JP2011162790A - Water-repellent oil-repellent agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-repellent oil-repellent agent using a copolymer of perfluoroalkyl alkyl(meth)acrylate having low bioaccumulation potential as an active ingredient, having a low curing temperature and good touch feeling of a fabric when the fabric is treated with the water-repellent oil-repellent agent. <P>SOLUTION: A water-repellent oil-repellent agent comprises an aqueous emulsion prepared by dispersing a fluorine-containing copolymer in water with a polyethylene oxide addition type nonionic surfactant. The fluorine-containing copolymer has a copolymer composition of (A) 61.6-80 wt.% perfluoroalkyl alkyl acrylates expressed by general formula, C<SB>n</SB>F<SB>2n+1</SB>C<SB>m</SB>H<SB>2m</SB>OCOCR=CH<SB>2</SB>(R: hydrogen or methyl group, (n): 4, 5 or 6, (m): 1, 2, 3 or 4) or corresponding methacrylates , (B) 5-80 wt.% benzyl acrylate or benzyl methacrylate, (C) 5-80 wt.% (i) vinylidene chloride and (ii) polyethylene glycol methacrylate or polyethylene glycol monomethacrylate and (D) 0.5-40 wt.% cross-linkable group-containing polymerizable monomer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a water / oil repellent. More specifically, the present invention relates to a water / oil repellent that has a low curing temperature during water / oil repellent treatment and that makes the fabric subjected to the water / oil repellent treatment feel better.

The expression of water and oil repellency is attributed to the low surface energy of fluorine. In general, fluorine-containing acrylate polymers are often used as active ingredients of water and oil repellents. In various studies so far, the crystallinity of the fluoropolymer has been required for practical use of water and oil repellency. In particular, the hydrophobicity of the fluoropolymer has a side chain fluoroalkyl content. Depending on the number of carbon atoms in the group, it has been recognized that crystallinity is observed when the number of carbon atoms is 8 or more (Non-patent Document 1) .

  Therefore, the fluoropolymer having a short fluoroalkyl group with a side chain fluoroalkyl group having a carbon number of 7 or less, particularly 6 or less, has low crystallinity or does not exist, and water repellent performance that can withstand practical use cannot be obtained. Has been considered. In addition, since the water and oil repellents are required to have washing durability and friction durability, a fluorine-containing acrylate polymer having a long side chain is used.

  However, a polymer having a side chain fluoroalkyl group having 8 or more carbon atoms is very hard because it has high crystallinity, and the flexibility of the fiber product is impaired. Furthermore, since high-temperature curing is required for water repellent finishing, there are problems such as discoloration of fibers. In addition, since long side chains having 8 or more carbon atoms are excessively hydrophobic, a large amount of emulsifier is required in the production of water and oil repellents.

The present applicant previously dispersed a copolymer of a fluoroalkyl group-containing polymerizable monomer and vinylidene chloride or benzyl (meth) acrylate and a carboxyl group-containing water-soluble polymer in water with a nonionic surfactant. We have proposed water and oil repellents consisting of aqueous emulsions. The fluoroalkyl group of the fluoroalkyl group-containing polymerizable monomer that is copolymerized with vinylidene chloride or benzyl (meth) acrylate is said to be a perfluoroalkyl group having 4 to 20 carbon atoms. The perfluoroalkyl group is a mixture of 6 to 14 carbon atoms with an average of 9.0 (Patent Document 1) .

  Therefore, if the fluoropolymer having a short fluoroalkyl group having 6 or less carbon atoms can exhibit water and oil repellency, it will be possible to obtain a water and oil repellent with excellent flexibility and washing durability. It is done.

A surface treatment agent exhibiting excellent water repellency, oil repellency, and antifouling properties using a polymer having 1 to 6 carbon atoms and a short fluoroalkyl group in the side chain has also been proposed. The alkyl group-containing monomer has the general formula
Rf-YO-CO-CX = CH ₂
X: F, Cl, Br, I, CFX ¹ X ² , CN, C1-C20 fluoroalkyl group, benzyl group, phenyl group
Y: an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group,
CH ₂ CH ₂ NR ¹ SO ₂ groups, CH ₂ CH (OY ¹ ) CH ₂ groups
Rf: a fluorine-containing monomer compound represented by a fluoroalkyl group having 1 to 6 carbon atoms, and an acrylic acid derivative with X = H is regarded as a comparative production example, and a methacrylic acid derivative with X = CH ₃ is also conscious (Patent Document 2) .

Further, (a) an Rf group-containing monomer in which the melting point of the microcrystal derived from the Rf group of the homopolymer does not exist or is 55 ° C. or less, and the glass transition point of the homopolymer is 20 ° C. or more and (b ) A water / oil repellent composition comprising a copolymer containing an Rf group-free monomer having a crosslinkable functional group as a polymerization unit as an essential component, and excellent in an article even when treated at a low temperature. A water- and oil-repellent material that can be imparted with water- and oil-repellency, can be processed with a soft texture, and has excellent durability has also been proposed (Patent Document 3) .

  Here, perfluoroalkylalkyl (meth) acrylate is used as component monomer (a), but 2-butanone oxime addition of ω-isocyanate alkyl (meth) acrylate is used as component monomer (b). Monomers, pyrazole adducts, ε-caprolactam adducts and the like are used in the copolymerization reaction.

Japanese Patent Laid-Open No. 11-80710 JP 2004-352976 A WO 2004/035708

Adhesion Vol.5 No.16 pp.22-22 (2006)

  An object of the present invention is a water- and oil-repellent agent comprising, as an active ingredient, a perfluoroalkylalkyl (meth) acrylate copolymer having a low bioaccumulation property. The copolymer is obtained by copolymerizing a special monomer. In addition, the present invention provides a water and oil repellent that has a low curing temperature during water and oil repellent treatment, and that makes the texture of the water and oil repellent treated fabric good, using this copolymer as an active ingredient. It is in.

The object of the present invention is to provide a general formula (A)
C _n F _{2n + 1} C _m H _2m OCOCR = CH ₂
(Wherein R is a hydrogen atom or a methyl group, n is 4, 5 or 6, and m is 1, 2, 3 or 4) or a corresponding methacrylate 61.6 to 80% by weight
(B) benzyl acrylate or benzyl methacrylate 5-80% by weight
(C) (i) vinylidene chloride and (ii) polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate 5-80% by weight
and
(D) Crosslinkable group-containing polymerizable monomer 0.5 to 40% by weight
This is achieved by a water / oil repellent comprising an aqueous emulsion in which a fluorine-containing copolymer having the following copolymer composition is dispersed in water with a polyethylene oxide addition type nonionic surfactant .

  The water / oil repellent according to the present invention is a water / oil repellent containing a perfluoroalkylalkyl (meth) acrylate copolymer having low bioaccumulation as an active ingredient, and the copolymer is a special monomer. In addition, the curing temperature during water / oil repellent treatment using this copolymer as an active ingredient is low, and the texture of the water / oil repellent treated fabric is improved. . In particular, with regard to the texture, there is an effect that the treated fabric after the water / oil repellent treatment is not hard, but rather soft and the texture is improved. Further, there is provided a water / oil repellent exhibiting sufficient water / oil repellency not only for synthetic fibers but also for natural fibers and having excellent washing durability.

Also, in the curing for cross-linking the cloth and the water / oil repellent, the reaction becomes insufficient if the curing crosslinking temperature is low, and the desired performance can be obtained by dropping off the water / oil repellent forming polymer. Disappear. For this reason, curing conditions such as 180 ° C. for 1 minute or 170 ° C. for 1 to 2 minutes are generally used, and rarely conditions such as 160 ° C. for 3 minutes are used, but the water and oil repellent of the present invention is used. Then, as will be described later in each example, curing at a lower temperature of 150 ° C. for 3 minutes is possible.

General formula of component (A)
C _n F _{2n + 1} C _m H _2m OCOCR = CH ₂
R: hydrogen atom, methyl group
n: 4, 5 or 6
m: 1, 2, 3 or 4
Preferred examples of the perfluoroalkylalkyl (meth) acrylate represented by the following include the following compounds.
C ₄ F ₉ CH ₂ CH ₂ OCOCH = CH ₂
C ₄ F ₉ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂
C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂
C ₆ F ₁₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂

These component (A) perfluoroalkylalkyl (meth) acrylates are subjected to a copolymerization reaction in such a proportion that they occupy about 61.6 to 80% by weight, preferably about 64 to 80% by weight, in the resulting copolymer. As a result of copolymerization of the component (A) monomer, an aqueous dispersion having excellent emulsification stability can be formed, and water and oil repellency can be exhibited.

  Component (B), benzyl acrylate or benzyl methacrylate, is a copolymerization reaction in such a proportion that it accounts for about 5 to 80% by weight, preferably about 5 to 50% by weight, more preferably about 5 to 35% by weight in the copolymer. To be served. By copolymerization of benzyl (meth) acrylate, the copolymer exhibits good film-forming properties and orientation.

The component (C) (i) vinylidene chloride and (ii) polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate are about 5 to 80% by weight, preferably about 5 to 60% by weight, more preferably about 5% in the copolymer. It is used for the copolymerization reaction at a ratio of ˜40% by weight.

Examples of the crosslinkable group-containing polymerizable monomer (D) include epoxy group-containing monomers such as allyl glycidyl ether and glycidyl (meth) acrylate, N-methylol (meth) acrylamide, N-butoxymethylol ( N-methylol group-containing monomers such as (meth) acrylamide, hydroxy such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate Alkyl group-containing monomer, (meth) acrylamide, N-methylacrylamide, diacetone acrylamide, formula
CH ₂ = C (CH ₃ ) CON ^-- N ⁺ (CH ₃ ) ₂ CH ₂ CH (OH) CH ₃
CH ₂ = C (CH ₃ ) CON ^-- N ⁺ (CH ₃ ) ₃
Amide group-containing monomers such as compounds represented by the formula, aziridinyl group-containing monomers such as aziridinylethyl (meth) acrylate, ethylene glycol di (meth) acrylate, polyoxyethylene di (meth) acrylate, polyoxypropyl Examples include polyol poly (meth) acrylates such as glycol di (meth) acrylate, and hydrophilic monomers are preferably used.

  When these crosslinkable group-containing polymerizable monomers are further copolymerized, the fluorine-containing copolymer used as an effective water- and oil-repellent component becomes stronger in adhesion to substrates such as fibers, and repellent. The effect of improving the durability, washing resistance, dry cleaning resistance, etc. of the water / oil repellent agent is observed, and there is also a secondary effect that the polymerization stability during emulsion polymerization is generally improved. For this reason, the component (D) is used in such a proportion that it accounts for about 0.5 to 40% by weight, preferably about 1 to 15% by weight in the copolymer.

The copolymerization reaction using each of these polymerizable monomers is carried out by an emulsion polymerization method in the presence of a polyethylene oxide addition type nonionic surfactant or the nonionic surfactant and a glycol compound emulsification aid. Is called. The surfactant emulsifier is used in an amount of about 1 to 20% by weight, preferably about 1 to 10% by weight, and the emulsification aid is about 10 to 100% by weight, preferably about 15 to Used at a ratio of 70% by weight.

The polyethylene oxide adduct type nonionic surfactants, such as polyethylene oxide with aliphatic alcohol, and aromatic alcohols, alkyl ethers, oleic acid, C ₁₂ -C ₁₈ alkyl amine, reaction products of sorbitan fatty acids Is used in a ratio of about 80% by weight or less, preferably about 30 to 80% by weight, based on the total amount of the polyethylene oxide addition type cationic surfactant.

As the glycol compound as emulsifying aid used in combination with emulsifiers, such as ethylene glycol, polyethylene (n = 2 to 4 or more) glycol, propylene glycol, polypropylene (n = 2 to 4 or more) glycol or These terminal monomethyl ethers, hexylene glycol, propylene glycol adducts of glycerin and the like can be mentioned, and a polypropylene glycol compound having a molecular weight of about 300 to 3000 or hexylene glycol is preferably used.

  Prior to the copolymerization reaction, an emulsification treatment of a polymerizable monomer mixture containing perfluoroalkylalkyl (meth) acrylate and other polymerizable monomers in the presence of a surfactant emulsifier and an emulsification aid is performed. Is called. The emulsification treatment is sufficiently performed using a high-pressure homogenizer or the like.

  The copolymerization reaction of the emulsified polymerizable monomer mixture is performed in the presence of a radical polymerization initiator added thereto. As the radical polymerization initiator, any of organic peroxides, azo compounds, persulfates and the like can be used, but preferably a water-soluble azo compound such as 2,2′-azobis (2-amidinopropane) Dihydrochloride or the like is used in a proportion of about 0.1 to 10% by weight, preferably about 0.5 to 7% by weight, based on the total weight of the polymerizable monomer mixture.

  The copolymerization reaction is carried out in an aqueous medium at about 40 to 80 ° C. for about 1 to 10 hours, thereby forming an aqueous dispersion (aqueous emulsion) as a stock solution having a solid concentration of about 15 to 35% by weight. As the aqueous medium, in addition to water alone, a water-soluble organic solvent preferably accounting for about 1 to 30% by weight in the aqueous medium, for example, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, Ethylene glycol, propylene glycol, dipropylene glycol or glycols such as monomethyl ether or tripropylene glycol are used. In the reaction, a molecular weight regulator can also be used. For example, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, and tertiary dodecyl mercaptan are preferably used.

  The aqueous dispersion as the stock solution thus obtained is diluted with water, preferably about 0.1 to 10% by weight with ion-exchanged water, and then fibers, cloth, woven fabric, paper, film, It is effectively applied as a water and oil repellent agent to carpets or fabric products made from filaments, yarns, fibers and the like. As an application method, coating, dipping, spraying, padding, roll coating, or a combination of these methods is used. For example, the solid content concentration of the bath is set to about 0.1 to 10% by weight, and it is used as a pad bath. The material to be treated is padded in this pad bath, and then the excess liquid is removed with a squeeze roll and dried, and the adhering fluorine-containing copolymer amount to the material to be treated is adhered to a ratio of about 0.01 to 10% by weight. . Thereafter, depending on the type of material to be treated, generally, drying is performed at a temperature of about 80 to 120 ° C. for about 1 minute to about 2 hours, and then about 150 to 180 ° C. for about 1 to 3 minutes, preferably Is cured under low curing conditions of about 150 to 170 ° C. for about 1 to 3 minutes, particularly preferably 150 ° C. for 3 minutes, and the water and oil repellent treatment is completed.

  Next, the present invention will be described with reference to examples. The percentage in parentheses is% by weight.

Example 1
2- (n-perfluorohexyl) ethyl methacrylate 78.5 g (61.6%)
Benzyl methacrylate 22.4g (17.6%)
2-hydroxyethyl methacrylate 5.6g (4.4%)
Polyethylene glycol (n = 4) monomethacrylate 4.2g (3.3%)
(Nippon Oil Products PE-200)
Lauryl mercaptan (chain transfer agent) 0.5g
Polyoxyethylene polycyclic phenyl ether (surfactant) 7.0g
(Japan emulsifier product New Coal-740)
Acetone (solvent) 76.7g
Ion exchange water 225.8g

The above components were placed in a 1 L glass reactor and mixed, and further emulsified and mixed using a high-pressure homogenizer, and the resulting emulsion was replaced with nitrogen gas for 30 minutes. Then gradually increase the temperature in the reactor and when it reaches 40 ° C,
Vinylidene chloride 11.2g (8.8%)
N-methylolacrylamide (dissolved in 29.3 g of ion-exchanged water) 5.6 g (4.4%)
2,2'-azobis (2-amidinopropane) dihydrochloride 2.8g
(Dissolved in 30.4 g of ion exchange water)
(Total amount 500.0 g including the total amount of ion-exchanged water 285.5 g), the internal temperature was gradually raised to 70 ° C., and the reaction was carried out at that temperature for 4 hours. After completion of the reaction, the reaction mixture was cooled to obtain an aqueous dispersion having a solid content concentration of 25.2% by weight. The melting point (DSC method) of the copolymer obtained by separation from the aqueous dispersion was 44 ° C.

  The solid content concentration of the aqueous dispersion thus obtained was diluted with ion exchange water to a concentration of 0.5% by weight, and a cotton cloth, a cotton-polyester blended cloth, a polyester cloth or a nylon cloth was immersed in the water-repellent property. (JIS L1092 compliant) and oil repellency (AATCC-TM118-1992 compliant) were measured. The wet pick-up after squeezing is 100% for cotton and blended fabrics, 40% for polyester and 60% for nylon. Drying conditions are 80 ° C for 10 minutes and curing conditions are all 150. C., 3 minutes.

The evaluation criteria for water repellency were performed in accordance with the JIS regulations.
Water repellency state
100 No moisture or water droplets on the surface
90 Slightly adhering water droplets to the surface
80 Individual partial wetting on the surface
70 Wetting on half of the surface
50 Wetting on the entire surface
0 Both front and back sides are completely wet

The evaluation standard for oil repellency is that one drop of test solution is dropped on an oil-repellent treated cloth in accordance with the above AATCC regulations, the state after 30 seconds is observed, and the dropped test solution is retained on the cloth. If this is the case, test with a test solution with a higher number, and with a test solution that is limited to be retained on the fabric, evaluate it based on the oil repellency rating in the following table (note that 100% Nujol is (If not retained, set to 0)
surface tension
Oil repellency No. test solution ( mN / m, 25 ℃)
8 n-heptane 20.0
7 n-octane 21.8
6 n-decane 23.5
5 n-dodecane 25.0
4 n-tetradecane 26.7
3 n-Hexadecane 27.3
2 Nujol-n-hexadecane 29.6
(Volume ratio 65%: 35%)
1 Nujol 31.2

Furthermore, the texture was evaluated by tactile sensation, and the following four stages of evaluation were performed.
◎: Very soft ○: Soft △: Equivalent to or slightly harder than the original fabric ×: Harder than the original fabric

Example 2
In Example 1, a copolymerization reaction was carried out using the same amount of 2- (n-perfluorobutyl) ethyl acrylate instead of 2- (n-perfluorohexyl) ethyl methacrylate, and the resulting diluted aqueous dispersion was obtained. Water repellency / oil repellency tests using the liquid and evaluation of the texture were performed.

Example 3
In Example 1, instead of 2- (n-perfluorohexyl) ethyl methacrylate, a copolymerization reaction was carried out using the same amount of 2- (n-perfluorohexyl) ethyl acrylate, and the resulting diluted aqueous dispersion Water repellency / oil repellency tests using the liquid and evaluation of the texture were performed.

Example 4
In Example 1, a copolymerization reaction was carried out using the same amount of 2- (n-perfluorobutyl) ethyl methacrylate instead of 2- (n-perfluorohexyl) ethyl methacrylate, and the resulting diluted aqueous dispersion was obtained. Water repellency / oil repellency tests using the liquid and evaluation of the texture were performed.

Example 5
In Example 1, 35.0 g of hexylene glycol was used as an emulsifying aid, acetone was not used, and the total amount of ion-exchanged water was changed to 327.2 g, and a copolymerization reaction was performed. Water repellency / oil repellency tests using the liquid and evaluation of the texture were performed.

Example 6
In Example 1, in the charged comonomer of the copolymerization reaction, for each of the following components, the copolymerization reaction was carried out by changing the amount of each component as follows, and the diluted aqueous dispersion obtained The water repellency / oil repellency test and the texture were evaluated.
2- (n-perfluorohexyl) ethyl methacrylate 87.2 g (64.0%)
Benzyl methacrylate 22.4g (16.4%)
2-hydroxyethyl methacrylate 5.6g (4.1%)
Polyethylene glycol (n = 4) monomethacrylate 4.2g (3.1%)
Vinylidene chloride 11.2g (8.2%)
N-methylolacrylamide 5.6g (4.1%)
In addition, 35.0 g of hexylene glycol was used as an emulsification aid, acetone was not used, and the total amount of ion-exchanged water was changed to 318.5 g.

Example 7
In Example 1, the following respective components in the comonomer charged in the copolymerization reaction were subjected to a copolymerization reaction by changing the amount of each component as follows (however, N-methylol acrylamide) Instead, N-methylol methacrylamide was used), and the water- and oil-repellency tests and the texture of the resulting diluted aqueous dispersion were evaluated.
2- (n-Perfluorohexyl) ethyl methacrylate 100.6 g (79.1%)
Benzyl methacrylate 7.4g (5.8%)
2-hydroxyethyl methacrylate 5.6g (4.4%)
Polyethylene glycol (n = 4) monomethacrylate 4.2g (3.3%)
Vinylidene chloride 3.8g (3.0%)
N-methylol methacrylamide 5.6g (4.4%)
In addition, 35.0 g of hexylene glycol was used as an emulsification aid, acetone was not used, and the total amount of ion-exchanged water was changed to 327.5 g.

Comparative Example 1
In Example 1, in the charged comonomer of the copolymerization reaction, for each of the following components, the copolymerization reaction was carried out by changing the amount of each component as follows, and the diluted aqueous dispersion obtained The water repellency / oil repellency test and the texture were evaluated.
2- (n-perfluorohexyl) ethyl methacrylate 58.3 g (45.6%)
Benzyl methacrylate 29.2g (22.8%)
2-hydroxyethyl methacrylate 5.6g (4.4%)
Polyethylene glycol (n = 4) monomethacrylate 11.7g (9.1%)
Vinylidene chloride 17.5g (13.7%)
N-methylolacrylamide 5.6g (4.4%)
In addition, 35.0 g of hexylene glycol was used as an emulsification aid, acetone was not used, and the total amount of ion-exchanged water was changed to 326.8 g.

Comparative Example 2
In Example 1, instead of 2- (n-perfluorohexyl) ethyl methacrylate in the raw materials for the copolymerization reaction, 2- (perfluoroalkyl) ethyl methacrylate (perfluoroalkyl group is C ₆ 6%, _{C 8 52%, C 10 24} %, C 12 7%, C 14 2%, a mixed group of total 91%, the average number of carbon atoms is 8.8) the same amount (the same ratio) using copolymerization reaction is carried out The water- and oil-repellency tests and the texture of the resulting diluted aqueous dispersion were evaluated.

Comparative Example 3
2- (n-perfluorohexyl) ethyl methacrylate 66.8g ( 45.5% )
Stearyl acrylate 74.2g (50.5%)
Lauryl mercaptan 0.5g
Stearyl trimethyl ammonium chloride [surfactant] 7.8g
Polyoxyethylene polycyclic phenyl ether (Newcol-740) 9.2g
Polypropylene glycol 28.5g
(Nippon Oil Products Uniol D-400; molecular weight 400)
Ion exchange water 244.1g
The above components were placed in a 1 L glass reactor and mixed, and further emulsified and mixed using a high-pressure homogenizer, and the resulting emulsion was replaced with nitrogen gas for 30 minutes. Then gradually increase the temperature in the reactor and when it reaches 40 ° C,
N-methylolacrylamide (dissolved in 30 g of ion-exchanged water) 5.9 g (4.0%)
2,2'-azobis (2-amidinopropane) dihydrochloride 3.0g
(Dissolved in 30 g of ion exchange water)
(Total amount 500.0 g including the total amount of ion-exchanged water 304.1 g), the internal temperature was gradually raised to 70 ° C., and the reaction was carried out at that temperature for 4 hours. After completion of the reaction, the reaction mixture was cooled to obtain an aqueous dispersion having a solid content concentration of 32.8% by weight. Using the obtained aqueous dispersion, the water and oil repellency tests and the texture were evaluated in the same manner as in Example 1.

Comparative Example 4
In Comparative Example 3 , instead of 2- (n-perfluorohexyl) ethyl methacrylate , the same amount of 2- (n-perfluorohexyl) ethyl acrylate was used, and the obtained aqueous dispersion was used. In the same manner as above, the water and oil repellency tests and the texture were evaluated.

The results obtained in Examples 1 to 7 and Comparative Examples 1 to 4 are shown in the following table. In this table, the melting point (DSC method) of each copolymer obtained except Comparative Examples 3 to 4 is also shown. As for water repellency and oil repellency, the evaluation results are shown in the form of water repellency evaluation / oil repellency evaluation.
table
Melting point water repellency evaluation / oil repellency evaluation
Example (℃) Cotton cloth blended cloth Polyester cloth Nylon cloth texture Example 1 44 100/3 100/5 100/5 100/6 ○
〃 2-70 / 4 50/4 70/4 70/5 ○
〃 3 44 70/6 80/6 70/6 70/6 ○
− 4-70 / 4 80/4 70/4 100/4 ○
45 5 45 100/3 100/5 100/5 100/6 ○
〃 6 45 100/4 100/5 100/5 100/6 ◎
46 7 46 100/5 100/5 100/6 100/6 ◎
Comparative Example 1 45 100/1 100/4 100/4 100/5 ○
〃 2 84 100/5 100/6 100/6 100/6 △
３ 3 100/2 100/3 100/4 100/4 ◎
〃 4 70/5 70/6 80/6 80/7 ◎

Claims (4)

(A) General formula
C _n F _{2n + 1} C _m H _2m OCOCR = CH ₂
(Wherein R is a hydrogen atom or a methyl group, n is 4, 5 or 6, and m is 1, 2, 3 or 4) or a corresponding methacrylate 61.6 to 80% by weight
(B) benzyl acrylate or benzyl methacrylate 5-80% by weight
(C) (i) vinylidene chloride and (ii) polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate 5-80% by weight
and
(D) Crosslinkable group-containing polymerizable monomer 0.5 to 40% by weight
A water / oil repellent comprising an aqueous emulsion in which a fluorine-containing copolymer having the following copolymer composition is dispersed in water with a polyethylene oxide addition type nonionic surfactant . The water / oil repellent according to claim 1, wherein a fluorine-containing copolymer in which the (D) component crosslinkable group-containing polymerizable monomer is a hydrophilic monomer is used. The water / oil repellent according to claim 1, wherein a fluorine-containing copolymer having a copolymer composition of (A) component of 64 to 80% by weight is used. The water / oil repellent according to claim 1, which can be cured under a curing condition of 150 ° C for 3 minutes.