JPH07229066A - Water repellent composition, water repellent article and method for water repellent treatment - Google Patents

Abstract

PURPOSE:To obtain the subject composition providing a target material for water repellency with excellent performances of water repellency having high permanence by spraying the composition on the target material for water repel lency, having no remaining stain, comprising a composition containing a pre scribed component in a specific ratio. CONSTITUTION:In a water repellency composition containing (A) 0.1-5wt.% of a fluorine resin, (B) 90-99.89wt.% of a 1-3C alcohol, preferably ethanol and (C) 0.01-5wt.% of a quaternary ammonium salt, a polyester fabric pretreated by the method A prescribed by JIS-L-1096 is immersed in a composition prepared by adding 1wt.% of the component A based on eathanol as a water repellent and the fabric is dried at 20 deg.C at 65% relative humidity for 24 hours. A water repellent composition containing a water repellent showing water repellent performances of >=90 point of water repellency prescribed by JIS-L-1092 is sprayed by an aerosol method on woven fabric of yarn, glass fibers, etc., to give a water repellent article having excellent permanence. CF3(CF2)7(CH3)7(CH2)11OCOCH=C2 may be cited as the fluorores in.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water repellent composition, a water repellent article, and a water repellent treatment method. More specifically, it has good water repellent performance, high durability, and is uncomfortable during water repellent treatment. The present invention relates to a water repellent composition, a water repellent article, and a water repellent treatment method in which generation of odor is suppressed, and unevenness and stains during water repellent treatment are suppressed.

[0002]

PRIOR ART AND PROBLEM TO BE SOLVED BY THE INVENTION A polymerized product of a polymerizable monomer containing a perfluoroalkyl group or a fluoroalkyl group in the molecule, or this monomer and another type of polymerizable monomer. The fluorine-based water repellent composed of a copolymer with a polymer is used in an amount of 0.05 to 2% owf (on the weight) per unit weight of fiber for an object to be water repellent treated, for example, a fiber woven fabric.
It exhibits excellent water repellency and antifouling effect even with a relatively small amount of of fabrics), and has recently attracted attention as a surface treatment agent for textiles, leather, interiors and building materials.

However, an aerosol containing a fluorine-based water repellent is sprayed onto clothing or the like, or the water repellent is treated with a chlorine-based solvent (dichloroethane, 1,1,1-trichloroethane, S-tetrachlorodifluoroethane, 1,1). , 2-Trichloro-1,2,2-trifluoroethane, etc.), or a mixed solvent of these chlorine-based solvents to which a monovalent or divalent alcohol is added, or a petroleum-based solvent (mineral terpene oil, etc.) When the above liquid is applied to a cloth, there is a problem that white stains conspicuously impair the appearance when the clothes or the like after being water-repellent have a dark color such as black or dark blue. Further, with these water repellents, although the water repellency immediately after the water repellent treatment is sufficiently observed, the effect is inferior in sustainability, so that there has been a problem that clothing and the like must be frequently subjected to the water repellent treatment.

Accordingly, the problem to be solved by the present invention is to provide a water repellent composition which has an excellent water repellent effect in water repellent treatment, has high durability, and has no stain residue on an object to be treated, and the water repellent agent. A water repellent article containing the agent composition and a water repellent treatment method using the water repellent article.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that by using a specific composition, the composition can be treated with a water-repellent material. It was found that the above-mentioned object can be achieved by spraying to the above, and the present invention has been completed.

That is, in the present invention, 0.1 to 5% by weight of a fluororesin (hereinafter referred to as the component (a)) satisfying the following conditions and an alcohol having 1 to 3 carbon atoms (hereinafter referred to as the component (b)) 90 to 99.89.
The present invention provides a water repellent composition characterized by containing 0.01% to 5% by weight of a quaternary ammonium salt (hereinafter referred to as component (c)). Condition 1 for ethanol
In the composition obtained by adding the component (a) by weight%, JIS-
According to 6.23.1 method A of L-1096 (however, the drying method is drip drying), pretreated polyester cloth is dipped and then dried for 24 hours in an environment of 20 ° C and 65% relative humidity. When the water repellency test (spray method) is performed on the cloth according to the method specified in JIS-L-1092, 90
Water repellency above the point should be obtained.

The present invention further provides a water repellent article obtained by filling the water repellent composition into a container equipped with a device for spraying a liquid filled inside the composition to the outside. is there. Further, the present invention provides a water repellent treatment method, which comprises using the water repellent article and spraying the water repellent composition onto an object to be water repellent treated. .

The present invention will be described in detail below. [Water repellent composition] The component (a) used in the water repellent composition of the present invention is a fluororesin that satisfies the above conditions, and a fluororesin that does not satisfy the above conditions is suitable for a treated product. Water repellency cannot be imparted. (A) of the present invention
Examples of the fluororesin used as a component include CF ₃
(CF ₂ ) ₇ (CH ₂ ) ₁₁ OCOCH = CH ₂ , CF ₃ (CF ₂ ) CH ₂ OCOC (CH ₃ ) = CH
₂ ,

[0009]

[Chemical 9]

CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₂ OCOCH = CH ₂ ,
CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇
(CH ₂ ) ₂ OCOCH = CH ₂ ,

[0011]

[Chemical 10]

Polymers of unsaturated esters represented by acrylates or methacrylates containing a perfluoroalkyl group having 3 to 20 carbon atoms (hereinafter referred to as fluorine group-containing monomer), or containing such a fluorine group Examples thereof include a copolymer with one or more compounds capable of polymerizing with a monomer (provided that the compound does not have a fluorine-containing group; hereinafter referred to as a copolymerization monomer). In this case, examples of the copolymerization monomer include ethylene, vinyl acetate, vinyl fluoride, vinyl chloride, vinylidene halide, acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, acrylic acid and its alkyl ester, and methacrylic acid. And its alkyl ester, acrylamide, methacrylamide, diacetone acrylamide, methylol diacetone acrylamide or methacrylamide,
Examples thereof include vinyl alkyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl acrylate, benzyl methacrylate, cyclohexyl methacrylate and maleic anhydride.

In this case, the reaction molar ratio of the fluorine group-containing monomer and the copolymerization monomer is preferably fluorine group-containing monomer / copolymerization monomer = 100/0 to 20/80,
100/0 to 50/50 are particularly preferable. If this ratio falls below 20/80, the water repellent effect of the present invention cannot be obtained in the water repellent composition.

In the method for producing the component (a) used in the present invention, various polymerization reaction modes and conditions can be arbitrarily selected,
Any of various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, radiation polymerization and photopolymerization can be adopted.
For example, a method of emulsifying a fluorine group-containing monomer or a mixture of a fluorine group-containing monomer and a copolymerization monomer (hereinafter referred to as fluorine group-containing monomer) in water in the presence of a surfactant or the like, and polymerizing with stirring, or a fluorine group It is possible to employ a method in which the contained monomer or the like is dissolved in an appropriate organic solvent and solution polymerization is performed by the action of a polymerization initiator (a polymerization initiator such as a peroxide or an azo compound or radiation).

The molecular weight of the fluororesin used as the component (a) is preferably 500 to 1,000,000, particularly preferably 500 to 100,000. (a) As a commercially available fluororesin that can be used as the component, DEFENSA MCF-312, DEFENSA MCF-323
(Registered trademark of Dainippon Ink and Chemicals, Inc.) and the like.

The amount of component (a) in the water repellent composition of the present invention is 0.1 to 5% by weight. In the water repellent composition obtained when the content of the component (a) is less than 0.1% by weight, the level of water repellency desired by the present invention is not achieved, while the content is 5
Even if it exceeds the weight%, a significant improvement in water repellency is not seen,
Not preferable from an economic point of view. The content of the component (a) in the water repellent composition of the present invention is more preferably 0.2 to 3% by weight.
Is.

Used in the water repellent composition of the present invention
The component (b) is an alcohol having 1 to 3 carbon atoms, and examples thereof include methanol, ethanol, propanol, isopropanol, ethylene glycol and propylene glycol. Among these, ethanol and isopropanol are preferable from the viewpoint of suppressing stain residue, and ethanol is particularly preferable. The amount of the component (b) in the water repellent composition of the present invention is
90 to 99.89% by weight, more preferably 92 to 99.7% by weight. If the content of the component (b) is less than 90% by weight, it is not preferable from the economical viewpoint, and if it is more than 99.89% by weight, the level of water repellency desired by the present invention cannot be achieved.

The quaternary ammonium salt used as the component (c) of the water repellent composition of the present invention is represented by the following general formula (1)
At least one selected from the compounds represented by (6) to (6) is preferable.

[0019]

[Chemical 11]

[Wherein R ¹ and R ^{2 are the} same or different and are linear or branched and have 8 carbon atoms]
22 alkyl groups, alkenyl groups or hydroxyalkyl groups. R ³ and R ^{4 are the} same or different and represent an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or a formula

[0021]

[Chemical 12]

A group represented by Here, Z represents a hydrogen atom or a methyl group, and n represents a number of 1 to 10. X ⁻ : Indicates an anionic group. ]

[0023]

[Chemical 13]

[In the formula, R ^{5 represents a} linear or branched alkyl group having 24 to 38 carbon atoms or a hydroxyalkyl group. R ⁶ : represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or a formula

[0025]

[Chemical 14]

The group represented by Here, Z 1 and n have the above-mentioned meanings. ^{R 3, R 4, X -} : The meanings of the. ]

[0027]

[Chemical 15]

[Wherein R ⁷ and R ^{8 are the} same or different and are linear or branched and have 7 to 7 carbon atoms]
21 represents an alkyl group or an alkenyl group. Q ¹ and Q ^{2 are the} same or different and represent —COO— or —CONH—. A ¹ and A ^{2 are the} same or different and represent an alkylene group having 1 to 3 carbon atoms. ^{R 3, R 4, X -} : The meanings of the. ]

[0029]

[Chemical 16]

[0030] ^{wherein, R 2, R 3, R} 4, A 1, X -: The meanings of the. R ⁹ : Shows a linear or branched alkyl group having 8 to 22 carbon atoms or a hydroxyalkyl group. Y: -COO- or -OCO- is shown. ]

[0031]

[Chemical 17]

[In the formula, E: -NHCO- or -OCO- is shown. ^{R 3, R 7, X -} : The meanings of the. ]

[0033]

[Chemical 18]

[0034] ^{wherein, R 3, R 7, E} , X -: The meanings of the. Examples of the compound represented by the general formula (1) include the following. -Di (alkyl derived from hardened tallow) -Dimethylammonium chloride-Distearyl-dimethylammonium chloride-Dioleyl-dimethylammonium chloride-Dieicosyl-dimethylammonium chloride-Di (alkyl derived from hardened tallow) -Diethylammonium chloride-di (Alkyl derived from cured tallow) -Di (2-hydroxyethyl) ammonium-p-toluenesulfonate-Distearyl-Di (2-hydroxyethyl) ammonium glycolate-Di (alkyl derived from cured tallow) -Polyoxyethylene-
Ethyl ammonium ethylsulfate (where "polyoxyethylene" group is -. (.N which a group represented by CH ₂ CH ₂ O) _n H is a number of 1 to 10), distearyl Polyoxyethylene ethyl ammonium ethylsulfate (the "polyoxyethylene" group where - (.n showing a CH ₂ CH ₂ O) groups represented by _n H 1
Indicates a number from ~ 10. ).

Examples of the compound represented by the general formula (2) are as follows. -(2-dodecyl) hexadecyl-trimethylammonium chloride- (2-tetradecyl) octadecyl-trimethylammonium chloride- (2-hexadecyl) docosyl-trimethylammonium chloride- (straight chain saturated alkyl having 24 carbon atoms) -trimethylammonium・ Chloride.

Examples of the compound represented by the general formula (3) are as follows. -N-[(2-hardened tallow-derived alkyloyloxy) ethyl] -N-[(3-hardened tallow-derived alkanoylamino)
Propyl] -dimethylammonium chloride-N-[(2-oleoyloxy) ethyl] -N-
[(3-oleoylamino) propyl] -dimethylammonium chloride-N-[(2-lauroyloxy) ethyl] -N-
[(3-Docosyloylamino) propyl] -dimethylammonium chloride-N-[(2-stearoyloxy) ethyl) -N-
[(3-oleoylamino) propyl] -dimethylammonium chloride-N-[(2-stearoyloxy) ethyl) -N-
[(3-Stearoylamino) propyl] -N- (2-
Hydroxyethyl) -methylammonium-methylphosphate-N-[(2-hardened tallow-derived alkyloyloxy) ethyl] -N-[(2-hardened tallow-derived alkanoylamino)
Ethyl] -dimethylammonium chloride-N, N-di [(2-cured tallow-derived alkyloyloxy) ethyl] -dimethylammonium chloride-N, N-di [(2-cured tallow-derived alkyloyloxy) ethyl] -N- (2-hydroxyethyl) -methylammonium chloride-N, N-di [(2-cured tallow derived alkanoylamino) ethyl] -dimethylammonium chloride-N, N-di [(3-cured beef derived Alkanoylamino) propyl] -dimethylammonium chloride-N, N-di [(2-stearoyloxy) ethyl]-
Dimethyl ammonium chloride N, N-di [(2-stearoyloxy) ethyl]-
N- (2-hydroxyethyl) ・ methylammonium ・
Methyl sulfate-N, N-di [(3-hardened tallow-derived alkanoylamino) propyl] -N- (2-hydroxyethyl) -methylammonium-p-toluenesulfonate.

Examples of the compound represented by the general formula (4) are as follows. -N-[(2-hardened tallow-derived alkyloyloxy) ethyl] -N-hardened tallow-derived alkyl-dimethylammonium chloride-N-[(3-hardened tallow-derived alkanoylamino) propyl] -N-hardened tallow-derived alkyl -Dimethylammonium chloride-N- (hardened beef tallow-derived alkyloxycarbonylmethyl) -N-hardened beef tallow-derived alkyl-dimethylammonium chloride.

Examples of the compound represented by the general formula (5) are as follows. -Alkyl-1-methyl-3-[(2
-Cured tallow-derived alkanoylamino) ethyl] imidazolinium chloride-2-oleyl-1-methyl-3-[(2-oleoylamino) ethyl] imidazolinium chloride-2-Cured tallow-derived alkyl-1- Methyl-3-[(2
Hardened tallow-derived alkyloyloxy) ethyl] imidazolinium chloride.2-oleyl-1-methyl-3-[(2-oleoyloxy) ethyl] imidazolinium chloride.

Examples of the compound represented by the general formula (6) are as follows. -Alkyl-1-methyl-1-[(2
-Hardened tallow-derived alkanoylamino) ethyl] imidazolinium chloride-2-oleyl-1-methyl-1-[(2-oleoylamino) ethyl] imidazolinium chloride-2-Hardened tallow-derived alkyl-1- Methyl-1-[(2
Hardened tallow-derived alkyloyloxy) ethyl] imidazolinium chloride.2-oleyl-1-methyl-1-[(2-oleoyloxy) ethyl] imidazolinium chloride.

Preferred compounds among these quaternary ammonium salts are as follows.・ Di (alkyl derived from hardened beef tallow) ・ Dimethyl ammonium chloride ・ Dioleyl ・ Dimethyl ammonium ・ Chloride ・ Di (alkyl derived from hardened beef tallow) ・ Polyoxyethylene ・
Ethyl ammonium ethylsulfate ( "polyoxyethylene" group herein -. (.N showing a CH ₂ CH ₂ O) groups represented by _n H is a number of 6-8) - (2-dodecyl) hexadecyl -Trimethylammonium chloride-N-[(2-hardened tallow-derived alkyloyloxy) ethyl] -N-[(3-hardened tallow-derived alkanoylamino)
Propyl] -dimethylammonium chloride-N-[(2-lauroyloxy) ethyl] -N-
[(3-Docosyloylamino) propyl] -dimethylammonium chloride-N-[(2-hardened tallow-derived alkyloyloxy) ethyl] -N-[(2-hardened tallow-derived alkanoylamino)
Ethyl) -dimethylammonium chloride-N, N-di [(2-hardened tallow-derived alkyloyloxy) ethyl] -dimethylammonium chloride-N, N-di [(2-hardened tallow-derived alkyloyloxy) ethyl] -N- (2-hydroxyethyl) -methylammonium chloride-N, N-di [(3-hardened beef tallow derived alkanoylamino) propyl] -dimethylammonium chloride-N, N-di [(2-hardened beef derived Alkanoylamino) ethyl] -dimethylammonium chloride-N-[(2-cured tallow-derived alkyloyloxy) ethyl] -N-cured tallow-derived alkyl-dimethylammonium chloride-N- (cured tallow-derived alkyloxycarboxymethyl) -N-Cured beef tallow derived alkyl dimethyl ammonium Roraido-2-hardened tallow-derived alkyl-1-methyl-3 - [(2
-Cured tallow-derived alkanoylamino) ethyl] imidazolinium chloride-2-Cured tallow-derived alkyl-1-methyl-3-[(2
-Cured tallow-derived alkyloyloxy) ethyl] imidazolinium chloride-2-Cured tallow-derived alkyl-1-methyl-1-[(2
-Cured tallow-derived alkanoylamino) ethyl] imidazolinium chloride-2-Cured tallow-derived alkyl-1-methyl-1-[(2
-Alkyloyloxy) ethyl] imidazolinium chloride derived from hardened tallow.

The content of the component (c) in the water repellent composition of the present invention is 0.01 to 5% by weight, preferably 0.1 to 5% by weight. When the content of the component (c) is less than 0.01% by weight, the desired level of water repellency and durability of the present invention and suppression of stains are not satisfied at the same time, and when it exceeds 5% by weight, the level of the present invention is desired. Water repellent performance of is not achieved.

Further, in the water repellent composition of the present invention, if necessary, a plasticizer such as dibutyl phthalate, dibutyl adipate, diisobutyl adipate, tricresyl phosphate, and butyl butylphthalyl glycolate (water repellent composition 0 to 3% by weight), a softening agent such as silicone (0 to 5% by weight based on the water repellent composition), and other fragrances and pigments can be added.

[Water repellent article] The water repellent composition of the present invention described above is preferably filled in a container equipped with a device for spraying the liquid filled therein to the outside. Used for water repellent treatment in the form of water repellent articles. By using such a water repellent article of the present invention, the unevenness during the water repellent treatment is further suppressed, and the water repellent treatment is performed extremely effectively on the object to be partially subjected to the water repellent treatment. be able to. Examples of the container used for the water repellent article of the present invention equipped with a device for spraying the liquid filled inside to the outside include an aerosol type container, a trigger type container, a manual pump container and the like.

A water repellent article obtained by filling the water repellent composition of the present invention in an aerosol container is obtained by filling an aerosol can with the propellant and the water repellent composition of the present invention in a conventional manner. To be As the propellant, it is preferable to use at least one selected from the group consisting of liquefied propane, liquefied butane and dimethyl ether, or a combination of these with CO ₂ or N ₂ . The weight ratio of the propellant and the water repellent composition of the present invention is as follows: propellant / water repellent composition of the present invention = 3/97 to 50 /
50 is preferable, and more preferably 5/95 to 40/60.

[Water-repellent treatment method] The water-repellent treatment method of the present invention uses the above-mentioned water-repellent agent article, and the above-mentioned water-repellent agent composition is treated with an object to be subjected to water-repellent treatment (hereinafter referred to as "object"). It is sprayed on the surface of the object and the component (a) is evenly applied to the surface of the object. In this case, the object is not particularly limited, but can be particularly advantageously applied to, for example, a fiber woven fabric. In addition, there are glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, ceramic products, plastic, painted surface and plaster.
Further, as the fiber woven fabric, natural animal and vegetable fibers such as cotton, hemp, wool and silk, polyamide, polyester, polyvinyl acetal, polyacrylonitrile, polyvinyl chloride,
Examples include various synthetic fibers such as polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers and asbestos fibers, or a woven fabric of these mixed fibers.

[0046]

INDUSTRIAL APPLICABILITY According to the present invention, a water repellent composition and a water repellent composition having excellent water repellent effect, high durability and no stain residue on an object to be treated in water repellent treatment. It is possible to provide a water repellent article containing a water repellent agent and a water repellent treatment method using the water repellent agent article.

[0047]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 44 and Comparative Examples 1 to 24 Preparation of Fluororesin Various fluororesins (component (a)) having the compositions shown in Tables 3 to 10 were prepared as follows. Methyl isobutyl ketone was used as a polymerization solvent, and azobisisobutyronitrile was used as a polymerization initiator. Polymerization temperature and time are 40 to 90 ° C, 5 to
It was about 20 hours. The molecular weight of the obtained fluororesin was determined by gel permeation chromatography (Gel Permeation Chromatography).
ation Chromatography).

Preparation of water repellent composition Various fluororesins obtained by the above method and the component (c) were
A water repellent composition was prepared by dissolving or dispersing it in the component (b) shown in Tables 3 to 10 or other components. Incidentally, (c)
The following were used as ingredients. In the formula below, the R group represents a group represented by (C-1) to (C-11). (C-1): Di (alkyl derived from hardened beef tallow), dimethyl ammonium chloride

[0050]

[Chemical 19]

(C-2): Dioleyl dimethyl ammonium chloride

[0052]

[Chemical 20]

(C-3): Di (alkyl derived from hardened beef tallow), polyoxyethylene (n = 6 to 8) ethylammonium, ethylsulfate

[0054]

[Chemical 21]

(C-4): N-[(2-hardened tallow-derived alkyloyloxy) ethyl] -N-[(3 hardened tallow-derived alkanoylamino) propyl] .dimethylammonium.
Chloride

[0056]

[Chemical formula 22]

(C-5): N, N-di-[(2-cured tallow-derived alkyloyloxy) ethyl] -N- (2-hydroxyethyl) -methylammonium chloride

[0058]

[Chemical formula 23]

(C-6): N, N-di-[(2-hardened tallow-derived alkanoylamino) ethyl] .dimethylammonium chloride

[0060]

[Chemical formula 24]

(C-7): N- (hardened tallow-derived alkyloxycarbonylmethyl) -N- (hardened tallow-derived alkyl)
・ Dimethyl ammonium chloride

[0062]

[Chemical 25]

(C-8): 2-Alkyl-1-derived from hardened beef tallow
Methyl-1-[(2-cured tallow-derived alkanoylamino) ethyl] imidazolinium chloride

[0064]

[Chemical formula 26]

(C-9): 2-Alkyl-1-derived from hardened beef tallow
Methyl-1-[(2-hardened tallow-derived alkyloyloxy) ethyl] imidazolinium chloride

[0066]

[Chemical 27]

(C-10): 2-Alkyl-1-derived from hardened beef tallow
Methyl-3-[(2-hardened tallow-derived alkanoylamino) ethyl] imidazolinium chloride

[0068]

[Chemical 28]

(C-11): 2-Alkyl-1-derived from hardened beef tallow
Methyl-3-[(2-cured tallow-derived alkyloyloxy) ethyl] imidazolinium chloride

[0070]

[Chemical 29]

Preparation of water repellent article When evaluated using an aerosol container, the water repellent composition /
The container was filled so that the propellant was 80/20 (weight ratio). As propellant, liquefied propane / liquefied butane = 50 /
A mixture of 50 (weight ratio) was used.

Performance Evaluation With respect to the water repellent article of the present invention and the comparative water repellent article obtained by the above method, the water repellency, its durability and the stain residue were evaluated by the following methods. The results are shown in Tables 11-13. (I) Pretreatment of fiber woven fabric for water repellent treatment Pretreatment was carried out according to A method of JIS-L-1096 6.23.1. That is, first, a test piece made of a 20 cm × 20 cm fiber woven fabric (polyester or cotton) was prepared. And washing machine (water capacity
40-70 liters, rotating blade rotation speed 65-90 rpm, rotating blade rotation angle 180-240 °, spin-drying tank rotation speed 500-72
Put water at about 40 ° C up to the level line of a water tank of 0 rpm, inner diameter 40-55 cm), add the specified detergent to JIS K 3371 (synthetic detergent for clothing) at a rate of 1 g / liter, and stir it thoroughly to remove the detergent. Dissolved. Add some load cloth to the three test pieces so that the bath ratio becomes 40/1 and add them to the washing liquid, and perform automatic washing operation (washing 12 minutes → drainage 2 minutes → centrifugal dehydration and spraying 2 minutes → water supply 3 ˜5 minutes → rinse 2 minutes → drainage 2 minutes → centrifugal dehydration and spray 2 minutes → centrifugal dehydration 4 minutes). The temperature of water used for rinsing was also set to about 40 ° C. After washing, the test pieces were drip dried. That is, without dehydrating the test piece, several parts were grasped such that the vertical direction was vertical, and the test piece was hung to dry at room temperature in a place without ventilation. (II) Water repellent treatment The test piece thus pretreated was sprayed with a water repellent composition onto the test piece from a distance of 20 cm using an aerosol container or a trigger container so that the test piece had a concentration of 60% owf. The test piece thus obtained was dried for 24 hours in an environment of 20 ° C. and 65% relative humidity.

(III) Evaluation of water repellency The test piece obtained above was subjected to a water repellency test (spray method) by the method shown below according to the method specified in JIS L-1092 to evaluate the water repellency. (1) Equipment and materials: The following equipment and materials were used. (a) Water repellency test device: The device shown in FIG. 1 was used. In FIG. 1, 1 is a glass funnel, 2 is a funnel holder, 3 is a rubber tube connecting the funnel and the spray nozzle, 4 is a spray nozzle, 5 is a stand, 6 is a test piece, 7 is a test piece holding frame, 8 Is a wooden holder. Further, an enlarged view of the spray nozzle 4 is shown in FIG. In addition, in FIG. 2, (a) is a front view,
(b) is a bottom view. The glass funnel 1 has a capacity of 250 ml or more, the spray nozzle 4 is capable of spraying 250 ml of water in 25 to 30 seconds, and the test piece holding frame 7 is made of metal having a diameter of 150 mm. (b) Water: Distilled water or ion-exchanged water was used, and the temperature during the test was set to 20 ± 2 ° C in principle, but in other cases, the temperature at that time was added. (2) Test method: 3 pieces of the test piece of about 20 × 20 cm obtained above
One piece is attached to each of the test piece holding frames 7 without wrinkling, and the water repellency test apparatus shown in FIG. 1 is used to align the center of the spray nozzle 4 with the center of the holding frame.
ml was put in the glass funnel 1 and sprinkled on the test piece 6 (time required: 25 to 30 seconds). Next, remove the holding frame 7 from the wooden holding tool 8, hold it horizontally at one end, with the front side of the test piece facing downward, and lightly touch the other end once with a solid object, rotate it 180 °, and operate as before. Dropped extra drops. The wet state of the test piece while being attached to the holding frame 7 was scored according to the judgment criteria shown in Table 1 and expressed as an average value of 3 times (up to an integer).

[0074]

[Table 1]

(IV) Evaluation of water repellency persistence (III) Evaluation of water repellency (2) In the test method "Move the center of the spray nozzle 4 to the center of the holding frame," and "Operate in the same manner as before. To remove excess water droplets. "
After repeating 50 times, the wet state of the test piece was scored according to the criteria shown in Table 1 by the method described in (III) and expressed as an average value of 3 times (up to an integer).

(V) Evaluation of Remaining Spots Regarding the remaining stains, the water repellent composition was sprayed onto a black wool cloth from a distance of 20 cm, and after the suspension was air-dried, the state of generation of stains was judged according to the criteria shown in Table 2. did.

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

[0084]

[Table 9]

[0085]

[Table 10]

Note) * 1:% by weight based on the total amount of the water repellent composition * 2: Perfluorooctylethyl acrylate C ₈ F ₁₇ C
₂ H ₄ OCOCH = CH ₂ * 3: Perfluoroisononylethyl acrylate (CF ₃ ) ₂ CF (CF ₂ ) ₆ C ₂ H ₄ OCOCH = CH ₂ * 4: Perfluorooctylethyl methacrylate C ₈ F
₁₇ C ₂ H ₄ OCOC (CH ₃ ) = CH ₂ * 5: Perfluoroisononyl hydroxyethyl acrylate (CF ₃ ) ₂ CF (CF ₂ ) ₆ C ₂ H ₄ (OH) OCOCH = CH ₂ * 6: Perfluoro Octylsulfonylpropylaminoethyl acrylate C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) C ₂ H ₄ OCOCH = CH ₂

[0087]

[Table 11]

[0088]

[Table 12]

[0089]

[Table 13]

[Brief description of drawings]

FIG. 1 is a front view of a water repellency test apparatus used in Examples.

FIG. 2 is an enlarged view of a spray nozzle, (a) is a front view and (b) is a bottom view.

[Explanation of symbols]

 1 Glass funnel 2 Funnel holder 3 Rubber tube 4 Spray nozzle 5 Stand 6 Test piece 7 Test piece holding frame 8 Wooden holder

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09K 3/18 102 D06M 13/463

Claims (5)

[Claims] 1. A fluororesin satisfying the following conditions (hereinafter
(a) component) 0.1 to 5% by weight, C1 to C3 alcohol (hereinafter referred to as (b) component) 90 to 99.89% by weight, and quaternary ammonium salt (hereinafter referred to as (c) component) 0.01 A water repellent composition, characterized by containing up to 5% by weight. Conditions Into a composition obtained by adding 1% by weight of component (a) to ethanol, method A of 6.23.1 of JIS-L-1096 (however,
The drying method shall be drip drying), and the pretreated polyester cloth is dipped and then dried for 24 hours in an environment of 20 ° C and 65% relative humidity.
When a water repellency test (spray method) is performed according to the method specified in 1092, a water repellency of 90 points or more should be obtained. 2. The water repellent composition according to claim 1, wherein the component (b) is ethanol. 3. The water repellent composition according to claim 1, wherein the quaternary ammonium salt as the component (c) is at least one selected from the compounds represented by formulas (1) to (6). [Chemical 1] [In the formula, R ¹ and R ^{2 are the} same or different and are linear or branched and have 8 carbon atoms.
22 alkyl groups, alkenyl groups or hydroxyalkyl groups. R ³ and R ^{4 are the} same or different and represent an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, or are represented by the formula: Represents a group represented by. Here, Z represents a hydrogen atom or a methyl group, and n represents a number of 1 to 10. X ⁻ : Indicates an anionic group. ] [Chemical 3] [In the formula, R ^{5 represents a} linear or branched alkyl group having 24 to 38 carbon atoms or a hydroxyalkyl group. R ⁶ : represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or has the formula: Represents a group represented by. Here, Z 1 and n have the above-mentioned meanings. ^{R 3, R 4, X -} : The meanings of the. ] [Chemical 5] [In the formula, R ⁷ and R ^{8 are the} same or different and have a linear or branched carbon number of 7 to
21 represents an alkyl group or an alkenyl group. Q ¹ and Q ^{2 are the} same or different and represent —COO— or —CONH—. A ¹ and A ^{2 are the} same or different and represent an alkylene group having 1 to 3 carbon atoms. ^{R 3, R 4, X -} : The meanings of the. ] [Chemical 6] ^{Wherein, R 2, R 3, R} 4, A 1, X -: The meanings of the. R ⁹ : Shows a linear or branched alkyl group having 8 to 22 carbon atoms or a hydroxyalkyl group. Y: -COO- or -OCO- is shown. ] [Chemical 7] [In formula, E: -NHCO- or -OCO- is shown. ^{R 3, R 7, X -} : The meanings of the. ] [Chemical 8] ^{Wherein, R 3, R 7, E} , X -: The meanings of the. ] 4. A repellant obtained by filling the water repellent composition according to claim 1 into a container equipped with a device for spraying a liquid filled inside the composition to the outside. Liquid drug articles. 5. The water repellent article according to claim 4 is used, and the water repellent composition according to any one of claims 1 to 3 is sprayed onto an object to be water repellent treated. A water repellent treatment method characterized by: