JP2001172673A - Soil releasing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soil releasing agent that show excellent soil-releasing effect on cellulosic fabrics. SOLUTION: A cationic compound represented by the following general formula (I) (wherein R1 is H or a 1-22C alkyl group; G is a monosaccharide unit ; R2 is a 1-22C alkylene group; R3, R4 and R5 are each a 1-6C alkyl group; n is a number of 1-4; X is an anion) is used as the objective soil-releasing agent or a detergent composition.

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 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 efficiency of adsorption of these compounds to fibers is strongly affected by surfactants, temperature, pH, and the like, and sufficient effects cannot be obtained in many cases.

[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]

SUMMARY OF THE INVENTION The present invention relates to a soil release agent comprising a cationic compound represented by the following general formula (1), and a cleaning composition containing 0.01 to 50% by weight of the cationic compound.

[0006]

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(Wherein, R ¹ is hydrogen or an alkyl group having 1 to 22 carbon atoms which may be substituted with a hydroxyl group, G is a monosaccharide unit, and R ² may be substituted with a hydroxyl group. An alkylene group having 1 to 22 carbon atoms, R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group, and n is 1 to 4 And X is an anion.)

[0008]

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 about 3 minutes to 2 hours, rinsed sufficiently with water, and then dehydrated and dried is performed. By repeating, a stain 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 washings increases.

The soil release agent of the present invention can be used not only in detergents but also in fiber treatment agents such as softeners, bleaching agents and bleaching detergents, if necessary.

(Soil Release Agent) The cationic compound used in the present invention is represented by the above general formula (1), and may be used alone or in a mixture.

R ¹ OG in the general formula (1) is a glucoside moiety forming the basic skeleton of the present compound. Here, R ¹ is an alkyl group having 1 to 22 carbon atoms which may be substituted with hydrogen or a hydroxyl group, for example, a methyl group, an ethyl group, a propyl group,
Butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, oleyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, 2-ethylhexyl group, glyceryl group, etc. It is preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably a methyl group or an ethyl group. The glucoside moiety R ¹ OG may be present in α- or β-anomeric form or a mixture thereof.

G in the general formula (1) is a monosaccharide unit,
It is preferably in pentose or hexose form, in particular cyclic furanose or pyranose form. Examples of suitable monosaccharides are glucose, fructose, ribose, galactose, mannose, arabinose or xylose.

The compound represented by the general formula (1) is a compound having a carboxyl group or a lower alcohol ester group such as a carboxylic acid or a carboxylic acid lower alcohol ester or a carboxylic acid halide at the terminal hydroxyl group of the glucoside moiety R ¹ OG. It has been esterified using. n indicates the number of esterified hydroxyl groups at the terminal hydroxyl group of the glucoside moiety R ¹ OG, and is specifically an integer of 1 to 4.

R ² in the general formula (1) is an alkylene group having 1 to 22, preferably 1 to 12, and particularly preferably 1 to 4 carbon atoms which may be substituted by a hydroxyl group.

R ³ , R ⁴ and R ⁵ in the general formula (1) each independently represent an alkyl group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group, for example, a methyl group, an ethyl group, A propyl group, an isopropyl group, a butyl group, a hexyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group are preferable, and a methyl group, an ethyl group, and a hydroxyethyl group are preferable.

X is an anion which forms a counter ion with the cationic compound, and is a halide ion such as chloride ion, bromide ion, iodide ion, or acetate ion, citrate ion, lactate ion, carbonate ion, succinate ion. It is an organic acid ion such as an acid ion and a malate ion, and is preferably a halide ion.

Specific examples of the compound represented by the above general formula (1) used in the present invention include, for example, the following compounds, but are not limited thereto.

[0018]

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The method for producing the cationic compound represented by the general formula (1) used in the present invention includes, for example, a dehydration reaction between a glucoside compound and a quaternary amino acid such as glycine betaine, A dehydration reaction with a monohalo organic acid such as acetic acid, followed by a nucleophilic substitution reaction with amines, and the like.

(Detergent composition) The detergent composition of the present invention contains the cationic compound of the present invention in an amount of 0.01 to 50% by weight,
Preferably, the content is 0.05 to 20% by weight, particularly preferably 1 to 10% by weight.

The cleaning composition of the present invention preferably contains a surfactant. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, an amphoteric surfactant, and a cationic surfactant. When a surfactant is used in combination, 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 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-sulfofatty acid salt and ester thereof. , An amino acid type surfactant and an N-acyl amino acid type surfactant are preferred. Among them, an alkylbenzene sulfonate is preferred in terms of improving detergency. 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 is 0.1% in the composition in terms of detergency.
It is preferably from 1 to 40% by weight, more preferably from 5 to 35% by weight, particularly preferably from 10 to 30% by weight.

The detergent composition of the present invention preferably contains a polycarboxylic acid compound. The polycarboxylic acid compound is a polyacrylic acid, a copolymer of acrylic acid and maleic acid, or a salt thereof, and is generally used as a calcium scavenger or a dispersant in a detergent. In addition, those obtained by adding a carboxylic acid to polysaccharide, polyglyoxylic acid and salts thereof, and the like are also included. When used in combination with a soil release agent, the polycarboxylic acid compound promotes dispersibility in a cleaning solution, and exhibits an effect of assisting efficient adsorption of the soil release agent to fibers. The content of the polycarboxylic acid compound in the composition is preferably 0.01 to 50% by weight, more preferably 0.05 to 20% by weight, and particularly preferably 1 to 10% by weight in terms of detergency.

The cleaning composition of the present invention preferably contains a sulfite. Sulfite functions to maintain the soil release effect during washing or when stored for a long time. The content of the sulfite is preferably 0.01 to 15% by weight, more preferably 0.01 to 5% by weight in the composition.

The detergent composition of the present invention further comprises a divalent metal ion scavenger other than a polycarboxylic acid compound such as a crystalline aluminosilicate and a chelating agent, and an alkali component such as sodium carbonate and sodium hydrogen carbonate. Enzyme components such as protease, amylase, cellulase, lipase, pectinase, bleaching agents such as sodium percarbonate and sodium perborate, stabilizers for peroxides such as magnesium silicate, prevention of re-contamination of polyethylene glycol, polyvinylpyrrolidone, etc. Agent, fluorescent dye, pigment, anti-caking agent, solubilizer,
Flavors and the like are blended as needed.

[0025]

EXAMPLES Synthesis Example 1 (Synthesis of Cationized Glucose) In a 1 L flask equipped with a Dean-Stark trap containing toluene, 155.5 g of methyl-α-glucoside was added.
After 152.8 g of monochloroacetic acid and 300 mL of toluene were added and the temperature was raised to 90 ° C., 0.55 g of p-toluenesulfonic acid monohydrate was added. Then, after raising the temperature to 110 ° C., a dehydration reaction was performed for 3 hours. After cooling, extraction and washing were performed using ethyl acetate. The ethyl acetate phase was concentrated and dried to obtain 186.2 g of a reaction intermediate. 150.0 g of the obtained reaction intermediate, 300 g of ethanol, and 52.3 g of trimethylamine were put in a 1000 mL autoclave, and reacted at 60 ° C. for 8 hours. After cooling, the reaction product in the autoclave was filtered, and the solid obtained was washed twice with cold ethanol and then dried to obtain the final purified product.
131.9 g were obtained.

Example 1 (1) 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. A 0.06% aqueous solution is prepared, and the pH is adjusted to 10.5 with NaOH and HCl. 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, use a centrifugal dehydrator to remove enough water, then 25 ℃, 50%
Dry in RH room for 1 hour or more. After repeating this washing treatment three times, cottonseed oil is applied to the cotton cloth after the washing treatment.
A sebum-stained cloth was prepared by uniformly applying 2 g of a model sebum stain composed of 60%, 10% cholesterol, 10% oleic acid, 10% palmitic acid and 10% solid paraffin per 10 cm × 10 cm. Contaminated cloths that were subjected to this treatment for each of the compositions in Table 1 were produced.

(2) 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 to prepare a 0.06% aqueous solution. Adjust the pH to 10.5 with NaOH and HCl. 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) Cationized glucose: Synthetic example 1. A methyl group is in the first position of glucose, and 4 is in any of the 2,3,4,6 positions.
Compound with two quaternary ammonium cation groups bonded ・ Polyacrylic acid: sodium salt, average molecular weight 10,000 ・ AM: sodium salt of maleic acrylate (molar ratio 7/3) copolymer, average molecular weight 70,000 ・ 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 ・ 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.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Kubo 1334 Minato 1334 Minato, Wakayama City, Wakayama Prefecture, Japan Inventor Akira Fujio 1334 Minato 1334 Minato, Wakayama City, Wakayama Prefecture, Kao Corporation Research Institute (72) Inventor Hideji Tagata 1334 Minato, Wakayama-shi, Wakayama Pref.

Claims (7)

[Claims] 1. A soil release agent comprising a cationic compound represented by the following general formula (1). Embedded image (Wherein, R ¹ is hydrogen or an alkyl group having 1 to 22 carbon atoms which may be substituted with a hydroxyl group, G is a monosaccharide unit,
² is an alkylene group having 1 to 22 carbon atoms that may be substituted with a hydroxyl group, and R ³ , R ⁴ , and R ⁵ independently of one another have 1 to 6 carbon atoms that may be substituted with a hydroxyl group. An alkyl group, n is a number from 1 to 4, and X is an anion. ) 2. The soil release agent according to claim 1, wherein the monosaccharide unit G is hexose or pentose. 3. A detergent composition containing 0.01 to 50% by weight of a cationic compound represented by the following general formula (1). Embedded image (Wherein, R ¹ is hydrogen or an alkyl group having 1 to 22 carbon atoms which may be substituted with a hydroxyl group, G is a monosaccharide unit,
² is an alkylene group having 1 to 22 carbon atoms that may be substituted with a hydroxyl group, and R ³ , R ⁴ , and R ⁵ independently of one another have 1 to 6 carbon atoms that may be substituted with a hydroxyl group. An alkyl group, n is a number from 1 to 4, and X is an anion. ) 4. The cleaning composition according to claim 3, wherein the monosaccharide unit G is hexose or pentose. 5. The cleaning composition according to claim 3, comprising 0.1 to 40% by weight of a surfactant. 6. Polycarboxylic acid compound 0.01 to 50% by weight
The cleaning composition according to claim 3, comprising: 7. The cleaning composition according to claim 3, comprising 0.01 to 15% by weight of a sulfite.