydroxypropane, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, N, N '-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diacryloyloxy-2 , 2, 6, 6-
A difunctional or higher functional monomer such as tetraacryloyloxymethyl-4-oxyheptane is preferably used.

The content of the polymerizable monomer (d) is not particularly limited, but if it is too much or too little, the adhesiveness may decrease, so the coating composition (B) of the present invention is used. It is preferably 10 to 99% by weight, more preferably 20 to 95% by weight, still more preferably 30 to 90% by weight based on the total weight of the polymerizable monomers.
Used in the weight% range.

As the polymerization initiator (e) used in the coating composition (B) of the present invention, known polymerization initiators can be used without limitation. Examples of such a polymerization initiator include α-diketones, ketals, thioxanthones, acylphosphine oxides, coumarins, halomethyl group-substituted-s-triazine derivatives, organic peroxides and the like.

Examples of α-diketones include camphorquinone, benzyl, 2,3-pentanedione and the like. Examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.
Examples of the acylphosphine oxides include, for example,
2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-Trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethylbenzoyl) phenylphosphine oxide, bis (2,6)
-Dimethoxybenzoyl) phenylphosphine oxide, tris (2,4,6-trimethylbenzoyl) phosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and JP-B-3 Examples of the water-soluble acylphosphine oxide compound disclosed in JP-A-57916.

As coumarins, 3,3'-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin and the like are described in JP-A-10-245525. There are compounds. As the halomethyl group-substituted-s-triazine derivative, 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4, 6-
Examples thereof include compounds described in JP-A-10-245525, such as bis (trichloromethyl) -s-triazine.

Examples of the organic peroxides include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides and the like. Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, and the like. Examples of peroxyesters include t-butylperoxybenzoate, bis-t-butylperoxyisophthalate, and 2,5-dimethyl-
2,5-bis (benzoylperoxy) hexane, t-
Butyl peroxy-2-ethyl hexanoate, t-butyl peroxy isopropyl carbonate, etc. are mentioned. Examples of the dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide and the like.

Examples of peroxyketals include, for example:
1,1-bis (t-butylperoxy) -3,3,5-
Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane and the like can be mentioned. Examples of the ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide and the like. Examples of hydroperoxides include t
-Butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene peroxide and the like can be mentioned.

When the polymerization is carried out by ultraviolet irradiation, benzoin alkyl ether, benzyl dimethyl ketal and the like are suitable. These polymerization initiators (e) are
Used in combination of one kind or plural kinds. The content of these polymerization initiators (e) is preferably in the range of 0.005 to 10% by weight, based on the total weight of the polymerizable monomers constituting the coating composition (B) of the present invention. It is preferably used in the range of 0.01 to 7% by weight, more preferably in the range of 0.05 to 5% by weight.

These polymerization initiators (e) may be used alone, but are preferably used in combination with a polymerization accelerator for the purpose of further promoting curability. Examples of the polymerization accelerator include tertiary amines, aldehydes, compounds having a thiol group, sulfinic acid and / or salts thereof, and the like. Examples of the tertiary amine include, for example, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-
Ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis ( 2-hydroxyethyl) -3,5-
Dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl)- 4-ethylaniline, N,
N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4
-T-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-diisopropylaniline, N, N-
Bis (2-hydroxyethyl) -3,5-dibutylaniline, n-butoxyethyl 4-dimethylaminobenzoate, (2-methacryloyloxy) ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Butyl 4-dimethylaminobenzoate, N-methyldiethanolamine, 4-dimethylaminobenzophenone, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn
-Butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanol Amine trimethacrylate etc. are mentioned.

Examples of aldehydes include dimethylaminobenzaldehyde and terephthalaldehyde.

Examples of the compound having a thiol group include
2-mercaptobenzoxazole, decanethiol,
3-mercaptopropyltrimethoxysilane, thiobenzoic acid and the like can be mentioned.

Examples of sulfinic acid and salts thereof include benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate,
Toluenesulfinic acid, sodium toluenesulfinate, potassium toluenesulfinate, calcium toluenesulfinate, lithium toluenesulfinate, 2,
4,6-Trimethylbenzenesulfinic acid, 2,4,6
-Sodium trimethylbenzenesulfinate, 2,
Potassium 4,6-trimethylbenzenesulfinate,
Calcium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid,
Sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, 2, Examples include sodium 4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate and calcium 2,4,6-triisopropylbenzenesulfinate.

These polymerization accelerators are used alone or in combination of plural kinds. The content of these polymerization accelerators is preferably 0.0 based on the total weight of the polymerizable monomers constituting the coating composition (B) of the present invention.
The range of 05 to 10% by weight, more preferably 0.01 to 7
It is used in the range of wt%, more preferably in the range of 0.05 to 5 wt%.

The inorganic filler (f) having a refractive index of 1.9 or more used in the coating composition (B) of the present invention can shield the color of the adherend, especially the metal color of the metal casting. Therefore, it is very important from an aesthetic point of view and needs to be mixed. The inorganic filler (f) having a refractive index of 1.9 or more includes titanium oxide (n = 2.49 to 2.9).
0), zirconium oxide (n = 2.13 to 2.19),
Examples thereof include zinc oxide (2.00 to 2.02). These inorganic fillers (f) are used in one kind or a combination of plural kinds. The content of these inorganic fillers (f) is the coating composition (B) of the present invention.
It is preferably used in the range of 0.1 to 90% by weight, more preferably in the range of 1 to 85% by weight, still more preferably in the range of 2 to 80% by weight, based on the total weight of If it is less than 0.1% by weight, the color of the adherend may not be able to be shielded, and if it is more than 95% by weight, the adhesiveness may be lowered.

In the coating composition (B) of the present invention, the above-mentioned inorganic filler (f) having a refractive index of 1.9 or more.
A filler other than the inorganic filler (f) can be used in combination in order to suppress sedimentation of the composition, improve mechanical strength, applicability, collectability from a container, adhesiveness, operability, and the like. Examples of such fillers include inorganic fillers or organic fillers other than those described above, and composites thereof. As the inorganic filler, silica or a mineral having silica as a base material such as kaolin, clay, mica, mica, etc., having silica as a base material, A
l ₂ O ₃ , B ₂ O ₃ , BaO, La ₂ O ₃ , SrO ₂ ,
Ceramics and glasses containing CaO, P ₂ O _5, etc., especially lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminum borosilicate glass, borosilicate glass, bioglass, etc. Is mentioned. Further, crystalline quartz, hydroxyapatite, calcium phosphate and the like are also preferably used. Examples of the organic filler include organic resins such as polymethyl methacrylate, polymers of polyfunctional methacrylate, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber. Further, inorganic fillers may be dispersed in these organic resins, or inorganic / organic composite fillers obtained by coating the inorganic fillers with the above organic resin may also be mentioned.

These fillers may be used, if necessary, in order to adjust the mechanical strength, operability, coatability and fluidity of the coating composition (B) of the present invention, a known surface treatment agent such as a silane coupling agent. It may be used after being surface-treated in advance. Examples of such surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane. , Γ-mercaptopropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane and the like can be mentioned. These fillers are blended in one kind or a combination of plural kinds. The content of these fillers is preferably 0.1 based on the total weight of the coating composition (B).
To 95% by weight, more preferably 0.5 to 90% by weight, still more preferably 1 to 85% by weight.

The coating method of the present invention will be specifically described. That is, after the adhesive composition (A) is applied to the surface of the adherend such as metal, metal alloy, resin, ceramics, porcelain, hardened composite resin, and hard tissue, dental air may be used as necessary. Dry with a syringe or the like until the adhesive composition (A) loses its fluidity, and then,
The coating composition (B) described above is preferably added in the range of 0.005 to 1 mm, more preferably 0.0 to 1 mm.
1 to 0.5 mm, more preferably 0.01 to 0.3 mm
This is a method of forming a coating layer on the surface of an adherend by applying multi-layer coating with a thickness in the range, and then polymerizing and curing the coating layer. As a method of polymerizing and curing the coating layer,
Although any of a photopolymerization curing method, a redox polymerization curing method, and a dual cure method having both polymerization functions is possible, from the viewpoint of operability, the photopolymerization curing method using an ultraviolet and / or visible light type light irradiator is used. It is suitable. Further, in the case of the photopolymerization curing method and the dual cure method, it is necessary to mix a photopolymerization initiator in the coating composition (B), and as a light source, a xenon lamp, a halogen lamp, a mercury lamp, a light emitting diode, etc. Is preferably used. The light irradiation time depends on the wavelength of light and the amount of light, but it can be cured in about 5 seconds to 10 minutes by using a dental irradiation device.

The coating kit of the present invention is particularly preferably used for forming a coating layer on the surface of an adherend such as a metal or a metal alloy, and is a cured composite resin, ceramics, porcelain or artificial tooth. It can also be applied to the surface of an adherend such as a tooth. Further, the case of applying the coating kit of the present invention will be described. (1) When a coating layer is formed on the surface of a metal frame such as a dental hard resin crown, (2) When a hard dental resin crown is used This is particularly useful for repairing a broken resin, when forming a coating layer on an exposed metal surface, and (3) when forming a coating layer on the surface of a metal floor.

[0064]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The abbreviations and abbreviations are as follows.

[Fluorocarbon Group-Containing Polymerizable Monomer]

[0066]

[Chemical formula 22]

[Adhesive Polymerizable Monomer]

[0068]

[Chemical formula 23]

[Polymerizable Monomer] UDMA: [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] dimethacrylate Bis-GMA: Bisphenol A diglycidylmethacrylate D-2,6E: 2 2-bis (4-methacryloyloxypolyethoxyphenyl) propane HD: 1,6-hexanediol dimethacrylate 3G: triethylene glycol dimethacrylate GDM: 1,3-dimethacryloyloxy-2-hydroxypropane

[Polymerization Initiator, Polymerization Accelerator, etc.] CQ: d, l-camphorquinone TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide BPO: benzoyl peroxide DEPT: N, N-di (2-hydroxy) Ethyl) -p-
Toluidine DMABE: 4-N, N-Dimethylaminobenzoate ethyl BHT: 2,6-di-t-butyl-4-methylphenol

Example 1 VBATDT (0.5 parts by weight) was dissolved in acetone (100 parts by weight) to prepare an adhesive composition. Furthermore, H1
2FDM (9 parts by weight), UDMA (21 parts by weight), CQ
(0.5 parts by weight), DMABE (0.3 parts by weight), silane-treated Japanese titanium oxide powder (2 parts by weight), silane-treated silica powder (68 parts by weight) and BHT (0.
015 parts by weight) was mixed to prepare a coating composition. A coating kit comprising the adhesive composition and the coating composition was used to prepare a sample having a coating layer formed on the surface of an adherend, and a gold alloy (Casting Gold) was tested according to the adhesive strength test method described below.
M. C. The adhesive strength to Type IV; manufactured by GC) and a gold-silver palladium alloy (Castwell MC; manufactured by GC) was measured. Further, the shielding property was evaluated according to the shielding property test method described later. The results are shown in Table 1.

Sample Preparation The surface of the adherend was smoothed with # 1000 silicon carbide paper (manufactured by Nippon Polishing Co., Ltd.), and then the surface was dried using a dental air syringe. A tape having a thickness of 0.10 mm and having a hole with a diameter of 5 mm was attached to the metal surface in order to define the adhesion area. The adhesive composition of Example 1 was applied to a metal surface and blown with a dental air syringe until the adhesive composition was no longer flowable. in addition,
After the coating composition of Example 1 was put on and covered with a polyester film, a slide glass was pressed from above. The slide glass was removed, and a coating layer was formed by irradiating the polyester film with a light irradiator “α-light; made by Morita” for 5 minutes to cure the glass.

Adhesion Testing Method A stainless steel cylindrical rod (diameter 5 mm, length 1.5 cm) was adhered to the upper surface of the coating layer of the prepared sample using a commercially available adhesive resin cement “Panavia 21; made by Kuraray”. did. The test piece was placed in water after 30 minutes and stored in a 37 ° C. incubator for 24 hours, and then the adhesive strength was measured. For another sample, place it in a 37 ° C incubator for 24 hours.
After storage for a period of time, it was further stored in a thermostat at 70 ° C. for 30 days, and then the adhesive strength was measured. A universal testing machine (manufactured by Instron) was used to measure the adhesive strength, and the tensile adhesive strength was measured under the condition of a crosshead speed of 2 mm / min.
Each adhesive strength was shown by the average value of the measured values of eight test pieces.

Shielding test method The prepared sample was further irradiated for 20 minutes with a light irradiator "α-light".
After irradiating with light to completely fade the color of CQ, the shielding property was visually examined. In the evaluation of the shielding property, x was used when the color of the adherend was clearly observed, Δ was used when it was slightly recognized, and ◯ was not recognized at all.

Examples 2 to 4 Adhesive polymerizable monomers and solvents were mixed in the weight ratios shown in Table 1 to prepare adhesive compositions. Also, H12FD
A coating composition was prepared by mixing M, UDMA, CQ, DMABE, silane-treated titanium dioxide titanium oxide powder, silane-treated zinc oxide powder and silane-treated silica powder, and BHT in the weight ratios shown in Table 1, respectively. did.
Using a coating kit composed of these adhesive composition and coating composition, the adhesive strength was measured according to the same adhesive strength test method as in Example 1. Also,
According to the same shielding test method as in Example 1, the color shielding property of the adherend was evaluated. The measurement results are shown in Table 1.

Comparative Examples 1 to 4 Coating compositions containing 3G instead of H12FDM in the coating compositions of Examples 1 to 4 were prepared. Using the adhesive compositions of Examples 1 to 4 and a coating kit composed of these coating compositions, the adhesive strength was measured according to the same adhesive strength test method as in Example 1. Further, the color shielding property of the adherend was evaluated according to the same shielding property test method as in Example 1. The measurement results are shown in Table 1.

[0077]

[Table 1]

As is clear from Table 1, an adhesive composition comprising an adhesive polymerizable monomer and a solvent, a fluorocarbon group-containing polymerizable monomer (H12FDM), a polymerizable monomer,
When a coating layer composed of a coating composition containing a polymerization initiator and an inorganic filler having a refractive index of 1.9 or more is used to form a coating layer on a metal surface, it is kept in an incubator at 70 ° C. Even after being stored for 30 days, it showed excellent adhesive strength to the gold alloy and the gold-silver-palladium alloy, and was excellent in durability of the adhesive strength. Moreover, the metallic color was shielded in all the samples (Example 1).
~ 4). On the other hand, when the coating composition containing 3G instead of the fluorocarbon group-containing polymerizable monomer (H12FDM) was used, the adhesive strength after storing for 24 hours in a 37 ° C. incubator was Excellent, but 7
The adhesive strength after storing for 30 days in an incubator at 0 ° C was reduced by half, and the durability of the adhesive strength was poor (Comparative Example 1).
~ 4). Moreover, when the coating composition of Comparative Example 4 in which the inorganic filler having a refractive index of 1.9 or more was not used was used, the metal color could not be shielded.

Examples 5 to 10 Coating compositions containing various fluorocarbon group-containing polymerizable monomers instead of the fluorocarbon group-containing polymerizable monomer (H12FDM) in the coating composition of Example 1 were respectively prepared. Prepared. Using the adhesive composition of Example 1 and the coating kit composed of these coating compositions, the adhesive strength was measured according to the same adhesive strength test method as in Example 1. In addition, Example 1
The color shielding property of the adherend was evaluated according to the same shielding property test method as described in 1. The measurement results are shown in Table 2.

[0080]

[Table 2]

As is clear from Table 2, even when the coating composition substituted with various fluorocarbon group-containing polymerizable monomers was used, durability of excellent adhesion strength to gold alloy and gold-silver-palladium alloy was obtained. showed that. When a coating composition (Examples 5 to 7) containing a fluorocarbon group-containing polymerizable monomer containing two or more olefinic double bonds in the molecule is used, one olefinic double bond is used. The adhesive strength was higher than that in the case of using the coating composition (Examples 8 to 10) using the contained fluorocarbon group-containing polymerizable monomer. In addition, the metallic color was shielded in all the samples (Examples 5 to 5).
10).

Examples 11 and 12, Comparative Examples 5 and 6 Adhesive compositions comprising M10AT, MDP, 3-MPS, ethanol and the like were prepared. Also, D-2,
6E, UDMA, Bis-GMA, H8FDM, 3G,
Coating compositions (I) were prepared by mixing BPO, CQ, BHT, silane-treated titanium dioxide titanium oxide, silane-treated silica powder and the like. Also, D-
2,6E, UDMA, Bis-GMA, HD, GDM,
Coating compositions (II) were prepared by mixing DEPT, DMABE, BHT, silanized silica powder and the like. Adhesive strength was measured according to the same adhesive strength test method as in Example 1 using a coating kit composed of these adhesive composition, coating composition (I) and coating composition (II). Also,
According to the same shielding test method as in Example 1, the color shielding property of the adherend was evaluated. The coating composition (I) and the coating composition (II) were sampled in equal weights immediately before use and kneaded uniformly for 30 seconds before use. The results are shown in Table 3.

[0083]

[Table 3]

As is clear from Table 3, the adhesive composition comprising the adhesive polymerizable monomer and the solvent, the fluorocarbon group-containing polymerizable monomer, the polymerizable monomer, the polymerization initiator and the refractive index are When a coating layer is formed on a metal surface using a coating kit composed of a coating composition containing an inorganic filler of 1.9 or more, 70
Even after being stored in a thermostat at 30 ° C. for 30 days, it showed excellent adhesive strength with respect to the gold alloy and the gold-silver-palladium alloy, and was excellent in durability of the adhesive strength. Moreover, the metallic color was shielded in all the samples (Examples 11 and 12). On the other hand, when the coating compositions of Comparative Examples 5 and 6 in which the fluorocarbon group-containing polymerizable monomer was not used were used, the adhesive strength after storage in a 37 ° C. incubator for 24 hours Was excellent, but the adhesive strength after storing it in a thermostat at 70 ° C. for 30 days was halved, and the durability of the adhesive strength was poor. Moreover, when the coating composition of Comparative Example 6 in which the inorganic filler having a refractive index of 1.9 or more was not used was used, the metal color could not be shielded.

Examples 13 to 16 Adhesive compositions were prepared by mixing M10AT, MDP and ethanol in the weight ratios shown in Table 4. H12FDM, B
A coating composition was prepared by mixing is-GMA, CQ, TMDPO, DMABE, silane-treated Japanese titanium oxide powder, silane-treated silica powder and BHT in a weight ratio shown in Table 4. Using a coating kit composed of these adhesive composition and coating composition, the adhesive strength was measured according to the same adhesive strength test method as in Example 1. Further, the color shielding property of the adherend was evaluated according to the same shielding property test method as in Example 1.

[0086]

[Table 4]

As is clear from Table 4, the adhesive composition comprising the adhesive polymerizable monomer and the solvent, the fluorocarbon group-containing polymerizable monomer, the polymerizable monomer, the polymerization initiator and the refractive index are When a coating layer is formed on a metal surface using a coating kit composed of a coating composition containing an inorganic filler of 1.9 or more, 70
Even after being stored in a thermostat at 30 ° C. for 30 days, it showed excellent adhesive strength to the gold alloy and the gold-silver-palladium alloy, and was excellent in durability of the adhesive strength (Examples 13 to 16). Further, the compounding amount of the inorganic filler having a refractive index of 1.9 or more is about 1
In the case of weight% (Example 13), a slight metallic color was observed, but in the case of 2% by weight or more, the metallic color was sufficiently shielded (Examples 14 to 16).

Examples 17 to 20 Adhesive polymerizable monomers (MDP, 4-MET and 3-MP)
S) and the solvent were mixed in the weight ratios shown in Table 5 to prepare adhesive compositions. In addition, H12FDM, UDM
A, CQ, DMABE, silane-treated Japanese titanium oxide powder, silane-treated zinc oxide powder, silane-treated silica powder, and BHT were mixed at the weight ratios shown in Table 5 to prepare coating compositions. . Using a coating kit composed of these adhesive composition and coating composition, the adhesive strength to metal was measured according to the same adhesive strength test method as in Example 1. Further, the color shielding property of the adherend was evaluated according to the same shielding property test method as in Example 1. As the adherend, nickel-chromium alloy (Nowchrome I; manufactured by Towa Giken) and silver alloy (Mirosilver; manufactured by GC) were used instead of the gold alloy and the gold-silver palladium alloy. The measurement results are shown in Table 5.

Comparative Examples 7-10 The adhesive compositions of Examples 17-20 were prepared individually.
In addition, H1 in the coating compositions of Examples 17 to 20
A coating composition was prepared in which 2FDM was removed and 3G was blended instead. Using a coating kit composed of these adhesive composition and coating composition, the adhesive strength was measured according to the same adhesive strength test method as in Example 17. Further, the color-shielding property of the adherend was evaluated according to the same shielding-testing method as in Example 17. The measurement results are shown in Table 5.

[0090]

[Table 5]

As is clear from Table 5, the adhesive composition comprising the adhesive polymerizable monomer and the solvent, the fluorocarbon group-containing polymerizable monomer, the polymerizable monomer, the polymerization initiator and the refractive index were When a coating layer is formed on a metal surface using a coating kit composed of a coating composition containing an inorganic filler of 1.9 or more, 70
Even after being stored in a thermostat at 30 ° C. for 30 days, the nickel-chromium alloy and the silver alloy exhibited excellent adhesive strength and excellent durability of the adhesive strength. Moreover, the metallic color was shielded in all the samples (Examples 17 to 20). On the other hand, a fluorocarbon group-containing polymerizable monomer (H
When a coating composition containing 3G instead of 12 FDM) was used, the adhesive strength after 24 hours storage in a 37 ° C. incubator was excellent, but 30 ° C. in a 70 ° C. incubator. The adhesive strength after storage for one day was halved, and the durability of the adhesive strength was poor (Comparative Examples 7 to 1).
0). Further, when the coating composition of Comparative Example 10 in which the inorganic filler having a refractive index of 1.9 or more was not used was used, the metal color could not be shielded.

Example 21 M10AT (0.5 parts by weight), MDP (1 part by weight), 3
-MPS (5 parts by weight) and ethanol (100 parts by weight)
Were mixed to prepare an adhesive composition. Using a coating kit composed of this adhesive composition and the coating composition of Example 1, the adhesive strength to various restorative materials was measured according to the same adhesive strength test method as in Example 1. Further, the color shielding property of the adherend was evaluated according to the same shielding property test method as in Example 1. All adherends are # 1
000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) was used for smooth polishing. The measurement results are shown in Table 6.

[0093]

[Table 6]

As shown in Table 6, an adhesive composition comprising an adhesive polymerizable monomer and a solvent, a fluorocarbon group-containing polymerizable monomer, a polymerizable monomer, a polymerization initiator and a refractive index of 1 When a coating layer is formed on the surface of various restoration materials using a coating kit composed of a coating composition containing 9 or more inorganic fillers,
Gold alloy (Casting Gold MC Type I) was stored in a thermostat at 70 ° C for 30 days.
V; made by GC), gold-silver-palladium alloy (Castwell
M. C. ; Made by GC), nickel chrome alloy (Now chrome I; made by Towa Giken), silver alloy (Miro silver; GC
Made), pure titanium (titanium 100; made by Shofu), porcelain (VI
TA CELAY BLANKS; manufactured by VITA), composite resin cured product [Clearfill AP-X (A
3), Esteneia (E1); made by Kuraray], and the adhesive strength was excellent. Moreover, the color of the adherend was shielded in all the samples.

[0095]

The coating kit of the present invention comprises an adhesive composition and a coating composition. First, the adhesive composition is applied to an adherend, and then the coating composition is laminated and applied. Then, by polymerizing and curing, a coating layer having excellent adhesive strength and durability can be formed on the surface of the adherend such as metal, porcelain, ceramics, cured composite resin, and hard tissue.
Moreover, since it can also shield the color of the adherend, it is useful in various fields such as medical care, electronics industry, precision machinery industry, jewelry, etc., but especially requires excellent durability and aesthetic appeal. It is very useful for dental treatment and so on.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4C089 AA12 BA06 BA07 BC03 BD20                       CA07                 4D075 AE03 BB26Z CA12 CA13                       CA36 CA38 CB07 DA06 DB01                       DB02 DB04 DB06 DB07 DB14                       DB31 DC15 DC18 DC21 DC30                       DC38 EB14 EB16 EB20 EB22                       EB24 EB33 EB42 EC02 EC13                       EC30 EC37 EC51                 4J038 FA011 KA04 KA06 KA08

Claims (2)

[Claims] 1. An adhesive composition (A) containing an adhesive polymerizable monomer (a) and a solvent (b), a fluorocarbon group-containing polymerizable monomer (c), a polymerizable monomer ( d),
A coating kit comprising a polymerization initiator (e) and a coating composition (B) containing an inorganic filler (f) having a refractive index of 1.9 or more. 2. An adhesive polymerizable monomer (a) on the surface of an adherend
After coating the adhesive composition (A) containing the solvent and the solvent (b), the fluorocarbon group-containing polymerizable monomer (c), the polymerizable monomer (d), and the polymerization initiator (e) are applied thereon. And a coating composition (B) containing an inorganic filler (f) having a refractive index of 1.9 or more is laminated and coated, and the coating layer is polymerized and cured to form a coating layer on the surface of an adherend. Characteristic coating method.