JP2001172674A - Soil releasing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soil-releasing agent or a detergent composition that show excellent soil-releasing effect on cellulosic fabrics. SOLUTION: Chitosan and/or glucosamine that bears a functional group represented by the following general formula (I) -R1-X (I) [wherein R1 is a 1-6C alkylene group; X is a group selected from OR2, COOM and N+R3R4R5Z (R2 is H or a 1-22C alkyl group), M is H or a cation, R3, R4 and R5 are each a 1-4C alkyl group; Z is an anion) is used as the objective 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 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 provides a soil release agent comprising a functional group-introduced chitosan and / or glucosamine represented by the following general formula (1), and 0.01 to 50% by weight of the chitosan and / or glucosamine. A cleaning composition comprising: -R ¹ -X (1) (wherein, R ¹ has 1 to 1 carbon atoms which may be substituted by a hydroxyl group.
6, preferably 1-3 alkylene groups, X is OR ² ,
One or more groups selected from COOM and N ⁺ R ³ R ⁴ R ⁵ Z, preferably OR ² and COOM in terms of the soil release effect, wherein R ² is hydrogen or a carbon number of 1 to 22, preferably 1 indicates ~ 16 alkyl group, M is hydrogen or a cation preferably alkali metal ions, ammonium ions, shows the alkanolamine ^{salts, R 3, R 4, R} 5 are each, independently of one another, be substituted by a hydroxyl group And preferably represents at least one group selected from alkyl groups having 1 to 4 carbon atoms, oxyalkylene groups having 1 to 4 carbon atoms, and benzyl group, wherein Z is an anion, preferably a chloride ion, a bromide ion, an iodide ion and the like. Or an organic acid ion such as an acetate ion, a citrate ion, a lactate ion, a carbonate ion, a succinate ion and a malate ion, particularly preferably a halide ion. )

[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 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.

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

(Soil Release Agent) The soil release agent of the present invention is represented by the above general formula (1) containing a compound known as chitosan or its monomer, glucosamine, containing a glycerol group, a carboxymethyl group and the like. It consists of a compound into which a functional group has been introduced.

The chitosan and / or glucosamine derivative which is an essential component of the present invention is derived from chitosan obtained by deacetylating chitin or glucosamine which is a monomer thereof. Preferably, the deacetylation rate of chitin is about 40% or more. Here, a dirt release effect can be obtained by using either the monosaccharide glucosamine or the polysaccharide chitosan as a raw material, but in consideration of the adsorptivity to fibers, chitosan which is a polysaccharide having an appropriate molecular weight is used. Is preferred. The average number of condensation of chitosan is from 1 (glucosamine) to 1000, preferably from 2 to 500, particularly preferably from 5 to 100.
When the condensation number is within the above range, the soil release performance is excellent, and it is also preferable in terms of fiber feel.

A plurality of functional groups represented by the general formula (1) introduced into chitosan and / or glucosamine may be introduced into the chitosan skeleton. For example, a glycerol group (—CH ₂ CH (OH) CH) ₂ OH), methoxyglycerol group,
Ethoxyglycerol group, carboxymethyl group (-CH ₂ CO
OM (M is the same as described above)], 2-hydroxy-3-trimethylammoniopropyl group and the like, and preferably a glycerol group and a carboxymethyl group.

The introduction of the functional group represented by the general formula (1) into these raw materials is performed by modifying the epoxy compound according to a standard method such as a ring opening reaction of an epoxy compound or a desalting reaction with a halide in the presence of an alkali catalyst. And a plurality of types of modification reactions may be performed to introduce a plurality of types of substituents.

(Cleaning composition) The cleaning composition of the present invention contains the chitosan and / or glucosamine of the present invention in an amount of 0.1%.
The content is 01 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 1 to 10% by weight.

The detergent 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 the surfactant is used in combination, the soil release effect is amplified. As the nonionic surfactant, polyoxyethylene alkyl ether having an average carbon number of an alkyl group of 10 to 20, preferably 12 to 18, particularly preferably 12 to 14, and an average addition mole number of ethylene oxide of 6 to 10 is used. preferable. 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. Also, amphoteric surfactants, fourth
A cationic surfactant such as a quaternary ammonium salt can also be used in combination. The content of the surfactant 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 cleaning 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. The polycarboxylic acid-based compound, when used in combination with the compound of the present invention, promotes dispersibility in a washing solution and exhibits an effect of assisting the compound to efficiently adsorb the fiber. 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 detergent 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 agent 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 Agent, fluorescent dye, pigment, anti-caking agent, solubilizer,
Flavors and the like are blended as needed.

[0017]

EXAMPLES Synthesis Example 1 (Synthesis of Glycerylated Chitosan) 480 g of water was placed in a 1 L flask, 5.66 g of 36% HCl was added, and 30.00 g of chitosan having a condensation degree of 10 was added.
The temperature was raised to ° C. While maintaining the temperature at 50 to 60 ° C., 6.90 g of glycidol was added dropwise. After dropping, keep the temperature 5
After aging for a time, the mixture was cooled to obtain 543 g of a reaction-completed product.

Synthesis Example 2 (Synthesis of carboxymethylated chitosan) 480 g of water and 5.66 g of 36% HCl were placed in a 1 L flask, 30.00 g of chitosan having a condensation degree of 10 and 6.50 g of sodium monochloroacetate.
Was added, the mixture was aged for 5 hours while maintaining the temperature at 60 to 70 ° C., and then cooled to obtain 522 g of a reaction-completed product.

Example 1 (1) 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 dissolved in 0.06%. % Aqueous solution and adjust the pH to 10.5 with NaOH or HCl. The above-mentioned cotton cloth 5
The sheet is added to a detergent aqueous solution, and washed by stirring with a tergotometer at 100 rpm at 20 ° C. for 10 minutes. 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 cleaning process three times, the cotton fabric after the cleaning process is 60% cottonseed oil,
Cholesterol 10%, oleic acid 10%, palmitic acid 10
Model sebum stain consisting of 10% solids and 10% solid paraffin
2 g was uniformly applied per cm × 10 cm to prepare a sebum stain-contaminated cloth. 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
溶解 Dissolve in DH hard water and prepare to be 0.06% aqueous solution,
Adjust the pH to 10.5 with NaOH or 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.

[0022]

[Table 1]

(Note) Glycerylated Chitosan: Synthetic Example 1 Carboxymethylated Chitosan: Synthetic Example 2 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 ・ Polyacrylic acid: Sodium salt, average Molecular weight 10,000 ・ AM: Sodium salt of maleic acid acrylate (molar ratio 7/3) copolymer, average molecular weight 70,000 ・ PEG: Polyethylene glycol (average molecular weight 600) ・ 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 Continued on the front page (72) Inventor Makoto Kubo 1334 Minato, Wakayama City, Wakayama Prefecture, Kao Co., Ltd. (72) Inventor Akira Fujio 1334 Minato, Wakayama City, Wakayama Prefecture, Kao Co., Ltd. Hideji Tagata 1334 Minato, Wakayama-shi, Wakayama Pref.

Claims (9)

[Claims] 1. A functional group represented by the following general formula (1):
Release of chitosan and / or glucosamine
Dispensing. -R¹-X (1) (where R¹Has 1 to 1 carbon atoms which may be substituted with a hydroxyl group.
6 is an alkylene group, and X is OR^Two, COOM and N⁺R^ThreeR^FourR^FiveZ
One or more groups selected from^TwoIs hydrogen or
Represents an alkyl group having 1 to 22 carbon atoms, and M represents hydrogen or positive
Indicates on, R^Three, R ^Four, R^FiveAre each independently of the other
An alkyl group having 1 to 4 carbon atoms which may be substituted with a group,
From an oxyalkylene group having 1 to 4 carbon atoms and a benzyl group
It represents one or more selected groups, and Z represents an anion. ) 2. The method according to claim 1, wherein the functional group represented by the general formula (1) is —CH ₂
Soil release agent of claim 1 wherein the CH (OH) CH ₂ OH. 3. The method according to claim 1, wherein the functional group represented by the general formula (1) is —CH ₂
The soil release agent according to claim 1, which is COOM (M is the same as described above). 4. A functional group represented by the following general formula (1):
Chitosan and / or glucosamine 0.01% to 50% by weight
A cleaning composition comprising: -R¹-X (1) (where R¹Has 1 to 1 carbon atoms which may be substituted with a hydroxyl group.
6 is an alkylene group, and X is OR^Two, COOM and N⁺R^ThreeR^FourR^FiveZ
One or more groups selected from^TwoIs hydrogen or
Represents an alkyl group having 1 to 22 carbon atoms, and M represents hydrogen or positive
Indicates on, R^Three, R ^Four, R^FiveAre each independently of the other
An alkyl group having 1 to 4 carbon atoms which may be substituted with a group,
From an oxyalkylene group having 1 to 4 carbon atoms and a benzyl group
It represents one or more selected groups, and Z represents an anion. ) 5. The method according to claim 1, wherein the functional group represented by the general formula (1) is —CH ₂
CH (OH) CH ₂ OH in which it claims 4 detergent composition. 6. The functional group represented by the general formula (1) is —CH ₂
The cleaning composition according to claim 4, which is COOM (M is the same as described above). 7. The cleaning composition according to claim 4, comprising 0.1 to 40% by weight of a surfactant. 8. Polycarboxylic acid compound 0.01 to 50% by weight
The cleaning composition according to any one of claims 4 to 6, further comprising: 9. The cleaning composition according to claim 4, comprising 0.01 to 15% by weight of a sulfite.