JP2002030268A - Method for preventing surface staining of interior material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for protecting surface staining of an interior material in which oil dusts, marker inks and the like attached on the surface of the interior material can be easily removed by wiping. SOLUTION: An ultraviolet-curing treating agent comprising (A) 1-99 pts.wt. of a cation polymeric compound and (B) 1-99 pts.wt. of a compound having at least one oxetane ring in a molecule, and 0.01-20 pts.wt. of a cationic polymerization initiator generating cations with ultraviolet radiation based on 100 pts.wt. of the sum of the compounds (A) and (B) is applied on the surface of an interior material, and a layer of the treating agent is formed on the surface of the interior material with ultraviolet radiation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing surface contamination of an interior material, and more particularly to a method for preventing surface contamination of an interior material which can easily wipe off and remove oil dust and marker ink on the surface of the interior material many times. About the method.

[0002]

2. Description of the Related Art Conventionally, paint has been applied to the interior of a house. As a paint used in such a coating, a material obtained by dissolving or dispersing a non-crosslinkable resin such as an acrylic, vinyl chloride, or vinyl acetate resin in an organic solvent or water is often used.

[0003] However, such a coating film using a non-crosslinkable resin has a problem that the stain resistance due to oil dust and ink is inferior. Further, there is also a two-component curable paint obtained by blending a polyurethane crosslinking agent with a hydroxyl group-containing resin. However, the coating film formed from such a paint does not have sufficient stain resistance due to oil dust, ink and the like as described above. Hard to say.
Therefore, various paints containing waxes and silicone resins having excellent stain resistance have been proposed. The coated surface can be removed by wiping oil and dirt off the ink. However, there is a problem that the dirt cannot be removed if the dirt is repeatedly applied to the same place.

[0004] The present invention has been made in view of such conventional problems, and an object of the present invention is to repeatedly remove the contamination by oil dust, markers, ink, etc. attached to the interior material surface. An object of the present invention is to provide a method for preventing contamination that can be easily wiped off to solve the above-mentioned conventional problems.

[0005]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, applied or impregnated with a specific treating agent on the surface of the base material for interior materials, and cured. As a result, they found that the problem could be solved by forming the treating agent layer, and completed the present invention.

[0006] Thus, the present invention provides an interior substrate
(A) 1 to 99 parts by weight of a cationically polymerizable compound, (B) 1 to 99 parts by weight of a compound having at least one oxetane ring in a molecule, and 100 parts by weight of the total amount of the compounds (A) and (B) On the other hand, (C) an interior obtained by coating an ultraviolet-curable treatment agent containing 0.01 to 20 parts by weight of a cationic polymerization initiator which generates cations by irradiation with ultraviolet light, and performing irradiation with ultraviolet light to form a treatment agent layer A method for preventing surface contamination of a material, wherein (A) 1 to 99 parts by weight of a cationically polymerizable compound on the sheet surface, (B) 1 to 99 parts by weight of a compound having at least one oxetane ring in a molecule, and (A) ) And (B) with respect to 100 parts by weight,
(C) A UV-curable treating agent containing 0.01 to 20 parts by weight of a cationic polymerization initiator which generates cations upon irradiation with UV rays is applied, irradiated with UV rays to form a treating agent layer, and then patterned with an embossing roll. The present invention relates to a method for preventing surface contamination of an interior material, characterized in that a wallpaper sheet formed with the above is bonded to the interior building material surface via an adhesive.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The base material for interior used in the method of the present invention can be used without any particular limitation as long as it has been conventionally used for interior of buildings. Specific examples include woods, papers, plastics, metals, glasses, and combinations of two or more of these. Examples of the plastics and papers include not only films or sheets for interiors that can be attached to a wall with an adhesive, but also, for example, those provided with an adhesive layer to form an adhesive sheet for interiors. .

In the method of the present invention, a method of coating the surface of the interior substrate with a processing agent described below is applied. In particular, a film or sheet such as plastics or paper is coated with the processing agent described below and cured. A method of attaching the obtained anti-contamination sheet to the surface of a building material such as a wall using an adhesive, or applying a treating agent to an adhesive sheet such as plastics or papers having an adhesive, and performing a curing treatment. It can be carried out by a method or the like in which the adhesive sheet for preventing pollution is attached to the surface of a building material such as a wall with the adhesive. In the method of the present invention, in particular, after forming the treatment agent layer, a pattern is formed with an embossing roll to form a wallpaper sheet, which can be adhered to the surface of the interior building material via an adhesive.

As the plastics, conventionally known plastics can be used without any particular limitation as long as they are used as plastic films or sheets for building materials. Examples of the plastic include polyethylene, polypropylene, polyisobutylene, polybutadiene, polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride (PVF), and polyethylene terephthalate (PE).
T), ethylene / tetrafluoroethylene copolymer (E
TFE), polytetrafluoroethylene / perfluoropropoxyvinyl ether copolymer (PFA), nylon, polystyrene, polyurethane, polycarbonate (PC), polyvinyl alcohol (PVA), ethylene / vinyl alcohol Thermoplastic or cross-linked plastic films such as copolymer (EVOH), polycarbonate, polyacetal, AS resin, ABS resin, melamine resin, acrylic resin, epoxy resin, silicone resin, polyester resin, etc. Can be mentioned. In addition, these plastic films are UV absorbers,
It may contain a filler, a heat stabilizer, a coloring agent and the like. Further, the surface of these plastic films and sheets can be subjected to a surface treatment such as a corona treatment.

The thickness of these films is usually in the range of about 5 to 2000 microns, preferably about 10 to 1000 microns. In particular, in the case of a sheet for wallpaper, the thickness is preferably in the range of about 30 to 2000 microns, preferably about 40 to 1000 microns. When the film thickness is less than about 30 microns, it is easy to peel off when an object comes into contact, If it exceeds about 2,000 microns, it is not preferable because it easily peels off due to heat.

The ultraviolet-curable treating agent used in the method of the present invention is a composition which undergoes cationic polymerization by irradiation with ultraviolet rays and cures, and comprises (A) a cationically polymerizable compound, and (B) an oxetane ring in the molecule. And (C) a cationic polymerization initiator that generates cations upon irradiation with ultraviolet light.

The cationically polymerizable compound (A) is a monomer that undergoes ionic polymerization using a cation as a chain carrier (growth species) and a vinyl compound (a compound having a carbon-carbon double bond) that undergoes vinyl cation polymerization using a carbon cation as a growth species. )
And a heterocyclic compound that undergoes ring-opening cationic polymerization using an onium ion as a growth species. However, the compound (B) having at least one oxetane group in the molecule is excluded.

Examples of the cationically polymerizable compound (A) include the following compounds (a) to (d).

(A) Compounds having an epoxy group: for example, dicyclopentadienedioxide, limonenedioxide, 4-vinylcyclohexenedioxide,
(3,4-epoxycyclohexyl) methyl-3,4-
Epoxycyclohexanecarboxylate, di (3,4
-Epoxycyclohexyl) adipate, phenylglycidyl ether, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-, m- or p-cresol novolak type epoxy resin, phenol novolak type epoxy resin, Polyglycidyl ethers of polyhydric alcohols and the like.

(B) vinyl compound: for example, styrene,
Aromatic vinyl compounds such as α-methylstyrene, p-chloromethylstyrene, vinyltoluene, substituted or unsubstituted alkyl or cycloalkyl vinyl ethers such as n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, allyl vinyl ether Alkenyl vinyl ethers such as ethenyl vinyl ether, 1-methyl-2-propenyl vinyl ether, and substituted or unsubstituted aryl vinyl ethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether;
Alkylene or cycloalkylene divinyl ethers such as butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, 1,4-benzenedimethanol divinyl ether, N, N-m-chlorophenyldiethanolamine divinyl ether, m-phenylene bis (Ethylene glycol) substituted or unsubstituted aralkylenedivinyl ethers such as divinyl ether; arylenedivinyl ethers such as hydroquinone divinyl ether and resorcinol divinyl ether; cationically polymerizable nitrogen-containing compounds such as N-vinylcarbazole and N-vinylpyrrolidone; .

(C) Bicyclo orthoester compounds: For example, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo- [2,2,2] -octane, 1-ethyl-4-hydroxymethyl- 2,6,7-trioxabicyclo- [2,2,2] -octane and the like.

(D) spiro orthocarbonate compound;
For example, 1,5,7,11-tetraoxaspiro-
[5,5] -undecane, 3,9-dibenzyl-1,
5,7,11-tetraoxaspiro- "5,5] -undecane, 1,4,6-trioxaspiro- [4,4]-
Nonane, 2-methyl-1,4,6-trioxaspiro-
"4,4] -nonane, 1,4,6-trioxaspiro-
"4,5] -decane and the like.

Of the above compounds (a) to (d), the compound (a) having an epoxy group is preferable, and the compound having an alicyclic epoxy group in the molecule is particularly preferable.
Here, the “alicyclic epoxy group” means that two of the carbon atoms (usually adjacent to each other) among the cyclically bonded carbon atoms forming the aliphatic ring of the alicyclic compound are oxygen. An epoxy group in which one atom is bonded.

Specifically, dicyclopentadienedioxide, limonenedioxide, di (3,4-epoxycyclohexyl) adipate, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate, (3 , 4-Epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2-
Examples thereof include di (3,4-epoxycyclohexanecarboxylic acid) esters and compounds represented by the following formulas (1) to (3). These compounds can be used alone or in combination of two or more.

[0020]

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In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have an epoxy group, or an acyl group having 1 to 12 carbon atoms which may have an epoxy group. R ² represents an alkylene group having 1 to 6 carbon atoms, n represents an integer of 0 to 15,

[0022]

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In the formula, two R ³ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and m is 0
Represents an integer of ~ 25,

[0024]

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In the formula, R ⁴ represents an alkylene group having 1 to 6 carbon atoms, and three R ^{5 s} are the same or different and each represent an alkyl group having 1 to 4 carbon atoms.

In the above formula (1), the alkyl group represented by R ¹ is linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n- or i-propyl, n- , I- or t-butyl, octyl, cyclohexyl group and the like. Specific examples of the alkyl group having an epoxy group include a 3,4-epoxycyclohexylmethyl group. An acyl group that R ¹ can represent is a group of formula RCO, where R is alkyl,
Represents an organic group such as alkenyl, cycloalkyl, aryl, and aralkyl), and specific examples thereof include formyl, acetyl, propionyl, butyroyl, octanoyl, lauroyl, acryloyl, methacryloyl,
Examples thereof include a benzoyl group, and specific examples of the acyl group having an epoxy group include a 3,4-epoxycyclohexanecarbonyl group. The alkylene group represented by R ² is linear, branched or cyclic, and specific examples thereof include methylene, ethylene, 1,2 and
-Or 1,3-propylene, butylene, cyclohexylene group and the like.

As a typical example of the compound represented by the above formula (1), when n is 0, 3,4-
Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl alcohol, di (3,4-epoxycyclohexylmethyl) Ether, etc., and n is an integer of 1 to 15, preferably 1 to 6, and when n is any integer of 1 to 15, R ¹ is a hydrogen atom and R ² Is a methylene group, R ¹ is a 3,4-epoxycyclohexanecarbonyl group and R ² is a methylene group, R ¹ is an acryloyl group and R ² is a methylene group, and R ¹ Is a methacryloyl group and R2 is a methylene group. It is possible.

In the above formula (2), the alkylene group represented by R ³ is linear, branched or cyclic, and specific examples thereof include methylene, ethylene, 1,2- or 1,3-propylene. , Butylene and cyclohexylene groups. Thus, as a typical example of the compound represented by the formula (2), a compound in which all two R ³ are 1,2-ethylene groups and m is an integer of 0 to 25 is mentioned. Can be.

In the above formula (3), the alkylene group represented by R ⁴ is linear, branched or cyclic, and specific examples thereof include methylene, ethylene, 1,2- or 1,3-propylene. , Butylene and cyclohexylene groups. Thus, as typical examples of the compound represented by the formula (3), a compound in which R ⁴ is an ethylene group and all three R ⁵ are methyl groups, and R ⁴ is 1,2- or Examples include compounds in which the compound is a 1,3-propylene group and all ^three R ³ are methyl groups.

Among the compounds having an alicyclic epoxy group in the molecule described above, particularly preferred compounds are 3,4.
-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl alcohol, 3,4-epoxycyclohexylethyltrimethoxysilane or the following formula

[0031]

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Compounds represented by the following formulas can be mentioned.

The compound (B) having at least one oxetane ring in the molecule can be subjected to ring-opening polymerization by irradiation with ultraviolet light in the presence of a cationic polymerization initiator.

[0034]

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Is a compound having at least one, preferably 1 to 15, more preferably 1 to 4 in one molecule (hereinafter referred to as an oxetane compound). Specifically, for example, the following formula (4) And the compounds represented by the following formulas (7), (8) and (9).

[0036]

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In the above formula, R ⁶ is a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, pentyl, hexyl, cyclohexyl group, etc.), a linear or branched fluoroalkyl group having 1 to 6 carbon atoms (for example, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
Perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluorohexyl group, etc.), allyl group, aryl group (eg, phenyl, naphthyl, tolyl, xylyl group, etc.), aralkyl group (eg, benzyl, phenethyl group, etc.), R ⁷ has a valency corresponding to the value of p and represents a hydrogen atom or a monovalent to tetravalent organic group; Z represents an oxygen atom or a sulfur atom; 4 is an integer.

The monovalent to tetravalent organic group represented by R ⁷ may have at least one kind of heteroatom selected from O, S, N and F and / or a siloxane bond. Examples thereof include 1 to 30 linear, branched or cyclic 1 to 4 valent hydrocarbon groups.

Among the compounds (B) having at least one oxetane ring in the molecule, (B-1) a compound having at least one, preferably one each of an oxetane ring and a hydroxyl group in the molecule; -2) A compound having at least two oxetane rings or an oxetane ring with an epoxy group in a molecule is preferable.

The oxetane compound (B-1) is, for example, a compound of the above formula (4) in which p is 1 and R ⁷ is a hydrogen atom, particularly represented by the following formula (4-1). Compounds can be mentioned.

[0041]

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In the formula, R ⁶¹ is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 6 carbon atoms,
Represents a linear or branched fluoroalkyl group having 1 to 6 carbon atoms or an allyl group.

A typical example of the compound represented by the formula (4-1) is a compound represented by the formula (4-1) when R ⁶¹ is an ethyl group.
Can be mentioned.

Among the oxetane compounds (B-2), compounds having at least two oxetane rings in the molecule (hereinafter referred to as polyoxetane compounds) include:
When p is an integer of 2 to 4, the compound of the formula (4) may be mentioned, and among them, the compound represented by the following formula (4-2) is preferable.

[0045]

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[0046] In the formula, R ⁶¹ are as defined above, R ⁷¹
Represents a divalent to tetravalent organic group defined for R ⁷ in the formula (4), and q represents an integer of 2 to 4.

As a typical example of the compound represented by the above formula (4-2), R ⁶¹ is an ethyl group and R ⁷¹ is 1,4-
A tetramethylene group, a dodecamethylene group, an o-, m- or p-xylylene group, or a group represented by the formula (4-) wherein R ⁹ is an ethylene group, a group of the following formula (5) or a group of the following formula (6):
The compound of 2) can be mentioned.

[0048]

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In the formula, R ⁹ represents an alkylene group having 1 to 6 carbon atoms, an arylene group, or a group represented by the following formula: or a carbon atom in which an alkylene group and an alkylene group are bonded by a (poly) siloxane chain. Number 2 to 30, preferably 2
(E.g., the alkylene group is an ethylene or propylene group, and the molecular weight of the (poly) siloxane chain is 1
30 to 15,000, particularly 130 to 500, and preferably those represented by the following formula (6)).

[0050]

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In the formula, k represents an integer of 1 to 6, and 1 is 2 or 3.

As the polyoxetane compound, in addition to the compound represented by the above formula (4-2), the following formula (7):
The compounds represented by (8) and (9) can be mentioned.

[0053]

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In the formula, two R ^{61 s} are the same or different, each has the same meaning as described above, and an ethyl group is particularly preferred.

[0055]

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In the formula, s represents an integer of 25 to 200.

Further, the oxetane compound (B-2)
Of which has an oxetane ring and an epoxy group in the molecule (hereinafter referred to as epoxy-containing oxetane compound)
Represents one oxetane ring and one epoxy group in the molecule.
The compounds include individual compounds, and specific examples include compounds represented by the following formula (10).

[0058]

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In the formula, R ¹³ represents an epoxy group-containing group;
R ⁶¹ has the same meaning as described above.

A typical example of the epoxy-containing oxetane compound is a compound in the above formula (10) in which R ⁶¹ is an ethyl group and R ¹³ is a glycidyl group or a 3,4-epoxycyclohexylmethyl group. .

The oxetane compound (B) described above is
Each can be used alone, or two or more can be used in combination. In particular, it is preferable to use the compound (B-1) and the compound (B-2) in combination. The amount of each of the oxetane compounds (B-1) and (B-2) used in combination is as follows:
The oxetane compound (B-1) is 5 to 6 at a ratio where the total amount of the cationic polymerizable compound (A) and the oxetane compounds (B-1) and (B-2) is 100 parts by weight.
0 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, and the oxetane compound (B-
2) may be in the range of 5 to 60 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight.

The cationic polymerization initiator (C) is a compound which generates a cation upon irradiation with ultraviolet rays to initiate polymerization, and includes, for example, hexafluoroantimonate salts represented by the following formulas (I) to (XV), pentafluoro Hydroxyantimonate salt, hexafluorophosphate salt,
Hexafluoroarsenate salts and other cationic polymerization initiators can be mentioned. Ar2I + .X- (I) wherein Ar represents an aryl group, for example, a phenyl group;
X- represents PF6-, SbF6- or AsF6-; Ar3S + .X- (II) wherein Ar and X- have the same meanings as above;

[0063]

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In the formula, R ²⁰ represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms;
X- has the same meaning as above,

[0065]

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Where Y ⁻ is PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻
Or SbF ₅ (OH) ^—

[0067]

Embedded image Wherein X ^- has the same meaning as above,

[0068]

Embedded image Wherein X ^- has the same meaning as above,

[0069]

Embedded image Wherein X ^- has the same meaning as above,

[0070]

Embedded image Wherein, R ²¹ represents an alkenyl group of an aralkyl group, or -C 3-9 of 7 to 15 carbon atoms, R ²² represents a hydrocarbon group or a hydroxyphenyl group having 1 to 7 carbon atoms, R ²³ Represents an alkyl group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, and X ^- has the above-mentioned meaning;

[0071]

Embedded image In the formula, R ²⁴ and R ²⁵ each independently represent an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms,

[0072]

Embedded image Wherein R ²⁴ and R ²⁵ have the same meanings as above,

[0073]

Embedded image .

As the cationic polymerization initiator (C), commercially available products can be used. Examples of the commercially available products include Cyracure UVI-6970, UVI-6974, and UCI-6974.
VI-6990 (all, manufactured by Union Carbide of the United States), Irgacure 264 (manufactured by Ciba-Geigy),
CIT-1682 (manufactured by Nippon Soda Co., Ltd.) and the like can be mentioned.

Of the cationic polymerization initiators described above,
From the viewpoints of toxicity, versatility, and the like, a compound having a hexafluorophosphate anion (PF ₆ ⁻ ) is preferable.

The treating agent used in the method of the present invention comprises (A)
Although the components (B) and (C) are essential, the composition may further contain a lubricity-imparting agent (D) for the purpose of improving the lubricity of the obtained coating film. Examples of (D) include waxes such as fatty acid ester wax, which is an esterified product of a polyol compound and a fatty acid, silicon-based wax, fluorine-based wax, polyolefin wax, animal-based wax, and plant-based wax. The above-mentioned lubricity imparting agents (D) can be used alone or in combination of two or more. Among them, fatty acid ester waxes and silicone waxes are preferred.

The polyol compound used as a raw material for the fatty acid ester wax includes ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexane. Diol, glycerin, di- or higher polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like can be mentioned. Of these, polyol compounds having three or more hydroxyl groups in one molecule are preferable, and polyglycerin, trimethylolpropane, and pentaerythritol are particularly preferable.

The fatty acid used as another raw material of the fatty acid ester wax may be a saturated or unsaturated fatty acid, and is preferably a fatty acid having 6 to 32 carbon atoms. Specific examples of suitable fatty acids include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachiic acid,
Saturated fatty acids such as behenic acid, cerotic acid, montanic acid, and melicic acid; caproleic acid, undecylenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, setreic acid, erucic acid, licanoic acid, ricinoleic acid And unsaturated fatty acids such as arachidonic acid.

The fatty acid ester wax is preferably one in which at least 1/3 of the number of hydroxyl groups of the above polyol compound is esterified with a fatty acid.

As the silicon-based wax, for example, B
YK-300, BYK-320, BYK-330 (all manufactured by BYK Chemie)
Silwet L-77, Silwet L-720, Silwet L-7602 (Nippon Konika Co., Ltd.)
Paintad 29, Paintad 32, Paintad M (above, manufactured by Dow Corning), Shin-Etsu Silicone KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.), and examples of the fluorine-based wax include shamrock wax. SST-1MG, shamrock wax SST-3,
Shamrock wax fluoroslip 231 (or more,
Shamrock Chemicals), POLYFLUO (Polyfluo) 120, 150, and 400 (Micro Powders).

The proportions of the above-mentioned cationically polymerizable compound (A), oxetane compound (B), cationic polymerization initiator (C) and lubricity imparting agent (D) can be as follows. That is, the cationically polymerizable compound (A) and the oxetane compound (B) have a compound (A) content of 1 to 1 at a ratio where the total amount of both is 100 parts by weight.
99 parts by weight, preferably 20 to 90 parts by weight, more preferably 40 to 80 parts by weight, and compound (B) is 1 to 9 parts by weight.
It can be used in the range of 9 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 60 parts by weight. Further, the amounts of the cationic polymerization initiator (C) and the lubricity-imparting agent (D) used are based on 100 parts by weight of the total amount of the cationically polymerizable compound (A) and the oxetane compound (B). C) is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, and the lubricity-imparting agent (D) is 0.01 to 20 parts by weight.
It can be in the range of 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight.

The above-mentioned treating agents may further include, if necessary, sensitizers, pigments such as coloring pigments and extenders which do not significantly inhibit curing, and dyes; polyol resins, phenol resins,
A modified resin such as an acrylic resin, a polyester resin, a polyolefin resin, an epoxy resin, and an epoxidized polybutadiene resin, organic resin fine particles, a solvent, and the like can be blended.

The above-mentioned sensitizer is compounded for the purpose of further improving the curability by ultraviolet rays, and examples thereof include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin. . The sensitizer is used in an amount of usually not more than 10 parts by weight, preferably not more than 3 parts by weight based on 100 parts by weight of the total of the cationically polymerizable compound (A) and the oxetane compound (B). You. The treatment agent is
It can be prepared by mixing the above-described components and stirring to obtain a uniform coating composition. For example, each component is mixed, and if necessary, heated (for example, 50 ° C.)
) And then stirred for about 10 minutes until the mixture becomes uniform with a stirrer such as a dissolver.

The method of applying the treatment agent is not particularly limited, but it can be applied by a coating method such as roll coating, spray coating, brush coating, bar coating, gravure coating, roller coating, or silk screen printing. The coating thickness can be appropriately selected depending on the application, but is usually about 0.5 to 30 μm as a dry coating thickness.
m, preferably in the range of about 1-20 μm.

After the above coating, ultraviolet rays are irradiated. The wavelength of the ultraviolet light to be irradiated is usually appropriately in the range of 200 to 600 nm, and an irradiation source having a wavelength with high sensitivity can be appropriately selected and used depending on the kind of the cationic polymerization initiator. . As the irradiation source of ultraviolet rays, for example,
High-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp,
Carbon arc, metal halide lamp, sunlight, and the like can be given. Irradiation conditions for the coating film are usually a dose of 10 to 1,000 mJ / cm ² , particularly 50 to 500 mJ / cm ² .
A range within J / cm ² is suitable.

In the method of the present invention, as described above, the sheet for preventing contamination obtained by applying and curing the treating agent on the surface of the interior base material can be attached to the surface of building materials such as walls using an adhesive. . In particular, a wallpaper sheet can be formed by forming a pattern such as unevenness on the contamination prevention sheet with an embossing roll or the like.

As the adhesive, a heat-sensitive or pressure-sensitive adhesive (adhesive) layer can be used. Specific examples of the adhesive (tacky) agent layer include, for example, vinyl-based, polyurethane-based,
Polyester, rubber, polyamide, vinyl acetate, acrylic, ethylene vinyl acetate, vinyl chloride /
Examples thereof include an uncured type such as vinyl acetate type and a cured type such as urea type, melamine type, epoxy type, phenol type, acrylic type, polyester type and urethane type. In the adhesive (adhesive) agent layer, for example, an adhesive (adhesive)
It may contain a imparting agent, an adhesion (adhesion) regulator, an antioxidant, a stabilizer, a coloring agent, and the like. When the adhesive is of a curing type, the curing type is moisture curing, moisture curing, and active energy.
Any method such as wire curing may be used. The thickness of the adhesive (adhesive) agent layer is about 10 to 1000 microns, particularly 2
A range from 0 to 500 microns is preferred. About 10 film thickness
If it is less than micron, the substrate to be affixed is likely to be peeled off when it is rough, while if it is more than 1000 micron it is not preferable because it is easily peeled off by heat.

[0088]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. In the description, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

Production of oxetane compound (B) A flask equipped with a stirrer and a condenser was charged with 67.0 g (0.5 mol) of trimethylolpropane and diethyl carbonate 5
9.0 g (0.5 mol) and potassium hydroxide 0.05 g
Was dissolved in 2 ml of anhydrous alcohol. The mixture was refluxed until the vessel temperature was lower than 105 ° C, then distilled while maintaining the distillation head temperature at 76 to 78 ° C, and the distillation was continued until the vessel temperature reached 145 ° C. Next, the pressure was gradually reduced to 15 mmHg while maintaining the container temperature at 140 to 150 ° C. Upon heating to a temperature above 180 ° C, the carbon dioxide evaporated quickly and most of the product distilled at 100-160 ° C.
Redistillation was performed to obtain 43.9 g of 3-ethyl-3-hydroxymethyloxetane.

Preparation Example 1 of Ultraviolet Curable Treatment Agent Preparation Example 1, 60 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of a cationically polymerizable compound represented by the following formula (11), and Production Examples 1 to 20 parts of 3-ethyl-3-hydroxymethyloxetane obtained in "1.
90 "(manufactured by Union Carbide Co., USA, 6 parts of a cationic photopolymerization initiator having PF ^6- ) was added, and the mixture was stirred at a temperature of 50 ° C for 20 minutes to obtain an ultraviolet curable treatment agent (a-1). Was.

[0091]

Embedded image (N indicates the number of 3 on average).

Preparation Example 2 In addition to the coating composition of Preparation Example 1, “Paintad M” (silicon wax, manufactured by Dow Corning) was added.
The UV curable treating agent (a-2) was obtained in the same manner as in Preparation Example 1.

Example 1 The treatment agent (a-1) obtained above was applied to the surface of an adhesive plastic film (vinyl chloride 50 μm, acrylic adhesive 10 μm) by gravure printing to a dry film thickness of 1 μm. And then using a metal halide lamp (120 W / cm) to irradiate 100 mJ /
Irradiated at ² cm ² to cure the treating agent layer to obtain a coated film.

Comparative Examples 1 to 3 The same adhesive plastic film as in Example 1 having no treatment on the vinyl chloride surface was used as Comparative Example 1, and the following silicone resin composition (Note 1) and silicon Each of the silicone resin-coated films obtained by coating the resin composition (Note 2) with a bar coater so as to have a dry film thickness of 3 μm and drying and curing at 160 ° C. for 90 seconds was used in Comparative Example 2,
Comparative Example 3 was used. (Note 1) Silicon resin composition: 35 parts of styrene, 20 parts of glycidyl methacrylate, 20 parts of 2-hydroxyethyl acrylate, CH ₂ ＣCCH ₃ COOC ₃ H _6- [S
_{i (CH 3) 2 O]} 20 ~ 30 -Si (CH 3) 3 5 parts, and polysiloxane macromonomer (number average molecular weight 200
0) A radical copolymerization reaction was carried out on the monomer mixture consisting of 20 parts according to a usual acrylic production method to obtain an organosilicon copolymer having a number average molecular weight of 20,000. 100 parts of this organic silicon copolymer (solid content) was mixed at a ratio of 2 parts of aluminum tris (ethyl acetoacetate), and toluene was added thereto to perform dispersion to obtain a silicon resin composition. (Note 2) Silicone resin composition: A silicone resin composition was prepared in the same manner as above except that 5 parts of "PRX413" (manufactured by Dow Corning Silicone Toray Co., Ltd., dimethylpolysiloxane having a terminal silanol group) was added to the silicone resin composition. I got

Example 2 The treating agent (a-2) obtained above was coated on a polyvinyl chloride sheet (50 μm thick) so that the dry film thickness became 1 μm.
Coat coating, then metal halide lamp (120
(W / cm) at a radiation dose of 100 mJ / cm ² to obtain a sheet having the treatment agent layer. Formed to obtain a sheet for wallpaper. Visual inspection of the embossed film pattern revealed no abnormalities (wrinkles, twists, etc.).

Stain resistance test The coated films and wallpaper sheets of Examples and Comparative Examples obtained as described above were subjected to the following oil and dust resistance test and oil resistance marker test. Table 1 shows the results.

(* 1) Oil and dust resistance test: Used discolored (degraded) (tempered) oil (discoloration degree is JIS Z
-8721.5 2.5Y based on color chart based on three attributes
7.0 / 12.0) was applied so as to have a thickness of about 100 μm, allowed to stand at room temperature for 1 hour, and thereafter, the appearance change of the surface after the oil was completely wiped off was observed.
異常 indicates that there was no abnormality such as discoloration, Δ indicates that slight discoloration was observed, and X indicates that discoloration was remarkably observed.

Further, in order to examine the persistence, the process of applying and wiping the oil on the surface from which the oil was wiped as described above was further repeated in the same manner. (Less than 49 times) was evaluated as Δ when there was no abnormality even after the repetition, and × when discolored after repeated 20 or more times.

(* 2) Oil resistance marker test: After writing a line with oil markers of three colors of red, blue and black, leave it at room temperature for 24 hours, then wipe the marker lightly with a cloth, and then appearance of the surface Changes were observed. ◎: Marker that does not leave any trace of marker that can be wiped lightly once. ○: Marker that does not leave a trace of marker that can be wiped lightly 2 to 4 times. A mark that markedly left a mark of the marker even after wiping twice was marked as x.

In order to examine the persistence, the marker was wiped off at the same place where the marker was wiped off as described above, and the process of wiping the marker was repeated in the same manner. (Less than 49 times) A mark without any trace after repeating was evaluated as △, and a mark with a trace remaining after repeating 20 or more times was evaluated as x.

[0101]

According to the present invention, by coating a specific treating agent on the sheet surface and performing a curing treatment, oil dust and marker ink on the interior material surface can be easily wiped off and removed many times. Excellent stain resistance can be imparted to the interior material surface.

[0102]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/16 C09D 5/16 163/00 163/00 171/00 171/00 201/00 201/00 ( 72) Inventor: Shigeru Shintani 5-24-15 Higashioi, Shinagawa-ku, Tokyo F-term in Kansai Paint Co., Ltd. AA09 AA11 BA00 BB01 BB02 4J038 BA212 CB002 CC021 CC081 CC101 CD092 CE051 CK021 CR071 DB051 DB061 DB071 DB131 DB261 DL032 EA011 GA15 JA55 JA69 JC24 JC34 JC37 KA03 PA17 PB02 PB03 PC08 PC10

Claims (7)

[Claims] 1. A surface of a base material for an interior material, comprising: (A) 1 to 99 parts by weight of a cationically polymerizable compound; and (B) 1 to 99 parts by weight of a compound having at least one oxetane ring in a molecule.
An ultraviolet-curable treating agent containing 0.01 to 20 parts by weight of a cationic polymerization initiator (C) that generates cations upon irradiation with ultraviolet rays is applied to 100 parts by weight of the total amount of the compounds (A) and (B). And a method for preventing surface contamination of an interior material formed by irradiating ultraviolet rays to form a treatment agent layer. 2. The composition according to claim 1, wherein (A) 1 to 99 parts by weight of a cationically polymerizable compound and (B) 1 to 99 parts by weight of a compound having at least one oxetane ring in the molecule, For 100 parts by weight of the total amount of B),
(C) An ultraviolet-curable treating agent containing 0.01 to 20 parts by weight of a cationic polymerization initiator that generates cations upon irradiation with ultraviolet rays is applied, irradiated with ultraviolet rays to form a treating agent layer, and then patterned with an embossing roll. A method for preventing surface contamination of an interior material, comprising: adhering a sheet for wallpaper formed of the above to the surface of a building material for interior via an adhesive. 3. The method for preventing surface contamination of an interior material according to claim 1, wherein the cationically polymerizable compound (A) is a compound having an alicyclic epoxy group in a molecule. 4. An oxetane compound (B) having the following formula: (Wherein, R ⁶ is a hydrogen atom, a fluorine atom, a carbon atom having 1 to 1)
6 represents a linear, branched or cyclic alkyl group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, an aralkyl group, a furyl group or a thienyl group, R ⁷ has a valency corresponding to the value of p, and represents a hydrogen atom or a monovalent to tetravalent organic group, Z represents an oxygen atom or a sulfur atom, and p is an integer of 1 to 4.) The method for preventing surface contamination of an interior material according to claim 1 or 2, which is a compound represented by the formula: 5. The method according to claim 1, wherein the cationic polymerization initiator (C) is a compound having a hexafluorophosphate anion (PF ⁶⁻ ). 6. The surface contamination of an interior material according to claim 1, further comprising 0.1 to 10 parts by weight of the lubricity imparting agent (D) based on the total amount of the compounds (A) and (B). Prevention method. 7. An interior material provided with stain resistance by the method for preventing surface contamination according to claim 1.