JP3403479B2 - 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. 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, a fluororesin (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 99.8 satisfying the following conditions are provided. A water repellent composition comprising 1% by weight and 0.1 to 5% by weight of a specific carboxylic acid ester (hereinafter referred to as component (c)) and containing no chlorine-based solvent. Is. Conditions Into the composition obtained by adding 1% by weight of the component (a) to ethanol, the 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.

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 good for treated products. 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 1]

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 2]

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 99.8% by weight, more preferably 94 to 99.6% by weight. If the compounding amount of the component (b) is less than 90% by weight, it is not preferable from the economical viewpoint, and if it is more than 99.8% by weight, the desired level of water repellency of the present invention cannot be achieved.

The carboxylic acid ester used as the component (c) of the water repellent composition of the present invention has the following general formula (1)
And the compounds represented by the general formula (2) or a mixture thereof. R ¹ COOR ² (1) [In the formula, R ¹ : a hydroxyl group, an acetyl group, and a carbon number of 2
22 which may be substituted with an acyloxy group or an aryl group, represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, or a hydroxyl group,
An acetyl group, an acyloxy group having 2 to 22 carbon atoms, or an aryl group which may be substituted with an alkyl group or alkenyl group having 1 to 20 carbon atoms is shown. R ² : represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, or substituted with a hydroxyl group or an alkyl group having 1 to 20 carbon atoms or an alkenyl group Represents an optionally substituted aryl group. ] ^{R 4 -OCO-R 3 -COOR 5} (2) wherein, R ^3: a hydroxyl group, an acetyl group, 2 carbon atoms
22 represents a linear or branched alkylene group having 1 to 20 carbon atoms, which may be substituted with an acyloxyl group or aryl group, or a hydroxyl group, an acetyl group, an acyloxy group having 2 to 22 carbon atoms or a carbon atom. The phenylene group which may be substituted with an alkyl group or an alkenyl group of the formula 1 to 20 is shown. R ⁴ and R ^{5 are the} same or different, and may be substituted with a hydroxyl group, an aryl group or an alkyloxycarbonyl group having 2 to 20 carbon atoms, which is linear or branched and has 1 carbon atom.
To 20 alkyl group or alkenyl group, or a hydroxyl group, a C2-20 alkyloxycarbonyl group, or a C1-20 alkyl group or an aryl group which may be substituted with an alkenyl group. In the compound represented by the general formula (1), examples of the R ¹ group include the following.

· Straight or branched chain carbon number 1, 5, 11, 17
Alkyl or alkenyl group of hydroxymethyl, hydroxyethyl, hydroxypentyl, dihydroxypentyl, hydroxydecyl, dihydroxydecyl, hydroxyheptadecyl, dihydroxyheptadecyl, etc. 1,
5, 11, 17 alkyl group or alkenyl group-A linear or branched alkyl group or alkenyl having 1, 5, 11, 17 carbon atoms substituted with a linear or branched C2-22 acyloxy group Group-A linear or branched alkyl group having 1, 5, 11, 17 carbon atoms having a phenyl group substituted (mono-substituted or di-substituted) with a linear or branched alkyl group having 1 to 20 carbon atoms, or Alkenyl group ・ Hydroxymethyl, hydroxyethyl, hydroxypentyl, dihydroxypentyl, hydroxydecyl, dihydroxydecyl, hydroxyheptadecyl, having a phenyl group substituted with dihydroxyheptadecyl group (mono-substituted or di-substituted) Carbon number 1, 5,
11 or 17 alkyl group or alkenyl group ・ Phenyl group substituted (mono- or di-substituted) with linear or branched alkyl group having 1 to 20 carbon atoms ・ Hydroxymethyl, hydroxyethyl, hydroxypentyl, dihydroxypentyl, hydroxy Phenyl group substituted with decyl, dihydroxydecyl, hydroxyheptadecyl, dihydroxyheptadecyl group (mono-substituted or di-substituted), phenyl group substituted with a straight-chain or branched-chain acyloxy group having 2 to 22 carbon atoms, straight-chain or branched A phenyl group in which a linear or branched alkyl or alkenyl group having 1, 5, 11, 17 carbon atoms substituted with an acyloxy group having 2 to 22 carbon atoms is a substituent (mono-substituted or di-substituted) in general Examples of the R ² group in the compound represented by the formula (1) include the following.

Linear or branched alkyl or alkenyl groups having 1 to 4 carbon atoms hydroxymethyl, hydroxyethyl, hydroxypropyl, dihydroxypropyl, hydroxypentyl,
Groups such as dihydroxypentyl, hydroxydecyl, dihydroxydecyl, hydroxyheptadecyl, dihydroxyheptadecyl, etc. ・ Phenyl group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms (mono-substituted or di-substituted) ・ hydroxymethyl, Phenyl group substituted by hydroxyethyl, hydroxypentyl, dihydroxypentyl, hydroxydecyl, dihydroxydecyl, hydroxyheptadecyl, dihydroxyheptadecyl group (mono-substituted or di-substituted) Examples of R ³ group in the compound represented by the general formula (2) The following may be mentioned.

A straight or branched chain carbon number of 1, 2, 4,
Substitute with 7,8,11,17 alkylene groups, hydroxymethylene, hydroxyethylene, hydroxypentylene, dihydroxypentylene, hydroxydecylene, dihydroxydecylene, hydroxyheptadecylene, dihydroxyheptadecylene, etc. A straight or branched chain carbon number 1,
2,4,7,8,11,17 alkylene group / straight or branched chain carbon number 2 to 22, substituted with a straight or branched chain carbon number 1, 2, 4, 7, 8 , 1
1, 17 alkylene group, having a phenyl group substituted (mono-substituted or di-substituted) with a linear or branched alkyl group having 1 to 20 carbon atoms, linear or branched carbon number 1, 2, 4, 7,8,11,17 alkylene groups ・ Hydroxymethyl, hydroxyethyl, hydroxypentyl, dihydroxypentyl, hydroxydecyl, dihydroxydecyl, hydroxyheptadecyl, phenyl groups substituted with dihydroxyheptadecyl groups (mono-substituted or di-substituted) Having 1 or 2 carbon atoms of a straight chain or a branched chain,
4, 7, 8, 11, 17 alkylene groups, unsubstituted phenylene groups, phenylene groups substituted (mono- or di-substituted) with linear or branched alkyl groups having 1 to 20 carbon atoms, hydroxymethyl, hydroxy Ethyl, hydroxypentyl, dihydroxypentyl, hydroxydecyl, dihydroxydecyl, hydroxyheptadecyl, phenylene group substituted (mono-substituted or di-substituted) with dihydroxyheptadecyl group ・ A straight-chain or branched-chain acyloxy group having 2 to 22 carbon atoms Substituted phenylene group-A straight-chain or branched-chain acyloxy group having 2 to 22 carbon atoms or a straight-chain or branched-chain alkyl group or alkenyl group having 1, 5, 11, 17 substituents (mono-substituted , Di-substituted) phenylene group in the compound represented by the general formula (2), examples of R ⁴ group and R ⁵ group include the following (R ⁴ group, R ^{The 5} groups may be the same or different).

Linear or branched alkyl or alkenyl group having 1 to 10 carbon atoms hydroxymethyl, hydroxyethyl, hydroxypentyl, dihydroxypentyl, hydroxydecyl, dihydroxydecyl, hydroxyheptadecyl, dihydroxyheptadecyl, etc. .A straight or branched chain carbon number 1-10 substituted with a phenyl group
Alkyl group or alkenyl group ・ Phenyl group substituted (mono-substituted or di-substituted) with a linear or branched alkyl group having 1 to 20 carbon atoms ・ Hydroxymethyl, hydroxyethyl, hydroxypentyl, dihydroxypentyl, hydroxydecyl, dihydroxy A phenyl group substituted with a decyl, hydroxyheptadecyl, or dihydroxyheptadecyl group (mono-substituted or di-substituted) / A straight-chain or branched-chain 1 substituted with a straight-chain or branched-chain alkyloxycarbonyl group having 2 to 20 carbon atoms To 10 alkyl groups Among the carboxylic acid esters represented by the general formula (1) or (2), preferred compounds are as follows.

Methyl dodecanoate, ethyl dodecanoate, butyl dodecanoate, methyl octadecanoate, ethyl octadecanoate, butyl octadecanoate, octadecanoic acid 2,3
-Dihydroxypropyl, methyl oleate, ethyl oleate, butyl oleate, 2,3-dihydroxypropyl oleate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-adipate
Ethylhexyl, dibutyl azelate, diisobutyl azelate, dihexyl azelate, di-2-ethylhexyl azelate, dibutyl sebacate, diisobutyl sebacate, dihexyl sebacate, di-2-ethylhexyl sebacate, dimethyl phthalate, diethyl phthalate. Dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate,
Diisononyl phthalate, octyl decyl phthalate,
Diisodecyl phthalate, butyl benzyl phthalate,
Butyl phthalyl butyl glycolate

[0024]

[Chemical 3]

More preferable examples of these carboxylic acid esters are as follows. Dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-ethylhexyl adipate, dimethyl phthalate, diethyl phthalate, diheptyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, phthalic acid -Octyl decyl, diisodecyl phthalate, butyl benzyl phthalate, butyl butyl phthalyl glycolate.

The content of the 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.
When the content of the component (c) is less than 0.1% 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.

Furthermore, in the water repellent composition of the present invention, if necessary, a quaternary ammonium salt, a softening agent such as silicone (0 to 5% by weight based on the water repellent composition), other fragrance, A pigment or the like 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.

[0031]

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.

[0032]

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 24 and Comparative Examples 1 to 24 Preparation of Fluororesin Various fluororesins (component (a)) having the compositions shown in Tables 3 to 7 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) shown in Tables 3 to 7 are dissolved in the component (b) shown in Tables 3 to 7 or other components or A water repellent composition was prepared by dispersing. Preparation of water repellent composition 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 The water repellent article of the present invention and the comparative water repellent article obtained by the above-described method were evaluated for water repellency, durability and stain residue by the following methods. The results are shown in Tables 8 and 9. (I) Pretreatment of fiber woven fabric for water repellent treatment Pretreatment was performed according to the method A of 6.2-3.1 of JIS-L-1096. 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 from a distance of 20 cm to the test piece 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 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 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).

[0037]

[Table 1]

(IV) Evaluation of water repellency lasting (III) Evaluation of water repellency (2) In the test method, "center the spray nozzle 4 at the center of the holding frame," and then "operate 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, a water repellent composition was sprayed onto a black wool cloth from a distance of 20 cm, and after the suspension was air-dried, the generation state of stains was judged according to the criteria shown in Table 2. did.

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

[0044]

[Table 6]

[0045]

[Table 7]

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

[0047]

[Chemical 4]

[0048]

[Table 8]

[0049]

[Table 9]

[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 tubes 4 spray nozzles 5 stand 6 test pieces 7 Test piece holding frame 8 wooden holder

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-294584 (JP, A) JP-A-50-140387 (JP, A) JP-A-59-59778 (JP, A) JP-A-61- 211390 (JP, A) JP 61-148208 (JP, A) JP 3-287615 (JP, A) JP 62-158730 (JP, A) JP 6-293882 (JP, A) International Publication 92/019663 (WO, A1) French Patent Invention 1438617 (FR, B1) Handbook Rubber / Plastic Compounds, Rubber Digest, October 30, 1993, Second Revised Edition, p. 163 (58) Areas (Int.Cl. ⁷ , DB name) C09K 3/18 102 D06M 15/277 D06M 23/06 C09D 127/12

Claims (4)

(57) [Claims] 1. A fluororesin satisfying the following conditions (hereinafter
(a) component) 0.1-5% by weight, C1-C3 alcohol (hereinafter referred to as (b) component) 90-99.8% by weight and general
One or more selected from compounds represented by formula (1) or (2)
Carboxylic acid ester (wherein, dividing the 8-acetylated sucrose
Ku) (hereinafter (c) referred to as components) containing 0.1 to 5 wt%,
A water repellent composition comprising no chlorine-based solvent . Conditions Into the composition obtained by adding 1% by weight of the component (a) to ethanol, the 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. R ¹ COOR ² (1) [In the formula, R ¹ : a hydroxyl group, an acetyl group, an acyl group having 2 to 22 carbon atoms.
Roxy or aryl may be substituted,
An alkyl group having 1 to 20 carbon atoms in a chain or a branched chain, or
Represents an alkenyl group, or a hydroxyl group, acetyl
Group, an acyloxy group having 2 to 22 carbon atoms or 1 to 20 carbon atoms
May be substituted with an alkyl group or an alkenyl group of
Represents an aryl group. R ² : linear or optionally substituted with a hydroxyl group
Represents a branched chain alkyl group having 1 to 20 carbon atoms, or
A droxyl group or an alkyl group having 1 to 20 carbon atoms
Represents an aryl group which may be substituted with an alkenyl group.
You ] ^{R 4 -OCO-R 3 -COOR 5} (2) wherein, R ^3: a hydroxyl group, an acetyl group, reed 2-22 carbon atoms
It may be substituted with a roxyl group or an aryl group,
Shows a straight or branched alkylene group having 1 to 20 carbon atoms.
Watermelon, hydroxyl group, acetyl group, carbon number 2-22
Is an acyloxy group or an alkyl group having 1 to 20 carbon atoms.
Or a phenylene group which may be substituted with an alkenyl group
Show. R ⁴ , R ⁵ : the same or different, hydroxyl group, aryl
Group or alkyloxycarbonyl group having 2 to 20 carbon atoms
Linear or branched carbon number 1 which may be substituted with
~ 20 alkyl or alkenyl groups, or
Hydroxyl group, C2-C20 alkyloxycarbo
Nyl group or C1-C20 alkyl group or alkyl
The aryl group which may be substituted with a kenyl group is shown. ] 2. The water repellent composition according to claim 1, wherein the component (b) is ethanol. 3. The water repellent composition according to claim 1 or 2 ,
A water-repellent article obtained by filling a container equipped with a device for spraying the liquid filled inside the container with the liquid. 4. Using the water repellent article of claim 3, wherein the claim 1 or 2 water repellent composition according, characterized in that spraying to the object to be water repellent repellent Water treatment method.