JP3405942B2 - Soil release agent - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a soil release agent and cleaning composition.

[0002]

2. Description of the Related Art Providing a soil release effect (soil release effect) to a fiber during washing of the fiber may bring an extremely excellent cleaning effect as compared with a conventional cleaning method. Have. Compounds based on terephthalate are known as effective soil release agents for cleaning hydrophobic synthetic fibers such as polyester blended fabrics (US 3416952, US 3557039, US 4795584).
etc). However, these soil release agents have an extremely excellent effect on a hydrophobic synthetic fiber cloth mixed with polyester, but do not exhibit a sufficient effect on a relatively highly hydrophilic cotton fiber. That was a problem.

Known stain release agents for cotton fibers are, for example, polyamine derivatives (WO 9742285) and nitrogen-containing polymers (DE 19649288). However, the adsorption efficiency of these compounds to the fiber is also strongly influenced by the surfactant, temperature, pH and the like, and in many cases, a sufficient effect cannot be obtained.

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]

The present invention provides the following general formula (1) and / or general formula (2)

[0006]

[Chemical 2]

[0007] (wherein, X ^1, X ^2, X ³ are each independently a hydrogen atom or an SO ₃ ^- is Y ^+, at least one SO ₃ ^-. A Y ⁺ Further, Y ⁺ is a cation In the formula, m and n each independently represent an integer of 1 to 1000. Further, R represents an alkyl group having 1 to 5 carbon atoms. ) And / or 0.01 to 50% by weight of the compound represented by the general formula (2).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The soil release agent of the present invention is capable of cleaning soil when laundering cloth and at the same time providing a soil protection function to the fabric. That is, the cloth for cotton fibers is subjected to ordinary cleaning with a cleaning agent containing the compound of the present invention or the like to impart a soil release function to the fiber surface. For example, a normal washing cycle in which cotton fibers are immersed in or washed with a detergent composition containing the compound of the present invention for 3 minutes to 2 hours in a washing machine or by hand washing, thoroughly rinsed with water, and then dehydrated and dried is repeated. As a result, the soil release function is imparted to the cloth, and a high cleaning effect is exhibited. The immersion or washing time is preferably 5 minutes or more and 1 hour or less, more preferably 8 minutes or more and 20 minutes or less. In particular, the feature of the present invention is that the greater the number of washings, the more excellent the effect can be obtained.

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 softening agent, a bleaching agent and a bleaching detergent, if necessary. .

(Soil Release Agent) The compound represented by the general formula (1) or (2) which is the soil release agent of the present invention is chitin,
A compound obtained by sulfating or sulfonation of glucosamine (hereinafter referred to as chitosans), which is chitosan or the like or a monomer thereof, and then neutralized, (1)
Any one of (2) and (2) may be used alone, or two or more kinds may be used in combination.

[0012] Here, although the soil release effect can be obtained by using either monosaccharide or polysaccharide, it is preferable to use a polysaccharide having an appropriate molecular weight in view of the adsorptivity to the fiber, particularly chitin or chitosan. preferable. That is, the number of repeating sugar skeletons (m or n in the formula) associated with the number of condensation of sugars is suitably 2 to 1000 on average, preferably 2 to 500, and particularly preferably 5 to 100. When this value is within the above range, the stain release performance is excellent, and it is also preferable in terms of the feel of the fiber.

[0012] In the general formula ^{(1), X 1, X} 2 is at least one SO ₃ ^- is Y ^+, both SO ₃ ^- may be a Y ^+. Also,
At least one of X ¹ , X ² and X ^{3 in the} general formula (2) is SO ₃ ^- Y ⁺
, And the two or three SO ₃ ^- may be a Y ^+.

As Y ⁺ , a cation such as hydrogen ion, alkali metal ion, alkaline earth metal ion,
Examples thereof include amine salts such as trimethylamine salts, alkanolamine salts, ammonium ions and the like. Preferred are alkali metal ions such as sodium ions and alkaline earth metal ions such as calcium ions.

The compounds of the general formulas (1) and (2) can be synthesized by a generally known sulfation reaction. For example, a method of dissolving or dispersing chitosans in an aprotic organic solvent and then dropping chlorosulfonic acid at a low temperature to react, or a substrate is added to SO ₃ / N, N-dimethylformamide complex. And a method in which a liquid in which chitosans are dissolved or dispersed in an aprotic organic solvent is reacted in a thin film type continuous sulfation reactor.

(Detergent Composition) The detergent composition of the present invention contains the compound represented by the general formula (1) and / or the general formula (2) 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 10% by weight.

The detergent composition of the present invention preferably contains a surfactant. Examples of the surfactant include nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants. The combined use of a surfactant amplifies the soil release effect. As the nonionic surfactant, the average carbon number of the alkyl group is 10 to 20, preferably
A polyoxyethylene alkyl ether having 12 to 18, particularly preferably 12 to 14 and an average addition mole number of ethylene oxide of 6 to 10 is preferable. As the anionic surfactant, alkylbenzene 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. Of these, alkylbenzene sulfonate is preferable in terms of improving detergency. As a counter ion,
Examples thereof include alkali metals, ammonium and alkanolamines. Further, a cationic surfactant such as an amphoteric surfactant or a quaternary ammonium salt can be used together.
The content of the surfactant is 0.1 to 4 in the composition in terms of detergency.
0 wt% is preferable, 5 to 35 wt% is more preferable, and 10 to 30 wt% is particularly preferable.

The detergent composition of the present invention preferably contains a polycarboxylic acid compound. The polycarboxylic acid compound is 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 for a detergent. In addition, those obtained by adding a carboxylic acid to a polysaccharide, polyglyoxylic acid and salts thereof, and the like are also included. The polycarboxylic acid compound, when used in combination with the soil release agent, promotes dispersibility in the cleaning liquid and exhibits an action of assisting the efficient adsorption of the soil release agent to the fibers. From the viewpoint of detergency, the content of the polycarboxylic acid compound is preferably 0.01 to 50% by weight, more preferably 0.05 to 20% by weight, and particularly preferably 1.0 to 10% by weight.

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

In addition to the polycarboxylic acid compounds such as crystalline aluminosilicates and chelating agents, the detergent composition of the present invention also contains divalent metal ion scavengers, alkaline agent components 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, peroxide stabilizers such as magnesium silicate, prevention of recontamination of polyethylene glycol, polyvinylpyrrolidone, etc. Agent, fluorescent dye, pigment, anti-caking agent, solubilizer,
Fragrances and the like are added as needed.

[0020]

EXAMPLES Synthesis Example 1 (Synthesis of Monosulfated Chitosan) Chitosan (25.76 g) having a condensation degree of 10 was placed in a 1 L flask,
Next, add 500 g of chloroform and disperse with stirring.
Cooled to below -20 ° C. Chlorosulfonic acid (21.30 g) was added dropwise while maintaining the temperature at -20 ° C or lower. After completion of dropping-20
After aging for 3 hours at ℃ or below, the reaction mixture is heated to 1000
Diluted in ice water (g). The pH of the diluted solution was adjusted to neutral with an aqueous solution of sodium hydroxide. The obtained mixed solution was concentrated, and the remaining crystals were washed with acetone and then with water for desalting. After drying, 23.41 g (92.9% pure) of the final product was obtained.

Synthesis Example 2 (Synthesis of Disulfated Chitosan) 200 g of N, N-dimethylformamide (DMF) was added to a 500 ml flask.
Then, liquid anhydrous sulfuric acid (41.90 g) was added dropwise at -20 ° C. 0
The resulting DMF-SO ₃ complex at 10 ℃, chitosan (4
0.00 g) was added as a powder and aged for 3 hours. The obtained reaction mixture was added to 200 g of ice water, and the pH was adjusted to neutral with a caustic soda aqueous solution. Concentrate the resulting mixture,
The obtained crystals were washed with acetone and then dried to obtain 73.3 g of a final product (95.7% pure content).

Synthesis Example 3 (Synthesis of Monosulfated Chitin) 200 g of N, N-dimethylformamide (DMF) was added to a 500 ml flask.
Then, liquid anhydrous sulfuric acid (16.07 g) was added dropwise at -20 ° C.
Chitin (40.00 g) was added as a powder to the obtained DMF-SO ₃ complex at 0 ° C., and the mixture was aged for 3 hours. The obtained reaction mixture was added to 200 g of ice water, and the pH was adjusted to neutral with a caustic soda aqueous solution. The obtained mixed liquid was concentrated, and the obtained crystals were washed with acetone and then dried to obtain 58.9 g of a final product.

Example 1 (1) Repeated washing of cotton fiber cloth and preparation of contaminated cloth A cotton cloth of 10 cm × 10 cm was dissolved in 4 ° DH hard water with a powder detergent composition containing the ingredients shown in Table 1. Prepare a 0.06% aqueous solution and adjust the pH to 10.5 with NaOH. Five pieces of the above-mentioned cotton cloth are added to the detergent aqueous solution, and the mixture is washed with stirring at 20 ° C. for 10 minutes at 100 rpm with a tergotometer. After rinsing under running water, a 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 3 times, a model sebum stain consisting of 60% cottonseed oil, 10% cholesterol, 10% oleic acid, 10% palmitic acid and 10% solid paraffin was applied to the washed cotton cloth.
2 g per 10 cm was evenly applied to prepare a sebum stain-contaminated cloth. A soiled cloth was prepared by this treatment for each of the compositions in Table 1.

(2) Washing conditions, washing method and evaluation method A detergent composition comprising the compounding ingredients 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. Five pieces of cotton-contaminated cloth corresponding to each composition are added to the detergent composition aqueous solution, and the mixture is washed with stirring at 20 ° C. for 10 minutes at 100 rpm with a tergotometer. After rinsing under running water, an iron press treatment was performed.

Then, the reflectance at 460 nm of the original cloth before cleaning, the contaminated cloth prepared after repeated cleaning, and the contaminated cloth after the final cleaning were measured with a self-recording colorimeter (Shimadzu Corporation), and the cleaning rate was calculated from the following formula. (%) Was calculated. Cleaning rate (%) = [(reflectance after final washing-reflectance after preparation of contaminated cloth) / (reflectance of original cloth-reflectance after preparation of contaminated cloth]]
× 100 Table 1 shows the average value of 5 sheets of contaminated cloth.

[0026]

[Table 1]

(Note) ・ LAS: long-chain alkyl (C ₁₂ ) benzenesulfonic acid sodium salt ・ SFE: α-sulfofatty acid methyl ester sodium salt ・ AS: alkyl (C ₁₂ ) sulfuric acid ester sodium salt ・ AE: polyoxyethylene (6 mol) Alkyl (C ₁₂ ) ether ・ LB: Alkyl (C ₁₂ ) dimethylbetaine ・ Polyacrylic acid: Sodium salt, average molecular weight 10000 ・ AM: Acrylic acid maleic acid (molar ratio 7/3) copolymer sodium Salt, 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 sabinase 12.0 Tt
2.0% by weight of the enzyme component, which is a mixture of ype W (manufactured by Novo Nordisk), KAC-500G (manufactured by Kao Corporation), and Termamyl 60T (manufactured by Novo Nordisk) at 2: 1: 1 and mirabilite. The total amount of the composition was adjusted to 100% by weight.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Fujio 1334 Kao Co., Ltd., Wakayama City, Wakayama Prefecture Research Institute (72) Inventor Shuji Takata 1334 Minato Minato, Wakayama City, Wakayama Prefecture (56) Reference Laboratory JP-A-62-138418 (JP, A) JP-A-63-12699 (JP, A) JP-A-59-106409 (JP, A) JP-A-63-162797 (JP, A) JP-A-63-54499 (JP , A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 3/37 C11D 3/384

Claims (5)

(57) [Claims] 1. The following general formula (1) and / or general formula (2): (In the formula, X ¹ , X ² , and X ³ are each independently a hydrogen atom or SO.
₃ ^- Y is ^+, at least one SO ₃ ^- is Y ^+. Also, Y ⁺
Represents a cation, m and n are each independently 1 to 1000
Is an integer. R is an alkyl group having 1 to 5 carbon atoms. ) A soil release agent comprising a compound represented by 2. A detergent composition for textiles, which comprises 0.01 to 50% by weight of the soil release agent according to claim 1. 3. The detergent composition for textile products according to claim 2, which contains 0.1 to 40% by weight of a surfactant. 4. A polycarboxylic acid compound 0.01 to 50% by weight
The detergent composition for a textile product according to claim 3, which comprises: 5. The detergent composition for textiles according to claim 3, which contains 0.01 to 15% by weight of sulfite.