JPH06248257A - Solvent type water and oil repellent composition - Google Patents

Abstract

PURPOSE:To obtain a solvent type water and oil repellent composition capable of imparting high water and oil repellency without any problems in the destruction of ozone. CONSTITUTION:This solvent type water and oil repellent composition comprises a solvent composed of an aliphatic hydrocarbon or a mixture of the aliphatic hydrocarbon with a polar solvent, an oil-soluble emulsifying agent and a fluorine-based water and oil repellent synthesized in the presence thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solvent-type water / oil repellent composition which does not require the use of a fluorine-based or chlorine-based solvent.

[0002]

2. Description of the Related Art In recent years, water- and oil-repellent treatments for clothes, carpets, upholstery, etc. have been actively carried out, and solvent-type water- and oil-repellent agents that can be easily used at home, or aerosol-type water and oil-repellent agents have attracted attention Has been done. However, fluorine-based water and oil repellents generally include trichlorotrifluoroethane and 1,1,1-trichloroethane, which have a high solubility for fluorine compounds. As a result, there is concern about the destruction of the ozone layer, and the use of water and oil repellents has begun to be restricted. Although a water- and oil-repellent agent using a solvent that does not cause a problem of ozone destruction is being studied, the current situation is that satisfactory performance such as low water- and oil-repellency and poor storage stability has not yet been obtained.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to newly provide a solvent-type water / oil repellent composition which has no ozone depletion problem and which can impart high water / oil repellency. is there.

[0004]

The present invention has been made to solve the above-mentioned problems, and comprises a solvent consisting of an aliphatic hydrocarbon or a mixture of an aliphatic hydrocarbon and a polar solvent, an oil-soluble emulsifier, and fluorine. A solvent-type water and oil repellent composition comprising a water- and oil-repellent agent.

Although various kinds of aliphatic hydrocarbons can be used in the present invention, mineral spirits, decane, undecane and dodecane are particularly preferable. A propylene glycol derivative is preferable as the polar solvent, and in particular, it has a high flash point and an appropriate boiling point, and therefore propylene glycol monomethyl ether, propylene glycol monoethyl ether, and their acetates, and dipropylene glycol,
Dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether are preferred. The mixing ratio (weight ratio) of the aliphatic hydrocarbon and the polar solvent is 100: 0.
〜30: 70 is suitable, especially 90:10 to 50: 5.
0 is preferred.

In addition to the above solvents, any solvent can be further mixed and used. For example, esters such as methyl acetate, ethyl acetate and butyl acetate, ketones such as methyl isobutyl ketone, methyl ethyl ketone and acetone, alcohols such as ethyl alcohol, butyl alcohol and isopropyl alcohol, tetrahydrofuran, toluene and xylene are preferable. It can be given as something. If necessary, a chlorine-based solvent such as 1,1,1-trichloroethane or perchloroethylene, or a fluorine-based solvent such as perfluorotributylamine or perfluoro-2-butyltetrahydrofuran may be mixed.

Any oil-soluble emulsifier can be widely used as long as it is soluble in the solvent to be used, and a nonionic surfactant is particularly preferable. The nonionic surfactant is preferably a polyhydric alcohol ester of a long-chain alkylcarboxylic acid. As the long-chain alkylcarboxylic acid, a linear alkylcarboxylic acid having 8 to 24 carbon atoms, particularly 12 to 18 carbon atoms is preferable. As the polyhydric alcohol forming an ester, a polyhydric alcohol having a hydroxy number of 2 to 8 is preferable. As a specific oil-soluble emulsifier,
Preferred examples include propylene glycol monostearate, glycerin monostearate, pentaerythritol monostearate, and polyoxyethylene glycol monostearate. The amount of oil-soluble emulsifier used is 0.1 with respect to the fluorine-based water and oil repellent.
10 to 10% by weight is suitable, and 0.5 to 5% by weight is particularly preferable.

The structure of the fluorine-based water and oil repellent agent according to the present invention is not particularly limited, but it is a polymer of α, β unsaturated monomers containing a polyfluoroalkyl group (hereinafter referred to as R _f group) or Copolymers are preferred. In particular, a polymer having an R _f group-containing acrylate or methacrylate as a monomer, particularly a copolymer of it with one or more kinds of other radically polymerizable unsaturated bond-containing monomers (hereinafter referred to as comonomers) is preferable. As the R _f group-containing acrylate or methacrylate (hereinafter referred to as R _f (meth) acrylate), for example, the following compounds can be preferably mentioned (wherein R ¹ represents a hydrogen atom or a methyl group). Further, two or more kinds of R _f (meth) acrylate can be used in combination, and in particular, two or more kinds of compounds having different polyfluoroalkyl group carbon numbers can be used in combination.

CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ R _f CH ₂ = C (R ¹ ) COOCH (CH ₃ ) CH ₂ R _f CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ N (CH ₃ ) COR _f CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ N (C ₂ H ₅ ) COR _f CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ N (C ₃ H ₇ ) COR _f CH ₂ = C ( R ¹ ) COOCH ₂ CH ₂ N (CH ₃ ) SO ₂ R _f CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ N (C ₂ H ₅ ) SO ₂ R _f CH ₂ = C (R ¹ ) COOCH ₂ CH ₂ N (C ₃ H ₇ ) SO ₂ R _f CH ₂ = C (R ¹ ) COOCH (CH ₂ Cl) CH ₂ OCH ₂ CH ₂ N (CH ₃ ) SO ₂ R _f

R _f has 1 to 20 carbon atoms, preferably 4 to
16 linear or branched polyfluoroalkyl groups, usually with a perfluoroalkyl group at the end, are selected, but those containing a hydrogen atom or chlorine atom at the end, or oxypoly Fluoroalkylene-containing groups and the like can also be used. A preferred embodiment of R _f is
A perfluoroalkyl group represented by C _n F _{2n + 1} (where n is an integer of 4 to 16), and n is preferably 6 to 12.

The comonomer is preferably (meth) acrylate or (meth) acrylamide, but is not limited thereto. In addition, (meth) acrylate means both acrylate and methacrylate,
The same applies to (meth) acrylamide and the like. In particular, long-chain alkyl (meth) acrylates, and long-chain alkyl methacrylates are particularly preferable as the comonomer because of the solubility of the resulting copolymer. A long-chain alkyl group having 6 to 20 carbon atoms is suitable. Examples of other comonomers include olefins, halogenated olefins, and styrenes. Specific examples thereof will be given below, but the present invention is not limited thereto.

Ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, styrene, α-methylstyrene, p-methylstyrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, polyoxyalkylene (meth) acrylate, ( (Meth) acrylamide, diacetone (meth) acrylamide, methylolation (meth)
Acrylamide, N-methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, benzyl (meth) acrylate, isocyanatoethyl (Meth) acrylate, cyclohexyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, maleic anhydride, hydroxyethyl (meth) acrylate, (meth) acrylate N-vinylcarbazole having polysiloxane, blocked isocyanate-containing (meth) acrylate.

The composition of the present invention comprises the above-mentioned R _f -group-containing α, β unsaturated compounds in the presence of an oil-soluble emulsifier in a solvent comprising the above-mentioned aliphatic hydrocarbon or a mixture of an aliphatic hydrocarbon and a polar solvent. It is preferably a composition obtained by polymerizing a monomer with a comonomer in some cases, and a composition obtained by diluting the obtained composition. This polymerization is usually carried out using a polymerization initiator. R _f group-containing α, β
Examples of the polymerization initiator used in the production of the unsaturated monomer polymer or copolymer include azo compounds, peroxides and ionizing radiation.

The water / oil repellent composition of the present invention can be applied to an article to be treated by any method depending on the preparation form and the like. For example, a method of adhering to the surface of the object to be processed and drying by a known method of coating such as dip coating is adopted. If necessary, curing may be performed. Further, the water / oil repellent composition of the present invention may be used by mixing with other compounds, and other water / oil repellent agents, cross-linking agents, insect repellents,
Of course, appropriate additives such as flame retardants, antistatic agents and anti-wrinkle agents may be added and used in combination.

The articles which can be treated with the water / oil repellent composition of the present invention include various examples without any particular limitation.
For example, fiber woven fabric, fiber knitted fabric, glass, paper, leather, fur, brick, cement and plastic. Woven fiber, as the fiber woven fabric, natural animal and vegetable fibers such as cotton, hemp, wool, silk, polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, synthetic fibers such as polypropylene, semi-synthetic fibers such as rayon acetate, or Woven fabrics and knitted fabrics of these mixed fibers can be mentioned.

Next, examples of the present invention will be specifically described, but it goes without saying that the description does not limit the present invention. In addition, the water repellency and oil repellency shown in the following examples are shown on the following scale. That is, the water repellency is represented by the water repellency number (see Table 1) by the spray method of JIS L-1092, and the oil repellency is obtained by applying the test solution shown in Table 2 to several drops (diameter about 4 m) at two places on the test cloth.
m), and after 30 seconds, it was judged by the permeation state (AAT
CC-TM118-1966).

[0017]

[Table 1]

[0018]

[Table 2]

[0018]

【Example】

[Example 1] A perfluoroalkylethyl acrylate (hereinafter referred to as FA) [R _f CH ₂ CH ₂ OCOCH = CH was placed in a glass autoclave (internal volume: 1 liter) equipped with a thermocouple type thermometer and a current type agitator. ₂ , R _{f has} an average carbon number of about 9] 1
20 g (60 parts by weight), stearyl acrylate 60 g
(30 parts by weight), dimethylaminoethyl methacrylate 16 g (8 parts by weight), 2-hydroxyethyl acrylate 4 g (2 parts by weight), undecane 300 g, dipropylene glycol monomethyl ether 100 g, propylene glycol monostearate (manufactured by Kao Corporation) 6 g of nonionic emulsifier) and 6 g of 2,2'-azobisisobutyronitrile (Wako Chemicals Co., Ltd. "V-60") were added, and nitrogen substitution was carried out for about 20 minutes while stirring, then the temperature was raised to 60 ° C. Then, the polymerization was started. The mixture was heated and stirred at 60 ° C. for 15 hours and then cooled to obtain a solution having a solid content concentration of 33%.

The conversion of the copolymerization reaction by gas chromatography was 99.0% (based on FA). The yield was 99%. The obtained solution was a transparent and stable dispersion system, and was further diluted with undecane to obtain a sample having a solid content concentration of 10%.

Example 2 In a glass autoclave (internal volume of 1 liter) equipped with a thermocouple type thermometer and an electric stirrer, FA 120 g (60 parts by weight), cetyl methacrylate 60 g (30 parts by weight), 2 -Ethylhexyl methacrylate 12 g (10 parts by weight), undecane 200
g, dipropylene glycol monoethyl ether 100
g, propylene glycol monoethyl acetate 100
g, 6 g of pentaerythritol monostearate, and 6 g of 2,2′-azobis-2-methylbutyronitrile (Wako Kasei “V-59”) are added, and the mixture is stirred to about 2
After purging with nitrogen for 0 minutes, the temperature was raised to 60 ° C. to start the polymerization. The mixture was heated and stirred at 60 ° C. for 15 hours and then cooled to obtain a solution having a solid content concentration of 33%. The conversion rate of the copolymerization reaction by gas chromatography was 99.0% (based on FA). The yield was 99%. The obtained solution was further diluted with undecane to obtain a sample having a solid content concentration of 10%.

[Comparative Example 1] A monomer was polymerized in the same manner as in Example 1 except that an emulsifier was not used to obtain a polymer solution having a adjusted concentration.

Comparative Example 2 Polymerization of the monomer was carried out in the same manner as in Example 2 except that the emulsifier was not used to obtain a polymer solution having a adjusted concentration.

The evaluation was performed by the following method. 1 above
A 0% solid content solution was diluted with a mineral spirit solution to a solid content concentration of 1%, nylon taffeta was dipped in the diluted solution, and a cloth was squeezed between rubber rollers to obtain a wet pickup of 30% by weight. Then 90 at 110 ° C
It was dried for 2 seconds and further heat-treated at 150 ° C. for 60 seconds. The water and oil repellency of the test cloth thus obtained was measured and the results are summarized in Table 3. The storage stability was 1 in a thermostatic bath adjusted to 5 ° C. for the products with 10% solid content of Examples and Comparative Examples.
The appearance was visually evaluated after standing for a week.

[0025]

[Table 3]

[0026]

EFFECT OF THE INVENTION By using a solvent composed of an aliphatic hydrocarbon or a mixture of an aliphatic hydrocarbon and a polar solvent and an oil-soluble emulsifier, it has excellent water and oil repellency and storage stability without causing ozone destruction. A solvent-type fluorine-based water / oil repellent composition having high properties is obtained.

Claims (5)

[Claims] 1. A solvent-type water / oil repellent composition comprising a solvent comprising an aliphatic hydrocarbon or a mixture of an aliphatic hydrocarbon and a polar solvent, an oil-soluble emulsifier, and a fluorine-based water / oil repellent. 2. The fluorine-based water / oil repellent is synthesized in the presence of an oil-soluble emulsifier in a solvent consisting of an aliphatic hydrocarbon or a mixture of an aliphatic hydrocarbon and a polar solvent. Composition. 3. The aliphatic hydrocarbon is mineral spirit,
The composition of claim 1, which is at least one selected from decane, undecane, and dodecane. 4. The composition according to claim 1, wherein the polar solvent is a propylene glycol derivative. 5. The composition of claim 1 wherein the oil soluble emulsifier is an ester of a long chain alkyl carboxylic acid.