JP2000234270A - Treatment of textile product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart a textile product with water-repellency and soil resistance by treating a textile product with an aqueous solution containing a polyvalent metal compound and then treating with a treating liquid containing a fluorine- based soil resisting component or by treating the product in a single bath containing both of the above components. SOLUTION: A textile product such as carpet made of nylon fiber, polypropylene fiber or polyester fiber is treated with an aqueous solution containing a polyvalent metal compound such as magnesium sulfate, brought into contact with a treating liquid having pH of <=2 and containing a fluorine- based soil resisting component such as a maleate or fumarate polymer containing a fluoroalkyl group, steamed, washed with water and dehydrated or the textile product is treated in a single bath of a treating liquid containing the above metal compound and the fluorine-based soil resisting component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a treatment method for imparting water repellency and stain resistance to textiles. The antifouling treatment method of the present invention is particularly useful for carpets.

[0002]

2. Description of the Related Art Conventionally, various treatment methods have been proposed for imparting water repellency and antifouling property to textiles (for example, carpet). However, according to the conventional processing method,
Sufficient water repellency and antifouling properties have not been obtained.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for treating textile products which provides excellent water repellency and stain resistance.

[0004]

The present invention comprises (a) a step of treating a textile with an aqueous solution containing a metal compound, and (b) a step of treating with a treatment liquid containing a fluorine-containing antifouling component. And a method for treating textile products. Further, the present invention provides a method for treating a textile product, comprising a step of treating the textile product with a treatment liquid containing a metal compound and a fluorine-containing antifouling component.

[0005] In the present invention, (1) a method of treating a textile product with an aqueous solution containing a metal compound and then treating it with a treatment liquid containing a fluorine-containing antifouling component, and (2) a metal compound and a fluorine-containing antifouling component. There is a method of treating with a treatment solution containing both of the above. “Treatment” means applying the liquid to the textile by dipping, spraying, coating, or the like. The processing solution containing the fluoropolymer functions as an antifouling agent. The treatment liquid containing the fluorine-containing antifouling component may be a solution or an emulsion, particularly an aqueous emulsion.

[0006] The metal compound and the fluorine-containing antifouling component can be applied to an object to be treated (fiber product) by a conventionally known method. The metal compound and the fluorine-containing antifouling component may be in the same bath. Usually, the aqueous solution of the metal compound and the treating solution of the fluorine-containing antifouling component are diluted with an organic solvent or water, and are coated on a carpet fabric or carpet yarn or raw cotton by dip coating, spray coating, foam coating, or the like. According to the method, it is attached to the surface of the object to be treated and dried. Also, if necessary, apply with a suitable crosslinking agent,
Curing may be performed. Further, an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent and the like can be added and used together. The concentration of the fluorinated antifouling component in the treatment liquid brought into contact with the article to be treated may be 0.05 to 10% by weight. The concentration of the metal compound in the processing solution brought into contact with the object to be processed is 0.005 to 0.005.
It may be 40% by weight.

[0007] The pH of the treatment liquid containing the fluorine-containing antifouling component and / or the metal compound is adjusted to 2 or less, the treatment liquid is applied to the textile, the textile is heated, washed with water, and dehydrated (hereinafter referred to as "dehydration"). , "Exhaust method"). According to the Exhaust method, the adhesion ratio of the fluorine-containing antifouling component and the metal to the fiber product increases, and higher water repellency and antifouling property can be obtained. To adjust the pH to 2 or less, an acid such as urea sulfate or sulfamic acid may be added to the treatment solution. The heat treatment is performed, for example, by changing the fiber product to 7
It can be performed by heating to 0 to 150 ° C. for 15 seconds to 60 minutes. The heat treatment is performed, for example, using steam (for example, 90
１１０110 ° C.) to the textile at normal pressure. Next, the heat-treated textile is washed with water at least once. Then, to remove excess water,
Dehydrate by centrifugation or vacuum.

[0008] The metal compound is a compound containing a metal.
The metal may be a polyvalent metal (a divalent or higher valent metal).

A metal compound is a compound that forms a metal ion in an aqueous solution. The metal compound may be, for example, a metal salt. Examples of metal salts are sulfites, sulfates, hydrochlorides, chlorides, phosphites, phosphates and the like. Specific examples of the metal compound include magnesium sulfate, aluminum sulfate, sodium sulfate, aluminum chloride, barium chloride, calcium chloride, magnesium chloride, sodium chloride, potassium chloride, and sodium sulfate.

The fluorinated antifouling component may comprise a fluorinated polymer and / or a fluorinated low molecular compound. The fluorinated polymer may be a polymer having a fluoroalkyl group-containing monomer, for example, a (meth) acrylate having a fluoroalkyl group, a fluoroalkyl group-containing maleate or fumarate, or a polymer derived from a fluoroalkyl group-containing urethane. .

The fluoroalkyl group-containing (meth) acrylate may be represented by the following general formula. ^{Rf-A-OCOR 3 = CH} 2 [ wherein, Rf is a fluoroalkyl group having 3 to 21 carbon atoms,
R ³ is hydrogen or a methyl group, and A is a divalent organic group. Examples of the (meth) acrylate containing a fluoroalkyl group include the following.

[0012]

Embedded image

[0013]

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Wherein Rf is a fluoroalkyl group having 3 to 21 carbon atoms, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ² is an alkylene group having 1 to 10 carbon atoms, R ³ is hydrogen or A methyl group and Ar are an arylene group which may have a substituent, and n is an integer of 1 to 10. ]

Specific examples of the fluoroalkyl group-containing (meth) acrylate are as follows. CF ₃ (CF ₂ ) ₇ (CH ₂ ) OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₆ (CH ₂ ) OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = 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 (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH = C
H ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) (CH ₂ ) ₂ OCOC (C
H ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ OCOCH
= CH ₂ , CF ₃ C ₆ F ₁₀ (CF ₂ ) ₂ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOC
H = CH ₂ ,

[0016]

Embedded image

The fluoroalkyl group-containing urethane for deriving the fluoropolymer includes (a) a compound having at least two isocyanate groups, (b) one carbon-carbon double bond and at least one hydroxyl group or amino group. And (c) a fluorine-containing compound having one hydroxyl group or amino group. Examples of the compound (a) are as follows.

[0018]

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[0019]

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Compound (a) is preferably a diisocyanate. However, triisocyanates and polyisocyanates can also be used in the reaction. For example, a trimer of diisocyanate, polymeric MDI (diphenyl metadiisocyanate), and an adduct of diisocyanate with a polyhydric alcohol such as trimethylolpropane, trimethylolethane or glycerin can be used for the reaction.

Examples of triisocyanates and polyisocyanates are as follows.

[0022]

Embedded image

[0023]

Embedded image

Compound (b) has, for example, the formula:

Embedded image

Embedded image May be a compound represented by

In the formula, R ¹ is a hydrogen atom or a methyl group. X is as follows.

Embedded image

[0026]

Embedded image Wherein m and n are numbers from 1 to 300. ]

The compound (c) has a formula: R _f -R ² -OH or R _f -R ² -NH _{2 wherein} R _f represents a fluoroalkyl group having 1 to 22 carbon atoms. R ² represents an alkylene group having 1 to 10 carbon atoms and may contain a hetero atom. ] It may be the compound shown by these.

Examples of compound (c) are

Embedded image It may be.

Compounds (a), (b) and (c) are
When (a) is a diisocyanate, (a) per 1 mol,
When (b) and (c) are both 1 mol, and when (a) is a triisocyanate, 1 mol of (a) and 1 mol of (b) per 1 mol of (a)
The reaction may be carried out in moles.

The fluorine-containing antifouling component used in the present invention includes, for example, (A) at least one fluoroalkyl group (R
a polymer having a constitutional unit derived from a maleic ester or a fumaric ester having (f group), (B)
(I) a structural unit derived from a monomer containing a fluoroalkyl group, (II) a structural unit derived from a monomer containing no fluorine, (III) a structural unit derived from vinyl chloride, and ( IV) It may be composed of an optionally present fluoroalkyl group-containing copolymer having a structural unit derived from a crosslinkable monomer, and (C) an optionally present fluorine-free acrylic copolymer. .

The polymer (A) has a structural unit derived from a fluorinated maleate or a fluorinated fumarate. In the polymer (A), the amount of the structural unit derived from the fluorinated maleate or fluorinated fumarate is at least 10% by weight, for example, 20% by weight based on the copolymer (A).
% By weight or more.

The polymer (A) has the formula (i):

Embedded image [Wherein, Rf is a perfluoroalkyl group having 3 to 21 carbon atoms. OH-containing fluorinated maleate represented by the formula:
formula:

Embedded image [Wherein, Rf is a perfluoroalkyl group having 3 to 21 carbon atoms. OH-containing fluorinated fumarate represented by the formula:
formula:

Embedded image [Wherein, Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, A ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms,
A ² is an alkylene group having 1 to 4 carbon atoms. And a fluorine-containing maleate represented by the formula:

Embedded image [Wherein, Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, A ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms,
A ² is an alkylene group having 1 to 4 carbon atoms. And a fluorine-containing polymer having at least one type of repeating unit derived from a monomer selected from the group consisting of the fluorine-containing fumarate represented by the formula (1).

The polymer (A) has, in addition to the structural unit (i), (ii) at least one type of repeating unit derived from an alkyl (meth) acrylate having 1 to 6 carbon atoms in the alkyl group. May be. The preferred weight ratio of the structural unit (i) to the structural unit (ii) in the polymer (A) is as follows:
100: 0 to 10:90, for example, 60:40 to 70: 3
It may be 0.

The polymer (A) may have a structural unit (iii) derived from another monomer in addition to the structural units (i) and (ii). Examples of the monomer of the structural unit (iii) include ethylene, butadiene, vinyl acetate, chloroprene, vinyl halide such as vinyl chloride, vinylidene halide, styrene, acrylonitrile, (meth)
Acrylamide, vinyl alkyl ether, diacetone
(Meth) acrylamide, N-methylol (meth) acrylamide, vinyl alkyl ketone, maleic anhydride, N-
Vinyl carbazole, (meth) acrylic acid and the like. The amount of the structural unit (iii) may be 20% by weight or less, for example, 5% by weight or less based on the polymer (A).

The monomer constituting the repeating unit of the copolymer to be used (B) (I) if necessary, the general ^{formula: Rf-R 4 -OCOC (R} 5) = CH 2 [ wherein, Rf is 3 A linear or branched perfluoroalkyl group having from 20 to 20 carbon atoms, R ⁴ is a linear or branched alkylene group having from 1 to 20 carbon atoms,-
SO ₂ N (R ⁶ ) R ⁷ — group or —CH ₂ CH (OR ⁸ ) CH ₂ —
A group (provided that R ⁶ is an alkyl group having 1 to 10 carbon atoms, R ⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms, R ⁸ is a hydrogen atom or 1 to 10 carbon atoms) And R ⁵ is a hydrogen atom or a methyl group. ] Is preferable.

Examples of such a monomer include the following. CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₆ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₈ CH ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOCH = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH _{2 (CF 3) 2 CF (CF} 2) 8 (CH 2) 2 OCOC (CH 3) = CH 2 (CF 3) 2 CF (CF 2) 10 (CH 2) 2 OCOC (CH 3) = CH
_Two

CF ₃ CF ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₁₀ (CH _{2) 2 OCOCH = CH 2 CF} 3 CF 2 (CF 2) 6 (CH 2) 2 OCOC (CH 3) = CH 2 CF 3 CF 2 (CF 2) 8 (CH 2) 2 OCOC (CH 3) = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH = C
_{H 2 CF 3 (CF 2)} 7 SO 2 N (C 2 H 5) (CH 2) 2 OCOCH = C
H ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OCOCH ₃ ) CH ₂ O
COC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH
= CH ₂ or more, but not limited thereto.

The structural unit (II) of the copolymer (B) is preferably derived from a fluorine-free vinyl monomer. Preferred monomers forming the structural unit (II) include, for example, ethylene, vinyl acetate, vinylidene halide, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol
(Meth) acrylate, methoxypolyethylene glycol
Examples include (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, vinyl alkyl ether, isoprene and the like, but are not limited thereto.

The monomer forming the structural unit (II) may be an alkyl group-containing (meth) acrylate. The carbon number of the alkyl group is 1 to 30, for example, 6 to
30, for example, 10 to 30. For example,
The monomer forming the structural unit (II) is represented by the general formula: CH ₂ ＣＡCA ³ COOA ⁴ [where A ³ is a hydrogen atom or a methyl group, A ⁴ is C _n H
It is an alkyl group represented by _{2n + 1} (n = 1 to 30). Acrylates represented by the formula: By copolymerizing these monomers, water repellency and antifouling properties and cleaning performance of these properties, washing resistance, abrasion resistance,
Various properties such as solubility in a solvent, hardness, and feel can be improved as necessary.

The crosslinkable monomer forming the structural unit (IV) may be a fluorine-free vinyl monomer having at least two reactive groups. The crosslinkable monomer may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group.

Examples of the crosslinkable monomer include diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl ( (Meth) acrylate, N,
N-dimethylaminoethyl (meth) acrylate, N, N
-Diethylaminoethyl (meth) acrylate, butadiene, chloroprene, glycidyl (meth) acrylate, and the like, but are not limited thereto. By copolymerizing these monomers, water repellency and antifouling properties and cleaning performance of these properties, washing resistance,
Various properties such as solubility in a solvent, hardness, and feel can be improved as necessary.

The weight average molecular weight of the copolymer (B) is 20
It is preferably from 100 to 1,000,000. Copolymer
(B) the amount of the structural unit (I) is 40 to 90% by weight,
More preferably 50 to 80% by weight, the amount of the structural unit (II) is 5 to 60% by weight, more preferably 10 to 40% by weight,
The amount of the structural unit (III) is 5 to 50% by weight, more preferably 10 to 40% by weight, and the amount of the structural unit (IV) is 0.1 to 1%.
It is preferably 0% by weight, more preferably 0.5 to 5% by weight.

The copolymer (C) is composed of at least two fluorine-free (meth) acrylic monomers. The fluorine-free (meth) acrylic monomer is represented by the general formula: CH ₂ ＣCX ¹ COOX ² [wherein X ¹ is a hydrogen atom or a methyl group, X ² is a linear or branched C _n H _{2n + 1]} Group (n = 1 to 5). ] Is preferable. The copolymer (C) may be a methyl methacrylate (MMA) / ethyl methacrylate (EMA) copolymer.

The weight average molecular weight of the copolymer (C) is 10
It is preferably from 100 to 1,000,000. Preferably it is 100,000 to 200,000. The amount of MMA is 40 to 9 based on the copolymer (C) which is a methyl methacrylate (MMA) / ethyl methacrylate (EMA) copolymer.
5% by weight, more preferably 75-85% by weight, the amount of EMA is 5-60% by weight, more preferably 15-25% by weight
It is preferred that

The weight ratio of the copolymer (A) to the copolymer (B) is from 100: 0 to 1:99, for example, from 1:99 to 99:
It may be 1. The weight ratio of the copolymer (A) to the copolymer (C) is 100: 0 to 1:99, for example, 1:99 to 9
9: 1.

The polymers (A), (B) and (C) in the present invention can be produced by any conventional polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Such polymerization methods include solution polymerization and emulsion polymerization. Emulsion polymerization is particularly preferred.

In order to obtain a polymer aqueous dispersion having excellent standing stability, the monomer is converted into fine particles in water using an emulsifying apparatus such as a high-pressure homogenizer or an ultrasonic homogenizer capable of imparting strong crushing energy. It is desirable to carry out the polymerization using an oil-soluble polymerization initiator. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 10 parts by weight based on 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers.

The fluorinated antifouling component may be a fluorinated low molecular compound. Fluorinated low molecular compounds, fluoroalkyl group-containing urethane compounds, for example, the general ^{formula: Rf 1 -X 11 -A 11 -CONH} -Y 11 -NHCO-A 12 -
Z [wherein, Rf ¹ is a 4 to 16 fluoroalkyl group having a carbon number, X ¹¹ is ^{-R 11 -, - CON (R} 12) -Q 1 - or ^{_{-SO 2 N (R 12),}} - Q ¹ - is one of, R ¹¹ is an alkylene group (e.g., C _{1 ~ 8} alkylene group), R ¹² is a hydrogen atom or a lower alkyl group (e.g., C _{1 ~ 4} alkyl group), Q ¹ is an alkylene group (e.g., C _{1 ~ 8} alkylene group), a ¹¹ and a ¹² are each -O -, - S-, or -N (R ^{1 2)} - is one of, R ¹² is a hydrogen atom or a lower an alkyl group (e.g., C _{1 ~ 4} alkyl group),
Y ¹¹ is a residue obtained by removing isocyanate from an aromatic or alicyclic diisocyanate, Z is an alkyl group (e.g., C _{1 ~ 8} alkyl group), an aryl group (e.g., C _{6 ~
12} aryl group) or —X ¹¹ —Rf ¹ . Urethane compound represented by] or the general ^{formula: Rf 2 -X 12 -A 13 -CONH} -Y 12 -NHCO-W [ wherein, Rf ² is a 4 to 16 fluoroalkyl group having a carbon number, X ^{12 -R 11 -, - CON (R} 12) -Q 1 -, or ^{_{-SO 2 N (R 12) -Q}} 1 - is one of, R ¹¹ is an alkylene group (e.g., C _{1 ~ 8} alkylene group), R ¹² is a hydrogen atom or a lower alkyl group (e.g., C _{1 ~ 4} alkyl group), Q ¹ is an alkylene group (e.g., C _{1 ~ 8} alkylene group), a ¹³ is -O -, - S -, or -N (R ¹³⁾
- is one of, R ¹³ is a hydrogen atom or a lower alkyl group (e.g., C _{1 ~ 4} alkyl group), Y ¹² is a residue obtained by removing isocyanate from an aromatic or alicyclic diisocyanate And W is a hydrophilic group (eg, an alkylene glycol group). And the urethane compound represented by the formula:

Examples of the fluoroalkyl-containing urethane compound include the following.

Embedded image

The object to be subjected to the antifouling treatment is a fiber product. Particularly, it is preferably a carpet. Various examples can be given as fiber products. For example, cotton,
Animal and plant natural fibers such as hemp, wool and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; glass fibers, carbon fibers, and asbestos fibers. Inorganic fiber or a mixed fiber thereof. The treatment method of the present invention can be suitably used for carpets made of nylon, polypropylene or polyester.

The fiber product may be in any form of fiber, yarn, cloth and the like. When treating a carpet according to the method of the present invention, the carpet may be formed after treating the fibers or yarns, or the formed carpet may be treated.

[0052]

EXAMPLES Examples of the present invention will be specifically described, but the examples do not limit the present invention. Example,
The carpets obtained in the comparative examples were evaluated for water repellency, antifouling property and adhesion rate. The test methods for water repellency, antifouling property and adhesion rate are as follows.

1) Water repellency A small droplet of the isopropyl alcohol (IPA) / water mixture shown in Table 1 was gently placed on the carpet surface to repel the maximum content of IPA in the liquid maintaining the shape of the droplet. Aqueous results. Specifically, the following procedure is performed. The carpet treated with a repellent is placed in a thermo-hygrostat at 21 ° C and 65% humidity.
Leave for more than an hour. Test solution (composition of Table 1) is also 21
Keep at ° C. The temperature of the measurement chamber is adjusted to about 21 ° C. Drop the liquid with a micropipette 50 μl.
Drop (droplet diameter is 5 mm). The micropipette stands upright and gently drops the liquid. Drop 5 drops. After leaving for 30 seconds, if 4 or 5 drops remain, the test liquid is considered to have passed. The water repellency is defined as the maximum content (% by volume) of isopropyl alcohol (IPA) in the passed test liquid.

[0054]

Table 1 Mixed composition (% by volume) Isopropyl alcohol Water 60 40 50 50 40 60 30 70 25 75 75 20 80 15 85 10 90 5 95 298 98 100

2) Antifouling property Carpet test piece treated with a repellent (size: 18.2 cm in the tufting direction, 8.2 in the direction perpendicular to the tufting direction).
9cm) and blank carpet test piece (carpet not treated with repellent) (size: 1 in tufting direction)
8.2 cm, 8.9 cm perpendicular to the tufting direction)
Leave for 4 hours or more in an atmosphere of 21 ° C. and 65% RH. Before the antifouling test, L ^* , a ^*, and b ^* of the carpet test piece are measured at five points each. Two carpet test pieces are stuck to the inner surface of the ball mill pot with double-sided tape. 10 g of Dry Soil (artificial soil having the composition shown in Table 2; dried in a desiccator for 48 hours or more) is put into the pot. Close the pot lid and shake the pot lightly to dry
Allow the Soil to ride on the carpet specimen almost uniformly. Open the lid of the pot and open the ceramic ball (AATC
Insert 50 pieces of C Test Method 123-1989 compliant product) and tightly close the lid of the pot. Spin on a ball mill at 80 rpm for 7 minutes and 30 seconds. Open the lid of the pot, take out the carpet test piece, and peel off the double-sided tape on the back of the carpet test piece. Vacuum the excess soil on the surface of the carpet specimen. Apply the vacuum cleaner in each (vertical and horizontal) directions 5 times. Finally, the Soil on the back side of the carpet test piece is also removed by one round trip suction. L ^* , a ^* and b of the carpet specimen from which excess Soil was removed by suction
^{* The} color difference meter (Minolta Co., Ltd., color difference meter CR-3)
10, the detection part is a circle having a diameter of 50 mm), and each carpet test piece is measured at five points.

[0056] before the antifouling test L ^*, a a ^* and b ^*, L ^* after the antifouling test, the a ^* and b ^*, color differences by the following formula (Delta] E ^*
Calculate ab). Since each carpet test piece is measured at five points, the values are calculated at the same point. ΔE ^* ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 ΔL ^* ... Difference in L ^* before and after antifouling test Δa ^*. Difference in a ^* before and after the stain test Δb ^* .... Difference in b ^* before and after the stain test The average of ΔE ^* ab was determined for each carpet test piece, and the average value was designated as ΔE, and the result of the stain resistance was determined. And

[0057]

Table 2 Composition of artificial soil (weight%) Peat Moss (dark) 38.4 Portland cement 18 Kaorin clay 18 Silica (200mesh) 18 Carbon Bonack 1.05 Red iron oxide 0.30 Mineral oil 6.25

3) Adhesion Rate At the time when the carpet was treated with the repellent treatment liquid, the measured value of the F content present on the carpet fiber was changed to “F (adsorption)”.
ppm ”. The F content present on the carpet fiber after the Exhaust treatment is defined as “F (adhesion) ppm”. The measurement of the F content is based on the oxyfuel combustion method. The adhesion rate (%) is determined by the following equation.

[0059]

(Equation 1)

[0060]Synthesis Example 1(Synthesis of Rf (OH) maleate) 3-perfluoroalkyl (Rf = C₆F₁₃, C₈F₁₇, C
_TenF_{twenty one}, C₁₂F_{twenty five}, C ₁₄F₂₉Molar ratio of 2:50:30:
15: 3 mixture, average molecular weight 528) -1,2-epo
To 317 g (0.600 mol) of xypropane, maleic
Add 35.4 g (0.305 mol) of acid and heat to 140 ° C
After dissolving, the reaction was carried out for 8 hours. Gas chromatog
Raffy 3-perfluoroalkyl-1,2-epoxy
The conversion of cipropane is 100% and new
Bis-3-perfluoroalkyl-
2-Hydroxy-propyl maleate (Rf (OH) male
Ate) was confirmed by mass spectrum.

Preparation Example 1 After sufficiently dissolving 268 g of Rf (OH) maleate obtained in Synthesis Example 1 in 68 g of methyl methacrylate, 62 g of ethyl methacrylate and 4 g of styrene, polyoxyethylene sorbitan monooleate (nonionic emulsifier)
7.0 g, polyoxyethylene nonylphenyl ether (nonionic emulsifier) 7.0 g, triethanolamine lauryl sulfate solution (42% aqueous solution) (anionic emulsion)
33.5 g, lauryl mercaptan 8 g, deionized water 6
31 g was charged and emulsified with a high-pressure homogenizer. The obtained emulsion is put into a 2 L four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer and a stirrer.
It was kept at 60 ° C. for a time. A solution prepared by separately dissolving 0.5 g of ammonium persulfate and 0.25 g of sodium pyrosulfite in 5 g of water was added, polymerization was started, and the mixture was heated and stirred at 60 ° C. for 3 hours to prepare an aqueous emulsion of a copolymer. The monomer composition of the copolymer almost coincided with the charged monomer composition.

Production Example 2 Emulsion of MMA / EMA copolymer having a weight ratio of methyl methacrylate (MMA) / ethyl methacrylate (EMA) of 47:53 and a weight average molecular weight of 180,000 (in terms of polystyrene) (solid content: 45 wt. %) Was prepared as a blender emulsion.

Production Example 3 The emulsion obtained in Production Example 1 and the blender emulsion obtained in Production Example 2 (methyl methacrylate (MMA)
An emulsion blend was prepared by blending the copolymer / ethyl methacrylate (EMA) copolymer emulsion (MMA and EMA at a weight ratio of 47:53) at a solids weight ratio of 1: 1.

Example 1 The following additives were added to the emulsion prepared in Production Example 3 and diluted with water so that the solid content of the emulsion was 0.088%. At this time, sulfamic acid was added so that the pH became 1.6 to obtain a treatment liquid. Additive 1: Magnesium sulfate 3.18% (based on solids 36
Additive 2: Polyoxyethylene (addition of 21 moles of ethylene oxide) lauryl ether 0.003% (based on solid content 3%)

A carpet (size: 8.9) was added to the treatment liquid.
cm x 18.2 cm, nylon 66, cut pile, density 28 oz / yd ² , light blue) for 30 seconds. Next, it was narrowed down with a mangle so that the WPU (wet pick up) amount became 150%. Next, normal pressure steam treatment (temperature: 100 ° C. to 106 ° C.) was performed for 90 seconds with the pile surface facing upward. Next, after rinsing lightly with 2 L of water, centrifugal dehydration was performed to reduce the amount of WPU to about 25%. Finally, heat cure at 130 ℃
For 6 minutes. Next, the water repellency, antifouling property and adhesion rate were evaluated. Table 3 shows the results.

Example 2 The following additives were added to the emulsion prepared in Production Example 3 and diluted with water so that the solid content of the emulsion was 0.088%. At this time, sulfamic acid was added so that the pH became 1.6 to obtain a treatment liquid. Additive 1: Barium chloride 0.60% (based on solid content 700
%) Additive 2: polyoxyethylene (ethylene oxide addition mole number 21) lauryl ether 0.003% (based on solid content 3%)

A carpet (size: 8.9) was added to this treatment solution.
cm x 18.2 cm, nylon 66, cut pile, density 28 oz / yd ² , light blue) for 30 seconds. Next, it was narrowed down with a mangle so that the WPU (wet pick up) amount became 150%. Next, normal pressure steam treatment (temperature: 100 ° C. to 106 ° C.) was performed for 90 seconds with the pile surface facing upward. Next, after rinsing lightly with 2 L of water, centrifugal dehydration was performed to reduce the amount of WPU to about 25%. Finally, heat cure at 130 ℃
For 6 minutes. Next, the water repellency, antifouling property and adhesion rate were evaluated. Table 3 shows the results.

COMPARATIVE EXAMPLE 1 The emulsion prepared in Production Example 3 was added to a solid content of 0.088%.
And diluted with water. At this time, sulfamic acid was added so that the pH became 1.6 to obtain a treatment liquid. A carpet (size: 8.9 cm × 18.2 cm, nylon 66, cut pile, density 28 oz / yd ² , light blue) was immersed in the treatment liquid for 30 seconds. Next, mangle the WPU (we
t pick up) The amount was reduced to 150%. Next, with the pile surface facing upward, normal pressure steam treatment (temperature 10
(0 ° C. to 106 ° C.) for 90 seconds. Next, after rinsing lightly with 2 L of water, centrifugal dehydration was performed to reduce the amount of WPU to about 25%. Finally, heat curing was performed at 130 ° C. for 6 minutes, and the same evaluation as in Example 1 was performed. Table 3 shows the results.

Comparative Example 2 A commercially available fluorine-containing repellent (Zonyl manufactured by Du Pont)
8779) was diluted with water to give a solid content of 0.108%. At this time, sulfamic acid was added so that the pH became 1.6 to obtain a treatment liquid. A carpet (size: 8.9 cm × 18.2 cm, nylon 66, cut pile, density 28 oz / yd ² , light blue) was immersed in the treatment liquid for 30 seconds. Next, the amount of WPU (wet pick up) is 1 with mangle
It was squeezed to 50%. Next, normal pressure steam treatment (temperature: 100 ° C. to 106 ° C.) was performed for 90 seconds with the pile surface facing upward. Next, after rinsing lightly with 2 L of water, centrifugal dehydration was performed to reduce the amount of WPU to about 25%. Finally, heat curing was performed at 130 ° C. for 6 minutes, and the same evaluation as in Example 1 was performed. Table 3 shows the results.

[0070]

[Table 3] Note) The values in parentheses in the antifouling property are the values of blank samples.

[0071]

According to the present invention, excellent adhesion, water repellency and stain resistance are imparted to textiles.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Norihito Otsuki 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Y-term, F-term (reference) 4L031 AA13 AB01 BA13 DA19 4L033 AA05 AA08 AB01 AC04 CA22 CA27 CA50 DA02

Claims (9)

[Claims] 1. A method for treating a textile product, comprising: (a) treating the textile product with an aqueous solution containing a metal compound; and (b) treating the textile product with a treatment solution containing a fluorine-containing antifouling component. 2. A method for treating textile products, comprising the step of treating textile products with a treatment liquid containing a metal compound and a fluorine-containing antifouling component. 3. The method according to claim 1, wherein the metal is a polyvalent metal.
The processing method described in 1. 4. The method according to claim 1, wherein the pH of the treatment liquid containing the fluorine-containing antifouling component is adjusted to 2 or less, the treatment liquid is applied to the textile, the textile is steam-treated, washed with water, and dehydrated. Method. 5. The method according to claim 1, wherein the metal compound is magnesium sulfate. 6. The method according to claim 1, wherein the fluorine-containing antifouling component comprises a fluoroalkyl group-containing maleate or fumarate-based polymer. 7. The method according to claim 1, wherein the textile is a carpet. 8. The method according to claim 6, wherein the carpet comprises nylon fibers, polypropylene fibers or polyester fibers. 9. A carpet treated by the method according to claim 1.