JP2014201866A - Aqueous resin treatment agent for fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber having oil repellency according to the AATCC 118 method of grade 7 or higher, which is a measurement limit, by treatment with a fluorine-containing acrylate-based polymer which has a distance between Rf groups greater than 5.2Å.SOLUTION: Provided are: (1) an aqueous resin processing agent for fiber processing comprising a fluorine-containing acrylate-based polymer (A) having a distance between Rf groups of equal to or greater than 5.2Å and has an average particle size of 1.50 μm or smaller, and a fiber and a fiber product produced by adhering or fixing the aqueous resin processing agent for fiber processing to the surface of a fiber; (2) a fiber processing method using, together with the fluorine-containing acrylate-based polymer, up to a nine-fold amount of a fluorine-containing acrylate-based polymer (B) having a distance between Rf groups of 5.1Å<(B)≤5.2Å, and a fiber and a fiber product produced by adhering or fixing the aqueous resin processing agent for fiber processing to the surface of a fiber; and (3) a fiber and a fiber product produced by adhering or fixing the aqueous resin processing agent for fiber processing described in (1) or (2) with a crosslinking agent.

Description

The present invention relates to a processing agent and a textile product that impart not only water repellency but also excellent oil repellency to the textile product.

Conventionally, for the purpose of imparting water / oil repellency, a water / oil repellent component having a perfluoroalkyl (hereinafter referred to as Rf) group having 6 or more carbon atoms has been used. For example, it is disclosed in the following patent documents. Such water and oil repellent finishing agents and processing methods are known.

However, although the water repellency according to JIS L-1092 spray method is 5th grade at present, there is no processing agent that can obtain oil repellency 7th grade or higher according to AATCC118 method.

JP2011-225837A JP2012-31285A JP2009-191272

  An object of the present invention is to provide oil repellency according to the AATCC 118 method of 7 or more by using a fluorine-containing acrylate polymer having a distance between Rf groups of more than 5.2 mm.

The present invention provides (1) a water-based resin processing for fiber processing, characterized in that the distance between Rf groups of the fluorine-containing acrylate polymer (A) is greater than 5.2 mm and the average particle size is 1.5 μm or less. A fiber or a fiber product obtained by adhering or fixing the agent and the aqueous resin processing agent for fiber processing to the fiber surface (2) The distance between Rf groups is 5 for the fluorine-containing acrylate polymer described in (1). . The fiber processing method characterized by using up to 9 times the amount of the fluorine-containing acrylate polymer (B) of 1 Å <(B) ≦ 5.2 付 着, and the water-based resin processing agent for fiber processing attached to the fiber surface or Fiber or fiber product formed by adhering (3) A fiber or fiber product formed by adhering or adhering to the fiber surface with an aqueous resin processing agent for fiber processing according to (1) or (2) and a crosslinking agent.

It is an object of the present invention to provide an oil repellency grade 7 or higher according to the AATCC118 method with a fluorine-containing acrylate polymer (A) having a distance between Rf groups of more than 5.2 mm.

  In the present invention, the fluorine-containing acrylate polymer (A) having a distance between Rf groups of more than 5.2 mm is an incident X-ray having a known wavelength and incident on a substance in a wide-angle X-ray analyzer, and a diffraction angle 2θ The value calculated by measuring the X-ray intensity refers to a fluorine-containing acrylate polymer in which 5.2 Å <(A) ≦ 5.6 、, and in particular, the distance between Rf groups is 5.2 Å <(A). It is preferably between ≦ 5.4 mm. When the distance between Rf groups is 5.2 mm or less, good oil repellency cannot be obtained, and when it exceeds 5.4 mm, good oil repellency durability cannot be obtained.

  The fluorine-containing acrylate polymer (B) having a distance between Rf groups of 5.2 mm or less is an incident X-ray having a known wavelength and incident on a substance in a wide-angle X-ray analyzer, and a diffraction angle 2θ and its X-ray It means a fluorine-containing acrylate polymer in which the numerical value calculated by measuring the strength is 5.1 Å <(B) ≦ 5.2 、, and the distance between Rf groups is 5.15 Å ≦ (B ) ≦ 5.2 mm is preferred. On the other hand, if the distance between Rf groups is greater than 5.2, oil repellency grade 7 or higher cannot be obtained.

The fluorine-containing acrylate polymers (A) and (B) in the present invention are those represented by the general formula (1)
CH2 = C (-X) -COO-Y-Rf (1)
(In the formula, X represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and Y represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and 6 to 6 carbon atoms. 10 represents an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, Rf in (A) is a C 1-5 carbon atom, and (B) Rf is a linear or branched C 6-7 carbon atom. Is a polymer derived from a monomer comprising a fluorine-containing (meth) acrylic acid ester represented by:

The general formula (1) of the present invention is preferably the general formula (2).
CH2 = C (-X) -COO- (CH2) m- (CF2) n-F (2)
(In the formula, X is as defined above, m is an integer of 1 to 10, and n of the fluorine-containing acrylate polymer (A) is 1 to 5, n of the fluorine-containing acrylate polymer (A). Is an integer of any one of 6 to 7.) and may be a monomer comprising a fluorine-containing (meth) acrylic acid ester. As a specific example of the monomer comprising the fluorine-containing (meth) acrylic acid ester of the general formula (2),
Fluorine-containing acrylate polymer (A)
CH2 = CH-COO-CH2- (CF2) F
CH2 = CH-COO-CH2- (CF2) 2F
CH2 = CH-COO-CH2- (CF2) 3F,
CH2 = CH-COO-CH2- (CF2) 4F,
CH2 = CH-COO- (CH2) 2- (CF2) F
CH2 = CH-COO- (CH2) 2- (CF2) 2F
CH2 = CH-COO- (CH2) 2- (CF2) 3F,
CH2 = CH-COO- (CH2) 2- (CF2) 4F,
CH2 = C (CH3) -COO-CH2- (CF2) F,
CH2 = C (CH3) -COO-CH2- (CF2) 2F,
CH2 = C (CH3) -COO-CH2- (CF2) 3F,
CH2 = C (CH3) -COO-CH2- (CF2) 4F,
CH2 = C (CH3) -COO- (CH2) 2- (CF2) F,
CH2 = C (CH3) -COO- (CH2) 2- (CF2) 2F,
CH2 = C (CH3) -COO- (CH2) 2- (CF2) 3F,
CH2 = C (CH3) -COO- (CH2) 2- (CF2) 4F,
CH2 = C (F) -COO-CH2- (CF2) F,
CH2 = C (F) -COO-CH2- (CF2) 2F,
CH2 = C (F) -COO-CH2- (CF2) 3F,
CH2 = C (F) -COO-CH2- (CF2) 4F,
CH2 = C (F) -COO- (CH2) 2- (CF2) 3F,
CH2 = C (F) -COO- (CH2) 2- (CF2) 4F,
Etc. Of these, preferably
CH2 = CH-COO-CH2- (CF2) 4F,
CH2 = CH-COO- (CH2) 2- (CF2) 4F,
CH2 = C (CH3) -COO- (CH2) 2- (CF2) 4F,
CH2 = C (CH3) -COO- (CH2) 2- (CF2) 4F,
CH2 = C (F) -COO-CH2- (CF2) 4F
CH2 = C (C1) -COO-CH2- (CF2) 4F
Etc. are used,
Fluorine-containing acrylate polymer (B)
CH2 = CH-COO-CH2- (CF2) 6F
CH2 = CH-COO-CH2- (CF2) 7F
CH2 = CH-COO- (CH2) 2- (CF2) 6F
CH2 = CH-COO- (CH2) 2- (CF2) 7F
CH2 = C (CH3) -COO-CH2- (CF2) 6F,
CH2 = C (CH3) -COO-CH2- (CF2) 7F,
CH2 = C (CH3) -COO- (CH2) 2- (CF2) 6F,
CH2 = C (CH3) -COO- (CH2) 2- (CF2) 7F,
CH2 = C (F) -COO-CH2- (CF2) 6F,
CH2 = C (F) -COO-CH2- (CF2) 7F,
CH2 = C (F) -COO- (CH2) 2- (CF2) 6F,
CH2 = C (F) -COO- (CH2) 2- (CF2) 7F,
Etc. Of these, preferably
CH2 = CH-COO-CH2- (CF2) 6F,
CH2 = CH-COO- (CH2) 2- (CF2) 6F,
CH2 = C (CH3) -COO- (CH2) 2- (CF2) 6F,
CH2 = C (CH3) -COO- (CH2) 2- (CF2) 6F,
CH2 = C (F) -COO-CH2- (CF2) 6F
CH2 = C (C1) -COO-CH2- (CF2) 6F
Etc. are used.

  Fluorine-containing acrylate polymers can be used in combination with monomers that do not contain fluorine.For example, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, benzyl acrylate, benzyl methacrylate, glycidyl acrylate, glycidyl methacrylate, aziridinyl acrylate, azide Acrylic acid or methacrylic acid ester such as lysinyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, alkylene diol acrylate, alkylene diol dimethacrylate, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, diacetone aqua Acrylamide or methacrylamide such as luamide, diacetone methacrylamide, methylolated diacetone acrylamide, alkyl maleate such as dibutyl maleate, alkyl phthalate, vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, styrene, α-methyl Examples thereof include styrene, β-methylstyrene, alkyl vinyl ether, halogenated alkyl vinyl ether, alkyl vinyl ketone, cyclohexyl acrylate, cyclohexyl methacrylate, maleic anhydride, butadiene, isoprene, and chloroprene.

  These copolymers can be produced by a known method of vinyl polymerization, but those produced by emulsion polymerization are preferred.

  Although there is no restriction | limiting in particular in the medium at the time of making it emulsion-polymerize, It is preferable to use the aqueous solvent which added the water-soluble organic solvent to water. When an aqueous solvent obtained by adding a water-soluble organic solvent to water is used, monomers and copolymers are hardly aggregated, and a stable emulsion can be obtained. There is no restriction | limiting in particular in the emulsifier used for emulsion polymerization, Almost all of nonionic, anionic, cationic, and amphoteric emulsifiers can be used. In emulsion polymerization, an acrylate and / or methacrylate having a perfluoroalkyl group in an aqueous solvent, other monomers copolymerizable therewith, an emulsifier, etc. are added, and a single amount is transmitted by transmitting ultrasonic waves while stirring. After emulsifying and dispersing the body mixture, it is preferable to add a water-soluble polymerization initiator and polymerize by heating. There are no particular limitations on the water-soluble polymerization initiator used, and examples include various polymerization initiators such as organic peroxides, azo compounds, and persulfates, and ionizing radiation such as γ rays. It can replace with a polymerization initiator and can also be used.

When blending the fluoropolymer (A) and the fluoropolymer (B) of the present invention, the blending ratio is preferably up to 1: 9, particularly preferably 1: 3 to 1: 4. When the amount of the fluoropolymer (B) exceeds 1: 9, good oil repellency cannot be obtained.

As the fiber material used in the present invention, any fiber material such as polyester, nylon, acrylic, cotton, silk, wool, rayon, vinylon, acetate can be used, and these are mixed, mixed, interwoven, and knitted. A material can be used, and the fiber form may be any form such as a filament, a stable, a woven or knitted fabric, and a non-woven fabric.

As for the particle diameter of the fluorine-containing acrylate-based polymers (A) and (B) in the present invention, the average particle diameter in the particle diameter measuring device is preferably 1.50 μm or less, and particularly the particle diameter is between 0.1 μm and 1.2 μm. preferable. When the average particle size is larger than 1.5 μm, the processing agent cannot be prepared because of sedimentation.

The crosslinking agent in the present invention is a melamine crosslinking agent, an isocyanate crosslinking agent, a blocked isocyanate crosslinking agent, a carbodiimide crosslinking agent, an epoxy crosslinking agent, an ethyleneimine crosslinking agent, an oxazoline crosslinking agent, or calcium or magnesium. These are used in combination of one or more of them.

Examples of the present invention will be described in detail, but the examples do not limit the present invention.

Washing durability test method The work cloths obtained in the examples and comparative examples were washed five times based on JIS L-0217 103 method (using a two-tank electric washing machine and using an attack made by Kao Corp.) ) After that, oil repellency and water repellency were evaluated for the tumble-dried cloth (hereinafter referred to as “L-5 cloth”) and the processed cloth before washing (hereinafter referred to as “L-0 cloth”) by the following methods. did.

Oil repellency test: AATCC118 method-treated test cloth is stored in a constant temperature and humidity machine at a temperature of 21 ° C. and a humidity of 65% for 4 hours or more. The test solution (shown in Table 1) is also stored at a temperature of 21 ° C. The test is performed in a constant temperature and humidity chamber at a temperature of 21 ° C. and a humidity of 65%. When 0.05 ml is gently dropped on the test cloth and left for 30 seconds, if the liquid remains on the test cloth, the test liquid is passed. The oil repellency is evaluated as 9 grades of 0, 1, 2, 3, 4, 5, 6, 7 and 8 from the poorest oil repellency to a good level with the highest number of test solutions passed.

Water repellency test method JISL-1092 Shown with water repellency by spray method (Table 2 below).

Measurement of average particle diameter Using a dynamic light scattering particle size distribution meter (manufactured by Particle Sizing Systems, "NICOMP model 380 ZLS-S"), the average particle diameter of the resin particles obtained in each of the examples and comparative examples was determined. It was measured.

Measurement of distance between Rf groups Calculated by measuring the diffraction angle 2θ and its X-ray intensity by making incident X-rays with a known wavelength in a wide-angle X-ray analyzer (Shimadzu Corporation XRD6100) incident on the material. Numeric

<Synthesis of processing agent>
(Synthesis Example 1)
In a flask, CH2 = CHCOOCH2CH2CnF2n + 1 (n = 4) 100 parts by mass, stearyl acrylate 15 parts by mass, N-methylolacrylamide 3 parts by mass, pure water 248.5 parts by mass, 3-methyl-3-methoxybutanol 50 parts by mass, poly 18 parts by mass of oxyethylene (10 mol) lauryl ether and 4 parts by mass of stearyltrimethylammonium chloride were charged and stirred and mixed at 45 ° C., and ultrasonic waves were transmitted and emulsified and dispersed. The obtained emulsion was charged in an autoclave, 1.5 parts by mass of 2,2-azobis (2-methylpropionamidine) dihydrochloride was added and sealed, and then 20 parts by mass of vinyl chloride was injected and the temperature was adjusted to 60 ° C. The mixture was reacted for 6 hours and diluted with pure water to obtain an emulsified dispersion having a solid content of 20%. The distance between Rf groups of this emulsified dispersion was 5.4 mm, and the average particle size was 1.1 μm.

(Synthesis Example 2)
In a flask, CH2 = CHCOOCH2CH2CnF2n + 1 (n = 6) 100 parts by mass, stearyl acrylate 15 parts by mass, N-methylolacrylamide 3 parts by mass, pure water 248.5 parts by mass, 3-methyl-3-methoxybutanol 50 parts by mass, poly 18 parts by mass of oxyethylene (10 mol) lauryl ether and 4 parts by mass of stearyltrimethylammonium chloride were charged and stirred and mixed at 45 ° C., and ultrasonic waves were transmitted and emulsified and dispersed. The obtained emulsion was charged in an autoclave, 1.5 parts by mass of 2,2-azobis (2-methylpropionamidine) dihydrochloride was added and sealed, and then 20 parts by mass of vinyl chloride was injected and the temperature was adjusted to 60 ° C. The mixture was reacted for 6 hours and diluted with pure water to obtain an emulsified dispersion having a solid content of 20%. The distance between Rf groups of this emulsified dispersion was 5.2 mm, and the average particle size was 0.1 μm.

(Synthesis Example 3)
In a flask, CH2 = CHCOOCH2CH2CnF2n + 1 (n = 8) 100 parts by mass, stearyl acrylate 15 parts by mass, N-methylolacrylamide 3 parts by mass, pure water 248.5 parts by mass, 3-methyl-3-methoxybutanol 50 parts by mass, poly 18 parts by mass of oxyethylene (10 mol) lauryl ether and 4 parts by mass of stearyltrimethylammonium chloride were charged and stirred and mixed at 45 ° C., and ultrasonic waves were transmitted and emulsified and dispersed. The obtained emulsion was charged in an autoclave, 1.5 parts by mass of 2,2-azobis (2-methylpropionamidine) dihydrochloride was added and sealed, and then 20 parts by mass of vinyl chloride was injected and the temperature was adjusted to 60 ° C. The mixture was reacted for 6 hours and diluted with pure water to obtain an emulsified dispersion having a solid content of 20%. The distance between Rf groups of this emulsified dispersion was 5.1 mm, and the average particle size was 0.5 μm.

(Synthesis Example 4)
In a flask, CH2 = CHCOOCH2CH2CnF2n + 1 (n = 4) 100 parts by mass, stearyl acrylate 15 parts by mass, N-methylolacrylamide 3 parts by mass, pure water 248.5 parts by mass, 3-methyl-3-methoxybutanol 50 parts by mass, poly 18 parts by mass of oxyethylene (10 mol) lauryl ether and 4 parts by mass of stearyltrimethylammonium chloride were charged and stirred and mixed at 45 ° C., and ultrasonic waves were transmitted and emulsified and dispersed. The obtained emulsion was charged into an autoclave, and 3.0 parts by mass of 2,2-azobis (2-methylpropionamidine) dihydrochloride was added and sealed, and then 20 parts by mass of vinyl chloride was injected and the mixture was heated to 60 ° C. The mixture was reacted for 6 hours and diluted with pure water to obtain an emulsified dispersion having a solid content of 20%. The average particle size of this emulsified dispersion was 1.7 μm. Further, this dispersion liquid was separated and settled, so it was not realized as a product.

Dilution water used in the following examples and comparative examples was all distilled water.

The fluorine-containing acrylate-based polymer emulsified dispersion (A) obtained in Synthesis Example 1 was prepared according to the following formulation 1, 100% polyester cloth was dipped, and the wet pick-up was made 80% with a mangle.
Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency. The results are shown in Table 3.
Formula 1
Synthesis example 1 emulsified dispersion (A): 5% soln.

(Comparative Example 1)
The fluorine-containing acrylate-based polymer emulsified dispersion (B) obtained in Synthesis Example 2 was prepared according to the following formulation 2, and 100% polyester cloth was dipped, and the wet pick-up was made 80% with a mangle.
Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency. The results are shown in Table 3.
Formula 2
Synthesis Example 2 Emulsified dispersion (B): 5% soln.

(Comparative Example 2)
The fluorine-containing acrylate polymer emulsified dispersion obtained in Synthesis Example 3 was prepared according to the following prescription 3, and a 100% polyester cloth was dipped, and the wet pick-up was made 80% with a mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency. The results are shown in Table 3.
Formula 3
Synthesis Example 3 Emulsified dispersion: 5% soln.

The fluorine-containing acrylate polymer emulsified dispersion (A) obtained in Synthesis Example 1 was prepared according to the following formulation 4, 100% polyester cloth was immersed, and the wet pick-up was made 80% with a mangle.
Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabric thus treated was evaluated for water repellency and oil repellency after initial and after 5 home washings. The results are shown in Table 4.
Formula 4
Synthesis example 1 emulsified dispersion (A): 5% soln.
Melamine resin: Becamine M-3 (manufactured by DIC Corporation): 0.3% soln.
Melamine resin catalyst: Catalyst ACX (manufactured by DIC Corporation): 0.1% soln.

The fluorine-containing acrylate polymer emulsion dispersion liquid (A) obtained in Synthesis Example 1 and the fluorine-containing acrylate polymer emulsion dispersion liquid (B) obtained in Synthesis Example 2 were prepared according to the following formulation 5, and 100% polyester cloth was immersed. Then, the wet pick-up was made 80% with a mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabric thus treated was evaluated for water repellency and oil repellency after initial and after 5 home washings. The results are shown in Table 4.
Formula 5
Synthesis Example 1 Emulsified dispersion (A): 1% soln.
Synthesis Example 2 Emulsified dispersion (B): 4% soln.
Melamine resin: Becamine M-3 (manufactured by DIC Corporation): 0.3% soln.
Melamine resin catalyst: Catalyst ACX (manufactured by DIC Corporation): 0.1% soln.

(Comparative Example 3)
The fluorine-containing acrylate-based polymer emulsified dispersion (B) obtained in Synthesis Example 2 was prepared according to the following formulation 6, 100% polyester cloth was immersed, and the wet pick-up was made 80% with a mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency after initial and after 5 home washings. The results are shown in Table 4.
Formula 6
Synthesis Example 2 Emulsified dispersion (B): 5% soln.
Melamine resin: Becamine M-3 (manufactured by DIC Corporation): 0.3% soln.
Melamine resin catalyst: Catalyst ACX (manufactured by DIC Corporation): 0.1% soln.

(Comparative Example 4)
The fluorine-containing acrylate polymer emulsion dispersion (A) obtained in Synthesis Example 1 and the fluorine-containing acrylate polymer emulsion dispersion (B) obtained in Synthesis Example 2 were prepared according to the following formulation 7, and 100% polyester cloth was immersed Then, the wet pick-up was made 80% with a mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency after initial and after 5 home washings. The results are shown in Table 4.
Formula 7
Synthesis example 1 emulsified dispersion (A): 0.5% soln.
Synthesis Example 2 Emulsified dispersion (B): 5% soln.
Melamine resin: Becamine M-3 (manufactured by DIC Corporation): 0.3% soln.
Melamine resin catalyst: Catalyst ACX (manufactured by DIC Corporation): 0.1% soln.

(Comparative Example 5)
The fluorine-containing acrylate polymer emulsified dispersion obtained in Synthesis Example 3 was prepared according to the following prescription 8, and 100% polyester cloth was dipped, and the wet pick-up was made 80% with mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency after initial and after 5 home washings. The results are shown in Table 4.
Formula 8
Synthesis Example 3 Emulsified dispersion: 5% soln.
Melamine resin: Becamine M-3 (manufactured by DIC Corporation): 0.3% soln.
Melamine resin catalyst: Catalyst ACX (manufactured by DIC Corporation): 0.1% soln.

The fluorine-containing acrylate-based polymer emulsified dispersion (A) obtained in Synthesis Example 1 was prepared according to the following formulation 9, 100% cotton cloth was dipped, and the wet pick-up was made 80% with a mangle. Next, the water and oil repellent treatment was completed by drying at 110 ° C. for 2 minutes and further heat treating at 160 ° C. for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency. The results are shown in Table 5.
Formula 9
Synthesis example 1 emulsified dispersion (A): 5% soln.

(Comparative Example 6)
The fluorine-containing acrylate-based polymer emulsified dispersion (B) obtained in Synthesis Example 2 was prepared according to the following formulation 10, 100% cotton cloth was dipped, and the wet pick-up was made 80% with a mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency. The results are shown in Table 5.
Formula 10
Synthesis Example 2 Emulsified dispersion (B): 5% soln.

(Comparative Example 7)
Fluorine-containing acrylate polymer emulsified dispersion obtained in Synthesis Example 3 was prepared according to the following formulation 11, 100% cotton cloth was immersed, and the wet pick-up was made 80% with mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency. The results are shown in Table 5.
Formula 11
Synthesis Example 3 Emulsified dispersion: 5% soln.

The fluorine-containing acrylate-based polymer emulsified dispersion (A) obtained in Synthesis Example 1 was prepared according to the following formulation 12, and 100% cotton cloth was dipped, and the wet pick-up was made 80% with a mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabric thus treated was evaluated for water repellency and oil repellency after initial and after 5 home washings. The results are shown in Table 6.
Formula 12
Synthesis example 1 emulsified dispersion (A): 5% soln.
Block isocyanate crosslinker: Paracat PGW-4 (Ohara Paradium Chemical Co., Ltd.)
: 2% soln.

The fluorine-containing acrylate polymer emulsion dispersion (A) obtained in Synthesis Example 1 and the fluorine-containing acrylate polymer (B) obtained in Synthesis Example 2 were prepared according to the following prescription 13, and 100% cotton cloth was dipped. The wet pick-up was 80% with a mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabric thus treated was evaluated for water repellency and oil repellency after initial and after 5 home washings. The results are shown in Table 6.
Formula 13
Synthesis Example 1 Emulsified dispersion (A): 1% soln.
Synthesis Example 2 Emulsified dispersion (B): 4% soln.
Block isocyanate crosslinker: Paracat PGW-4 (Ohara Paradium Chemical Co., Ltd.)
: 2% soln.

(Comparative Example 8)
The fluorine-containing acrylate polymer emulsified dispersion (B) obtained in Synthesis Example 2 was prepared according to the following formulation 14, 100% cotton cloth was dipped, and the wet pick-up was made 80% with a mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency after initial and after 5 home washings. The results are shown in Table 4.
Formula 14
Synthesis Example 2 Emulsified dispersion (B): 5% soln.
Block isocyanate crosslinker: Paracat PGW-4 (Ohara Paradium Chemical Co., Ltd.)
: 2% soln.

(Comparative Example 9)
The fluorine-containing acrylate polymer emulsion dispersion (A) obtained in Synthesis Example 1 and the fluorine-containing acrylate polymer (B) obtained in Synthesis Example 2 were prepared according to the following formulation 15, and 100% cotton cloth was dipped. The wet pick-up was 80% with a mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes. The fabrics thus treated were evaluated for water repellency and oil repellency after initial and after 5 home washings. The results are shown in Table 6.
Formula 15
Synthesis example 1 emulsified dispersion (A): 0.5% soln.
Synthesis Example 2 Emulsified dispersion (B): 5% soln.
Block isocyanate crosslinker: Paracat PGW-4 (Ohara Paradium Chemical Co., Ltd.)
: 2% soln.

(Comparative Example 10)
The fluorine-containing acrylate polymer emulsified dispersion obtained in Synthesis Example 3 and the melamine resin were prepared according to the following prescription 16, and 100% polyester cloth was dipped, and the wet pick-up was made 80% with a mangle. Subsequently, it dried at 110 degreeC for 2 minutes, and also heat-processed at 160 degreeC for 2 minutes.
The fabrics thus treated were evaluated for water repellency and oil repellency after initial and after 5 home washings. The results are shown in Table 6.
Formula 16
Synthesis Example 3 Emulsified dispersion: 5% soln.
Block isocyanate crosslinker: Paracat PGW-4 (Ohara Paradium Chemical Co., Ltd.)
: 2% soln.

  From the above results, it is difficult to achieve the object of the present invention with a fluorine-containing acrylate polymer having an Rf group distance of 5.2 mm or less. Therefore, the distance between Rf groups of the present invention is greater than 5.2. It can be seen that the use of a fluorine acrylate polymer is an indispensable condition for obtaining oil repellency by the AATCC118 method of 7 or higher.

Claims (3)

A water-based resin processing agent for fiber processing, wherein the distance between Rf groups of the fluorine-containing acrylate polymer (A) is greater than 5.2 mm, and the average particle diameter is 1.50 μm or less, and the water for fiber processing Or fiber product formed by attaching or fixing a resin processing agent to a fiber surface The fluorine-containing acrylate polymer according to claim 1, wherein the distance between the Rf groups is 5.1 Å <(B) ≦ 5.2 フ ッ 素, and the fluorinated acrylate-based polymer (B) is used in combination up to 9 times the amount. Fiber processing method characterized, and fiber or fiber product formed by attaching or fixing the water-based resin processing agent for fiber processing to the fiber surface A fiber or a fiber product formed by adhering or fixing to the fiber surface with the water-based resin processing agent for fiber processing according to claim 1 and 2, and a resin binder or a crosslinking agent.