JPH011786A - Water and oil repellent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fluorine-based high performance TNN water/oil agent composition.

[Conventional technology]

Fluorine-based water and oil repellents have been commonly used since they have superior performance compared to other types of water and oil repellents, but they are relatively expensive, so some of them have been replaced with inexpensive acrylics. It was previously proposed to reduce costs while maintaining performance by replacing acid-based polymers, ■polyhydric alcohols such as sorbitol and lactose, ■inorganic salts or amine salts, and ■glyoxylic acid. 38-22487
Publication No. 41-8579, Special Publication No. 53-2
Publication No. 999, Japanese Patent Publication No. 53-4160, Japanese Patent Application Publication No. 1983
0-88178, etc.).

However, although these methods were able to achieve their objectives to some extent, their effects were not sufficient.

[Purpose of the invention]

The inventors of the present invention searched for something that would have an effect greater than that of glyoxylic acid, and as a result of their extensive research, they discovered that oxyacids or their salts are superior, and have arrived at the present invention.

An object of the present invention is to provide a high-performance and inexpensive TA water IB oil composition.

[Structure of the invention]

The present invention is a t8 water oil repellent composition comprising a fluorine-based 1B water tΩ oil agent, an I8 water I8 oil treatment medium, and one or more additives selected from the group consisting of the following (1) to (2).

■ Oxyacid or its salt containing 3 or more hydroxyl groups; ■ Salt of oxyacid containing 1 to 2 hydroxyl groups; ■ Salt of fatty acid having 3 to 7 carbon atoms; ■ At least one carboxyl group has been converted to a salt. Polybasic carboxylic acids, ■ Compounds with imide or amide groups, ■ Carbamic acid compounds.

In the present invention, (1) The oxyacid containing three or more hydroxyl groups may be cyclic or linear, regardless of the steric configuration. Examples of the oxyacid include ascorbic acid, glucon a,! ! , glucuron M, and the like. Examples of the oxyacid salts include alkali metal salts and ammonium salts. ■ Examples of salts of oxyacids containing 1 to 2 hydroxyl groups include alkali metal salts and ammonium salts of malic acid, iftaric acid, lactic acid, glycolic acid, hydroxyglucuric acid, glyceric acid, etc. . ■As salts of fatty acids with 3 to 7 carbon atoms,
Examples include alkali metal salts and ammonium salts of butyric acid, hexanoic acid, propionic acid, chloropropionic acid, and the like.

■ Polybasic carboxylic acids in which at least one carboxyl group has been converted into a salt include, for example, alkali metal salts such as succinic acid, oxalic acid, adipic acid, malonic acid, maleic acid, chlorosuccinic acid, and glutaric acid, and ammonium salts. Examples include salt. (2) Examples of compounds having an imide group include succinimide, chlorosuccinimide, succinimide, glutarimide, and phthalimide. Compounds having an amide group include propionic acid amide, succinic acid amide, butyramide, nicotinic acid amide, toluenesulfonic acid amide, methylolacrylamide, dimethylformamide, isobutyramide,
Examples include malonamide and chloroacetamide. (2) Examples of the carbamic acid compound include carbamic acid, ethyl carbamate, methyl ethyl carbamate, butyl carbamate, and ammonium carbamate.

The addition ratio of the additives (■ to ■) is 0.01 parts by weight per 100 parts by weight of the water-repellent and oil treatment medium (liquid in the treatment bath).
The addition ratio is preferably in the range of 7.00 parts by weight in order to improve the 18 water tB oiliness and its wash resistance, and the more preferred addition ratio is in the range of 0.01 to 4.0 parts by weight.

In the present invention, the fluorine-based water-carrying TA oil agent is not particularly limited as long as it is what is called a fluorine-based IR water tΩ oil agent in this technical field.

The fluorine-based IB water TA oil agent is normally contained in 1041 parts of fri water 1G oil treatment medium in a range of 0.1 to 1.0 parts by weight. As an example of this TA water 1B oil agent, carbon number is 4~
Examples include homopolymers of acrylates or methacrylates containing 21 fluoroaliphatic groups, or copolymers of these with monomers containing no fluoroaliphatic groups (for example, Japanese Patent Publication No. 60-8068). (see official bulletin).

A specific example of the acrylate or methacrylate containing the fluoroaliphatic group is CF x (CF t
)? (C)I z) + + 0COCHENGCH.

CFs (CFz) acH20cOc(CHs)-C
lbCFs (CFri b (CHz) zOcOc(
CIli)=CHzCFs (CF,) 4 (CL)
JCOC(CI(,)-CHzCF(CFz)
z (CF z)! (CHz) xOcOcH=c
HzCF (CF ri z (CF i) +.(CH
z) 5OcOcH-CHzCFs (CF z) q
sOJ (CsHt) (CHz) zOcOcH-C
8zCF! (Ch) 7SO□N (CH3) (CI
lz) zOcOc(CL)=CHzCF(CF+)z
(CFz)acHtcH(OH)CHzOCOCH=C
HzCF (CF:+)! (CF2)6CHICH(OC
OCH3)OCOC(CI(3)=CHICCIFz
(CFt) +. CHzOCOC(CM:+)=CHz
H(CFz)+. Examples include CH20COCH=CHz. In addition to these, monomers containing fluoroaliphatic groups include CF (CFs) (CGIFri(Ch)tcONHcOO
c+(=C1lz, etc.) can also be used in place of all or part of the acrylate or methacrylate.

Specific examples of monomers that do not contain fluoroaliphatic groups include ethylene, vinyl acetate, vinyl fluoride, vinyl chloride,
Vinylidene fluoride, vinylidene chloride, acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, acrylic acid or its alkyl ester, methacrylic acid or its alkyl ester, acrylamide, diacetone acrylamide, methylolated diacetone acrylamide, methylolated diacetone acrylamide acetone methacrylamide,
Examples include vinyl alkyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl acrylate, maleic anhydride, and the like.

The acrylate or methacrylate polymer or copolymer can be produced by bulk polymerization, solution polymerization, emulsion polymerization, etc., but is usually produced by emulsion polymerization. Therefore, the main component of the 1R water tidal oil treatment medium is usually water. Emulsion polymerization does not require special conditions, and for example, the method described in Japanese Patent Publication No. 8068/1983 can be used.

The composition of the present invention may contain known additives such as cross-linking agents, antistatic agents, dye fixing agents, anti-wrinkle agents, flame retardants, insect repellents, etc., as well as general-purpose organic solvents such as Isoproper tools etc. can be added.

The water-repellent I8 oil composition of the present invention can be applied to an article to be treated by a known method such as a spray method or a dipping method (see, for example, Japanese Patent Laid-Open No. 61-264081).

(The following is a blank space, continued on the next page) [Example] Examples 1 to 9 (■Example in which oxyacid containing 3 or more hydroxyl groups or its salt was added) Formula: %Formula% (However, the average value of n is 8 60 parts by weight of a mixture of fluorine-containing acrylates represented by . 3 parts by weight of 3-hydroxy-2-chloropropyl methacrylate, 5 parts by weight of emulsifier (manufactured by Nippon Oil & Fats Corporation) 1s220), 6 parts by weight of emulsifier (Nichika Kagaku Kogyo Junsei L-3419), 0.2 parts by weight of n-lauryl mercaptan A flask was charged with 0.5 parts by weight of glacial acetic acid, 50 parts by weight of acetone, 12 parts by weight of ethylene glycol and 120 parts by weight of deionized water, and stirred at 60°C for 1 hour under a nitrogen stream, followed by azobisisobutyramidine hydrochloride. A solution prepared by dissolving 0.7 parts by weight of the salt in 10 parts by weight of deionized water was added, and the mixture was further stirred at 60° C. for 5 hours under a nitrogen stream to perform copolymerization. Solid content concentration 32% by weight
An emulsified dispersion was obtained.

Analysis of the reaction mixture by gas chromatography revealed that the conversion rates of acrylate, methacrylate, and acrylamide were all 99% or higher, and the composition of the produced copolymer was approximately equal to the ratio of the charged acrylate, methacrylate, and acrylamide. It turned out to be equal.

The emulsified dispersion obtained above with a solid content concentration of 32% by weight was diluted with water.
The composition of the present invention [(1
) to (9)] were prepared.

A polyester processed woven tropical cloth (hereinafter referred to as PE) and a nylon taffeta cloth (hereinafter referred to as N) were dipped in the compositions of the present invention [(1) to (9)] and wetted with two rubber rolls. The sample was squeezed so that the pickup was 50%, dried at 110°C for 3 minutes, and then heat-treated at 150°C for 3 minutes to prepare a sample for the tests described below (18 water ↑ Ω oil resistance and wash resistance 1 Ω oil resistance). .

7-1n Water-oil repellency test method tS The water-based test followed the spray method of JIS L-1092. IC oil test is AATCC-TM-118-
The method of 1966 was followed. Water repellency No. in Table 1 (1) and (2).

and oil repellency No.

Washing Resistance 1B Water 1B Oil Resistance Test Method (1) Dry Cleaning Using a round-o-meter, the product was treated with tetrachloroethylene at 30°C for 30 minutes, dried at room temperature, and then tested for ↑Ω water resistance and oil repellency in the same manner as above. Table 1 (1) and (2) show water repellency No. and ↑Ω oiliness No.

(2) Home Laundry: Wash at 40℃ for 5 minutes using a fully automatic household washing machine.Detergent: Zabu manufactured by Kao ■, concentration: 2g/l, amount used:
301 for 1 kg of cloth), rinse 1 kg of cloth for 5 minutes with 30 F water (however, twice in total), dehydrate for 5 minutes, ・11
After drying at 0°C for 3 minutes, water repellency and 1
8 Oiliness was investigated. Water repellency N in Table 1 (1) and (2)
o, and I8 oily no.

shows.

Comparative Examples 1 to 4 The above tests were conducted in the same manner as in Examples 1 to 9, except that the oxyacids in Examples 1 to 9 were changed to those shown in Table 1 (3). The results are shown in Table 1 (3).

Examples 10 to 14 (■ Examples in which an oxyacid containing 3 or more hydroxyl groups or a salt thereof was added) Fluorine-containing acrylate represented by the formula: % formula % (however, the average value of n is 8.2) 65 parts by weight of a mixture of, 33 parts by weight of stearyl acrylate, 2 parts by weight of N-methylol acrylamide, 4 parts by weight of emulsifier (H3220 manufactured by NOF ■), 3 parts by weight of emulsifier (Cation AB manufactured by NOF),
0.2 parts by weight of n-lauryl mercaptan, 0.5 parts of glacial acetic acid
Chungshin part, 50 parts by weight of acetone, 12 parts by weight of ethylene glycol
A flask was charged with 120 parts by weight of deionized water and stirred at 60°C for 1 hour under a nitrogen stream.
Add the solution dissolved in 0 parts by weight, and further add 6 parts by weight under nitrogen stream.
The mixture was stirred at 0° C. for 5 hours to carry out copolymerization. Solid content concentration 33
An emulsified dispersion of % by weight was obtained.

Analysis of the reaction mixture by gas chromatography revealed that the conversion rates of acrylate, methacrylate, and acrylamide were all 99% or higher, and the composition of the produced copolymer was approximately equal to the ratio of the charged acrylate, methacrylate, and acrylamide. It turned out to be equal.

The obtained emulsified dispersion having a solid content concentration of 33% by weight was diluted with water.
The compositions of the present invention ((10) to (14)
) was prepared.

Same as the compositions of the present invention [(1) to (9)] except that the cloth was changed to a cotton fabric (hereinafter referred to as C) and a blended fiber fabric of polyester and cotton (hereinafter referred to as PE/C). The test was conducted using the same procedure. The results are shown in Table 2 (1).

Comparative Examples 5 to 8 The oxyacids or salts thereof of Examples 10 to 14 were
) The above test was conducted in the same manner as in Examples 10 to 14, except that the test results were changed to those shown in (). The results are shown in Table 2 (2).

Examples 15 to 19 (■ Examples in which an oxyacid containing 3 or more hydroxyl groups or a salt thereof was added) Fluorine-containing acrylate represented by the formula: % formula % (however, the average value of n is 8.2) 60 parts by weight of a mixture of, 30 parts by weight of stearyl acrylate, 5 parts by weight of cyclohexyl methacrylate, 3 parts by weight of glycidyl nucleate, 2 parts by weight of N-methylolacrylamide, emulsifier (NOF ■
HS220) 5 parts by weight, emulsifier (Nicca Chemical Industry side type 1)
-3419) 6 parts by weight, n-lauryl mercaptan 0.
2 parts by weight, 0.5 parts by weight of glacial acetic acid, 50 parts by weight of acetone,
12 parts by weight of ethylene glycol and 120 parts by weight of deionized water
Part by weight was charged into a flask and stirred at 60°C for 1 hour under a nitrogen stream, and then 0.0% of azobisisobutyramidine hydrochloride was added.
A solution of 7 parts by weight dissolved in 10 parts by weight of deionized water was added, and the mixture was further stirred at 60° C. for 5 hours under a nitrogen stream to perform copolymerization. The solid content was doubled to obtain an emulsified dispersion with a solid content of 32% by weight.

When the reaction mixture was analyzed by gas chromatography, the conversion rates of acrylate, methacrylate, and acrylamide were all 99% or higher, and the composition of the produced copolymer was approximately equal to the ratio of the charged acrylate, methacrylate, and acrylamide. It turned out to be equal.

The emulsified dispersion obtained above with a solid content concentration of 32% by weight was diluted with water.
Compositions C(15) to (19) of the present invention were diluted to 2% by weight and added with the oxyacid or its salt shown in Table 3 (1).
) was prepared.

The above tests were conducted in the same manner as in the case of the compositions of the present invention [(1) to (9)]. The results are shown in Table 3 (1).

Comparative Examples 9 to 12 The oxyacids or salts thereof of Examples 15 to 19 were
) The test was conducted in the same manner as in Examples 15 to 19, except that the test was changed to that shown in (). The results are shown in Table 3 (2).

Examples 20 to 28 (■Example in which a salt of an oxyacid containing 1 to 2 hydroxyl groups was added) The additives in Examples 1 to 9 were changed to the additives shown in Table 4 (1) and (2). prepared and tested the compositions of the present invention in the same manner as in Examples 1-9. The results are shown in Table 4 (1
) and (2).

Examples 29 to 33 (■Example in which a salt of an oxyacid containing 1 to 2 Hg of water was added) Examples 10 to 14 except that the additives in Examples 10 to 14 were changed to the additives shown in Table 5. The composition of the present invention was prepared and tested in the same manner as described above. The results are shown in Table 5.

Examples 34 to 38 (■Example in which a salt of an oxyacid containing 1 to 2 hydroxyl groups was added) The same as Examples 15 to 19 except that the additives in Examples 15 to 19 were changed to the additives shown in Table 6. iJ! of the composition of the present invention using a similar procedure. Manufactured and tested. The results are shown in Table 6.

Examples 39 to 47 (■Example in which a salt of a fatty acid having 3 to 7 carbon atoms was added) The additives in Examples 1 to 9 were changed to the additives shown in Table 7 (1) and (2). The compositions of the present invention were tested with tPfJ in the same manner as in Examples 1-9. 7th result
Shown in Tables (1) and (2).

Comparative Examples 13-14 The test was conducted in the same manner as in Examples 39-47, except that the additives in Examples 39-47 were changed to the additives shown in Table 10. The results are shown in Table 10.

Examples 48 to 52 (■Example in which salts of fatty acids having 3 to 7 carbon atoms were added) Same as Examples 10 to 14 except that the additives in Examples 10 to 14 were changed to the additives shown in Table 8. The compositions of the invention were prepared and tested according to the procedure. The results are shown in Table 8.

Comparative Examples 15-16 The test was conducted in the same manner as in Examples 48-52, except that the additives in Examples 48-52 were changed to those shown in Table 10. The results are shown in Table 10.

Examples 53 to 57 (■ Examples in which salts of fatty acids having 3 to 7 carbon atoms were added) The additives of Examples 15 to 19 were added to the additives shown in Table 9.

The compositions of the present invention were prepared and tested in the same manner as in Examples 15 to 19, except for the modifications. The results are shown in Table 9.

Comparative Examples 17-18 The test was conducted in the same manner as in Examples 53-57, except that the additives in Examples 53-57 were changed to those shown in Table 10. The results are shown in Table 10.

Examples 58 to 66 (■ Example of adding polybasic carboxylic acid in which at least one carboxyl group has been converted to a salt) The additives of Examples 1 to 9 are shown in Table 11 (1) and (2). The compositions of the present invention were prepared and tested in the same manner as in Examples 1 to 9, except that the additives were changed. The results are shown in Table 11 (1) and (2).

Examples 67 to 71 (Examples in which a polybasic carboxylic acid having at least one carboxyl group converted to a salt was added) The additives in Examples 10 to 14 were changed to the additives shown in Table 12. Compositions of the invention were prepared and tested using procedures similar to Examples 10-14. The results are shown in Table 12.

Examples 72 to 76 (■ Examples in which a polybasic carboxylic acid in which at least one carboxyl group has been converted to a salt was added) The additives in Examples 15 to 19 were changed to the additives shown in Table 13. The compositions of the present invention manufactured by gJl were tested in the same manner as in Examples 15-19. The results are shown in Table 13. Comparative Example 19 The test was conducted in the same manner as in Examples 58 to 66, except that the additives in Examples 58 to 66 were changed to the additives shown in Table 14. . The results are shown in Table 14.

Comparative Example 20 The test was conducted in the same manner as in Examples 67 to 71, except that the additives in Examples 67 to 71 were changed to the additives shown in Table 14. The results are shown in Table 14.

Comparative Example 21 The test was conducted in the same manner as in Examples 72 to 76, except that the additives in Examples 72 to 76 were changed to the additives shown in Table 14. The results are shown in Table 14.

Comparative Example 22 The test was conducted in the same manner as in Examples 58 to 66, except that the additives in Examples 58 to 66 were changed to the additives shown in Table 14. The results are shown in Table 14.

Examples 77 to 81 (Examples in which a compound having an imide group or an amide group was added) Example 1 except that the additives in Examples 1 to 9 were changed to the additives shown in Table 15 (1) and (2). The composition of the present invention was prepared and tested in the same manner as in Example 9. The results are shown in Table 15 (1) and (2).

Examples 86 to 90 (■Example in which a compound that grows an imide group or an amide group was added) Same as Examples 10 to 14 except that the additives in Examples 10 to 14 were changed to the additives shown in Table 16. The compositions of the invention were prepared and tested according to the procedure. The results are shown in Table 16.

Examples 91 to 95 (■Example in which a compound having an imide group or an amide group was added) The additives of Examples 15 to 19 were added to the additives shown in Table 17.
Compositions according to the present invention were prepared and tested in the same manner as in Examples 15 to 19, except for the following changes. The results are shown in Table 17. ” Examples 96 to 104 (■ Example in which a carbamic acid compound was added) The same as Examples 1 to 9 except that the additives in Examples 1 to 9 were changed to the additives shown in Table 18 (1) and (2). Compositions of the present invention were prepared and tested using similar procedures.The results are shown in Table 18 (1) and (2).

Examples 105 to 109 (Examples in which a carbamic acid compound was added) Compositions of the present invention were prepared in the same manner as in Examples 10 to 14, except that the additives in Examples 10 to 14 were changed to the additives shown in Table 19. were prepared and tested. The results are shown in Table 19.

Examples 110 to 114 (■ Examples in which a carbamic acid compound was added) The compositions of the present invention were prepared in the same manner as in Examples 15 to 19, except that the additives in Examples 15 to 19 were changed to the additives shown in Table 20. A test was conducted with a product manufactured by W. The results are shown in Table 20.

[Effects of the Invention] The i8 water 1Ω oil composition of the invention to which the above-mentioned additives (■ to ■) have been added has a 107 klG oil performance equal to or higher than that of the conventional composition and its resistance to treated articles. It can provide washing performance and is inexpensive.

that's all Patent applicant: Daikin Industries, Ltd.

Claims (1)

[Scope of Claims] 1. A water and oil repellent composition comprising a fluorine-based water and oil repellent, a water and oil repellent treatment medium, and one or more additives selected from the group consisting of (1) to (6) below. . (1) Oxyacid or salt thereof containing 3 or more hydroxyl groups, (2) Salt of oxyacid containing 1 to 2 hydroxyl groups, (3) Salt of fatty acid having 3 to 7 carbon atoms, (4) At least one carboxyl group. polybasic carboxylic acids whose groups have been converted to salts, (5) compounds having imide or amide groups, (6)
Carbamate compounds. 2. The water and oil repellent composition according to claim 1, wherein the additive is added in a proportion of 0.01 to 7.00 parts by weight based on 100 parts by weight of the water and oil repellent treatment medium.