JPH10245419A - Surface modification by fluorine-based photo-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for making the surface of a base material have durable functional properties for a long period of time by making the composition contain a fluorine-based compound having excellent dust-proofing property and/or antibacterial property caused from hydrophilic and oil-repelling properties in a photo-curable resin composition, coating the surface of a plastic, wood, fibers or a metal, etc., with it, and curing by an activation energy of ultraviolet rays, electron beams, etc. SOLUTION: This fluorine-based photo-curable resin composition is obtained by uniformly dissolving 0.05-20 pts.wt. of a fluorine-based compound having a fluoroalkyl group having excellent hydrophilic and oil-repelling properties into 3-50 pts.wt. of a photopolymerizable monomer in which the fluorine-based component is dissolvable and mixing with at least one kind selected from among another photopolymerizable monomer and a photopolymerizable prepolymer to make total amount of the resultant photo-curable resin as 100 pts.wt. Then, the photo-curable resin is applied on the surface of a base material and cured by irradiation with light or radioactive rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photocurable composition comprising a fluorine-containing compound having a fluoroalkyl group having excellent antifouling and / or antibacterial properties due to hydrophilicity and oil repellency. A surface characterized by providing a modified layer with a long-lasting effect on the substrate surface by coating it on the surface of plastic, wood, fiber, metal, etc., and curing it with active energy such as ultraviolet rays or electron beams. It relates to a reforming method.

[0002]

2. Description of the Related Art A solid surface treated with a compound having a fluoroalkyl group has a low surface energy and exhibits water repellency, oil repellency, and weather resistance. It is used as a modifying material (JP-A-5-117546, etc.).

[0003] However, because of its water and oil repellency, once the surface is contaminated, there is a drawback that dirt does not come off. Furthermore, since the surface energy is low, the adhesion to the substrate to be coated is poor, and a treatment at a high temperature such as baking is necessary. Therefore, a material having low heat resistance such as resin or wood is used as the substrate. This was very difficult, and the adhesion was not yet sufficient, and the use was limited.

In order to solve these problems, synthesis of a fluorine compound having hydrophilicity and oil repellency has been developed (“surface”).
Vol 33 No. 4 (1995)). However, a treatment method excellent in adhesion to a substrate such as a resin, wood, or fiber, and a treatment method for maintaining the effect for a long time have not been sufficiently studied.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photocurable resin composition containing a fluorine compound having excellent antifouling and / or antibacterial properties due to hydrophilicity and oil repellency, and Coating method and curing by active energy such as ultraviolet rays and electron beams, the surface modification method is not limited by the type of substrate, and has good adhesion and long-lasting effect. It is cheap and easy to provide.

[0006]

According to the present invention, a fluorine-containing compound (A) having a fluoroalkyl group and a functional group is provided.
Is uniformly dissolved in a photopolymerizable monomer (B) in which a fluorine-based compound is soluble, and then at least one selected from other photopolymerizable monomers (C) and photopolymerizable prepolymers (D) Is applied to the surface of a substrate, and cured by irradiation with light or radiation, to provide a surface modification method.

[0007] In the present invention: 1. The fluorine-based compound (A) is present in an amount of 0.05 to 20 parts by weight per 100 parts by weight of the photocurable resin; 2. 3 to 50 parts by weight of a photopolymerizable monomer (B) capable of dissolving a fluorine-based compound per 100 parts by weight of a photocurable resin; The photopolymerizable prepolymer (D) is a photocurable resin 100
3. 0 to 97 parts by weight per part by weight; When the fluorine-based photocurable resin composition is a photocurable resin 100
4. a composition further containing 0.05 to 10 parts by weight of a photopolymerization initiator per part by weight; It is preferable that the thickness of the surface modified layer obtained from the fluorine-based photocurable resin composition is 1 to 300 μm.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

[Action] According to the present invention, after the fluorine-based compound (A) having a fluoroalkyl group and a functional group is uniformly dissolved in the photopolymerizable monomer (B) in which the fluorine-based compound can be dissolved, A fluorine-based photocurable resin composition obtained by mixing at least one selected from the photopolymerizable monomer (C) and the photopolymerizable prepolymer (D) is coated on the surface of a substrate, and irradiated with light or radiation. By hardening, a surface-modified layer excellent in hydrophilicity / oil repellency and its durability can be formed on any substrate.

The fluorine compound (A) used in the present invention is:
It is characterized by having a fluoroalkyl group and a functional group.The presence of the fluoroalkyl group reduces the surface energy of the surface-modified layer and reduces the friction coefficient of the surface. The presence makes it possible to impart hydrophilicity, bond or adherence to a resin or a substrate, maintain hydrophilicity and oil repellency, impart antibacterial properties, and the like. A fluorine-based compound having a fluoroalkyl group,
It has already been pointed out that it is excellent in water repellency and oil repellency, but once dirt adheres, there is a problem that it is not always easy to remove the dirt. On the other hand, if hydrophilicity is imparted at the same time as oil repellency, the adhesion of dirt is suppressed, and at the same time, the once-adhered dirt is easily removed, and the advantage that stain resistance is improved is obtained.

In general, it is of course known to lower the surface energy and reduce the coefficient of friction by blending a fluoroalkyl group-containing fluorine compound into the coating layer. Has the disadvantage that the effect is reduced within a relatively short period. In the present invention, a fluorine-based compound (A) having a fluoroalkyl group and a functional group is selected,
By combining this fluorine-based compound (A) with a photocurable resin in a mechanism described below, it becomes possible to form a surface-modified layer excellent in the persistence of these actions.

In the present invention, the fluorine compound (A)
Is dissolved in a photopolymerizable monomer (B) in which a fluorine compound can be dissolved, and then the other photopolymerizable monomer (C) is dissolved.
And / or mixing the photopolymerizable prepolymer (D),
It is also characterized by a fluorine-based photocurable resin composition,
This makes it possible to form a surface-modified layer excellent in the continuity of the above-mentioned various actions, adhesion to a substrate, and durability.

The photocurable resin composition has the advantage that a coating layer can be formed on various substrates and the curing operation is easy. When simply added to the polymerizable monomer (C) or the photopolymerizable prepolymer (D) and then applied to the substrate and subjected to photocuring, the above-mentioned continuity of various actions and adhesion to the substrate are obtained. It was also found that they still gave only unsatisfactory results in terms of properties and durability. The reason is that the above-mentioned fluorine-based compound (A) is converted into a photopolymerizable monomer (C).
It is difficult to uniformly dissolve in a photocurable resin composition comprising a polymer or a photopolymerizable prepolymer (D), and it is difficult to effectively fix or bond the fluorine compound (A) to the cured resin. It seems to be related to

The present inventors have found that among the photopolymerizable monomers, there is one in which the fluorine compound (A) can be dissolved, and this soluble photopolymerizable monomer (B) is selected and used. By dissolving the fluorine compound (A) and then mixing the photopolymerizable monomer (C) and the photopolymerizable prepolymer (D), the fluorine compound (A) is added to the photocurable resin composition. ) Is uniformly dissolved or dispersed, and the fluorine-based compound (A) can be effectively fixed or bound in the photocurable resin.

In general, photocurable resin coatings have the advantage that the heat resistance of the base material does not pose a problem during curing, but, on the other hand, compared to thermosetting coatings, etc., photocurable resin coatings are more likely to be applied by mechanical contact or impact. Although there is a tendency that scratches and cracks are easily generated, the surface-modified layer of the present invention has a remarkable advantage that such scratch resistance is also excellent.

In the present invention, the fluorine compound (A)
As the functional group, a functional group having two or more functions can be used, or a plurality of functional groups having different functions can be used. It is also possible to give a function such as antibacterial property.

[Fluorine Compound] The fluorine compound (A) used in the present invention is a fluorine compound having a fluoroalkyl group and a functional group, and particularly has a fluoroalkyl group at both ends and is hydrophilic in the molecule. A fluorine-based compound containing at least one of a functional group, an antibacterial function group, and a functional group capable of binding to a substrate or a resin is preferable.

Examples of the fluoroalkyl 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 a 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 two or more carbon atoms are preferably present on both sides of the oxygen atom. Of course, a fluorine atom and a hydrogen atom may coexist in the fluoroalkyl group, but generally, all of the hydrogen atoms are substituted with fluorine atoms, that is, a perfluoroalkyl group or a perfluorooxaalkyl group. Is preferred.

On the other hand, as the functional group, a nonionic group,
Examples include an anionic group and a cationic group. Examples of the nonionic group include a hydroxyl group (OH) and an ether group (—O
-), A carbonyl group (C = O), a carbonyloxy group (-COO-), an amide group, a silyl group, an organosiloxane unit, and the like. Examples of the anionic group include a carboxyl group (-COOH), Sulfonic acid group (-
SO ₃ H), a phosphonic acid group (—PO ₃ H) and the like. Further, as the cationic group, primary, secondary or tertiary
And a quaternary ammonium group or a quaternary ammonium group. These functional groups may be present in the main chain of the fluorine compound (A) or in the side chain.

As a suitable example of the fluorine compound (A),
As shown by the following general formula (1), it has a fluoroalkyl group at both ends and has a hydrophilic functional group, an antibacterial functional group, or a functional group capable of bonding to a substrate or resin in the side chain in the molecule. Are included. In the formula, R _F is a fluoroalkyl group, R ₁ is a hydrophilic functional group, an antibacterial functional group or a functional group capable of binding to a substrate or a resin, R 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 or a group R ₁ , x and y are mol% when x + y = 100, and x = 0 to 0 100 y = 0 to 100, and the groups R ₂ and R ₃ may be the same or different from each other. When x is zero, at least a part of the group R ₄ shall R ₁ is the same as.

[0020] More particularly for the compounds of formula (1), groups R _F is a perfluoroalkyl group, a backbone remembering oil repellency, such as perfluoroalkyl oxaalkyl group, 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.

R ₁ is a functional group having a silane group, a sulfone group, and the like, and having a bonding force with a substrate. This will be described more specifically below. R ₁ ; a functional group having a silyl group, for example, Si (CH ₃ ) ₃ CO ₂ (CH ₂ ) ₃ [Si (CH ₃ ) ₂ O] _z Si (C
H _{3) 3;} functional groups, such as CO ₂ SO having a sulfonic acid group _{3 H CO 2 CH 2 SO 3} H CO 2 (CH 2) 2 SO 3 H or a functional group for example CH ₂ NH ₃ ⁺ Cl having antimicrobial ^- , A nitrogen-containing alicyclic group. Further, other hydrophilic functional groups described above: for example, C
OOH, OH, COCH ₃ , COOCH ₃ .

The radical R ₂ is a hydrogen atom or an alkyl group, in particular 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, most preferably methyl groups.

The group R ₄ is a hydrophilic functional group, an alkyl group, a halogen atom 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 to 5
And so on.

The above fluorine compound, ie, oligomer, is
Equation (2) Formula (3) in the presence of a fluorinated peroxide represented by And the monomer represented by the formula (4) CH ₂ ４CR ₂ R ₃ ‥ (4).

[Photopolymerizable monomer] Examples of the photopolymerizable monomer include a hydroxyl group-containing ethylenically unsaturated compound, an amino group or an amide group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound,
Examples include unsaturated carboxylic acids or derivatives thereof, vinyl ester compounds, ethylenically unsaturated compounds containing ether groups, vinyl chloride, and polyfunctional monomers.

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, and 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecene-1-ol; 1-octen-3-ol; -Methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether,
Hydroxybutyl vinyl ether, α-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether,
Allyl alcohol, allyloxyethanol, 2-butene-1,4-diol and glycerin monoallyl alcohol.

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. Phenylaminoethyl acid,
Alkyl ester derivatives of acrylic acid or methacrylic acid 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-dimethylaminopropylacrylamide, acrylamide, N-methylacrylamide, morpholine (meth) acrylate,
Examples include aminostyrenes such as p-aminostyrene, and maleimides such as 6-aminohexylmaleimide and 2-aminoethylmaleimide.

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. Such epoxy group-containing ethylenically unsaturated compounds include, for example, glycidyl acrylate, glycidyl methacrylate, etc., mono- and diglycidyl esters of maleic acid, mono- and diglycidyl esters of fumaric acid, mono- and diglycidyl esters of crotonic acid, Mono and diglycidyl esters of tetrahydrophthalic acid, mono and glycidyl esters of itaconic acid, mono and diglycidyl esters of butenetricarboxylic acid, mono and diglycidyl esters of citraconic acid,
Mono- and diglycidyl esters of endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^™ ), endo-cis-bicyclo [2,
2,1] mono- and diglycidyl esters of hept-5-ene-2-methyl-2,3-dicarboxylic acid (methylnadic acid ^TM ), mono- and alkylglycidyl esters of dicarboxylic acids such as mono- and glycidyl esters of allylsuccinic acid ( In the case of monoglycidyl ester, the alkyl group has 1 to 12 carbon atoms, alkyl glycidyl ester of p-styrene carboxylic 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 aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene and p-methylstyrene.
-Methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5 Vinyl pyridine, 2-isopropenyl pyridine, 2-vinyl quinoline, 3-vinyl isoquinoline, N-vinyl carbazole and N-vinyl pyrrolidone.

Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo [2,2,1 ] Unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid and derivatives thereof (for example, acid anhydrides, acid halides, amides, imides, esters and the like). Examples of the derivative include maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride. Dimethyl maleate, monomethyl maleate, ethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,
2,1] hept-2-ene-5,6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate, aminopropyl methacrylate and the like. It is. Among these, (meth) acrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate, and aminopropyl methacrylate are preferred.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate,
Examples thereof include vinyl persatic acid, vinyl laurate, vinyl stearate, vinyl benzoate, pt-butyl vinyl benzoate, vinyl salicylate, vinyl chlorohexanecarboxylate, and the like.

Examples of the ethylenically unsaturated compound having an ether group include 4-hydroxybutyl ether, 1,6-hexanediol monovinyl ether, neopentyl glycol monovinyl ether, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, Dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, dibutylene glycol monovinyl ether, tributylene glycol monovinyl ether, pentaerythritol divinyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether, pentaerythritol monovinyl ether, dipentaerythritol divinyl Vinyl ether, ethi Carbitol (meth) acrylate, propyl carbitol (meth) acrylate, and butyl carbitol (meth) acrylate.

Examples of the polyfunctional monomer include a polyfunctional acrylic monomer. Examples of such an acrylic monomer include 1,6-hexanediol diacrylate.
(HDDA), 1,6-hexanediol dimethacrylate (HDD
MA), neopentyl glycol diacrylate (NPGD
A), 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), tetramethylolmethanetetraacrylate, N, N, N ', N'-tetra Acrylate of kiss (β-hydroxyethyl) ethylenediamine, 2,2-bis [4- (3-methacryloyloxy-
2-hydroxypropoxy) phenyl) propane and the like are used.

Further, divinylbenzene, diallyl phthalate (DAP), diallyl isophthalate, diallyl adipate, diallyl glycolate, diallyl maleate, diallyl sebacate, triallyl phosphate,
Other polyfunctional monomers such as triallyl aconitate, allyl trimellitate, allyl pyromellitic acid and the like may also be used.

[Monomer Soluble in Fluorine Compound] In the present invention, any of the above-mentioned photopolymerizable monomers which can dissolve the fluorine compound can be used as the monomer soluble in the fluorine compound. Preferable examples of the photopolymerizable monomer capable of uniformly dissolving these fluorine compounds include morpholine (meth) acrylate or a derivative thereof polyethylene glycol (meth) acrylate or a derivative thereof trimethylolpropane (meth) acrylate or a derivative thereof carbitol Examples thereof include (meth) acrylates and derivatives thereof, and are not particularly limited as long as they are photopolymerizable monomers that can uniformly dissolve the fluorine-based compound.

[Ultraviolet-polymerizable prepolymer] As the ultraviolet-polymerizable prepolymer, a prepolymer having a plurality of ethylenically unsaturated groups in a molecule or a mixture thereof is used. Suitable examples are epoxy acrylate resins,
Examples include urethane acrylate resin, polyester acrylate, and thermosetting polyester resin.

As the epoxy acrylate resin, an adduct of the bisphenol type epoxy resin of the above formula (1) with an ethylenically unsaturated carboxylic acid, for example, acrylic acid or methacrylic acid, or an adduct of this adduct with an ethylenically unsaturated polyvalent A reaction product with a carboxylic anhydride such as maleic anhydride, itaconic anhydride or the like is used.

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

Examples of the thermosetting polyester resin include polyesters containing an ethylenically unsaturated bond in the molecule, for example, ethylenically unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid and tetrahydrophthalic acid. , Isophthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, combinations with other acid components such as polymerized fatty acids, and ethylene glycol, diethylene glycol, propylene glycol, glycerin, neopentyl glycol, trimethylolpropane, pentane Polyester resins obtained by condensation with polyhydric alcohols such as erythritol and bisphenols are used.

[Photocurable Resin Composition] The fluorine-based compound having a fluoroalkyl group having excellent hydrophilicity and oil repellency of the formula 1 is used in an amount of 0.05 to 20 parts by weight per 100 parts by weight of the photocurable resin.
It is good to include 0.1 parts by weight, preferably 0.1 to 5 parts by weight. When the amount is less than 0.05 part by weight, no manifestation of hydrophilicity and oil repellency is observed, and when the amount exceeds 20 parts by weight, poor photocuring occurs and a good cured resin is not formed.

The photopolymerizable monomer in which the fluorine compound can be dissolved contains 3 to 50 parts by weight per 100 parts by weight of the photocurable resin.
Preferably, it contains 5 to 20 parts by weight. If the amount is less than 3 parts by weight, poor dissolution of the fluorine compound occurs, and if it exceeds 50 parts by weight, practical physical properties cannot be obtained.

On the other hand, the photopolymerizable monomer is contained in a total amount of 3 to 100 parts by weight, preferably 20 to 80 parts by weight, per 100 parts by weight of the photocurable resin. The photopolymerizable prepolymer is contained in an amount of 0 to 100 parts by weight of the photocurable resin.
It may contain 97 parts by weight, preferably 20 to 80 parts by weight.

The order in which the fluorine-based compound is dissolved is such that the compound is previously dissolved in the above-mentioned soluble photopolymerizable monomer, and then other photopolymerizable monomers and prepolymers are mixed to obtain a finished composition. To In the method of directly dissolving the fluorine-based compound in 100 parts by weight of the photocurable resin which is the completed composition, it is difficult to dissolve the compound,
In particular, a photocurable resin containing a photopolymerizable prepolymer has a high viscosity, so that workability is poor and it is difficult to uniformly dissolve the resin.

In the photopolymerizable composition of the present invention, known initiators, leveling agents, defoamers, coloring agents, thickeners and the like can be used as other additives.

As the initiator, a radical initiator or a cationic initiator is used.

As the radical initiator, benzoin, benzoin methyl ether, benzoin ethyl ether,
Benzoin such as benzoin isopropyl ether and its alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]
Acetophenones such as -2-morpholino-propan-1-one; anthraquinones such as 2-methylanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,
Thioxanthones such as chlorothioxanthone and 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone or xanthones, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis ( Acylphosphine oxides such as (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

The photopolymerization initiator can be used in combination with one or more known and commonly used photopolymerization accelerators such as benzoic acid or tertiary amine.

In the radical polymerizable resin composition, the photopolymerization initiator is used in an amount of 0.0
It is preferable to use 5 to 10 parts by weight, preferably 1 to 8 parts by weight.

As the ultraviolet cationic polymerization type resin composition, in addition to the above components, a combination of an ultraviolet curing type epoxy resin and a photo cationic polymerization catalyst is used.

The ultraviolet-curable epoxy resin includes 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, for example, an epoxycyclohexane ring, an epoxycyclopentane ring, or the like is used alone or in combination.

Suitable examples include, but are not limited to,
Vinylcyclohexene diepoxide, vinylcyclohexene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2- (3,4-epoxycyclohexyl-5,
5-spiro-3,4-epoxy) cyclohexane-m-
Dioxane, bis (3,4-epoxycyclohexyl)
Adipate and the like.

The cationic ultraviolet polymerization initiator used in combination with the above epoxy resin is one which is decomposed by ultraviolet rays to release a Lewis acid, and this Lewis acid has an action of polymerizing an epoxy group. An aromatic iodonium salt, an aromatic sulfonium salt, an aromatic selenium salt, an aromatic diazonium salt and the like can be mentioned.

Examples of the diallyliodonium salt include diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, 4-chlorophenyliodonium tetrafluoroborate, di (4-methoxyphenyl) iodonium chloride and (4-methoxyphenyl) phenyl And iodonium.

The triarylsulfonium salts include, for example, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, 4-chloro Phenyldiphenylsulfonium hexafluorophosphate and the like.

Examples of the triarylselenium salt include triphenylselenium hexafluorophosphate, triphenylselenium hexafluoroantimonate and the like.

As other cationic polymerization initiators,
(2,4-cyclopentagen-1-yl) [(1-methoxythiethyl) -benzene] -iron-hexafluorophosphate, diphenylsulfonium hexafluoroantimonate, dialkylphenylsulfonium hexafluoroantimonate, dialkylphenylsulfonium Hexafluorophosphate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio]
Phenylsulfide-bis-hexafluoroantimonate, 4,4-bis [di (β-hydroxyethoxy) phenylsulfonio] phenylsulfide-bis-hexafluorophosphate, and the like can be mentioned.

This cationic curing initiator is used in the resin composition 1
It is preferably used in an amount of 0.05 to 10 parts by weight, particularly 1 to 8 parts by weight, per 100 parts by weight, and the cationically curable epoxy resin is used in an amount of 0 to 97 parts by weight per 100 parts by weight of the resin composition.
It is advisable to use them in parts by weight, in particular 20 to 80 parts by weight.

As the leveling agent, various silicons,
In particular, an organopolysiloxane having a polyalkyleneoxy group is 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-mentioned 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.

The following colorants can be used alone or in combination. Black pigments 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, Hanza yellow G, Hanza yellow 10G, benzidine yellow G,
Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake. Orange pigments Red mouth lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, induslen brilliant orange RK, benzidine orange G, induslen brilliant orange GK. Red pigment Bengala, cadmium red, lead red, cadmium mercury sulfide, permanent red 4R, lithol 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, partially chlorinated phthalocyanine blue, first sky blue, indaslen blue B
C. Green pigment chrome green, chromium oxide, pigment green B,
Malachite Green Lake, Fanal Yellow Green G. White pigment Zinc white, titanium oxide, antimony white, zinc sulfide. Extender barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white. These pigments are used in an amount of 0 to 1 per 100 parts by weight of the resin composition.
It is preferred to use 0 parts by weight, especially 0 to 5 parts by weight.

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

The photocurable resin composition containing such a fluorine compound can contain a commonly used solvent and is not particularly limited. That is, various alcohols, ketones, ethers, amides, aromatic hydrocarbons and the like can be used.

[Formation of Modified Layer] Further, the formation of the modified layer with the fluorine-based photocurable resin composition may be performed by a known coating method, for example, spray coating, roll coating, flow coating, bar coating, dip coating, etc. Can be used. After coating, apply the composition at low, medium or high pressure
The modified layer can be obtained by irradiating ultraviolet rays with an ultraviolet fluorescent lamp, a xenon lamp, a metal halide lamp, or the like, or by irradiating an electron beam to cure the coating film.

At this time, the thickness of the surface modified layer is 1 to 300.
μm, preferably 5 to 80 μm.

As the substrate to which the surface modification with the fluorine-based photocurable resin composition of the present invention can be applied, there are various kinds of plastics, woods, fibers, metals, etc., of which the use has been limited. Application to plastics, woods and fibers with relatively low heat resistance is effective.

[0066]

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.

(Examples 1 to 6) In the formulation shown in Table 1 below, first, a fluorine-based compound was uniformly dissolved in a photopolymerizable monomer for dissolution, and then other photopolymerizable monomers / photopolymerizable prepolymers were added. By mixing, an ultraviolet curable resin composition was obtained. This resin composition was coated on a vinyl chloride resin with a 20 μm bar, and irradiated with a high-pressure mercury lamp of 80 W at an irradiation distance of 10 cm for 2 seconds to obtain a sample. Table 2 shows the results.

Comparative Examples 1 to 5 Comparative examples were carried out in the same manner as in the above examples (Table 1). Table 2 shows the results.

[0069]

[Table 1]

Description of each component in the above table

──────────────────────────────────── Component Product name Manufacturer name ──── ──────────────────────────────── (1) Morpholine acrylate NK ester A-MO Shin-Nakamura Chemical (2) Polyethylene glycol NK ester A-400 Shin-Nakamura Chemical ^# 400 Diacrylate (3) Trimethylolpropane tri KAYARAD KS-TMPTA Nippon Kayaku Acrylate (4) Urethane acrylate NK Oligo UA-512 Shin-Nakamura Chemical (5) Urethane acrylate KAYARAD UX-6101 Japan Kayaku (6) Urethane acrylate Aronix M-1600 Toa Gosei Chemical (7) Polyester acrylate KAYARAD PAR-300 Nippon Kayaku (8) Neopentyl glycol NK ester A-NPG Shin-Nakamura Chemical diacrylate (9) Dipentaerythritol NK ester A-95 30 Shin-Nakamura Chemical Polyacrylate (10) 1,6-hexanediol KAYARAD KS-HDDA Nippon Kayaku diacrylate (11) Methylbenzoyl formate VICURE-55 Akzo Nobel ────────────── ──────────────────────

[0072]

[Table 2]

(Evaluation Items) The formed modified layer was cured immediately after curing (initial stage) and at 40 ° C. × 95% relative humidity.
After being left for a period of months (after treatment), each was evaluated by the following test method. (1) Appearance: Visually check for cracks / hardening defects (Evaluation criteria ○: No abnormality, ×: Cracks / hardening defects, etc.) (2) Adhesion: JIS K5400 (cross cut test) (Evaluation criteria) ：: no peeling, ×: peeling) (3) Evaluation of hydrophilicity and oil repellency; evaluation by the contact angle (°) after 1 minute from the dropping of the reagent on the surface of the modified layer of the substrate (Kyowa Interface Science Co., Ltd. )) (Evaluation criteria) Hydrophilicity: Water → The lower the contact angle, the more hydrophilic the oil repellency: Dodecane → The higher the contact angle, the more oil repellent) (4) Antibacterial: Escherichia coli and Staphylococcus aureus (Evaluation criteria ○: Effective, ×: No effect)

[0074]

According to the present invention, after a fluorine compound (A) having a fluoroalkyl group and a functional group is uniformly dissolved in a photopolymerizable monomer (B) in which the fluorine compound is soluble. A fluorine-based photocurable resin composition obtained by mixing at least one selected from other photopolymerizable monomers (C) and photopolymerizable prepolymers (D) on the surface of the substrate, By curing by irradiation, it is possible to form a surface-modified layer having excellent hydrophilicity and oil repellency, and having antifouling property and / or antibacterial property. This modified layer is made of plastic, wood, fiber, metal, etc. Can be formed on the surface of any substrate by coating and curing by activation energy such as ultraviolet rays or electron beams, and the above-mentioned functionality can be maintained on the substrate surface for a long period of time.

Claims (10)

[Claims] 1. A photopolymerizable monomer (A) having a fluoroalkyl group and a functional group (A) is uniformly dissolved in a photopolymerizable monomer (B) in which the fluorine compound is soluble, and then the other photopolymerizable monomer is dissolved. Applying a fluorine-based photocurable resin composition obtained by mixing at least one selected from a monomer (C) and a photopolymerizable prepolymer (D) to the surface of a base material, and curing the composition by irradiation with light or radiation. A surface modification method characterized by the following. 2. A photocurable resin 1 comprising a fluorine compound (A).
2. The method according to claim 1, wherein the amount is 0.05 to 20 parts by weight per 100 parts by weight. 3. A photopolymerizable monomer (B) in which a fluorine-based compound is soluble is contained in an amount of 3 to 100 parts by weight of a photocurable resin.
3. The composition according to claim 1, wherein the amount is 50 parts by weight.
3. The surface modification method according to item 1. 4. The fluorine-containing compound (A) has a fluoroalkyl group at both ends and contains at least one of a hydrophilic functional group, an antibacterial functional group and a substrate-binding functional group in the molecule. The surface modification method according to claim 1, wherein the surface modification method is a fluorine compound. 5. The fluorine compound (A) represented by the general formula (1) In the formula, R _F is a fluoroalkyl group, R ₁ is a hydrophilic functional group, an antibacterial functional group or a functional group capable of binding to a substrate or a resin, R 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 or a group R
_And x and y are mol% when x + y = 100, and are numbers satisfying x = 0 to 100 y = 0 to 100, and the groups R ₂ and R ₃ are the same as each other. And when x is zero, at least part of the group R ₄ is a group R ₁
The surface modification method according to claim 1, wherein the fluorine-based compound is represented by the following formula: 6. The photopolymerizable monomer (B) is composed of morpholine (meth) acrylate or a derivative thereof, polyethylene glycol (meth) acrylate or a derivative thereof, trimethylolpropane (meth) acrylate or a derivative thereof, or carbitol (meth) acrylate. The surface modification method according to any one of claims 1 to 5, which is a derivative thereof. 7. The method according to claim 1, wherein the photopolymerizable prepolymer (D) is an epoxy acrylate resin, a urethane acrylate resin, a polyester acrylate, or a thermosetting polyester resin. 8. The method according to claim 1, wherein the photopolymerizable prepolymer (D) is present in an amount of 0 to 97 parts by weight per 100 parts by weight of the photocurable resin. 9. The photocurable resin composition according to claim 1, wherein the photocurable resin composition further contains 0.05 to 10 parts by weight of a photopolymerization initiator per 100 parts by weight of the photocurable resin. The surface modification method as described in the above. 10. The surface modification method according to claim 1, wherein the thickness of the surface modification layer obtained from the fluorine-based photocurable resin composition is 1 to 300 μm.