JP5154038B2 - Cleaning composition - Google Patents

Description

  The present invention relates to a detergent composition suitable for textile products.

  In some cases, a base is adsorbed on the fiber in advance so that dirt components are easily released from the fiber during washing. If the fiber is subjected to such a treatment, a higher cleaning effect than normal washing can be expected. A base that exhibits such an effect is generally called a “soil release agent”.

Various bases have been proposed for soil release agents. For example, compounds mainly composed of terephthalate (Patent Documents 1 to 3) have been proposed. Further, polyamine derivatives (Patent Documents 4 and 5), chitosan derivatives (Patent Document 6), cross-linked amines (Patent Document 7) and the like have been proposed. Further, Patent Document 8 describes a soil release agent comprising a polysaccharide having a cationic group and a hydrophobic group such as ammonium and polyvinyl alcohol, but it is still not fully satisfactory in terms of the soil release effect.
US Pat. No. 3,416,952 US Pat. No. 3,557,039 US Pat. No. 4,955,584 WO 97/42285 pamphlet Japanese National Patent Publication No. 11-508319 JP 2004-175882 A JP 2004-197241 A Japanese Patent No. 3253972

  Usually, the treatment with the soil release agent is often performed at the time of rinsing of the washing process in order to sufficiently remain in the fiber. In this case, the operation of adding the soil release agent is necessary in addition to the washing with the detergent. . Therefore, if there is a treatment agent that can sufficiently impart both the cleaning effect and the soil release effect, it can be applied without changing the normal washing process, and thus the convenience is further improved. There is no mention that can lead to improvement from this perspective.

  The object of the present invention is to provide an excellent cleaning effect in a single treatment not only for fiber products, particularly highly hydrophobic fibers such as polyester fibers, but also for relatively hydrophilic fibers such as cotton fibers. It is an object of the present invention to provide a cleaning composition that can exhibit a soil release effect.

The present invention comprises the following structural unit (A) and structural unit (B) at a weight ratio of (A) / (B) = 20/80 to 98/2, and having a weight average molecular weight of 2,000 to 100,000. A cleaning composition containing polymer (I), wherein an aqueous buffer solution (concentration: 1 g / L) of the composition has an alkaline buffer capacity at 25 ° C. (in order to make the pH of the aqueous solution at 25 ° C. not more than 9.5) The present invention relates to a cleaning composition having a required 0.1N hydrochloric acid amount of 5 ml or less.
Structural unit (A): Structural unit derived from a monomer having a primary to tertiary amino group [hereinafter referred to as monomer (a)] Structural unit (B): A hydrophobic group and having a primary to tertiary amino group A structural unit derived from a monomer that does not have [hereinafter referred to as monomer (b)]

  Moreover, this invention is a cleaning medium of pH 6-9.5 containing the cleaning composition of the said invention so that the weight of the said polymer (I) per kg of textiles may be 0.01-10g. The present invention relates to a method for cleaning textile products.

  When used for cleaning textile products, the cleaning composition of the present invention can perform both cleaning of textile products and imparting a soil release effect to the textile products in a single cleaning process. By using this textile product and then washing with the cleaning composition of the present invention, dirt is easily released, and an excellent cleaning effect can be exerted. In addition, a new dirt releasing effect is imparted. Such an effect of the present invention is exhibited not only for highly hydrophobic fibers such as polyester fibers, but also for relatively hydrophilic fibers such as cotton fibers.

[Monomer (a)]
The monomer (a) of the present invention is a monomer having at least one amino group selected from primary to tertiary amino groups. When the amino group is a quaternary ammonium group, a high effect as in the present invention cannot be obtained.

  Examples of the monomer (a) include (meth) acrylic acid esters, (meth) acrylamides, styrenes, diallyl compounds and the like having at least one amino group selected from primary to tertiary amino groups. Here, “(meth) acryl” means acrylic or methacrylic.

  Among these monomers, monomers represented by the general formulas (I) to (III) are preferable.

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, or An alkenyl group or a benzyl group, X represents an —O— or —NH— group, and Y represents a linear or branched alkylene group having 1 to 4 carbon atoms.

(In the formula, R ¹ , R ² , R ³ and Y are as defined above. N represents 0 or 1.)

(In the formula, R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, or Represents an alkenyl group or a benzyl group.)

  Examples of the monomer represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) ) Acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl ( (Meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butylaminopropyl ( Data) with a dialkylamino group such as acrylamide (meth) acrylic acid ester or (meth) acrylamide.

  Examples of the monomer represented by the general formula (II) include styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene. Examples of the monomer represented by the general formula (III) include diallylamine compounds such as diallylmethylamine and diallylamine.

  Among these monomers, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diallylmethylamine, and diallylamine are particularly preferable.

[Monomer (b)]
The monomer (b) of the present invention is a monomer having a hydrophobic group and not having a primary to tertiary amino group. Examples of the hydrophobic group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

  As the monomer (b), a (meth) acrylic acid ester having a linear, branched or cyclic alkyl group or alkenyl group having 1 to 22 carbon atoms, preferably 4 to 22 carbon atoms, or an arylalkyl group, (meta ) At least one selected from acrylamide, vinyl ester, vinyl ether and styrenes.

  Specific examples of the monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, oleyl (meth) acrylate, etc. (Meth) acrylic acid ester having a linear, branched or cyclic alkyl group or alkenyl group having 1 to 22 carbon atoms; (meth) acrylic acid having an arylalkyl group such as benzyl (meth) acrylate Steal; methyl (meth) acrylamide, ethyl (meth) acrylamide, isopropyl (meth) acrylamide, butyl (meth) acrylamide, t-butyl (meth) acrylamide, cyclohexyl (meth) acrylamide, 2-ethylhexyl (meth) acrylamide, lauryl ( C1-C22 linear, branched or cyclic alkyl or alkenyl groups such as meth) acrylamide, stearyl (meth) acrylamide, behenyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, etc. (Meth) acrylamide having an arylalkyl group such as benzyl (meth) acrylamide; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, Vinyl esters having a linear, branched or cyclic alkyl group or alkenyl group having 1 to 22 carbon atoms, such as vinyl titanate, vinyl decanoate, vinyl laurate, vinyl palmitate, vinyl stearate; methyl vinyl ether; Examples include vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; styrenes such as styrene, α-methyl styrene, methyl styrene, butyl styrene, t-butyl styrene, and dimethyl styrene.

  Among these monomers, (meth) acrylic acid ester or (meth) acrylamide or styrene having a linear, branched or cyclic alkyl group or alkenyl group having 1 to 22 carbon atoms, particularly 4 to 22 carbon atoms is used. More preferred.

[Polymer (I)]
The polymer (I) of the present invention has a structural unit (A) / structural unit (B) = 20/80 to 98/2 weight ratio, and the monomer (a) and the monomer (b) a) / monomer (b) = obtained by copolymerizing monomer components having a weight ratio of 20/80 to 98/2.

  One or more types of monomer (a) and monomer (b) can be used. The weight ratio of the monomer (a) to the monomer (b) is such that monomer (a) / monomer (b) = 20/80 or more from the viewpoint of adsorption / desorption to the fiber, affinity for dirt, and water solubility. 98/2, 30/70 to 95/5 are preferable, and 40/60 to 95/5 are more preferable.

  In addition to monomer (a) and monomer (b), a monomer copolymerizable with monomer (a) and monomer (b) (hereinafter referred to as monomer (c)) is copolymerized within a range that does not impair the effects of the present invention. May be.

  As the monomer (c), for example, vinyl alcohol; (meth) acrylic acid ester or (meth) acrylamide having a hydroxyalkyl group having 1 to 22 carbon atoms such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylamide; Polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, lauroxy polyethylene glycol (meth) acrylate (degree of polymerization of ethylene glycol 1 to 100), polypropylene glycol (meth) acrylate (degree of polymerization of propylene glycol 1 to 1) 50), polyalkylene (carbon number of alkylene group: 1 to 8; linear or branched) oxy such as polybutylene glycol (meth) acrylate (the degree of polymerization of butylene glycol is 1 to 50) (Meth) acrylic acid ester having a chain; (meth) acrylic acid ester of polyhydric alcohol such as glycerin (meth) acrylate; diacetone (meth) acrylamide; N-vinyl cyclic amide such as N-vinylpyrrolidone; N- (meta ) Acroylmorpholine; Vinyl chloride; Acrylonitrile; Vinyl compounds having a carboxyl group such as (meth) acrylic acid, maleic acid, itaconic acid, styrene carboxylic acid; 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, etc. Examples include vinyl compounds having a sulfonic acid group.

  The copolymerization amount of these monomers (c) is preferably 0 to 80% by weight based on the total amount of monomers.

  The weight average molecular weight of the polymer (I) of the present invention is 2,000 to 100,000, preferably 2,000 to 60,000, from the viewpoint of easy control of adsorption / desorption to the fiber.

  The weight average molecular weight of the polymer (I) of the present invention is a weight average molecular weight measured by gel permeation chromatography (GPC), and eluents are water, alcohol, chloroform, dimethylformamide, tetrahydrofuran, acetonitrile. And any combination of these solvents.

  The polymer (I) of the present invention is prepared by subjecting the monomer component to addition polymerization such as radical polymerization or ionic polymerization using a general polymerization method such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or a dispersion polymerization method. Although it can be obtained, radical polymerization is preferred from the viewpoint of ease of synthesis and freedom of composition. The radical polymerization is performed using a general radical polymerization initiator. Specifically, in the case of the solution polymerization method, the monomer and the polymerization initiator are dissolved in an organic solvent, and dissolved oxygen in the system is removed by substitution with an inert gas such as nitrogen, and then the temperature is raised to polymerize. A method is illustrated. Examples of the polymerization initiator include peroxide initiators such as lauroyl peroxide and azo initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile). The polymerization initiation temperature is usually about 30 to 100 ° C., and the reaction time is about 1 to 20 hours.

  In the polymer (I) of the present invention, it is preferable in terms of adsorptivity to fibers and solubility in water that a part or all of amino groups are acid-neutralized before blending into the detergent composition. . Preferred acids for obtaining the acid neutralized product include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; acetic acid, propionic acid, formic acid, maleic acid, fumaric acid, citric acid, tartaric acid, adipic acid, sulfamic acid, Examples thereof include organic acids having a total carbon number of 1 to 22, such as toluenesulfonic acid, lactic acid, pyrrolidone-2-carboxylic acid, succinic acid, glycolic acid, malic acid and the like.

[Cleaning composition]
The cleaning composition of the present invention is suitable for textile products, and can contain a surfactant, an alkaline agent, a builder, and other components.

[Surfactant]
The content of the surfactant in the cleaning composition of the present invention is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, and still more preferably 10 to 45% by mass from the viewpoint of cleaning performance. . The surfactant contains a nonionic surfactant and / or an anionic surfactant, and may contain a cationic surfactant and an amphoteric surfactant as necessary.

  Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyalkylene alkyl amines, glycerin fatty acid esters, higher fatty acid alkanolamides. , Alkyl glucoside, alkyl glucose amide, alkyl amine oxide and the like.

  From the standpoint of detergency, an adduct of an ethylene oxide of an alcohol having 10 to 18 carbon atoms, preferably 12 to 14 carbons, or a mixed adduct of ethylene oxide and propylene oxide, having an average alkylene oxide addition mole number of 53 to 30, preferably 64-20 polyoxyalkylene alkyl ethers are preferred.

  From the viewpoint of detergency and soil release effect, the content of the nonionic surfactant in the surfactant is 50% by mass or more, preferably 60% by mass or more, and more preferably 80% by mass or more.

  As an anionic surfactant, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonic acid, α-sulfo fatty acid salt or ester, alkyl or alkenyl ether carboxylate, fatty acid salt, etc. Is mentioned.

  From the viewpoint of the soil release effect, the content of the anionic surfactant in the cleaning composition is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

  Examples of the cationic surfactant include alkyltrimethylammonium salts, and examples of the amphoteric surfactant include carbobetaine-type and sulfobetaine-type surfactants.

[Alkaline agent]
In order to obtain a high soil release effect, the alkaline buffering capacity at 25 ° C. of the aqueous solution (concentration 1 g / L) of the cleaning composition of the present invention (0 required to reduce the pH of the aqueous solution at 25 ° C. to 9.5 or less) .1N hydrochloric acid amount) is 5 ml or less, preferably 3 ml or less, more preferably 1 ml or less, particularly preferably 0 ml. The alkaline buffer capacity was measured by dispersing 1 g of the detergent composition in distilled water at 25 ° C. and stirring for 2 minutes, then dropping and stirring 0.2 ml of 0.1N hydrochloric acid every 10 seconds to produce a composite electrode (Horiba Seisakusho). 6367-10D), pH meter (H-23, manufactured by Horiba, Ltd.) is used to measure the pH, and the amount of 0.1N hydrochloric acid required for the pH value to be 9.5 or less is determined as the alkaline buffer capacity. did.

  In order to maintain the alkaline buffer capacity of the composition within the above range, the content of the alkaline agent in the cleaning composition is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. Particularly preferably, it is not substantially contained. Here, the alkaline agent is a component having a pH of 10.1 or more when 0.1 g of the component is dissolved or dispersed in 1 L of distilled water at 25 ° C. The pH was measured using a composite electrode (Horiba Seisakusho 6367-10D) and a pH meter (Horiba Seisakusho F-23), and the value was obtained when the pH value was sufficiently stabilized.

  Examples of the alkaline agent in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, atypical sodium silicate (for example, JIS No. 1, No. 2 sodium silicate, etc.), crystalline sodium silicate (for example, And the like described in JP-A-60-227895 and JP-A-7-89712.

  Moreover, when mix | blending the said alkali agent, the component which weakens alkalinity is mix | blended and the cleaning composition whose buffer capacity is 5 ml or less can be obtained. As the component that weakens the alkalinity, it can be used without limitation as long as it has the above effect, but it may be an acidic component such as citric acid, fatty acid, alkylbenzene sulfonic acid, sodium bicarbonate, disodium hydrogen phosphate, citric acid Examples include partially neutralized salts of polybasic acids such as monosodium and disodium citrate.

[builder]
Moreover, crystalline aluminosilicates, such as A type, X type, and P type zeolite, can be mix | blended with the cleaning composition of this invention as a sequestering agent. A cation exchange polymer having a carboxylic acid group and / or a sulfonic acid group can be blended.

  Water-soluble inorganic salts such as carbonates, hydrogen carbonates, silicates, sulfates, sulfites and phosphates can be blended. The blending of water-soluble inorganic salts is preferable because the salt strength in water is increased and the cleaning performance of sebum dirt is improved.

[Other ingredients]
In addition, organic acid salts such as citrate and ethylenediaminetetraacetate, bleaching agents such as percarbonate, compounds described in JP-A-6-316700, bleach activators such as tetraacetylethylenediamine, cellulase, amylase, and lipase Enzymes, fluorescent dyes, antifoaming agents, antioxidants, fragrances, softening agents, anti-shrinking agents, anti-fading agents, anti-transfer agents and the like can be blended.

  The form of the cleaning composition may be any form such as powder detergent, solid detergent, paste detergent, liquid detergent, and sheet detergent.

[Treatment method for textile products]
The cleaning composition of the present invention can be used as a laundry detergent for ordinary clothes and the like. That is, a cleaning medium (preferably containing a pH of 6 to 9) containing the cleaning composition of the present invention (preferably containing the polymer compound (I) in a weight of 0.01 to 10 g per 1 kg of the textile product). .5, more preferably 7-9, and most preferably 7-8) textile products such as clothing are treated. Thereby, while removing the stain | pollution | contamination of a textile product, polymer (I) is made to adsorb | suck to a textile product. It is inferred that after the dirt is adhered using the textile product, a part of the polymer (I) is detached together with the dirt by washing with the cleaning composition of the present invention, thereby exhibiting the dirt releasing effect. .

Synthesis example 1
35.60 g of dimethylaminoethyl methacrylate, 14.40 g of lauryl methacrylate, and 180.0 g of ethanol were uniformly mixed, put into a glass separable flask having an internal volume of 300 mL, and stirred for a certain time under a nitrogen atmosphere. Thereto was added a solution prepared by dissolving 1.41 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65; manufactured by Wako Pure Chemical Industries, Ltd.) in 20.0 g of ethanol, and around 60 ° C. The temperature was raised to. Polymerization and aging were carried out by maintaining the temperature at around 60 to 70 ° C. for a total of 8 hours. 100.0 g of ethanol was added and diluted there, and then the temperature was lowered to room temperature. This reaction solution was dropped into 4000.0 g of ion-exchanged water and purified by reprecipitation, and the precipitate was dried to obtain polymer 1. The weight average molecular weight of polymer 1 (water / ethanol = 7/3 system, converted to polyethylene oxide) was 11,000. The composition of polymer 1 analyzed by ¹ H-NMR was the same as the charged monomer composition.

Synthesis example 2
In Synthesis Example 1, the amount of dimethylaminoethyl methacrylate was 36.03 g, 1397 g of butyl methacrylate instead of lauryl methacrylate, 111.7 g of ethanol added first, and 2,2′-azobis (2, Polymer 2 was obtained in the same manner as in Synthesis Example 1 except that the amount of 4-dimethylvaleronitrile) and the amount of ethanol were changed to 0.41 g and 5.0 g, respectively. The weight average molecular weight of polymer 2 (water / ethanol = 7/3 system, converted to polyethylene oxide) was 47000. Further, the composition of polymer 2 analyzed by ¹ H-NMR was in accordance with the charged monomer composition.

Synthesis example 3
In Synthesis Example 1, the amount of dimethylaminoethyl methacrylate was 36.85 g, instead of lauryl methacrylate, 13.15 g of styrene, the amount of ethanol added first was 111.7 g, and then 2,2′-azobis (2,4 -Dimethylvaleronitrile) Polymer 3 was obtained in the same manner as in Synthesis Example 1 except that the amounts of ethanol and ethanol were changed to 0.45 g and 5.0 g, respectively. The weight average molecular weight of the polymer 3 (dimethylformamide series, polystyrene conversion) was 9,200. Moreover, the composition of the polymer 3 analyzed by ¹ H-NMR was the same as the charged monomer composition.

Synthesis example 4
In Synthesis Example 1, instead of dimethylaminoethyl methacrylate, 37.22 g of diethylaminoethyl methacrylate, 12.78 g of lauryl methacrylate, 111.7 g of ethanol added first, and 2,2′-azobis (2 , 4-dimethylvaleronitrile) and the amount of ethanol were changed to 0.31 g and 5.0 g, respectively, to obtain polymer 4 in the same manner as in Synthesis Example 1. The weight average molecular weight of polymer 4 (water / ethanol = 7/3 system, converted to polyethylene oxide) was 28000. Further, the composition of polymer 4 analyzed by ¹ H-NMR was in accordance with the charged monomer composition.

Synthesis example 5
In Synthesis Example 4, the amount of ethanol added first is changed to 160.0 g, and the amount of 2,2′-azobis (2,4-dimethylvaleronitrile) and ethanol added thereafter are changed to 2.49 g and 40.0 g, respectively. Except for the above, Polymer 5 was obtained in the same manner as in Synthesis Example 4. The weight average molecular weight of polymer 5 (water / ethanol = 7/3 system, converted to polyethylene oxide) was 9,500. The composition of polymer 5 analyzed by ¹ H-NMR was the same as the charged monomer composition.

Synthesis Example 6
Dimethylaminoethyl methacrylate 10.00 g, lauryl acrylate 6.67 g, methoxypolyethylene glycol methacrylate (average polymerization degree of ethylene glycol 23, NK ester M-230G; manufactured by Shin-Nakamura Chemical Co., Ltd.) 33.33 g, 2-butanone 33.3 g and 2,2′-azobis (2,4-dimethylvaleronitrile) 0.80 g were uniformly mixed, put into a glass separable flask having an internal volume of 300 mL, and stirred for a certain time under a nitrogen atmosphere. The solution was heated to around 60 ° C. and kept at around 60 ° C. for 7 hours to polymerize and ripen. After diluting with 200.0 g of 2-butanone, the temperature was lowered to room temperature. This reaction solution was dropped into 4000.0 g of n-hexane and purified by reprecipitation, and the precipitate was dried to obtain polymer 6. The weight average molecular weight of polymer 6 (water / ethanol = 7/3 system, converted to polyethylene oxide) was 52,000. The composition of polymer 6 analyzed by ¹ H-NMR was the same as the charged monomer composition.

Synthesis example 7
15.00 g of lauryl methacrylate, methoxypolyethylene glycol methacrylate (average polymerization degree of ethylene glycol 9, NK ester M-90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) 35.00 g, 2-butanone 50.0 g, 2,2 ′ -0.50 g of azobis (2,4-dimethylvaleronitrile) was uniformly mixed, put in a glass separable flask having an internal volume of 300 mL, and stirred for a certain time under a nitrogen atmosphere. The solution was heated to around 65 ° C. and kept at around 65 ° C. for 6 hours for polymerization and aging. The reaction solution was dried to obtain polymer 7. The weight average molecular weight (chloroform series, polystyrene conversion) of the polymer 7 was 84000. The composition of polymer 7 analyzed by ¹ H-NMR was the same as the charged monomer composition.

Synthesis Example 8
3.35 g of acrylic acid, 1.65 g of lauryl acrylate, 3.3 g of isopropyl alcohol, 0.025 g of 2,2′-azobis (2,4-dimethylvaleronitrile) are uniformly mixed, and a glass separable having an internal volume of 300 mL It put into the flask and heated up to about 75 degreeC under nitrogen atmosphere. A solution in which 30.15 g of acrylic acid, 14.85 g of lauryl acrylate, 29.6 g of isopropyl alcohol, and 0.225 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were uniformly mixed was dropped over 3 hours. Furthermore, it superposed | polymerized and age | cure | ripened by hold | maintaining at 75 degreeC vicinity for 0.5 hour. A solution in which 1.7 g of isopropyl alcohol and 0.21 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were uniformly mixed was added dropwise over 1 hour, and further aged at around 70 ° C. for 1 hour. . This reaction solution was dried to obtain polymer 8. The weight average molecular weight of the polymer 8 (dimethylformamide series, in terms of polystyrene) was 28000. The composition of polymer 8 analyzed by ¹ H-NMR was the same as the charged monomer composition.

Synthesis Example 9
Dimethylaminoethyl methacrylate (50.00 g) and ion-exchanged water (11.04 g) were uniformly mixed and placed in a glass separable flask having an internal volume of 300 mL. After the temperature was raised to 50 ° C., 48.79 g of diethyl sulfate was added dropwise over 2 hours with stirring. After dropping, the mixture was kept at 50 ° C. with stirring for 1 hour to synthesize a methacryloyloxyethyldimethylethylammonium ethyl sulfate (MOEDES) aqueous solution.

In Synthesis Example 1, instead of dimethylaminoethyl methacrylate, 47.81 g of the above MOEDES aqueous solution, 6.30 g of lauryl methacrylate, 175.9 g of ethanol initially added, and 2,2′-azobis (2,4 -Dimethylvaleronitrile) amount was changed to 1.64 g, and polymer 9 was obtained in the same manner as in Synthesis Example 1 except that reprecipitation purification was performed with hexane. The weight average molecular weight of the polymer 9 (water / ethanol = 7/3 system, converted to polyethylene oxide) was 33,000. The composition of polymer 9 analyzed by ¹ H-NMR was the same as the charged monomer composition.

Table 1 summarizes the compositions of the polymers 1-9 synthesized in Synthesis Examples 1-9. In addition, the symbol in a table | surface shows the following meanings. Moreover, the polymers 1-9 obtained by the synthesis example were used as a hydrochloric acid neutralized material (neutralization degree 100%).
DMAEMA: dimethylaminoethyl methacrylate DEAEMA: diethylaminoethyl methacrylate LMA: lauryl methacrylate LA: lauryl acrylate BMA: butyl methacrylate St: styrene PEG (23) MA: methoxy polyethylene glycol methacrylate (average degree of polymerization of ethylene glycol 23)
PEG (9) MA: methoxy polyethylene glycol methacrylate (average degree of polymerization of ethylene glycol is 9)
AA: Acrylic acid / MOEDES: Methacryloyloxyethyldimethylethylammonium ethyl sulfate

Examples 1-8 and Comparative Examples 1-8
Using the cleaning composition containing the polymer (neutralized product) obtained in Synthesis Examples 1 to 9, the cleaning effect was evaluated by the following method. The results are shown in Tables 2-4. Moreover, it showed to Tables 2-4 about the alkaline buffer capacity of each cleaning composition measured by the method mentioned above.

<Evaluation method of cleaning effect>
(1) Fiber treatment (first wash)
0.35 g of the cleaning composition was added to 500 mL of tap water at 20 ° C. to obtain treatment solutions having pH values shown in Tables 2 and 3. 10 pieces (total 10 g) of 6 cm × 6 cm cut cotton broad cloth (made by Tanigami Shoten Co., Ltd., dyeing test material Co., Ltd., standard condition) were put in, and a targotometer was used. After stirring for 10 minutes at a rotational speed of 80 rpm, after dehydrating for 1 minute in a dewatering tank of a two-tank washing machine (PS-H35L manufactured by Hitachi, Ltd.), a dewatering cloth is placed in 500 ml of tap water, and a tartometer is used. The mixture was rinsed with stirring at a rotation speed of 80 rpm for 5 minutes, dehydrated in a two-tank washing machine for 1 minute, and then naturally dried.

(2) Preparation of model sebum soil Sebum component mixture (oleic acid / triolein / squalene (both manufactured by Wako Pure Chemical Industries, Ltd.) = 45/40/15 (weight ratio) 10 g of pigment (oil orange SS; Tokyo 0.01 g of Kasei Kogyo Co., Ltd.) was added and prepared.

(3) Preparation of model sebum-contaminated cloth 80 mg of model sebum soil was dropped on one cotton broad cloth (6 cm x 6 cm) treated with the detergent composition by the method of (1) above, and allowed to stand in the dark for 12 hours. A dirty cloth was used.

(4) Fiber cleaning (second cleaning)
10 cotton test cloths treated by the method of (1) above (model sebum stains adhered to 5 of them by the method of (3) above, and the rest is white cloth, total 10 g) and the detergent composition 0 .35 g was poured into 500 ml of tap water at a temperature of 20 ° C., and stirred and washed at a rotation speed of 80 rpm for 10 minutes using a turgotometer, followed by a dewatering tank of a two-tank washing machine (PS-H35L manufactured by Hitachi, Ltd.) After dehydrating for 1 minute, the dehydrated cloth was placed in 500 ml of water and rinsed with a tartometer for 5 minutes at a rotation speed of 80 rpm, dehydrated in a two-tank washing machine for 1 minute and then naturally dried.

(5) Fiber cleaning (third cleaning)
Of the 10 test cloths washed and dried by the above method (4), model sebum was again adhered by the method (3) to 5 cloths to which dirt was adhered before the second washing. The five contaminated cloths and the remaining five white cloths (10 g in total) were washed again by the method (4).

(6) Calculation of washing rate The reflectance (460 nm) of untreated cloth, pre-washed contaminated cloth, and washed cloth is measured with a colorimetric colorimeter (ND-300A; manufactured by Nippon Denshoku Industries Co., Ltd.). The cleaning rate D (%) was calculated by the following formula (I), and this cleaning rate D was used as an index of the dirt release effect. Tables 2 and 3 show the cleaning rates at the second cleaning, and Table 4 shows the cleaning rates at the second and third cleanings.

Cleaning rate D (%) = [(L ₂ −L ₁ ) / (L ₀ −L ₁ )] × 100 (I)
(Here, L _{0 represents} the reflectance of the untreated cloth, L _{1 represents} the reflectance of the contaminated cloth before washing, and L ₂ represents the reflectance of the contaminated cloth after washing.)

* 1 Emulgen 108 (alkyl chain length: 12, ethylene oxide average addition moles: 6), manufactured by Kao Corporation * 2 Weight average molecular weight 13000
* 3 Zeobuilder * 4 Weight average molecular weight 10,000
* 5 Neoperex F15, manufactured by Kao Corporation

Claims (7)

The following structural unit (A) and the constituent unit (B), (A) / (B) = 20/13 ~98 / having 2 weight ratio, weight average molecular weight 2,000 to 60,000 of the polymer (I) A cleaning composition containing an aqueous solution (concentration 1 g / L) of the composition at an alkali buffering capacity at 25 ° C. (0.1 N required for adjusting the pH of the aqueous solution at 25 ° C. to 9.5 or less) A detergent composition for textiles having a hydrochloric acid amount of 5 ml or less.
Structural unit (A): a structural unit derived from a monomer having a primary to tertiary amino group (excluding a structural unit in which the amino group is a quaternary ammonium group).
Structural unit (B): a structural unit derived from a monomer having a hydrophobic group and not having a primary to tertiary amino group , which is a linear, branched or cyclic alkyl having 1 to 22 carbon atoms. A structural unit derived from at least one monomer selected from a (meth) acrylic acid ester, (meth) acrylamide, vinyl ester, vinyl ether and styrene having a group, an alkenyl group, or an arylalkyl group The structural unit (A) is a structural unit derived from at least one monomer selected from (meth) acrylic acid esters having 1 to 3 primary amino groups, (meth) acrylamide, styrenes, and diallyl compounds. A detergent composition for textile products . The detergent composition for textiles according to claim 1 or 2 , wherein the polymer (I) is a polymer in which a part or all of amino groups are acid-neutralized . The cleaning composition for textiles according to any one of claims 1 to 3, comprising 0.01 to 20% by mass of the polymer (I) and 5 to 60% by mass of a surfactant. The detergent composition for textiles according to any one of claims 1 to 4, wherein the content of the anionic surfactant is 15% by mass or less. The cleaning composition for textiles according to any one of claims 1 to 5, which is used for treating cotton fibers. The pH 6-9. Containing the detergent composition for textiles according to any one of claims 1 to 6 so that the weight of the polymer (I) per kg of textiles is 0.01 to 10 g. 5. A method of washing a textile product with the washing medium of 5.