JP2000178600A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition, which is capable of improving a softening effect on and an infiltration in clothes, by comprising a nonionic surface active agent and an amino-modified silicone derivative. SOLUTION: Five to fifty wt.% of a nonionic surface active agent of formula I and 0.05 to 5 wt.% of an amino-modified silicone derivative of formula II are dissolved in water. In the formulas, R represents 8-20C alkyl or alkenyl; EO represents ethylene oxide; PO represents propylene oxide; (j) and (k) are each the number of average addition moles provided that (j) is 6 to 14 and (k) is 1 to 4 so that EO and PO may independently represent a random adduct or block adduct; (l) is 100 to 600; (m) and (n) are such that l:m=100 to 10:1 and m:n=10:1 to 1:10; R1 represents 1 to 4C alkyl, hydroxyl or the like, R2 represent 1-4 alkyl; A is of formula III to V provided that a group of formula IV in A is 50 mole% or below, (in which (a) and (b) are each 2 to 6; R3 represents h or 1-4C alkyl; (p) is 1 to 6; (q) is 1 to 20; (r) is 0 to 20; and R4 1-8C alkyl); and B is of formula VI wherein R5 is 1-10C alkyl or R2; (x) is 1 to 20; and (y) is 0 to 20.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid detergent composition.

[0002]

2. Description of the Related Art Conventionally, liquid detergents have a soft image on clothing such as cotton, linen, and synthetic fibers, and therefore, liquid detergents having a softening effect on clothing. Has been developed for a long time. JP-A-60-215099, JP-A-9-67
JP-A 594 describes that a detergent containing an amino-modified silicone or a derivative thereof has an excellent softening effect or an excellent felt contraction preventing effect. Further, JP-A-10-60480 discloses that a detergent containing an amino-modified silicone derivative and a specific nonionic surfactant has an appropriate detergency and is excellent in texture and dimensional stability. ing. However, the softening effect on clothing by these techniques is insufficient, and development of a liquid detergent having an excellent softening effect is desired.
In addition, clothes such as wool are not sufficiently wet with water-based washing liquid and have poor penetrability into the inside of fabrics, etc., so that the washability is insufficient, and improvement in this respect is strongly desired. ..

[0003]

[In the formula, R represents an alkyl group or an alkenyl group having 8 to 20 carbon atoms, EO represents ethylene oxide, and PO represents propylene oxide. j and k are average addition mole numbers, j is 6 to 14, and k is 1 to 4. EO and PO may be either random adducts or block adducts, and the order of adding EO and PO does not matter. ]

[0004]

[Chemical 3]

[Wherein l=100 to 600, m,
n is l:m=100:1 to 10:1, and m:n=1:
The number is 10 to 10:1. R ¹ is an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an alkoxy group, R 1
² is an alkyl group having 1 to 4 carbon atoms, which may be different from each other. A is a group represented by the following (a) or a group represented by (i) and (b)

[0006]

[Chemical 4]

(Here, a=2-6, b=2-6, R ³
Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p=1 to
6, q=1 to 20, r=0 to 20, R ⁴ has 1 to 1 carbon atoms
8 alkyl group), and in the latter case, the proportion of (b) in A is 50 mol% or less. The B - (CH _{2) a} -O-
_{(C 2 H 4 O) x} - (C 3 H 6 O) y -R 5 ( wherein, R ⁵ is an alkyl group having 1 to 10 carbon atoms, x = 1~20, y = 0~2
0) or R ² . ]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) is represented by the general formula (I) above.
Is a nonionic surfactant represented by. In the general formula (I), R is a linear alkyl group having 10 to 14 carbon atoms, j
Is preferably 6 to 12, particularly 8 to 10, and k is preferably 1 or 2. In the general formula (I), EO and PO may be random addition, or block addition in which EO is added and then PO is added, or vice versa.

As the nonionic surfactant of the general formula (I), those which are usually commercially available may be used, and EO and PO may be added to alcohols synthesized by a known method or derived from natural fats and oils. Can be manufactured by adding.

Particularly, as the nonionic surfactant of the general formula (I), the nonionic surfactant represented by the following general formula (I)-1 is preferable in terms of stability. _{^{R 'O (EO) u (}} PO) v (EO) w H (I) -1 wherein ^R' represents an alkyl or alkenyl group having 8 to 20 carbon atoms, EO, PO are as defined above. u, v and w represent the average number of moles added, u>0, v=1 to 4, w>0,
u+v+w=6 to 14, u+w=6 to 12. Preferably u+v+w=8-14, especially 10-12, u+w
=6-12, especially 8-10, v=1-2. The nonionic surfactant represented by the general formula (I)-1 is obtained by adding EO and PO in this order to an alcohol synthesized by a known method or derived from a natural fat and oil, and then adding EO again. Is synthesized by.

The liquid detergent composition of the present invention preferably contains the nonionic surfactant represented by the general formula (I) in an amount of 5 to 50% by weight, particularly 10 to 50% by weight.

The silicone derivative represented by the above formula (II) which is the component (b) of the present invention contains 0.05 to 5 in the composition.
It is preferable to blend the composition in an amount of 0.1% by weight, especially 0.1 to 3% by weight, from the viewpoint of the softening effect on clothes. The silicone derivative of the formula (II) has a softening effect of 1=100 to 400,
1:m=60:1 to 10:1, m:n=1:5 to 5:
1, R ¹ and R ² are methyl groups, A is (a) or a mixture of (a) and (b) [where (a)/(b)=5 to 1/1/
1 (molar ratio), a = 2 to 4, R ³ is a hydrogen atom, p = 1 to
3, q=1 to 15, r=0 to 10, R ⁴ has 6 to 1 carbon atoms
6 alkyl group], the _{B - (CH 2) a -O-} (C 2 H 4 O) x
_{- (C 3 H 6 O)} y -R 5 ( wherein, R ⁵ is a methyl group, x = 5
˜20, y=0 to 10) or R ² is preferred.

In the present invention, the following nonionic surfactants (1) to (3) can be used in combination. (1) A polyoxyethylene alkyl or alkenyl ether obtained by adding 1 to 20 mol of EO on average to an alcohol having an alkyl group or an alkenyl group having 8 to 20 carbon atoms. (2) An alkyl polysaccharide surfactant represented by the following general formula (IV). R ⁶ —(OR ⁷ ) _s G _t (IV) [wherein R ⁶ is an alkyl group or an alkenyl group having 8 to 18 carbon atoms, or an alkylphenyl group, and R ⁷ is 2 to 2 carbon atoms].
4 is an alkenyl group, G is a residue derived from a reducing sugar having 5 or 6 carbon atoms, s is a number having an average value of 0 to 6, and t is an average value of 1 to 10.
Indicates the number of (3) Fatty acid alkanolamide and polyhydroxy fatty acid amide. The nonionic surfactants (1) to (3) are preferably added to the composition in an amount of 1 to 30% by weight.

Anionic surfactants such as alkylbenzene sulfonates and polyoxyalkylene alkyl ether sulphates are used to improve detergency, and fatty acid salts derived from beef tallow or coconut are used in combination for low foaming properties. Is preferred. Further, as the counterion of these anionic surfactants, ions derived from alkali metals such as sodium and potassium, alkaline earth metals such as magnesium, alkanolamines such as mono-, di- and triethanolamine can be used. .. Particularly, sodium, potassium and monoethanolamine are preferable. The anionic surfactant is preferably incorporated in the composition in an amount of 1 to 20% by weight.

Further, an amphoteric surfactant may be added in view of the stability of the liquid and the cleaning property of mud stains. As the amphoteric surfactant, alkylcarbobetaine, alkylsulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine-type betaine, alkylimidazoline-type betaine and the like can be blended. The amphoteric surfactant is preferably incorporated in the composition in an amount of 1 to 20% by weight.

Further, in the detergent composition of the present invention, alkali metal hydroxides, silicates, carbonates such as sodium carbonate, and alkali agents such as alkanolamines of 0.01 to
10% by weight; alcohols such as ethanol, glycols such as ethylene glycol and propylene glycol,
Paratoluene sulfonic acid, benzoate (also effective as a preservative), and thinning agent and solubilizing agent such as urea 0.0
1 to 30% by weight; 0.01 to 10% by weight of phase modifiers and detergency improvers such as polyoxyalkylene benzyl ether and polyoxyalkylene phenyl ether; nitrilotriacetic acid salt, ethylenediaminetetraacetic acid salt, iminodiacetic acid salt,
Aminopolyacetates such as diethylenetriamine pentaacetate, glycol ether diamine tetraacetate, hydroxyethyliminodiacetate and triethylenetetramine hexaacetate, malonic acid, succinic acid, diglycolic acid, malic acid,
Metal ion scavengers such as salts of tartaric acid and citric acid 0.1
~ 20 wt%; polyacrylate, polymaleate,
Carboxymethyl cellulose, polyethylene glycol having an average molecular weight of 5000 or more, acrylic acid-maleic acid copolymer or a salt thereof, maleic anhydride-diisobutylene copolymer or a salt thereof, maleic anhydride-methyl vinyl ether copolymer or a salt thereof, anhydrous Maleic acid-isobutylene copolymer or its salt, maleic anhydride-vinyl acetate copolymer or its salt, naphthalene sulfonate formalin condensate, and claims 1 to 6 of JP-A-59-62614.
21 (page 1, column 3, line 5 to page 3, column 4, line 14) 0.01 to 10% by weight of anti-soil redeposition agent and dispersant such as polyvinylpyrrolidone; %; bleaching agents such as sodium percarbonate or sodium perborate 0.01 to 10% by weight; tetraacetylethylenediamine, general formula (I-2) of JP-A-6-316700
Bleach activator such as a compound represented by (I-7) 0.01
0.001 to 2% by weight of enzymes such as amylase, protease, lipase and cellulase; 0.001 to 2% by weight of enzyme stabilizers such as calcium chloride, calcium sulfate, formic acid and boric acid (boron compound) Chino Pearl CBS (manufactured by Ciba Geigy) and Whitex SA(
0.001 to 1% by weight of fluorescent dyes such as Sumitomo Chemical Co., Ltd.; 0.01 to 2% by weight of antifoaming agents such as silica and silicone; Oxidation of butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium hydrogen sulfite. Inhibitors 0.01 to 2% by weight; bluing agents; fragrances; antimicrobial preservatives and the like can be added. The composition of the present invention has the above (a)
And (b) component, an optional component, and the balance water. The cleaning composition of the present invention is intended for cleaning clothes such as cotton, hemp, and synthetic fibers, and preferably has a pH of 8-11.

[0017]

Example 1 A liquid detergent composition shown in Table 1 was prepared, and the following softness and permeability were evaluated. The results are shown in Table 1.

(1) Softness evaluation Preparation of pre-treated cloth Automatic two-tub type washing machine (Toshiba, Galaxy 3.6 VH-36
Put 40 liters of tap water into the 0S1) washing tub, and add a total of 2.0 kg of cotton towel, cotton underwear without Melias, and acrylic jersey. Furthermore, compact type powder detergent is added according to the standard usage amount, and washed for 10 minutes, 1
Partially dehydrated, rinsed with running water for 8 minutes (water volume of 15 liters/minute), and dried in a dryer. This washing cycle is repeated 5 times to obtain a pretreated cloth.

Evaluation Method 30 liters of tap water is put in the above-mentioned washing tub, and two pieces of cotton towels, two pieces of cotton Melias non-wearing underwear and one piece of acrylic jersey are put in the pretreatment cloth for evaluating flexibility. Further, 20 mL of the liquid detergent composition shown in Table 1 is put therein and washed normally for 10 minutes. Next, it is dehydrated for 1 minute, and then rinsed with 30 liters of tap water for 5 minutes x 2 times and rinsed. Finally, it was dehydrated for 1 minute, air-dried indoors, and allowed to stand for 1 day in a thermo-hygrostat at 20° C./65% RH.

Criteria for Judgment: Two cotton towels, two cotton Melias non-wearing underwear, and one acrylic jersey, a total of 5 sheets, were evaluated as follows by comparing the unwashed product and the touch. It is considerably softer than unwashed items; +2 points Softer than unwashed items; +1 point Same as unwashed items; 0 points or more are evaluated by 5 trained panelists The flexibility was evaluated by the average value.

(2) Preparation of penetrability test piece A wool jersey knit cloth was cut into 2.0 cm×2.0 cm and used as a wool test piece.

Preparation of Hard Water Calcium chloride (dihydrate) 105m
g was weighed out, dissolved in distilled water to 1 L, and hard water was used.

Preparation of detergent solution for evaluation 1.333 g of each of the liquid detergent compositions shown in Table 1 was weighed and dissolved in the above hard water to prepare 1 L of solution. 10.5 cm in diameter and 1 in height with these cleaning agent aqueous solutions for evaluation.
It was put in a beaker of 4.5 cm and evaluated. The temperature of the solution was controlled at 20°C.

Evaluation Method The above-mentioned wool test piece was gently placed horizontally on the above-mentioned solution surface, the time from the moment of contact with water until the wool test piece left the water surface and entered the water was measured, and the time was permeated. It was time. The measurement was performed 5 times, and the average value was adopted. Evaluation criteria ○: Penetration time of less than 60 seconds (good permeability) △: Penetration time of 60 seconds or more and less than 100 seconds (penetrability is poor) ×: Penetration time of 100 seconds or more (poor permeability)

[0025]

[Table 1]

The components used in Table 1 are shown below. Nonionic surfactant (1a): linear primary alcohol having 10 to 14 carbon atoms, 5 mol of EO on average and 2 mol of PO on average.
Molar, EO averaged in the order of 3 moles block-added ・Nonionic surfactant (1b): average 10 moles EO and average 2 POs in a linear primary alcohol having 10 to 14 carbon atoms
Mol, EO block-added in the order of 3 mol on average Nonionic surfactant (1c): 5 mol of EO and 1.5 mol of PO on average in a linear primary alcohol having 10 to 14 carbon atoms. , EO having an average of 5 moles added in a block order ・Nonionic surfactant (2d): an average of 7 moles of EO added to a linear secondary alcohol having 10 to 14 carbon atoms ・Nonionic surface activity Agent (2e): Linear secondary alcohol having 10 to 14 carbon atoms, containing 6 mol of EO on average and 1 mol of PO on average.
Molecule added ・Nonionic surfactant (2f): average of 8 moles of EO and average of 1 mole of PO in linear secondary alcohol having 10 to 14 carbon atoms
Molar random addition ・Nonionic surfactant (3 g): C10-14 linear primary alcohol with 10 mol of EO added on average ・Silicone h: Structure in general formula (II) Are the following compounds R ¹ :CH ₃ , R ² :CH ₃ , A: (a)-(CH ₂ ) ₃ -NH-CO-CH ₂ -O-
A mixture of (C ₂ H ₄ O) ₅ -C ₁₂ H ₂₅ and (b)-(CH ₂ ) ₃ -NH ₂ ,
(A) / (b) = 7/3 (molar _{ratio), B :-( CH 2) 3} -O- (C
₂ H ₄ O) ₁₀ -CH ₃ , l=300, m=7, n=4 Silicone i: a compound having the following structure in general formula (II): R ¹ : CH ₃ , R ² : CH ₃ , A :( _{b) - (CH 2) 3 -NH} -CO-CH 2 -O-
(C ₂ H ₄ O) ₅ -C ₁₂ H ₂₅ , B:-CH ₃ , l=300, m=7, n
= 4 Silicone j: General compound structure of the following formula _{^{(II) R 1: CH 3}} , R 2: CH 3, A :( b _{-1) - (CH 2) 3} -NH-CO-CH
_{2 -O- (C 2 H 4 O} ) 5 -C 12 H 25 and (b _{-2) - (CH 2) 3} -NH-CO-CH 2
-O-(C ₂ H ₄ O) ₅ -C ₁₄ H ₂₉ mixture, (I-1)/(I-2)
= 7/3 (molar _{ratio), B :-( CH 2) 3} -O- (C 2 H 4 O) 10 -CH 3,
1=200, m=14, n=8 LAS-S agent: linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms Fatty acid: coconut oil fatty acid having 12 to 14 carbon atoms Cationic surfactant: carbon number 16-18 monoalkyltrimethylammonium chloride (C16 and C18)
Polymer compound: maleic anhydride diisobutylene copolymer (maleic anhydride/diisobutylene molar ratio is 6/)
4, average molecular weight 5000)-Polyethylene glycol phenyl ether: polyoxyethylene monophenyl ether (EO average 3 mol addition)-Enzyme: Durazyme 16.0 L (protease, manufactured by Novo Nordisk BioIndustry Co., Ltd.)-Fluorescent dye: Chinopearl CBS -X (manufactured by Japan Ciba-Geigy Co., Ltd.)-Balance: The amount for making the whole 100% by weight.

As shown in Table 1, each of the products 1 to 7 of the present invention is excellent in the softening effect on clothes and the permeability to clothes. On the other hand, since Comparative product 1 does not contain the amino-modified silicone derivative (b), it has excellent permeability but is poor in softening effect on clothing. The comparative products 2 and 3 are
Since it does not contain the nonionic surfactant (a), its permeability to clothes is particularly poor.

[0028]

EFFECT OF THE INVENTION The liquid detergent composition of the present invention is excellent in the softening effect on clothes and also excellent in the permeability to clothes.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kuniyoshi Shigematsu 1334 Minato Minato, Wakayama, Wakayama Kao Corporation Research Laboratory F-term (reference) 4H003 AB19 AC08 AC09 AC23 BA12 DA01 EA12 EB07 EB14 EB25 EB32 EC01 ED02 ED28 ED29 FA22

Claims (1)

[Claims] 1. A liquid detergent composition containing (a) a nonionic surfactant represented by the following general formula (I) and (b) an amino-modified silicone derivative represented by the following general formula (II). RO(EO) _j /(PO) _k H (I) [In the formula, R represents an alkyl group or an alkenyl group having 8 to 20 carbon atoms, EO represents ethylene oxide, and PO represents propylene oxide. j and k are average addition mole numbers, and j
Is 6 to 14, and k is 1 to 4. EO and PO may be either random adducts or block adducts, and EO and P
The order of adding O does not matter. ] [Chemical 1] [Wherein, l=100 to 600, and m and n are l:m=
100:1 to 10:1, and m:n=1:10 to 10:
The number is 1. R ¹ is an alkyl group having 1 to 4 carbon atoms,
It is a hydroxy group or an alkoxy group, and R ² has 1 carbon atom
To 4 alkyl groups, which may be different from each other. A
Is a group represented by the following (a) or a group represented by (a) and (b): (Here, a=2 to 6, b=2 to 6, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p=1 to 6, q=1 to 2
0, r=0 to 20, R ⁴ is an alkyl group having 1 to 18 carbon atoms), and in the latter case, the proportion of (b) in A is 50 mol% or less. The _{B - (CH 2) a -O-} (C 2 H 4 O) x -
_{(C 3 H 6 O) y} -R 5 ( wherein, R ⁵ is an alkyl group having 1 to 10 carbon atoms, x = 1~20, y = 0~20 ) is or R ^2. ]