JPH0768509B2 - Antifouling water and oil repellent - Google Patents

Description

The present invention relates to a water and oil repellent agent. More specifically, the present invention relates to a water and oil repellent agent for fiber treatment, which has improved dirt release performance.

[Conventional technology]

It has been conventionally proposed to copolymerize a polymerizable monomer that imparts soil release performance in a copolymer used as an active ingredient of a water / oil repellent, and as such a polymerizable monomer, for example, Polyoxyalkylene glycol di (meth) acrylate (JP-A-53-134,787), polyoxyalkylene group-containing hydrophilic compound (53-134,786)
Gazette), (meth) acrylonitrile and hydrophilic compound (gazette 50-140,387 gazette), (meth) acrylonitrile and polyethylene glycol group-containing hydrophilic compound (gazette 50-20,991 gazette), polyethylene glycol group-containing monomer compound (Japanese Patent Laid-Open No. 49-75,472) and the like are used respectively.

When acrylonitrile or methacrylonitrile is used among these copolymers, it is difficult to complete the copolymerization reaction, and accordingly, a step of removing a highly toxic nitrile compound is required. Furthermore,
It may be necessary to use a solvent with a high dielectric constant. Also,
In the case of other copolymers, the soil release performance itself is not sufficiently satisfactory.

[Problems to be solved by the invention]

The present inventors have used a water-repellent fiber treatment which uses an oxyalkylene group-containing monomer compound which does not cause a toxicity problem as in the case of copolymerizing a nitrile compound, and is comparable to the stain release performance. As a result of various investigations for a polymer as an active ingredient of the oil repellent, a polymer of an oxyalkylene group-containing monomer compound as represented by the following general formula is found to be sufficiently suitable for such purpose. I found it.

[Means for Solving Problems] and [Operation] Accordingly, the present invention relates to an antifouling water and oil repellent agent for fiber treatment, which is represented by the general formula CH ₂ = CR′COO ( RO) _n R _f (wherein R _f is a group containing a perfluoroalkyl group or a perfluoroalkylene glycol group, R is an alkylene residue, R ′ is a hydrogen atom or a methyl group, and n Is a positive integer).

As the polymerizable monomer represented by the above general formula, for example, the following ones are used.

CH ₂ = CR′COO (C ₂ H ₄ O) _n C ₂ H ₄ C _m F _{2m + 1} CH ₂ = CR′COO (C ₃ H ₆ O) _n C ₂ H ₄ C _m F _{2m + 1} CH ₂ ＝ CR′COO (C ₄ H ₈ O) _n C ₂ H ₄ C _m F _{2m + 1} n: 6,8 etc. m: 6,8,10,12,14 etc. CH ₂ ＝ CR′COO (C ₂ H ₄ O) _{6 to 8} CH ₂ CF (CF ₃ ) (OC ₃ F ₆ )
_{2~4 OC 3 F 7 CH 2 =} CR'COO in _{(C 2 H 4 O) n} CH 2 CH 2 N (CH 3) SO 2 C 8 F 17 fold during coalescence, the range that does not impair the object of the present invention In general, about 10 mol% of the polymerizable monomer represented by the above general formula is used so that the stain release property and the stain adhesion preventive property are not impaired.
Above, preferably in a range such that about 20 mol% or more are copolymerized, other polymerizable monomers, such as vinyl halide, vinylidene halide, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid,
Esters such as alkyl, aryl or allyl of acrylic acid or methacrylic acid, styrene, α-methylstyrene, alkyl vinyl ether, alkyl vinyl ketone, butadiene, isoprene, chloroprene, acrylate or methacrylate of polyalkylene glycol, carboxylic acid vinyl ester, p -Vinylbenzene sulfonic acid, phosphoric acid ester of 2-hydroxyethyl methacrylate, etc. can be copolymerized.

Among these comonomers, it is desirable to copolymerize a polymerizable monomer having an ionic (anionic) residue, generally about 0.1 to 30% by weight, preferably about 1 to 20% by weight. Copolymerization at such a ratio will further improve dry soil resistance, but copolymerization of about 20% by weight or more is
Problems arise in the solvent resistance of the polymer and its stability in aqueous systems. Further, the copolymerization of acrylate or methacrylate of polyalkylene glycol can further supplement the antifouling property exhibited by the polymer of the polymerizable monomer represented by the above general formula.

The polymerization reaction is performed by using ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and diisobutyl ketone,
Ethyl cellosolve, methyl cellosolve, propyl cellosolve, ethyl cellosolve acetate, cellosolves such as methyl cellosolve acetate, ethylene glycol diacetate, glymes such as diglyme, triglyme, tetraglyme, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, hexa Amides such as methylphosphoramide,
It is carried out almost quantitatively using a polymerization catalyst in a solvent such as ethers such as tetrahydrofuran and dioxane or in an aqueous solvent in the presence of an emulsifier.

The obtained polymer was prepared as a water and oil repellent by diluting the solution polymerization liquid with an organic solvent and the emulsion polymerization liquid with water to a solid content concentration of about 0.5% by weight. It is applied to certain objects to be processed.

〔The invention's effect〕

Conventionally, there is no water- and oil-repellent agent excellent in dry soil resistance and oil stain release property, and if one property is excellent, it is always inferior to the other property. However, the water- and oil-repellent agent for fiber treatment according to the present invention is not only excellent in both of these two properties, but also excellent in the ability to remove various kinds of daily soil. Such an effect is first exhibited by introducing an oxyalkylene group into the side chain of the polymer, and when the polymer has no oxyalkylene group, neither antifouling effect is exhibited.

〔Example〕

Next, the present invention will be described with reference to examples. In addition, each reference example shows a synthesis example and a polymerization example of a monomer for the polymer used.

Reference Example 1 CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ C ₈ F ₁₇ Synthesis of C ₈ F ₁₇ C ₂ H ₄ (OC ₂ H ₄ ) ₈ OH ₈₀ g (0.1 mol) And 9.46 g (1.1 mol) of methacrylic acid, 0.5 g of p-toluenesulfonic acid
Is refluxed in benzene in the presence of, water is distilled off azeotropically,
The reaction was terminated when the methacrylic acid disappeared in the gas chromatographic analysis. Sodium carbonate was added to the reaction mixture, p
-Toluenesulfonic acid is neutralized and then filtered and benzene is distilled off under reduced pressure.

84.8 g (yield: 97.7%) of the desired product, whose ester group (1730 cm ^-1 presence was confirmed by infrared absorption spectrum), was obtained.

Reference Example 2 (Solution Polymerizer) 100 g of the ester obtained in Reference Example 1 and 400 g of methyl ethyl ketone are placed in a separable flask having a volume of 500 ml, and the atmosphere is replaced with nitrogen while being sufficiently stirred. After 30 minutes, 0.5 g of azobisisobutyronitrile is added, and the mixture is reacted under reflux for 16 hours and then cooled. A polymerization resistant solution having a solid content concentration of 20.1% was obtained, and it can be seen from this result that the polymerization reaction is progressing almost quantitatively.

Reference Example 3 (Example of emulsion polymerization) After heating and stirring the above components sufficiently to make them uniform, nitrogen substitution was carried out for 30 minutes under reflux, 1 g of ammonium persulfate was added thereto, and the reaction was carried out for 10 hours. An aqueous emulsion having a solid content concentration of 20.3% was obtained, and it can be seen from this result that the polymerization reaction proceeded almost quantitatively.

Examples 1-18 Following Reference Example 1, solution polymerization in methyl ethyl ketone was carried out. The resulting polymer solution, solids concentration is 0.
Prepare a water and oil repellent by diluting it with methyl ethyl ketone to 5% by weight, and then fully immerse and dry a 25 x 25 cm twill cloth (polyester 65 / cotton 35). Cured at 150 ° C for 3 minutes. The following test was conducted on this water- and oil-repellent treated twill cloth.

Dry soil resistance test (DSR) diatomaceous earth 56%, erosile 15%, ferric oxide 1%, cement 15%, carbon black 3% and n-octane
An artificial dry soil having a weight composition of 10% and the treated twill cloth are mixed and stirred at a weight ratio of 2: 1 to be contaminated. After that, the excess stain was removed with an electric vacuum cleaner, and the contamination degree and the contamination rank were measured.

Oil stain resistance test (OSR) 2g of B heavy oil was dropped on the treated twill cloth, and it was sandwiched between polyethylene sheets, and a load of 8.5kg of iron plate was applied.
In this state, it was left in an atmosphere of 80 ° C. for 1 hour. afterwards,
A 0.1% aqueous solution of a detergent (Kao Soap Product Superzab) was used for washing at 40 ° C for 15 minutes and drying at 80 ° C for 15 minutes. The stain degree and stain rank of this laundry cloth were measured.

Life Stain Resistance Test (LSR) Instead of the B heavy oil used in the oil stain resistance test, a mixture of soy sauce, kechiappu, sauce, mayonnaise and coffee (0.5 g each) was used.

The contamination degree and the contamination rank were measured as follows.

R _o : Reflectance of uncontaminated cloth R _p : Reflectance of contaminated cloth (Reflectance: Based on Toyo Seiki's Digital Photoholt reaction rate meter) Evaluation of contamination rank 5: No stain remaining 4: Stain remaining almost none 3 : Slight stain remaining 2: Stain remains considerably 1: Stain remains significantly The results obtained, together with the comonomer composition, are shown in Table 1 below.

Examples 19-21 In Example 2, instead of methyl ethyl ketone, the same amount of another solvent was used.

Example 22 The water- and oil-repellent agent was prepared by diluting the aqueous emulsion obtained in Reference Example 2 with water so that the solid content concentration was 0.5% by weight.

The results obtained in Examples 19-22 are shown in Table 2 below.

Comparative Examples 1 to 8 As the R _f group-containing monomer, a monomer having no polyoxyalkylene group is used, and the polymer solution obtained by solution polymerization in methyl ethyl ketone following Reference Example 1 is used. Similar to 18, a water and oil repellent was prepared and evaluated. The results obtained are shown in Table 3 below. In addition, Comparative Example 1 is an untreated cloth.

Claims (1)

[Claims] 1. A general formula CH ₂ ═CR′COO (RO) nRf (wherein Rf is a group containing a perfluoroalkyl group or a perfluoroalkylene glycol group, R is an alkylene residue, and R ′ is Is a hydrogen atom or a methyl group, and n is a positive integer).