JP4223165B2 - Dirt release agent - Google Patents

Description

【００２１】
（注）
・ポリアクリル酸：平均分子量10,000、ナトリウム塩
・AM：アクリル酸マレイン酸(モル比7/3)共重合体のナトリウム塩、平均分子量70,000
・LAS：長鎖アルキル(C₁₂)ベンゼンスルホン酸ナトリウム塩
・SFE：α−スルホ脂肪酸メチルエステルナトリウム塩
・AS：アルキル(C₁₂)硫酸エステルナトリウム塩
・AE：ポリオキシエチレン(6モル)アルキル(C₁₂)エーテル
・LB：アルキル(C₁₂)ジメチルベタイン
・ゼオライト：結晶性アルミノ珪酸塩、M₂O・Al₂O₃・2SiO₂・2H₂O、平均粒子径２μm、イオン交換容量290CaCO₃mg/g
・共通成分：蛍光成分0.5重量％と、サビナーゼ12.0 Ttype W（ノボノルディスク社製）、KAC-500G（花王株式会社製）、ターマミル60T（ノボノルディスク社製）を２：１：１で混合した酵素成分2.0重量％と芒硝であり、芒硝で組成物全体の量が100重量％になるように調整した。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a soil release agent and a cleaning composition.
[0002]
[Prior art and problems to be solved by the invention]
Providing the fiber with a soil release effect (soil release effect) in advance during washing of the fiber has a possibility of providing a very excellent cleaning effect as compared with a normal cleaning method. As an effective soil release agent for cleaning hydrophobic synthetic fibers such as polyester blended fabrics, compounds based on terephthalate are known (US 3416952, US 3557039, US 4795584, etc.). However, these soil release agents have an extremely excellent effect on a hydrophobic synthetic fiber cloth blended with polyester, but do not exhibit a sufficient effect on relatively hydrophilic cotton fibers. It was regarded as a problem.
[0003]
As soil release agents for cotton fibers, for example, polyamine derivatives (WO 9742285), nitrogen-containing polymers (DE 19649288) and the like are known. However, these compounds are also often affected by the effect of surfactant, temperature, pH, etc. on the adsorption efficiency to the fibers, 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 cleaning composition that exhibit an excellent soil release effect on cotton fabric and can exhibit a high cleaning effect.
[0005]
[Means for Solving the Problems]
The present invention relates to a soil release agent comprising a cyclic sugar compound represented by the general formula (1) and a cleaning composition containing 0.01 to 50% by weight of the compound.
[0006]
[G] _m- (AO) _n- [G] _m (1)
(In the formula, [G] is a residue indicating the smallest unit of cyclic sugar, m is an integer of 1 to 1000, A is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 1 to 1000.)
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The soil release agent of the present invention is capable of imparting a soil protection function to the fabric at the same time as cleaning the soil when washing the fabric. That is, by performing normal cleaning of a cotton fiber cloth with a cleaning agent containing the compound of the present invention, a soil 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 3 minutes to 2 hours, thoroughly rinsed with water, and then dehydrated and dried is repeated. As a result, a soil release function is imparted to the fabric, and a high cleaning effect is exhibited. The preferable immersion or cleaning time is 5 minutes or more and 1 hour or less, and more preferably 8 minutes or more and 20 minutes or less. In particular, a feature of the present invention is that a more excellent effect can be obtained as the number of times of cleaning increases.
[0008]
Here, the soil release agent of the present invention can be blended not only in the cleaning agent, but also in a fiber treatment agent such as a softening agent, a bleaching agent or a bleaching cleaning agent, if necessary.
[0009]
(Stain release agent)
The sugar derivative, which is an essential component of the present invention, has the general formula (1)
[G] _m- (AO) _n- [G] _m (1)
(In the formula, [G] is a residue indicating the smallest unit of cyclic sugar, m is an integer of 1 to 1000, A is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 1 to 1000.)
Indicated by The minimum unit of the cyclic sugar which is [G] in the general formula (1) includes glucose, ribose, arabinose, galactose, mannose and the like, preferably glucose and glucosamine. m is an integer of 1-1000 indicating the number of repeating monosaccharide skeletons accompanying the condensation of sugar, preferably 1-100, more preferably 1-20, and particularly preferably 1-3. If this value is within the above range, the soil release performance is excellent, and the fiber feel is also preferred. A is a linear or branched alkylene group having 1 to 4 carbon atoms, and is, for example, a group selected from ethylene, propylene, isopropylene, and butylene, and two or more types may be mixed. Preferred is ethylene and / or isopropylene. n is an integer of 1-1000 indicating the number of repeating oxyalkylene chains, that is, the degree of condensation, preferably 1-500, more preferably 1-100, and particularly preferably 5-20. It is. If n is in the above range, it is preferable in terms of adsorption efficiency to the fiber. These sugar derivatives can be synthesized, for example, by heating and refluxing a sugar compound and polyalkylene glycol in the presence of an acid catalyst.
[0010]
(Cleaning composition)
The cleaning composition of the present invention contains 0.01 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 1.0 to 10% by weight of the compound of the present invention represented by the above general formula (1). .
[0011]
Moreover, it is preferable that the cleaning composition of this invention contains surfactant. Examples of the surfactant include nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants. When a surfactant is used in combination, the soil release effect is amplified. As the nonionic surfactant, polyoxyethylene alkyl ether having an alkyl group having an average carbon number 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 preferred. Examples of the anionic surfactant include 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 sulfonates are preferred from the standpoint of improving detergency. Examples of the counter ion include alkali metal, ammonium, alkanolamine and the like. In addition, cationic surfactants such as amphoteric surfactants and quaternary ammonium salts can be used in combination. The content of the surfactant is preferably 0.1 to 40% by weight, more preferably 5 to 35% by weight, and particularly preferably 10 to 30% by weight in the composition in terms of detergency.
[0012]
Moreover, it is preferable that the cleaning composition of this invention contains a polycarboxylic acid type compound. Examples of polycarboxylic acid compounds include polyacrylic acid, copolymers of acrylic acid and maleic acid, and salts thereof, and are generally used as cleaning agents as calcium scavengers and dispersants. Moreover, what added carboxylic acid to the polysaccharide, polyglyoxylic acid, these salts, etc. are mentioned. When used in combination with a soil release agent, the polycarboxylic acid compound promotes dispersibility in the cleaning liquid and exhibits an effect of assisting the soil release agent to be efficiently adsorbed to the fibers. 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 in the composition in terms of detergency.
[0013]
Moreover, it is preferable that the cleaning composition of this invention contains a sulfite. The sulfite serves to maintain the effect of the soil release agent during washing or when stored for a long time. The content of sulfite is preferably 0.01 to 15% by weight, more preferably 0.01 to 5% by weight in the composition.
[0014]
The detergent composition of the present invention includes, in addition, divalent metal ion scavengers other than polycarboxylic acid-based compounds such as crystalline aluminosilicates and chelating agents, alkaline agent components such as sodium carbonate and sodium bicarbonate, protease, Enzyme components such as amylase, cellulase, lipase, pectinase, bleaching agents such as sodium percarbonate and sodium perborate, peroxide stabilizers such as magnesium silicate, anti-contamination agents such as polyvinylpyrrolidone, sulfites, etc. Dyes, pigments, anti-caking agents, solubilizers, fragrances and the like are blended as necessary.
[0015]
【Example】
Synthesis Example 1 (Synthesis of Compound 1)
D-glucose (147.07 g), 10% methanol / hydrochloric acid (75 ml), methanol (200 ml), and polyethylene glycol (240.00 g) having an average molecular weight of 600 were placed in a flask, and the mixture was heated to reflux at 70 ° C. for 15 hours. After allowing to cool, 500 ml of water was added, and the pH was adjusted to neutral with caustic soda, followed by concentration. Isopropanol was added to the resulting reaction mixture to remove salts and unreacted glucose, and then concentrated and dried again to obtain 343 g of the desired product. In the general formula (1) of the compound, m is 1 and n is 12.2.
[0016]
Synthesis Example 2 (Synthesis of Compound 2)
Maltose hydrate (108.09 g), 10% hydrochloric acid methanol (80 g), methanol (250 ml), and polyethylene glycol (90.00 g) having an average molecular weight of 600 were placed in the flask, and the mixture was heated to reflux at 70 ° C. for 15 hours. After allowing to cool, 500 ml of water was added, and the pH was adjusted to neutral with caustic soda, followed by concentration. Methanol was added to the resulting reaction mixture to remove the salt, and then concentrated and dried again to obtain 192 g of the desired product. In the general formula (1) of the compound, m is 2 and n is 12.2.
[0017]
Example
(1) Repeated washing of cotton fiber cloth and creation of contaminated cloth
A 10 cm × 10 cm cotton cloth is dissolved in a 4 ° DH hard water with a powder detergent composition comprising the ingredients shown in Table 1 to prepare a 0.06% aqueous solution, and the pH is adjusted to 10.5 with NaOH. Add 5 pieces of the above cotton cloth to the detergent aqueous solution and stir and wash with a turgotometer at 20 ° C. for 10 minutes at 100 rpm. After rinsing under running water, it is dried in a room at 25 ° C. and 50% RH for 1 hour or more after removing water sufficiently by a centrifugal dehydrator. After repeating this washing process three times, model sebum soil consisting of 60% cotton seed oil, 10% cholesterol, 10% oleic acid, 10% palmitic acid and 10% solid paraffin is applied to the washed cotton cloth 10cm × 2 g per 10 cm was uniformly applied to prepare a sebum-stained cloth. Contaminated cloth which performed this process about each composition of Table 1 was produced.
[0018]
(2) Cleaning conditions, cleaning methods and evaluation methods A cleaning composition comprising the compounding ingredients described in Comparative Product 1 in Table 1 is dissolved in 4 ° DH hard water to prepare a 0.06% aqueous solution, and NaOH is used. Adjust the pH to 10.5. Five cotton-stained cloths corresponding to the respective compositions are added to the cleaning composition aqueous solution, and the mixture is washed with stirring by a tartometer at 20 ° C. for 10 minutes at 100 rpm. After rinsing under running water, an iron press treatment was performed.
[0019]
Next, the reflectance at 460 nm of the raw cloth before washing, the contaminated cloth prepared after repeated washing, and the contaminated cloth after the final washing was measured with a self-recording colorimeter (Shimadzu Corporation). Was calculated.
Washing rate (%) = [(reflectance after final cleaning−reflectance after preparation of contaminated cloth) / (reflectance of raw cloth−reflectance after preparation of contaminated cloth) × 100
Table 1 shows the average values for the five contaminated cloths.
[0020]
[Table 1]

[0021]
(note)
-Polyacrylic acid: average molecular weight 10,000, sodium salt-AM: sodium salt of acrylic acid maleic acid (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 ) Dimethylbetaine / Zeolite: Crystalline aluminosilicate, M ₂ O · Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O, average particle size 2μm, ion exchange capacity 290CaCO ₃ mg / g
・ Common component: 0.5% by weight of fluorescent component, sabinase 12.0 Ttype W (manufactured by Novo Nordisk), KAC-500G (manufactured by Kao Corporation), Termamyl 60T (manufactured by Novo Nordisk) are mixed at a ratio of 2: 1: 1. The enzyme component was 2.0% by weight and mirabilite, and the amount of the entire composition was adjusted to 100% by weight with mirabilite.

Claims (6)

A soil release agent comprising a cyclic sugar compound represented by the general formula (1).
[G] _m- (AO) _n- [G] _m (1)
(In the formula, [G] is a residue indicating the smallest unit of cyclic sugar, m is an integer of 1 to 3, A is an ethylene group, and n is an integer of 5 to 20).   The soil release agent according to claim 1, wherein [G] in the general formula (1) is a glucose residue. A cleaning composition containing 0.01 to 50% by weight of the soil release agent according to claim 1 or 2.   The cleaning composition according to claim 3, comprising 0.1 to 40% by weight of a surfactant.   The cleaning composition according to claim 3 or 4, comprising 0.01 to 50% by weight of a polycarboxylic acid compound.   The cleaning composition according to any one of claims 3 to 5, comprising 0.01 to 15% by weight of sulfite.