JP3986868B2 - Dirt release agent - Google Patents

Description

【００３５】
注）
・汚れ放出剤
化合物１：合成例１で得られた化合物
化合物２：合成例２で得られた化合物
化合物３：合成例３で得られた化合物
化合物４：合成例４で得られた化合物
・界面活性剤
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（Ｃ₁₆）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）ジメチルアミノ酢酸ベタイン
・ポリカルボン酸系高分子化合物
ポリアクリル酸Ｎａ：平均分子量１０，０００
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
・その他の成分
ＰＥＧ：ポリエチレングリコール（平均分子量１３，０００）
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％と、サビナーゼ１２．０ＴtypeＷ（ノボザイムズ社製）、ＫＡＣ−５００Ｇ（花王株式会社製）、ターマミル６０Ｔ（ノボザイムズ社製）を２：１：１で混合した酵素成分２．０％と芒硝であり、芒硝で組成物全体の量が１００％になるように調整した。蛍光成分はCiba.S.C.社のTinopal CBS-XとTinopal AMS-GXを０．２５％ずつ配合したもの。[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]
A base is adsorbed on the fiber so that the dirt component is easily released from the fiber during the washing of the fiber. If the dirt component is easily released from the fibers during washing, it is possible to bring about an extremely excellent cleaning effect as compared with a normal cleaning method. Such an effect is called a soil release effect (soil release effect), and a base that exhibits such an effect is generally called a soil release agent. Regarding the soil release agent, several findings have been obtained as shown below.
[0003]
It is known that a compound mainly composed of terephthalate is effective as a soil release agent for hydrophobic synthetic fibers such as polyester blended fabrics (US3416952, US35557039, US4795854, etc.).
[0004]
However, these soil release agents exhibit an extremely excellent effect on hydrophobic synthetic fibers such as polyester, but do not exhibit a sufficient effect on relatively hydrophilic cotton fibers.
[0005]
On the other hand, as soil release agents for hydrophilic cotton fibers, for example, polyamine derivatives (WO9742285), nitrogen-containing polymers (DE19649288), and the like are known. However, these compounds are also strongly affected by the effect of the surfactant, temperature, pH, etc. on the adsorption efficiency to the fiber, and sufficient effects cannot be obtained.
[0006]
An object of the present invention is to provide a soil release agent capable of exhibiting an excellent soil release effect to soil components such as sebum stains on a hydrophilic cotton cloth, that is, a cleaning composition containing the same. That is.
[0007]
[Means for Solving the Problems]
The present invention relates to a soil release agent comprising a cellulose or starch sulfate or a neutralized product thereof having an average of 0.1 to 3.0 sulfate ester groups per unit glucose residue, and the soil release agent. A cleaning composition is provided.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
[Soil release agent]
The soil release agent of the present invention is used to wash soil when washing fabrics, and at the same time, is adsorbed on clothes and imparts a soil release effect. For example, when washing a cotton fiber cloth, the soil release agent of the present invention is added to the cleaning agent and the like to perform a normal cleaning, so that the soil release agent is adsorbed on the fiber surface and imparts a soil release effect. Can do. That is, the cloth is given a soil release effect by repeating a normal washing cycle in which the cloth is immersed or washed for about 3 minutes to 2 hours in a washing machine or by hand washing, rinsed thoroughly with water, and then dehydrated and dried. High cleaning effect is expressed. 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 addition, as the number of washings increases, a more excellent soil release effect can be obtained.
[0009]
The soil release agent of the present invention is not only applied to cleaning agents, but also applied to fiber treatment agents such as softeners and bleaching agents, and imparts a soil release effect by blending as necessary. Can do.
[0010]
The soil release agent of the present invention is not particularly limited in quality such as the origin and shape of cellulose and starch as raw materials, and neutralizes sulfates obtained by sulfating cellulose or starch, or the sulfates thereof. It is a neutralized product obtained by doing. Cellulose and starch as raw materials may be cellooligosaccharides or maltooligosaccharides having a low molecular weight.
[0011]
The number of sulfate groups per unit glucose residue (degree of sulfation) of cellulose or starch sulfate or neutralized product thereof as the soil release agent of the present invention is 0.1 to 3 on average per glucose residue. 0.0, and preferably from 0.2 to 2.0 from the viewpoint of adsorption performance to fibers.
[0012]
The method of synthesizing cellulose or starch sulfate or neutralized product thereof, which is the soil release agent of the present invention, is not particularly limited, but for example, synthesized by the method described in JP-A-2000-143686. Is possible. As an example, a sulfate can be obtained by reacting cellulose or starch with a sulfating reagent, and a neutralized product can be obtained by neutralizing the sulfate with a base.
[0013]
Examples of the sulfating reagent include anhydrous sulfuric acid, trimethylamine sulfur trioxide complex, triethylamine sulfur trioxide complex, dimethylformamide sulfur trioxide complex, pyridine sulfur trioxide complex, chlorosulfonic acid and the like. It is 0.1-5.0 mol with respect to one glucose residue which forms a cellulose or starch, Preferably it is 0.1-3.5 mol. As a solvent used for sulfation, dimethylformamide, pyridine, hexamethylphosphoamide (also referred to as HMPA or hexamethylphosphoric triamide (HMPT)), dimethylsulfoxide (DMSO), methylene chloride, Examples include chloroform. The reaction temperature is usually −30 to 80 ° C., and the reaction time is usually 5 minutes to 1 week. Examples of the base used for neutralization include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as triethylenetetramine, tetraethylenepentamine and aminoethylethanolamine.
[0014]
[Cleaning composition]
The cleaning composition of the present invention contains the soil release agent of the present invention as described above. The content of the soil release agent in the composition of the present invention is preferably 0.01 to 50% by mass, more preferably 0.05 to 20% by mass, and particularly preferably 1.0 to 10% by mass.
[0015]
The cleaning composition of the present invention preferably further contains an amine compound. Examples of amine compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylethanolamine, and triethanolamine. Of these, preferred amine compounds are polyamines, and particularly preferred are triethylenetetramine, tetraethylenepentamine, and aminoethylethanolamine.
[0016]
The amine compound may be added as a counter ion of a sulfate ester group in cellulose or starch sulfate during neutralization of the sulfate.
[0017]
The content of the amine compound in the cleaning composition of the present invention is preferably 0.01 to 50% by mass, more preferably 0.05 to 20% by mass, and particularly preferably 1.0 to 10% by mass.
[0018]
The cleaning composition of the present invention preferably further contains a surfactant. Examples of the surfactant include nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants. When a surfactant is used in combination with the soil release agent of the present invention, the soil release effect is amplified.
[0019]
As the nonionic surfactant used in the present invention, polyoxyethylene alkyl ether is preferable, and the alkyl group of the polyoxyethylene alkyl ether has 10 to 20, more preferably 12 to 18, particularly preferably 12 to 14, The average added mole number of ethylene oxide is preferably 4 to 16, more preferably 4 to 14, and particularly preferably 5 to 12. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl sulfate ester salt, polyoxyalkylene alkyl or alkenyl ether sulfate ester, alkane sulfonate, fatty acid salt, polyoxyalkylene alkyl or alkenyl ether carboxylate , Α-sulfo fatty acid salt or ester salt, amino acid type surfactant, N-acyl amino acid type surfactant and the like, alkylbenzene sulfonate, alkyl or alkenyl sulfate ester salt is preferable, and alkylbenzene sulfonate is particularly preferable. . Examples of the counter ion of the anionic surfactant include alkali metals, ammonium and alkanolamine. Examples of amphoteric surfactants include alkyldimethylaminoacetic acid betaines and fatty acid amidopropyl betaines. Examples of the cationic surfactant include quaternary ammonium salts. Further, an anionic surfactant and / or a nonionic surfactant and an amphoteric surfactant and / or a cationic surfactant can be used in combination.
[0020]
The content of the surfactant in the cleaning composition of the present invention is preferably 0.1 to 40% by mass, more preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass in terms of detergency. .
[0021]
The cleaning composition of the present invention preferably further contains a polycarboxylic acid polymer compound. Examples of polycarboxylic acid-based polymer compounds include polyacrylic acid, copolymers of acrylic acid and maleic acid, or salts thereof, and are generally used as cleaning agents as calcium scavengers and dispersants. is there. Moreover, what added carboxylic acid to the polysaccharide, the polymer of glyoxylic acid, etc. can be used. The average molecular weight of the polycarboxylic acid polymer compound is preferably 8,000 to 100,000, and more preferably 10,000 to 70,000.
[0022]
When used in combination with the soil release agent of the present invention, the polycarboxylic acid-based polymer compound promotes dispersibility in the cleaning liquid and has an effect of assisting the soil release agent to be efficiently adsorbed to the fibers. . The content of the polycarboxylic acid polymer compound in the cleaning composition of the present invention is preferably 0.01 to 50% by mass, more preferably 0.05 to 20% by mass in terms of detergency. 0-10 mass% is especially preferable.
[0023]
The cleaning composition of the present invention is a divalent metal ion scavenger other than polycarboxylic acid-based polymer compounds such as zeolite (crystalline aluminosilicate) and chelating agent, potassium carbonate, sodium carbonate, sodium bicarbonate, Alkaline agent components such as sodium silicate, enzyme components such as protease, amylase, cellulase, lipase and pectinase, bleaching agents such as sodium percarbonate and sodium perborate, peroxide stabilizers such as magnesium silicate, polyethylene glycol, Anti-staining agents such as polyvinylpyrrolidone, sulfites, fluorescent dyes, pigments, anti-caking agents, solubilizers, fragrances and the like can be blended as necessary.
[0024]
【Example】
Unless otherwise specified,% in the examples is% by mass.
[0025]
Synthesis Example 1 Synthesis of Cellulose Sulfate Sodium Salt After adding dimethylformamide (200 g) to a 1000 mL four-necked flask and stirring at −20 ° C., liquid SO ₃ (23.3 g) was added. While maintaining the temperature at 0 ° C. or lower, 45 g of cellulose powder [Funakoshi Funacel SF (registered trademark)] was added. After aging at 0 ° C. for 3 hours, the reaction product was added to 1000 g of ice water and neutralized with an aqueous caustic soda solution while stirring. The obtained product was filtered, and the solid content was sufficiently washed with water, followed by drying to obtain the desired product (69.7 g). As a result of conducting elemental analysis of the obtained compound, it was carbon 28.2%, hydrogen 3.6%, oxygen 48.5%, sulfur 11.5%, sodium 8.2%. Moreover, in the IR spectrum, there were peaks indicating sulfate ester groups in the vicinity of 1240 cm ⁻¹ and 800 cm ⁻¹ . From the value calculated using the carbon and sulfur values of the elemental analysis described above and an IR spectrum, it was confirmed that each unit glucose residue had 0.92 sulfate ester groups (counter ion was Na).
[0026]
Synthesis Example 2: Synthesis of starch sulfate sodium salt After adding dimethylformamide (200 g) to a 1000 mL four-necked flask and stirring at −20 ° C., liquid SO ₃ (23.3 g) was added. While maintaining the temperature at 0 ° C. or lower, 45 g of corn starch (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After aging at 0 ° C. for 3 hours, the reaction product was added to 1000 g of ice water and neutralized with an aqueous caustic soda solution while stirring. The obtained product was filtered, and the solid content was sufficiently washed with water, followed by drying to obtain the desired product (63.5 g). As a result of elemental analysis of the obtained compound, it was 27.7% carbon, 3.5% hydrogen, 48.5% oxygen, 11.8% sulfur, and 8.5% sodium. Moreover, in the IR spectrum, there were peaks indicating sulfate ester groups in the vicinity of 1240 cm ⁻¹ and 800 cm ⁻¹ . From the value calculated using the carbon and sulfur values of the elemental analysis described above and an IR spectrum, it was confirmed that each unit glucose residue had 0.92 sulfate ester groups (counter ion was Na).
[0027]
Synthesis Example 3 Synthesis of Cellulose Sulfate / Tetraethylenepentamine Salt The target product (72.8 g) was obtained in the same manner as in Synthesis Example 1 except that neutralization was performed with an aqueous tetraethylenepentamine solution instead of an aqueous caustic soda solution. It was. The obtained compound has 0.96 sulfate ester groups per unit glucose residue (counter ion is tetraethylenepentamine) from the carbon and sulfur values of elemental analysis and IR spectrum as in Synthesis Example 1. Confirmed that.
[0028]
Synthesis Example 4 Synthesis of Cellulose Sulfate / Aminoethylethanolamine Salt The desired product (71.5 g) was obtained in the same manner as in Synthesis Example 1 except that neutralization was performed with an aminoethylethanolamine aqueous solution instead of a caustic soda aqueous solution. It was. The obtained compound has 0.96 sulfate ester groups (counter ion is aminoethylethanolamine) per unit glucose residue from the carbon and sulfur values of elemental analysis and IR spectrum as in Synthesis Example 1. Confirmed that.
[0029]
Example 1
A cleaning composition having the composition shown in Table 1 was prepared using the formulation components shown in Table 1, and the detergency against sebum soil was evaluated by the following method. The results are shown in Table 1.
The product 6 of the present invention is a reference product.
[0030]
<Detergency evaluation method>
(1) Repeated washing of cotton fiber cloth and preparation of contaminated cloth Each detergent composition shown in Table 1 was dissolved in 4 ° DH hard water to prepare a 0.06% aqueous detergent solution, and the pH was adjusted to 10. with NaOH. Adjusted to 5. Five pieces of 10 × 10 cm cotton cloth were placed in the detergent aqueous solution and washed by stirring with a targotometer at 20 ° C. for 10 minutes at 100 rpm. After rinsing under running water, the water was removed sufficiently by a centrifugal dehydrator, and then dried in a room at 25 ° C. and 50% RH for 1 hour or more. After repeating this washing process three times, 100% of a mixture of 60% cottonseed oil, 10% cholesterol, 10% oleic acid, 10% palmitic acid and 10% solid paraffin is added to the washed cotton cloth. A model sebum soil with 0.02% added was uniformly applied in an amount of 2 g per 10 × 10 cm to prepare a sebum soil-contaminated cloth.
[0031]
(2) Cleaning conditions, cleaning method and evaluation method The cleaning composition of Comparative product 1 shown in Table 1 was dissolved in 4 ° DH hard water to prepare a 0.06% detergent aqueous solution, and the pH was adjusted using NaOH. Was adjusted to 10.5. Five cotton-stained cloths treated with each of the cleaning compositions described above were placed in a detergent aqueous solution and washed by stirring with a tartometer at 20 ° C. for 10 minutes at 100 rpm. After rinsing under running water, an iron press treatment was performed.
[0032]
Next, the reflectance at 460 nm of the raw cloth before washing, the contaminated cloth prepared after repeated washing, and the contaminated cloth after final washing was measured with a self-recording colorimeter (Shimadzu Corporation), and the sebum dirt washing rate ( %) Was calculated and shown as an average value for five contaminated cloths.
[0033]
Washing rate (%) = [(reflectance after final cleaning−reflectance after preparation of contaminated fabric) / (reflectance of raw fabric−reflectance after preparation of contaminated fabric)] × 100
[0034]
[Table 1]

[0035]
note)
Soil releaser compound 1: Compound obtained in Synthesis Example 1: Compound obtained in Synthesis Example 2: Compound obtained in Synthesis Example 4: Compound obtained in Synthesis Example 4: Compound / interface obtained in Synthesis Example 4 active agents LAS: long-chain alkyl (C ₁₂₎ sodium benzenesulfonate SFE: alpha-sulfo fatty acid (C ₁₆₎ 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 ) dimethylaminoacetic acid betaine polycarboxylic acid polymer compound polyacrylic acid Na: average molecular weight 10,000
AM: sodium salt of acrylic acid maleic acid (molar ratio 7/3) copolymer, average molecular weight 70,000
Other components PEG: polyethylene glycol (average molecular weight 13,000)
Zeolite Crystalline _{aluminosilicates, 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 component: Enzyme component 2 in which fluorescent component 0.5%, sabinase 12.0TtypeW (manufactured by Novozymes), KAC-500G (manufactured by Kao Corporation), Termamyl 60T (manufactured by Novozymes) were mixed at a ratio of 2: 1: 1. 0.0% and mirabilite, and the amount of the entire composition was adjusted to 100% with mirabilite. The fluorescent component is a combination of 0.25% each of Cino.SC's Tinopal CBS-X and Tinopal AMS-GX.

Claims (5)

Contains a soil release agent composed of cellulose or starch sulfate or a neutralized product thereof having an average of 0.2 to 2.0 sulfate ester groups per unit glucose residue , and a polycarboxylic acid polymer compound A cleaning composition . Claim 1 detergent composition according the content of the soil release agent in the composition is 0.01 to 50 mass%. The cleaning composition according to claim 1 or 2, wherein the content of the polycarboxylic acid polymer compound in the composition is 0.01 to 50% by mass . Furthermore, the cleaning composition in any one of Claims 1-3 which contains 0.01-50 mass% of amine compounds in a composition. The detergent composition according to any one of claims 1 to 4, further comprising a surfactant in an amount of 0.1 to 40% by mass.