JPH05302271A - Solvent-type water and oil repellent composition and water and oil repellent processing method - Google Patents

Abstract

(57) [Summary] [Purpose] Even if room temperature drying is adopted during water and oil repellency treatment, it imparts high water and oil repellency to natural fibers. A solvent-type fluoropolymer-based water and oil repellent composition containing a solvent composed of a secondary alcohol having 4 to 8 carbon atoms or propylene glycol monoalkyl ether acetate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel water / oil repellent composition capable of imparting high water / oil repellency to textiles and the like.

[0002]

It has been widely known and used that it is possible to impart a water / oil repellency to a fiber material by treating the fiber material with a water / oil repellent agent made of a fluoropolymer dissolved in a suitable solvent. There is. As the fluoropolymer, a polyfluoroalkyl group-containing fluoropolymer,
In particular, polyfluoroalkyl group-containing (meth) acrylate copolymers are widely known. In addition, (meth) acrylate is used as a term that means both acrylate and methacrylate.

[0003]

When a fiber material or the like is treated with a water / oil repellent agent, it is necessary to apply the water / oil repellent agent to the fiber material or the like to impregnate it and then dry it to remove the solvent. Usually, heat drying is adopted, but it may be dried at room temperature.
However, it has been difficult to impart high water / oil repellency to natural fibers, especially cotton, by drying at room temperature.

In order 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, an ethyleneimine group and an epoxy group in the polymer. However, a polymer having a highly reactive functional group has a problem in storage stability and is liable to be deteriorated during storage.

[0005]

Means for Solving the Problems The present inventor has found that by adding a specific polar solvent to a water / oil repellent solution, even if room temperature drying is adopted during the water / oil repellent treatment, natural fibers, particularly cotton, It has been found that the water and oil repellency against can be significantly improved. The present invention is the following invention relating to a water and oil repellent agent using a specific polar solvent.

Fluorine-containing polymer containing a polyfluoroalkyl group capable of exhibiting water and oil repellency, and 10% by weight or more of the fluorine-containing polymer, a secondary alcohol having 4 to 8 carbon atoms and propylene glycol monoalkyl ether acetate. A solvent-based water / oil repellent composition comprising at least one solvent selected from

The water / oil repellent treatment using the water / oil repellent composition of the present invention can impart high performance to cotton. It is presumed that this is because the action of the specific polar solvent contained in the composition improves the film-forming property and the orientation of the fluorine component. This effect is obtained only by the selected specific polar solvent, and it is difficult to obtain such an effect by other solvents.

The particular solvent used in the present invention is
It is a secondary alcohol having 4 to 8 carbon atoms or propylene glycol monoalkyl ether acetate, and both can be used together. It is necessary to use this specific solvent in an amount of 10% by weight or more, and usually 20% by weight or more based on the fluoropolymer. The upper limit is not particularly limited, but it is used in an amount of 15 times, especially 8 times by weight of the fluoropolymer. If the amount of this specific solvent used is too small, the solubility of the fluoropolymer becomes insufficient.

Further, it is not preferable to use this particular solvent in an excessively large amount in view of the influence on the object to be treated.
Therefore, this specific solvent is used together with the main solvent described later. When treating an object to be treated, the amount of this specific solvent is preferably 10% by weight or less, more preferably 5% by weight or less, based on all the solvents. The lower limit is the lower limit for the fluoropolymer. However, it is not necessarily limited to such a high-concentration solution that is used by diluting.

As the secondary alcohol having 4 to 8 carbon atoms,
There are secondary butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol, etc.,
Particularly, secondary butanol is preferable. The propylene glycol monoalkyl ether acetate is preferably propylene glycol monomethyl ether acetate or propylene glycol monoethyl acetate.

In addition to the above-mentioned specific solvent, it is preferable to use a solvent other than the above-mentioned specific solvent (hereinafter referred to as a main solvent) such as a commonly used solvent. This main solvent is usually used in a large amount as compared with the above specific solvent. Examples of the main solvent include chlorine-based solvents, fluorine-based solvents,
Examples include petroleum-based solvents and ketone-based solvents.

Examples of preferred main solvents include 1,
Chlorine-based solvents such as 1,1-trichloroethane and perchlorethylene, such as trichlorotrifluoroethane (R
-113) and tetrachlorodifluoroethane (R-11
Suitable examples include fluorine-based solvents such as 2), petroleum-based solvents such as mineral spirits, and ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone. Particularly, 1,1,1-trichloroethane, perchlorethylene, mineral spirits, and methyl isobutyl ketone are preferable.

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

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

CH ₂ = CRCOO-AR _f (1) (wherein 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) )

As the divalent linking group A, -R ^2- , -R ² N (R ³ )
SO _2- , -R ² N (R ³ ) CO-, and other divalent linking groups are suitable. R ² represents an alkylene group, particularly an alkylene group having 2 to 6 carbon atoms, and R ³ represents an alkyl group, particularly 4 carbon atoms.
The following alkyl groups (hereinafter referred to as lower alkyl groups) are represented. R _f represents a perfluoroalkyl group having 6 to 16 carbon atoms, and this perfluoroalkyl group is preferably a linear perfluoroalkyl group having a branch at the end. The following compounds are illustrated as preferable specific fluorine-containing monomers (a). In addition, n represents the integer of 6-16.

CH ₂ = CHCOOC ₂ H ₅ C _n F _{2n + 1} CH ₂ = C (CH ₃ ) C 00 C ₂ H ₅ C _n F _{2n + 1} CH ₂ = CHCOOC ₂ H ₅ N (CH ₃ ) SO ₂ C _n F _{2n + 1} CH ₂ = C (CH ₃ ) COOC ₂ H ₅ N (C ₂ H ₅ ) SO ₂ C _n F _{2n + 1} CH ₂ = CHCOOC ₂ H ₅ C _n F _2n-1 (CF ₃ ) ₂ CH ₂ = C (CH ₃ ) C00C ₂ H ₅ C _n F _2n-1 (CF ₃ ) ₂

Various monomers can be used as the monomer copolymerizable with the fluorine-containing monomer (hereinafter referred to as a copolymerizable monomer). Two or more kinds of these copolymerizable monomers can be used in combination. For example, (meth) acrylates, vinyl halides, olefins, acrylonitriles, acrylamides, and other widely used monomers. Specific examples of the copolymerizable monomer include hydrocarbon group-containing (meth) acrylates having various functional groups such as amino groups and epoxy groups, various alkyl (meth) acrylates, vinyl chloride, vinylidene chloride, Examples include ethylene, styrene, butadiene, acrylonitrile, acrylamide, methacrylamide, diacetoacrylamide, vinyl acetate, acrylic acid, methacrylic acid, alkyl vinyl ether, chloroprene, and maleic anhydride.

Preferred as the copolymerizable monomer are (meth) acrylates and acrylamides, and particularly (meth) acrylates having an alkyl group, a glycidyl group, an amino group-containing hydrocarbon group or the like are preferred. Among them, long-chain alkyl group-containing (meth) acrylates and aminoalkyl group-containing (meth) acrylates are preferable. The acrylamides are preferably dialkyl acrylamide and dialkyl methacrylamide, and the alkyl group is preferably a lower alkyl group.

The most preferable copolymerizable monomer is a monomer (b) represented by the following general formula (2), which is a long-chain alkyl group-containing (meth) acrylate, and an aminoalkyl group-containing (meth) acrylate. It is the monomer (c) represented by the general formula (3), and either of them, or more preferably, both are used in combination.

CH ₂ = CRCOOC _m H _{2m + 1} (2) (where m is an integer of 12 to 23) CH ₂ = CRCOO-R ² N (R ¹ ) ₂ (3) (however) , R ¹ is a lower alkyl group, R ² is an alkylene group)

In the general formula (3), R ¹ has 1 to ¹ carbon atoms.
As described above, 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 the copolymer of the polyfluoroalkyl group-containing (meth) acrylate and the copolymerizable monomer,
A polymer obtained by polymerizing a monomer mixture in a proportion of 40% by weight or more, and particularly 50% by weight or more, of a polyfluoroalkyl group-containing (meth) acrylate based on the total of both is preferable. As the copolymerizable monomer to be used, its 60
Weight% or more is (meth) acrylates or (meth)
Acrylamides are preferred. The most preferable copolymer is a copolymer of the monomer (a), the monomer (b) and the monomer (c), and the copolymerization ratio of the monomer in that case is 55 to 55% of the total of the three.
70% by weight, 20-44% by weight of monomer (b) and 0.5-10% by weight of monomer (c) are preferred.

The polymerization method is not particularly limited,
Known polymerization methods can be used. At this time, it is preferable to carry out solution polymerization using the main solvent as a polymerization medium. The above-mentioned specific solvent can be added to the obtained polymer solution to produce the composition of the present invention. Further, the main solvent may be added to dilute it. Of course, the polymerization may be carried out in a solvent containing a specific solvent during the polymerization.

The composition of the present invention is usually commercialized as a high-concentration polymer solution, and it is customarily used by diluting it when treating an object to be treated. Therefore, the composition of the present invention refers to the composition used for this treatment, and 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.

When a fiber material such as cloth is treated with the solvent-type water and oil repellent composition of the present invention to be processed for water and oil repellency, the solvent type water and oil repellent composition is applied to the fiber material as described above. It is customary to impregnate and dry. In this drying, the characteristics of the present invention are exhibited particularly when the room temperature drying is adopted, but even if the drying is performed by heating, a good water / oil repellency is exhibited. The room temperature is not particularly limited,
A temperature of about 60 ° C. or lower, usually 40 ° C. or lower.

The present invention will be specifically described below with reference to Examples and Comparative Examples. In the text, "part" and "%" are based on weight unless otherwise specified.

[0029]

【Example】

[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 the water repellency, the water repellency No. by the spray method of JIS L-1092 was used. (Table 1 below), and regarding oil repellency, AATCC-118-196 shown in Table 2 below.
A few drops of 6 test solution on the sample cloth at 2 places (diameter about 4mm)
Highest N with no penetration and absorption into fabric after 30 seconds
o. Was used as the oil repellency. In addition, each No. "+" Attached to the No. Better than.

[0031]

[Table 1]

[0032]

[Table 2]

[Polymerization Example 1] The raw materials shown in Table 3 were charged in a 500 ml autoclave, nitrogen gas was blown therein for 5 minutes, and then polymerization was carried out at 60 ° C. for 20 hours to obtain a pale yellow transparent liquid having a solid content of 33%. From the resulting solution, solid content 20%, propylene glycol monoethyl ether acetate 20%,
A liquid consisting of 60% of 1,1,1-trichloroethane was prepared to obtain a pale yellow transparent liquid.

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

[0035]

[Table 3]

[Polymerization Example 2] The raw materials shown in Table 4 were charged in a 500 ml autoclave, and after substitution with nitrogen gas, polymerization was carried out at 60 ° C for 20 hours to obtain a pale yellow transparent liquid having a solid content of 33%. When a liquid containing 10% solids, 10% propylene glycol monoethyl ether acetate, and 80% perchlorethylene was prepared from the obtained solution, a pale yellow transparent liquid was obtained.

[0037]

[Table 4]

[Example 1] Solid content 3 obtained in Polymerization Example 1
To 1.5 parts of a 3% solution, 98 parts of 1,1,1-trichloroethane and 0.5 part of propylene glycol monoethyl ether acetate were added to give a solid content of 0.5% and propylene glycol monoethyl ether acetate content. 0.5
% Solution was prepared.

Example 2 A solid 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, Comparative Examples 1 to 5] Compositions were produced in the same manner as in Examples 1 and 2. The compositions including Examples 1 and 2 are shown in Tables 5 to 7. Tables 5 and 6 show the compositions of Examples, Table 7
Indicates 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 shown are as follows. Fluorine-containing polymer solution A; the solution prepared in Polymerization Example 1 (33
%) Fluorine-containing polymer solution B; solution prepared in Polymerization Example 2 (33
%) Main solvent A; 1,1,1-trichloroethane Main solvent B; Perchlorethylene Main solvent C; Mineral terpene 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; Secondary 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]

[Water and oil repellency test results] Using the compositions prepared in Examples and Comparative Examples, a cotton broad cloth was dipped in the composition, squeezed with a mangle, and then air dried at room temperature for 12 hours to obtain a test cloth. Using this test cloth, the above-mentioned oil repellency and water repellency tests were conducted. The results are shown in Table 7. In the table, the compositions used are indicated by the numbers of Examples and Comparative Examples.

[0046]

[Table 7]

[0047]

EFFECTS OF THE INVENTION By adding a small amount of a specific polar solvent to a solvent-type water and oil repellent composition, even if room temperature drying is adopted during the water and oil repellent treatment, the water and oil repellent performance of natural fibers, especially cotton, is improved. Can be improved. It is presumed that this is because the action of the specific polar solvent contained in the composition improves the film-forming property and the orientation of the fluorine component.

Claims (7)

[Claims] 1. A fluoropolymer containing a polyfluoroalkyl group capable of exhibiting water and oil repellency, and 10% by weight or more of a secondary alcohol having 4 to 8 carbon atoms and propylene glycol monoalkyl with respect to the fluoropolymer. A solvent-based water / oil repellent composition containing at least one solvent selected from ether acetates. 2. The fluorine-containing polymer is a copolymer of at least two monomers of an acrylate or methacrylate containing a polyfluoroalkyl group and an acrylate or methacrylate containing a hydrocarbon group containing an amino group or a long chain alkyl group. 1. The solvent-based water / oil repellent composition of 1. 3. A fluoropolymer comprising a fluoromonomer (a) represented by the following general formula (1), a monomer (b) represented by the following general formula (2), and a general formula (3) below. The solvent-based water and oil repellent composition according to claim 1, which is a copolymer of the monomer (c) represented. CH ₂ = CRCOO-AR _f (1) (where R is a hydrogen atom or a methyl group, A is a divalent linking group, R _f is a carbon atom having 6 carbon atoms)
CH ₂ = CRCOOC _m H _{2m + 1} ... (2) (where m is an integer of 12 to 23) CH ₂ = CRCOO-R ² N (R ¹ ) ₂ · .. (3) (provided that R ¹ is a lower alkyl group and R ² is an alkylene group) 4. The solvent is secondary butanol, propylene glycol monomethyl ether acetate, or propylene glycol monoethyl ether acetate.
The solvent-type water and oil repellent composition according to claim 1. 5. The solvent-based water / oil repellent composition according to claim 1, further comprising 1,1,1-trichloroethane, perchlorethylene, or mineral spirits as a solvent. 6. A water-repellent and oil-repellent finishing method for a fiber material, which comprises treating the fiber material with the solvent-type water- and oil-repellent composition according to any one of claims 1 to 5. 7. The water- and oil-repellent finishing method according to claim 6, wherein the solvent-based water- and oil-repellent composition is applied to and impregnated in a fiber material and dried at room temperature.