JP2001295179A - Treating agent for textile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a treating agent for textiles capable of easily removing foulings at the time of the next washing. SOLUTION: This treating agent for the textiles comprises (I) an amphoteric polymer comprising a monomer unit having an anionic group and a monomer unit having a cationic group in which the sum total of the monomer unit having the anionic group and the monomer unit having the cationic group accounts for >=40 mol% of the whole constituent monomer units, an electrolyte and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a textile product treating agent capable of improving the property of removing stains during washing of textile products.

[0002]

2. Description of the Related Art In order to improve the stain removal property of textiles, there are a method of improving the cleaning power of the detergent itself and a method of modifying the surface condition of the textile. . At present, textile products are also being modified because sufficient cleaning properties cannot be obtained only by the detergency of the detergent. They are industrially applied to textile products to improve the stain removal property which also has washing resistance, and are difficult to treat at home. Further, as a material which can be used at home, there is known a treatment agent which utilizes water repellency and oil repellency typified by a fluorine-based polymer to improve the stain removal property. However, this treatment impairs the hygroscopicity, so that it is not preferable to apply it to socks, underwear, and inner garments (such as shirts).

[0003] The problem to be solved by the present invention relates to a textile treating agent which can easily remove stains at the time of the next washing, a textile treating agent which can be applied to socks and the like and can be easily used at home. .

[0004]

The present invention comprises a monomer unit (A) having an anionic group and a monomer unit (B) having a cationic group (excluding an amino group and a salt thereof). The present invention relates to a fiber product treating agent containing an amphoteric polymer (I) in which the total of the monomer unit (A) and the monomer unit (B) accounts for 40 mol% or more, an electrolyte, and water.

Further, the present invention comprises a monomer unit (A) having an anionic group and a monomer unit (C) having an amino group, and the monomer unit (A) and the monomer unit (C) in all the constituent monomer units are included. The present invention relates to a fiber product treating agent containing amphoteric polymer (II) occupying a total of 40 mol% or more and water, and having a pH of less than 7.0.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION 2
There are two forms. One is an amphoteric polymer containing a monomer unit (A) having an anionic group (hereinafter referred to as monomer unit (A)) and a monomer unit (B) having a cationic group (hereinafter referred to as monomer unit (B)). (I) is used (hereinafter, referred to as form (i)), and the other includes a monomer unit (A) and a monomer unit (C) having an amino group (hereinafter, referred to as monomer unit (C)). This is the one using the amphoteric polymer (II) [hereinafter referred to as form (ii)]. In the case of the form (i), an electrolyte needs to be blended, and in the case of the form (ii), the pH needs to be adjusted to less than 7.0 with a pH adjuster.

The form (i) will be described in detail. In order to obtain the monomer unit (A) used for the amphoteric polymer (I) in the form (i), a monomer containing a carboxy group, a sulfate group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, etc. (A) will be used. Specific examples of the monomer (A) include acrylic acid, methacrylic acid, maleic acid, itaconic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, vinylsulfonic acid, and methallylsulfonic acid. , Mono-10-methacryloyloxydecyl phosphate, and salts thereof. Among them, acrylic acid, methacrylic acid,
Maleic acid, styrene sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, phosphoric acid mono-10-
Methacryloyloxydecyl and their alkali metal, ammonium or amine salts are preferred.

The monomer unit (B) has a cationic group other than an amino group or a salt thereof, and includes a monomer unit containing a quaternary ammonium group and a quaternary phosphonium group. Specific examples of the monomer used to obtain the monomer unit (B) (hereinafter, referred to as monomer (B)) include 2- (methacryloyloxy) ethyldimethylethylammonium ethyl sulfate and 2- (methacryloyloxy) ethyl chloride. Trimethyl ammonium,
(Meth) acrylamidopropyltrimethylammonium chloride, 4-vinylbenzyltrimethylammonium chloride, 4-vinylbenzyltrimethylphosphonium chloride and the like. Among them, 2- (methacryloyloxy) ethyldimethylethylammonium ethyl sulfate, 2- (methacryloyloxy) ethyltrimethylammonium chloride,
(Meth) acrylamidopropyltrimethylammonium chloride is preferred.

The monomer unit (A) and the monomer unit (B)
Is the ratio of the anionic unit equivalent (a) to the cationic unit equivalent (b), and the ratio (a) :( b) = 90: 10
The range is preferably from 10:90 to 80:20 to 20: 8.
The range of 0 is more preferable, and the range of 70:30 to 30:70 is particularly preferable.

In the amphoteric polymer (I) of the form (i), the total of the monomer units (A) and (B) is at least 40 mol%, preferably 50 mol%, of all the constituent monomer units.
It occupies more than 60 mol% more preferably.

The amphoteric polymer (I) may contain a nonionic monomer unit (D) (hereinafter, referred to as a monomer unit (D)). As a monomer for constituting the monomer unit (D) (hereinafter, referred to as monomer (D)),
C1-C20 linear or branched alkyl ester of (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth)
Acrylamide, diacetone (meth) acrylamide,
(Meth) acrylamide, N-vinylformamide, N-vinylacetamide, ethylene, propylene, n- or i-butylene having two same or different linear or branched alkyl groups having 1 to 10 carbon atoms on a nitrogen atom Butadiene, diisobutylene, cyclopentadiene, dicyclopentadiene, n- or i-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, indene, vinyl acetate, N-vinylpyrrolidone, N-vinylamidazole, N-vinyl-ε -Caprolactam and the like. Among them, linear or branched alkyl esters of (meth) acrylic acid having 1 to 20 carbon atoms, and (meth) acrylamides having the same or different two linear or branched alkyl groups having 1 to 10 carbon atoms on the nitrogen atom , Diacetone acrylamide, hydroxyethyl (meth) acrylate, styrene and vinyl acetate are preferred. The amount of the monomer unit (D) is preferably less than 40 mol% of all the monomer units constituting the amphoteric polymer (I). In addition, the ratio of each monomer unit in the amphoteric polymer (I) may be a monomer mixing ratio used at the time of copolymerization.

As a method for polymerizing the amphoteric polymer (I), a conventionally known method can be used. For example, an anionic group-containing monomer and a cationic group-containing monomer are dissolved in water in the presence of an electrolyte such as sodium chloride or sodium sulfate. There is a method of performing polymerization by heating with a radical polymerization initiator.

The weight average molecular weight of the amphoteric polymer (I) is
1,000 to 500,000 (gel permeation liquid chromatography (hereinafter referred to as GPC) method, polyethylene glycol (hereinafter referred to as PEG) conversion) is preferable, and 2,0 to 500,000 is preferable.
00-300,000 is more preferable.

The compounding amount of the amphoteric polymer (I) is preferably 5 to 5 in the fiber product treating agent in view of the concentration and the measuring property.
It is 70% by weight, more preferably 10 to 50% by weight.

In the embodiment (i), the electrolyte is an important component for the amphoteric polymer (I) to act on the textile and to improve the soil removability. More specifically, the electrolyte has a function of uniformly dispersing or dissolving the amphoteric polymer (I) in the fiber product treating agent, and the concentration of the electrolyte itself is reduced by the dilution water during the treatment of the fiber product. The solubility of the polymer (I) is reduced, and as a result, the polymer (I) has an effect of expressing the adsorption of the amphoteric polymer (I) to the fiber product. At the next washing, the amphoteric polymer adsorbed on the textile product is promoted by the large amount of electrolyte contained in the detergent to promote the desorption of the amphoteric polymer (I) from the textile product. Some dirt is removed together with the amphoteric polymer (I), so that the dirt removal property is improved.

The electrolyte blended in the form (i) preferably has a molecular weight of less than 1,000, such as sodium, potassium, lithium, magnesium, calcium such as hydrochloric acid, sulfuric acid, phosphoric acid, lactic acid, glycolic acid and citric acid. And may be used either alone or as a mixture of two or more.

The compounding amount of the electrolyte is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight in the fiber product treating agent.
5% by weight.

The balance of the form (i) is water, and the same components as described in the form (ii) can be arbitrarily mixed.

Next, the form (ii) will be described in detail.
The monomer for constituting the monomer unit (A) constituting the amphoteric polymer (II) used in the form (ii) includes:
The same monomer (A) as in form (i) is preferred.

As the monomer for constituting the monomer unit (C) constituting the amphoteric polymer (II) (hereinafter, referred to as monomer (C)), primary to tertiary amines can be used. For example, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, (meth) acrylic acid N,
N-dimethylaminoethyl, N, N (meth) acrylate
-Dimethylaminopropyl, (meth) acrylic acid N, N
-Dimethylaminobutyl, N, N- (meth) acrylate
Preferred are diethylaminomethyl, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, and N-vinylimidazole.

Amphoteric polymer (II) used in form (ii)
Is that the total of the monomer units (A) and (C) is at least 40 mol% of all the constituent monomer units, preferably 5
It accounts for 0 mol% or more, more preferably 60 mol% or more.

The monomer unit (A) and the monomer unit (C)
Is the ratio of the anion unit equivalent (c) and the amino group unit equivalent (d) as (c) :( d) = 90:10.
The range of 10:90 is preferred, and 80:20 to 20:80.
Is more preferable, and the range of 70:30 to 30:70 is particularly preferable.

The amphoteric polymer (II) may contain the above-mentioned nonionic monomer unit (D) as another monomer unit, and the same monomer (D) can be used. The monomer unit (D) is an amphoteric polymer (II)
Is preferably less than 40 mol% of all the constituent monomer units.

The weight average molecular weight of the amphoteric polymer (II) is 1,000 to 500,000 (GPC method, PEG conversion).
Is preferable, and 2,000 to 300,000 is more preferable.

The amount of the amphoteric polymer (II) is 5 to 70% by weight in the textile product treating agent in view of concentration and weighing properties.
Is preferable, and 10 to 50% by weight is more preferable.

In the form (ii), the pH is lower than 7.0, preferably 2.0 to 6.5, more preferably 2.0 to 5.5.
The following pH adjuster is used for adjusting the pH.

Examples of the pH adjuster include hydrochloric acid, sulfuric acid, phosphoric acid, lactic acid, glycolic acid, citric acid, etc., ammonia water,
Ammonium chloride, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium hydrogen carbonate and the like can be used.

In the form (ii), the amphoteric polymer (II) whose solubility in water has a pH dependency can be uniformly dispersed or dissolved in a textile treatment agent by adjusting the pH to an appropriate value with a pH adjuster. are doing. The water bath for treating textiles with this treatment agent approaches the pH of tap water,
When the anionic group of the amphoteric polymer (II) is weakly acidic, it becomes uncharged by hydrogen ions and the amino group has a positive charge, so that adsorption to textiles is promoted. Alternatively, when the anionic group is strongly acidic, it has a negative charge and the amino group has a positive charge, so that the solubility is reduced as in the case of the form (i), and the amphoteric polymer (II) is adsorbed on the textile. Is promoted. In any case, at the time of the next washing, the pH of the detergent solution is higher than that of tap water, so that the anionic groups are dissociated and the amino groups are in an uncharged state, thereby facilitating desorption from the textile. You. As a result, the stain removal property is improved as in the case of the embodiment (i).

The remainder of the form (ii) is water, and the following components can be arbitrarily compounded similarly to the form (i).

In order to impart variety to the texture of textile products treated with the textile product treating agent of the present invention, the following texture modifiers can be blended.

Examples of the texture control agent include, for example, silicone compounds such as polydimethylsiloxane oil, polymethylphenylsiloxane oil, emulsions thereof, or a part thereof, which is polyether-modified, amino-modified, epoxy-modified, or carboxy-modified. Examples include oils modified with one or more functional groups such as denaturation and long-chain alkyl modification, and emulsions thereof. Among them, polydimethylsiloxane oil, polyether-modified polydimethylsiloxane oil,
An amino-modified polydimethylsiloxane oil, a polyether-modified and amino-modified co-modified polydimethylsiloxane oil or an emulsion thereof are preferred. The viscosity of each silicone oil (25 ° C, Ubbelohde viscometer) is 1
0mm ² / s~1,000,000mm ² / s, preferably 1,000mm ² / s~100,000mm ² / s. Emulsified products obtained by emulsion polymerization or mechanical emulsification or self-emulsifying products can be used. As the emulsifier, one or more arbitrarily selected surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants can be used. The compounding amount of these silicone compounds is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, in the fiber product treating agent.

Further, a softening base such as a long-chain alkyl group-containing cationic softening base can be blended as a feeling control agent. For example, JP-A-63-6168, JP-A-8-113871, and JP-A-10-219567.
Japanese Patent Application Publication No. JP-A-2006-15095 can be used. The amount of these compounds is preferably 0.1 to 30% by weight, more preferably 3 to 20% by weight.
% By weight.

In order to maintain the color of the textile product treated with the textile product treating agent of the present invention, the following color adjusting agent can be blended. WO97 / 28242
Patent Document No. Dye Fixative Agents (Dye Fixative Agents), chelating agents (Chelating Agents), chlorine scavenger (Chlorine Scav
enging Agents), Dye Transfer Inhibiting
Agents), Cellulase Enzyme, Free Radical Scavengers, and the like. The blending amounts of these are not particularly limited, but the blending amounts described in the publication are preferable.

Further, the following agents can be added to the fiber product treating agent of the present invention as required. (1) In order to improve the wettability and permeability of the treating agent to textiles, for example, the Japanese Patent Office Publication “Known and Commonly Used Techniques (Powder Detergent for Clothing)” (issued March 26, 1998) And at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. (2) Perfume components described in, for example, JP-A-10-195773, JP-A-9-209275, and JP-A-8-113871. (3) Dyes described in, for example, JP-A-63-69899 and JP-A-4-332765. (4) Denatonium benzoate, 8-acetylated sucrose, brucine, 1,2-benzisothiazolin-3-one, dithiobisbenzamide, polyhexamethylene biguanide acid addition salt, 5-chloro-2-methyl-4-isothiazoline One or more compounds selected from -3-one, 2-methyl-4-isothiazolin-3-one, bromonitropropanediol, and the like. (5) JP-A-7-216744 and JP-A-10-1
Polyhydric alcohols described in Japanese Patent No. 95773. (6) Antifoaming agents, fluorescent dyes, pigments, lower alcohols and the like.

The textile product treating agent of the present invention is applied to textile products, especially textile products after washing by a method such as dipping, coating or spraying, thereby improving the removability of stains adhering to textile products. It is to let. After application, it is preferable to dry naturally by a usual method such as hanging and drying. When a textile is immersed, it is preferable to use a water bath having a concentration of the amphoteric polymer (I) or (II) of 0.1 to 20% by weight to obtain a sufficient immersion amount. When applied or sprayed, the concentration of the amphoteric polymer (I) or (II) is preferably 0.01 to 10% by weight, and when applied, use the container used for washing part of the laundry. Can be used for parts that are easily soiled, such as collars and sleeves.
When spraying, a general trigger-type sprayer can be used. Also in the case of application or spraying, it is preferable to sufficiently apply or spray such that the treatment agent penetrates inside the fiber.

[0036]

According to the present invention, there is obtained a textile product treating agent which can easily remove stains adhered to textile products, particularly socks, underwear, inner garments, etc. at the next washing by simple processing. Can be The fiber product treating agent of the present invention is suitable as a stain removal improver.

[0037]

EXAMPLES Synthetic Examples In the following synthetic examples, the preparation and mixing compositions were all in parts by weight. The obtained polymers are summarized in Table 1.

Synthesis Example 1 Synthesis of Polymer (a-1) 400 parts of ion-exchanged water were stirred at 68 to 72 ° C. in a nitrogen atmosphere. Here, sodium styrene sulfonate 69.4
Parts (purity 89.2%, pure content 61.9 parts) and ethyl sulfate 2
A solution obtained by mixing 63.4 parts of methacryloyloxyethyldimethylethylammonium (110 parts of an 84.6% aqueous solution) and 280 parts of ion-exchanged water, and 2,2′-azobis (2-amidinopropane) dihydrochloride 0 .814 parts and 120 parts of ion-exchanged water were separately dropped over 2 hours. During the dropping, the temperature of the stirring liquid was 68
７２72 ° C. After completion of the dropwise addition, stirring was continued at 68 to 72 ° C. for 5 hours, and then the temperature was returned to room temperature, and 7.3% by weight of poly (2-methacryloyloxyethyldimethylethylammonium styrenesulfonate) and 2.9% of sodium ethyl sulfate were added. % Was obtained. This solution was used in the examples.

To 17.6 parts of this solution, 42.4 parts of a 1N aqueous sodium hydroxide solution was added, and the mixture was maintained at 80 ° C. for 16 hours, returned to room temperature, and neutralized with phosphoric acid to pH 7.4.
The weight average molecular weight of the hydrolyzate thus obtained was 270,000. The weight average molecular weight was determined by a GPC method. The measurement conditions are as follows. Column: Two TSK GMPWXL manufactured by Tosoh Corporation Eluent: 9: 1 volume ratio of an aqueous solution containing 0.1 mol / L of potassium dihydrogen phosphate and 1 mol / L of disodium hydrogen phosphate to acetonitrile mixture. Detector: Differential refractometer Flow rate: 1.0 mL / min Temperature: 40 ° C. Standard: PEG (weight average molecular weight 9.20 × 10 ⁵ , 5.
10 × 10 ⁵ , 2.50 × 10 ⁵ , 9.50 × 10 ⁴ ,
4.60 × 10 ⁴ , 3.90 × 10 ⁴ ) Sample concentration: 0.20 g / 100 mL Eluent Sample solution injection volume: 0.20 mL.

Synthesis Example 2: Synthesis of polymer (a-2) [Preparation of first solution] 15.4 parts of sodium hydroxide was dissolved in 300 parts of ion-exchanged water, cooled with ice, and stirred. To this, 80.00 parts of 2-acrylamido-2-methylpropanesulfonic acid was added over 20 minutes to dissolve, and then 120.2 parts of 2-methacryloyloxyethyldimethylethylammonium ethylsulfate (142.
1 part) and adjusted to pH 6.59 with 0.5N aqueous sulfuric acid.
And returned to room temperature. This was returned to room temperature and used as a first liquid.

[Preparation of second liquid] 2,2'-azobis (2
-Amidinopropane) dihydrochloride (1.05 parts) was dissolved in ion-exchanged water (120 parts) and kept at room temperature to prepare a second liquid.

[Polymerization] While 500 parts of ion-exchanged water was kept at 68 to 72 ° C. while stirring under a nitrogen atmosphere, the first liquid and the second liquid were simultaneously dropped over 2 hours.
During the dropping, the temperature of the stirring liquid was kept at 68 to 72 ° C, and after completion of the dropping, stirring was continued at 68 to 72 ° C for 5 hours, and then returned to room temperature.
A solution containing 12.8% by weight of poly (2-acrylamido-2-methylpropanesulfonic acid 2-methacryloyloxyethyldimethylethylammonium) and 4.8% by weight of a salt such as sodium ethyl sulfate or sodium sulfate was obtained. This solution was used in the examples.

49.8 parts of a 1N aqueous sodium hydroxide solution was added to 10.2 parts of this solution, and the mixture was kept at 80 ° C. for 16 hours, then returned to room temperature, and neutralized with phosphoric acid to pH 7.4.
The weight-average molecular weight of the hydrolyzate thus obtained was 190,000. The measurement conditions are the same as in Synthesis Example 1.

Synthesis Example 3 Synthesis of Polymer (a-3) A solution of 55.5 parts of sodium hydroxide in 600 parts of ion-exchanged water was stirred under a nitrogen atmosphere while cooling with ice. To this, 115 parts of methacrylic acid was added so that the temperature of the stirring liquid did not exceed 30 ° C., and 178 parts of 2-methacryloyloxyethyldimethylethylammonium ethyl sulfate (211% of an 84.6% aqueous solution) were added. Melted 1N
The pH was adjusted to 6.7 by adding an aqueous sodium hydroxide solution, and then the temperature was returned to room temperature. To this, 41.3 parts of thioglycerin was added, followed by a solution of 5.18 parts of 2,2′-azobis (2-amidinopropane) dihydrochloride in 50 parts of ion-exchanged water, and the mixture was stirred at 68 to 72 ° C. for 5 hours. The solution was returned to room temperature to obtain a solution containing 20.6% by weight of poly (2-methacryloyloxyethyldimethylethylammonium methacrylate) and 7.9% of sodium ethyl sulfate. This solution was used in the examples.

To 11.7 parts of this solution, 48.3 parts of a 1N aqueous sodium hydroxide solution was added, and the mixture was kept at 80 ° C. for 16 hours, returned to room temperature, and neutralized with phosphoric acid to pH 7.4.
The weight-average molecular weight of the hydrolyzate thus obtained was 500000. The measurement conditions are the same as in Synthesis Example 1.

Synthesis Example 4: Synthesis of polymer (a-4) 13.0 parts of sodium hydroxide was dissolved in 650 parts of ion-exchanged water, cooled with ice, and stirred under a nitrogen atmosphere. 140 parts of sodium 2-methylpropanesulfonate were gradually added and dissolved so that the temperature of the stirring liquid did not exceed 30 ° C. Further, 45.5 parts of N, N-dimethylaminoethyl methacrylate was gradually added thereto so that the temperature of the mixed solution did not exceed 30 ° C., and 6N
The pH was adjusted to 4.46 with an aqueous solution of sodium hydroxide, and the temperature was returned to room temperature. Here, 10.4 parts of thioglycerin,
A solution of 2.62 parts of 2,2′-azobis (2-amidinopropane) dihydrochloride and 50 parts of ion-exchanged water was added, and 68-
The mixture was stirred at 72 ° C. for 5 hours, and then returned to room temperature. The solution thus obtained containing 21.30% by weight of poly (sodium 2-acrylamido-2-methylpropanesulfonate / N, N-dimethylaminoethyl methacrylate) was used in the examples.

To 8.8 parts of the obtained solution, 51.2 parts of a 1N aqueous sodium hydroxide solution was mixed, heated at 80 ° C. for 16 hours, returned to room temperature, and phosphoric acid was added to adjust the pH to 7.4.
The weight-average molecular weight of the hydrolyzate thus obtained was 15,000. The measurement conditions are the same as in the case of Synthesis Example 1.

Synthesis Example 5: Synthesis of polymer (a-5) 80.0 parts of sodium styrenesulfonate (purity 89.
2%) was dissolved in a mixture of 650 parts of ion-exchanged water and 2.8 mL of concentrated hydrochloric acid, and the mixture was cooled with ice while stirring under a nitrogen atmosphere. Here, 6.05 parts of N, N-dimethylaminoethyl methacrylate was gradually added so that the temperature of the stirring liquid did not exceed 30 ° C., and the pH was adjusted to 4.51 with concentrated hydrochloric acid, and the temperature was returned to room temperature. . To this, 4.16 parts of thioglycerin was added, followed by a solution of 1.04 parts of 2,2′-azobis (2-amidinopropane) dihydrochloride in 50 parts of ion-exchanged water, and the mixture was heated at 68 to 72 ° C. for 5 hours. After stirring, the temperature was returned to room temperature. The poly (sodium styrenesulfonate / N, N-dimethylaminoethyl methacrylate) thus obtained has a content of 9.6.
A weight percent aqueous solution was used in the examples.

To 18.5 parts of the obtained solution, 52.5 parts of a 1N aqueous solution of sodium hydroxide was mixed, heated at 80 ° C. for 16 hours, returned to room temperature, and phosphoric acid was added to adjust the pH to 7.4. .

The hydrolyzate thus obtained had a weight average molecular weight of 16,000. The measurement conditions are the same as in the case of Synthesis Example 1.

Synthesis Example 6: Synthesis of polymer (a-6) [Preparation of first solution] 115 parts of methacrylic acid was dissolved in 100 parts of ion-exchanged water, and cooled with ice while stirring. Here, N, N-dimethylaminoethyl methacrylate 23.
3 parts and about 0.19 L of a 6N sodium hydroxide aqueous solution are gradually added so that the temperature of the mixture does not exceed 30 ° C., and a small amount of a 6N sodium hydroxide aqueous solution is further added to adjust the pH to 6.88. It was adjusted. This was returned to room temperature and used as a first liquid.

[Preparation of a second liquid] 2,2'-azobis (2
-Amidinopropane) dihydrochloride (2.818 parts) was dissolved in ion-exchanged water (120 parts) and kept at room temperature to prepare a second liquid.

[Polymerization] While maintaining a mixture of 200 parts of ion-exchanged water and 300 parts of 2-propanol at 74 to 78 ° C. while stirring under a nitrogen atmosphere, the first liquid and the second liquid Drop it over time, and after finishing the drop, 74-7
Stirring was continued at 8 ° C. for 5 hours and then returned to room temperature. The resulting solution was concentrated under reduced pressure to remove 2-propanol, and ion-exchanged water was added to obtain a solution containing 15.2% by weight of poly (sodium methacrylate / N, N-dimethylaminoethyl methacrylate). Was. This solution was used in the examples described below.

18.5 parts of the obtained solution was mixed with 52.5 parts of a 1N aqueous solution of sodium hydroxide, heated at 80 ° C. for 16 hours, returned to room temperature and phosphoric acid was added to adjust the pH to 7.4. .

The thus obtained hydrolyzate had a weight average molecular weight of 47,000. The measurement conditions are the same as in the case of Synthesis Example 1.

Comparative Synthesis Example 1: Synthesis of Polymer (b-1) A flask was charged with 6 parts of cationized starch, 3.0 parts of polyvinyl alcohol (80% saponification, 1500 degree of polymerization), and 100 parts of ion-exchanged water, and added to the flask. Dissolved at 60 ° C, cooled to 60 ° C, 10 parts of vinyl acetate and Emulgen 147 (polyoxyethylene nonionic emulsifier, manufactured by Kao Corporation)
2 parts, and further 0.5 parts of sodium carbonate, 2,2′-
0.1 parts of azobis (2-amidinopropane) hydrochloride and 20 parts of ion-exchanged water were added, and the temperature was raised to 75 ° C. to initiate polymerization. From 30 minutes to 350 minutes after the initiation of the polymerization, a mixture of 85.5 parts of vinyl acetate and 4 parts of methacrylic acid in advance was continuously dropped into the reaction solution. After the completion of the dropwise addition, the temperature was raised to 80 ° C., and after aging for 1 hour, the polymerization reaction was terminated. Thereafter, the mixture was cooled to 25 ° C., and the obtained emulsion was adjusted to pH 5.0 using a 10% aqueous sodium carbonate solution to obtain a polymer emulsion having a solid content of about 50%. This solution was used in a comparative example described later.

[0057]

[Table 1]

Example << Evaluation of Stain Removal >> (Preparation of Test Cloth) A 100% cotton knitted fabric (obtained from Dynasty Test Materials Co., Ltd., Tanika Shoten) was used with Kao Corporation's clothing detergent "Attack" for household use. Washing using a fully automatic washing machine 12
After repeating the process of 5 minutes for a cycle of 1 minute, 1 rinse, and 3 minutes of dehydration, a running water rinse is performed with a home two-tub washing machine.
Min-dehydration for 5 minutes, and air-dry to obtain a test cloth.

(Treatment Conditions for Textile Products) Test cloth piece: The test cloth prepared by the above method was about 15 cm ×
A set of 10 pieces cut to 12 cm. Treatment liquid; Example 1 of Tables 2 and 3 using the polymer of Table 1.
-8 and Comparative Examples 1-2, 4-5 were prepared, and further 4 ° so that each concentration was 10% by weight.
A solution diluted with DH hard water (adjusted with calcium chloride, 71.2 mg / L as calcium carbonate, the same applies hereinafter) is used as a treatment liquid. Adsorption treatment: Targotometer, 50 r / min, 5 minutes, drying at 20 ° C., bath ratio 10; Dehydration for 1 minute in a domestic two-tub washing machine, followed by natural drying by flat drying.

(Contamination treatment conditions) Test cloth piece: A set of four test cloth pieces obtained by cutting a treated cloth after immersion treatment and air drying into 8 cm × 8 cm. Pollutant;
1.8 g of the product passed through a sieve. Contamination method; 150% o. w.
f. Spray to become. Test cloth pieces, contaminants and glass beads (diameter: about 15 mm, weight: about 6 g) moistened into a vinyl bag
8) and shaken for 10 minutes to allow the contaminants to adhere to the test cloth. Dry at 70 ° C for 30 minutes.

(Washing conditions) Washing solution: Preparation of 0.067% attack solution in 4 ° DH hard water, 1 L, washing at 20 ° C .; washing with tergotometer, 100 r / min for 10 minutes, rinsing with running water, dehydration, and pressing Drying. 460n
The reflectivity of m is measured and determined as the dirt removal property. The larger this value is, the better the stain removal property is. Tables 2 and 3 show the results.
It was shown to.

[0062]

[Table 2]

[0063]

[Table 3]

Claims (3)

[Claims] 1. A monomer unit (A) having a monomer unit (A) having an anionic group and a monomer unit (B) having a cationic group (excluding an amino group and a salt thereof), and comprising all monomer units And an amphoteric polymer (I) in which the total of the monomer units (B) accounts for at least 40 mol%;
A textile treatment agent containing an electrolyte and water. 2. It comprises a monomer unit (A) having an anionic group and a monomer unit (C) having an amino group,
Textile product treatment containing amphoteric polymer (II) in which the total of monomer units (A) and monomer units (C) in all constituent monomer units accounts for 40 mol% or more, and water, and having a pH of less than 7.0 Agent. 3. The method according to claim 1, which is applied to a textile to improve the removability of dirt attached to the textile.
The textile product treating agent according to the above.