JP2003025520A - Molded article excellent in antistaining properties and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded article having an antistaining treatment film preventing the generation of a hydrogen bond effectively to achieve the development and stabilization of a hydrophilic function originating from a fluorine compound and excellent in lasting properties and durability, and a method for manufacturing the same. SOLUTION: The molded article excellent in antistaining properties has the antistaining treatment film comprising the photosetting primer layer applied to the surface of a molded article substrate and a fluorine compound layer having hydrophilic and oil-repellent properties applied to the photosetting primer layer. The fluorine compound layer and the photosetting primer layer are bonded to the molded article within a range not damaging the hydrophilic and oil- repellent properties of the fluorine compound by the reaction with a crosslinking agent containing both of a group having reactivity with respect to the hydrophilic compound contained in the fluorine compound layer and/or the photosetting primer layer and a group having reactivity with respect to the photosetting primer. The fluorine compound is subjected to cation treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article having excellent antifouling properties and a method for producing the same, and more specifically, it efficiently utilizes a fluorine compound having excellent hydrophilic and oil repellency to provide long-lasting and durable products. TECHNICAL FIELD The present invention relates to a molded article having an antifouling treatment film excellent in properties and a method for producing the same.

[0002]

2. Description of the Related Art A solid surface treated with a compound having a fluoroalkyl group has low surface energy and exhibits water repellency, oil repellency and weather resistance. Although it is used as a material for reforming (Japanese Patent Laid-Open No. 5-117546, etc.),
Due to its water and oil repellency, it has the drawback that once the surface is contaminated it will not come off. Furthermore, since the surface energy is low, the adhesion to the substrate to be coated is poor, and treatment at high temperatures such as baking is required,
It is extremely difficult to use a material having low heat resistance such as resin or wood as a base material, and it cannot be said that the adhesiveness is sufficient, and its use is limited.

As a solution to such a problem, Japanese Patent Application Laid-Open No. 10-245419 filed by the applicant of the present invention discloses that a fluorine-containing compound (A) having a fluoroalkyl group and a functional group is used as a fluorine-containing compound. Is uniformly dissolved in the photopolymerizable monomer (B) which is soluble, and then other photopolymerizable monomer (C) and photopolymerizable prepolymer (D)
A surface-modifying method is described, which comprises applying a fluorine-based photocurable resin composition obtained by mixing at least one selected from the following to the surface of a substrate and curing the composition by irradiation with light or radiation. According to the prior art, since the coating film is cured by irradiation with light or radiation, the substrate to be treated has the advantage of not being restricted by heat resistance, but is coated with a fluorine compound having hydrophilic oil repellency. Since it is mixed in the film layer, the effect of the flip-flop mechanism between the hydrophilic group and the oil-repellent group in the molecular structure becomes difficult to function, and the original hydrophilic oil-repellency is sufficiently obtained. There was a problem of not having.

In order to solve such problems, the applicant of the present invention applied a layer of a photocurable primer on the surface of a molded article substrate, and a hydrophilic oil-repellent layer applied on the layer of the photocurable primer. And a layer of a fluorine compound having a fluorine-containing compound, and the layer of the photocurable primer is cured, and the layer of the fluorine compound and the layer of the photocurable primer are chemically bonded to each other as long as the hydrophilic oil repellency of the fluorine compound is not impaired. A molded article having excellent antifouling property is proposed (Japanese Patent Application No. 2).
000-86266).

[0005]

The above-mentioned prior art by the applicant of the present invention is based on a large number of hydrophilic groups R _h present in the fluorine compound.
By using a part of the above and reacting it with a crosslinking agent, it can be fixed to the base material of the molded article without impairing the hydrophilic oil repellency of the fluorine compound, and it has excellent durability and durability. Although the antifouling function is expressed, in this method, a hydrogen bond is generated between the bonding portion and the residual hydrophilic group due to the integral reaction of the fluorine compound and the crosslinking agent,
This phenomenon may result in capturing the hydrophilic group of the fluorine compound and reducing the expression of the hydrophilic performance derived from the fluorine compound. Therefore, in the above-mentioned prior art, by adding a basic nitrogen compound such as urea to the solution of the fluorine compound, the hydrogen bond generated between the fluorine compound and the hydrophilic group of the fluorine compound is prevented, and the hydrophilicity is lowered. Was prevented.

The addition of the basic nitrogen compound in the above prior art had some effect on the decrease in hydrophilicity of the fluorine compound, but it was not sufficiently satisfactory in the following points. That is, in the above-mentioned prior art, a fluorine compound solution containing a basic nitrogen compound is applied onto a photocurable primer, and "curing of the primer", "crosslinking of the fluorine with the primer" and "prevention of hydrogen bond with the crosslinking point" by active energy. Are carried out simultaneously in one reaction system, and in such a complicated method, the reactivity becomes unstable, and in particular, there is a possibility that the "hydrogen bond with the cross-linking point" action may vary. Therefore, an object of the present invention is to effectively prevent the generation of hydrogen bonds in the above prior art, to stabilize the expression of the hydrophilic function derived from the fluorine compound, and to form an antifouling treatment film having excellent durability and durability. The present invention provides a molded article and a manufacturing method thereof.

[0007]

According to the present invention, a layer of a photocurable primer applied to the surface of a molded article substrate and a hydrophilic oil repellency applied on the layer of the photocurable primer are provided. A fluorine compound layer, wherein the fluorine compound layer and the photocurable primer layer are reactive with the hydrophilic group of the fluorine compound contained in the fluorine compound layer and / or the photocurable primer layer. By a reaction with a cross-linking agent containing both a group having a group and a group having reactivity with a photocurable primer, the fluorine-containing compound is bonded to the extent that hydrophilic oil repellency of the fluorine compound is not impaired. Provided is a molded article having excellent antifouling property, which is characterized in that the compound is cation-treated.

In the antifouling molded article of the present invention, (1) the pH of the cation-treated fluorine compound is less than 7.0 (2) the cation-treated fluorine compound is changed by a monovalent or divalent cation. Cation-treated (3) The cation-treated fluorine compound is cation-treated with an alkylamine (4) The fluorine compound has a fluoroalkyl group or an oxafluoroalkyl group at the terminal and is hydrophilic in the molecular chain. A fluorine compound containing polymerized units of a group-containing monomer, (5) a photocurable primer is a composition containing a photopolymerizable prepolymer and a photopolymerizable monomer, and (6) a crosslinking agent A monomer containing an ethylenically unsaturated group and a group reactive with the hydrophilic group of the fluorine compound is preferable.

Further, according to the present invention, a layer of a photocurable primer is formed on the surface of a molded article substrate, and then a fluorine compound having hydrophilic oil repellency and previously subjected to a cationic treatment is formed on the layer of the photocurable primer. The layer of the fluorine compound and / or the layer of the photocurable primer is reactive to the hydrophilic group of the fluorine compound and to the photocurable primer. A cross-linking agent containing both a base and a fluorine compound is contained in advance in an amount within a range that does not impair the hydrophilic oil repellency of the fluorine compound, and finally the surface layer of the molded article is irradiated with active energy for antifouling properties. An excellent method for producing a molded article is provided. In this production method, the cation treatment is performed by adjusting the pH of the fluorine compound solution.
Is preferably less than 7.0, and then the cation species-containing solution is added, followed by evaporation of the solvent.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION [Function] Also in the molded article of the present invention, a photocurable primer and a fluorine compound having hydrophilic oil repellency are used for antifouling treatment of the surface of the molded article, and The primer layer and the layer of the fluorine compound having hydrophilic oil repellency on the layer of the photocurable primer are provided in a two-layer structure, and the hydrophilic layer of the fluorine compound is added to the layer of the fluorine compound and / or the layer of the photocurable primer. It contains a cross-linking agent containing both a group reactive with a group and a group reactive with a photocurable primer. The use of compounds is an important feature.

As described above, the molded article of the present invention has the above-mentioned 2
Although it has a layer structure, since the layer of the photocurable primer is cured and the layer of the fluorine compound and the layer of the photocurable primer are chemically bonded, the fluorine compound is an external factor such as cleaning and friction. It is reliably fixed on the surface of the molded product without coming off, and a durable and durable antifouling function is exhibited. Further, by combining the above characteristics, the fluorine compound having hydrophilic oil repellency is preferentially present on the surface and is fixed in that state, so that the hydrophilic group and the oil repellency contained in the molecular structure of the fluorine compound are retained. There is an effect that the flip-flop mechanism with the base functions smoothly and the expression of the antifouling function is enhanced. Incidentally, the flip-flop mechanism of the hydrophilic group and the oil repellent group, the oil repellent group of the fluorine compound acts selectively on oil stains, the hydrophilic group selectively acts on water, It means that the function is performed by switching. The above mechanism does not exclude the function of preventing stains due to the water adsorbed on the hydrophilic groups.

In the present invention, the layer of the cation-treated fluorine compound and the layer of the photocurable primer are the hydrophilic groups of the fluorine compound contained in the layer of the fluorine compound and / or the layer of the photocurable primer. Since they are bound by the reaction of a cross-linking agent containing both a functional group having reactivity with the photo-curable primer and a group having reactivity with the photo-curable primer, the functional group of the cross-linking agent and the hydrophilic group of the fluorine compound are A chemical bond is formed between the surface-curing agent and the photocurable primer, and a reaction such as polymerization and curing proceeds between the cross-linking agent and the photocurable primer, so that the antifouling surface layer can be fixed reliably and easily.

On the other hand, when the fluorine compound reacts with the cross-linking agent, a hydrogen bond is generated, and the generation of this hydrogen bond causes a decrease in hydrophilic function, for the following reason. That is, the fluorine compound used in the present invention has the following formula (1)

[0014]

[Chemical 1] In the formula, R _f is a fluoroalkyl group or an oxafluoroalkyl group that contributes to oil repellency, and R _h is a hydrophilic group that contributes to hydrophilicity. And has a hydrophilic group R _h in the molecular chain, and flip-flops (flip-f) of these both functional groups.
Hydrophilic oil repellency is achieved by the lop) mechanism. On the other hand, the cross-linking agent has reactivity with both the fluorine compound and the photocurable primer, as already pointed out. For example, one of the functional groups of the cross-linking agent is chemically bonded to the fluorine compound, and The other of the functional groups contributes to a chemical bond with the photocurable primer, and immobilizes both of them.

In the present invention, a part of a large number of hydrophilic groups R _h existing in the fluorine compound is utilized and reacted with a cross-linking agent, so that the hydrophilic oil repellency of the fluorine compound is not impaired, and As shown in the following formula (2), a hydrogen bond is formed between the bonding site (-OH) between the cross-linking agent and the fluorine compound and the hydrophilic group (-COOH) of the fluorine compound. To generate. This phenomenon results in capturing the hydrophilic group (—COOH) and lowering the expression of the hydrophilic function derived from the fluorine compound.

As a specific example, the case where the hydrophilic group R _h is a carboxyl group (—COOH) and the cross-linking agent is glycidyl methacrylate will be described. The reaction between the fluorine compound and the cross-linking agent is represented by the following formula ( 2)

[0017]

[Chemical 2] It progresses like.

In the present invention, the cross-linking reaction between the fluorine compound and the cross-linking agent is carried out by substituting a part of the hydrophilic groups in the fluorine compound with a cation species before the preparation of the fluorine compound solution used for the reaction. Even if it progresses, it becomes possible to prevent the "hydrophobic group capturing phenomenon due to hydrogen bond" which has occurred conventionally. That is, as shown in the following formula (3), the fluorinated compound is substituted with a cation species (X ⁺ ), and the fluorinated compound thus cation-treated is:
Even if it reacts with the cross-linking agent, the generation of hydrogen bond as shown in the above formula (2) is effectively prevented.

[0019]

[Chemical 3]

In the substitution of the above-mentioned fluorine compound with a cationic species, if all the hydrophilic groups in the fluorine compound are substituted with a cationic species, there will be no reaction site with the cross-linking agent, and therefore some of the hydrophilic groups will be substituted. It is important to. Although depending on the structure of the fluorine compound, the pH of the fluorine compound generally shows an acidity of about 3.0, and this pH is closely related to the number of hydrophilic groups (-COOH etc.) in the compound, and the cation substitution treatment is performed. When this pH exceeds 7.0,
All the hydrophilic groups have been replaced by the cationic species. Therefore, in the present invention, it is preferable to carry out the substitution treatment so that the pH of the cation substitution-treated fluorine compound is more than 3.0 and less than 7.0.

When the generation of hydrogen bonds is prevented by carrying out the above cation substitution treatment, the selective action (flip-flop mechanism) of the hydrophilic group and the oil repellent group possessed by the fluorine compound is smoothed and the function is manifested. It was found to bring immediate effect.

Further, in a molded article comprising a layer of a photocurable primer and a layer of a fluorine compound having hydrophilic oil repellency provided on the layer of the photocurable primer, there is a chance of contact with water. When used in many environments, the photocurable primer layer gradually absorbs moisture, and between the hydrophilic groups of the fluorine compound and the adsorbed water absorbed in the primer layer, hydrogen bond trapping similar to that described above occurs, Although the hydrophilicity may decrease, the use of the cation substitution-treated fluorine compound makes it possible to develop a flip-flop mechanism with good durability even in such a use environment.

As a more specific example, using the above-mentioned cation-treated fluorine compound (the above formula (3)), the case where the crosslinking agent is glycidyl methacrylate will be described as an example. The cation-treated fluorine compound and the crosslinking agent will be described. Reaction with the following formula (4)

[0024]

[Chemical 4] Proceed as follows. In this case, if the crosslinking agent is used in an excessively large amount, the reaction of the above formula (4) proceeds more than necessary, the residual amount of the hydrophilic group of the fluorine compound decreases, and the hydrophilic function of the fluorine compound is impaired. Need attention.

On the other hand, the reaction between the photo-curable primer and the reaction product of the cation-treated fluorine compound produced by the above formula (4) and the crosslinking agent is represented by the following formula (5).

[0026]

[Chemical 5] Proceed as follows. That is, since the reaction product of the fluorine compound and the crosslinking agent has a polymerizable methacrylate group,
It reacts with the ethylenically unsaturated group in the photocurable primer to cause polymerization and curing.

In FIG. 1 for explaining the manufacturing process of the antifouling molded article according to the present invention, that is, in the preparation process,
A molded article substrate 1 to be subjected to antifouling treatment is prepared. Next, in the photocurable primer application step, the photocurable primer 2 is prepared and applied to the base material 1 to form the photocurable primer layer 20. Next, in the fluorine compound coating step, a solution 3 of a cation-treated fluorine compound having hydrophilic oil repellency is prepared and coated on the photocurable primer layer 20 to form a fluorine compound solution layer 30. Further, in the drying step, the fluorine compound solution layer 3
0 is dried to form a monomolecular film of a fluorine compound or a thin film 31 close thereto.

In the coating step and the step, a monomer or prepolymer (not shown) containing a photopolymerizable group and a functional group reactive with the hydrophilic group of the fluorine compound is added to the photocurable primer 2 and And / or it is contained in the fluorine compound solution 3 in advance. Finally, in the curing step, active energy is irradiated to cure the photocurable primer layer 20 into the cured film 21, and the fluorine compound film 31 is chemically bonded to the cured film 21.

According to the production method of the present invention, a layer of a photocurable primer is formed on the surface of a molded article substrate, a solution of a fluorine compound is applied onto the layer, and dried to obtain excellent hydrophilic and oil repellency. It is possible to efficiently arrange or dispose the fluorine compound having the above as a monomolecular film or a thin film close thereto. Further, the photocurable primer and / or the fluorine compound is preliminarily contained with a crosslinking agent containing both a functional group reactive with a hydrophilic group of the fluorine compound and a group reactive with a primer. Thereby, the photo-curing of the photo-curable primer to be the underlayer and the fixing of the fluorine compound layer to the under-layer can be performed at the same time.

Further, at the stage of preparing the fluorine compound solution, the fluorine compound can be previously cation-treated,
It is possible to effectively prevent the generation of hydrogen bonds without going through complicated steps. Thus, according to the present invention, the hydrophilic oil repellency of the fluorine compound can be immediately effective, durable, and highly functionalized, and an antifouling coating having durability and durability can be formed on any molded article substrate, particularly It can be easily formed on the surface of a substrate having poor heat resistance with excellent workability and productivity, and the antifouling function of a fluorine compound can be effectively exhibited with a small amount of use.

[Molded Article Base Material] The base material to which the surface modification with the fluorine-based photocurable resin composition of the present invention can be applied is:
There are various plastics, woods, fibers, metals, etc. Among them, the application to plastics, woods, and fibers having relatively low heat-resistant temperatures whose use has been limited so far is effective.

[Photocurable primer] As the photocurable primer, any photocurable resin composition known per se, for example, a photoradical polymerizable one or a photocationic polymerizable one is used. I. Photo-radical-polymerizable primer: This photo-radical-polymerizable primer is preferably a composition containing a photo-polymerizable prepolymer and a photo-polymerizable monomer in terms of both coating workability and photo-curability. Moreover, this photocurable primer may contain a photopolymerization initiator and various other known additives. Further, a cross-linking agent containing both a functional group reactive with the hydrophilic group of the fluorine compound and a group reactive with the photocurable primer can be contained in the photocurable primer. Less than,
These components will be described.

(Photopolymerizable Prepolymer) As the photopolymerizable prepolymer, a prepolymer having a plurality of ethylenically unsaturated groups in the molecule or a mixture thereof is used. Suitable examples are epoxy acrylate resin, urethane acrylate resin, polyester acrylate resin,
Thermosetting polyester resin and the like.

As the epoxy acrylate resin, an adduct of a bisphenol type epoxy resin and an ethylenically unsaturated carboxylic acid such as acrylic acid or methacrylic acid, or this adduct and an ethylenically unsaturated polycarboxylic acid anhydride, for example, A reaction product with maleic anhydride, itaconic anhydride, or the like is used.

The urethane acrylate resin is a urethane acrylate resin obtained by reacting an isocyanate-terminated polyester or isocyanate-terminated polyol with a functional group-containing acrylic monomer such as acrylic acid, methacrylic acid, or hydroxyethyl (meth) acrylate. Is used.

The thermosetting polyester resin is a polyester containing an ethylenically unsaturated bond in the molecule, for example, an ethylenically unsaturated polyvalent carboxylic acid such as maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid and the like. , Isophthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, combination with other acid components such as polymerized fatty acid, ethylene glycol, diethylene glycol, propylene glycol, glycerin, neopentyl glycol, trimethylolpropane, penta A polyester resin obtained by condensing a polyhydric alcohol such as erythritol and bisphenols is used.

(Photopolymerizable Monomer) As the photopolymerizable monomer, a polyfunctional or monofunctional monomer, that is, a monomer having one or more ethylenically unsaturated groups in one molecule, particularly a polyfunctional monomer, is used. The acrylic acrylic monomer is preferably used alone or in combination of two or more kinds, or in combination with a monofunctional monomer.

As such a polyfunctional acrylic monomer, 1,6-hexanediol diacrylate (HDDA), 1,6
6-hexanediol dimethacrylate (HDDMA), neopentyl glycol diacrylate (NPGDA), neopentyl glycol dimethacrylate, ethylene glycol diacrylate (EGDA), ethylene glycol dimethacrylate (EGDMA), polyethylene glycol dimethacrylate (PEGMA-4) Polyethylene glycol diacrylate (PEGDA), polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, pentaerythritol diacrylate, 1,4-butanediol diacrylate, trimethylolpropane triacrylate (TMPTA) ), Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, dipentaerythritol Hexaacrylate (DPHA), tetramethylolmethane tetraacrylate, N, N, N ', N'-tetrakis (beta-hydroxyethyl) acrylic acid ester of ethylene diamine, 2,2
-Bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane and the like are used.

Further examples of the polyfunctional monomer include divinylbenzene, diallyl phthalate (DAP), diallyl isophthalate, diallyl adipate, diallyl glycolate, diallyl maleate, diallyl sebacate and triallyl phosphonate. , Other polyfunctional monomers such as triallyl aconitate, allyl ester of trimellitic acid, allyl ester of pyromellitic acid may also be used.

Examples of the photoradical initiator include benzoyl formate esters such as methyl benzoylformate and ethyl benzoylglyoxylate; benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2
Acetophenones such as -hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2
-Anthraquinones such as methylanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal and benzyldimethyl ketal Such as ketals; benzophenones such as benzophenone or xanthones,
There are acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-tri-methylpentylphosphine oxide.
Such a photopolymerization initiator can be used in combination with one or two or more known and commonly used photopolymerization accelerators such as benzoic acid type or tertiary amine type.

(Crosslinking Agent) In the present invention, the crosslinking agent contained in the layer of the fluorine compound and / or the layer of the photocurable primer is a group having reactivity with the hydrophilic group of the fluorine compound and the photocurable primer. It includes both a group having reactivity with the group. When the photocurable primer is composed of a radically polymerizable resin composition, the group reactive with the photocurable primer is generally preferably an ethylenically unsaturated group, while the hydrophilic group of the fluorine compound is The reactive group may be, but is not limited to, an epoxy group, an amino group, a cyclic ether group, a hydroxyl group, or the like. The optimum cross-linking agent is selected and used according to the type of photocurable primer and the type of fluorine compound.

As the epoxy group-containing ethylenically unsaturated compound, a monomer having at least one polymerizable unsaturated bond and at least one epoxy group in one molecule is used. Examples of such an epoxy group-containing ethylenically unsaturated compound include glycidyl acrylate and glycidyl methacrylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, Tetrahydrophthalic acid mono and diglycidyl esters, itaconic acid mono and diglycidyl esters, butene tricarboxylic acid mono and diglycidyl esters, citraconic acid mono and diglycidyl esters, endo-cis-bicyclo [2,2,1] Hept 5-
Mono- and diglycidyl esters of ene-2,3-dicarboxylic acid (Nadic Acid ™), endo-cis-bicyclo [2,2,1] hept-5-ene-2-methyl-2,3
Dicarboxylic acid mono- and diglycidyl esters such as dicarboxylic acid (methyl nadic acid TM), mono- and diglycidyl esters of allyl succinic acid such as mono- and diglycidyl esters (1-12 carbon atoms of the alkyl group in the case of monoglycidyl ester), Alkyl glycidyl ester of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1
-Butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1
-Hexene, vinylcyclohexene monoxide and the like.

Examples of the ethylenically unsaturated compound containing an amino group or an amide group include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and methacrylic acid. Acid phenylaminoethyl,
Acrylic acid or methacrylic acid alkyl ester derivatives such as cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine derivatives such as allylamine, methacrylamide, N-methylacrylamide , N, N-dimethylacrylamide,
Acrylamide derivatives such as N, N-dimethylaminopropyl acrylamide, acrylamide, N-methyl acrylamide and morpholine acrylate, aminostyrenes such as p-aminostyrene, 6-aminohexyl maleic acid imide, 2-aminoethyl maleic acid imide Maleimides such as

Examples of the cyclic ether group-containing ethylenically unsaturated compound include tetrahydrofuryl (meth) acrylate.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (meth) acrylate,
3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono ( (Meth) acrylates such as (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate, 10-undecen-1-ol, 1-octen-3-ol, 2 -Methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether,
Hydroxybutyl vinyl ether, α-methylol acrylamide, 2- (meth) acroyloxyethyl acid phosphate, glycerin monoallyl ether,
Allyl alcohol, allyloxy ethanol, 2-butene-1,4-diol, glycerin monoallyl alcohol and the like can be mentioned.

Further, as the cross-linking agent, an epoxy-based silane coupling agent such as γ-glycidoxypropyltriethoxysilane, an amine-based silane coupling agent such as γ-aminopropyltriethoxysilane, and vinyltriethoxysilane. It is also possible to use a vinyl silane coupling agent such as

(Photoradical Polymerizable Primer Composition) In the photoradical polymerizable primer used in the present invention, the photoradical polymerizable prepolymer is 5 to 95% by weight, particularly 20 to 80% by weight, and the photoradical polymerizable monomer is 5 to 95
It is preferably present in a weight percentage, especially 20 to 80 weight percent. The photopolymerization initiator is 0.05 to 10 parts by weight, preferably 1 to 8 parts by weight with respect to 100 parts by weight of the ultraviolet curable resin.
It is preferable to use it in a ratio of parts by weight.

II. Photocationically Polymerizable Primer Composition In the present invention, a photocationically polymerizable composition can also be used as a primer. As the cationic photopolymerizable resin composition, a cationic photopolymerizable monomer, particularly a photocurable epoxy resin, a cationic photopolymerization catalyst, or a resin composition further containing a prepolymer is used.

(Photocurable Epoxy Resin) The photocurable epoxy resin contains an epoxy resin component having an alicyclic group in the molecule and adjacent carbon atoms of the alicyclic group forming an oxirane ring. For example, an epoxy compound having at least one epoxycycloalkane group in the molecule, for example, an epoxycyclohexane ring, an epoxycyclopentane ring, or the like is used alone or in combination.

Suitable examples thereof include, but are not limited to:
Vinylcyclohexene diepoxide, vinylcyclohexene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,
5-spiro-3,4-epoxy) cyclohexane-m-
Dioxane, bis (3,4-epoxycyclohexyl)
Such as adipate.

(Cationic Photopolymerization Catalyst) The cationic polymerization initiator used in combination with the above-mentioned epoxy resin has a function of decomposing by ultraviolet rays to release a Lewis acid, and the Lewis acid polymerizing an epoxy group. Examples thereof include aromatic iodonium salts, aromatic sulfonium salts, aromatic selenium salts, aromatic diazonium salts and the like.

Examples of diallyl iodonium salts include diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, 4-chlorophenyliodonium tetrafluoroborate, di (4-methoxyphenyl) iodonium chloride and (4-methoxyphenyl) phenyl. Examples thereof include iodonium.

Examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate and 4-chloro. Examples thereof include phenyldiphenylsulfonium hexafluorophosphate.

Examples of the triaryl selenium salt include triphenyl selenium hexafluorophosphate, triphenyl selenium hexafluoroantimonate and the like.

As other cationic polymerization initiators,
(2,4-Cyclopentan-1-yl) [(1-methoxythiethyl) -benzene] -iron-hexafluorophosphate, diphenylsulfonium hexafluroantimonate, dialkylphenylsulfonium hexafluoroantimonate, dialkylphenylsulfonium Hexafluorophosphate, 4,4'-bis [di (βhydroxyethoxy) phenylsulfonio]
Examples thereof include phenyl sulfide-bis-hexafluoroantimonate and 4,4-bis [di (βhydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluorophosphate.

(Prepolymer) As the prepolymer used in combination with the photocurable epoxy resin, a usual bisphenol type epoxy resin can be mentioned.
As the bisphenol type epoxy resin, an epoxy resin derived from bisphenols and epichlorhydrin is used, and as the bisphenols,
2,2'-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2'-bis (4-hydroxyphenyl) butane (bisphenol B), 1,1'-
Bis (4-hydroxyphenyl) ethane, bis (4-,
3- or 2-hydroxyphenyl) methane (bisphenol F), 4-hydroxyphenyl ether, p-
(4-hydroxy) phenol and the like. In addition, the epoxy acrylate resin, urethane acrylate resin, polyester acrylate resin, thermosetting polyester resin and the like described in the section of the photo-radical polymerizable resin composition can also be used as the prepolymer.

(Cationic Photopolymerizable Primer Composition) In the cationic photopolymerizable primer used in the present invention, the photopolymerizable epoxy resin is 5 to 95% by weight, particularly 20 to 80% by weight, and the prepolymer is 5 to 95% by weight. In particular, it is desirable that the content is 20 to 80% by weight. The cationic photopolymerization initiator is preferably used in an amount of 0.05 to 10 parts by weight, preferably 1 to 8 parts by weight, based on 100 parts by weight of the resin.

(Other compounding agents) When the photocurable primer of the present invention is compounded with a crosslinking agent, it is necessary to compound it in such an amount that the hydrophilic oil repellency of the fluorine compound to be crosslinked is not impaired. This amount is determined by the composition of the fluorine compound.

In the photopolymerizable composition of the present invention, other additives such as leveling agents, defoaming agents, colorants, thickeners and the like which are known per se can be used.

As the leveling agent, various silicones,
In particular, organopolysiloxanes having polyalkyleneoxy groups are used. This is preferably used in an amount of 0 to 5 parts by weight, particularly 0.05 to 2 parts by weight, per 100 parts by weight of the resin composition.

As the defoaming agent, various surfactants are used in addition to the above organopolysiloxane. This is preferably used in an amount of 0 to 5 parts by weight, particularly 0.05 to 2 parts by weight, per 100 parts by weight of the resin composition.

As the colorant, the following can be used alone or in combination. Black pigment carbon black, acetylene black, run black, aniline black. Yellow pigment Yellow lead, Zinc yellow, Cadmium yellow, Yellow iron oxide, Mineral fast yellow, Nickel titanium yellow, Navels yellow, Naphthol yellow S, Hansa yellow G, Hansa yellow 10G, Benzidine yellow G,
Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake. Orange pigment Red lead yellow lead, molybden orange, permanent orange GTR, pyrazolone orange, vulcan orange, induslen brilliant orange RK, benzidine orange G, induslen brilliant orange GK. Red pigment red iron oxide, cadmium red, red lead, mercury cadmium sulfide, permanent red 4R, resole red, pyrazolone red, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, brilliant carmine 3B. Purple pigment manganese purple, fast violet B, methyl violet lake. Blue Pigment Navy Blue, Cobalt Blue, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue Partial Chloride, Fast Sky Blue, Induslen Blue B
C. Green pigments chrome green, chrome oxide, pigment green B,
Malachite Green Rake, Fanal Yellow Green G. White pigment zinc white, titanium oxide, antimony white, zinc sulfide. Extension pigment barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white. These pigments are preferably used in an amount of 0 to 10 parts by weight, particularly 0 to 5 parts by weight, per 100 parts by weight of the resin composition.

As the thickener, an inorganic or organic thickener known per se is used in a formulation known per se.

[Fluorine Compound] The fluorine compound used in the present invention has hydrophilic oil repellency, and has a fluorohydrocarbon group, generally a fluoroalkyl group and / or an oxafluoroalkyl group, and a hydrophilic group. is there.

Examples of the fluorohydrocarbon group include a fluoroalkyl group having 1 to 18 carbon atoms and an oxafluoroalkyl group. An oxafluoroalkyl group is defined as a group in which some of the carbon atoms in the middle of the fluoroalkyl group have been replaced by oxygen atoms. In this oxafluoroalkyl group, the number of intervening oxygen atoms may be one or two or more, and it is preferable that two or more carbon atoms be present on both sides of the oxygen atom. It is of course possible for a fluorine atom and a hydrogen atom to coexist in a fluoroalkyl group, but generally, all of the hydrogen atoms are replaced with a fluorine atom, that is, a perfluoroalkyl group or a perfluorooxaalkyl group. It is preferable.

On the other hand, examples of the hydrophilic group include a nonionic, anionic or cationic hydrophilic group, and examples of the nonionic group include a hydroxyl group (OH) and an ether group (-O).
-), A carbonyl group (= CO), a carbonyloxy group (-COO-), an amide group, a silyl group, an organosiloxane unit, and the like, and examples of the anionic group include a carboxyl group (-COOH) and a sulfone. Acid group (-
SO ₃ H), and phosphonic acid group _(-PO 3 H) and the like. Further, as the cationic group, primary, secondary or tertiary
Examples thereof include a primary amino group and a quaternary ammonium group. Among these hydrophilic groups, a carboxyl group and a hydroxyl group are preferable.

As a suitable example of the fluorine-containing compound, as shown by the following general formula (6), it has a fluoroalkyl group and / or an oxafluoroalkyl group at both ends and has a hydrophilic functional group in the molecule as a side chain. What has in.

[0068]

[Chemical 6] In the formula, R _f is a fluoroalkyl group and / or an oxafluoroalkyl group, R ₁ is a hydrophilic group, and R is
₂ is a hydrogen atom or an alkyl group, R ₃ is a hydrogen atom or an alkyl group, R ₄ is a hydrogen atom, an alkyl group, a halogen atom, an alkoxycarbonyl group or a group R
₁ and x and y are x / y = 0/100 to 100/0
Is the number. The groups R ₂ and R ₃ may be the same or different from each other.

The compound of the above formula (6) will be described in more detail. The group R _f is an oil-repellent main chain such as a perfluoroalkyl group or a perfluorooxaalkyl group, and specifically,-(CF ₂ ) n CF ₃ (n = 0 to 11)-[OCF ₂ CF (CF ₃ )] m OC ₃ F ₇ (m = 0 to
5) and the like.

R₁Is a hydrophilic group, and
It is a functional group that has been made reactive. More concrete explanation
Then, for example, COOH, OH, SO_ThreeH, CO_TwoCH
_TwoSO_Three H, CO_Two(CH_Two)_TwoSO_ThreeIn H etc.
It Of these groups, COOH is particularly preferred.

The group R ₂ is a hydrogen atom or an alkyl group, especially an alkyl group having 4 or less carbon atoms, most preferably a hydrogen atom. The group R ₃ is a hydrogen atom or an alkyl group, especially having 4 carbon atoms.
The following alkyl groups are most preferred, and methyl groups are most preferred.

The group R ₄ is a hydrophilic functional group R ₁ , a hydrogen atom, an alkyl group, a halogen atom, an alkoxyalkyl group or the like. More specifically, for example _{COOH, OH, COCH 3, COOCH} 3 H, CH 3, CH 2 (CH 2) i CH 3 i = 0
Is ~ 5 mag.

The above-mentioned fluorine compound, that is, an oligomer is
Formula (7)

[0074]

[Chemical 7] In the presence of a fluorine-containing peroxide represented by the formula (8)

[0075]

[Chemical 8] And a monomer represented by the formula (9)

[0076]

[Chemical 9] It is obtained by polymerizing the monomer represented by

When the fluorine compound contains a crosslinking agent, the amount thereof is determined by the composition of the fluorine compound. Crosslinking with a fluorine compound utilizes a large number of hydrophilic groups R _h present in the compound, and therefore the range of the amount of the crosslinking agent to be added is “amount crosslinkable with one hydrophilic group R _h ” to “hydrophilic group R _h ”. _The amount is the amount that crosslinks with the (maximum number-1) of _h ", and the specific number can be calculated by molar calculation. Here, when the number of cross-linking points is small, the hydrophilicity is excellent, but the degree of immobilization is low. On the other hand, when the number of cross-linking points is large, the degree of immobilization is high, but the expression of hydrophilicity is poor. The right amount can be found from the trade-off. As the cross-linking agent to be contained in the fluorine compound, an appropriate one is selected from the cross-linking agents already explained in the section of the primer and used.

[Cation Treatment] In the present invention, a cation-treated purified fluorine compound is prepared by dissolving the fluorine compound in a solvent, adding a solution containing an ionic species, and evaporating the solvent. As the solvent in which the fluorine compound is soluble, a commonly used solvent can be used, for example, water, various alcohols, ketones,
Ether, amide, aromatic hydrocarbon and the like can be used. Among these, it is preferable to use a solvent having a small dissolving power, for example, an alcohol solvent such as isopropanol so that the primer layer serving as the base is less affected. Generally, it is desirable that the concentration of the fluorine compound or the like in the solution, that is, the solid content concentration is 0.01 to 30% by weight, particularly 0.05 to 20% by weight.

As the cation species used for the cation treatment, monovalent and divalent ones can be mentioned, and monovalent ones such as Li, Na and K can be preferably used. When actually used, NaOH, KOH, Ca (OH) ₂ or the like is dissolved in a solvent before use. As the solvent to be used, the solvents listed above as the solvent for the fluorine compound can be used. Generally, the content of cationic species in the treatment liquid is
The amount is preferably 0.01 to 10 mol, and more preferably 0.1 to 5 mol. When the cation species is divalent,
The general structural formula of the cation-treated fluorine compound is shown in the following formula (10).

[0080]

[Chemical 10]

When alkylamines (RNH ₄ ) are used as the cation species, an antibacterial function can be added in addition to the prevention of hydrogen bonding, and higher functionality can be achieved. As the alkyl group, those having 0 to 4 carbon atoms can be preferably used. A catalytic amount of an acid catalyst for promoting the reaction between the fluorine compound and the cross-linking agent can be added to the solution of the fluorine compound.

[Antifouling Treatment] The antifouling treatment according to the present invention is performed by the operation already described. That is, the photocurable primer is applied to the surface of the molded article substrate to be treated. For this coating, known coating methods such as spray coating, roll coating, flow coating, bar coating and dip coating can be used. The coating thickness of the photocurable primer is generally 5 to 500 μm, especially 10 to 300 μm.
The range of m is preferable from the viewpoint of durability and economical efficiency of the antifouling treatment layer.

Then, a fluorine compound is applied to the thin film on the formed photo-curable primer layer. For forming the thin film of the fluorine compound, the above-mentioned cation-treated purified fluorine compound or a dilute solution containing a crosslinking agent is used. The solvent used at this time may be the same as that used for the cation treatment. Generally, it is desirable that the concentration of the fluorine compound or the like in the solution, that is, the solid content concentration is 0.01 to 10% by weight, particularly about 0.05 to 8% by weight.

In the present invention, the reaction between the fluorine compound and the crosslinking agent added to the solution may be carried out in advance, or the reaction may be carried out when the solvent in the solution is dried. it can. The reaction conditions are not particularly limited, but it is generally preferable to carry out the reaction at a temperature of 20 to 100 ° C. for about 0 to 5 minutes.

In the antifouling molded article of the present invention, a durable antifouling effect can be exhibited even when the formed fluorine compound layer is an extremely thin layer such as a monomolecular layer. The coating amount of the fluorine compound varies depending on the composition and cannot be generally stated. However, it is preferably in the range of 0.5 to 300 mg / dm ² in terms of area-based weight. The fluororesin layer can be formed by applying a solution by dropping or by the above-mentioned coating means.

After applying the solution of the fluorine compound, the organic solvent is dried and removed. Drying can be carried out under normal pressure while being blown with hot air, or can be carried out under reduced pressure.

The treated layer of the molded article after coating is irradiated with active energy to be cured. Ultraviolet rays, especially rays having a wavelength of 200 to 450 nm, are used as the active rays. As the light source, a low / medium pressure or high pressure mercury lamp, an ultraviolet fluorescent lamp, a xenon lamp, a metal halide lamp or the like can be used. Alternatively, the modified layer can be obtained by curing the coating film by irradiating it with an electron beam.

[0088]

EXAMPLES The present invention will be specifically described below with reference to examples. In addition, the numerical value of each component in an example shows a weight part.

(Cation Treatment Example 1) (1) Preparation of Solution of Fluorine Compound Fluorine compound (HFPO2) 2.00 in 18 g of methanol
g and dissolve. Here, (HFPO2) is represented by the following formula (11), and the number average molecular weight Mn is 5000.

[0090]

[Chemical 11] (2) Addition of cationic species-A pH meter is installed in the solution of (1) above.・ Add 1N concentration of sodium hydroxide solution to the same solution.
Add dropwise within a range where the H meter value does not exceed 7.0.
Here, 10 ml of a 1N aqueous sodium hydroxide solution was added dropwise to adjust the pH to 3.0 to 5.5. (3) Evaporation of solvent-The cation-treated solution of (2) above is placed in a vacuum dryer and dried at 2 mmHg / 50 ° C for 24 hours. After the drying step, a cation-treated purified fluorine compound (NOB represented by the following formula (12) and having a number average molecular weight of 5000 (NOB
-104) 2.10 g was obtained.

[0091]

[Chemical 12]

(Cation Treatment Example 2) (1) Preparation of Solution of Fluorine Compound Fluorine compound (HFPO2) was added to 18 g of methanol solution.
Add 00 g and dissolve. (2) Addition of cationic species-A pH meter is installed in the solution of (1) above. -A 1N potassium hydroxide / methanol solution is added dropwise to the same solution within the range where the value on the pH meter does not exceed 7.0. Here, 10 ml of a 1N sodium hydroxide aqueous solution / methanol solution was dropped, and the pH was adjusted to 3.0 to 5.
It was set to 5. (3) Evaporation of solvent-Put the cation-treated solution in (2) above into the dryer and
Drying is performed at 0 ° C. for 8 hours. After the drying step, a cation-treated purified fluorine compound (NOB represented by the following formula (13) having a number average molecular weight of 5,000 (NOB
-105) 2.10 g was obtained.

[0093]

[Chemical 13]

(Cation Treatment Example 3) (1) Preparation of Fluorine Compound Dissolving Solution Fluorine compound (HFPO2) (2.00 g) is dissolved in water (18 g). (2) Addition of cationic species-A pH meter is installed in the solution of (1) above. -Ammonia aqueous solution having a concentration of 0.5 N is added dropwise to the same solution within the range where the value of pH meter does not exceed 7.0. Here, 20 ml of a 0.5 N aqueous ammonia solution was added dropwise to adjust the pH to 3.0 to 5.5. (3) Evaporation of solvent-The cation treatment solution of (2) above is placed in a vacuum dryer and dried at 2 mmHg and 50 ° C for 48 hours. After the drying step, a cation-treated purified fluorine compound (NOB represented by the following formula (14) having a number average molecular weight of 5,000 (NOB
-106) 2.10 g was obtained.

[0095]

[Chemical 14]

(1) Preparation of Fluorine Compound Dissolving Solution Fluorine compound (HFPO2) (2.00 g) is dissolved in water (18 g). (2) Addition of cationic species-A pH meter is installed in the solution of (1) above. -Saturated aqueous solution of calcium hydroxide is added dropwise to the same solution as long as the value on the pH meter does not exceed 7.0. here,
20 ml of 0.5N saturated calcium hydroxide aqueous solution was added dropwise to adjust the pH to 3.0 to 5.0. (3) Evaporation of solvent-The cation treatment solution of (2) above is placed in a vacuum dryer and dried at 2 mmHg and 50 ° C for 48 hours. After the drying step, a cation-treated purified fluorine compound (NOB represented by the following formula (15) and having a number average molecular weight of 5000 (NOB
-107) 2.08 g was obtained.

[0097]

[Chemical 15]

The materials used in the following examples are indicated by the following abbreviations (alphabets). -Substrate / Primer Photopolymerizable prepolymer (A) Photopolymerizable monomer (B) Crosslinking agent (C) Polymerization initiator (D) Other additives (E) -Fluorine compound liquid Fluoroalkyl group and hydrophilic functional group Fluorine compound (F) having a solvent capable of dissolving the same fluorine compound (G) Crosslinking agent (C) Catalyst (H) Other additives, etc. (I)

[Example 1] (1) Selection of base material: A hard vinyl chloride plate "PVC plate". (2) Preparation category of primer Chemical name Brand name Composition ratio (A) Urethane acrylate “KAYARAD UX-4101 / Nippon Kayaku” 50 parts by weight (B) Polyethylene glycol # 400 diacrylate “NK Ester A-400 / Shin Nakamura Chemical” "30 parts by weight (B) trimethylol propane triacrylate" Light acrylate TMP-A / Kyoeisha chemistry "10 parts by weight (B) Syntheta erythritol hexaacrylate" Light acrylate DPE-6A / Kyoei Morikagaku "10 parts by weight (C) N, N-Dimethylaminoethyl acrylate “DMAEA / Kojin Co., Ltd.” 1 part by weight (D) Methyl benzyl diformate “VICURE-55 / Axonogen” 5 parts by weight Obtained by mixing and stirring the above composition ratio The primer "P
1 ”.

(3) Preparation classification of fluorine compound liquid Chemical name Composition ratio (F) Fluorine compound (NOB-104) 3.5 parts by weight (G) Methanol 50 parts by weight (G) Water 50 parts by weight Mixing of the above composition ratios The fluorine liquid obtained by stirring is
1 ”.

(4) Coating process- "P1" is bar-coated on the "vinyl chloride board" to a thickness of about 10 μm.
To form an uncured coating film. -F1 is applied as a thin film onto it. -(G) Methanol and water are evaporated by warm air 100 degreeC x 3min, and the integral compound of (F) and (C) is deposited on "P1." -Finally, the target antifouling treated molded article "Example No. 1" is obtained by irradiation for 2 seconds under the irradiation distance of 120 mm and the high pressure mercury lamp of 80 W.

[Example 2] (1) Selection of base material --- Same as in Example 1, a "vinyl chloride plate" is prepared. (2) Preparation of primer: Same as in Example 1, designated as "P1".

(3) Preparation classification of fluorine compound liquid Chemical name Composition ratio (F) Fluorine compound (NOB-105) 3.5 parts by weight (G) Methanol 50 parts by weight (G) Water 50 parts by weight Mixing of the above composition ratios The fluorine liquid obtained by stirring is
2 ".

(4) Coating step The same procedure as in Example 1 was carried out except that "F2" was used as the fluorine solution to obtain the desired antifouling treated article "Example No. 2".

[Embodiment 3] (1) Selection of base material ... As in Embodiment 1, a “vinyl chloride plate” is used. (2) Preparation of primer: Same as in Example 1, designated as "P1".

(3) Preparation classification of fluorine compound liquid Chemical name Composition ratio (F) Fluorine compound (NOB-106) 3.5 parts by weight (G) Methanol 50 parts by weight (G) Water 50 parts by weight Mixing of the above composition ratios The fluorine liquid obtained by stirring is
3 ”.

(4) Coating step The same procedure as in Example 1 was carried out except that "F3" was used as the fluorine solution to obtain the desired antifouling treated article "Example No. 3".

[Embodiment 4] (1) Selection of base material: A hard vinyl chloride plate "vinyl chloride plate" is used. (2) Preparation category of primer Chemical name Brand name Composition ratio (A) Urethane acrylate “KAYARAD UX-4101 / Nippon Kayaku” 50 parts by weight (B) Polyethylene glycol # 400 diacrylate “NK Ester A-400 / Shin Nakamura Chemical” "30 parts by weight (B) trimethylol propane triacrylate" Light acrylate TMP-A / Kyoeisha chemistry "10 parts by weight (B) Syntheta erythritol hexaacrylate" Light acrylate DPE-6A / Kyoei Morikagaku "10 parts by weight (D) Methyl benzoyl formate “VICURE-55 / Axonobel” 5 parts by weight The primer obtained by mixing and agitating the above compositional ratio is “P
2 ".

(3) Preparation classification of fluorine compound liquid Chemical name Brand name Composition ratio (F) Fluorine compound (NOB-104) 3.5 parts by weight (G) Methanol 70 parts by weight (G) Water Wako Pure Chemical 30 parts by weight (C) Glycidyl Methacrylate Light Ester G / Kyoeisha Chemical 2.5 parts by weight (H) Hydrochloric acid Wako Pure Chemicals 0.1 part by weight The fluorine solution obtained by mixing and stirring the above composition ratio is “F”.
4 ”.

(4) Coating step The same procedure as in Example 1 was carried out except that "P2" was used as the primer and "F4" was used as the fluorine solution, and the desired antifouling treated molded article [Example No. 4] is obtained.

[Example 5] (1) Selection of base material: A transparent acrylic plate and an [acrylic plate]. (2) Preparation of primer A primer "P3" was prepared in the same manner as in Example 1 except that 5 parts by weight of the polymerization initiator (D) methylbenzoyl formate was not added.

(3) Preparation category of fluorine compound liquid Chemical name Composition ratio (F) Fluorine compound (NOB-106) 3.5 parts by weight (G) Methanol 30 parts by weight (G) Water 70 parts by weight Mixing of the above composition ratios The fluorine liquid obtained by stirring is
5 ”.

(4) Application process-Bar coating of "P3" on "acrylic plate",
An uncured coating film of μm is formed.・ F5 is applied as a thin film onto it. -(G) Methanol and water are evaporated by warm air 100 degreeC x 3min, and the integrated compound of (F) and (C) is deposited on "P3."・ Finally, under the condition of electron beam energy of 100 keV,
The desired antifouling treated molded product "Example No. 5" is obtained by irradiation for 0 or 2 seconds.

[Embodiment 6] (Treatment with divalent cation) (1) Selection of base material ... Similar to Embodiment 1, a "vinyl chloride plate" is prepared. (2) Preparation of primer: Same as in Example 1, designated as "P1".

(3) Preparation classification of fluorine compound liquid Chemical name Composition ratio (F) Fluorine compound (NOB107) 2.5 parts by weight (G) Methanol 50 parts by weight (G) Water 50 parts by weight By mixing and stirring the above composition ratio The obtained fluorine solution is referred to as "F
6 ”.

(4) Coating step The same procedure as in Example 1 was carried out except that "F6" was used as the fluorine solution to obtain the desired sample "Example No. 6".

[Comparative Example 1] (Japanese Patent Application No. 2000-86266)
(Basic format based on No. 1) (1) Selection of base material ... As in Example 1, a “vinyl chloride board” is used. (2) Preparation of primer: Same as in Example 1, designated as "P1".

(3) Preparation category of fluorine compound liquid Chemical name Composition ratio (F) Fluorine compound (HFPO2) 2.5 parts by weight (G) Methanol 50 parts by weight (G) Water 50 parts by weight By mixing and stirring the above composition ratio The obtained fluorine solution is referred to as "F
7 ".

(4) Coating Step The same procedure as in Example 1 was carried out except that "F7" was used as the fluorine solution to obtain the target sample "Comparative Example No. 1".

[Comparative Example 2] (Urea is added to the above-mentioned basic form) (1) Selection of base material ... As in Example 1, a “vinyl chloride plate” is prepared. (2) Preparation of primer: Same as in Example 1, designated as "P1".

(3) Preparation Category of Fluorine Compound Liquid Chemical Name Composition Ratio (F) Fluorine Compound (HFPO2) 2.5 parts by weight (G) Methanol 50 parts by weight (G) Water 50 parts by weight (I) Urea 1.0 By weight, the fluorine liquid obtained by mixing and stirring the above composition ratio is "F
8 ".

(4) Coating step The same procedure as in Example 1 was carried out except that "F8" was used as the fluorine solution to obtain the target sample "Comparative Example No. 2".

[Comparative Example 3] (Excessive treatment of Na) (1) Selection of base material ... As in Example 1, a “vinyl chloride plate” is prepared. (2) Preparation of primer: Same as in Example 1, designated as "P1".

(3) Preparation Category of Fluorine Compound Liquid Chemical name Composition ratio (F) Fluorine compound (NOB-104) 3.5 parts by weight (G) Methanol 30 parts by weight (G) Water 70 parts by weight Mixing of the above composition ratios The fluorine liquid obtained by stirring is
9 ”.

(4) Coating Step The same procedure as in Example 1 was carried out except that "F9" was used as the fluorine solution to obtain the target sample "Comparative Example No. 3".

[Test Data, Comparative Data] [Method] For each sample, (1) initial state (sample preparation, immediately after and 3 days after) (2) after humidity treatment (40 ° C. × 95% RH for 3 months) And left for 6 months) (3) Evaluation was carried out by the following test method based on the conditions after being rinsed with water (leaving under running water for 6 hours and 12 hours). Visually check the presence of cracks, curing defects, etc. (Evaluation criteria ○: No abnormality, ×: Abnormal) Adhesion JIS K5400 (Cross-cut peeling test) (Evaluation criteria ○: No peeling, ×: Peeling) Hydrophilic repellency After dropping the reagent on the surface of each oily sample, the contact angle (°) after 3 minutes was measured and evaluated. Measuring instrument: Kyowa Interface Science Co., Ltd. CA-D (evaluation standard hydrophilicity: water → contact angle ( The lower (°) is, the more hydrophilic it is and the oil repellency is: dodecane → The higher the contact angle (°) is, the more oil repellency is.) Antibacterial property JIS Z2801 (Film adhesion method)

[Results] The results obtained are shown in Table 1 below.

[Table 1]

[0128]

According to the present invention, a layer of a photocurable primer applied to the surface of a molded article substrate, and a cation treatment having hydrophilic oil repellency applied to the layer of the photocurable primer. A layer of a fluorine compound and a layer of the fluorine compound and the layer of the photocurable primer react with the hydrophilic group of the fluorine compound contained in the layer of the fluorine compound and / or the layer of the photocurable primer. Layer of the photocurable primer and the layer of the photocurable primer and the layer of the photocurable primer are cured by the reaction with the cross-linking agent containing both the group having the property of reacting and the group having the reactivity with the photocurable primer. By chemically bonding and to the extent that the hydrophilic and oil repellency of the fluorine compound is not impaired, and effectively preventing the occurrence of hydrogen bonds due to the integration reaction with the cross-linking agent, the fluorine compound with excellent hydrophilic and oil repellency can be efficiently produced. Often And use, immediate, it is possible to provide a sustained and moldings, and a manufacturing method thereof to form an excellent antifouling treatment film durability.

[Brief description of drawings]

FIG. 1 is an explanatory view for explaining a manufacturing process of an antifouling treated molded product of the present invention.

Claims (9)

[Claims] 1. A layer of a photocurable primer applied on the surface of a molded article substrate, and a layer of a fluorine compound having hydrophilic oil repellency applied on the layer of the photocurable primer,
A group having a fluorine compound layer and a photocurable primer layer, which are contained in the fluorine compound layer and / or the photocurable primer layer, and which are reactive with a hydrophilic group of the fluorine compound and a photocurable primer. In a molded article that is bound within a range that does not impair the hydrophilic oil repellency of the fluorine compound by the reaction with a cross-linking agent containing both a group having reactivity with A molded product with excellent antifouling properties, which is characterized by 2. The p of the cation-treated fluorine compound.
The molded article having excellent antifouling property according to claim 1, wherein H is less than 7.0. 3. The cation-treated fluorine compound is
The molded article according to claim 1 or 2, which is cation-treated with a monovalent or divalent cation. 4. The cation-treated fluorine compound is
A cation treatment with an alkylamine.
Or the molded article according to 2. 5. The fluorine compound is a fluorine compound having a fluoroalkyl group or an oxafluoroalkyl group at the terminal and containing a polymerized unit of a hydrophilic group-containing monomer in the molecular chain. The molded product according to any one of 1 to 4. 6. The molded article according to claim 1, wherein the photocurable primer is a composition containing a photopolymerizable prepolymer and a photopolymerizable monomer. 7. The cross-linking agent is a monomer containing an ethylenically unsaturated group and a group having reactivity with a hydrophilic group of a fluorine compound, according to any one of claims 1 to 6. Molded product. 8. A layer of a photocurable primer is formed on the surface of a molded article substrate, and then a layer of a fluorine compound having hydrophilic oil repellency and previously subjected to cation treatment is formed on the layer of the photocurable primer. , Where the fluorine compound layer and / or
Alternatively, in the layer of the photocurable primer, a cross-linking agent containing both a group reactive with the hydrophilic group of the fluorine compound and a group reactive with the photocurable primer is added to the hydrophilic layer of the fluorine compound. A method for producing a molded article having excellent antifouling properties, which comprises preliminarily containing an amount in a range that does not impair oiliness, and finally irradiating the surface layer of the molded article with active energy. 9. The method according to claim 8, wherein the cation treatment is performed by adding a cation species-containing solution so that the pH of the fluorine compound solution becomes less than 7.0 and then evaporating the solvent.