JP3720325B2 - Dirt release agent - Google Patents

Description

【００３８】
注）
・汚れ放出剤
化合物１：製造例１で得られた架橋体
化合物２：製造例２で得られた架橋体
化合物３：製造例３で得られた架橋体
化合物４：製造例４で得られた架橋体
化合物５：製造例５で得られた架橋体
化合物６：ローディア社製Repel-O-Tex SRP-4
・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
ＡＥ：ポリオキシエチレン（６モル）アルキル（Ｃ₁₂）エーテル
・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
ＰＥＧ：ポリエチレングリコール（平均分子量１０００）
・その他の成分
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
蛍光成分：Ciba.S.C.社のTinopal CBS-XとTinopal AMS-GXを１：１で配合したもの
酵素成分：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で混合したもの[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a soil release agent and a cleaning composition containing the same.
[0002]
[Prior art]
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.
[0003]
Regarding the soil release agent, some knowledge has been obtained. For example, Patent Document 1 discloses that a compound containing at least 3 NH groups is crosslinked with at least a bifunctional crosslinking agent that reacts with NH groups. The obtained soil release agent comprising a crosslinked nitrogen-containing compound is disclosed in Patent Document 2, and the soil release agent comprising a modified polyamine compound is disclosed. However, these soil release agents exhibit an excellent effect on hydrophilic cotton fibers, but cannot obtain a sufficient effect on hydrophobic synthetic fibers such as polyester.
[0004]
On the other hand, 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 (Patent Literature 3, Patent Literature 4, Patent Literature 5, etc.). . However, these soil release agents do not exhibit sufficient effects on relatively hydrophilic cotton fibers.
[0005]
Thus, conventionally, no soil release agent has been found that can exert an effect on both hydrophilic fibers such as cotton and hydrophobic fibers such as polyester.
[0006]
[Patent Document 1]
JP-T-2001-502735 [Patent Document 2]
Japanese Patent Publication No. 11-508319 [Patent Document 3]
US Pat. No. 3,416,952 [Patent Document 4]
US Pat. No. 3,557,039 [Patent Document 5]
US Pat. No. 4,955,584 specification
[Problems to be solved by the invention]
An object of the present invention is to provide a soil release agent effective for both hydrophilic fibers such as cotton and hydrophobic fibers such as polyester, and a cleaning composition containing the same.
[0008]
[Means for Solving the Problems]
The present invention relates to a compound of formula (I)
R ¹ —NH—R ² —NH ₂ (I)
[Wherein, R ¹ represents a hydrogen atom or a group represented by the formula —R ³ —OH (R ³ is an alkylene group having 2 to 6 carbon atoms), and R ² represents an alkylene group having 2 to 9 carbon atoms. . ]
And a crosslinked product obtained by reacting a polyglycidyl ether of a polyhydric alcohol or a polychlorohydrin of a polyhydric alcohol (hereinafter referred to as the component (b)). Provided are a soil release agent that releases fiber dirt from the fiber , and a cleaning composition containing the soil release agent.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
[Crosslinked product]
As the component (a) constituting the crosslinked product of the present invention, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, nonanediamine, aminoethylethanolamine, aminoethylpropanolamine, aminopropylethanolamine, amino Examples thereof include propylpropanolamine, and ethylenediamine, propylenediamine, and aminoethylethanolamine are preferable.
[0010]
The component (b) is a compound having at least 2, preferably 2 to 32 functional groups that react with the NH group, and polyglycidyl ether of polyhydric alcohol or polychlorohydrin of polyhydric alcohol is more preferred.
[0011]
As the polyhydric alcohol, the formula (II)
HO— (R ⁴ O) _n —H (II)
(In the formula, R ⁴ represents an alkylene group having 2 to 3 carbon atoms, and n represents a number of 1 to 30.)
In the formula (II), R ⁴ is an ethylene group, and n is 1 to 30, preferably 1 to 20 in the formula (II). Glycol or polyethylene glycol (hereinafter referred to as (poly) ethylene glycol), glycerin, polyglycerin having a polymerization degree of 2 to 10 or sorbitol is preferred, and (poly) ethylene glycol is more preferred.
[0012]
Particularly preferred as component (b) is diglycidyl ether or dichlorohydrin of (poly) ethylene glycol, and (poly) ethylene glycol diglycidyl ether is most preferred.
[0013]
The component (a) and the component (b) are used in the temperature range of 0 to 200 ° C., preferably 20 to 100 ° C., in the absence of a catalyst or using a lower tertiary amine such as dimethyloctylamine as a catalyst. It can be easily produced by dropping the component (b) into the component a) or charging it all together. In this case, in order to appropriately control the viscosity in the system, it is preferable to use water, other nonpolar solvents, or polar solvents. In particular, water is preferable from the viewpoint of economy. The reaction molar ratio [(a) / (b)] between the component (a) and the component (b) is preferably 1/1 to 1 / 0.05, more preferably 1/1 to 1 / 0.2.
[0014]
The viscosity of the crosslinked product of the present invention is preferably 10 to 10,000 mPa · cm, more preferably 30 to 1,000 mPa · cm. The viscosity here was measured at room temperature (25 ° C.) using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
[0015]
[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 or polyester fiber cloth, the soil release agent is adsorbed on the fiber surface by adding the soil release agent comprising the crosslinked product of the present invention to the cleaning agent, etc. A dirt release effect can be imparted. 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.
[0016]
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.
[0017]
[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.
[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 crosslinked product of the present invention, the polycarboxylic acid-based polymer 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 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, pectinase, bleaching agents such as sodium percarbonate and sodium perborate, peroxide stabilizers such as magnesium silicate, polyvinylpyrrolidone, etc. The anti-staining agent, sulfite, fluorescent dye, pigment, anti-caking agent, solubilizer, fragrance and the like can be blended as necessary.
[0024]
【Example】
Unless otherwise specified,% in the examples is% by mass. In the examples, the oxirane number was measured by the following method, and the viscosity was measured at room temperature (25 ° C.) using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
[0025]
<Measurement method of oxirane number>
When 1 g of a sample was chlorohydrinized with hydrochloric acid, the amount of hydrochloric acid consumed was expressed in mg of potassium hydroxide. After reacting the sample with hydrochloric acid at 120 to 130 ° C. for 30 minutes, phenolphthalein was added. Use as indicator and titrate with potassium hydroxide.
[0026]
Production Example 1
In a 1 liter reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 60 g of ethylenediamine (MW60) and 336.6 g of ion-exchanged water were charged and heated to 40 ° C. Thereafter, 52.2 g of ethylene glycol diglycidyl ether (MW174) was added dropwise over 30 minutes, and the reaction was continued for 30 minutes, followed by cooling. Completion of the reaction was confirmed by measuring the oxirane number and showing 1 or less. The obtained product was a viscous liquid of 25.0% active ingredient (crosslinked product) (viscosity: 150 mPa · cm).
[0027]
Production Example 2
In a 2 liter reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 60 g of ethylenediamine and 700 g of ion-exchanged water were charged and heated to 40 ° C. Thereafter, 173.5 g of polyethylene glycol diglycidyl ether (MW526, manufactured by ALDRICH) was dropped in 30 minutes, and the reaction was continued for 30 minutes, followed by cooling. Completion of the reaction was confirmed by measuring the oxirane number and showing 1 or less. The obtained product was a viscous liquid of 25.0% active ingredient (crosslinked product) (viscosity: 300 mPa · cm).
[0028]
Production Example 3
A reaction vessel similar to Production Example 1 was charged with 60 g of ethylenediamine and 350 g of ion-exchanged water and heated to 40 ° C. Thereafter, 69.6 g of ethylene glycol diglycidyl ether was added dropwise over 30 minutes, and the reaction was continued for 30 minutes, followed by cooling. The obtained product was a highly viscous gel. Thereafter, the total amount of this compound was transferred to a 2 liter beaker, 1000 g of ion exchange water was added, and the mixture was stirred for 10 minutes at 10,000 r / min using a homogenizer, and the active ingredient (crosslinked product) was 8.8%. A dispersion was obtained (viscosity: 30 mPa · cm).
[0029]
Production Example 4
A reaction vessel similar to Production Example 1 was charged with 52 g of aminoethylethanolamine (MW104) and 242 g of ion-exchanged water and heated to 40 ° C. Thereafter, 28.7 g of ethylene glycol diglycidyl ether was added dropwise over 30 minutes, and the reaction was continued for 30 minutes before cooling. Completion of the reaction was confirmed by measuring the oxirane number and showing 1 or less. The obtained product was a viscous liquid of 25.0% active ingredient (crosslinked product).
[0030]
Production Example 5
In the same reaction vessel as in Production Example 1, 74 g of 1,3-propanediamine (MW74) and 335 g of ion-exchanged water were charged and heated to 40 ° C. Thereafter, 69.6 g of ethylene glycol diglycidyl ether was added dropwise over 30 minutes, and the reaction was continued for 30 minutes, followed by cooling. The obtained product was a highly viscous gel. Thereafter, the total amount of this compound was transferred to a 2-liter beaker, 1000 g of ion-exchanged water was added, and the mixture was stirred for 10 minutes at 10,000 r / min using a homogenizer, and the active ingredient (crosslinked product) was 9.7%. A dispersion of was obtained.
[0031]
Example 1
A cleaning composition having the composition shown in Table 1 was prepared using the crosslinked products obtained in Production Examples 1 to 5. About this detergent composition, the washability with respect to sebum dirt was evaluated by the following method. The results are shown in Table 1.
[0032]
<Detergency evaluation method>
(1) Repeated washing of cotton fiber cloth and polyester 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 solution of detergent and NaOH. The pH was adjusted to 10.5. 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 cottonseed oil 60%, cholesterol 10%, oleic acid 10%, palmitic acid 10% and solid paraffin 10% is added to carbon black on 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.
[0033]
As for the polyester fiber cloth, five pieces of 10 × 10 cm cloth were washed by the same method as that for cotton cloth, dried, and then a sebum-stained cloth was prepared.
[0034]
(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 fabrics or 5 polyester-stained fabrics treated with each of the above cleaning compositions were placed in a detergent aqueous solution and stirred and washed at 20 ° C. for 10 minutes at 100 rpm with a tartometer. After rinsing under running water, an iron press treatment was performed.
[0035]
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.
[0036]
Washing rate (%) = [(reflectance after final cleaning−reflectance after preparation of contaminated fabric) / (reflectance of raw fabric−reflectance after preparation of contaminated fabric)] × 100
[0037]
[Table 1]

[0038]
note)
Soil releaser compound 1: Crosslinked compound obtained in Production Example 1: Crosslinked compound obtained in Production Example 2: Crosslinked compound obtained in Production Example 4: Obtained in Production Example 4 Crosslinked compound 5: Crosslinked compound 6 obtained in Production Example 5: Repel-O-Tex SRP-4 manufactured by Rhodia
Surfactant LAS: long-chain alkyl (C ₁₂ ) benzenesulfonic acid sodium salt AE: polyoxyethylene (6 mol) alkyl (C ₁₂ ) ether 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
PEG: Polyethylene glycol (average molecular weight 1000)
And other components zeolites: 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
Fluorescent component: Ciba.SC Tinopal CBS-X and Tinopal AMS-GX blended 1: 1 Enzyme component: Sabinase 12.0T type W (Novozymes), KAC-500G (Kao Corporation), Termamyl 60T (Novozymes) mixed 2: 1: 1

Claims (4)

Formula (I)
R ¹ —NH—R ² —NH ₂ (I)
[Wherein, R ¹ represents a hydrogen atom or a group represented by the formula —R ³ —OH (R ³ is an alkylene group having 2 to 6 carbon atoms), and R ² represents an alkylene group having 2 to 9 carbon atoms. . ]
And a crosslinked product obtained by reacting a polyglycidyl ether of a polyhydric alcohol or a polychlorohydrin of a polyhydric alcohol (hereinafter referred to as the component (b)). A soil release agent that releases fiber stains from fibers .   The soil release agent according to claim 1, wherein the component (a) is ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, nonanediamine or aminoethylethanolamine. The polyhydric alcohol has the formula (II)
HO— (R ⁴ O) _n —H (II)
(In the formula, R ⁴ represents an alkylene group having 2 to 3 carbon atoms, and n represents a number of 1 to 30.)
The soil release agent according to claim 1 or 2 , which is a compound represented by the formula: glycerin, polyglycerin having a polymerization degree of 2 to 30, or sorbitol. A cleaning composition containing the soil release agent according to any one of claims 1 to 3 .