JP2001131590A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition capable of exhibiting excellent releasing effects on soils such as sebum soils for a cotton cloth. SOLUTION: This detergent composition comprises (a) an amphoteric polymer obtained by copolymerizing an anionic monomer with a cationic monomer and (b) a polyethylene glycol in respective specific ratios.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to 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 a soil release agent for cotton fibers, for example, polyamine derivatives (WO 9742285), nitrogen-containing polymers (DE 19649288) and the like are known. However, the adsorption efficiency of these compounds to fibers is strongly affected by surfactants, temperature, pH, etc., and sufficient effects cannot be obtained by themselves.

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

[0005]

According to the present invention, there are provided (a) 0.01 to 50% by weight of an amphoteric polymer (excluding a graft copolymer) obtained by copolymerizing an anionic monomer and a cationic monomer; A cleaning composition comprising 0.01 to 50% by weight of polyethylene glycol is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention improves the adsorption efficiency of the amphoteric polymer to the fiber by combining the amphoteric polymer obtained by copolymerizing an anionic monomer and a cationic monomer with polyethylene glycol, thereby improving the amphoteric polymer. An object of the present invention is to provide a detergent composition capable of obtaining a soil release effect.

[0007] The detergent composition of the present invention is capable of washing stains at the time of washing the cloths and at the same time, imparting a function of protecting the stains to the cloths. That is, by performing ordinary cleaning of a cotton fiber cloth using the cleaning composition of the present invention, a stain release function can be imparted to the fiber surface. For example, cotton fibers are washed in a washing machine or
After soaking or washing for about 2 to 2 hours, rinsing well with water,
By repeating a normal washing cycle of dehydration and drying, a soil release function is imparted to the cloth, and a high washing effect is exhibited. Preferred soaking or washing time is 5 minutes or more and 1
It is within an hour, more preferably within a range from 8 minutes to 20 minutes. In particular, as a feature of the present invention, more excellent effects can be obtained as the number of times of washing increases.

The amphoteric polymer which is the component (a) of the present invention comprises:
It is a compound obtained by copolymerizing an anionic monomer and a cationic monomer (however, excluding a graft copolymer), and the weight average molecular weight is preferably 2,000 to 2 million, more preferably 5,000 to 500,000.

The amphoteric polymer (a) is obtained by copolymerizing an anionic monomer and a cationic monomer. If necessary, a monomer other than these ionic monomers can be copolymerized. In this case, the polymerization method may be any conventionally known one, for example, heating an anionic monomer and a cationic monomer together with a water-soluble radical polymerization initiator in water in the presence of a low molecular electrolyte such as sodium chloride or sodium sulfate. And the like. In this polymerization, in order to control the molecular weight using a chain transfer reaction, aliphatic alcohols such as ethanol and 2-propanol and water-soluble mercaptans such as 2-mercaptoethanol and 3-mercapto-1,2-propanediol are used. Some coexist.

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, particularly a monomer having a carboxyl group, is preferred.
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 is preferred, especially acrylic acid, maleic acid and methacrylic acid.

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,
2- (N, N-dimethylamino) ethyl methacrylate,
N- {3- (N, N-dimethylamino) propyl} acrylamide and N- {3- (N, N-dimethylamino) propyl} methacrylamide are preferred.

The molar ratio of the anionic monomer to the cationic monomer is preferably in the range of 10:90 to 90:10,
0: 70-70: 30 is more preferred. In addition, both ionic monomers may be single or a mixture of two or more. The amount of the monomer other than the ionic monomer is desirably 40% by weight or less in the polymer.
When the monomer other than the ionic monomer is within this range, the properties of the polymer of the present invention can be easily obtained.

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.

The amphoteric polymer of the component (a) is contained in the composition in an amount of 0.0
1 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 1.0 to 10% by weight.

As the polyethylene glycol as the component (b) of the present invention, those generally used in detergents as activators and dispersants can be used. In the present invention, when used in combination with the amphoteric polymer as the component (a), the amphoteric polymer is efficiently dispersed in the cleaning solution, and has an effect of promoting adsorption to fibers. Component (b) polyethylene glycol is contained in the composition in an amount of 0.01 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 1.0 to 10% by weight in terms of detergency.
Be blended.

The detergent composition of the present invention comprises a surfactant (c)
Is preferable. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, an amphoteric surfactant, and a cationic surfactant. Surfactant (c)
When used together with the amphoteric polymer (a) 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 12 to 18, particularly preferably 12 to 14, and the average addition mole number of ethylene oxide is 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 surfactant (c) is preferably from 0.1 to 40% by weight, more preferably from 5 to 35% by weight, and particularly preferably from 10 to 30% by weight in the composition from the viewpoint of detergency.

The detergent composition of the present invention preferably contains a sulfite (d). The sulfite (d) functions to maintain the effect of the amphoteric polymer during washing or when stored for a long time. The content of the sulfite (d) in the composition,
It is preferably 0.01 to 15% by weight, more preferably 0.01 to 5% by weight.

Further, the detergent composition of the present invention may contain an alkali agent such as an alkali metal carbonate such as potassium carbonate, sodium carbonate and sodium hydrogen carbonate, and an alkali metal silicate such as sodium silicate and potassium silicate. preferable. The alkali agent is preferably incorporated in the composition in an amount of 0.1 to 40% by weight, more preferably 5 to 35%, in terms of detergency.
%, Particularly preferably from 10 to 30% by weight.

The detergent composition of the present invention further includes a divalent metal ion scavenger such as a polyacrylic maleic acid copolymer, a crystalline aluminosilicate, a chelating agent, a protease, an amylase, a cellulase, a lipase, a pectinase. Enzyme components such as sodium percarbonate, sodium perborate, etc., bleaching agents such as magnesium silicate, etc., anti-recontamination agents such as sodium polyacrylate, polyvinylpyrrolidone, etc., fluorescent dyes, pigments, anti-caking Agents, solubilizers, fragrances and the like can be added as necessary.

[0021]

EXAMPLES (1) Synthesis Examples of Amphoteric Polymers In the following synthesis examples, all preparations were performed in parts by weight (denoted by "parts") unless otherwise specified, and ion-exchanged water was used as water. The weight average molecular weight of the amphoteric polymer is a pullulan-converted value determined by gel permeation liquid chromatography, and the measurement conditions are as follows. Column: 1 TSK α-M manufactured by Tosoh Corporation Eluent: 0.15 mol / L sodium sulfate, 1% acetic acid aqueous solution Detector: Differential refractometer Flow rate: 1.0 mL / min Temperature: 40 ° C Standard: Showa Denko ) Shodex Standard P-
82 (Pullulan), weight average molecular weight 787,000, 194,000,
46,700, 5,900 Sample concentration: 0.50 g / 100 mL Eluent Sample solution injection volume: 0.10 mL.

Synthesis Example 1 (Synthesis of Amphoteric Polymer 1) To 16.42 parts of acrylic acid, 320 parts of water and 15 parts of concentrated hydrochloric acid were added, and the mixture was stirred while being cooled with ice water, and the electrode of a pH meter was immersed for tracking the pH. . Here, 83.58 parts of 2- (N, N-dimethylamino) ethyl methacrylate and concentrated hydrochloric acid are alternately added at such a rate that the temperature of the mixed solution is kept at less than 20 ° C. and the pH of the content solution is less than 7. In addition, the pH was finally adjusted to 6.61 and then the pH meter electrode was removed. The resulting solution was placed under a nitrogen atmosphere, a solution of 4.120 parts of 2,2′-azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) and 50 parts of water was added, and the mixture was immediately heated. 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 the obtained polymer is
463,000.

Synthesis Example 2 (Synthesis of Amphoteric Polymer 2) 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 2,2 ′
A solution of 8.917 parts of azobis (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) and 50 parts of water was added, heated immediately, and stirred at 68 to 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 the obtained polymer was 10,100.

Synthesis Example 3 (Synthesis of Amphoteric Polymer 3) 280 parts of water and 16 parts of concentrated hydrochloric acid were added to 12.28 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. . Here, 67.72 parts of N- {3- (N, N-dimethylamino) propyl} methacrylamide and concentrated hydrochloric acid are added so that the temperature of the mixed solution is maintained at less than 20 ° C. and the pH of the content solution is less than 7. The pH meter electrode was removed after the pH was adjusted to 6.38, alternately at a constant rate. The resulting solution was placed under a nitrogen atmosphere and 2,2′-azobis (2
3.082 parts of amidinopropane) dihydrochloride (V, manufactured by Wako Pure Chemical Industries, Ltd.)
-50) and 50 parts of water.
Stirred at 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 the obtained polymer was 223,000.

(2) Synthesis of Comparative Polymer Synthesis Example 4 (Synthesis Example of Polyacrylic Acid (Comparative Product)) 100 parts of acrylic acid, 550 parts of 2-propanol, and 2,2′-
A mixture of 6.90 parts of azobis (2,4-dimethylvaleronitrile) was maintained at 62 to 63 ° C. for 5 hours while stirring under a nitrogen atmosphere, and then returned to room temperature. This solution was added dropwise to 7000 parts of hexane stirred at room temperature over 30 minutes. The generated precipitate was collected by decantation, and was collected at 10.7-13.3 kPa (80-100 torr).
r) / Drying under reduced pressure at 60 to 65 ° C. for 16 hours to obtain a white powdery polyacrylic acid. The weight average molecular weight determined by gel permeation type liquid chromatography was 38,000. The conditions for measuring the weight average molecular weight of this polymer are as follows. Column: 2 pieces of TSK GMPWXL manufactured by Tosoh Corporation Eluent: 9: 1 volume ratio mixture of an aqueous solution containing 0.1 mol / L of potassium dihydrogen phosphate and 1 mol / L of disodium hydrogen phosphate and acetonitrile : Differential refractometer Flow rate: 1.0 mL / min Temperature: 40 ° C. Standard: TSK standard manufactured by Tosoh Corporation, polyethylene oxide weight average molecular weight 920,000, 510,000, 250,00
0, 95,000, 46,000, 39,000 Sample concentration: 0.20 g / 100 mL Eluent Sample solution injection volume: 0.10 mL.

(3) Repeated washing of cotton fiber cloth and preparation of contaminated 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.

(4) Cleaning Conditions, Cleaning Method and Evaluation Method A cleaning composition comprising the components described in Comparative Product 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.

[0029]

[Table 1]

(Note)-Amphoteric polymer 1: Synthetic example 1. Copolymer of acrylic acid and 2- (N, N-dimethylamino) ethyl methacrylate (3/7 molar ratio, sodium salt) Amphoteric polymer 2: Synthetic example 2. Copolymer of acrylic acid and 2- (N, N-dimethylamino) ethyl methacrylate (5/5 molar ratio, sodium salt) Amphoteric polymer 3: Synthetic example 3. Acrylic acid and N-
Copolymer with {3- (N, N-dimethylamino) propyl} methacrylamide (molar ratio 3/7, sodium salt) Polyacrylic acid: Synthesis Example 4. Acrylic acid homopolymer (sodium salt) • PEG1: polyethylene glycol (average molecular weight 600) • PEG2: polyethylene glycol (average molecular weight 1000) • CMC: carboxymethylcellulose sodium salt (400
-800 cP, manufactured by Wako Pure Chemical Industries) ・ LAS: long-chain alkyl (C ₁₂ ) benzenesulfonic acid sodium salt ・ SFE: α-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: Sodium salt of maleic acrylate (molar ratio 7/3) 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 EA12 EA15 EA16 EA28 EB30 EB32 EB36 EC01 ED28 4L033 AC15 CA19 DA02

Claims (5)

[Claims] (1) 0.01 to 50% by weight of an amphoteric polymer (excluding a graft copolymer) obtained by copolymerizing an anionic monomer and a cationic monomer, and (b) 0.01 to 50% by weight of polyethylene glycol. A cleaning composition containing the same. 2. The cleaning composition according to claim 1, wherein the anionic monomer is a monomer having a carboxyl group. 3. The method according to claim 1, wherein the cationic monomer 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 cleaning composition according to claim 1, which is at least one monomer selected from {3- (N, N-dimethylamino) propyl} methacrylamide and quaternized products thereof. 4. The cleaning composition according to claim 1, comprising (c) 0.1 to 40% by weight of a surfactant. 5. The cleaning composition according to claim 1, comprising (d) 0.01 to 15% by weight of a sulfite.