JP2968366B2 - Water / oil repellent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water / oil repellent composition which is particularly effective for imparting high durability to water / oil repellency.

[0002]

2. Description of the Related Art In recent years, water- and oil-repellent finishing of clothing has been actively performed, and various compositions have been provided according to purposes. Sports clothes require high water and oil repellency and high durability against washing and dry cleaning. For the purpose of obtaining durability, it has been proposed to copolymerize a copolymer of a polyfluoroalkyl group-containing acrylate and vinyl chloride (Japanese Patent Publication No. 50-3438) and N-methylolacrylamide, glycidylacrylamide or the like as a crosslinking component. However, satisfactory durability has not yet been obtained.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a water- and oil-repellent composition which provides a high durability, which has not been known before.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is based on 100 parts by weight of a polyfluoroalkyl group-containing (meth) acrylate .
A compound represented by the formula [CH ₂ ＣC (R ¹ ) COO] _n R ² OH (where R ¹ is H or CH ₃ , R ² is (n +
1) A residue obtained by removing (n + 1) hydroxyl groups from a valent alcohol, and n is an integer of 1 to 6. ) And a water- and oil-repellent composition comprising a copolymer having 1 to 17 parts by weight of a polyfunctional (meth) acrylate having a urethane bond, which is a reaction product of a di- or tri-functional polyisocyanate, as an essential copolymer component. It provides things. In this specification, acrylate and methacrylate are collectively referred to as (meth) acrylate, and the same applies to (meth) acrylamide and the like. Me is a methyl group, Et is an ethyl group, Ph
Represents a phenyl group, respectively.

As the (meth) acrylate containing a polyfluoroalkyl group (hereinafter referred to as Rf group) in the present invention, the following (meth) acrylate containing an Rf group is preferable. Two or more of these compounds or two or more compounds having different carbon numbers in the Rf group may be used in combination.

[0006]

Embedded image ^{_{CH 2 = C (R 1)}} COOCH 2 CH 2 Rf, CH 2 = C (R 1) COOCH 2 CH 2 N (C 3 H 7) CORf, CH 2 = C (R 1) COOCH (CH _{3) CH 2 Rf, CH 2} = C (R 1) COOCH 2 CH 2 N (CH 3) SO 2 Rf, CH 2 = C (R 1) COOCH 2 CH 2 N (CH 3) CORf, CH 2 = C _{^{(R 1) COOCH 2 CH 2}} N (C 2 H 5) SO 2 Rf, CH 2 = C (R 1) COOCH 2 CH 2 N (C 2 H 5) CORf, CH 2 = C (R 1) COOCH 2 _{CH 2 N (C 3 H 7} ) SO 2 Rf, CH 2 = C (R 1) COOCH (CH 2 Cl) CH 2 OCH 2 - -CH 2 N (CH 3) SO 2 Rf. (Where R ¹ is H or CH ₃ )

The above-mentioned Rf group is a linear or branched polyfluoroalkyl group having 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms. However, those containing a hydrogen atom or a chlorine atom at the terminal or an oxypolyfluoroalkylene-containing group can also be used. A preferred embodiment of the Rf group is a perfluoroalkyl group represented by C _n F _{2n + 1} (where n is an integer of 4 to 16), and n
6 to 12 are particularly preferred.

The polyfunctional (meth) acrylate having a urethane bond is preferably a compound represented by the following formula (1). Preferred examples include compounds represented by the following formulas (2) to (5).

[0009]

Embedded image [CH ₂ ＣC (R ¹ ) COO] _n R ² OCONH-R ³ —NHCOOR ⁴ [OCOC (R ¹ ) = CH ₂ ] _m (1)

(In the formula (1), R ¹ is H or CH
₃ , R ² is a residue obtained by removing (n + 1) OH groups from a (n + 1) -valent alcohol, R ³ is a residue obtained by removing 2-3 NCO groups from a 2-3 functional polyisocyanate, R ⁴ is a residue obtained by removing (m + 1) OH groups from a (m + 1) -valent alcohol, and n + m is an integer of 2 to 6. )

[0011]

Embedded image R ³ [NHCOOCH (CH ₂ OPh) CH ₂ OCOCH ＝ CH ₂ ] ₂ (2) R ³ [NHCOOCH (CH ₂ OCOCMe = CH ₂ ) ₂ ] ₂ (3) R ³ [NHCOOOCH ₂ C (CH ₂ OCOCMe = CH ₂ ) ₃ ] ₂ (4)

[0012]

Embedded image

[0013] In the equation (2) ~ (4), R ³ is - (CH _{2) 6} -, a lower following formula (6) or (7).

[0014]

Embedded image

[0015]

The above polyfunctional (meth) having a urethane bond
The acrylate is a (meth) acrylate 1 containing an Rf group.
1 to 17 parts by weight are copolymerized with respect to 00 parts by weight. Bird
For example, 1 to 10 parts by weight, particularly 1 to 5 parts by weight, is preferably copolymerized. If the amount is less than 1 part by weight, the effect of crosslinking is insufficient and the object of the present invention cannot be achieved. If the amount is more than 17 parts by weight, the amount of crosslinking becomes excessive, and conversely high initial performance cannot be obtained.

In the present invention, in addition to the above-mentioned monomers, one or more monomers having a radical polymerizable unsaturated bond may be further copolymerized. The copolymerization ratio is 10 to 10 parts by weight of the Rf group-containing (meth) acrylate.
100 parts by weight are preferred.

Preferred monomers include ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinylidene halide, styrene, α-methylstyrene, β-methylstyrene, (meth) acrylic acid and its alkyl ester, and poly (meth) acrylic acid. Oxyalkylene (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, N-
Methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aziridinyl (meth) acrylate, benzyl (meth) Examples include, but are not limited to, acrylate, isocyanatoethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, maleic anhydride, (meth) acrylate having polysiloxane, and N-vinylcarbazole. It is not something to be done.

In order to obtain the copolymer of the present invention, various polymerization reaction methods and conditions can be arbitrarily selected, and any of bulk polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, photopolymerization and the like are employed. it can.

For example, a method in which a mixture of compounds to be polymerized is emulsified in water in the presence of a surfactant or the like and polymerized with stirring can be adopted. As a polymerization initiation source, various polymerization initiators such as organic peroxides, azo compounds, and persulfates, and ionizing radiation such as γ-rays can be employed. Almost all of various anionic, cationic or nonionic emulsifiers can be used as the surfactant.

[0021] The raw material is dissolved in a suitable organic solvent, the polymerization initiating source (peroxides soluble in an organic solvent to be used, azo compounds or the like ionizing radiation) by the action of, can also be solution polymerization. Solvents suitable for solution polymerization include chlorinated and fluorinated solvents such as trichlorotrifluoroethane, tetrachlorodifluoroethane, dichloropentafluoropropane, and methyl chloroform, as well as methyl isobutyl ketone, methyl ethyl ketone, butyl acetate, and ethyl acetate.

The water / oil repellent composition of the present invention comprising the polymer thus obtained is prepared in an arbitrary form such as an emulsion, a solvent solution, or an aerosol according to a conventional method. For example, aqueous emulsions can be prepared directly by emulsion polymerization and solvent-solution types can be prepared directly by solution polymerization.

The water / oil repellent composition of the present invention can be applied to the article to be treated by any method according to the kind of the article to be treated and the preparation form.

For example, in the case of an aqueous emulsion or a solvent solution type , a method of adhering to the surface of the object to be treated and drying by a known method of coating such as dip coating is adopted. If necessary, curing may be performed.

Furthermore water and oil repellent composition of the present invention, other polymers with rather it may also be mixed using, other water repellents, oil repellents or crosslinking agents, insect repellents, flame retardants, antistatic agents, Additives such as an anti-wrinkle agent may be added and used as appropriate.

The article which can be treated with the water / oil repellent composition of the present invention is not particularly limited, and includes various examples such as fiber woven fabric, fiber knitted fabric, leather and fur. As textile fabrics and fiber knits, animal and plant natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; and semi-synthetic fibers such as rayon and acetate. ,
Alternatively, a woven or knitted fabric of these mixed fibers may be used.

[0027]

EXAMPLES Examples of the present invention will be described more specifically, but the description does not limit the present invention.

The water repellency and oil repellency shown in the following examples are as follows.
The following scale was used. That is, the water repellency is JIS L-
The water repellency number by the spray method of 1092 (see Table 1) was used.
A few drops (about 4 mm in diameter) were placed at two places on the test cloth and discriminated by the permeation state after 30 seconds (AATCC-TM118-
1966). The water repellent number and the oil repellent number with a plus sign indicate that the respective performances are slightly better.

[0029]

[Table 1]

[0030]

[Table 2]

The durability test was performed as follows. That is, the treated cloth is weighed with a ballast cloth to 1 kg, placed in an electric washing machine, washed with a liquid detergent (new beads: trade name) at 60 g and a bath volume of 33 liters, washed at 40 ° C. for 25 minutes, and then rinsed for 10 minutes. This is one cycle, and after repeating four times,
Air dry. Measure the water and oil repellency of the cloth air-dried for 15 hours,
Determine durability.

Example 1 An acrylate containing a perfluoroalkyl group [RfCH ₂ CH ₂ OC] was placed in a glass autoclave (1 liter internal volume) equipped with a thermocouple thermometer and an electromagnetic stirrer.
OCH = CH _2] (hereinafter, FA) 120 g (60 parts by weight), acrylate [R ¹ having a urethane bond represented by previous following formula (1) H, R ² is _{- (CH 2) 2 -,} R 3
Is _{- (CH 2) 6 -,} R 4 is _{- (CH 2) 2 -,} n = m
= 1] 4 g (2 parts by weight), 2-ethylhexyl methacrylate (hereinafter 2EHMA) 76 g (38 parts by weight), polyoxyethylene lauryl ether 10 g, stearyltrimethylammonium chloride 2 g, acetone 12
0 g (60 parts by weight), water 350 g (175 parts by weight), azobis (dimethyleneisobutyramide) <Wako Chemical V
A-061> 1 g was added.

After purging with nitrogen for about 20 minutes while stirring, the temperature is raised to 60 ° C. to initiate polymerization. 1 at 60 ° C
After stirring while keeping the temperature for 5 hours, the mixture was cooled to obtain an emulsion having a solid content of 31%. The conversion of the copolymerization reaction by gas chromatography was 99.0 to 99.8% (based on the Rf group-containing polymerizable compound). Further, the yield of the stable emulsified emulsion based on all the reaction monomers is 95 to 9
9%.

Examples 2 to 6, Comparative Examples 1 to 3 Emulsion polymerization was carried out in the same manner as in Example 1, except that the monomers, emulsifier and polymerization initiator were changed. Table 3 shows the monomers used and the mixing ratio, and Tables 4 and 5 show the emulsifier and the polymerization initiator. Note that, in the column of emulsifier, a hatched line indicates a combination of two emulsifiers.

[0035]

[Table 3]

[0036]

[Table 4]

[0037]

[Table 5]

A latex having a solid content concentration of 20% by weight of the emulsion obtained by the above method was used as a stock solution, and the stock solution was diluted so that the ratio of the stock solution of latex to water was 1.5%. The oil repellency performance was tested.

The test was performed on a nylon taffeta cloth,
The water / oil repellent treatment was performed as follows. That is, the test cloth is immersed in the latex treatment solution diluted as described above,
The cloth was squeezed between the rubber rollers to reduce the wet pickup to 30%. Next, drying was performed at 110 ° C. for 90 seconds, and heat treatment was performed at 170 ° C. for 60 seconds. Washing durability was repeated 5 times according to JIS L-0217103 method, then dried at 100 ° C. for 3 minutes, and subjected to a test. Table 6 shows the results of measuring the water / oil repellency of the test cloth thus obtained.

[0040]

[Table 6]

[0041]

According to the present invention, by using a copolymer of a polyfluoroalkyl group-containing (meth) acrylate and a polyfunctional (meth) acrylate having a urethane bond, high durability which could not be attained conventionally can be attained. It has become possible to provide an excellent water / oil repellent having:

Continued on the front page (51) Int.Cl. ⁶ identification code FI D06M 15/277 (58) Investigated field (Int.Cl. ⁶ , DB name) C09K 3/18 C08F 220/22-220/36 WPI / L (QUESTEL)

Claims (3)

(57) [Claims] (1 ) a (meth) a containing a polyfluoroalkyl group;
The formula [CH ₂ ＣC (R
¹ ) COO] _n A compound represented by R ² OH (provided that R
¹ is H or CH ₃ , R ² is a residue obtained by removing (n + 1) hydroxyl groups from a (n + 1) -valent alcohol, and n is an integer of 1 to 6. ) And a water- and oil-repellent composition comprising a copolymer having 1 to 17 parts by weight of a polyfunctional (meth) acrylate having a urethane bond, which is a reaction product of a di- or tri-functional polyisocyanate, as an essential copolymer component. Stuff. 2. A polyfluoroalkyl group-containing (meth) amine.
The acrylate has the formula CH ₂ ＣC (R ¹ ) COOCH ₂ CH ₂
A compound represented by Rf (where Rf has 4 to 16 carbon atoms)
R ¹ is H or CH ₃ . The water / oil repellent composition according to claim 1, wherein 3. The water / oil repellent composition according to claim 1, wherein the polyfunctional (meth) acrylate is a compound represented by the following formula (2), (3) or (4). Embedded image R ³ [NHCOOOCH (CH ₂ OPh) CH ₂ OCOCH = CH ₂ ] ₂ (2) R ³ [NHCOOCH (CH ₂ OCCMe = CH ₂ ) ₂ ] ₂ (3) R ³ [NHCOOOCH ₂ C (CH ₂ OCOCMe = CH ₂ ) ₃ ] ₂ (4) wherein R ³ is — (CH ₂ ) ₆ —, a group represented by the following formula (6), or a group represented by the following formula (7); Me
Is a methyl group, and Ph is a phenyl group . Embedded image