JPS60190408A - Water and oil-repellent composition - Google Patents

Abstract

PURPOSE:The titled composition that contains, as a major component, a copolymer from a polymerizable compound containing fluoroalkyl groups and a specific organosilicon compound, thus being capable of giving especially fiber products water and oil repellency without any adverse effect on their flexibility and touch. CONSTITUTION:A polymer which has been obtained by copolymerization of (A) 30-99.5wt% of a polymerizable compound, preferably bearing 6-20C perfluoroalkyl groups, such as perfluorooctylethyl acrylate, (B) 0.5-70wt% of an organosilicon compound of formula I (R<1> is monovalent unsaturated polymerizable organic group; R<2> is H, 20 or less C monovalent unsaturated hydrocarbon group; 0<a<2; 0<=b<4 and 0<a+b<4) such as an organopolysiloxane of formula II(m, n are positive numbers) and (C) 0-50wt% of an F-free polymerizable compound such as styrene is used as an major component and diluted with a solvent such as 1,1,1-trichloroethane to give the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water- and oil-repellent composition, particularly to a water- and oil-repellent composition that can impart water and oil repellency to textile products without impairing their flexibility and texture. It is something.

Water and oil repellents have conventionally been used as electrolyte combinations of compounds containing perfluoroalkyl groups, such as acrylic acid or methacrylic esters, or with such compounds and acrylic esters or styrene.

Copolymers with polymerizable compounds that do not contain fluorine atoms, such as hydrothermal maleic acid and vinyl chloride, are known. However, although these types of water and oil repellents have a considerable effect on oil repellency (j-F water-based agents do not necessarily show satisfactory effects, and textile products treated with these agents may be hard and stiff. This has the disadvantage that the textile product has a sticky feel and the original feel of the textile product is lost.

The present invention relates to a water- and oil-repellent composition that solves these disadvantages, and is composed of a) a fluoroalkyl group-containing polymerizable compound having 30 to 99.5 fluoroalkyl groups; unsaturated polymerizable organic group, R
2 is a hydrogen atom or a same or different unsubstituted or substituted monovalent saturated hydrocarbon group having 20 or less carbon atoms; 0<a<2.
0≦b<4 and 0<a+b<4) Contains as a structural unit an organosilicon compound 05 to 70%, c) a polymerizable compound containing no fluorine atom, O to 5ON. It is characterized by being made of a copolymer as the main ingredient.

That is, the present invention@ et al. conducted various studies on a slight water and oil repellent that does not have the disadvantages mentioned above.

When a textile product is treated with an organosilicon compound containing a fluoroalkyl group obtained by copolymerizing a polymerizable compound containing a fluoroalkyl group with an organosilicon compound containing a polymerizable unsaturated group, it becomes oil repellent. In addition, it provides excellent water repellency - in this case, the flexibility and texture of the textile product is not impaired, and it also provides stain resistance, slipperiness, and mold release properties, and it also provides various adhesives, especially silicone-based ones. It was discovered that this copolymer can be used as a mold release agent with excellent releasability and residual adhesive strength for adhesives, and a three-component copolymer is added to this copolymer with a polymerizable compound that does not contain fluorine. Improved solubility in door-machine solvents,
After confirming that the copolymer has the additional effect of improving water drainage, the present invention was completed by conducting research on the composition of this copolymer and the method for treating textile products using it.

The fluoroalkyl group-containing polymerizable compound as component a) constituting the water-repellent composition of the present invention may be a known compound that has been conventionally used in water and oil repellents of this type. Examples include unsaturated esters shown in
Preferably, it contains 20 perfluoroalkyl groups.

Next, the organosilicon compound as component b) to be copolymerized with component a) is represented by the general formula RB10, where R1 is an alkenyl group such as a vinyl group, an allyl group, or an acryloxy group. Same or different unsubstituted or substituted monovalent unsaturated polymerizable organic groups selected from alkyl groups, methacryloxyalkyl groups, etc. - R2 is a hydrogen atom or a methyl group, an ethyl group, a butyl group, an octyl group - a lauryl group, Alkyl groups such as stearyl groups, cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, aryl groups such as phenyl groups, tolyl groups and naphthyl groups, aralkyl groups such as 2-phenylethyl groups, or those bonded to carbon atoms of these groups. Interpolated or different unsubstituted or substituted monovalent saturated hydrocarbons selected from groups in which part or all of the hydrogen atoms are substituted with halogen atoms such as chlorine atoms and fluorine atoms, cyano groups, aono groups, epoxy groups, etc. group, a is O<a<2. b is (]≦b<4 and 0 < a + b < 4, and examples thereof include the following.

OH3 --8i-OI-1.

0) 1゜0H3- OH, -0HOOO(OH,), -81-□] (°"D~'" □3J O5i-081-0] 1 to \ to m, n is a positive number) Also, this common The fluorine-free polymerizable compound contained in the polymer as component C) may be used as necessary, but it may also be a known compound, including acrylic acid and its alkyl esters, methacrylic acid, etc. Acids and their alkyl esters, styrene/α-methylstyrene, chloromethylstyrene, ethylene, propylene, phthadiene.

Chloroprene, vinyl chloride, vinylidene chloride, vinyl carboxylate-acrylonitrile, divinylbenzene, acrylamide, methacrylamide, N-methy4-acrylamide, alkyl vinyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, glycidyl acrylate.

Examples include glycidyl methacrylate and Kumamoto maleic acid, but two or more of these may be used in combination.

The water- and oil-repellent product of the present invention has the above-described components a) and b) or a copolymer of components a) and b) and C) as a main ingredient, and each component in this copolymer is The copolymerization ratio of (a) is 30 to 99.5 because the higher the ratio of the fluoroalkyl group-containing polymerizable compound as the component, the better the water repellency but the lower the solubility in organic solvents. Weight % range.

Preferably it is 40 to 80% by weight and 14%.

b) If the proportion of the organosilicon compound as a component is too small, the property of improving water repellency and not impairing the flexibility of the textile product to be treated will not be exhibited; if it is too large, the water and oil repellency will be impaired. 05 to 70% by weight, preferably 5 to 50% by weight. In addition, if the blending ratio of the polymerizable compound that does not contain a fluorine atom as the component 0) is too large, the water and oil repellency will decrease. 1. Copolymerization of components a)-b) or a), b), and C) may be carried out by a known vinyl polymerization method (e.g., solution polymerization in the presence of a polymerization initiator, emulsion polymerization). In the case of solution polymerization, the polymerization initiator may be an organic peroxide such as benzoyl peroxide, t-butyl hydroperoxide-cumene hydroperoxide-di-t-butyl peroxide, or azobis Examples include azo compounds such as isobutyronitrile, and examples include hydrogen peroxide, ammonium peracetate, ammonium persulfate, etc. in the case of emulsion polymerization, but this copolymerization is performed using photosensitive compounds such as benzoin, benzophenone, etc. Photopolymerization may be carried out by irradiation with ultraviolet rays in the presence of UV light.

The water- and oil-repellent composition of the present invention has a copolymer obtained by the above method as a main ingredient, and when used, it contains aliphatic hydrocarbons and aromatic hydrocarbons.

By diluting chlorinated hydrocarbons, fluorinated hydrocarbons, ketones, esters, ether threads, alcohols, etc. with an appropriate organic solvent or water, or by dispersing it in the solvent to an appropriate concentration. However, this may also include various additives conventionally added to this type of water repellent and oil repellent, such as other water repellents, oil repellents, antistatic agents, flame retardants, I
! 7j Anti-wrinkle agents and the like may be added to the extent that they do not impede the object of the present invention.

To treat textile products with the composition of the present invention, the textile products may be dipped in this composition or applied to the textile products by spraying, etc., and then dried or further heated if necessary. flexibility.

It is possible to impart excellent water and oil repellency to the target textile product without impairing its texture, and it also imparts stain resistance, slipperiness, and mold release properties.

Next, examples of the present invention will be given.

Example 1. Comparative Example 1 Internal volume 300m1 equipped with stirrer, thermometer, reflux condenser
Purful 8172 with the formula OHOH0OOOH=OH in the flask of
4 11 18 g of orooctylethyl acrylate (hereinafter abbreviated as PFAO), 6 g of styrene, 6y of organopolysiloxane (formula %), 70 g of 1,1,1-trichloroethane, and 0.3 g of azobisinbutyronitrile. P was charged and a copolymerization reaction was carried out at 60°C for 15 hours under a nitrogen gas flow.

A viscous, pale yellow, transparent copolymer was obtained, with a nonvolatile content of 29.4%.

Next, this copolymer solution was diluted with 1.1.1-trichloroethane so that the solid content concentration was 1% to prepare a treatment bath, and a 65735 blended fabric of polyester cotton (hereinafter referred to as T/O) was added to this. ), cotton cloth, or nylon cloth is soaked and then squeezed with a mangle.

After air-drying and heating at 170°C for 2 minutes, treated fabrics were prepared, and the water repellency, imitation/lh properties, and texture (flexibility) were measured, and the results shown in Table 1 were obtained. It was done.

For comparison, treated fabrics were prepared in the same manner as above without using the organopolysiloxane mentioned above, but using a copolymer prepared by the same reaction as 12 g of styrene. When the texture was examined, the results shown in Table 1 were obtained.

Table 1 ■ Water repellency: Measured by JIS L-1079 spray method %% Oil repellency: Measured by 3M method ■■■ Texture: Measured using Ueno style texture meter 1
5 A constant bending resistance value of the treated fabric (expressed as !i+1).

Examples 2 to 6 Copolymers were prepared in the same manner as in Example 1, except that the organopolysiloxanes used in Example 1 were the following four citrons, and these were added in the amounts shown in Table 2. When this was used to treat T/O cloth in the same manner as in Example 1, the results shown in Table 2 were obtained.

(Type of organopolysiloxane) OH3 Siloxane A... 0H2=OCoo(OH2), -
--81 (081(OH,),).

16- Siloxane O...0H2=OHO00(OH2)3-
OH 1゛Siloxane D...OH=(3000(OH) -22
3 Examples 7 to 9, Comparative Examples 2 to 4 Example 1 with a weight ratio of PFAO/styrene/orkanosiloxane of 7515/20, and this P
A copolymer was prepared in the same manner as in Example 1 using FAO as the formula % lylate (hereinafter abbreviated as PFSAO) and styrene as methyl methacrylate (hereinafter as MMA). This was used to treat T 70 in the same manner as in Example 1, and its water repellency, oil repellency and texture were measured, and the results shown in Table 3 were obtained.

'zrs, ratio +s, a similar test was conducted using a copolymer obtained by the same method as above without adding organosiloxane, and the results shown in Table 3 were obtained.

20-Example 10. Comparative Example 5 -PFAO was added to the same flask used in Example 1.
75 g, Siloxane A used in Example 1.2 7.5
g, acetone 15g.

Formula 0. □H2,N■(oH3), 1.0g of lauryltrimethylammonium chloride represented by aze, formula
Polyoxyethylene lauryl ether (HL
B=16.9) 1.0. Pour 0.01 i' of L t-dodecyl mercaptan, 64.5 g of ion-exchanged water and 0.3 g of potassium persulfate, and heat at 60°C under a nitrogen gas stream.
When a copolymerization reaction was carried out for 8 hours, a milky white emulsion of a monocopolymer was obtained, and the nonvolatile content of this was 16.2 yen.

Next, make a treatment bath by diluting this emulsion with water so that the solid content concentration is 1:1, soak T10 cloth, cotton cloth, and nylon cloth in this, squeeze it with a mangle, and then heat it to 100℃.
2 minutes at 170℃ and 2 minutes at 170℃ to produce a treated cloth,
The water repellency, oil repellency and texture of these were measured and the results shown in Table 4 were obtained.

For comparison, the same test as above was conducted on an emulsion obtained in the same manner as described above using styrene instead of siloxane A, and the results were as shown in Table 4.

Table 4 Example 11. , Comparative Example 6 The copolymer solutions obtained in Example 1 and Comparative Example 1 were diluted with n-hexane so that the solid content concentration was 4%, and then applied to polyethylene laminate paper using a ÷14 percoder. When heated at 140°C for 20 seconds, the amount of solid matter received was about 0.3g/n? A polyethylene laminated paper was obtained.

Next, we measured the peeling force of this polyethylene laminate paper against an adhesive tape using a silicone adhesive KR-101-10 (part name manufactured by Shin-Etsu Chemical Co., Ltd.) and the residual adhesive strength of this adhesive tape against a stainless steel plate afterwards. As a result, the results shown in Table 5 were obtained.

Table 5

Claims (1)

[Claims] 1.a) Fluoroalkyl group-containing polymerizable compound 30-
99.5 weight cake R"5iO a 4 to a-b \N R is the same or different unsubstituted or substituted monovalent unsaturated polymerizable organic group, R2 is a hydrogen atom or the same or different having 20 or less carbon atoms unsubstituted or substituted monovalent saturated hydrocarbon group -0<a<2-0≦b<4 and 0
<a0b<4) Organosilicon compound 0.
A water- and oil-repellent composition comprising, as a main ingredient, a copolymer containing as a constituent unit 0-50% by weight of a polymerizable compound that does not contain fluorine atoms.