JP3241431B2 - Solvent type water / oil repellent composition and water / oil repellent processing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel water / oil repellent composition capable of imparting high water / oil repellency to textiles and the like.

[0002]

2. Description of the Related Art It has been widely known and used that a fiber material can be imparted with water / oil repellency by treating the fiber material with a water / oil repellent comprising a fluoropolymer dissolved in an appropriate solvent. I have. As the fluorine-containing polymer, a fluorine-containing polymer containing a polyfluoroalkyl group,
In particular, polyfluoroalkyl group-containing (meth) acrylate copolymers are widely known. In addition, (meth) acrylate is used as a term meaning both acrylate and methacrylate. (Meth) acrylic acid, etc.
Is the same.

[0003]

If the fiber material, etc. [0008] is treated with water repellent oil repellent coating a water-repellent oil-repellent agent to the fiber material, etc. The
It is necessary to remove the solvent by drying after the impregnation. Drying is usually carried out by heating, but may be dried at room temperature. However, it was difficult to impart high water / oil repellency to natural fibers, especially cotton, by drying at room temperature.

To solve this problem, there has been proposed a method of copolymerizing a monomer having a highly reactive functional group such as an isocyanate group, a 1,2-iminoethyl group and an epoxy group in a polymer. However, a polymer having a highly reactive functional group has a problem in storage stability, it has a drawback have ease deteriorated during storage.

[0005]

SUMMARY OF THE INVENTION The present inventor has proposed that by adding a specific polar solvent to a water / oil repellent solution, natural fibers, especially cotton, can be used even if drying at room temperature is adopted during the water / oil repellent treatment. It has been found that the water and oil repellency of the oil can be remarkably improved. The present invention is the following invention relating to a water / oil repellent using a specific polar solvent.

[0006] repellent capable of exhibiting polyfluoroalkyl group-containing fluoropolymer, and a solvent type water and oil repellent composition containing 10 wt% or more of the following solvents with respect to the fluorine-containing polymer. Solvent: secondary alcohol having 4 to 8 carbon atoms and propylene
Selected from glycol monoalkyl ether acetate
At least one.

[0007] water- and oil-repellent process using a water and oil repellent composition of the present invention, Ru can give better performance on cotton. this is,
A specific polar solvent contained in the composition (hereinafter referred to as a specific solvent)
This is presumed to be due to the fact that the film-forming property and the orientation of the fluorine component are improved by the action of (iii ) . This effect is that obtained only by JP Tei溶 <br/> agent selected, such effect is obtained hardly in other solvents.

[0008] Japanese Tei溶 agent used in the present invention, also secondary alcohol having 4 to 8 carbon atoms is propylene glycol monoalkyl ether acetate, may be used in combination of both. The Japanese Tei溶 agent is necessary to use 10 wt% or more of the fluorine-containing polymer, usually used 20 wt% or more. The upper limit is particularly LIMITED Lena Iga, 15 times by weight of the fluorine-containing polymer, in particular 8
Double the amount . If the amount of this particular solvent agent is too small solubility of the fluoropolymer becomes insufficient.

Further, it is too excessive use of this Japanese Tei溶 agent is not preferable from the viewpoint of such effects on the object to be processed. I
And although we, the Japanese Tei溶 agent are combined with below main solvent. The particular relative to the total solvent in processing an object to be processed is
The amount of solvent agent, 10 wt% or less, particularly 5 wt% or less. The lower limit is the lower limit for the fluoropolymer. However, the present invention is not necessarily limited to a high-concentration solution or the like that is used after dilution.

The secondary alcohol having 4 to 8 carbon atoms includes
2 - butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol and the like,
Particularly, 2 - butanol is preferred. As propylene glycol monoalkyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate are preferable.

[0011] Apart from the above-mentioned specific solvent, it is preferable to use a solvent other than the above-mentioned specific solvent such as a commonly used solvent (hereinafter referred to as a main solvent). The main solvent is usually used in a large amount compared to the above-mentioned Japanese Tei溶 agent. As the main solvent, for example, chlorinated solvents, fluorine-based solvent,
There are petroleum solvents, ketone solvents and the like.

Preferred main solvents include, for example, 1,
Chlorinated solvents such as 1,1-trichloroethane and perchlorethylene, for example, trichlorotrifluoroethane (R
-113) and tetrachlorodifluoroethane (R-11
2) fluoropolymer solvents such as petroleum-based solvents such as mineral spirits, and it <br/> Ru which include ketone solvents such as methyl ethyl ketone or methyl isobutyl ketone as suitable. In particular, 1,1,1-trichloroethane, perchlorethylene, mineral spirit, and methyl isobutyl ketone are preferred.

As the fluoropolymer containing a polyfluoroalkyl group capable of exhibiting water and oil repellency, a homopolymer of a polyfluoroalkyl group-containing (meth) acrylate or a copolymer of the same with another monomer is suitable. is there. As the polyfluoroalkyl group-containing (meth) acrylate, two or more kinds may be used in combination. Usually, a mixture of two or more polyfluoroalkyl group-containing (meth) acrylates having different carbon numbers of the polyfluoroalkyl group is used. You.

The polyfluoroalkyl group-containing (meth)
As the acrylate, a fluorine-containing monomer (a) represented by the following general formula (1) is preferable. As the fluorinated monomer (a), a compound well known as a polyfluoroalkyl group-containing fluorinated monomer is suitable.

[0015] _{CH 2 = CRCOO-A-R} f ··· (1) ( wherein, R represents a hydrogen atom or a methyl group, A is a divalent linking group, R _f is perfluoroalkyl of 6 to 16 carbon atoms Represents a group)

As the divalent linking group A, -R ^2- , -R
_{^{2 N (R 3) SO 2}} -, - R 2 N (R 3) CO-, other divalent linking groups are suitable. Incidentally, R ² represents an alkylene group, especially an alkylene group having 2 to 6 carbon atoms, R ³
Is an alkyl group, especially an alkyl group having 4 or less carbon atoms (hereinafter, referred to as
Lower alkyl group). R _f has 6 to 16 carbon atoms
Of represents a perfluoroalkyl group, the perfluoroalkyl group is branched perfluoroalkyl group having a branched to or distal portion is preferably linear. Preferred specific examples of the fluorine-containing monomer (a) include the following compounds. In addition, n represents the integer of 6-16.

[0017]

## STR1 ## _{CH 2 = CHCOOC 2 H 4 C} n F 2n + 1 CH 2 = C (CH 3) COOC 2 H 4 C n F 2n + 1 CH 2 = CHCOOC 2 H 4 N (CH 3) SO 2 C _n F
_{2n + 1 CH 2 = C (} CH 3) COOC 2 H 4 N (C 2 H 5) S
_{O 2 C n F 2n + 1} CH 2 = CHCOOC 2 H 4 C n F 2n-1 (CF 3) 2 CH 2 = C (CH 3) COOC 2 H 4 C n F 2n-1 (CF
₃ ) ₂

As the monomer copolymerizable with the fluorine-containing monomer (hereinafter, referred to as a copolymerizable monomer), various monomers can be used. Examples of the copolymerizable monomers kills with a two or more併. For example, there are (meth) acrylates, vinyl halides, olefins, acrylonitriles, acrylamides, and other widely used monomers. As the copolymerizable monomer, specifically,
Hydrocarbon group-containing (meth) acrylates having various functional groups such as amino groups and epoxy groups, various alkyl (meth) acrylates, vinyl chloride, vinylidene chloride, ethylene, styrene, butadiene, acrylonitrile, (meth) acrylamide, Jiaseto down acrylamide <br/> de, vinyl acetate, (meth) acrylic acid, alkyl vinyl ether, chloroprene, maleic anhydride, and the like.

Preferred as copolymerizable monomers are (meth) acrylates and acrylamides, and particularly preferred are (meth) acrylates having an alkyl group, a glycidyl group, an amino group-containing hydrocarbon group and the like. Among them, long chain alkyl group-containing (meth) acrylates and aminoalkyl group-containing (meth) acrylates are preferred. As the acrylamides, dialkylacrylamide and dialkylmethacrylamide are preferable , and as the alkyl group, a lower alkyl group is preferable.

The most preferred copolymerizable monomers are a monomer (b) represented by the following general formula (2), which is a (meth) acrylate containing a long-chain alkyl group, and a (meth) acrylate containing an aminoalkyl group, a monomer represented by the general formula (3) (c), both either, yo Ri preferably both, but is used.

CH ₂ = CRCOOC _m H _{2m + 1} (2) (where R is a hydrogen atom or a methyl group, and m is 12 to 2)
CH ₂ ＣＲCRCOO—R ² N (R ¹ ) ₂ (3) (where R is a hydrogen atom or a methyl group, R ¹ is a lower alkyl group, and R ² is an alkylene group)

In the general formula (3), R ¹ has 1 to ¹ carbon atoms.
An alkyl group of 3 is preferable, and R ² is preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably a dimethylene group.

As the monomer (b), lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate and the like are preferable. As the monomer (c), dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and the like are preferable.

In a copolymer of a polyfluoroalkyl group-containing (meth) acrylate and a copolymerizable monomer,
A polymer obtained by polymerizing a monomer mixture having a polyfluoroalkyl group-containing (meth) acrylate in an amount of 40% by weight or more, especially 50% by weight or more based on the total of both, is preferred. As the copolymerizable monomer to be used, 60
% By weight or more is preferably a (meth) acrylates or (meth) acrylamides. The most preferred copolymer is a copolymer of monomer (a), monomer (b), and monomer (c). In this case, the copolymerization ratio of the monomer is 55 to monomer (a) based on the total of the three. 7
0% by weight, 20 to 44% by weight of monomer (b) and 0.5 to 10% by weight of monomer (c) are preferred.

The polymerization method is not particularly limited, and a known polymerization method can be used. At this time, it is preferable to carry out solution polymerization using the main solvent as a polymerization medium. The resulting polymer solution was added to the particular solvent kill the compositions of the present invention in <br/> Manufacturing. Further, a main solvent may be added for dilution . By performing polymerization in a solvent containing a specific solvent during Polymerization may.

The composition of the present invention is usually commercialized as a high-concentration polymer solution, and is usually used after being diluted when treating an object to be treated. It was although I, the compositions of the present invention refers to a composition used in this process, does not necessarily mean the composition before dilution. The polymer concentration of the high-concentration polymer solution is usually 10% by weight or more, and the concentration of the polymer solution used for the treatment is usually 5% by weight or less.

[0027] When a solvent type water and oil repellent composition by processing the fiber material of the fabric such as water-repellent oil-repellent of the present invention, applying the solvent type water and oil repellent composition as the fiber material or It is customary to impregnate and dry. In this drying, the characteristics of the present invention are exhibited particularly when room temperature drying is employed, but good water / oil repellency is exhibited even with heating and drying. The room temperature is not particularly limited, but refers to a temperature of about 60 ° C. or lower, usually 40 ° C. or lower.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In the description, “parts” and “%” are based on weight unless otherwise specified.

[0029]

Examples [Water repellency and oil repellency] The water repellency and oil repellency shown in Examples and Comparative Examples were measured by the following methods.

That is, regarding water repellency, JIS L-1
No. 092 by the spray method. (Table 1 below), and the oil repellency was represented by AATC shown in Table 2 below.
The test solution of C-118-1966 was placed on the sample cloth at a few drops (about 4 mm in diameter) at two places, and after 30 seconds, the highest No. And its oil repellency.
In addition, each No. The + added to the No. indicates that No. Better than

[0031]

[Table 1]

[0032]

[Table 2]

The raw materials shown in Table 3 were charged into a 500 ml autoclave, and nitrogen gas was blown for 5 minutes.
Polymerization was carried out for 0 hour, and a pale yellow transparent liquid ( solid content: 33%)
Hereinafter, it is referred to as a fluoropolymer solution A. ) Got. A liquid consisting of 20% solids, 20% propylene glycol monoethyl ether acetate, and 60% 1,1,1-trichloroethane was prepared from the obtained solution to obtain a pale yellow transparent liquid.

The polyfluoroalkyl group-containing monomers in Table 3 consist of a mixture of compounds having k of 6, 8, 10, 12, and 14 in a weight ratio of 2: 60: 20: 7: 1. Is a monomer in which k is 9 (Polymerization Example 2)
In the same way). AIBN represents azobisisobutyronitrile.

[0035]

[Table 3]

[Polymerization Example 2] The raw materials shown in Table 4 were charged into a 500 ml autoclave, replaced with nitrogen gas, and then polymerized at 60 ° C for 20 hours to obtain a solid content of 3
3% pale yellow transparent liquid (hereinafter referred to as fluoropolymer solution B)
Write. ) Got. From the resulting solution, a solid content of 10%, propylene glycol monoethyl ether acetate 10
% And perchlorethylene 80%, a pale yellow transparent liquid was obtained.

[0037]

[Table 4]

Example 1 The solution having a solid content of 33% obtained in Polymerization Example 1 (fluorinated poly
Mer solution A) To 1.5 parts, 98 parts of 1,1,1-trichloroethane and 0.5 parts of propylene glycol monoethyl ether acetate were added, and the solid content was 0.5%, and the content of propylene glycol monoethyl ether acetate was 0.5%. 0.
A 5% solution was prepared.

Example 2 A solution having a solid content of 0.5% was prepared in the same manner as in Example 1 except that perchlorethylene was used as the diluting solvent in Example 1.

Examples 3 to 10 and Comparative Examples 1 to 5 Compositions were produced in the same manner as in Examples 1 and 2. Examples 1 and 2
The compositions are shown in Tables 5 and 6. Table 5 shows the composition of the example,
6 shows the composition of the comparative example. When a very small amount of a main solvent different from the diluting solvent was contained, the solvent was omitted.

The types of raw materials described are as follows. Containing fluorocarbon polymer solution A; solution prepared in Polymerization Example 1 (3
3%) containing fluorine polymer solution B; solution prepared in Polymerization Example 2 (3
Main solvent A; 1,1,1-trichloroethane Main solvent B; Perchlorethylene Main solvent C; Mineral spirit Main solvent D; Methyl isobutyl ketone

Specific solvent A; propylene glycol monoethyl ether acetate Specific solvent B; propylene glycol monomethyl ether acetate Specific solvent C; 2 - Butanol Specific solvent D; 2-Pentanol Specific solvent E; 2-Hexanol Specific solvent F; 2- Octanol Specific solvent G; 2-propanol Specific solvent H; Propylene glycol monomethyl ether

[0043]

[Table 5]

[0044]

[Table 6]

[0045] [water repellency, oil repellency test results Example, using the compositions manufactured adjusted in Comparative Example, was air-dried test cloth at room temperature for 12 hours after squeezing cotton broadcloth fabric by dip mangle thereto . The test for oil repellency and water repellency described above was performed using this test cloth. Table 7 shows the results. In the table, the compositions used are indicated by the numbers of Examples and Comparative Examples.

[0046]

[Table 7]

[0047]

By adding a small amount of Japanese Tei溶 agent in a solvent type water and oil repellent composition according to the present invention, natural fibers be employed dried at room temperature during water- and oil-repellent treatment, water and oil repellency particularly cotton against, Can be improved. This orientation of the film forming property and the fluorine component is presumed to be due to enhanced by the action of JP Tei溶 agent contained in the composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI D06M 13/17 D06M 13/17

Claims (5)

(57) [Claims] 1. A solvent-type water- and oil-repellent composition comprising a polyfluoroalkyl group-containing fluorine-containing polymer capable of exhibiting water- and oil-repellency and 10% by weight or more of the following solvent based on the fluorine-containing polymer. . Solvent: at least one selected from secondary alcohols having 4 to 8 carbon atoms and propylene glycol monoalkyl ether acetate. 2. The fluoropolymer is a copolymer of at least two monomers of a (meth) acrylate containing a polyfluoroalkyl group and a (meth) acrylate containing an amino group-containing hydrocarbon group or a long-chain alkyl group. The solvent-type water / oil repellent composition according to claim 1. 3. A fluorine-containing polymer comprising a fluorine-containing monomer (a) represented by the following general formula (1), a monomer (b) represented by the following general formula (2) and a monomer represented by the following general formula (3): The solvent-type water / oil repellent composition according to claim 1, which is a copolymer of the monomer (c) represented. CH ₂ ＣＲCRCOO-A-R _f (1) (where R is a hydrogen atom or a methyl group, A is a divalent linking group, and R _f is a perfluoroalkyl group having 6 to 16 carbon atoms) CH ₂ = CRCOOC _m H _{2m + 1} (2) (where R is a hydrogen atom or a methyl group, and m is 12 to 2)
3 ^{_{integer) CH 2 = CRCOO-R 2}} N (R 1) 2 ··· (3) ( wherein, R represents a hydrogen atom or a methyl group, ^{R 1} is a lower alkyl group, ^{R 2} is an alkylene group) 4. The solvent-type water / oil repellent composition according to claim 1, wherein the solvent is 2-butanol, propylene glycol monomethyl ether acetate, or propylene glycol monoethyl ether acetate. 5. A method for treating water and oil repellency of a fiber material, comprising treating the fiber material with the solvent-type water and oil repellent composition according to claim 1, 2, 3 or 4 .