JP2001131587A - Soil releasing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a soil releasing agent capable of exhibiting excellent releasing effects on soils such as sebum soils for a cotton cloth. SOLUTION: A graft copolymer comprising an ionic polymer main chain connected to an ionic polymer side chain having electric charges opposite to those of the main chain is used as the soil releasing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a soil release agent and a cleaning composition.

[0002]

2. Description of the Related Art The provision of a soil release effect (soil release effect) to fibers during washing of the fibers in advance may result in a much superior cleaning effect as compared with a normal cleaning method. Having. Compounds mainly composed of terephthalate are known as effective soil release agents for washing hydrophobic synthetic fibers such as polyester blended fabrics (US 3416952, US 3557039, US 479558).
4 etc.). However, these soil release agents exhibit an extremely excellent effect on hydrophobic synthetic fiber cloth mixed with polyester, but do not exert a sufficient effect on relatively hydrophilic cotton fiber. That was a problem.

As soil release agents for cotton fibers, for example, polyamine derivatives (WO 9742285) and amphoteric polymers which are not graft type as a nitrogen-containing polymer (DE 19649288) are known. However, these compounds also have a high adsorption efficiency to fibers, surfactants, temperatures,
In many cases, it is strongly affected by pH and the like, and a sufficient effect cannot be obtained.

[0004] An object of the present invention is to provide a soil release agent and a detergent composition which exhibit an excellent soil release effect on cotton cloth and can exhibit a high cleaning effect.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a soil release agent comprising a graft copolymer comprising an ionic polymer main chain and an ionic polymer side chain having the opposite charge linked thereto, and 0.01 to 50% by weight of the graft copolymer. % Of the cleaning composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The soil release agent of the present invention is capable of washing stains at the time of washing the cloths and at the same time, imparting a stain protection function to the cloths. That is, by performing ordinary washing of a cotton fiber cloth using a detergent containing the compound of the present invention, a stain release function can be imparted to the fiber surface. For example, a normal washing cycle in which cotton fibers are immersed or washed in a detergent composition containing the compound of the present invention in a washing machine or by hand washing for 3 minutes to 2 hours, rinsed sufficiently with water, and then dehydrated and dried is repeated. As a result, a soil release function is imparted to the cloth, and a high cleaning effect is exhibited. The preferred immersion or washing time is from 5 minutes to 1 hour, more preferably from 8 minutes to 20 minutes. In particular, a feature of the present invention is that a greater effect can be obtained as the number of times of washing increases.

Here, the soil release agent of the present invention can be added not only to a detergent but also to a fiber treating agent such as a softener, a bleaching agent and a bleaching detergent as required. .

(Soil Release Agent) The graft copolymer used in the soil release agent of the present invention is obtained by graft-polymerizing an ionic monomer having an opposite charge as a side chain in the presence of an ionic polymer as a main chain. can get. The ionic polymer serving as the main chain is an anionic polymer or a cationic polymer, and the weight average molecular weight of the main chain is particularly preferably 5,000 to 2,000,000, and 10,000 to 1,1.
000,000 is more preferred. When an anionic polymer is used for the main chain, one or more monomers including a cationic monomer are polymerized in the presence of the polymer, and when a cationic polymer is used for the main chain, the polymer is used in the presence of the polymer. At least one monomer including an anionic monomer is polymerized to form a graft copolymer by a radical chain transfer reaction. Water is most preferred as the polymerization solvent, and low molecular electrolytes such as sodium chloride, potassium chloride, lithium chloride, odor, etc. are used in order to suppress remarkable thickening and precipitation due to ionic complex formation of the graft copolymer formed as the polymerization proceeds. Lithium chloride, sodium sulfate, potassium sulfate, and the like may coexist. In this case, the radical polymerization initiator is preferably a water-soluble peroxide, for example, sodium persulfate, potassium persulfate, ammonium persulfate, t-butyl hydroperoxide and the like. The confirmation of the formation of the graft copolymer can be carried out by extracting only a small amount of the single anionic polymer or cationic polymer which has not been grafted by the separation operation such as extraction, which is smaller than the total amount charged. .
The structure of each single ionic polymer can be confirmed by general means such as a nuclear magnetic resonance spectrum.

[0009] In the graft copolymer used in the present invention, the molar ratio of the anionic monomer to the cationic monomer is preferably in the range of 10:90 to 90:10, and more preferably in the range of 30:70 to 90:90.
70:30 is more preferred. As long as the properties and effects of the present invention are not impaired, the polymer may have a structure derived from a monomer other than the ionic monomer, for example, 40% by weight or less, preferably 1 to 30% by weight.

Here, the anionic monomer is a monomer having an anionic group such as a carboxyl group, a sulfate group, a sulfonic acid group, a phosphoric acid group and a phosphonic acid group in a molecule. Particularly, a monomer having a carboxyl group or a sulfonic acid group, and among them, a monomer having a carboxyl group is preferable. The cationic monomer is a monomer having a cationic group such as a quaternary ammonium salt, an amino group, and a quaternary phosphonium group in a molecule.

The anionic monomers include acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid,
2-acrylamido-2-methylpropanesulfonic acid,
Mono-10-methacryloyloxydecyl phosphate, particularly one or more monomers selected from acrylic acid, maleic acid and methacrylic acid are preferred.

As the cationic monomers, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dimethylamino) ethyl acrylate, N- {3-
(N, N-dimethylamino) propyl {acrylamide, N- {3- (N, N-dimethylamino) propyl}
Methacrylamide, 2- (methacryloyloxy) ethyldimethylethylammonium ethyl sulfate, 2-chloride
(Methacryloyloxy) ethyltrimethylammonium, (meth) acrylamidopropyltrimethylammonium chloride, 4-vinylbenzyltrimethylammonium chloride, especially 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethyl methacrylate) Amino) ethyl, N- {3- (N, N-dimethylamino) propyl} acrylamide, N- {3- (N, N-dimethylamino) propyl} methacrylamide are preferred.

Examples of the monomer other than the ionic monomer include methacrylates such as ethyl methacrylate, N, N
-Dimethylacrylamide, diacetoneacrylamide, styrene, vinyl acetate and the like are particularly preferred.

(Cleaning composition) The cleaning composition of the present invention contains the above graft copolymer of the present invention in an amount of 0.01 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 1.0 to 20% by weight.
-10% by weight.

It is desirable that one or more components selected from the group consisting of the following (a) to (d) be blended into the detergent composition. (a) 0.1 to 40% by weight of a surfactant (b) 0.01 to 50% by weight of polyethylene glycol (c) 0.1 to 40% by weight of potassium carbonate (d) 0.01 to 15% by weight of sulfite.

As the surfactant which is the component (a) of the present invention, a nonionic surfactant, an anionic surfactant, an amphoteric surfactant and a cationic surfactant can be blended. When this component is used in combination with the graft copolymer of the present invention, the soil release effect is amplified. As the nonionic surfactant, the average carbon number of the alkyl group is 10 to 20, preferably
Polyoxyethylene alkyl ethers having 12 to 18, particularly preferably 12 to 14, and having an average addition mole number of ethylene oxide of 6 to 14, preferably 6 to 10, are preferred. Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, alkane sulfonate, fatty acid salt, alkyl or alkenyl ether carboxylate, α-sulfo fatty acid salt or ester, Amino acid type surfactants and N-acyl amino acid type surfactants are preferred. In particular, an alkylbenzene sulfonate is preferred from the viewpoint of improving the cleaning power. Examples of the counter ion include alkali metals, ammonium, and alkanolamines. Further, a cationic surfactant such as an amphoteric surfactant or a quaternary ammonium salt can be used in combination. The content of the component (a) is 0.1 to 40% by weight, preferably 5 to 35% by weight, and particularly preferably 10 to 30% by weight in the composition in terms of detergency.

The polyethylene glycol which is the component (b) of the present invention is generally used as an activator or dispersant in detergents. When this component is used in combination with the graft copolymer, the graft copolymer is efficiently dispersed in the cleaning solution, and exhibits an effect of promoting adsorption to fibers. The content of the component (b) is 0.0% in the composition in terms of detergency.
It is 1 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 1.0 to 10% by weight.

The potassium carbonate as the component (c) in the present invention is effective as an alkaline agent component and has a function of increasing the solubility of the powder detergent. It has the function of promoting efficient adsorption of the graft copolymer to the fiber. Potassium carbonate can be used in combination with another alkali agent. Examples thereof include alkali metal carbonates such as sodium carbonate and sodium hydrogen carbonate, and alkali metal silicates such as sodium silicate and potassium silicate. The content of potassium carbonate depends on the graft copolymer and the cleaning composition of the present invention.
It is desirable that the aqueous solution having a concentration of 0.1% by weight be blended in an amount such that the pH of the aqueous solution exceeds 9.0 at 25 ° C., particularly, an amount of pH 10.0 to 10.6. In particular, 0.1 to 40% by weight, preferably 5 to 35% by weight, particularly preferably 10 to 30% by weight in the composition in terms of detergency.
% By weight.

The sulfite as the component (d) in the present invention has a function of maintaining the soil release effect during washing or when stored for a long time. The component (d) is 0.01 to 1 in the composition.
5% by weight, preferably 0.01 to 5% by weight.

The detergent composition of the present invention may further include an acrylic acid-maleic acid copolymer, a crystalline aluminosilicate, a divalent metal ion scavenger such as a chelating agent, a protease, an amylase, a cellulase, a lipase, a pectinase. Enzymes such as, bleaching agents such as sodium percarbonate and sodium perborate,
A peroxide stabilizer such as magnesium silicate, a redeposition inhibitor such as sodium polyacrylate and polyvinylpyrrolidone, a fluorescent dye, a pigment, a caking inhibitor, a solubilizer, a fragrance, and the like can be added as required.

[0021]

EXAMPLES (1) Synthesis Examples of Polymers In the following synthesis examples, unless otherwise specified, all preparations were performed in parts by weight, and ion-exchanged water was used as water.

Synthesis Example of Polymer 1 (Graft Copolymer) [Preparation of First Liquid] Sodium polyacrylate (degree of polymerization 2,
(700-7,500) 181 parts of water was added to 233.9 parts, and the mixture was cooled with ice water. While maintaining the internal temperature at 30 ° C or less, about 10N hydrochloric acid
Five parts were added to dissolve, and hydrochloric acid was further added to adjust the pH to 1.9. This was returned to room temperature and used as a first liquid. [Preparation of the second liquid] 40 parts of 10N hydrochloric acid was added to 120 parts of water to dissolve and cooled with ice water. Here, methacrylic acid 2- (N,
127.3 parts of N-dimethylamino) ethyl and concentrated hydrochloric acid were alternately added at such a rate that the temperature of the mixture was lower than 20 ° C. and the pH was lower than 7, and the pH was finally adjusted to 1.9. This was returned to room temperature and used as a second liquid. [Preparation of third liquid] 19.27 parts of sodium persulfate was dissolved in 100 parts of water to prepare a third liquid. [Polymerization] 85-90 ° C while stirring the first liquid under a nitrogen atmosphere
, The second liquid and the third liquid were simultaneously added dropwise over 2 hours, and after completion of the addition, the mixture was stirred at 85 to 90 ° C. for 6 hours and then returned to room temperature to complete the polymerization. The resulting solution 1
When 19.7 g of water was added to 0.3 g of water, the solution became slightly turbid. A few drops of concentrated hydrochloric acid were added to make a clear solution, which was dropped into 450 cc of acetone which was vigorously stirred at room temperature. The resulting suspension was centrifuged to collect a supernatant, and volatiles were removed by a rotary evaporator to obtain a white solid 0.20%.
5 g were obtained. The proton NMR spectrum (3% concentration in heavy water solvent) of the solid thus obtained does not show absorption due to polyacrylic acid (broad absorption of δ 2.2 to 2.6 ppm). You know what's going on. The solution obtained after the polymerization is freeze-dried,
A white solid was obtained.

Synthesis Example of Polymer 2 (Graft Copolymer) [Preparation of First Liquid] Preparation was performed in the same manner as in Polymer 1. [Preparation of second liquid] 20 parts of concentrated hydrochloric acid was added to 100 parts of water to dissolve, and the mixture was cooled with ice water. Here, methacrylic acid 2- (N, N
54.54 parts of -dimethylamino) ethyl and concentrated hydrochloric acid were added alternately at such a rate that the temperature of the mixture was below 20 ° C and the pH was below 7, finally adjusting the pH to 1.9. This was returned to room temperature and used as a second liquid. [Preparation of third liquid] 4.30 parts of sodium persulfate was dissolved in 120 parts of water to prepare a third liquid. [Polymerization] 85-90 ° C while stirring the first liquid under a nitrogen atmosphere
, The second liquid and the third liquid were simultaneously added dropwise over 2 hours, and after completion of the addition, the mixture was stirred at 85 to 90 ° C. for 6 hours and then returned to room temperature to complete the polymerization. The resulting solution 2
When 9.6 g of water was added to 0.4 g, a slightly turbid solution was obtained. To this solution, a few drops of concentrated hydrochloric acid were added to make a clear solution, which was added dropwise to 450 cc of vigorously stirred acetone at room temperature. The resulting suspension was centrifuged to collect the supernatant, and volatiles were removed with a rotary evaporator to obtain a white solid 0.22%.
7 g were obtained. The proton NMR spectrum (3% concentration in heavy water solvent) of the solid thus obtained does not show absorption due to polyacrylic acid (broad absorption of δ 2.2 to 2.6 ppm). You know what's going on. The solution obtained after the polymerization is freeze-dried,
A white solid was obtained.

Synthesis Example of Polymer 3 (Random Copolymer: Comparative Product) 450 parts of water was added to 59.24 parts of acrylic acid, and the mixture was stirred while being cooled with ice water, and the electrode of a pH meter was immersed for tracking the pH. To this, 129.3 parts of 2- (N, N-dimethylamino) ethyl methacrylate was added at such a rate that the temperature of the mixed solution could be kept at less than 20 ° C. Add a few drops of concentrated hydrochloric acid
Finally, the pH was adjusted to 6.80 and then the pH meter electrode was removed. The resulting solution was placed under a nitrogen atmosphere, and 71.12 parts of 3-mercapto-1,2-propanediol, followed by 8.917 parts of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-Pharma Corporation) A solution of 50) and 50 parts of water was added, heated immediately, and stirred at 68-72 ° C for 6 hours. The obtained colorless and transparent solution was freeze-dried to obtain a white solid polymer. The weight-average molecular weight of this polymer measured by gel permeation type liquid chromatography was 10,100 (in terms of polyethylene oxide).

(2) Repeated washing of cotton fiber cloth and preparation of stained cloth A 10 cm × 10 cm cotton cloth was dissolved in a 4 ゜ DH hard water with a powder detergent composition comprising the components shown in Table 1, and a 0.06% aqueous solution was prepared. And adjust the pH to 10.5 with NaOH. Five cotton cloths are added to the aqueous detergent solution, and the mixture is stirred and washed at 20 ° C. for 10 minutes at 100 rpm with a tergotometer. After rinsing under running water, centrifugal dehydrator is used to sufficiently remove water, and then dried in a room at 25 ° C. and 50% RH for 1 hour or more. After repeating this washing treatment three times, a 10 cm × model sebum stain composed of 60% cottonseed oil, 10% cholesterol, 10% oleic acid, 10% palmitic acid and 10% solid paraffin was applied to the cotton cloth after the washing treatment.
2 g per 10 cm was evenly applied to prepare a sebum stained cloth. Contaminated cloths that were subjected to this treatment for each of the compositions in Table 1 were produced.

(3) Washing conditions, washing method and evaluation method A detergent composition comprising the components described in Comparative Example 1 in Table 1 was dissolved in 4 ゜ DH hard water and prepared to be a 0.06% aqueous solution. Adjust the pH to 10.5 with NaOH. Five cotton-contaminated cloths corresponding to the respective compositions are added to the aqueous cleaning composition solution, and the mixture is stirred and washed at 20 ° C. for 10 minutes at 100 rpm with a tergotometer. After rinsing under running water, an iron press treatment was performed.

Next, the reflectance at 460 nm of the original cloth before cleaning, the contaminated cloth prepared after repeated cleaning, and the contaminated cloth after final cleaning were measured with a self-recording colorimeter (Shimadzu Corporation). (%) Was calculated. Cleaning rate (%) = [(reflectance after final cleaning−reflectance after preparing stained cloth) / (reflectivity of original cloth−reflectance after preparing stained cloth)]
× 100 Table 1 shows the average value of five contaminated cloths.

[0028]

[Table 1]

(Note) • Polymer 1: graft copolymer (Na salt) obtained by graft-polymerizing 2- (N, N-dimethylamino) ethyl methacrylate onto polyacrylic acid having an average molecular weight of 32,000 (molar ratio of main chain monomer / side chain monomer) 3/7) Polymer 2: graft copolymer (Na salt) obtained by graft-polymerizing 2- (N, N-dimethylamino) ethyl methacrylate onto polyacrylic acid having an average molecular weight of 32,000 (molar ratio of main chain monomer / side chain monomer: 5 / 5) Polymer 3: acrylic acid and methacrylic acid 2- (N, N
- copolymers of dimethylamino) ethyl (Na salt) · PEG: Polyethylene glycol (average molecular weight 600) · LAS: long chain alkyl (C ₁₂₎ sodium benzenesulfonate · SFE: alpha-sulfo fatty acid methyl ester sodium salt · AS : Alkyl (C ₁₂ ) sulfate sodium salt ・ AE: Polyoxyethylene (6 mol) alkyl (C ₁₂ ) ether ・ LB: Alkyl (C ₁₂ ) dimethyl betaine ・ AM: Maleic acrylate (7/3 molar ratio) Sodium salt of copolymer, average molecular weight 70,000 ・ Zeolite: crystalline aluminosilicate, M ₂ O ・ Al ₂ O ₃・ 2SiO
₂ · 2H ₂ O, an average particle diameter of 2 [mu] m, the ion exchange capacity 290CaCO ₃ mg /
g ・ Common components: 0.5% by weight of fluorescent component and 12.0 Tt of Savinase
ype W (manufactured by Novo Nordisk), KAC-500G (manufactured by Kao Corporation) and Termamyl 60T (manufactured by Novo Nordisk) were mixed at a ratio of 2: 1: 1. The composition was adjusted so that the total amount was 100% by weight.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hideji Takata 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term (reference) 4H003 AB19 AB21 AB27 AC08 AD04 BA09 DA01 DB01 EA12 EA15 EA16 EA28 EB28 EB30 EB32 EB36 EC01 FA04 FA06 4L033 AC04 CA19 CA70

Claims (6)

[Claims] 1. A soil release agent comprising a graft copolymer in which an ionic polymer main chain is connected to an ionic polymer side chain having an opposite charge. 2. The soil release agent according to claim 1, wherein the main chain and the side chain of the graft copolymer are an anionic polymer or a cationic polymer, each of which comprises one or more kinds of repeating units. 3. The soil release agent according to claim 2, wherein the anionic polymer comprises a monomer having a carboxyl group. 4. The method according to claim 1, wherein the cationic polymer is acrylic acid 2-
(N, N-dimethylamino) ethyl, methacrylic acid 2-
(N, N-dimethylamino) ethyl, N- {3- (N,
N-dimethylamino) propyl @ acrylamide, N-
3. The soil release agent according to claim 2, comprising one or more monomers selected from {3- (N, N-dimethylamino) propyl} methacrylamide and quaternized products thereof. 5. A detergent composition comprising from 0.01 to 50% by weight of the graft copolymer according to claim 1. 6. The cleaning composition according to claim 5, comprising one or more components selected from the group consisting of the following (a) to (d). (a) surfactant 0.1 to 40% by weight (b) polyethylene glycol 0.01 to 50% by weight (c) potassium carbonate 0.1 to 40% by weight (d) sulfite 0.01 to 15% by weight