JP3279426B2 - Water repellent composition, water repellent article, and water repellent treatment 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 water repellent composition, a water repellent article, and a water repellent treatment method, and more particularly, to a water repellent material having good water repellency, high durability, and unpleasantness 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 spots are suppressed during the water-repellent treatment.

[0002]

2. Description of the Related Art A polymer of a polymerizable monomer containing a perfluoroalkyl group or a fluoroalkyl group in a molecule, or a polymerizable monomer of this type and another type of polymerizable monomer. The fluorine-based water repellent comprising a copolymer with a monomer is used in an amount of 0.05 to 2% owf (on the weight) per unit weight of the fiber to be subjected to the water repellent treatment, for example, a fiber fabric.
It exhibits excellent water-repellent effect and antifouling effect even in a relatively small amount of a relatively small amount of fabrics, and has recently attracted attention as a surface treatment agent for textile fabrics, leather, interiors, building materials and the like.

However, an aerosol containing a fluorine-based water repellent is sprayed on clothing or the like, or the water-repellent is washed with a chlorine-based solvent (dichloroethane, 1,1,1-trichloroethane, S-tetrachlorodifluoroethane, 1,1 , 2-trichloro-1,2,2-trifluoroethane, etc.), a mixed solvent obtained by adding a monohydric or dihydric alcohol to these chlorine-based solvents, or a petroleum-based solvent (mineral turpentine oil, etc.). When such a liquid is applied to a cloth, if the clothing or the like after the water-repellent treatment has a dark color such as black or dark blue, there is a problem that white stains stand out and significantly impair the appearance. In addition, although the water repellency of these water repellents immediately after the water repellency treatment is sufficiently recognized, there is a problem that the water repellency treatment must be frequently performed on clothing and the like because the effect is inferior in durability.

[0004] Accordingly, an object of the present invention is to provide a water repellent composition which is excellent in water repellency, has high durability, and has no stain remaining on an object to be treated. It is an object of the present invention to provide a water repellent article containing the agent composition and a water repellent treatment method using the water repellent article.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by using a specific composition, furthermore, an object to be subjected to a water-repellent treatment of this composition. The present inventors have found that the above object can be achieved by spraying on the liquid, and have completed the present invention.

That is, the present invention provides a fluoropolymer (hereinafter referred to as component (a)) 0.1 to 5% by weight and an alcohol having 1 to 3 carbon atoms (hereinafter referred to as component (b)) 90 to 9 which satisfies the following conditions.
9.8% by weight and a polymer having at least one bond selected from the group consisting of -NHCOO-bond, -NHCONH-bond and -NHCOS-bond (hereinafter referred to as component (c)) 0.1 to
It is intended to provide a water repellent composition containing 5% by weight. Condition 1% by weight of ethanol
(a) Dip the pretreated polyester cloth into the composition obtained by adding the components according to the method A of 6.23.1 of JIS-L-1096 (however, the drying method is drip drying). Then, a polyester cloth dried for 24 hours in an environment of 20 ° C. and 65% relative humidity is subjected to a water repellency test (spray method) in accordance with the method of JIS-L-1092, and has a water repellency of 90 points or more. Can be obtained.

Further, the present invention provides a water-repellent article obtained by filling the water-repellent composition into a container equipped with a device for spraying a liquid filled therein to the outside. is there. Further, the present invention provides a water-repellent treatment method, characterized by using the water-repellent article and spraying the water-repellent composition on an object to be subjected to water-repellent treatment. .

Hereinafter, the present invention will be described in detail. (Water repellent composition) The component (a) used in the water repellent composition of the present invention is a fluoropolymer that satisfies the above-mentioned conditions. Water repellency cannot be imparted. As the fluoropolymer used as the component (a) of the present invention,
For example, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₁ OCOCH = CH ₂ , CF ₃ (CF ₂ ) CH ₂ OCO
C (CH ₃ ) = CH ₂ ,

[0009]

Embedded image

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]

Embedded image

A polymer of an unsaturated ester represented by an acrylate or methacrylate containing a perfluoroalkyl group having 3 to 20 carbon atoms (hereinafter referred to as a fluorine-containing monomer), or such a fluorine-containing monomer And a copolymer with one or more compounds (provided that they have no fluorine-containing group; hereinafter, referred to as copolymerized monomers). In this case, as the copolymerized monomer, for example, ethylene, vinyl acetate, vinyl fluoride, vinyl chloride, vinylidene halide, acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, acrylic acid and its alkyl ester, methacrylic acid And its alkyl esters, acrylamide, methacrylamide, diacetone acrylamide, methylolated diacetone acrylamide or methacrylamide, vinyl alkyl ether, vinyl alkyl ketone,
Examples thereof include butadiene, isoprene, chloroprene, glycidyl acrylate, benzyl methacrylate, cyclohexyl methacrylate, and maleic anhydride.

In this case, the reaction molar ratio of the fluorine-containing monomer to the copolymerized monomer is preferably fluorine-containing monomer / copolymerized monomer = 100/0 to 20/80,
100/0 to 50/50 are particularly preferred. If the ratio is less than 20/80, the water repellent composition of the present invention cannot have the desired level of water repellency.

The method for producing the component (a) used in the present invention can be arbitrarily selected from various polymerization reaction systems and conditions.
Any of various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, and photopolymerization can be employed.
For example, a method in which a fluorine-containing monomer or a mixture of a fluorine-containing monomer and a copolymerized monomer (hereinafter referred to as a fluorine-containing monomer) is emulsified in water in the presence of a surfactant or the like and polymerized with stirring, or A method of dissolving the contained monomers and the like in an appropriate organic solvent and performing solution polymerization by the action of a polymerization initiator (a polymerization initiator such as a peroxide or an azo compound or radiation) may be employed.

The molecular weight of the fluoropolymer used as component (a) is preferably from 500 to 1,000,000, more preferably from 500 to 100,000.
0 is particularly preferred. (a) As commercially available fluoropolymers that can be used as components, DEFENSA MCF-312, DEFENSA MC
F-323 (registered trademark of Dainippon Ink and Chemicals, Inc.) and the like.

The compounding amount of the component (a) in the water repellent composition of the present invention is 0.1 to 5% by weight. If the amount of component (a) is less than 0.1% by weight, the resulting water repellent composition does not achieve the desired level of water repellency according to the present invention, while the amount is less than 5%.
Even if it exceeds 10% by weight, there is no significant improvement in water repellency.
It is not preferable from an economic viewpoint. The amount of the component (a) in the water repellent composition of the present invention is more preferably 0.2 to 3% by weight.
It is.

Used in the water repellent composition of the present invention
The component (b) is an alcohol having 1 to 3 carbon atoms, examples of which include methanol, ethanol, propanol, isopropanol, ethylene glycol and propylene glycol. Among them, ethanol and isopropanol are preferred in terms of suppressing stain residue, and ethanol is particularly preferred. The amount of the component (b) in the water repellent composition of the present invention is
90 to 99.8% by weight, more preferably 94 to 99.6% by weight. If the amount of component (b) is less than 90% by weight, it is not preferable from an economic viewpoint. If it is more than 99.8% by weight, the desired level of water repellency of the present invention cannot be achieved.

As the component (c) of the water repellent composition of the present invention, a polymer having at least one bond selected from the group consisting of a -NHCOO bond, a -NHCONH bond and a -NHCOS bond is used. . Such polymers include:
General formula (I)

[0019]

Embedded image

[Wherein, X and Y are the same or different and each represent -O (A
O) represents _p- , -NH- or -S-. Where A has 2 to 2 carbon atoms
3 represents an alkylene group, and p represents a number of 0 to 200.

[0021]

Embedded image

(When the group contains an aromatic ring, the aromatic ring may be substituted with one or more alkyl groups having 1 to 20 carbon atoms), or

[0023]

Embedded image

Represents a linear or branched alkylene group or alkenylene group having 1 to 40 carbon atoms which may be inserted.

[0025]

Embedded image

A linear or branched alkylene group or alkenylene group having 1 to 40 carbon atoms, into which the group represented by may be inserted. Here, the R ³ and R ⁴ groups may be the same or different and represent H, or may have a linear or branched carbon number of 1 to 20.
Represents an alkyl group or an alkenyl group, or-(B
O) _q H (B represents an alkylene group having 2 to 3 carbon atoms, and q represents 1
Indicates a number of ~ 200. ) Or an aryl group, a cyclohexyl group or a pyridyl group.
Z ^- is represents an anion group. Is preferred, and the polymer is obtained by the following production methods (i) to (ii).

<Production method (i) of component (c)> As shown in the following reaction formula, a polymer having a repeating unit represented by the general formula (I-1) is obtained by reacting diisocyanate D with compound E. Obtainable.

[0028]

Embedded image

[Wherein

[0030]

Embedded image

Represents a linear or branched alkylene or alkenyl group having 1 to 40 carbon atoms, into which the group represented by may be inserted. Here, the R ³ group has the above-mentioned meaning. R ¹ , X,
Y: Means as described above. As the diisocyanate D in the above reaction formula, an aromatic, aliphatic or alicyclic polyisocyanate having two or more isocyanate groups, a mixture of two or more thereof, and a modified polyisocyanate obtained by modifying these Are used, for example, the following are exemplified.

1,5-naphthylene-diisocyanate, 4,
4'-diphenylmethane-diisocyanate, 4,4'-diphenyl-dimethylmethane diisocyanate, di- and tetraalkyl-diphenylmethane-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, xylylene-diisocyanate, toluylene-diisocyanate , Butane-1,4-diisocyanate, hexane-1,6-diisocyanate,
Dicyclohexylmethane-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.

Examples of compounds used as compound E in the above reaction scheme are as follows. Polyether diol 1) A polymer obtained by polymerizing at least one selected from the group consisting of ethylene oxide, propylene oxide and tetrahydrofuran 2) Ethanediol, propanediol, hexanediol, methylhexanediol, heptanediol, octanediol 3) 1 2,2-polybutadiene diol, 1,4-polybutadiene diol 4) A diol obtained by adding ethylene oxide and / or propylene oxide to the diol described in the above 2), 3) 5) Butadiene monooxide and ethylene oxide and / or
Or a polymer of propylene oxide; a polymer of a polyhydric alcohol ester of an unsaturated carboxylic acid 1) ethylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, 2-hydroxypropyl mono (meth) acrylate, Homopolymers such as dipropylene glycol mono (meth) acrylate 2) The monomers described in 1) above and (meth) acrylates (methyl acrylate, methyl methacrylate, etc.),
Copolymers with vinyl acetate, etc.Polyesters, polyamides, polyester polyamides Polyesters, polyamides or polyesters obtained by using a polyhydric alcohol and a polycarboxylic acid and esterifying by a known method in the presence of a diamine or an amino alcohol if necessary Polyester polyamide having both ester group and amide group in the chain Polyacetal Diol obtained by reacting the above-mentioned diol with formaldehyde Polythioethers such as thiodiglycol alone or condensate of thiodiglycol and other glycols Polyamine For example, ethylenediamine, hexamethylenediamine, pentidine diaminodiphenylmethane, polyethylene polyamine, polypropylene polyamine, polybutylene polyamine, bis- (3-aminopropyl) -me Ruamine, bis- (3-aminopropyl) -cyclohexylamine, bis- (3-aminopropyl) -aniline, bis- (3-aminopropyl) -toluidine, diaminocarbazole, bis- (aminopropoxyethyl) -butylamine, tris -(3-aminopropyl) amine, N, N '
-Bis-carbonamidopropyl-hexamethylenediamine and the like.

An alkoxylated aliphatic, alicyclic,
Aromatic or heterocyclic amine ethanolamine, N-methylethanolamine, propanolamine, N-methylpropanolamine, N-
Oleylethanolamine, N-methyl-diethanolamine, N-butyl-diethanolamine, N-oleyl-diethanolamine, N-cyclohexyl-diethanolamine, N-methyl-diisopropanolamine, N-cyclohexyl-diisopropanolamine,
N, N-di (hydroxyethyl) aniline, N, N-di (hydroxyethyl) -p-toluidine, N, N-di (hydroxypropyl) -naphthylamine, N, N-di (hydroxyethyl) -α-amino Pyridine, di (hydroxyethyl) piperazine, polyethoxylated butyl-diethanolamine, polypropoxylated N-methyl-diethanolamine, tri (2-hydroxypropyl) amine, N,
N-di (2,3-dihydroxypropyl) -aniline, N,
N-methyl-N- (3-aminopropyl) ethanol obtained by hydrogenating an adduct of an alkoxylated amine and acrylonitrile, such as N'-dimethyl-N, N'-bis-hydroxypropyl-ethylenediamine Amine, N-cyclohexyl-N- (3-aminopropyl) propanol-2-amine, N, N-bis (3-aminopropyl) ethanolamine, N- (3-aminopropyl) diethanolamine, etc. (meth) acrylamide and diamine Or an adduct with a diol.

In carrying out the reaction represented by the above reaction formula, a catalyst such as an amine may be present, and by changing the charged molar ratio of diisocyanate D and compound E, the compound represented by the general formula (I-1) is obtained. The degree of repetition of the repeating unit can be adjusted. The repetition rate is generally 1 to 1000
It is about 0, preferably 5 to 10,000.

<(C) Component Production Method (ii)> Among the polymers having a repeating unit represented by the general formula (I-1) obtained by the above-mentioned production method (i), N is contained in the polymer main chain. For those having an atom (polymer having a repeating unit represented by the general formula (I-2)), the N atom is neutralized or quaternized according to the following formula, and is represented by the following general formula (I-3). To obtain a polymer having repeating units
(c) It can also be used as a component.

[0037]

Embedded image

[Where

[0039]

Embedded image

Represents a linear or branched alkylene or alkenylene group having 1 to 40 carbon atoms into which the group represented by is inserted. Here, R ³ has the above-mentioned meaning.

[0041]

Embedded image

Represents a linear or branched alkylene or alkenylene group having 1 to 40 carbon atoms into which the group represented by is inserted. Here, R ³ , R ⁴ and Z ⁻ have the above-mentioned meanings.

R ¹ , X: The meaning is as described above. In this case, a compound represented by the formula:
R ⁴ Z (R ⁴ has the above-mentioned meaning, Z represents a halogen atom, or a residue obtained by removing one alkyl group from dialkyl sulfate, or a hydrogen atom which can be dissociated as a proton from an acid molecule. Examples of the compound represented by the following formula are as shown in the following (1) and (2).

(1) As a neutralizing agent for N atoms, hydrochloric acid,
Examples include nitric acid, hypophosphorous acid, amidosulfonic acid, hydroxylamine-monosulfonic acid, acetic acid, sulfuric acid, glycolic acid, and lactic acid. (2) As quaternizing agents for N atoms, chloroacetic acid, bromoacetic acid, methyl chloride, butyl bromide, benzyl chloride, methyl bromide, ethylene chlorohydrin, ethylene bromhydrin, chloroacetate, chloroacetamide, bromoacetamide , Dibromoethane, chlorobromobutane, dibromobutane, dimethyl sulfate, diethyl sulfate, p-toluenesulfonic acid methyl ester.

Further, as a quaternization method for N atoms, N atoms present in the polymer main chain are neutralized by the above-mentioned neutralizing agent, and then alkylene oxide having 2 to 3 carbon atoms (ethylene oxide, propylene oxide or these compounds). ) Can be quaternized. In this case, the N atom is quaternized by a group represented by-(BO) _qH (wherein B and q have the same meanings as described above). A polymer in which the N atom present in the polymer main chain has been quaternized by such a method is also used as the component (c). here
In the general formula (I) representing the repeating unit of the component (c), preferred examples of the R ¹ group are as follows.

[0046]

Embedded image

Preferred examples of the R ² group in the repeating unit represented by the general formula (I) are as follows. − (CH ₂ ) ₂ −, − (CH ₂ ) ₃ −, − (CH ₂ ) ₄ −, − (CH ₂ ) ₆ −, −
(CH ₂ ) ₇ −, − (CH ₂ ) ₈ −,

[0048]

Embedded image

[0049] ^{wherein, (Z 1) -: Cl} -, NO 3 -, HSO 4 -, CH 3 COO -,

[0050]

Embedded image

[0051] CH ₃ -CH (OH) COO ^- show the. Below (Z ^{1) -} represents this meaning. ]

[0052]

Embedded image

[Wherein, R ⁴¹ : CH ₃ −, C ₂ H ₅ , CH ₃ (CH ₂ ) ₃ −,

[0054]

Embedded image

[0055] ^{(Z 2) -: Cl -} , Br -, CH 3 SO 4 - or C ₂ H ₅ S
O ₄ ^- is shown. Preferred examples of the R ² group in the repeating unit represented by the general formula (I) include polyethylene glycol (polymerization degree 1 to 200), polypropylene glycol (polymerization degree 1 to 200), and a copolymer of ethylene oxide and propylene oxide (polymerization). Residues excluding both terminal OH from the degree of 1 to 200) are also included.

Further, in the repeating unit represented by the general formula (I), the X group and the Y group are groups represented by —O (AO) _p — (wherein A and p have the same meanings as described above). In some cases, ie (c)
It is particularly preferred that the component is a polyurethane. The repeating unit represented by the general formula (I) has a repetition degree of 1 to 1000.
It is about 0, preferably 5 to 10,000. In the component (c) comprising a polymer having a repeating unit represented by the general formula (I), a diisocyanate D is used in combination with a triisocyanate (for example, phenyltriisocyanate), or a compound E is used as a trihydric alcohol (for example, glycerin or polyglycerin). ) May be used in combination to form a partially crosslinked polymer.

The amount of component (c) in the water repellent composition of the present invention is 0.1 to 5% by weight, preferably 0.5 to 3% by weight. (c) If the compounding amount of the component is less than 0.1% by weight, the desired level of water repellency, the sustainability thereof and the suppression of stains are not simultaneously satisfied. If the amount exceeds 5% by weight, the desired level of the present invention is obtained. 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 or butyl butyl phthalyl glycolate (water repellent composition) 0-3 wt%), a softening agent such as silicone (0-5 wt% based on the water repellent composition), other fragrances, pigments and the like.

[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 in the form of water repellent articles for water repellent treatment. By using such a water-repellent agent article of the present invention, the unevenness during the water-repellent treatment is further suppressed, and the water-repellent treatment is extremely effectively performed on an object to be partially subjected to the water-repellent treatment. be able to. Examples of the container equipped with a device for spraying the liquid filled therein to the outside used in the water repellent article of the present invention include, for example, an aerosol container, a trigger container, and a manual pump container.

The water repellent article obtained by filling the water repellent composition of the present invention into an aerosol container can be obtained by filling the water repellent composition of the present invention together with a propellant in an aerosol can according to a conventional method. Can 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 (propellant / water repellent composition of the present invention) = 3/97 to 50 /
50 is preferred, 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 article, and applies the above-mentioned water-repellent composition to an object to be subjected to water-repellent treatment (hereinafter referred to as an object). ), And the component (a) is evenly applied on the surface of the object. In this case, the object is not particularly limited, but can be particularly advantageously applied to, for example, a textile fabric. Others include glass, paper, wood, leather, fur, asbestos, brick, cement, hardware and oxides, ceramic products, plastics, painted surfaces and plasters.
In addition, as the textile fabric, animal and plant natural 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, and woven fabrics of mixed fibers thereof.

[0062]

According to the present invention, a water repellent composition which is excellent in water repellency, has high durability, and has no stain remaining on an object to be treated. And a water-repellent treatment method using the water-repellent article.

[0063]

EXAMPLES 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. In the examples, parts and percentages are by weight unless otherwise specified.

Examples 1 to 40 and Comparative Examples 1 to 24 Preparation of Fluoropolymer Various fluoropolymers having the compositions shown in Tables 3 to 8 ((a)
Component) was prepared as follows. Methyl isobutyl ketone was used as a polymerization solvent, and azobisisobutyronitrile was used as a polymerization initiator. The polymerization temperature and time are 40-90 ° C, 5
Approximately 20 hours. The molecular weight of the obtained fluoropolymer was measured by gel permeation chromatography (Gel
Permeation Chromatography).

Preparation of Water Repellent Composition Various fluoropolymers obtained by the above method and the component (c) are dissolved or dispersed in the component (b) or other components shown in Tables 3 to 8 to obtain a water repellent composition. An agent composition was prepared. still
(c) The component was prepared as follows.

(C-1): 200 parts of polytetramethylene ether glycol (hydroxyl value (OHV) 56, molecular weight 2000)
After adding 27.7 parts of hexamethylene diisocyanate, 75
The mixture was stirred and reacted at 10 ° C. for 10 hours. Analysis of the isocyanate groups was 1.2%. Then, after adding 8.7 parts of N-methyldiethanolamine, the mixture was stirred at 75 ° C. for 5 hours to carry out a chain extension reaction. Then, 750 parts of a 0.74% aqueous solution of hydroxyacetic acid are added with stirring, and hydroxyacetic acid and water are added to the polymer (c-1) having a solid content of 25% (number average molecular weight 10,000).
I got

(C-2): 200 parts of methyl ethyl ketone was added to 200 parts of polybutylene adipate having a terminal hydroxyl group (molecular weight: 2,000), and then 31.0 parts of xylylene diisocyanate, followed by stirring at 75 ° C. for 10 hours. Was. Next, 26.1 parts of N-stearyldiethanolamine was added, followed by stirring at 75 ° C for 5 hours to carry out a chain extension reaction. Then, 750 parts of 0.74% hydroxyacetic acid was added with stirring, the temperature was raised to 40 to 50 ° C, and the pressure was reduced. After removing the solvent in the system, a small amount of hydroxyacetic acid and water were further added to obtain a polymer (c-2) having a solid content of 25% (number average molecular weight 15,000).

(C-3): 200 parts of polyethylene glycol (molecular weight: 600) was mixed with 37.3 of hexamethylene diisocyanate.
After adding a part, the mixture was stirred and reacted at 75 ° C. for 10 hours,
(c-3) (number average molecular weight 100,000) was obtained.

(C-4): 225 parts of polypropylene glycol having an average molecular weight of 2,000, N-methyldiethanolamine 15
And 60 parts of isophorone diisocyanate were reacted under a nitrogen atmosphere at 120 to 125 ° C. for 4 hours.
Diluted in parts. Add 15 parts of dimethyl sulfuric acid, and add
And dried under reduced pressure to obtain a polymer (c-4) (number average molecular weight
50,000).

(C-5): 225 parts of polypropylene glycol having an average molecular weight of 3000, N-methyldiethanolamine 14
And 4,4'-dicyclohexylmethane diisocyanate were reacted under a nitrogen atmosphere at 120 to 125 ° C for 4 hours, and diluted with 200 parts of acetone. 14 parts of dimethyl sulfate was added, quaternized at 45 to 55 ° C., dried under reduced pressure, and polymer (c-
5) (number average molecular weight 500,000) was obtained.

(C-6): 270 parts of an oxyethylene / oxypropylene copolymer having an average molecular weight of 2400 (oxyethylene / oxypropylene = 3/7), 15 parts of N-ethyldiethanolamine, and hexamethylene diisocyanate
45 parts were reacted under nitrogen atmosphere at 120 ~ 125 ℃ for 4 hours,
Diluted with 200 parts of acetone. Add 15 parts of dimethyl sulfate,
The polymer was quaternized at 45 to 55 ° C and dried under reduced pressure to obtain a polymer (c-6) (number average molecular weight 200,000).

(C-7): IMPRANIL DLS (registered trademark), an aqueous dispersion of a weakly anionic aliphatic polyester polyurethane (Bayer Co., 50% solid content). (c-8): Bayer, IMPRANIL DLV® anionic aliphatic polyester polyurethane aqueous dispersion (40% solids).

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 a propellant, liquefied propane / liquefied butane = 50 /
A mixture of 50 (weight ratio) was used.

Evaluation of Performance The water repellent article of the present invention and the comparative water repellent article obtained by the above-mentioned methods were evaluated for water repellency, their persistence, and stain residue by the following methods. The results are shown in Tables 9 to 11. (I) Pre-treatment of fiber woven fabric to be subjected to water-repellent treatment The pre-treatment was performed according to the method A of JIS-L-1096 6.23.1. That is, first, a test piece composed of a 20 cm × 20 cm fiber woven fabric (polyester or cotton) was prepared. And the washing machine (water capacity
40-70 liters, rotating blade rotation speed 65-90rpm, rotating blade rotation angle 180-240 °, dehydration tank rotation speed 500-72
(0 rpm, 40-55 cm inside diameter) Pour water at about 40 ° C up to the level line of a water tank, add the specified detergent to JIS K 3371 (synthetic detergent for clothing) at a rate of 1 g / liter, and stir well to mix the detergent. Dissolved. Add a small number of load cloths to the three test pieces so that the bath ratio becomes 40/1 and put them into the washing liquid. Automatic washing operation (washing 12 minutes → drainage 2 minutes → centrifugal dehydration and spray 2 minutes → water supply 3) ５5 minutes → rinse 2 minutes → drain 2 minutes → centrifugal dehydration and spray 2 minutes → centrifugal dehydration 4 minutes). The temperature of the water used for rinsing was also about 40 ° C. After washing, the test pieces were drip-dried. That is, without dehydrating the test piece, several places were grasped so that the vertical direction was vertical, and the test piece was suspended and dried at room temperature in a place without ventilation. (II) Water-repellent treatment The water-repellent composition was sprayed 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 60% owf per test piece. 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 pieces obtained above were subjected to a water repellency test (spray method) according to the method specified in JIS L-1092 by the following method to evaluate 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, and 8 is a wooden holder. FIG. 2 is an enlarged view of the spray nozzle 4. In FIG. 2, (a)
Is a front view, and (b) is a bottom view. 250ml for glass funnel 1
The spray nozzle 4 having the above capacity and capable of spraying 250 ml of water in 25 to 30 seconds, and the test piece holding frame 7 made of metal having a diameter of 150 mm were used. (b) Water: Distilled water or ion-exchanged water was used, and the temperature during the test was, as a rule, 20 ± 2 ° C. In other cases, the temperature at that time is added. (2) Test method: Approximately 20 × 20 cm test pieces obtained above
The test piece holding frame 7 was attached one by one so as not to cause wrinkling, and the center of the spray nozzle 4 was made to coincide with the center of the holding frame using a water repellency test device shown in FIG.
ml was placed in the glass funnel 1 and sprayed on the test piece 6 (required time: 25 to 30 seconds). Next, the holding frame 7 is detached from the wooden holder 8, held at one end horizontally, with the front side of the test piece facing down, lightly applied once to the solid object at the other end, and further turned 180 °, and operated as before. Extra drops were dropped. The wet state of the test piece was scored according to the criterion shown in Table 1 while being attached to the holding frame 7, and represented by an average value of three times (up to an integer).

[0076]

[Table 1]

(IV) Evaluation of water repellency persistence (III) Evaluation of water repellency (2) In the test method, "operate in the same manner as before" from "Make the center of the spray nozzle 4 coincide with the center of the holding frame." To drop extra water drops. "
After the test was repeated 50 times, the wet state of the test piece was scored by the method described in (III) in accordance with the criteria shown in Table 1, and expressed as an average value of three times (up to an integer).

(V) Evaluation of stain residue Regarding stain residue, the water repellent composition was sprayed onto a black wool fabric from a distance of 20 cm, and after hanging and air-drying, the state of occurrence of the stain was judged according to the criteria shown in Table 2. did.

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

[Table 4]

[0082]

[Table 5]

[0083]

[Table 6]

[0084]

[Table 7]

[0085]

[Table 8]

Note) * 1: 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: Perfluoroisononylhydroxyethyl 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 9]

[0088]

[Table 10]

[0089]

[Table 11]

[Brief description of the drawings]

FIG. 1 is a front view of a water repellency test device 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]

 DESCRIPTION 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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-58-76481 (JP, A) JP-A-2-2099984 (JP, A) JP-A-58-214587 (JP, A) JP-A-7-78 173774 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06M 13/00-15/715 C09K 3/18

Claims (6)

(57) [Claims] 1. A fluoropolymer satisfying the following conditions (hereinafter referred to as component (a)): 0.1 to 5% by weight, an alcohol having 1 to 3 carbon atoms (hereinafter referred to as component (b)): 90 to 99.8% by weight, and A polymer having at least one bond selected from the group consisting of -NHCOO-, -NHCONH-, and -NHCOS- bonds (hereinafter referred to as component (c)), containing 0.1 to 5% by weight. Solution composition. Conditions A method prepared by adding 1% by weight of the component (a) based on ethanol to the composition obtained in 6.23.1 A of JIS-L-1096 (however,
Drying method shall be drip drying), soak the pretreated polyester cloth and then dry the polyester cloth at 20 ° C and 65% relative humidity for 24 hours in accordance with JIS-L-
When a water repellency test (spray method) is performed according to the method specified in 1092, a water repellency of 90 points or more is obtained. 2. The water repellent composition according to claim 1, wherein the component (c) is a polymer having a repeating unit represented by the following general formula (I). Embedded image [Wherein, X and Y are the same or different and are -O (AO) _p- , -NH-
Or -S-. Here, A represents an alkylene group having 2 to 3 carbon atoms, and p represents a number of 0 to 200. Embedded image (When the group contains an aromatic ring, the aromatic ring may be substituted with one or more alkyl groups having 1 to 20 carbon atoms), or ] Represents a linear or branched alkylene group or alkenylene group having 1 to 40 carbon atoms which may be inserted. Embedded image Represents a linear or branched alkylene group or alkenylene group having 1 to 40 carbon atoms, into which a group represented by may be inserted. Here, the groups R ³ and R ⁴ are the same or different and represent H, or represent a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, or-(BO) _q H (B Represents an alkylene group having 2 to 3 carbon atoms, and q represents a number of 1 to 200), or represents an aryl group, a cyclohexyl group or a pyridyl group. Z ^- is represents an anion group. ] 3. The water repellent composition according to claim 1, wherein the component (b) is ethanol. 4. The composition according to claim 1, wherein the component (c) is a polyurethane.
The water repellent composition according to any one of claims 1 to 3. 5. A water-repellent composition obtained by filling the water-repellent composition according to claim 1 into a container equipped with a device for spraying a liquid filled therein to the outside. Liquid medication articles. 6. Use of the water repellent article according to claim 5 and spraying the water repellent composition according to any one of claims 1 to 4 onto an object to be subjected to water repellency treatment. A water repellent treatment method characterized by the following.