JPS6186972A - Surface treatment of wood - Google Patents

Abstract

PURPOSE:To enhance the anti-staining property of wood, by cografting a specific polymerizable monomer and a vinyl monomer on wood. CONSTITUTION:A polymerization monomer to be used is one having an org. group with high fluorine content and represented by general formula (wherein R<1> is a 1-16C high fluorine content org. group, R<2> is an 1-4C alkylene group and R3 is a hydrogen atom or a methyl group). As a vinyl monomer having high grafting efficiency, one or more of a monomer selected from ethylene, acrylate and styrene is used. By together using both monomers, water and oil repellency is imparted to the surface of wood and, by making grafting efficiency high, the fine surface uneveness of wood can be filled with the branched polymer prepared from both monomers and an anti-staining property and durability are enhanced to a large extent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] This invention relates to a surface treatment method used to impart stain resistance to wood.

[Background technology]

Various chemical treatments have been attempted to modify wood, and one treatment method involves converting cellulose, a wood component, into radicals and grafting monomers onto cellulose. Although there are many unknowns about the grafting mechanism, when Ce4+ in an aqueous ceric ammonium nitrate solution is used as a radical polymerization initiator (graft initiator),
The next reaction route has been planned. CH2=CH in the formula
R' is R (one unit) to be grafted onto cellulose.

R-CH20H+Ce' ” 1+R-CHOH+H” +(:, e3 ”R-CH
OH+C! (2=CHR' Also, when a peroxide, an azu compound, or a metal compound is used as a polymerization initiator, the polymerization initiator radical or homopolymer radical extracts the hydrogen atom of cellulose. Then, It is predicted that unpaired electrons (radicals) are created in cellulose to generate cellulose radicals, which causes monomers to be grafted onto cellulose.The reaction route when using azobisisobutyronitrile is shown below. show.

A monomer is grafted onto the cellulose radicals in the wood obtained through the above reaction.

It is known that by grafting monomers with perfluoroalkyl groups onto wood, the critical surface tension of the wood can be lowered, thereby imparting water and oil repellency to the wood surface. . By the way, polluted objects are generally occluded on the surface of the contaminated object by the following mechanism.

■ Macro occlusion (particles of 50 nm or more) ■ Micro occlusion (particles of 50 nm or less) ■ Coulomb force occlusion ■ Van der Waa
ls) Occlusion by force ■ Occlusion by surface potential (epsilon potential, zeta potential) When a monomer having a perfluoroalkyl group is grafted onto the wood surface to impart water and oil repellency to the wood, contaminants are absorbed onto the wood surface. Since it becomes difficult for the objects to approach, the occlusion of contaminated objects due to some kind of attractive force between the objects, that is, the above-mentioned (1), (2), and (2) are suppressed, so that the effect of preventing contamination can be obtained.

However, even if a monomer having a perfluoroalkyl group is grafted using the conventional method, there are many irregularities of various sizes on the wood surface after treatment. That is, it was difficult to suppress the above-mentioned (1) and (2).

Therefore, it has been extremely difficult to further improve the lη dyeing resistance using the methods described above.

[Purpose of the invention]

This invention was made in view of these circumstances,
A tree that can provide high stain resistance.

[Disclosure of the Invention] The inventors have developed a method for grafting the perfluoroalkyl group-containing monomer onto wood, thereby achieving the methods described in (1) to (1) above.
An attempt was made to obtain a wood surface treatment method that can suppress (1) or (2) without impairing the inhibitory effect of (2) and impart high stain resistance.

The inventors first found that by increasing the grafting efficiency of perfluoroalkyl groups and filling the irregularities on the wood surface with branched polymers created by perfluoroalkyl groups, the stain resistance of wood could be improved. We conducted our research based on the idea that this might be possible. However, for example, in the case of grafting perfluoroalkyl onto wood using a cerium salt catalyst, the grafting efficiency of perfluoroalkyl is limited to a weight increase rate of approximately jO%, so there is an upper limit to the grafting efficiency of perfluoroalkyl. It was found that it was difficult to further increase the grafting efficiency. Therefore, as a result of further research, we found that if a vinyl monomer with high grafting efficiency is co-grafted with a polymerizable monomer having perfluoroalkyl groups on wood, the total amount of perfluoroalkyl groups It is now possible to perform a larger amount of grafting (generally several 10% increase in weight) than when a polymerizable monomer having It has been found that, even if the effect of suppressing the above-mentioned (1) is not so great, it is possible to sufficiently suppress (2). Furthermore, we have discovered that the above object can be achieved by using other polymerizable monomers having high fluorine-containing organic groups instead of polymerizable monomers having perfluoroalkyl groups, and hereby completed this invention.

Therefore, the gist of the present invention is a method for surface treatment of wood in which a polymerizable monomer having a high fluorine-containing organic group and a hinyl-based monomer with high grafting efficiency are co-grafted onto wood. The present invention will be explained in detail below.

Here, as a polymerizable monomer having a high fluorine-containing organic group, for example, the following general formula % formula % () (where R1 is a high fluorine-containing organic group having 1 to 16 carbon atoms, R2 is an alkylene group having 0 to 4 carbon atoms, R3 is a hydrogen atom or a methyl group), and only one type may be used, or two or more types may be used in combination. There may be.

In formula (1'), R1 may be linear, monobranched, or cyclic, or may be a combination of these. Furthermore, the skeleton is not limited to being composed only of carbon atoms, and may include an ether bond, a carboxylic acid ester bond, a ketone group, an amino group, an imino group, an imide group, a sulfone group, etc. . Furthermore, it is not limited to the case where only fluorine atoms are bonded to the skeleton of the organic group, and some of the fluorine atoms may be substituted with hydrogen atoms. In short, the higher the fluorine content in the organic group, the better. In addition, in the carbon number O to 4 of R2, carbon number 0 means R1 or directly, -COO
CR3=means bonding with CH2. More specific examples of the polymerizable R-mer in the case where R1 is a perfluoroalkyl group are given below.

(Margin below) CF3 (CF2) m (CH2) n C0
0CH=CH2 (0≦m≦15, 0≦n≦4) CF3 (CF2) m (CH2) n C0
0C(CH3) =CH2(0≦m≦15.0≦n≦4
) CF3 CF2 CF (CF2) m (CH2
) n COOCH=CH2CF3 CF2 (0≦rn≦11.0≦n≦4) CF3 CF2 CF3 CF2 CF (CF2) m (CH2
) n COOCH=CH2CF3 CF2 (0≦m≦9.0≦n≦4) (0≦m≦8, 0≦n≦4) (Left below) R1, J)<, the fluorine atom of the perfluoroalkyl group More specific examples of polymerizable monomers partially substituted with hydrogen atoms or containing ether bonds or the like in the skeleton are given below.

(Left below) CF3 CH2CF2 CH2C00CH=CH2CF
3 CF2 Ch CF2 0 CH2(CH2)I C0
0CR=CH2CF3 (CF2)s COOCH
2(CH2)3 C00CH=CH2U lower margin) Examples of vinyl monomers with high grafting efficiency used for co-grafting include olefins such as ethylene, propylene and butylene, acrylates, methyl acrylate, methacrylate, methyl methacrylate, 1 selected from acrylic monomers such as alkylene acrylate and methyl meta-alkylene acrylate, carboxylic acid vinyl esters, styrene, vinyl halides, vinyl ethers, vinyl ketones, butadiene, etc.
A species, or two or more species, may be used.

When cografting the polymerizable monomer and vinyl monomer in a solution (liquid phase grafting method), the graft reaction (graft copolymerization reaction) solvent may be water, water containing a dispersant, l. Alkyl halides such as 1,1-trichloroethane, 1,2-dichloroethane, methylene chloride, trichlorotrifluoroethane, esters such as ethyl acetate, lobutyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl ether, isopropyl ether Ethers such as methanol, alcohols such as ethanol, isopropyl alcohol, benzene derivatives such as benzene, toluene and xylene, alkanes such as n-hexane and n-octane, organic solvents such as diochitin and tetrahydrofuran alone, or, A mixture of two or more types is used. The type of organic solvent is selected in consideration of the compatibility with the polymerizable monomer and the vinyl monomer. In addition, as radical polymerization initiators (reaction initiators), peroxides such as alkyl hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxide esters, ab compounds such as azobisisobutyronitrile, peroxides, etc. Hydrogen-ferrous salt system,
Penduyl dimethyl aniline peroxide, cerium (r
V) Redox initiators such as salts and organometallic compounds are used and added to the solution.

Grafting efficiency and homopolymer production in the grafting reaction can be varied by adjusting the polymerization initiator concentration and monomer (septumer) concentration, or by adding a chain transfer agent (e.g. mercaptan) to change the type and concentration of these. By doing so, it can be adjusted within a preferable range.

Next, a case where a polymerizable monomer having a high fluorine-containing organic group and a vinyl monomer with high grafting efficiency are used as a gas (gas phase grafting method) will be explained. The types of polymerizable monomers having high fluorine-containing organic groups and vinyl monomers used for cografting are basically the same as in the case of the liquid phase grafting method. However, in the case of the gas phase grafting method, it is necessary to select a monomer having a vapor pressure suitable for the reaction conditions and the like. To initiate radical grafting, polymerization initiators such as peroxides, azo compounds, redox initiators, and organometallic compounds mentioned above can be used, as in the liquid phase grafting method. When using such a polymerization initiator, the polymerization initiator is dissolved in a solvent and impregnated into the wood in advance, and the wood is co-grafted (vapor phase grafted) under a nitrogen stream. good. Further, in the gas phase grafting method, a radical graft initiation method using ultraviolet irradiation or a combination of a photosensitizer and ultraviolet irradiation is also possible.

Such an initiation method may be used in combination with a method using a polymerization initiator. Examples of photosensitizers include:
Peroxides such as benzoyl peroxide, azo compounds such as azobisisobutyronitrile, carbonyl compounds such as diacetyl and dibenzyl, diphenyl monosulfide, diphenyl disulfide, dibenzoyl monosulfide,
Sulfur compounds such as dihenzoyl disulfide, halides such as carbon tetrachloride, and metal salts such as ferric trichloride are used. The radical graft initiation method using ultraviolet irradiation can be used under any temperature and pressure conditions, and therefore has a wide range of usable conditions, and in this respect is more advantageous than initiation using a radical polymerization initiator.

In addition, in the gas phase grafting method, the temperature varies depending on the combination of the polymerizable monomer having a high fluorine-containing organic group, the vinyl monomer, and the polymerization initiator.

It is necessary to adjust reaction conditions such as pressure 2 and reaction time as appropriate.

In the wood surface treatment method according to the present invention, as described above, a polymerizable monomer having a high fluorine-containing organic group is used together with a vinyl monomer having a high grafting efficiency, so that the wood surface is coated with repellents. In addition to imparting water and oil repellency, it is possible to increase grafting efficiency and fill in minute irregularities on the wood surface with branched polymers made from amphomers. Therefore,
The stain resistance can be improved compared to the case where only a polymerizable monomer having a high fluorine content is used. Furthermore, since the amphomer chemically bonds to the wood surface, the effect is much more durable than when it is simply attached to the wood surface by applying a water-hydrophobic treatment agent or the like.

Next, examples will be described.

[Example 1] The surface of wood was treated using the following materials.

LH, IH shown by the following formula.

2H,2H-hebutadecafluorodecyl acrylate CH2=CHCOO(CH2)2 (CF2)7 CF3 monomer (7-mer); Methyl methacrylate wood;
Hot water extraction treated wood polymerization initiator; Benzene peroxide solvent;
After immersing the wood in water and adding a polymerization initiator, N2
It was heated to 80°C under a stream of air and with vigorous stirring. Next, the above two types of monomers were added dropwise and reacted for 6 hours. As a result, grafted wood with a total grafting efficiency of approximately 8% was obtained, and it was able to impart a high degree of water and oil repellency, as well as higher stain resistance than when methyl methacrylate was not used. .

[Example 2] The surface of wood was treated using the following materials.

Monomer: IH, IH shown by the following formula.

2H,2H,-hebutadecafluorodecyl acrylate CH2=CHCOO(CH2)2 (CF2)7 CF3 monomer (7-mer); Methyl methacrylate wood;
Hot water extraction treated wood polymerization initiator; ceric ammonium nitrate solvent;
Ethyl acetate 0, IN&! Dissolve dicerium ammonium in an aqueous solution of acid and rinse the wood for 1 hour.

Thereafter, the wood was immersed in ethyl acetate and heated to 50° C. with strong stirring under a N2 stream. Next, the above two types of monomers were added dropwise and reacted for 6 hours. As a result, a grafted wood with a total grafting efficiency of 16% was obtained, and it was possible to impart a high degree of water and oil repellency, as well as a higher stain resistance than when methyl methacrylate was not used.

〔Effect of the invention〕

The wood surface treatment method according to the present invention co-grafts a polymerizable monomer with a high fluorine-containing organic group and a vinyl monomer with high grafting efficiency onto the wood.
It has become possible to impart high stain resistance to wood.

Agent Patent Attorney Takehiko Matsumoto Procedural Amendment (December 10, 1980 Patent Application No. 209971 3, Relationship with the person making the amendment Case) Patent applicant Location: 1048 Kadoma, Kadoma City, Osaka Prefecture Name (583) Matsushita Electric Works Co., Ltd. Representative Iku Hiyaku Kobayashi 4, Agent style 6, Specification subject to amendment 7, Contents of amendment (1) The entire text of the specification will be corrected as shown in the attached sheet.

Description 1, Name of the invention Wood surface treatment method 2, Claims (1) Co-grafting a polymerizable monomer with a high fluorine-containing organic group and a vinyl monomer with high grafting efficiency onto wood. Wood surface treatment method.

(2) The polymerizable monomer having a high fluorine-containing organic group has the following general formula % (where R1 is a high fluorine-containing organic group having 1 to 16 carbon atoms, and R2 is a high fluorine containing organic group having 0 to 4 carbon atoms). The method for surface treatment of wood according to claim 1, wherein the wood surface treatment method is at least one selected from the group consisting of an alkylene group and R3 is a hydrogen atom or a methyl group.

(The method for surface treatment of wood according to claim 2, wherein 31R1 is a perfluoroalkyl group having 1 to 16 carbon atoms.

(4) Vinyl monomers with high grafting efficiency are ethylene, propylene, and butylene 5-acrylate.

A patent claim that is at least one member selected from the group consisting of methyl acrylate, methacrylate, methyl methacrylate, alkylene acrylate, methyl metaalkylene macrylate, carboxylic acid vinyl ester, styrene, vinyl halide, vinyl ether, vinyl ketone, and butadiene. The method for surface treatment of wood according to any one of items 1 to 3.

(5) Claims 1 to 4, wherein the co-grafting reaction is a reaction using a polymer monomer having a high fluorine-containing organic group and a vinyl monomer with high grafting efficiency in a solution. The wood surface treatment method described in any of the above.

(6) The solvent is water in which water 2 dispersant is dissolved, 1.1.1
- ) +J Chloroethane, 1,2-dichloroethane, methylene chloride, trichlorotri°fluoroethane, ethyl acetate, n-butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl ether, isopropyl ether, methanol, ethanol, isopropyl alcohol, Hensen ,toluene,
6. The method for surface treatment of wood according to claim 5, wherein at least one selected from the group consisting of xylene, n-hexane, n-octane, dioxane and tetrahydrofuran is used.

(7) Claims 1 to 4, wherein the co-grafting reaction is a reaction using a polymer monomer having a high fluorine-containing organic group and a vinyl monomer with high grafting efficiency as a gas. The wood surface treatment method described in any of the above.

(8) Claim 5 in which the reaction initiation method is heating
The method for surface treatment of wood according to any one of Items 7 to 7.

(9) The heating initiator is an alkyl hydroperoxide,
dialkyl peroxide, diacyl peroxide, peroxide ester,
Azobisisobutyronitrile, hydrogen peroxide-ferrous salt system, benzoyl peroxide-dimethylaniline system, cerium (
rV) The method for surface treatment of wood according to claim 8, which is at least one selected from the group consisting of salts and organometallic compounds.

QO) The wood surface treatment method according to any one of claims 5 to 9, wherein the reaction initiation method is ultraviolet irradiation.

(11) The ultraviolet initiator consists of benzoyl peroxide, azobisisobutyronitrile, diacetyl, dibenzyl, diphenyl monosulfide, diphenyl disulfide, dibenzoyl monosulfide, dibenzoyl disulfide, carbon tetrachloride, and ferric trichloride. 11. The wood surface treatment method according to claim 10, which is at least one selected from the group.

3. Detailed Description of the Invention [Technical Field] This invention relates to a surface treatment method used to impart stain resistance to wood.

[Background technology]

Various chemical treatments have been attempted to modify wood, and one treatment method involves converting cellulose, a wood component, into radicals and grafting monomers onto the cellulose. Although there are many unknowns about the grafting mechanism, when Ce4'' in an aqueous ceric ammonium nitrate solution is used as a radical polymerization initiator (graft initiator), the following reaction route is predicted. CH2=CHR'
is a monomer to be grafted onto cellulose.

RCH20H+Ce' ” -IIR-CHOH+H” +Ce3+R-Self-HOH+
CH2=CHR' -→R-CHOH H2-dHR' Furthermore, when a peroxide, an azo compound, or an organometallic compound is used as a polymerization initiator, the polymerization initiator radical or homopolymer radical The hydrogen atom is extracted. As a result, unpaired electrons (radicals) are created in cellulose, producing cellulose radicals, which are predicted to graft monomers onto cellulose. Shown below.

A monomer is grafted onto the cellulose radicals in the wood obtained through the above reaction.

It is known that by grafting polymerizable monomers with perfluoroalkyl groups onto wood, the critical surface tension of the wood can be lowered, thereby imparting water and oil repellency to the wood surface. ing.

By the way, contaminated objects are generally occluded on the surface of a contaminated object by the following mechanism.

■ Macro occlusion (particles of 50 nm or more) ■ Micro occlusion (particles of 50 nm or less) ■ Coulomb force occlusion ■ Van der Waa
ls) Occlusion by force ■ Occlusion by surface potential (epsilon potential, zeta potential) When a polymerizable monomer with a perfluoroalkyl group is grafted onto the wood surface to impart water and oil repellency to the wood, contaminants are removed. Since it becomes difficult to approach the wood surface, the occlusion of contaminated objects due to some kind of attraction between objects, i.e.
Since the above-mentioned (1), (2) and (2) are suppressed, the effect of preventing contamination can be obtained.

However, even if a polymerizable monomer having a perfluoroalkyl group is grafted using the conventional method, the surface of the treated wood has many irregularities of various sizes. , the above ■ and ■
was difficult to suppress. Therefore, it has been extremely difficult to further improve stain resistance using the methods described above.

[Purpose of the invention]

This invention was made in view of these circumstances,
The present invention aims to provide a method for surface treatment of wood that can impart high stain resistance [Disclosure of the Invention] By improving the method, an attempt was made to obtain a wood surface treatment method that can suppress (1) or (3) without impairing the above-mentioned inhibitory effects (1) to (3) and impart high stain resistance. The inventors first increased the grafting efficiency of the polymerizable R-mer having a perfluoroalkyl group and filled the unevenness of the wood surface with a branched polymer made from a polymerizable monomer having a perfluoroalkyl group. This research was based on the idea that it might be possible to improve the stain resistance of wood. However, for example, when grafting a polymerizable monomer containing perfluoroalkyl to wood using a cerium salt catalyst, the grafting efficiency is only about 10% in terms of weight increase. It was found that there is an upper limit to the grafting efficiency of the polymerizable monomer, and it is difficult to increase the grafting efficiency beyond that limit. Therefore, as a result of further research, we found that if a vinyl monomer with high grafting efficiency is co-grafted with a polymerizable monomer having perfluoroalkyl groups on wood, the total amount of perfluoroalkyl groups It is now possible to perform a larger amount of grafting (generally several tens of percent in weight increase) than when using a polymerizable monomer with It has been found that, even though the effect of suppressing the above-mentioned (1) is not so great, the (2) can be sufficiently suppressed. We have also discovered that the above objective can be achieved by using other polymerizable monomers with high fluorine-containing organic groups instead of polymerizable monomers with perfluoroalkyl groups, and hereby completed this invention.

Therefore, the gist of the present invention is a method for surface treatment of wood, in which a polymerizable monomer having a high fluorine-containing organic group and a vinyl monomer with high grafting efficiency are co-grafted onto wood. The present invention will be explained in detail below.

Here, as a polymerizable monomer having a high fluorine-containing organic group, for example, the following general formula % formula % () (where R1 is a high fluorine-containing organic group having 1 to 16 carbon atoms, R2 is a carbon 0 to 4 alkylene groups, R3 is a hydrogen atom or a methyl group), and only one type may be used, or two or more types may be used in combination. good.

In formula (1), R1 may be linear, bibranched, or cyclic, or may be a combination of these. Furthermore, the skeleton is not limited to being composed only of carbon atoms, and may include an ether bond, a carboxylic acid ester bond, a ketone group, an amino group, an imino group, an imide group, a sulfone group, etc. . Furthermore, it is not limited to the case where only fluorine atoms are bonded to the skeleton of the organic group, and some fluorine atoms may be substituted with hydrogen atoms.In short, fluorine atoms in the organic group In addition, in the carbon number O to 4 of R2, the carbon number O means that R1 is directly -0
COCR3=means bonding with CH2. R1
More specific examples of the polymerizable monomer in the case where is a perfluoroalkyl group are given below.

(Margin below) J CH= CR2 CF3 L) m
(CH2) n 0COCH=CH2F3 (0≦m≦9, 0≦n≦4) (0≦m≦8. O≦n≦4) (Left below) R1 is the fluorine atom of the perfluoroalkyl group More specific examples of polymerizable monomers partially substituted with hydrogen atoms or containing ether bonds or the like in the skeleton are given below.

(Margin below) CF3CH2CF2 CH20COCH”CH2CF3
CF2 [CF2OF2 CHCH20COC) (= CH2■ CF3 CF2 CF3 CF2-0-CH2(CH2) 30COCH
=CH2CF3 (CF2) 6 COOCH2(
CH2) ] ococH=cH2 (Hereafter, blank) Vinyl monomers with high grafting efficiency used for cografting include, for example, olefins such as ethylene, propylene, and butylene, acrylate, methyl acrylate, methacrylate, and methyl methacrylate. ,
One or more selected from acrylic monomers such as alkylene acrylate and methyl meta-alkylene acrylate, carboxylic acid vinyl esters, styrene, vinyl halides, vinyl ethers, vinyl ketones, butadiene, etc. are used.

When cografting the polymerizable monomer and the vinyl monomer in a solution (liquid phase grafting method), the graft reaction (graft copolymerization reaction) solvent may be water, water containing a dispersant, or -1-) Halogenated alkanes or halogenated alkyls such as dichloroethane, 1,2-dichloroethane, methylene chloride, and trichlorotrifluoroethane, esters such as ethyl acetate and n-butyl acetate, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , ethers such as ethyl ether and isopropyl ether, alcohols such as methanol, ethanol and isopropyl alcohol, Hensen derivatives such as benzene, toluene and xylene, alkanes such as n-hexane and n-octane, and organic solvents such as dioxane and tetrahydrofuran alone. or a mixture of two or more types. The type of organic solvent is selected in consideration of the compatibility with the polymerizable monomer and the vinyl-based monomer. Further, as a method for initiating the reaction, heating alone or heating using a heating initiator can be mentioned. As the heating initiator (radical polymerization initiator 1 and reaction initiator),
Alkylhydrobarogicide, iI! Peroxides such as Jm-dialkyldiacyl, peroxide esters, azo compounds such as azobisisobutyronitrile, hydrogen peroxide-ferrous salts, benzoyl peroxide-dimethylaniline, cerium ε■) salts Redox initiators and organometallic compounds such as are used and added to the solution.

When a reaction initiator such as a redox initiator is used, the reaction can also be started without heating. Furthermore, a radical graft initiation method using ultraviolet irradiation or a combination of an ultraviolet initiator (photosensitizer) and ultraviolet irradiation is also possible. Such an initiation method may be used in combination with heating or a method using a heating initiator in addition to heating. Examples of the ultraviolet initiator include peroxides such as benzoyl peroxide, azo compounds such as azobisisobutyronitrile, carbonyl compounds such as diacetyl and dibenzyl, diphenyl monosulfide, diphenyl disulfide, dibenzoyl monosulfide, and dibenzoyl. Grafting efficiency and homopolymer formation in graft reactions that use sulfur compounds such as disulfides, halides such as carbon tetrachloride, and metal salts such as ferric trichloride are determined by the reaction initiator concentration, monomer )1! It can be adjusted within a preferred range by adjusting the i degree or by adding a chain transfer agent (for example, mercaptan) and varying the type and concentration thereof.

Next, a case where a polymerizable monomer having a high fluorine-containing organic group and a vinyl monomer with high grafting efficiency are used as a gas (gas phase grafting method) will be explained. The types of polymerizable monomers having high fluorine-containing organic groups and vinyl monomers used for cografting are basically the same as in the case of the liquid phase grafting method. However, in the case of gas phase grafting, it is necessary to select a monomer that is suitable for the reaction conditions and has a suitable vapor pressure. In order to initiate radical grafting, as in the liquid phase grafting method, heating alone, heating using a heating initiator (9 reaction initiator only), ultraviolet irradiation, ultraviolet irradiation using an ultraviolet initiator, or a combination thereof are used. The following method is used. As the heating initiator, the same ones mentioned in the liquid phase grafting method are used. When using a heating initiator or an ultraviolet initiator, first dissolve the initiator in a solvent,
It is advisable to impregnate wood with the material and perform grafting (vapor phase grafting) on the wood under a nitrogen stream.

Furthermore, a vinyl monomer may also be impregnated into the wood.

The radical graft initiation method using ultraviolet irradiation can be used under any temperature and pressure conditions, so it can be used over a wide range of conditions, and in this respect is more advantageous than initiation using a heating initiator (radical polymerization initiator).

In addition, in the gas phase grafting method, the temperature varies depending on the combination of the polymerizable monomer having a high fluorine-containing organic group, the vinyl monomer, and the reaction initiator.

It is necessary to adjust reaction conditions such as pressure 1 and reaction time as appropriate.

In the wood surface treatment method according to the present invention, as described above, a polymerizable monomer having a high fluorine-containing organic group is used together with a vinyl monomer having a high grafting efficiency, so that the wood surface is coated with repellents. In addition to providing water and oil repellency, the grafting efficiency can be increased to fill in minute irregularities on the surface of the wood with the technical polymer made from the two-dimensional polymer. Therefore,
Stain resistance can be improved compared to the case where only a polymerizable monomer having a high fluorine-containing organic group is used. Furthermore, since the two-wheel mass is chemically bonded to the wood surface, the durability of the effect is also much better than when it is simply attached to the wood surface by applying a water- and oil-repellent treatment agent or the like.

Next, examples will be described.

(Example 1) The surface of wood was treated using the following FO material.

Monomer (monomer) A: LH, IH, 2H shown in the following formula,
2H-Hebutadecafluorodecyl acrylate CH2=CHCOO(CH2)2 (CF2 )7 CF3 Monomer (Nanatsuma) B: Methyl methacrylate Wood: Two types of veneers each made of cedar and cypress, i.e., thickness l mm rotary veneer and thickness Q,
A sliced veneer of l s* was extracted with hot water as a pretreatment. However, the length and width dimensions were 109 mm x 100 m.Heating initiator (polymerization initiator): benzene peroxide solvent: water Four types of wood were all subjected to surface treatment as follows.

600 cc of water was charged into a separable flask with a capacity of 11. Then, the back sides of the seven pieces of wood were fixed to a stainless steel net, and the net was rolled up and placed in a flask. After the inside of the flask was degassed and replaced with N2, the inside of the flask was heated to 80° C. with strong stirring. 20 g of monomer A and 820 g of monomer were mixed, and 4 g of a 10% toluene solution of Hensen peroxide was added thereto. This was added dropwise into the flask over 1 hour, and heated to 80°C while stirring vigorously.
The co-grafting reaction was carried out for 6 hours. Grafted wood with a total grafting efficiency of about 8% was then obtained.

As a result of the surface treatment, it was possible to impart a high degree of water and oil repellency and stain resistance to all four types of wood. Furthermore, it was possible to provide higher stain resistance than when methyl methacrylate was not used.

(Example 2) The surface of wood was treated using the following materials.

Monomer (monomer) A: IH used in Example 1, IH,
2H,2H-hebutadecafluorodecyl acrylate CH2=CHCOO(CH2)2 - (CF2)7 CF3 Monomer (seventhmer) B: Methyl methacrylate Wood: Same heating initiator as used in Example 1 (Polymerization initiator): Ceric ammonium nitrate Solvent: Ethyl acetate Four types of wood were all subjected to surface treatment as follows.

Ceric ammonium nitrate was dissolved in 80 cc of a 0.0, IN nitric acid aqueous solution, and five pieces of wood were immersed in this for 1 hour.

On the other hand, capacity 1! 600 cc of ethyl acetate was charged into a separable flask. Then, without drying the five pieces of wood, the back surfaces thereof were fixed to a stainless steel net, and the net was rolled up and placed in a flask. After deaerating the inside of the flask and replacing it with N2, heat it at 50° without stirring strongly.
The temperature inside the flask was raised to C. Next, 20g of monomer A
A mixture of 820 g of the monomer and the monomer was dropped into the flask over 1 hour, and co-grafting reaction was carried out at 50° C. for 6 hours with strong stirring. As a result, a grafted wood with a grafting efficiency of 16% was obtained.

As a result of the above pre-treatment, it was possible to impart high water and oil repellency to all four types of wood and impart high stain resistance. Furthermore, it was possible to provide higher stain resistance than when methyl methacrylate was not used.

〔Effect of the invention〕

The wood surface treatment method according to the present invention grafts a polymerizable monomer having a high fluorine-containing organic group and a vinyl monomer with high grafting efficiency to the wood, thereby imparting high stain resistance to the wood. It is now possible to grant.

Agent: Takehiko Matsumoto, Patent Attorney, Proceeding Officer (self-motivated), February 4, 1985, 1059, 1985. Relationship with the case of 1st milk Udayan Kuyu address
1048 Kadoma, Kadoma City, Osaka Name (583)
Matsushita Electric Works Co., Ltd. Representative Director Iku Kobayashi 4, No representative 6, Target of amendment +lX of the content of the amendment to the procedural amendment submitted on December 10, 1980 7, Contents of the amendment (1) 1980 "R'R" 0C on page 10, line 13 of the full text amended specification attached to the procedural amendment dated December 10, 1959
OR3=CHz j, -R' R20C,
Correct it as “OCR” = CHz j.

(2) On page 12, line 7, -CF3CF2 is replaced with r ChCF2 CF3CF2C(CF2), (C)Iz) fiO
Correct as COCH=CHzCF3CF2.

(3) On the second line of page 14, V CF3CF2 翫CF 3CF ZCHCII□0COCH= CH2C
F3CF2 is corrected to CF:lCF 2 .

Claims (11)

[Claims] (1) A wood surface treatment method in which a polymerizable monomer having a high fluorine-containing organic group and a highly efficient vinyl monomer are co-grafted onto wood. (2) The polymerizable monomer having a high fluorine-containing organic group has the following general formula R^1R^2COOCR^3=CH_2 (where R^1 is a high fluorine-containing organic group having 1 to 16 carbon atoms, R^2 is an alkylene group having 0 to 4 carbon atoms, and R^3 is a hydrogen atom or a methyl group. surface treatment method. (3) The wood surface treatment method according to claim 2, wherein R^1 is a perfluoroalkyl group having 1 to 16 carbon atoms. (4) Vinyl monomers with high grafting efficiency include ethylene, propylene, butylene, acrylate, methyl acrylate, methacrylate, methyl methacrylate,
Alkylene acrylate Methyl metaalkylene acrylate Any one of claims 1 to 3 which is at least one member selected from the group consisting of carboxylic acid vinyl ester, styrene, vinyl halide, vinyl ether, vinyl ketone, and butadiene. Wood surface treatment method described in Crab. (5) Claims 1 to 4, wherein the co-grafting reaction is a reaction using a polymerizable monomer having a high fluorine-containing organic group and a vinyl monomer with high grafting efficiency in a solution. The wood surface treatment method described in any of the above. (6) The solvent is water, water in which a dispersant is dissolved, 1.1.1
-trichloroethane, 1,2-dichloroethane, methylene chloride, trichlorotrifluoroethane, ethyl acetate, n-butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl ether,
Isopropyl ether, methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene,
At least one selected from the group consisting of n-hexane, n-octane, dioxane and tetrahydrofuran
The method for surface treatment of wood according to claim 5, which is a species. (7) The co-grafting reaction is an alkyl hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxide ester, azobisisobutyronitrile, hydrogen peroxide-ferrous salt system, benzoyl peroxide-dimethylaniline system, The wood surface treatment method according to claim 5 or 6, which is carried out using at least one selected from the group consisting of cerium (IV) salts and organometallic compounds as a radical polymerization initiator. (8) Claims 1 to 4, wherein the co-grafting reaction is a reaction using a polymerizable monomer having a high fluorine-containing organic group and a vinyl monomer with high grafting efficiency as a gas. The wood surface treatment method described in any of the above. (9) The co-grafting reaction is an alkyl hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxide ester, azobisisobutyronitrile, hydrogen peroxide-ferrous salt system, benzoyl peroxide-dimethylaniline system, 9. The method of surface treatment of the material according to claim 8, which is carried out using at least one selected from the group consisting of cerium (IV) salts and organometallic compounds as a radical polymerization initiator. (10) The wood surface treatment method according to claim 8 or 9, wherein the co-grafting reaction is carried out under ultraviolet irradiation. (11) The co-grafting reaction includes benzoyl peroxide, azobisisobutyronitrile, diacetyl, dibenzyl, diphenyl monosulfide, diphenyl disulfide, dibenzoyl monosulfide, dibenzoyl disulfide,
11. The wood surface treatment method according to claim 10, which is carried out using at least one selected from the group consisting of carbon tetrachloride and ferric trichloride as a photosensitizer.