JP2006152487A - Method for producing durable stainproof fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing durable stainproof fiber products which imparts fiber products resistant to adhesion of stains and easily releasing adherent stains by washing. <P>SOLUTION: The invention relates to the method for producing durable stainproof fiber products comprising a step imparting (A) an aqueous liquid containing 1-40% by mass of sulfoisophthalic acid or a derivative thereof as a condensation component, (B) an aqueous liquid containing a fluoroacrylate copolymer comprising (a) a (meth)acrylate containing a fluoroalkyl group, (b) a polyalkylene glycol (meth)acrylate, (c) a 3-chloro-2-hydroxypropyl (meth)acrylate and (d) a glycerol mono(meth)acrylate, as constituting monomers, and (C) a crosslinking agent at least one selected from a group comprising a melamine resin based crosslinking agent, an isocyanate based crosslinking agent and a glyoxal resin based crosslinking agent, to the fiber products and a step drying. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a durable antifouling fiber product. More specifically, the present invention relates to a method for producing a durable antifouling fiber product excellent in the detachability of soil adhering to a fiber product, particularly soil containing an oil component and an inorganic substance and / or a pigment.

  2. Description of the Related Art Conventionally, antifouling processing has been performed on fiber products and the like to make it difficult for dirt to adhere to fibers and to easily remove dirt attached to fibers by washing or the like. As such an antifouling method for textiles, a processing method using an antifouling agent containing a hydrophilic polyester resin obtained by polycondensation of a diol component such as polyoxyalkylene glycol and a dicarboxylic acid component is disclosed. (Patent Document 1, Patent Document 2).

  However, these antifouling finishing agents are not always satisfactory in terms of not only the washing durability but also the initial soil detachability depending on the type of material of the fiber product and the type of dirt. For example, these antifouling finishing agents are excellent in the ability to remove aqueous stains (sauce, soy sauce, juice, etc.) and the ability to prevent washing recontamination of oil component stains (heavy oil, salad oil, etc.), but the oil component stains can be removed. Was not always satisfactory. Furthermore, there was almost no effect on the detachability of dirt (dirty motor oil, lipstick, etc.) containing oil components and inorganic substances and / or pigments.

  In addition, by imparting water and oil repellency to textiles and the like, antifouling processing is performed to make it difficult for dirt to adhere to fibers or to easily remove dirt attached to fibers by washing or the like. . The antifouling agent used at this time is an acrylic ester or methacrylic ester having a perfluoroalkyl group, an acrylic ester or methacrylic ester having a hydrophilic group such as a polyoxyalkylene group, and a copolymer thereof. A copolymer obtained by copolymerizing other possible monomers has been proposed (Patent Document 3).

  However, even with these antifouling finishing agents, depending on the type of the raw material of the fiber product and the type of dirt, not only the washing durability but also the initial dirt release properties are not always satisfactory. For example, these antifouling finishing agents are superior in preventing soil re-contamination, although they are excellent in the prevention of soil adhesion of water-based soils, soil releasability, soil adhesion prevention of oil component soils, and soil removability. I was not satisfied. Furthermore, the detachability of the soil containing the oil component and the inorganic substance and / or the pigment was insufficient.

  Furthermore, an antifouling processing method has also been proposed in which a water-repellent / hydrophobic agent having a hydrophilic group is treated after treating a fiber product with a hydrophilic resin (Patent Documents 4 and 5).

  However, this processing method is a contradictory technique in which hydrophilicity is imparted by treatment with a hydrophilic resin and water / oil repellency is imparted by a water / oil repellent. Therefore, the effect of imparting hydrophilicity by the hydrophilic resin is reduced by the effect of imparting water repellency by the water / oil repellent, while the effect of imparting water repellency by the water / oil repellent is hydrophilic. It is reduced by the effect of imparting hydrophilicity by the resin. Therefore, the effect of making it difficult for dirt to adhere to the fiber and the effect of making the attached dirt easy to wash away by washing appears to be inferior to the effect of using a hydrophilic resin or water / oil repellent alone. . Further, since the water- and oil-repellent agent having a hydrophilic group is treated after the hydrophilic resin is treated, there is a disadvantage that the washing durability is inferior even when the crosslinking agent is used together. When the water / oil repellent treatment was performed at the same time, sufficient antifouling properties could not be obtained because the hydrophilic resin and the water / oil repellent were mixed in the same surface layer of the fiber.

Thus, even in the antifouling processing methods described in Patent Document 4 and Patent Document 5, depending on the type of material of the fiber product and the type of dirt, not only the washing durability but also the initial dirt release property However, it was not always satisfactory. For example, this antifouling processing method is excellent in the prevention of soil adhesion, soil release and washing recontamination prevention of aqueous stains and oil component stains, but the ability to remove stains containing oil components and inorganic substances and / or pigments. Was not enough.
JP 57-5983 A JP-A-4-343766 JP-A-6-116340 Japanese Patent Application Laid-Open No. 64-6178 Japanese Patent Laid-Open No. 9-3771

  The present invention has been made in view of the above-mentioned problems of the prior art, and is used for dirt attached to textiles, particularly dirt containing oil components such as dirty motor oil and lipstick and inorganic substances and / or pigments. The purpose of the present invention is to provide a method for producing a durable antifouling fiber product that makes it difficult to adhere to and adheres dirt easily by washing and also has excellent washing durability of these effects. is there.

  As a result of intensive studies to achieve the above object, the present inventors have found that an aqueous liquid containing a polyester resin having a specific structure in a fiber product, an aqueous liquid containing a fluorinated acrylic copolymer having a specific structure, and In addition to aqueous stains and oil component stains, textile products obtained by applying a specific cross-linking agent and drying are also suitable for stains containing oil components such as dirty motor oil and lipstick and inorganic substances and / or pigments. The present invention was completed based on this finding, which was found to be excellent in antifouling properties such that dirt hardly adheres and the attached dirt is easy to be removed by washing, and the effect is excellent in washing durability. .

That is, the manufacturing method of the durable antifouling fiber product of the present invention is:
(A) The following general formula [1] containing 1 to 40% by mass of sulfoisophthalic acid or a derivative thereof as a polycondensation component:

{In Formula [1], R ₁ is HO— or HO (R ₂ O) _a —, R ₂ is an alkylene group having 2 to 4 carbon atoms, and R ₂ O may be only one kind. Two or more types of R ₂ O may be added in a random or block form, a is an integer of 1 to 200, and a may be the same or different in the same molecule. B is an integer of 2 to 100, R ₃ is a hydrogen atom or the following general formula [2]:

(Wherein [2], _{R 5} is a hydrogen atom, a carboxyl group, or -SO ₃ X, X is a hydrogen atom or an alkali metal.)
R ₄ is a hydrogen atom, a carboxyl group or —SO ₃ X, and X is a hydrogen atom or an alkali metal. }
An aqueous liquid containing a polyester resin represented by
(B) (a) Acrylic acid ester or methacrylic acid ester having a fluoroalkyl group, (b) polyalkylene glycol acrylate or polyalkylene glycol methacrylate, (c) 3-chloro-2-hydroxypropyl acrylate or 3-chloro-2 An aqueous liquid comprising hydroxypropyl methacrylate and (d) a fluorinated acrylic copolymer containing structural units derived from glycerol monoacrylate or glycerol monomethacrylate, and
(C) at least one crosslinking agent selected from the group consisting of a melamine resin crosslinking agent, an isocyanate crosslinking agent and a glyoxal resin crosslinking agent,
Is applied to a fiber product and dried.

  In the method for producing a durable antifouling fiber product of the present invention, the polyester resin preferably has a weight average molecular weight of 1,000 to 50,000, and the fluorine-based acrylic copolymer has a weight average molecular weight. It is preferable that it is 1,000-500,000.

  Moreover, in the manufacturing method of the durable antifouling textiles of this invention, the said aqueous liquid (A) so that the said polyester resin may be 10-300 mass parts with respect to 100 mass parts of said fluorine-type acrylic copolymers. And the aqueous liquid (B) is preferably used.

  The durable antifouling fiber product obtained by the production method of the present invention adheres to soils adhering to the fiber products, particularly soils containing oil components such as dirty motor oil and lipstick, and inorganic substances and / or pigments. It has a high level of washing durability, and is excellent in antifouling properties such that it is difficult to remove and the attached dirt is easily removed by washing.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  The method for producing a durable antifouling fiber product of the present invention comprises (A) an aqueous liquid containing a specific polyester resin, (B) an aqueous liquid containing a specific fluorine-based acrylic copolymer, and (C) a melamine. It is a method characterized in that at least one crosslinking agent selected from the group consisting of a resin crosslinking agent, an isocyanate crosslinking agent and a glyoxal resin crosslinking agent is applied and dried.

  First, the aqueous liquid (A) containing a specific polyester resin used in the method for producing a durable antifouling fiber product of the present invention will be described.

  The polyester resin used in the present invention contains 1 to 40% by mass (more preferably 2 to 35% by mass) of sulfoisophthalic acid or a derivative thereof as a polycondensation component, and is represented by the following general formula [1]. It is expressed. When the content of the sulfoisophthalic acid or its derivative is less than 1% by mass, the antifouling property is inferior. On the other hand, when it exceeds 40% by mass, the washing durability decreases and the antifouling property decreases.

Here, in the general formula [1], R ₁ is HO— or HO (R ₂ O) _a —, R ₂ is an alkylene group having 2 to 4 carbon atoms, and R ₂ O is only one kind. Or two or more types of R ₂ O may be added in a random or block form, and a is an integer of 1 to 200, and a may be the same in the same molecule. B is an integer of 2 to 100, R ₃ is a hydrogen atom or a group represented by the following general formula [2], and R ₄ is a hydrogen atom, a carboxyl group or —SO ₃ X X is a hydrogen atom or an alkali metal.

Here, in the general formula [2], R ₅ is a hydrogen atom, a carboxyl group, or —SO ₃ X, and X is a hydrogen atom or an alkali metal.

The polyester resin represented by the general formula [1] used in the present invention is composed of a sulfoisophthalic acid or a derivative thereof as an essential polycondensation component, another aromatic polyvalent carboxylic acid or a derivative thereof, and a general formula HO- (R _The glycol represented by ₂ O) _a -H can be used as a polycondensation component and can be produced by a conventionally known method. And it contains 1-40 mass% of sulfoisophthalic acid or its derivative with respect to the whole quantity of these polycondensation components, It is characterized by the above-mentioned.

  Examples of the sulfoisophthalic acid or derivative thereof used in the present invention include sulfoisophthalic acid, sulfoisophthalate whose sulfone group is an alkali metal salt, and lower alkyl esterified product, hydroxyethyl esterified product of these sulfoisophthalic acid or sulfoisophthalic acid salt, Specific examples include hydroxypropyl esterified products, such as sulfoisophthalic acid, sulfoisophthalic acid sodium salt, sulfoisophthalic acid potassium salt, sulfoisophthalic acid dimethyl ester, sulfoisophthalic acid diethyl ester, sulfoisophthalic acid dipropyl ester, sulfo Isobutyl dibutyl ester, sulfoisophthalic acid dimethyl ester sodium salt, sulfoisophthalic acid diethyl ester sodium salt, sulfoisophthalic acid dipropyl ester sodium salt, Rufoisophthalic acid dibutyl ester sodium salt, sulfoisophthalic acid dimethyl ester potassium salt, sulfoisophthalic acid diethyl ester potassium salt, sulfoisophthalic acid dipropyl ester potassium salt, sulfoisophthalic acid dibutyl ester potassium salt, sulfoisophthalic acid dihydroxyethyl ester, sulfoisophthalic acid And polycondensable derivatives such as dihydroxypropyl ester, sulfoisophthalic acid dihydroxyethyl ester sodium salt, sulfoisophthalic acid dihydroxypropyl ester sodium salt, sulfoisophthalic acid dihydroxyethyl ester potassium salt, and sulfoisophthalic acid dihydroxypropyl ester potassium salt. . These sulfoisophthalic acids or derivatives thereof can be used alone or in combination of two or more.

  Other aromatic polyvalent carboxylic acids used in the present invention include terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, pyromellitic acid and the like. In addition, examples of the derivatives include anhydrides of the above aromatic polyvalent carboxylic acids, dimethyl esters, diethyl esters, dipropyl esters, dibutyl esters, and other lower alkyl esterified products, dihydroxyethyl esterified products, dihydroxypropyl esterified products, and acid chloride products. The polycondensable derivative of can be mentioned. As other aromatic polyvalent carboxylic acids or derivatives thereof, terephthalic acid or derivatives thereof are preferably used. These other aromatic polyvalent carboxylic acids or derivatives thereof can be used alone or in combination of two or more.

General formula HO- (R ₂ O) _a -H used in the present invention
Examples of the glycol represented by the formula include alkylene glycol and polyalkylene glycol. Examples of the alkylene glycol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and 1,4-butanediol. These alkylene glycols can be used individually by 1 type, and can also be used in combination of 2 or more type. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, and a random or block copolymer of ethylene oxide and propylene oxide each having a hydroxyl group at both ends. These polyalkylene glycols can be used alone. It can also be used in combination of two or more. Among these, polyethylene glycol is preferable, and polyethylene glycol having an average molecular weight of 1000 to 6000 is more preferable.

  In the said General formula [1], a is an integer of 1-200, More preferably, it is an integer of 1-150. When a exceeds 200, the viscosity of the polyester resin represented by the general formula [1] becomes too high and handling becomes difficult. The polyester resin represented by the general formula [1] includes, for example, dimethyl ester of polyvalent carboxylic acid such as sulfoisophthalic acid sodium salt, terephthalic acid, isophthalic acid, phthalic acid, ethylene glycol, propylene glycol, diethylene glycol, dipropylene. It is manufactured by reacting alkylene glycol such as glycol, 1,4-butanediol, or polyethylene glycol having a certain molecular weight, and performing polycondensation by performing an ester exchange reaction involving demethanol or dealkylene glycol. Can do.

  The polyester resin represented by the general formula [1] includes, for example, dihydroxyethyl ester or dihydroxypropyl ester of polycarboxylic acid such as sodium sulfoisophthalate, terephthalic acid, isophthalic acid, phthalic acid, ethylene glycol, Propylene glycol, diethylene glycol, dipropylene glycol, alkylene glycol such as 1,4-butanediol, and polyethylene glycol having a certain molecular weight are reacted to perform transesterification reaction with deethylerin glycol or depropylene glycol. It can manufacture by performing and performing polycondensation. In General formula [1], b is an integer of 2-100, More preferably, it is an integer of 2-30. When b exceeds 100, the viscosity of the polyester resin represented by the general formula [1] becomes too high and handling becomes difficult.

  In the present invention, the weight average molecular weight of the polyester resin represented by the general formula [1] is preferably 1,000 to 50,000, and more preferably 5,000 to 20,000. If the weight average molecular weight of the polyester resin is less than 1,000, the soil detachment effect tends to be insufficient. On the other hand, when the weight average molecular weight of the polyester resin exceeds 50,000, the viscosity of the polyester resin becomes too high and the handling tends to be difficult. The weight average molecular weight of the polyester resin can be determined by gel permeation chromatography using monodisperse polyethylene glycol having a known molecular weight as a measurement standard substance.

  The aqueous liquid (A) according to the present invention is an aqueous liquid containing the above-described polyester resin, and such an aqueous liquid may be an aqueous solution or a suspension (dispersion). The solvent in the aqueous liquid (A) according to the present invention is not particularly limited, but preferably contains at least 50% by mass of water, and examples of the solvent other than water include DMF, ethylene glycol, diethylene glycol, glycerin, N- And methyl pyrrolidone. The content of the polyester resin in the aqueous liquid (A) according to the present invention is not particularly limited, but is preferably about 5 to 40% by mass.

  Next, the aqueous liquid (B) containing the specific fluorine-type acrylic copolymer used with the manufacturing method of the durable antifouling textile product of this invention is demonstrated.

  The fluorinated acrylic copolymer used in the present invention includes (a) an acrylic ester or methacrylic ester having a fluoroalkyl group, (b) polyalkylene glycol acrylate or polyalkylene glycol methacrylate, (c) 3-chloro-2- It contains a structural unit derived from hydroxypropyl acrylate or 3-chloro-2-hydroxypropyl methacrylate and (d) glycerol monoacrylate or glycerol monomethacrylate, and has a weight average molecular weight of 1,000 to 500,000. A polymer is preferred.

Although there is no restriction | limiting in particular in the acrylic ester or methacrylic ester containing the fluoroalkyl group used for a monomer (a), It is preferable that carbon number of a fluoroalkyl group is 3-20. Specific examples of the monomer (a) are as follows.
_{CF 3 (CF 2) 4 CH} 2 OCOC (CH 3) = CH 2
_{CF 3 (CF 2) 7 (} CH 2) 2 OCOC (CH 3) = CH 2
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₄ (CH ₂ ) 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 ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH _{2
(CF 3) 2 CF (CF} 2) 6 CH 2 CH (OCOCH 3) OCOC (CH 3) = CH 2
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOCH═CH _{2
CF 3 (CF 2) 9 (} CH 2) 2 OCOC (CH 3) = CH 2
_{CF 3 (CF 2) 9 CONH} (CH 2) 2 OCOC (CH 3) = CH 2
(CF ₃ ) (CF ₂ Cl) CF (CF ₂ ) ₇ CONH (CH ₂ ) ₂ OCOCH═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 OCOCH═CH ₂
(CF ₃ ) (CF ₂ Cl) CF (CF) ₇ CONH (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH _{2
CF 3 CF 2 CH 2 CH (} OH) CH 2 OCH 2 CH 2 OCOCH = CH 2.

  The monomer (b) polyalkylene glycol acrylate or polyalkylene glycol methacrylate is preferably represented by the following general formula [3].

_{H 2 C = CR 6 -COO (} R 7 O) n R 8 ··· [3]
Here, in the general formula [3], R ₆ is a hydrogen atom or a methyl group, R ₇ is a linear or branched alkylene group having 2 to 6 carbon atoms, and R ₈ is a hydrogen atom or carbon. It is a linear or branched alkyl group having 1 to 21, and n is an integer of 3 to 50.

Of course, the type of R ₆ , R ₇ , R _{8 in} the general formula [3] or a mixture of two or more different n may be used. R ₇ in the general formula [3] is preferably —CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —, and more preferably a combination thereof. Although n is an integer of 3-50, it is more preferable that it is an integer of 6-25. Specific examples of the monomer (b) are as follows.
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 3-9 H
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 9 H
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 6 H
_{CH 2 = CHCOO (CH 2 CH} (CH 3) O) 11 CH 3
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 5 (CH 2 CH (CH 3) O) 3 H
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 9 CH 3
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 23 CH 3
_{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 40 H.

  Furthermore, as the 3-chloro-2-hydroxypropyl acrylate or 3-chloro-2-hydroxypropyl methacrylate of the monomer (c), those represented by the following general formula [4] are preferable.

_{CH 2 = C (R 9)} COOCH 2 CH (OH) CH 2 Cl ··· [4]
Here, in the general formula [4], R ₉ is a hydrogen atom or a methyl group.

  As the monomer (d) glycerol monoacrylate or glycerol monomethacrylate, those represented by the following general formula [5] are preferable.

_{CH 2 = C (R 10)} COOCH 2 CH (OH) CH 2 OH ··· [5]
Here, in the general formula [5], R ₁₀ is a hydrogen atom or a methyl group.

  In the fluorinated acrylic copolymer used in the present invention, the copolymerization ratio of each monomer is preferably as follows. That is, the copolymerization ratio of the monomer (a) is preferably at least 25% by mass, and more preferably 30 to 70% by mass. If it is less than 25% by mass, the water and oil repellency and antifouling properties tend to be insufficient. Moreover, it is preferable that it is at least 15 mass%, and, as for the copolymerization ratio of a monomer (b), it is more preferable that it is 20-60 mass%. If it is less than 15% by mass, the dispersibility in water is not good, and the durability to washing and antifouling tend to be insufficient. Furthermore, the copolymerization ratio of the monomer (c) is preferably at least 0.5% by mass, and more preferably 0.5-30% by mass. Moreover, it is preferable that the copolymerization ratio of a monomer (d) is at least 0.5 mass%, and it is more preferable that it is 0.5-30 mass%. The total copolymerization ratio of the monomer (c) and the monomer (d) is preferably at least 5% by mass and 8 to 30% by mass. If it is less than 5% by mass, the dirt release property and the washing durability tend to be insufficient. The ratio of the monomer (c) to the total of the monomer (c) and the monomer (d) is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. . If it is less than 10% by mass or more than 90% by mass, the washing durability tends to be insufficient.

  The weight average molecular weight of the fluorinated acrylic copolymer used in the present invention is preferably 1,000 to 500,000, and more preferably 5,000 to 200,000. If the weight average molecular weight is less than 1,000, the washing durability is not sufficient. On the other hand, if it exceeds 500,000, the viscosity of the aqueous liquid tends to be too high and the workability tends to be lowered. In addition, the weight average molecular weight of a fluorine-type acrylic copolymer is the value calculated | required by gel permeation chromatography by polystyrene conversion. The fluorinated acrylic copolymer used in the present invention may be random copolymer or block copolymer.

In addition to the monomers (a), (b), (c) and (d), the fluorine-based acrylic copolymer of the present invention includes acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, ethylene, vinyl chloride, vinylidene halide, styrene, alkyl acrylate or methacrylic acid _(C 1 ~C ₂₁₎ esters, benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl ether, Isoprene, chloroprene, butadiene, N-methylol acrylamide, diacetone acrylamide, glycidyl acrylate, polyoxydiene acrylate, trimethoxysilyl acrylate, blocked isocyanate group-containing acrylate, N-methylol methacrylamide, diacetone methacrylamide, glycerin Other fluorine-free copolymerizable with acrylic acid ester or methacrylic acid ester having fluoroalkyl group such as sidyl methacrylate, polyoxyl dimethacrylate, trimethoxysilyl methacrylate, blocked isocyanate group-containing methacrylate, etc. Monomers can be copolymerized. The amount of these other monomers not containing fluorine is preferably 0 to 40% by mass, and more preferably 0 to 20% by mass.

  In the present invention, a conventionally known copolymerization method can be applied as a production method for obtaining the fluorine-based acrylic copolymer.

  The aqueous liquid (B) according to the present invention is an aqueous liquid containing the above-mentioned fluorinated acrylic copolymer, and such an aqueous liquid may be an aqueous solution or a suspension (dispersion). The solvent in the aqueous liquid (B) according to the present invention is not particularly limited, but preferably contains at least 1% by mass of water, and examples of the solvent other than water include isopropyl alcohol, ethyl alcohol, acetone, tripropylene glycol. , Dipropylene glycol, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol and the like. Further, the content of the fluorinated acrylic copolymer in the aqueous liquid (B) according to the present invention is not particularly limited, but is preferably about 5 to 50% by mass.

  In the method for producing a durable antifouling fiber product of the present invention, the proportion of the fluorine-based acrylic copolymer and the polyester resin used is 10 to 10 parts by weight of the polyester resin with respect to 100 parts by mass of the fluorine-based acrylic copolymer. It is preferably used so as to be 300 parts by mass, more preferably used so as to be 20 to 200 parts by mass, and most preferably used so as to be 30 to 100 parts by mass. When the amount of the polyester resin used is less than 10 parts by mass, there is a tendency that sufficient dirt detachability and washing durability cannot be expressed. A reasonable effect cannot be obtained and the cost tends to be disadvantageous.

  The fluorine-based acrylic copolymer is preferably a resin component and is added to the fiber product in an amount of 0.2 to 2% by mass, considering the texture, performance, and economy, 0.3 to 1.5% by mass. More preferably, it is given.

  In the method for producing a durable antifouling fiber product of the present invention, in addition to the polyester resin and the fluorinated acrylic copolymer, a melamine resin crosslinking agent, an isocyanate crosslinking agent and a glyoxal resin crosslinking agent are used. The durability is improved by adding at least one selected crosslinking agent. Among these crosslinking agents, it is preferable to use a melamine resin crosslinking agent and an isocyanate crosslinking agent in combination from the viewpoint of further improving durability. In the case of a melamine resin-based crosslinking agent or an isocyanate-based crosslinking agent, the amount of these crosslinking agents used is preferably 0.05 to 1% by mass and more preferably 0.1 to 1% by mass with respect to the fiber product as an active ingredient. preferable. When the amount of the crosslinking agent used is less than 0.05% by mass, the durability to washing is inferior, and when it exceeds 1% by mass, the texture tends to be hard. The amount of glyoxal resin-based crosslinking agent used is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the fiber product as an active ingredient. When the amount of the crosslinking agent used is less than 0.5% by mass, the washing durability is inferior, and when it is more than 10% by mass, the texture tends to become hard.

  In the method for producing a durable antifouling fiber product of the present invention, an epoxy resin-based crosslinking agent, a silane coupling agent-based crosslinking agent, an oxazoline-based crosslinking agent, a carbodiimide-based crosslinking agent, etc. may be used in combination as other crosslinking agents. Is possible.

  Examples of the melamine resin-based crosslinking agent used in the present invention include trimethylol-based melamine, hexamethylol-based melamine, and the like. These methylol-based melamines include an alkoxymethylol group in which a methylol group hydrogen is substituted with an alkyl group. You can leave. Among these melamine resin crosslinking agents, it is preferable to use trimethylol melamine.

  In addition, when these melamine resin crosslinking agents are used, the reactivity can be improved by using a catalyst such as an organic amine salt catalyst, dimmonium phosphate, or ammonium chloride, and durability is further improved. To do. Among these catalysts, use of an organic amine salt-based catalyst is preferable, and the amount of the catalyst used is preferably 1 to 20% by mass and more preferably 2 to 10% by mass with respect to the melamine resin-based crosslinking agent. If the amount of the catalyst used is less than 1% by mass relative to the melamine resin-based crosslinking agent, the reactivity of the melamine resin is inferior and the washing durability is lowered, and if unreacted melamine resin remains, an odor problem tends to occur. . On the other hand, when the amount of the catalyst used is more than 10% by mass based on the melamine resin-based crosslinking agent, the reactivity of the melamine resin is good, but in particular, the organic amine salt-based catalyst tends to lower the antifouling property.

  The isocyanate crosslinking agent used in the present invention is not particularly limited as long as it can be emulsified and dispersed in water. Examples of the aromatic polyisocyanate used for the production of the isocyanate-based crosslinking agent include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and the like. Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene. Examples include diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and hydrogenated xylylene diisocyanate. Among these polyisocyanates, it is preferable to use an aliphatic polyisocyanate or an alicyclic polyisocyanate because yellowing of the treated fiber product is not observed.

  The polyisocyanate derived from the polyisocyanate can also be used as an isocyanate-based cross-linking agent, and is not particularly limited as long as it has two or more isocyanate groups. For example, a biuret structure, an isocyanate structure, Examples thereof include polyisocyanates having a urethane structure, a uretdione structure, an allophanate structure, a trimer structure, and the like, and adducts of aliphatic isocyanates of trimethylolpropane. These polyisocyanates can be produced by a conventionally known method.

  Moreover, as an isocyanate type crosslinking agent used for this invention, what is called a blocked isocyanate compound which liberates an isocyanate group may be sufficient. Here, as the blocking agent for the blocked isocyanate group, alkyl ketoximes, phenols, alcohols, β-diketones, and lactams are preferable, and methyl ethyl ketoxime, ε-caprolactam, phenol, cresol, acetylacetone, malonic acid Diethyl, isopropyl alcohol, t-butyl alcohol, maleic imide and the like are particularly preferable, and in particular, a blocking agent composed of methyl ethyl ketoxime is more preferable.

  Further, the isocyanate-based crosslinking agent used in the present invention may be an aqueous polyisocyanate compound. The aqueous polyisocyanate compound to be used is not particularly limited as long as it can be emulsified and dispersed in water, but from the group consisting of aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate and polyisocyanate derived therefrom. A compound in which an alkylene oxide chain is bonded to at least one selected is preferable, and a lipophilic chain may be further bonded as necessary. Such an aqueous polyisocyanate compound can be used in an aqueous solution for a long time while having a high reactivity of an isocyanate group, and is excellent in self-emulsifying property in water, so that the polyester resin and the fluorinated acrylic copolymer are used as fibers. When applied to a product, it can also be used in the treatment liquid.

  The glyoxal resin-based crosslinking agent used in the present invention is a dimethylol dihydroxyethylene urea-based resin, and may contain an alkoxymethylol group in which a hydrogen of a methylol group is substituted with an alkyl group. Further, when these glyoxal resin-based crosslinking agents are used, the reactivity can be improved by using a metal salt-based catalyst such as magnesium chloride and zinc nitrate together, and the washing durability can be further improved. The amount of these catalysts used is preferably 5 to 15% by mass with respect to the glyoxal resin-based crosslinking agent. If the amount of the catalyst used is less than 5% by mass relative to the glyoxal resin-based crosslinking agent, the reactivity of the glyoxal resin tends to be inferior and the washing durability tends to decrease. On the other hand, if the amount used is more than 15% by mass, the reactivity of the glyoxal resin is good. However, the amount of the catalyst tends to increase and the texture becomes harder.

  In the method for producing a durable antifouling fiber product of the present invention, as a method for imparting an aqueous liquid containing the polyester resin, an aqueous liquid containing the fluorinated acrylic copolymer, and the cross-linking agent to the fiber product, There is no particular limitation, and a conventional method can be used as appropriate. For example, an aqueous liquid containing the polyester resin, an aqueous liquid containing the fluorinated acrylic copolymer, and the cross-linking agent are applied to the fiber product by a pad method, a dipping method, a spraying method, a foam processing method, a coating method, or the like. It can then be dried.

  In addition, in the manufacturing method of the durable antifouling textiles of the present invention, the specific order which gives the textiles the aqueous liquid containing the polyester resin, the aqueous liquid containing the fluoroacrylic copolymer, and the cross-linking agent. Etc. are not particularly limited, and preferable methods include the following methods (i) to (iii).

  (i) Applying an aqueous liquid containing the polyester resin, the fluorinated acrylic copolymer and the crosslinking agent to a fiber product and drying it to produce the durable antifouling fiber product of the present invention, by so-called one-bath treatment Method.

  (ii) Applying the aqueous liquid containing the polyester resin to the fiber product and then drying, then applying the aqueous liquid containing the fluorinated acrylic copolymer and the crosslinking agent, followed by drying to provide the durable antifouling of the present invention A so-called two-bath process for producing a porous fiber product.

  (iii) After applying the aqueous liquid containing the polyester resin to the fiber product, the aqueous liquid containing the fluorine-based acrylic copolymer and the cross-linking agent is then applied and dried to provide the durable antifouling fiber product of the present invention. A process by so-called two-bath treatment.

  Thus, in the present invention, the specific production method is not particularly limited, but an aqueous liquid containing the polyester resin, the fluorinated acrylic copolymer, and the cross-linking agent is applied to a fiber product and dried to obtain the present product. The so-called one-bath treatment method for producing the durable antifouling fiber product of the invention is preferred from the viewpoint of the effect of the initial soil release. Further, after drying, a curing (heat treatment) step may be incorporated as necessary. As a drying method, a conventionally used method can be used without limitation, and either a dry heat method or a wet heat method may be used. The temperature during the drying step is not particularly limited, but is preferably about 80 to 140 ° C. Further, the temperature during the curing (heat treatment) step that is performed as necessary is not particularly limited, but is preferably about 150 to 200 ° C.

  According to the method for producing a durable antifouling fiber product of the present invention, a polyester resin containing 1 to 40% by mass of sulfoisophthalic acid or a derivative thereof as a polycondensation component to enhance anionicity is applied to the fiber product. Even if the fluorine-based acrylic copolymer is added, the effect of imparting the hydrophilic property of the polyester resin is not reduced. Therefore, the excellent effect of the polyester resin, which makes it easy to remove attached dirt by washing, is efficient and reliable. Expressed in In addition, the ability of the fluorine-based acrylic copolymer to easily take in the washing liquid due to the hydrophilic group of the fluorine-acrylic copolymer can be easily removed without reducing the effect of making the fluorine-based acrylic copolymer difficult to adhere. However, the adhered dirt is facilitated by washing because it is promoted by the polyester resin having enhanced anionic property. Therefore, even when the polyester resin and the fluorinated acrylic copolymer are applied to the fiber product, the effects of each other, that is, the adhesion of dirt and the dirt release property are not reduced, but rather synergistically. The effect is exhibited, and an unprecedented excellent antifouling fiber product can be obtained. Therefore, according to the present invention, a sufficient effect can be achieved even for dirt containing oil components such as dirty motor oil and lipstick and inorganic substances and / or pigments, which has been insufficient in antifouling properties. The

  Moreover, in this invention, it is disclosed by patent document 4 and patent document 5 by using the polyester resin which contained 1-40 mass% of sulfo isophthalic acid or its derivative as a polycondensation component, and strengthened anionic property. Such a processing method of applying a hydrophilic resin to a fiber product first and then applying a fluorinated acrylic copolymer is not limited to the processing method. In the manufacturing method of the present invention, the polyester resin, the fluorine By treating the acrylic copolymer and the crosslinking agent at the same time, a more excellent antifouling effect can be obtained.

  Moreover, in the manufacturing method of the durable antifouling textile product of this invention, 1-40 mass% of sulfoisophthalic acid or its derivative (s) is contained as a polycondensation component, It represents with the said General formula [1] which strengthened anionic property. An aqueous liquid containing a polyester resin, and (a) an acrylic ester or methacrylic ester having a fluoroalkyl group, (b) a polyalkylene glycol acrylate or a polyalkylene glycol methacrylate, (c) 3-chloro-2-hydroxypropyl acrylate or In addition to an aqueous liquid containing 3-chloro-2-hydroxypropyl methacrylate and (d) a fluorinated acrylic copolymer containing a structural unit derived from glycerol monoacrylate or glycerol monomethacrylate, a melamine resin-based crosslinking agent, isocyanate Cross-linking agent By applying at least one cross-linking agent selected from the group consisting of glyoxal resin-based cross-linking agents to textiles, washing is also performed with respect to antifouling properties against dirt containing oil components such as dirty motor oil and lipstick and inorganic substances and / or pigments. Durability can be improved, and a textile product excellent in washing durability with antifouling performance that could not be obtained conventionally can be produced.

  In addition, in the method for producing a durable antifouling fiber product of the present invention, processing agents commonly used in textile products such as flame retardants, antistatic agents, dye stabilizers, shrink-proofing agents, antibacterial agents, and insecticides are used in combination. May be.

  The material of the textile product to which the production method of the present invention can be applied is not particularly limited, such as natural fibers such as cotton, hemp, silk, wool, semi-synthetic fibers such as rayon, acetate, nylon, polyester, polyurethane, polypropylene, etc. Examples thereof include synthetic fibers, composite fibers of these, and mixed fibers. The form of the textile product may be any form such as woven fabric, knitted fabric, yarn, non-woven fabric, paper, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

  In addition, about the work cloth obtained by the Example and comparative example which are mentioned later, stain | pollution | removal property was evaluated by the following method.

(1) Diamond paste method (Japan Chemical Fiber Association standard JCFA TM-104)
The work cloth obtained by the example or the comparative example is spread on the filter paper laid horizontally. A fixed amount of soil components with the following blending ratio was attached to this, and allowed to stand at room temperature for 1 hour, followed by washing (bath ratio 1:30, liquid temperature 40 ° C., detergent attack (trade name, manufactured by Kao Corporation) 25 g, 2 tank type electric washing machine) for 15 minutes. Then rinse, dehydrate and air dry. The state of stains remaining on the dried work cloth was determined by a gray scale for contamination (JIS L 0805).

Contamination component ratio (mass)
Carbon black 0.167
Liquid paraffin 0.625
Beef tallow oil 0.208
Motor oil (manufactured by Shell) 100.

(2) Lipstick detachment test On a glass plate placed horizontally, the work cloth obtained by the example or the comparative example is spread. A certain amount of lipstick (makeup planet lip color RD1 (trade name, Shiseido Co., Ltd.)) was attached to this, and allowed to stand at room temperature for 20 hours, followed by washing (bath ratio 1:30, liquid temperature 40 ° C., detergent attack) (Trade name, manufactured by Kao Corporation) 25 g, 2 tank type electric washing machine) is performed for 15 minutes. Then rinse, dehydrate and air dry. The state of stains remaining on the dried work cloth was determined by a gray scale for contamination (JIS L 0805).

Synthesis Example 1 (Aqueous liquid of fluorinated acrylic copolymer A)
In a four-necked flask, 20 g of C _n F _{2n + 1} CH ₂ CH ₂ COOCH═CH ₂ (n = 6, 8, 10, 12, 14; average 8), CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ CH ₃ 10 g, CH ₂ ═C (CH ₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H 5 g, CH ₂ ═C (CH ₃ ) COOCH ₂ CH (OH) CH ₂ Cl 1 g of CH ₂ ═C (CH ₃ ) COOCH ₂ CH (OH) CH ₂ OH and 60 g of isopropyl alcohol were added, and the inside of the system was sufficiently substituted with nitrogen, followed by 0.1 g of azobisisobutyronitrile. Was added and the reaction was stirred at 70 ° C. for 10 hours. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, and 40 g of isopropyl alcohol and 60 g of ion-exchanged water were added and diluted with stirring. The obtained copolymer had a solid content of 20.0% by mass. Moreover, the molecular weight of the copolymer was 12,000 (converted to styrene) as a result of measurement by gel permeation chromatography.

Synthesis example 2 (aqueous liquid of fluorine-based acrylic copolymer B)
In the same manner as in Synthesis Example 1, 20 g of C _n F _{2n + 1} CH ₂ CH ₂ COOCH═CH ₂ (n = 6, 8, 10, 12, 14; average 8), CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₆ H 8 g, CH ₂ ═C (CH ₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H 7 g, CH ₂ ═C (CH ₃ ) COOCH ₂ CH (OH) CH ₂ 4 g of Cl, 1 g of CH ₂ ═C (CH ₃ ) COOCH ₂ CH (OH) CH ₂ OH, and 60 g of isopropyl alcohol were added, and the inside of the system was sufficiently substituted with nitrogen, and then azobisisobutyronitrile 0. 1 g was added, and the reaction was stirred at 70 ° C. for 10 hours. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, and 40 g of isopropyl alcohol and 60 g of ion-exchanged water were added and diluted with stirring. The obtained copolymer was 19.8 mass% solid content. The molecular weight of the copolymer was 15,000 (converted to styrene) as a result of measurement by gel permeation chromatography.

Comparative Synthesis Example 1 (Aqueous liquid of fluorinated acrylic copolymer C)
In the same manner as in Synthesis Example 1, 20 g of C _n F _{2n + 1} CH ₂ CH ₂ COOCH═CH ₂ (n = 6, 8, 10, 12, 14; average 8), CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ CH ₃ (15 g), CH ₂ = C (CH ₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H, 5 g of isopropyl alcohol and 60 g of isopropyl alcohol are added, and the inside of the system is sufficiently replaced with nitrogen After that, 0.1 g of azobisisobutyronitrile was added and the reaction was stirred at 70 ° C. for 10 hours. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, and 40 g of isopropyl alcohol and 60 g of ion-exchanged water were added and diluted with stirring. The obtained copolymer had a solid content of 20.0% by mass. Moreover, the molecular weight of the copolymer was 12,000 (converted to styrene) as a result of measurement by gel permeation chromatography.

Comparative Synthesis Example 2 (Aqueous liquid of fluorinated acrylic copolymer D)
In the same manner as in Synthesis Example 1, 20 g of C _n F _{2n + 1} CH ₂ CH ₂ COOCH═CH ₂ (n = 6, 8, 10, 12, 14; average 8), CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ CH 10 g, CH ₂ ═C (CH ₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H 5 g, CH ₂ ═C (CH ₃ ) COOCH ₂ CH (OH) CH ₂ After 5 g of OH and 60 g of isopropyl alcohol were added and the inside of the system was sufficiently substituted with nitrogen, 0.1 g of azobisisobutyronitrile was added, and the mixture was stirred at 70 ° C. for 10 hours. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, and 40 g of isopropyl alcohol and 60 g of ion-exchanged water were added and diluted with stirring. The obtained copolymer was 19.9 mass% solid content. The molecular weight of the copolymer was 11,000 (in terms of styrene) as a result of measurement by gel permeation chromatography.

Comparative synthesis example 3 (aqueous liquid of fluorine-based acrylic copolymer E)
In the same manner as in Synthesis Example 1, 20 g of C _n F _{2n + 1} CH ₂ CH ₂ COOCH═CH ₂ (n = 6, 8, 10, 12, 14; average 8), CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ CH ₃ 10 g, CH ₂ ═C (CH ₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H 5 g, CH ₂ ═C (CH ₃ ) COOCH ₂ CH (OH) CH the ₂ Cl 5 g, put isopropyl alcohol 60 g, was thoroughly purging the system with nitrogen, was added azobisisobutyronitrile 0.1 g, was stirred for 10 hours at 70 ° C.. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, and 40 g of isopropyl alcohol and 60 g of ion-exchanged water were added and diluted with stirring. The obtained copolymer had a solid content of 20.0% by mass. The molecular weight of the copolymer was 10,000 (in terms of styrene) as a result of measurement by gel permeation chromatography.

Comparative Synthesis Example 4 (Aqueous liquid of fluorinated acrylic copolymer F)
In the same manner as in Synthesis Example 1, 20 g of C _n F _{2n + 1} CH ₂ CH ₂ COOCH═CH ₂ (n = 6, 8, 10, 12, 14; average 8), CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₆ H 10 g, CH ₂ = C (CH ₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H 5 g, CH ₂ = CHCONHCH ₂ OH 5 g, isopropyl alcohol 60 g, nitrogen Then, 0.1 g of azobisisobutyronitrile was added, and the mixture was stirred at 70 ° C. for 10 hours. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, and 40 g of isopropyl alcohol and 60 g of ion-exchanged water were added and diluted with stirring. The obtained copolymer had a solid content of 20.1% by mass. The molecular weight of the copolymer was 11,000 (in terms of styrene) as a result of measurement by gel permeation chromatography.

Synthesis Example 3 (Aqueous liquid of polyester resin A)
In a reaction vessel equipped with a stirrer, thermometer, methanol outflow tube, and rectification tube, 77.6 g (0.4 mol) of dimethylterephthalic acid and 29.6 g (0.1 mol) of sodium salt of 5-sulfoisophthalic acid dimethyl ester , 279 g (0.09 mol) of polyethylene glycol (PEG 4000, manufactured by Sanyo Chemical Industries, trade name, average molecular weight: about 3100), 68.2 g (1.1 mol) of monoethylene glycol and 0.1 g of antimony trioxide Then, 0.1 g of zinc acetate is charged and N ₂ gas is introduced. The temperature is raised by heating, and the temperature is slowly raised to 130 to 180 ° C. over 2 hours to conduct a transesterification reaction. Methanol outflow begins at 140 ° C. Further, after slowly raising the temperature from 180 ° C. to 250 ° C. over 2 hours, the N ₂ gas flow was stopped, and after reacting at 250 to 260 ° C. under reduced pressure of about 5 mmHg for 2 hours, further reduced pressure of 260 ° C. and about 2 mmHg. Under the reaction for 30 minutes, 400 g of a polyester resin was obtained. The weight average molecular weight of this polyester resin was about 14,000 as a result of measurement by gel permeation chromatography [High-speed GPC manufactured by Tosoh Corporation, HLC-8120, measurement standard substance: polyethylene glycol]. 100 g of this polyester resin was dissolved in 50 g of N, N-dimethylformamide (DMF) and emulsified in 850 g of hot water to obtain an aqueous liquid of polyester resin A.

Synthesis Example 4 (Aqueous liquid of polyester resin B)
In a reaction vessel equipped with a stirrer, thermometer, methanol outflow tube, and rectification tube, 87.3 g (0.45 mol) of dimethyl terephthalic acid and 14.8 g (0.05 mol) of sodium salt of 5-sulfoisophthalic acid dimethyl ester , 310 g (0.1 mol) of polyethylene glycol (PEG 4000, manufactured by Sanyo Chemical Industries, Ltd., trade name, average molecular weight: about 3100), 68.2 g (1.1 mol) of monoethylene glycol and 0.1 g of antimony trioxide Then, 0.1 g of zinc acetate was charged, and a transesterification reaction was performed under the same conditions as in Synthesis Example 3 to obtain 425 g of a polyester resin. The weight average molecular weight of this polyester resin was about 15,000 as a result of measurement by gel permeation chromatography [High-speed GPC manufactured by Tosoh Corporation, HLC-8120 type, measurement standard substance: polyethylene glycol]. 100 g of this polyester resin was dissolved in 50 g of N, N-dimethylformamide (DMF) and emulsified in 850 g of hot water to obtain an aqueous liquid of polyester resin B.

Synthesis Example 5 (Aqueous liquid of polyester resin C)
In a reaction vessel equipped with a stirrer, thermometer, methanol outflow tube, and rectification tube, 116.4 g (0.6 mol) of dimethyl terephthalic acid and 118.4 g (0.4 mol) of sodium salt of 5-sulfoisophthalic acid dimethyl ester , 60 g (0.03 mol) of polyethylene glycol (PEG2000, manufactured by Sanyo Chemical Industries, Ltd., trade name, average molecular weight: about 2000), 136.4 g (2.2 mol) of monoethylene glycol and 0.1 g of antimony trioxide Then, 0.1 g of zinc acetate was charged, and transesterification was performed under the same conditions as in Synthesis Example 3 to obtain 380 g of a polyester resin. The weight average molecular weight of this polyester resin was about 5,000 as a result of measurement by gel permeation chromatography [High-speed GPC manufactured by Tosoh Corporation, HLC-8120 type, measurement standard substance: polyethylene glycol]. 100 g of this polyester resin was dissolved in 50 g of N, N-dimethylformamide (DMF) and emulsified in 850 g of hot water to obtain an aqueous liquid of polyester resin C.

Comparative Synthesis Example 5 (Aqueous liquid of comparative polyester resin D)
In a reaction vessel equipped with a stirrer, thermometer, methanol outflow tube, and rectification tube, 67.9 g (0.35 mol) of dimethyl terephthalic acid, 29.1 g (0.15 mol) of dimethyl isophthalic acid, polyethylene glycol (PEG 4000, Sanyo Chemical Industries, Ltd., trade name, average molecular weight: about 3100) 310 g (0.1 mol), monoethylene glycol 68.2 g (1.1 mol), antimony trioxide 0.1 g, zinc acetate 0.1 g Was transesterified under the same conditions as in Synthesis Example 3 to obtain 420 g of a polyester resin. The weight average molecular weight of this polyester resin was about 10,000 as a result of measurement by gel permeation chromatography in the same manner as in Synthesis Example 3. 100 g of this polyester resin was dissolved in 50 g of N, N-dimethylformamide (DMF) and emulsified in 850 g of hot water to obtain an aqueous solution of comparative polyester resin D.

Comparative Synthesis Example 6 (Aqueous liquid of comparative polyester resin E)
In a reaction vessel equipped with a stirrer, thermometer, methanol outflow tube, and rectification tube, 77.6 g (0.4 mol) of dimethyl terephthalic acid, 19.4 g (0.1 mol) of dimethyl isophthalic acid, polyethylene glycol (PEG 4000, Sanyo Chemical Industries, Ltd., trade name, average molecular weight: about 3100) 387.5 g (0.125 mol), monoethylene glycol 68.2 g (1.1 mol) and antimony trioxide 0.1 g, zinc acetate 0 .1 g was charged and subjected to a transesterification reaction under the same conditions as in Synthesis Example 3 to obtain 500 g of a polyester resin. As a result of measurement by gel permeation chromatography in the same manner as in Synthesis Example 3, the weight average molecular weight of this polyester resin was about 12,000. 100 g of this polyester resin was dissolved in 50 g of N, N-dimethylformamide (DMF) and emulsified in 850 g of hot water to obtain an aqueous solution of comparative polyester resin E.

Example 1 (One bath treatment)
5% by mass of an aqueous liquid of fluorine-based acrylic copolymer A obtained in Synthesis Example 1, 5% by mass of an aqueous liquid of polyester resin A obtained in Synthesis Example 3, and “Sumitex Resin M-3 which is a melamine resin-based crosslinking agent” (S / R M-3) ”(trade name, manufactured by Sumitomo Chemical Co., Ltd.) 0.3 mass%,“ Sumite Accelerator ACX (S / Acc ACX), which is an organic amine catalyst for promoting the crosslinking reaction of melamine resin ”(Sumitomo Chemical Co., Ltd., trade name) 0.03% by mass and NK Assist NY (trade name, Nikka Chemical Co., Ltd.), which is a dispersion of a block adduct of an aliphatic polyisocyanate derivative as an isocyanate crosslinking agent. (Product made) The processing liquid containing 1 mass% was produced.

  A 100% polyester woven fabric was dipped in this treatment solution, and then wrung with mangle to make 60% by weight of wet pickup, then dried at 120 ° C. for 1 minute, and further heat treated at 180 ° C. for 1 minute. About the obtained processed cloth, the stain | pollution | contamination removability after the initial stage and 20 times of washing was evaluated. In addition, washing was performed using a two-tank electric washing machine with a bath ratio of 1:30, a liquid temperature of 40 ° C., and a detergent attack of 25 g. The washing was performed for 5 minutes, and the rinsing and dehydration steps were repeated 20 times, followed by air drying. Things were evaluated as 20 washes. The results are shown in Table 1.

Examples 2 to 6 (one bath treatment)
The same treatment as in Example 1 was performed except that a treatment liquid containing 5% by mass of an aqueous liquid of a fluorinated acrylic copolymer shown in Table 1, 5% by mass of an aqueous liquid of a polyester resin, and a crosslinking agent was used. Evaluation was performed. The results are shown in Table 1.

Example 7 (Two bath treatment)
With a treatment liquid containing 5% by mass of an aqueous liquid of polyester resin A obtained in Synthesis Example 3, a 100% polyester woven fabric was used in a bath ratio of 1:15 using a mini-color dyeing machine [manufactured by Tecsum Giken Co., Ltd.] The treatment was performed at a temperature of 130 ° C. for 30 minutes. Thereafter, the liquid was removed at a squeezing rate of 60% by mass, and dried at 120 ° C. for 1 minute. Next, 5% by mass of the aqueous liquid of the fluorinated acrylic copolymer A obtained in Synthesis Example 1, “Sumitex Resin M-3” (trade name, manufactured by Sumitomo Chemical Co., Ltd.) which is a melamine resin-based crosslinking agent. 3% by mass, “Sumitex Accelerator ACX” (trade name, manufactured by Sumitomo Chemical Co., Ltd.), an organic amine catalyst for promoting the crosslinking reaction of melamine resin, and aliphatic polyisocyanate derivative as an isocyanate-based crosslinking agent After immersing in a treatment liquid containing 1% by mass of NK Assist NY (trade name, manufactured by Nikka Chemical Co., Ltd.), which is a dispersion of the block adduct, and then squeezing with a mangle to a wet pickup of 60% by mass, It dried at 120 degreeC for 1 minute, and also heat-processed at 180 degreeC for 1 minute. About the obtained processed cloth, the stain | pollution | contamination removability after the initial stage and 20 times of washing was evaluated. In addition, washing was performed using a two-tank electric washing machine with a bath ratio of 1:30, a liquid temperature of 40 ° C., and a detergent attack of 25 g. The washing was performed for 5 minutes, and the rinsing and dehydration steps were repeated 20 times, followed by air drying. Things were evaluated as 20 washes. The results are shown in Table 1.

Example 8 (Two bath treatment)
With a treatment liquid containing 5% by mass of an aqueous liquid of polyester resin B obtained in Synthesis Example 4, a 100% polyester woven fabric was used with a mini-color dyeing machine [manufactured by Tecsum Giken Co., Ltd.], with a bath ratio of 1:15. The treatment was performed at a temperature of 130 ° C. for 30 minutes. Thereafter, the liquid was removed at a squeezing rate of 60% by mass, and dried at 120 ° C. for 1 minute. Next, 5% by mass of the aqueous liquid of the fluorinated acrylic copolymer A obtained in Synthesis Example 1, “Sumitex Resin M-3” (trade name, manufactured by Sumitomo Chemical Co., Ltd.) which is a melamine resin-based crosslinking agent. 3% by mass, “Sumitex Accelerator ACX” (trade name, manufactured by Sumitomo Chemical Co., Ltd.), an organic amine catalyst for promoting the crosslinking reaction of melamine resin, and aliphatic polyisocyanate derivative as an isocyanate-based crosslinking agent After immersing in a treatment liquid containing 1% by mass of NK Assist NY (trade name, manufactured by Nikka Chemical Co., Ltd.), which is a dispersion of the block adduct, and then squeezing with a mangle to a wet pickup of 60% by mass, It dried at 120 degreeC for 1 minute, and also heat-processed at 180 degreeC for 1 minute. About the obtained processed cloth, the stain | pollution | contamination removability after the initial stage and 20 times of washing was evaluated. In addition, washing was performed using a two-tank electric washing machine with a bath ratio of 1:30, a liquid temperature of 40 ° C., and a detergent attack of 25 g. The washing was performed for 5 minutes, and the rinsing and dehydration steps were repeated 20 times, followed by air drying. Things were evaluated as 20 washes. The results are shown in Table 1.

Comparative Examples 1 to 12 (one bath treatment)
The same treatment as in Example 1 was performed except that a treatment liquid containing 5% by mass of an aqueous liquid of a fluorinated acrylic copolymer shown in Table 1, 5% by mass of an aqueous liquid of a polyester resin, and a crosslinking agent was used. Evaluation was performed. The results are shown in Table 1.

Example 9 (One bath treatment)
5% by mass of an aqueous liquid of fluorine-based acrylic copolymer A obtained in Synthesis Example 1, 5% by mass of an aqueous liquid of polyester resin A obtained in Synthesis Example 3, and “Sumitex Resin M-3 which is a melamine resin-based crosslinking agent” "(Sumitomo Chemical Co., Ltd., trade name) 0.3 mass%," Sumitex Accelerator ACX "(Sumitomo Chemical Co., Ltd., trade name) which is an organic amine catalyst for promoting the crosslinking reaction of melamine resin. A treatment liquid containing 03% by mass and 1% by mass of NK assist NY (trade name, manufactured by Nikka Chemical Co., Ltd.), which is a dispersion of a block adduct of an aliphatic polyisocyanate derivative as an isocyanate-based crosslinking agent, was prepared.

  A mixed fabric of 35% cotton and 65% polyester was dipped in this treatment liquid, then squeezed with a mangle to make 60% by weight of wet pickup, dried at 120 ° C. for 1 minute, and further heat treated at 160 ° C. for 1 minute. About the obtained processed cloth, the stain | pollution | contamination removability after the initial stage and 20 times of washing was evaluated. In addition, washing was performed using a two-tank electric washing machine with a bath ratio of 1:30, a liquid temperature of 40 ° C., and a detergent attack of 25 g. The washing was performed for 5 minutes, and the rinsing and dehydration steps were repeated 20 times, followed by air drying. Things were evaluated as 20 washes. The results are shown in Table 2.

Examples 10 to 14 (one bath treatment)
The same treatment as in Example 9 was performed, except that a treatment liquid containing 5% by mass of an aqueous liquid of a fluorinated acrylic copolymer shown in Table 2, 5% by mass of an aqueous liquid of a polyester resin, and a crosslinking agent was used. Evaluation was performed. The results are shown in Table 2.

Example 15 (Two bath treatment)
A treatment liquid containing 5% by mass of an aqueous liquid of polyester resin A obtained in Synthesis Example 3 was used to bathe a 35% cotton and 65% polyester blended fabric using a mini-color dyeing machine [manufactured by Texam Giken Co., Ltd.]. The treatment was performed for 30 minutes under the conditions of a ratio of 1:15 and a temperature of 130 ° C. Thereafter, the liquid was removed at a squeezing rate of 60% by mass, and dried at 120 ° C. for 1 minute. Next, 5% by mass of an aqueous liquid of the fluorine-based acrylic copolymer A obtained in Synthesis Example 1, “Sumitex Resin M-3” (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a melamine resin-based crosslinking agent, 0.3 "Sumitex Accelerator ACX" (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is an organic amine catalyst for accelerating the crosslinking reaction of melamine resin, is 0.03% by mass and an aliphatic polyisocyanate derivative as an isocyanate crosslinking agent. After immersing in a treatment liquid containing 1% by mass of NK Assist NY (trade name, manufactured by Nikka Chemical Co., Ltd.), which is a dispersion of the block adduct, and then squeezing with a mangle to make 60% by mass of the wet pickup, 120 It was dried at 1 ° C. for 1 minute and further heat-treated at 180 ° C. for 1 minute. About the obtained processed cloth, the stain | pollution | contamination removability after the initial stage and 20 times of washing was evaluated. In addition, washing was performed using a two-tank electric washing machine with a bath ratio of 1:30, a liquid temperature of 40 ° C., and a detergent attack of 25 g. The washing was performed for 5 minutes, and the rinsing and dehydration steps were repeated 20 times, followed by air drying. Things were evaluated as 20 washes. The results are shown in Table 2.

Example 16 (Two bath treatment)
A treatment liquid containing 5% by mass of an aqueous liquid of polyester resin A obtained in Synthesis Example 4 was used to bathe a 35% cotton and 65% polyester blended fabric using a mini-color dyeing machine [manufactured by Texam Giken Co., Ltd.]. The treatment was performed for 30 minutes under the conditions of a ratio of 1:15 and a temperature of 130 ° C. Thereafter, the liquid was removed at a squeezing rate of 60% by mass, and dried at 120 ° C. for 1 minute. Next, 5% by mass of an aqueous liquid of the fluorine-based acrylic copolymer A obtained in Synthesis Example 1, “Sumitex Resin M-3” (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a melamine resin-based crosslinking agent, 0.3 "Sumitex Accelerator ACX" (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is an organic amine catalyst for accelerating the crosslinking reaction of melamine resin, is 0.03% by mass and an aliphatic polyisocyanate derivative as an isocyanate crosslinking agent. After immersing in a treatment liquid containing 1% by mass of NK Assist NY (trade name, manufactured by Nikka Chemical Co., Ltd.), which is a dispersion of the block adduct, and then squeezing with a mangle to make 60% by mass of the wet pickup, 120 It was dried at 1 ° C. for 1 minute and further heat-treated at 180 ° C. for 1 minute. About the obtained processed cloth, the stain | pollution | contamination removability after the initial stage and 20 times of washing was evaluated. In addition, washing was performed using a 2 漕 type electric washing machine with a bath ratio of 1:30, a liquid temperature of 40 ° C. and a detergent attack of 25 g, and was performed for 5 minutes, followed by rinsing and dehydration 20 times, and then air drying. Things were evaluated as 20 washes. The results are shown in Table 2.

Comparative Examples 13 to 24 (one bath treatment)
The same treatment as in Example 9 was performed, except that a treatment liquid containing 5% by mass of an aqueous liquid of a fluorinated acrylic copolymer shown in Table 2, 5% by mass of an aqueous liquid of a polyester resin, and a crosslinking agent was used. Evaluation was performed. The results are shown in Table 2.

  As can be seen from the results of Examples 1 to 16, the fiber product produced by the production method of the present invention is a stain excellent in durability against a stain containing an oil component and an inorganic substance and / or a pigment. Detachability was shown. However, as in Comparative Examples 1 to 24, the fiber product produced without any of the specific polyester resin, the specific fluorine-based acrylate copolymer and the cross-linking agent used in the present invention has an oil component, an inorganic substance, and / or Or the effect which shows the detachability | excellence excellent in durability with respect to the stain | pollution | contamination containing a pigment was not acquired. Further, in the examples, the one-bath treatment was particularly excellent in the initial soil detachability compared to the two-bath treatment.

As described above, according to the present invention, dirt adheres to textiles, particularly dirt containing oil components such as dirty motor oil and lipstick and inorganic substances and / or pigments. As a result, it is possible to efficiently and reliably obtain a durable antifouling fiber product having a high level of washing durability.

Claims (4)

(A) The following general formula [1] containing 1 to 40% by mass of sulfoisophthalic acid or a derivative thereof as a polycondensation component:

{In Formula [1], R ₁ is HO— or HO (R ₂ O) _a —, R ₂ is an alkylene group having 2 to 4 carbon atoms, and R ₂ O may be only one kind. Two or more types of R ₂ O may be added in a random or block form, a is an integer of 1 to 200, and a may be the same or different in the same molecule. B is an integer of 2 to 100, R ₃ is a hydrogen atom or the following general formula [2]:

(Wherein [2], _{R 5} is a hydrogen atom, a carboxyl group, or -SO ₃ X, X is a hydrogen atom or an alkali metal.)
R ₄ is a hydrogen atom, a carboxyl group or —SO ₃ X, and X is a hydrogen atom or an alkali metal. }
An aqueous liquid containing a polyester resin represented by
(B) (a) Acrylic acid ester or methacrylic acid ester having a fluoroalkyl group, (b) polyalkylene glycol acrylate or polyalkylene glycol methacrylate, (c) 3-chloro-2-hydroxypropyl acrylate or 3-chloro-2 An aqueous liquid comprising hydroxypropyl methacrylate and (d) a fluorinated acrylic copolymer containing structural units derived from glycerol monoacrylate or glycerol monomethacrylate, and
(C) at least one crosslinking agent selected from the group consisting of a melamine resin crosslinking agent, an isocyanate crosslinking agent and a glyoxal resin crosslinking agent,
A method for producing a durable antifouling fiber product, which comprises applying to a fiber product and drying the product.   The method for producing a durable antifouling fiber product according to claim 1, wherein the polyester resin has a weight average molecular weight of 1,000 to 50,000.   The method for producing a durable antifouling fiber product according to claim 1 or 2, wherein the fluorine-based acrylic copolymer has a weight average molecular weight of 1,000 to 500,000.   The aqueous liquid (A) and the aqueous liquid (B) are used so that the polyester resin is 10 to 300 parts by mass with respect to 100 parts by mass of the fluorinated acrylic copolymer. The manufacturing method of the durable antifouling | stain-proof fiber product as described in any one of 1-3.