JPH0753862B2 - Water and oil repellent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water and oil repellent agent which simultaneously satisfies the feeling flexibility and the practical durability of water and oil repellency.

[Prior Art and Problems to be Solved by the Invention] A copolymer obtained by polymerizing a polymerizable monomer having a perfluoroalkyl group, or a perfluoroalkyl group-containing compound in an organic solvent solution or an aqueous system. A technique is known in which a fiber product or the like is treated as a dispersion liquid to impart water and oil repellency to the surface of the material. Originally, this water and oil repellency is due to the formation of a low surface energy surface on the material due to the surface orientation of the perfluoroalkyl group. Flexibility and durability as performance [wash resistance (hereinafter referred to as HL resistance),
Dry cleaning resistance (hereinafter referred to as DC resistance), abrasion resistance],
Flexibility and antifouling property, antifouling property and SR property (stain removal property) are required. In particular, it is strongly demanded for the water / oil repellent agent for fibers to make the accompanying effects centering on the flexibility compatible with the water / oil repellency which is the main function. From a practical point of view, as a technique for satisfying contradictory effects such as flexibility and durability, a method of improving the molecular structure of a processing agent and a method of using a concomitant agent during processing have been conventionally adopted. Regarding the molecular structure of the processing agent, a method of introducing an organopolysiloxane as a flexibility-imparting component, that is, a method of using a copolymer of a fluorine-containing (meth) acrylate and a siloxane-containing (meth) acrylate (JP-A-60-190408). No.), a method using a reaction product of a fluorine-containing urethane compound and a reactive organopolysiloxane (JP-A-60-81278), and a method using perfluoropolyether as a side chain of poly (meth) acrylate (JP-B-61). No. 6187) is known, but a highly flexible processing agent has low durability and low water / oil repellency, and a highly durable processing agent tends to have a coarse and hard texture.

As one attempt to improve durability, a technique of using a concomitant agent during fiber treatment is known. Generally, a melamine-based resin, a glyoxal-based resin, a urea-based resin, or the like is used as a concomitant agent for fibers, but the use of these resins has a drawback in that the texture becomes coarse and hard. For the purpose of improving flexibility, a method in which an organosilicone is used in combination with a fluorine-containing processing agent or by two-step treatment is disclosed (Japanese Patent Laid-Open No. 59-157380), but the durability is at a satisfactory level. However, as far as flexibility is concerned, as long as a fluorine-containing polymer that is a hard component is used as a processing agent, it is not a fundamental solution.

In addition, a technique of blending a fluorine-containing polymer emulsion and a urethane compound emulsion at a latex stage is also known, particularly as an aqueous fiber treatment (Japanese Patent Laid-Open No. 62-16454), which is one of the methods for achieving both flexibility and durability. Although the direction is shown, in the case of a simple latex blend, the dry film becomes macroscopically non-uniform, which causes deterioration of durability (especially HL resistance and abrasion resistance).

In addition, mixing different kinds of latex is a problem because the selection of an emulsifier becomes an important issue from the viewpoint of stability.

[Means for Solving the Problems] The present invention has been made to solve the above-described problems, and one particle contains at least two kinds of polymers, and at least two kinds of polymers are contained. One type relates to a water and oil repellent agent containing polymer particles, which are polymers having a polyfluoroalkyl group, as an active ingredient, and a method for producing the polymer particles.

The water- and oil-repellent agent of the present invention has flexibility and practical durability that are difficult to achieve with conventional processing agents or treatment methods, that is, resistance to
It is compatible with HL, DL resistance, and abrasion resistance.

The water- and oil-repellent agent of the present invention contains water and / or polymer particles dispersed therein.
Alternatively, use in a solvent dispersion system is preferable. 2 in the present invention
Polymer particles containing one or more polymers in one particle are obtained, for example, by a seed emulsion polymerization method, and the first polymer formed into particles by the emulsion polymerization method and the first polymer It is a particle formed from a second polymer formed by polymerization on the surface or inside of the particle, and a core-shell type phase-separated into layers is preferable in terms of performance, but the phase-separated form is sea-island structure or polymer One may be localized, or one in which different polymer molecular chains are entangled. Of the two or more polymers forming the polymer particles in the present invention, at least one is a polyfluoroalkyl group (hereinafter Rf
Abbreviated as group. ) Containing a polymer.

The two or more polymers in the present invention are different from those obtained by simply blending two or more polymer particles.
Two or more kinds of polymers are not secondary particles which are micro-mixed and formed by so-called agglomeration by, for example, a seed emulsion polymerization method, and the individual particles are present independently without aggregating with other particles. Particles, that is, primary particles of polymer particles are formed.

The polymer containing an Rf group in the present invention is not limited at all, but a homopolymer consisting of one of the following vinyl monomers containing an Rf group or a copolymer containing two or more kinds thereof Coalescence is preferred. The Rf group preferably has 3 to 21 carbon atoms, and particularly preferably 6 to 18 carbon atoms. Of the Rf groups, perfluoroalkyl groups containing no atoms other than fluorine atoms such as hydrogen atoms and chlorine atoms are preferable, and those located at the terminal of the vinyl-based monomer are particularly preferable. The preferred specific examples are as follows.

CF ₃ (CF ₂ ) ₄ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH = CH _{2 CF 3 (CF 2) 7 SO} 2 N (C 3 H 7) (CH 2) 2 OCOCH = CH 2 CF 3 (CF 2) 7 (CH 2) 4 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 SO 2 N (C 2 H 5) (CH 2) 2 OCOCH = CH 2 CF 3 (CF 2) 7 CONH (CH ₂ ) ₂ OCOCH = CH _{2 CF 3 (CF 2) 8 (} CH 2) OCOCH = CH 2 CF 3 (CF 2) 8 (CH 2) OCOC (CH 3) = CH 2 CF 3 (CF 2) 8 CONH (CH 2) 2 OCOC (CH ₃ ) = CH ₂ H (CF ₂ ) ₁₀ CH ₂ OCOCH = CH ₂ CF ₂ Cl (CF ₂ ) ₁₀ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCH ₂ CH ₂ OCH = CH ₂ Polymers other than the Rf group-containing polymer in the present invention include the following various vinyl-based monomer containing no Rf group.
A homopolymer consisting of one kind or a copolymer consisting of two or more kinds can be adopted, and these monomers are formed by forming a copolymer with the above-mentioned vinyl monomer containing an Rf group, Rf
It is possible to improve the adhesiveness or crosslinkability of a group-containing polymer to a substrate, film-forming property, flexibility, antifouling property, SR property and the like. Specific preferred examples of the monomer not containing the Rf group are as follows.

For example, ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinylidene halide, styrene, α-methylstyrene, p-methylstyrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, poly (oxyalkylene) (meth ) Acrylate, (meth)
Acrylamide, diacetone (meth) acrylamide,
Methylolated diacetone (meth) acrylamide, N-
Methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aziridinylethyl (meth) acrylate, benzyl (Meth) acrylate, isocyanatoethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, maleic anhydride, aziridinyl (meth)
Examples thereof include acrylates, (meth) acrylates having polysiloxane, and N-vinylcarbazole.

The polymer containing an Rf group may be polymerized in the presence of a mercaptan compound as a molecular weight regulator for the purpose of expressing durability or imparting flexibility. For example, R ¹ -SH R ¹ : alkyl group, aryl group HS- (R ² ) -SH R ² : alkylene group In order to obtain particles containing two or more polymers in one particle in the present invention, various polymerization initiators such as organic peroxides, azo compounds and persulfates, or ionizing properties such as γ-rays. It is preferable to employ the so-called seed emulsion polymerization method in the presence of radiation.

Among particles containing two or more polymers in one particle, for example, in order to obtain core-shell type particles phase-separated into layers, one kind of the polymer forming the core part is first prepared in the first stage. It is possible to employ a method in which the monomer of the other polymer forming the shell portion in the presence of the above-mentioned polymer is divided into multiple stages of two or more stages and then emulsion-polymerized after the formation by the emulsion polymerization. When this method is adopted to obtain the water / oil repellent of the present invention, the following precautions must be taken for the Nth stage emulsion polymerization. That is, the amount of new emulsifier in the emulsion obtained by the emulsion polymerization of the previous stage (N-1 stage) is the minimum amount necessary for stabilizing the emulsion particles, or the micelle of the monomer forming the shell polymer. It is necessary to adjust the amount so that it is difficult to generate. Specifically, it is preferable to confirm whether or not the emulsifier is present in an excess amount equal to or higher than its critical micelle concentration by measuring the surface tension of the emulsion at the time when the N-1th stage polymerization is completed. . If present in excess, the emulsion can be diluted to adjust the emulsifier below the critical micelle concentration. By this operation, the polymerization field of the emulsion polymerization of the Nth stage is limited to the particles of the particles obtained in the N-1th stage or within the particles, and the particles intended by the present invention can be obtained. .

Under the condition that the emulsifier is present in an excess amount above the critical micelle concentration, new particles consisting of only the Nth stage composition are generated during polymerization, and particles in which two or more polymers are phase-separated into layers are obtained. I can't. The generation of desired particles and the generation of new particles can be confirmed by, for example, observing the particles using a staining method, measuring the zeta potential of the particles, or measuring the particle size distribution. It can also be confirmed by measuring small-angle X-ray scattering, small-angle light scattering, and small-angle neutron scattering after film formation. In order to obtain particles composed of two or more kinds of polymers, in addition to the above multi-stage polymerization, a combination of monomers having remarkably different copolymerization reactivity or a combination of monomers having different solubilities in a polymerization medium is used. By using it, it is possible to realize it by one-step polymerization.

The core portion is preferably a polymer containing an Rf group, and the shell portion is preferably a polymer containing an Rf group different from this polymer or a polymer not containing an Rf group.

The ratio of the polymer units derived from the Rf group-containing monomer in the polymer containing the Rf group to be the core part (Rf-containing polymer units) is the polymer derived from the Rf-containing polymer unit and the Rf group-free monomer. Rf-containing polymerized units are 30 to 10 relative to the total of units (Rf-free polymerized units)
It is 0 wt%, preferably 50 to 100 wt%, and if this ratio is too small, the water / oil repellency performance deteriorates.

The proportion of the Rf-containing polymerized units in the polymer which becomes the shell part is also 0 to 95 wt%, preferably 0 to 80 wt%, and particularly 0 to 70 wt%.
%, And if this ratio is too large, the adhesiveness, film-forming property, cross-linking property, etc. are not sufficiently improved, and the durability of water / oil repellency is reduced. Moreover, the improvement of flexibility is insufficient. Further, the ratio of the Rf-containing polymerized units in the core portion is at least a numerical value expressed in wt% as compared with the ratio of the Rf-containing polymerized units in the shell portion.
A higher value of 10, preferably 20 or more is preferable for performance.

As the polymer of the core portion and the shell portion, as described above, Rf
In addition to selecting from those with different ratio of contained polymer units,
It may be selected from those having different types of Rf-containing polymerized units or those having different types of Rf-free polymerized units.

The ratio of the core part / shell part is selected from 1/100 to 100/1 in terms of the weight ratio of the monomers constituting each part, but it gives practical durability without damaging the texture during processing. For purposes such as
It is preferably 100/5 to 100/50. For the same purpose, the weight average molecular weight of the core polymer is preferably smaller than that of the shell polymer. The weight average molecular weight of the polymer of the core portion is about 100,000 or less, preferably 50,000 or less.

As the emulsifier used in the emulsion polymerization, one or more selected from various emulsifiers such as nonionic, cationic, and anionic can be used, and the addition amount of the emulsifier during the preceding stage emulsion polymerization is It is 1 to 20 parts by weight, preferably 3 to 10 parts by weight, based on 100 parts by weight of the polymer constituting the core part, and the shell part is formed during the second-stage emulsion polymerization so as not to form a polymer other than on the core part. It is 0 to 10 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the polymer constituting During the second-stage emulsion polymerization, the emulsifier used during the first-stage emulsion polymerization may be continuously used. Therefore, the amount of the emulsifier added during the second-stage emulsion polymerization may be 0 parts by weight. The emulsifiers used in the first and second stages may be the same or different.

In the water- and oil-repellent agent of the present invention, particles composed of two or more kinds of polymers exist without agglomeration or the particles are present in a partially agglomerated form. If the amount of a large number of particles or agglomerated particles thereof or particles of a single type of polymer is small in the water / oil repellent agent of the present invention, they may be mixed. The particle size of the particles formed from two or more polymers in the present invention is 0.01 to 1
[mu], preferably 0.1 to 1 [mu].

The water- and oil-repellent agent of the present invention has practical durability of water- and oil-repellency (HL resistance, DC resistance
Of the higher fatty acids, ethylene oxide adducts of higher fatty acids, and higher fatty acids at the time of the emulsion polymerization or after the above-mentioned polymerization for the purpose of further improving the texture. It is advantageous to add an alkyl ester, long-chain alcohol, sorbitan-based or pentaerythritol-based long-chain alkyl ester, polyamide polyamine-based surface modifier, synthetic wax, liquid paraffin, paraffin wax, silicone oil, or the like.

The water and oil repellents of the present invention include other water and oil repellents or other polymer blenders, insect repellents, flame retardants, antistatic agents, dye stabilizers, antiwrinkle agents, melamine resins, glyoxal. A durability improver such as a base resin or a urea resin may be added together.

The water- and oil-repellent agent of the present invention is preferably an aqueous emulsion, and can be treated by a known method of coating such as dip coating and the like by attaching it to the surface of the object to be treated and drying. Further, if necessary, it may be applied together with a suitable crosslinking agent and cured. With the aerosol-type water and oil repellent agent, it is sufficient to simply spray it onto the object to be treated, and it can be immediately dried to exhibit sufficient performance.

The article which can be treated with the water and oil repellent of the present invention includes various examples without particular limitation. Examples include fibers, textile fabrics, glass, paper, wood, leather, fur, asbestos, bricks, cements, ceramics, metals and oxides, ceramic products, plastics, painted surfaces and plasters. Thus, as the material of the fiber or the fiber woven fabric, natural animal and vegetable fibers such as cotton, hemp, wool and silk, polyamide, polyester,
Examples thereof include various synthetic fibers such as polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers and asbestos fibers, and woven fabrics of these mixed fibers.

[Function] Although the mechanism by which the water and oil repellent of the present invention achieves both high durability and flexibility is not clear, when the particles are, for example, a core-shell type, a high molecular weight or a crosslinkable monomer that forms a shell part is used. Due to the micro-blending effect of the polymer contained in the core fluoropolymer, the mechanical strength of the water / oil repellent coating is improved, and the surface orientation of the polyfluoroalkyl group is strengthened. Conceivable. Further, it was observed that the film-forming property on the article was remarkably improved, which is considered to also contribute to the improvement of durability. Further, since it is a microblend in the particles, it is considered that it does not cause the rough hardening of the texture such as the post-addition (simple blend) of the combined resin.

[Examples] Production Example 1 Method for producing core polymer particles C ₈ F ₁₇ C ₂ H ₄ OCOCH = CH ₂ (FA) 92.52 g (178.6 mmol) Formula: 5.64 g (5.95 mmol) of a chain transfer agent represented by: 2.94 g (3 parts) of water-soluble silicone (SF8427 manufactured by Toray Silicone Co., Ltd.),
Dimethyl alkyl acetate (Pharmine DMC manufactured by Lion)
Acetate) 0.49 g (0.5 part), acetone 49.1 g (50 parts), distilled water 147.2 g (150 parts) mixture was emulsified at 450 kg / cm ² using a high pressure emulsifier (Menton Goulin homogenizer). After that, 70 g of the obtained emulsion and 0.34 g of α-α'-azobisisobutyronitrile were charged into a 100 ml-polymerization ampoule and purged with nitrogen, and then polymerized at 75 ° C for 5 hours. The yield of the core polymer particles in the obtained dispersion was 99% or more, and the particles were composed of spherical particles having an average particle diameter of 0.082 μm based on the results of particle size distribution measurement by electron microscopy and light scattering method.

Production Examples 2 to 4 Polymerization was carried out in the same manner as in Production Example-1 with the formulation shown below to obtain core polymer particles.

Example 1 In a 100 ml-glass polymerization ampoule, 20 g of a dispersion liquid of core polymer particles produced in Production Example-1 (solid content 34%, 6.8 g; 10
0 part), methyl methacrylate (MMA) 0.68 g (10 parts),
Water-soluble silicone (SF8427) 0.0068g (0.1 part), 2-2
-Azobis (2-amidinopropane) -2-hydrochloride (V-50 manufactured by Wako Pure Chemical Industries, Ltd.) 0.017 g (2.5 parts) and 4.3 g of water were further added to prepare a solid concentration of 30%. The atmosphere was replaced with nitrogen, and the mixture was polymerized at 60 ° C for 10 hours. The core-shell type polymer particles in the obtained dispersion had a yield of 99%, and an average particle size of 0.09 according to the results of particle size distribution measurement by electron microscope observation and a light scattering method.
It consisted of 5 μm spherical particles. This was diluted with pure water to a solid content of 1.6 wt%, a PET (Doskin) cloth was dipped, squeezed to 100% pickup with a mangle, dried at 100 ° C. for 3 minutes, and then heat-treated at 175 ° C. for 1 minute. The fabric has a soft texture, water repellency (JIS-L-1005) 100, oil repellency (AATCC-TM)
−118-1966) 6 ⁻ . Wash (JIS-L-0217-10
3) After 5 times [HL5], dry cleaning (JIS-L
-1092-322) After 5 times [DC5], 5/80 ⁺ , 5 /
It was 100.

Examples 2 to 7 Particles having the polymer particles produced in Production Examples 2 to 4 as the core portion and the polymer shown in <Table-1> as the shell portion were used in Example-1.
Was prepared in the same manner as described above and treated into PET fabric. The table below shows the performance.

Comparative Examples 1 to 4 The dispersion liquid (solid content concentration: 1.6 wt%) of the core polymer particles produced in Production Examples 1 to 4 was diluted as it was, and treated into a PET cloth in the same manner as in Example 1.

Comparative Example 5 A dispersion liquid of core polymer particles and a dispersion liquid of polymethylmethacrylate particles having the composition shown in Production Example 2 (solid content: 17 wt.
%) Was blended at a blend ratio of 100/10 to prepare a processing bath (total solid content concentration: 1.6 wt%), and the PE fabric was treated in the same manner as in Example 1.

Production Example 5 Method for producing core polymer particles FA 92.52 g (178.6 mmol) n-C ₁₈ H ₃₇ SH 3.35 g (11.9 mmol) Polyoxyethylene oleyl ether (Emulgen 430 manufactured by Kao Corporation) 2.94 g (FA, total mercaptan) Using a high-pressure emulsifier (manton-goulin homogenizer) while maintaining a mixture of 100 parts 3 parts), Pharmin DMC acetate 0.29 g (0.3 parts), acetone 47.9 g, and distilled water 143.8 g at 50 ° C. After emulsification at 450 kg / cm ² , 70 g of the obtained emulsion and α
0.34 g of -α'-azobisisobutyronitrile was charged into a 100 ml-polymerization ampoule and, after purging with nitrogen, polymerization was carried out at 70 ° C for 5 hours.

The obtained core part polymer particles had a monomer conversion rate of 99% or more.

Example 8 20 g (solid content 34%; 6.8 g; 100 parts) of a dispersion liquid of core polymer particles produced in Production Example 5 was added to a 100 ml glass polymerization ampoule.
On the other hand, the following monomers (total 2.04 g; 30 parts) were charged.

2,2'-azobis (2-amidinopropane) -2
-Hydrochloride 0.051 g (2.5 parts) and water 13.3 g were added to prepare a solid concentration of 25%, and then the atmosphere was replaced with nitrogen and the temperature was changed to 60 ° C.
It was polymerized for 12 hours. The yield of the core-shell type polymer particles in the obtained dispersion was 99% or more. As a result of observing with an electron microscope and measuring the particle size distribution by a light scattering method, the particles were spherical with a particle size of 0.21 μm. The zeta potential of the particles showed a single peak of 48.2 mV.

A processing bath shown below was prepared using the obtained dispersion liquid of the core-shell type polymer particles.

After the nylon fabric was dipped in the processing bath, the pickup was squeezed to 70% of the pickup with a mangle and heat-treated at 110 ° C for 90 seconds and 170 ° C for 1 minute. The treated fabric had a soft texture, water repellency of 100 and oil repellency of 6. Washing After 20 times, respectively after dry cleaning 20 times 3 / 80,4 / 80 ^- it was.

Comparative Example 6 Production of Copolymer by Batch Charge The following monomers were charged in a 100 ml polymerization ampoule. This charged composition has substantially the same polymer composition as the core-shell type polymer particles obtained in Example 8.

When the mixture shown in the above table was polymerized at 60 ° C. for 12 hours, a copolymer was obtained with a yield of 99% or more.

The results of treating this with a nylon fabric in the same manner as in Example 8 are shown in Table 2.

Comparative Example 7 A 100 ml polymerization ampoule was charged with the following monomers, and the temperature was 60 ° C x 1
When polymerized for 2 hours, a copolymer was obtained with a yield of 99% or more.

The obtained copolymer dispersion and the dispersion of core polymer particles produced in Production Example 5 were blended in the following blending ratio to prepare a processing bath (total solid content concentration: 1.6 wt%). Was processed. The results are shown in Table 2. This blend ratio gives substantially the same polymer composition as in Example 5.

Processing bath composition Dispersion liquid of Production Example 5 10.8g (solid content concentration 34wt%) Copolymer dispersion liquid 3.2g (solid content concentration 34.5wt%) Sumitex Resin M-30.45g (Sumitika) ACX 0.45 g water 300 g total Table 2 shows the results of treating nylon cloth with this processing bath.

Examples 9-10 Instead of the polymerizable monomer tert-butyl methacrylate,
The same treatment as in Example 8 was carried out except that stearyl methacrylate (StMA) and n-butyl methacrylate (n-BuMA) were used. The results are shown in Table 2.

Example 11 Polymerization was carried out in the same manner as in Example 8 except that 0.3 g of liquid paraffin was added to the charged composition of Example 8. The yield of the obtained dispersion liquid of core-shell type polymer particles was 99% or more, and floating of liquid paraffin was not observed on the liquid surface.

The nylon fabric was treated in the same manner as in Example 8 below. The treated fabric had a moist feel compared with the fabric of Example 8 and had water repellency of 100 and oil repellency of 6. After 20 washes,
Each After dry cleaning 20 times 3 / 80,4 / 80 ^- was.

Production Example 6 Method for producing core polymer particles Polymerization was carried out in the same manner as in Production Example 5 except that C ₁₇ H ₃₅ COOC ₄ H ₉ 3 g was added to the charged composition of Production Example 5, and the yield was 99%.
Thus, core polymer particles were obtained.

Example 12 Polymerization was carried out in the same manner as in Example 8 except that the core polymer particles of Production Example 5 used in Example 8 were changed to the core polymer particles of Production Example 6. The yield of the obtained core-shell type polymer particles was 99% or more. A nylon woven fabric was treated in the same manner as in Example 8 using the dispersion liquid of the polymer particles.

The treated fabric had a moist feel compared to the fabric of Example 8 and was water repellent 100 and oil repellent 6. Washing After 20 times, respectively after dry cleaning 20 times 3 / 80,4 / 80 ^- it was.

Examples 13 to 16 The polymer produced in Production Example 5 was used as core part polymer particles, and the polymerizable monomer composition shown in Example 8 was used as a shell part, and the compounds shown in Table 3 were added at the time of synthesizing the shell part. Core-shell type polymer particles were produced in the same manner as in Example 8 and treated on a nylon woven cloth (Table 3 shows its performance and texture).

Examples 17 to 20 The compounds shown in Table 3 were simultaneously emulsified and dispersed at the time of synthesizing the core polymer particles of Production Example 5, and then core-shell type polymer particles were produced in the same manner as in Example 8 to obtain a Nanron woven fabric. It was treated (Table 3 shows its performance and texture).

Comparative Examples 8 to 10 Liquid dispersions of liquid paraffin, butyl stearate and lanolin alcohol (examples of liquid paraffin are shown in Table 4).
Shown in. Butyl stearate and lanolin alcohol had the same composition) was mixed with the dispersion liquid of the core-shell type polymer particles of Example 8 to treat a nylon woven fabric (Table 5 shows its performance and texture).

Comparative Example 11 Core part polymer particles were produced in the same procedure as in Production Example 5, except that the preparation composition in Production Example 5 was changed as follows.

A part of the obtained dispersion was poured into methanol, the polymer was purified, and the molecular weight was measured by GPC, and it was about 200,000.

This emulsion was used as a core part polymer particle dispersion liquid, and second-stage polymerization was carried out with the same composition as in Example 8. In addition,
The molecular weight of the shell part was about 100,000.

The obtained dispersion was treated with a nylon fabric in a treatment bath having the same composition as in Example 8. The results are shown in the table below.

Example 21 50 g of dispersion of particles prepared in Example 9 (solid content 25%; 12.
5: 100 parts) to the following monomers (total 2.5 g; 20 parts)
And charged with an emulsifier for stabilizing particles and a polymerization initiator,
The third stage polymerization was carried out at 60 ° C. for 12 hours.

FA 0.5g (20wt%) Steariacrylate 1.75g (70wt%) Glycidyl methacrylate 0.25g (10wt%) Emulgen 430 (10% aqueous solution) 0.25g V-50 (10% aqueous solution) 0.5g As a result of microscopic observation and particle size and particle size distribution measurement, it was found to be spherical particles having a particle size of 0.25 μ. When this was treated with the same formulation as in Example 8, the obtained fabric had a soft texture, water repellency of 100, and oil repellency of 6.
After washing 20 times and after dry cleaning 20 times 4 / 80,3 respectively
It was / 80-.

[Effect of the Invention] The water and oil repellent agent of the present invention has a polymer as a water and oil repellent component and a polymer as a durable component coexisting in the particles, for example, in a core-shell type. When treated with oil, high water and oil repellency and practical durability (HL resistance, DC resistance, abrasion resistance, wear durability, etc.) can be obtained without impairing the texture of treated cloth. .

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location D06M 15/353

Claims (23)

[Claims] 1. A polymer particle containing at least two kinds of polymers in one particle, and at least one kind of the at least two kinds of polymers is a polymer having a polyfluoroalkyl group as a repellent agent. Water repellent. 2. A polymer in which at least two polymers contain at least one polyfluoroalkyl group in a high proportion and a polymer which does not contain a polyfluoroalkyl group or contains it in a relatively small proportion. The water and oil repellent according to claim 1, which comprises at least one of 3. A first formed into particles by an emulsion polymerization method.
And a second polymer formed by polymerization on the surface or inside of the particles of the first polymer, wherein at least one of the first polymer and the second polymer is polyfluoro. A water and oil repellent agent comprising polymer particles, which are polymers containing an alkyl group, as an active ingredient. 4. One of the first polymer and the second polymer is a polymer containing a high proportion of polyfluoroalkyl groups, and the other contains no polyfluoroalkyl groups or a relatively small amount thereof. The water- and oil-repellent agent according to claim 3, which is a polymer contained in a ratio. 5. The water and oil repellent agent according to claim 3, wherein the first polymer is a polymer obtained by polymerizing a first monomer containing 30 to 100% by weight of a polyfluoroalkyl group-containing vinyl monomer. 6. The second polymer contains a polyfluoroalkyl group-containing vinyl monomer in a ratio smaller than the weight ratio of the polyfluoroalkyl group-containing vinyl monomer in the first monomer forming the first polymer. Or a polymer obtained by polymerizing a second vinyl monomer containing no polyfluoroalkyl group-containing vinyl monomer, wherein the proportion of the polyfluoroalkyl group-containing vinyl monomer is 0 to 80% by weight. The water / oil repellent according to claim 3. 7. The first polymer has a proportion of the polyfluoroalkyl group-containing vinyl monomer in the first monomer of 30 to 10.
0% by weight of the first monomer is the polymer, the second polymer is the second monomer in which the proportion of the polyfluoroalkyl group-containing vinyl monomer is 0 to 80% by weight of the second monomer. The water and oil repellent agent according to claim 3, wherein the water and oil repellent agent is a coalesced product, and the numerical value of the proportion of the polyfluoroalkyl group-containing vinyl monomer in the first monomer expressed by weight% is 20 or more higher than the numerical value in the second monomer. 8. The water- and oil-repellent agent according to claim 3, wherein the first polymer is an acrylate or methacrylate polymer having a polyfluoroalkyl group or a copolymer thereof with a polyfluoroalkyl group-free monomer. 9. The second polymer is a polymer of acrylate or methacrylate having no polyfluoroalkyl group or a copolymer of the acrylate or methacrylate with an acrylate or methacrylate having a polyfluoroalkyl group. The water and oil repellent described. 10. The water / oil repellent according to claim 9, wherein a part of the acrylate or methacrylate having no polyfluoroalkyl group is a compound having an epoxy group. 11. An emulsifier in which particles of a first polymer obtained by emulsion polymerization of a first monomer composed of at least one vinyl monomer, a polymerization medium, and a micelle of the following second monomer are difficult to form. In the presence of an emulsifier or in the absence of an emulsifier, a second polymer comprising at least one vinyl monomer is polymerized to obtain a second polymer, which is a polymer of the second monomer. Of polymer particles having a polyfluoroalkyl group, characterized in that they are formed on the surface or inside of the particles, and at least one of the first monomer and the second monomer contains a polyfluoroalkyl group-containing vinyl monomer. Method. 12. One of the first monomer and the second monomer contains a high proportion of polyfluoroalkyl group-containing vinyl monomer and the other contains no or relatively less polyfluoroalkyl group-containing vinyl monomer. 12. The method of claim 11 comprising in percentage. 13. The method according to claim 11, wherein the content of the polyfluoroalkyl group-containing vinyl monomer in the first monomer is 30 to 100% by weight. 14. The content ratio of the polyfluoroalkyl group-containing vinyl monomer in the second monomer is 0 to 80% by weight.
12. The method according to claim 11, which is lower than the content of the polyfluoroalkyl group-containing vinyl monomer in the first monomer. 15. The proportion of the polyfluoroalkyl group-containing vinyl monomer in the first monomer is 30 to 100% by weight, and the proportion of the polyfluoroalkyl group-containing vinyl monomer in the second monomer is 0 to 80% by weight. Moreover, the method according to claim 11, wherein the proportion of the polyfluoroalkyl group-containing vinyl monomer in the first monomer, expressed in wt%, is 20 or more higher than the numerical value in the second monomer. 16. The method according to claim 11, wherein the first monomer is an acrylate or a methacrylate having a polyfluoroalkyl group, or a mixture thereof with a polyfluoroalkyl group-free vinyl monomer. 17. The method according to claim 11, wherein the second monomer is an acrylate or methacrylate having no polyfluoroalkyl group, or a mixture thereof with an acrylate or methacrylate having a polyfluoroalkyl group. 18. The method according to claim 17, wherein a part of the acrylate or methacrylate having no polyfluoroalkyl group is a compound having an epoxy group. 19. A first monomer as an emulsifier, a polymerization initiator,
And emulsion-polymerizing in the presence of a polymerization medium to produce an emulsion-polymerized composition containing particles of the first polymer, and then, substantially without newly adding an emulsifier to the emulsion-polymerized composition,
12. The method according to claim 11, wherein the second monomer is polymerized in the emulsion polymerization composition to which a polymerization medium is optionally added. 20. The method of claim 19, wherein the polymerization medium comprises a mixture of water and a water soluble organic solvent. 21. The method according to claim 19, wherein the first monomer is emulsion polymerized in the presence of an emulsifier, a polymerization medium, a polymerization initiator, and a chain transfer agent. 22. A polymerization medium is added when the emulsifier used for the polymerization of the first monomer is the second monomer and the concentration of the emulsifier is such that micelles of the second monomer are easily formed. 20. The method according to claim 19, wherein the polymerization is carried out in the presence of a new polymerization initiator in the emulsion-polymerized composition diluted to an amount in which the emulsifier concentration is such that micelles of the second monomer are difficult to form. 23. A water and oil repellent agent comprising the polymer particles obtained by the method according to claim 11 as an active ingredient.