JP2001172678A - 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) -CO[NH]n-R (I) (wherein R is a 5-21C alkyl or phenyl group both of which may be substituted with hydroxyl group; n is 0 or 1) 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]

According to the present invention, there is provided a compound represented by the general formula (1):
And a soil release agent comprising chitosan and / or glucosamine in which a functional group represented by is introduced into at least a part (preferably 10 to 100%) of all amino groups, and a chitosan and / or glucosamine (hereinafter referred to as a chitosan derivative) 0.01 to 50
The present invention provides a cleaning composition containing about 100% by weight. -CO- [NH] _n -R (1) (wherein, R is a group having 5 to 2 carbon atoms which may be substituted with a hydroxyl group)
1 alkyl group or phenyl group, preferably a linear or branched saturated or unsaturated alkyl group, and n is 0 or 1. )

[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 chitosan derivative used in the present invention comprises at least a part, preferably 10 to 100%, of all amino groups of chitosan and / or glucosamine, and a functional group represented by the general formula (1). And any of these may be used alone or in combination of two or more.

In the general formula (1), n represents a number of 0 or 1, and when n = 0, the general formula (1) represents an acyl group;
When = 1, it is preferably an alkylcarbamoyl group. R represents an alkyl group having 5 to 21 carbon atoms which may be substituted with a hydroxyl group, or a phenyl group, for example, heptyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Tetradecyl group, heptadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, octyl group, 2-ethylhexyl group, phenyl group, etc. Good. Further, as the substituent represented by the general formula (1),
For example, hexanoyl, octanoyl, decanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, oleoyl, isostearyl, hexylcarbamoyl, octylcarbamoyl, decylcarbamoyl, dodecyl Examples include a carbamoyl group, a tetradecylcarbamoyl group, a hexadecylcarbamoyl group, an octadecylcarbamoyl group, a phenylcarbamoyl group, and the like.

The saccharide-based compound forming the basic skeleton of the chitosan derivative of the present invention can obtain a soil release effect by using either a monosaccharide or a polysaccharide. It is preferable to use a polysaccharide of the formula (1), and particularly preferable is chitosan. That is, the number of repeating saccharide skeletons associated with the number of condensed saccharides is appropriately from 2 to 1000 on average, preferably from 2 to 500, and particularly preferably from 5 to 100. Excellent condensation release performance if the condensation number is within the above range,
It is also preferred in terms of fiber feel.

The functional group represented by the general formula (1) is introduced into at least a part of all amino groups of chitosans.
In terms of soil release performance, preferably 10 to 100 of all amino groups
%, More preferably 30 to 100%.

Each of the chitosan derivatives used in the present invention can be produced by a known synthesis method. N-acylated derivatives are described in Carbohydr.Res., 83, 389 (1980), Bull., Che.
m., Soc., Jpn., 61, 927 (1988), Carbohydr. Res., 41,
C1 (1975), as described in Makromol.Chem., 178, 2595, (1977), carboxylic acid, carboxylic acid chloride,
It can be synthesized by reacting an acid anhydride with chitosan. The N-alkylcarbamoylated derivative can be synthesized by a conventional method of synthesizing a urea derivative, and specifically, can be synthesized by reacting chitosan with an alkyl isocyanate.

(Cleaning composition) The cleaning composition of the present invention contains the chitosan derivative of the present invention in an amount of 0.01 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 1 to 10% by weight.
contains.

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 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 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 compound, when used in combination with the chitosan derivative, has an effect of promoting dispersibility in the washing solution and assisting the efficient adsorption of the chitosan derivative to the fiber. The content of the polycarboxylic acid compound is
From the viewpoint of detergency, it is preferably 0.01 to 50% by weight, more preferably 0.05 to 20% by weight, particularly preferably 1 to 10% by weight in the composition.

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 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.

[0018]

EXAMPLES Synthesis Example 1 (Synthesis of acylated chitosan) An aqueous solution obtained by dissolving 40.00 g of chitosan having a condensation degree of 10 and 300 g of chloroform and 5.01 g of caustic soda in 300 mL of water was placed in a 1 L flask, and vigorously stirred. 20.19 g of octanoic acid chloride was added while maintaining the temperature at or below ° C. Two
After aging for 3 hours while maintaining the temperature at 0 ° C. or lower, the solid content was filtered, and washed with water until the filtrate became neutral. Next, after washing with acetone, drying was performed to obtain 52.69 g of an intended product.

Synthesis Example 2 (Synthesis of phenylcarbamoylated chitosan) In a 1 L flask, 48.89 g of chitosan having a condensation degree of 10 and 500 g of chloroform were placed, and phenyl isocyanate was added at room temperature.
7.87 g were added dropwise. After completion of the dropwise addition, the temperature was raised to 60 ° C., and after aging for 3 hours, the mixture was allowed to cool. The solid content is separated by filtration, dried,
65.41 g of the desired product was 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 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.

[0023]

[Table 1]

(Note) ・ Acylated chitosan: Synthetic example 1 ・ Phenylcarbamoylated chitosan: Synthetic example 2 ・ Polyacrylic acid: sodium salt, average molecular weight 10,000 ・ AM: maleic acrylate (molar ratio 7 / 3) Sodium salt of copolymer, average molecular weight 70,000 • PEG: polyethylene glycol (average molecular weight 600) • 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 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 Prefecture F-term (reference) 4H003 AB19 AB21 AB27 AC08 AD04 BA09 DA01 EA12 EA15 EA16 EA28 EB30 EB32 EB36 EB41 EC02 EC03 FA21 4L033 AC04 AC15 BA18 BA44 BA71 CA02

Claims (5)

[Claims] 1. A soil release agent comprising chitosan and / or glucosamine having a functional group represented by the general formula (1) introduced into at least a part of all amino groups. -CO- [NH] _n -R (1) (wherein, R is a group having 5 to 2 carbon atoms which may be substituted with a hydroxyl group)
1 is an alkyl group or a phenyl group, and n is 0 or 1. ) 2. A detergent composition containing 0.01 to 50% by weight of chitosan and / or glucosamine in which a functional group represented by the general formula (1) is introduced into at least a part of all amino groups. -CO- [NH] _n -R (1) (wherein, R is a group having 5 to 2 carbon atoms which may be substituted with a hydroxyl group)
1 is an alkyl group or a phenyl group, and n is 0 or 1. ) 3. The cleaning composition according to claim 2, comprising 0.1 to 40% by weight of a surfactant. 4. A polycarboxylic acid compound in an amount of 0.01 to 50% by weight.
3. The cleaning composition according to claim 2, comprising: 5. The cleaning composition according to claim 2, comprising 0.01 to 15% by weight of a sulfite.