JP2001072995A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition which imparts softness to clothes and is excellent in stability and detergency by incorporating a surfactant and a compound formed by the addition of an alcohol to the 1-position of an epoxy compound into the same. SOLUTION: This composition contains 0.1-20 wt.% compound represented by the formula: R1-OCH2CH(OH)CH2OH and 30-60 wt.% surfactant. The surfactant is preferably a nonionic surfactant and/or a cationic surfactant represented by formula I. When a cationic surfactant is jointly used, the use of a nonionic surfactant as the main surfactant is especially preferable. In the formulas, R1 is a 1-16C hydrocarbon group; one or two of R2 to R5 are each a 12-22C hydrocarbon group and the rest are each H, 1-4C alkyl, hydroxyalkyl or-(CH2CH2O)kH; k is 1-15; and X is halogen, CH3SO4, C2H5SO4, CH3COO or HCOO. The wt. ratio of nonionic surfactant/cationic surfactant is preferably (100/1)-(1/1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cleaning composition.

[0002]

BACKGROUND OF THE INVENTION Liquid detergents can be applied undiluted to stains, and can be used more effectively to stain stains on clothing. Since a relatively large amount of liquid surfactant, which is difficult to use in detergents, can be blended, it is easy to formulate, for example, a nonionic surfactant that is effective against oil stains as a main base material. . In addition, by using a nonionic surfactant as the main base, the flexibility of the fiber can be increased by using a cationic surfactant, which has been insufficient in the system where the anionic surfactant is the main base. , While maintaining the detergency.

[0003] However, although the liquid detergent has the above-mentioned advantages, it has a problem caused by being a liquid. For example, an increase in viscosity, turbidity of liquid, sedimentation or liquid / liquid separation can be cited, and these problems must be solved in environmental changes that can be considered as commercial products. In particular, when a large amount of a nonionic surfactant is blended or when the above-mentioned cationic surfactant is blended, the liquid detergent tends to be unstable.

Conventionally, to solve the above problems, it has been proposed to set the concentration of the surfactant relatively low and to use a phase stabilizer or a viscosity reducing agent. Viscous agents are often ineffective as cleaning ingredients and have been obstacles in increasing the concentration of liquid detergents.

It is an object of the present invention to provide a detergent composition which can improve the stability and detergency in a high-concentration surfactant system and can also impart flexibility to clothing.

[0006]

[Wherein, R ¹ represents a hydrocarbon group having ¹ to 16 carbon atoms. ]

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) of the present invention is incorporated in a composition at 0.1 to 20% by weight, preferably 1 to 10% by weight. By blending the component (a), the detergency, especially the detergency during coating, is excellent, and the solution stability and low-temperature fluidity are improved. From the viewpoint of detergency and solution stability at low temperatures, R ¹ in the general formula (I) has ¹ to 16 carbon atoms, preferably 3 to ¹ carbon atoms.
4, more preferably 4 to 10, particularly preferably 5 to 8 hydrocarbons, preferably alkyl groups. An alkyl group having 8 carbon atoms is particularly preferable in terms of detergency, and an alkyl group having 5 carbon atoms is particularly preferable in terms of low-temperature stability.

The compound of the general formula (I) is obtained by converting R ¹ -OH and an epoxy compound such as epihalohydrin or glycidol into BF.
A method of producing by reacting using an acid catalyst such as ₃ is common. However, the reaction between the alcohol and the epoxy compound reacts randomly at the 1-position and the 2-position of the epoxy compound, and further generates a polyadduct. For this reason, in addition to the compound of the general formula (I) in which an alcohol is added at the 1-position, 2-alkoxy-1,3-propanediol as an isomer or a multimer having a large number of glyceryl groups (eg, alkyl diglyceryl ether) Exists. In the present invention, a compound containing the above isomer or multimer may be used.However, from the viewpoint of improvement in washing performance, an aluminum catalyst of the general formula (III) is used in order to reduce isomers and multimers. To produce the compound of general formula (I). Al (OSO ₂ -R ³¹ ) ₁ (OR ³² ) _m (OR ³³ ) _n (III) wherein R ³¹ represents a hydrocarbon which may have a substituent, and R ³² and R ³³ are the same Or differently, a hydrocarbon group which may have a substituent. 1 is 1-3, m and n are each 0-2, and l + m + n = 3. ].

The catalyst may be produced, for example, by reacting a sulfonic acid or the like with a trialkylaluminum, trialkoxyaluminum or aluminum trihalide, and converting the alkyl group, alkoxyl group or halogen group of the aluminum compound with the sulfonic acid salt. After partial or total substitution, the compound can be produced by further substituting the remaining alkyl group, alkoxyl group or halogen group with an appropriate alcohol or phenol. The substitution reaction is performed by heating and mixing in a solvent such as a hydrocarbon or an alcohol.

When the above-mentioned aluminum catalyst is used in the present invention, an epoxy compound such as epihalohydrin or glycidol is used in an amount of 0.5 to 1.5 molar equivalents with respect to R ¹ -OH.
It is preferably used in an amount of 1.0 to 1.2 molar equivalents and has the general formula (II)
The aluminum catalyst of I) is added in an amount of 0.001 to R ¹ -OH.
To 0.1 mol equivalent, preferably 0.01 to 0.05 mol equivalent, and the reaction temperature is 10 to 120 ° C., preferably 70 to
It is good to react at ~ 110 ° C for 1-5 hours.

The surfactant (b) of the present invention includes:
Conventionally known surfactants, for example, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants and the like can be used. Among them, a nonionic surfactant and / or a cationic surfactant are preferable in terms of oil stain cleaning property and fiber flexibility. In particular, when used in combination with a cationic surfactant for the purpose of imparting flexibility,
Preferably, a nonionic surfactant is used as the main surfactant. In order to enhance the detergency, it is preferable to use an anionic surfactant or an anionic surfactant and a nonionic surfactant as the main surfactant.

As the nonionic surfactant in the component (b) of the present invention, the following (1) to (4) can be used from the viewpoint of cleaning property against dirt. (1) having an alkyl group or alkenyl group having an average carbon number of 8 to 20, such as an alkyl group derived from a linear primary or linear secondary alcohol or an alkyl group or an alkenyl group derived from a branched alcohol, and ethylene oxide ( A polyoxyethylene alkyl or alkenyl ether to which 1 to 20 moles of EO is added on average. (2) Polyoxyalkylene alkyl or alkenyl having an alkyl group or alkenyl group having an average carbon number of 8 to 20, and having EO added on average of 1 to 15 mol and propylene oxide (hereinafter PO) on average of 1 to 5 mol. ether.
In this case, EO and PO may be either random addition or block addition. (3) A saccharide or polysaccharide surfactant represented by the following general formula (IV). R ^41- (OR ⁴² ) _x G _y (IV) wherein R ⁴¹ is a hydrocarbon group having 8 to 18 carbon atoms, for example, a linear or branched alkyl or alkenyl group;
Or an alkylphenyl group, R ⁴² is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar having 5 or 6 carbon atoms,
x is an average value of 0 to 6, preferably 0, and y is an average value of 1 to
It indicates a number of 10, preferably 1 to 1.5. (4) Fatty acid alkanolamides and polyhydroxy fatty acid amides.

The nonionic surfactant is preferably contained in the detergent composition at 30 to 50% by weight, more preferably at 40 to 50% by weight.
% By weight.

As the cationic surfactant in the component (b) of the present invention, for example, a cationic surfactant represented by the general formula (II) can be used to impart flexibility to clothes and the like.

[0015]

Embedded image

Wherein one or two of R ² , R ³ , R ⁴ and R ⁵ are the same or different and are a hydrocarbon group having 12 to 22 carbon atoms; , Carbon number 1
To 4 alkyl groups, hydroxyalkyl groups or-(CH ₂
CH ₂ O) _k H (where k is 1 to 15), X is a halogen atom, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , CH ₃ COO or HCO
O is shown. ].

Preferred cationic surfactants are those wherein R ² in the general formula (II) is an alkyl group having 14 to 20 carbon atoms,
R ^3, R ^4, R ⁵ is mono long-chain alkyl type compounds is an alkyl group having 1 to 4 carbon atoms such as a methyl group (hereinafter, abbreviated as monoester) and R ² and R ³ 14 carbon atoms And di-long-chain alkyl-type compounds (hereinafter abbreviated as di-forms) wherein the alkyl group is 20 and R ⁴ and R ⁵ are an alkyl group having 1 to 4 carbon atoms such as a methyl group. Since the solution stability improves as the ratio of the isomer increases, the weight ratio of the monoisomer and the diisomer is preferably 20/1 or more, more preferably 100/1 or more.

The cationic surfactant is preferably contained in the detergent composition in an amount of 1 to 9% by weight, more preferably 2 to 7% by weight.

Here, the weight ratio of the nonionic surfactant to the cationic surfactant is such that the ratio of the nonionic surfactant to the cationic surfactant is improved from the viewpoint of improving the cleaning property against oil stains and improving the flexibility to clothing and the like. The ionic surfactant is preferably from 100/1 to 1/1, more preferably from 50/1 to 5/1.

Examples of the anionic surfactant in the component (b) of the present invention include a linear alkylbenzene sulfonate having an alkyl group having 10 to 18 carbon atoms, an alkyl sulfate, a polyoxyalkylene alkyl ether sulfate, and an alpha Alkali metal salts such as sulfo fatty acid alkyl ester salts are preferable, and a small amount of a fatty acid salt derived from tallow or coconut may be added. As counter ions, in addition to alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and / or alkanolamines such as mono, di, and triethanolamine are used. This is preferable because the property is improved.

The anionic surfactant is preferably contained in the detergent composition in an amount of 1 to 50% by weight, more preferably 1 to 24% by weight.

In the present invention, the component (b) is used in an amount of 30 to 60% by weight, preferably 40 to 55%, in order to obtain good detergency.
% By weight.

The cleaning composition of the present invention comprises (b)
Even if the surfactant concentration is as high as 30 to 60% by weight, ethanol, ethylene glycol, molecular weight 100
When it contains only a small amount of a stabilizer or a thickener such as polyethylene glycol, propylene glycol or paratoluenesulfonate of 0 or less, specifically 3% by weight
Even when the amount is less than the above, the compound can be stably blended without gelling or thickening.

The detergent composition of the present invention contains an alkali agent. Examples of the alkali agent to be blended include alkanolamine, ammonia, N-alkylalkanol, N-aminoalkylalkanolamine, dialkylenetriamine and the like. Among them, alkanolamine and ammonia are preferable, and monoethanolamine, diethanolamine and triethanolamine are particularly preferable in terms of detergency. One or more of these alkali agents can be used as a mixture. These alkaline agents are blended in an amount of 1 to 20% by weight so that the pH of the composition is 6 to 12, particularly preferably 7 to 11.

The balance of the cleaning composition of the present invention is water. However, alcohols such as ethanol, ethylene glycol, etc., which are used as a stabilizer and a viscosity reducing agent for general liquid cleaning compositions, have a molecular weight of 1000 or less. Glycols such as polyethylene glycol and paratoluenesulfonic acid may be added as long as the detergency is not impaired.

Other optional components include polyvalent carboxylate having a divalent metal ion trapping ability, such as nitrilotriacetate, ethylenediaminetetraacetate, iminodiacetate, diethylenetriaminepentaacetate, and glycoletherdiaminetetraacetate. , Aminopolyacetates such as hydroxyethyliminodiacetate and triethylenetetramine hexaacetate,
Sequestering agents such as malonic acid, succinic acid, diglycolic acid, malic acid, tartaric acid, citric acid and salts thereof.
1 to 20% by weight; polyacrylic acid, polymaleic acid, carboxymethylcellulose, polyethylene glycol having an average molecular weight of 5000 or more, maleic anhydride-diisobutylene copolymer, maleic anhydride-methylvinyl ether copolymer, maleic anhydride-isobutylene copolymer Polymer, maleic anhydride-vinyl acetate copolymer, naphthalene sulfonate formalin condensate, and JP-A-59-626
No. 14 (page 1, column 3, line 5 to page 3, column 4, line 14) the anti-staining agent and dispersant for polymers and the like according to claim 1; and 0.01 to 10% by weight; color transfer such as polyvinylpyrrolidone 0.01 to 10% by weight of a bleaching agent such as sodium percarbonate or sodium perborate; tetraacetylethylenediamine, JP-A-6-31670
Bleaching activators such as bleach activators represented by general formulas (I-2) to (I-7) of No. 0 0.01 to 10% by weight; enzymes 0.001 such as amylase, protease, lipase and cellulase 0.002 to 2% by weight; enzyme stabilizers such as calcium chloride, calcium sulfate, formic acid, and boric acid (boron compound) 0.001 to 2% by weight; 0.001 to 1% by weight of a fluorescent dye such as a silicone derivative; 0.01 to 2% by weight of a soft base such as a silicone derivative;
0.01 to 2% by weight of antifoaming agent such as silicone; antioxidant 0.0 such as butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium hydrogen sulfite
1-2% by weight; bluing agents; fragrances; antimicrobial preservatives and the like.

[0027]

The cleaning composition of the present invention is excellent in usability without solidification or excessively high viscosity even when left at a low temperature, and can impart flexibility to a target garment, and It has the feature of being excellent in detergency, especially in detergency during coating.

[0028]

EXAMPLES Synthesis Example 1 (Synthesis of pentyl monoglyceryl ether) n-pentyl alcohol (1.78 mol), 3.61 g of aluminum triisopropoxide (17.7 mmol)
l) and 9.40 g (5.4) of p-phenolsulfonic acid
mol) was placed in a 1 L reaction vessel and heated to 90 ° C. while stirring. After further stirring under reduced pressure (200 mmHg) for 1 hour, the temperature was raised to 100 ° C., and 170 g of epichlorohydrin was added.
Was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours. The reaction mixture is kept at 50 ° C. and a 48% aqueous sodium hydroxide solution 80
0 ml was dropped in 1 hour, and after stirring for 3 hours, 400 m
1 of water was added and the layers were separated. After removing the aqueous layer, the oil layer was washed twice with 500 ml of water to obtain 280 g of a crude reaction product. Next, 140 g of the crude reaction product, 140 g of water, 7.64 g of lauric acid and 2.14 g of potassium hydroxide were placed in a 2 L autoclave, and the temperature was raised to 157 ° C. while stirring.
After stirring for 5 hours, cooled to room temperature, the reaction was extracted with ethyl acetate 500 ml, and further washed twice with water 300 ml, the ethyl acetate was distilled off under reduced pressure, the R ¹ in the general formula (I) Pentyl monoglyceryl ether of n-pentyl group was obtained.

Synthesis Example 2 (Synthesis of octyl monoglyceryl ether) In Synthesis Example 1, n-pentyl alcohol was used instead of n-pentyl alcohol.
In the same manner except that 1.78 mol of -octanol was used, octyl monoglyceryl ether in which R ¹ in the general formula (I) was an n-octyl group was obtained.

Example The detergent compositions shown in Table 1 were prepared, and the following compositions were evaluated for detergency, low-temperature stability, and flexibility using the resulting compositions. Table 1 shows the results.

[Evaluation of Detergency] Eli stain test piece A cotton / polyester blended shirt worn for three days was cut and collected, and the Eli pieces were divided into five groups according to the degree of dirt. Wash evaluation was performed using the Eri pieces of the group No. 1. Washing conditions A two-tank type washing machine (Toshiba Galaxy 3.6 VH-360S1) was prepared, 40 L of tap water was poured into the washing tub, and 1.4 was added thereto.
kg of cotton underwear and 0.6 kg of cotton / polyester blended underwear shirt. 30 × 30
One piece of five pieces of cloth for sewing evaluation sewn on a cotton cloth of cm ² is prepared, put into a washing tub, and 26.67 mL of the detergent composition shown in Table 1 is further put therein and washed normally for 10 minutes. Then one
And then rinse with running water at a flow rate of 15 L / min for 8 minutes. After that, it is dehydrated for 5 minutes and air-dried indoors. Detergency Evaluation Criteria One skilled panelist (hereinafter referred to as one skilled panelist) judged the elimination dirt cleaning ability according to the following criteria. Table 1 shows the results. ；: Satisfactory level with dirt removed. ▽: Satisfactory level with slight dirt remaining.

The reliability of the result of this judgment by one skilled panelist was confirmed by a paired comparison method of Scheffe by ten other panelists. In other words, among the Eri stain test pieces determined by one skilled panelist, ○ and ▽, △ and △,
When the other 10 panelists tested the test pieces adjacent to each other as samples as Δ and × by the Scheffe's one-pair comparison method, the result of judgment for one experienced panelist was significantly different with a 95% confidence limit. It was determined to be.

[Evaluation of low-temperature stability] A 50-mL sample bottle (No. 6 wide-mouthed standard bottle, made of glass, 40 m in diameter)
m, a cylindrical shape having a height of 80 mm) was filled with 40 mL of the cleaning composition shown in Table 1 and capped, followed by standing in a constant temperature room at −5 ° C. for 30 days. The stability of the composition was visually evaluated based on the following criteria. ；: Uniform liquid phase, excellent in fluidity. Δ: Uniform liquid phase, but slightly poor fluidity. X: separated or precipitated.

[Evaluation of Flexibility] Preparation of Pretreatment Cloth A two-tank type washing machine (Toshiba Galaxy 3.6 VH-360S1) was prepared, 40 L of tap water was poured into the washing tub, and a total of 2.0 kg was added thereto. Mix cotton towels, cotton melias underwear, and acrylic jersey. Further, a compact type powder detergent is charged according to the standard usage amount, and washed for 10 minutes, dehydrated for 1 minute, rinsed with running water for 8 minutes (water amount of 15 L / min), and dried in a dryer. This washing cycle is repeated five times to obtain a pre-treated cloth. Evaluation method 30 L of tap water is poured into the washing tub of the washing machine, and two cotton towels, two cotton Melias underwear and one acrylic jersey are put among the pretreatment cloths for evaluating flexibility. Table 1
20 ml of the detergent composition of Example 1 and wash for 10 minutes.
Next, dehydrate for 1 minute, and rinse with 30 L of tap water twice for 5 minutes. Finally, it was dehydrated for 1 minute, air-dried indoors, and allowed to stand in a constant temperature / humidity room at 20 ° C./65% RH for one day. Evaluation criteria for flexibility Two cotton towels, two cotton melias underwear, and one acrylic jersey were evaluated as follows by comparing the unwashed products with the hand. +2 points Softer than unwashed items; +1 point Same as unwashed items; 0 points or more are scored by five skilled panelists and determined as a total of 5 pieces of clothing judged The flexibility was compared on average.

[0035]

[Table 1]

The pH of each of the compositions in Table 1 was adjusted to 10.5 with sodium hydroxide. The components in Table 1 are as follows. -Nonionic surfactant a: linear first having 10 to 14 carbon atoms
Non-ionic surfactant b: A linear secondary alcohol having 10 to 14 carbon atoms added with an average of 12 mol of EO Nonionic surfactant c: Non-ionic surfactant c: Non-ionic surfactant c: C1-C14 straight-chain first
5 mol of EO on average, 2 mol of PO on average,
EO in which blocks are added in order of 3 mol on average. Cationic surfactant d: mono long chain alkyl (having 1 carbon atom)
6/18, the ratio of C16 to C18 is 3/7) trimethylammonium chloride LAS-S agent: linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms Glyceryl ether e: Pentyl monoglyceryl ether of Synthesis Example 1 Glyceryl ether f: octyl monoglyceryl ether of Synthesis Example 2

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Akira Ishikawa 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term in Kao Corporation Research Laboratory 4H003 AB19 AC08 AC09 AC23 AE05 BA12 DA01 DA03 DB01 EA12 EB04 EB06 EB14 ED02 ED28 FA22 FA35

Claims (5)

[Claims] (1) 0.1 to 20% by weight of a compound represented by the following general formula (I) and (b) a surfactant 30 to 60:
% By weight. R ¹ -OCH ₂ CH (OH) CH ₂ OH (I) wherein R ¹ represents a hydrocarbon group having ¹ to 16 carbon atoms. ] 2. The compound of the formula (I) wherein R ¹ has 4 to 10 carbon atoms.
The cleaning composition according to claim 1, which is a hydrocarbon group. 3. The cleaning composition according to claim 1, wherein the surfactant is a nonionic surfactant and / or a cationic surfactant. 4. The cationic surfactant according to the following general formula (I)
The cleaning composition according to claim 3, which is a cationic surfactant represented by I). Embedded image [Wherein one or two of R ² , R ³ , R ⁴ and R ⁵ are the same or different and are a hydrocarbon group having 12 to 22 carbon atoms, and the rest are the same or different and are a hydrogen atom, a carbon atom number; 1-4 alkyl group, hydroxyalkyl group or _{- (CH 2 CH 2 O)} k H
(Where k is 1 to 15), X is a halogen atom, CH ₃ S
O ₄ , C ₂ H ₅ SO ₄ , CH ₃ COO or HCOO is shown. ] 5. The cleaning composition according to claim 1, which is used for coating and cleaning.