JP2002249799A - Liquid detergent composition - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To provide a liquid detergent composition having an excellent softening effect on cotton clothing and an excellent color care effect. SOLUTION: a) A silicone derivative of the general formula I, b)
A liquid detergent composition comprising at least one selected from a quaternary ammonium salt having a C8-36 hydrocarbon group and a tertiary amine having a C8-36 hydrocarbon group or an acid salt thereof. [1 is 100-600, m and n are 1: m = 100: 1-
10: 1, and m: n = 1: 10 to 10: 1.
R is an alkyl group of C1 -4, hydroxy group or an alkoxy group, ^{R 1} is an alkyl group C1 -4. A is a group a or a +
In the latter case, the ratio of the latter is 50 mol% or less. (A and b are 2 to 6, R ² is H or a C1 to 4 alkyl group, p is 1 to 6, q is 1 to 20, r is 0 to 20, R ³ is a C1 to 18 alkyl group), the B _{- (CH} 2) a -O-
_{(C 2 H 4 O) s} - (C 3 H 6 O) t -R 2 ' or ^{R 2}
(R ^{2 ′} is a C1-10 alkyl group, s is 1-20, t
Is 0 to 20)]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition having an excellent softening effect on cotton clothing and an excellent color care effect.

[0002]

2. Description of the Related Art Conventionally, liquid detergents have a soft image for clothing, and therefore, liquid detergents having a softening effect on clothing have been developed. Was. JP-A-60-21
JP-A-5099 and JP-A-9-67594 describe that a detergent containing an amino-modified silicone or a derivative thereof has an excellent softening effect or an excellent felt shrinkage preventing effect. Also, Japanese Patent Application Laid-Open No. H10-604
No. 80 describes 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. However, the softening effect of clothing, especially cotton fiber products by these techniques is insufficient, and it is desired to develop a liquid detergent having a more excellent softening effect. Further, in addition to the above-mentioned softening effect, it is desirable that the detergent composition also has an excellent color care effect for preventing fading of clothing due to repeated washing, but the above-mentioned technology does not mention improvement of the color care effect.

[0003]

The present invention relates to (a) a silicone derivative represented by the following general formula (I) [hereinafter, (a)
(B) a hydrocarbon group having 8 to 36 carbon atoms
Liquid detergent containing at least one quaternary ammonium salt having at least one tertiary amine having at least one hydrocarbon group having 8 to 36 carbon atoms or an acid salt thereof (hereinafter, referred to as component (b)) Composition.

[0004]

Embedded image

[Wherein l = 100-600, m,
n is l: m = 100: 1 to 10: 1, and m: n = 1:
The number is 10 to 10: 1. R is an alkyl group, hydroxy group or an alkoxy group having 1 to 4 carbon atoms, R ¹
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 the following (A) and (B), and in the latter case, the (B) in A
Is 50 mol% or less.

[0006]

Embedded image

(Where a = 2 to 6, b = 2 to 6, R ²
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 ³ has 1 to 1 carbon atoms
8), B is-(CH ₂ ) _a -O- (C ₂ H ₄ O) _s- (C
^{_{3 H 6 O) t -R 2}} ' or R ² (wherein, R ^2' is from 1 to 10 carbon atoms
Alkyl group, s = 1 to 20, t = 0 to 20).
When -C ₂ H ₄ O- and -C ₃ H ₆ O- are present in the formula (I), block addition or random addition may be performed. ]

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <(a) Component> Liquid washing of the present invention
The agent composition is represented by the formula (I), which is the component (a).
0.05 to 15% by weight of the silicone derivative, and 0.1% by weight
05 to 10% by weight, especially 0.1 to 5% by weight
Is preferred from the viewpoint of a softening effect on clothing. The formula
As the silicone derivative (I), in terms of the softening effect,
l = 100-400, l: m = 60: 1-10: 1,
m: n = 1: 5 to 5: 1, R and R¹Is a methyl group, A is
(A) or a mixture of (a) and (b) [where (a) /
(B) = 5/1 to 1/1 (molar ratio), a = 2 to 4, R^Two
Is a hydrogen atom, p = 1-3, q = 1-15, r = 0-1
0, R^ThreeIs an alkyl group having 6 to 16 carbon atoms], and B is-(C
H_Two)_a-O- (C_TwoH_FourO) _s-(C_ThreeH₆O)_t-R^{1 '}Or R¹(here
In R^{1 '}Is a methyl group, s = 5 to 20, t = 0 to 10)
Is preferred. Incidentally, in the general formula (I), -C_TwoH_FourO- and-
C_ThreeH₆If O- is present, the
May be added, but the addition of a block is
preferable.

The silicone derivative of the formula (I) can be obtained by the method described in claim 1 of JP-B-56-29691.

<Component (b)> As the component (b) of the present invention, those having at least one ester group and / or amide group in the molecule are preferable, and in particular, compounds represented by the following general formula (II) And / or a compound represented by the following general formula (III) or a salt thereof is preferable.

[0011]

Embedded image

[Where R^FourHas 8 to 36 carbon atoms, preferably
10 to 24, particularly preferably 12 to 20 alkyl groups or
Is an alkenyl group, and R^FiveHas 1 to 5 carbon atoms, preferably
Is an alkylene group of 1-3, and X is -COO-, -C
ONR⁹-, -OCO-, -NR⁹A group selected from CO-
It is. Where R⁹Is a hydrogen atom, an alkyl having 1 to 3 carbon atoms
Or a hydroxyalkyl group, preferably hydrogen
Is an atom. R⁶, R⁷Each independently has 1 to 3 carbon atoms
Alkyl group or hydroxyalkyl group or R ^Four-X
-R^Five-, R⁸Is an alkyl group having 1 to 3 carbon atoms or hydride
A roxyalkyl group;^-Is an inorganic or organic anion
, Preferably halogen ion, sulfate ion, phosphate ion
ON, alkyl sulfate ion having 1 to 3 carbon atoms, charcoal
It is a fatty acid ion having a prime number of 1 to 12, particularly preferably
Rogen ion, sulfate ion, alkyl sulfur having 1 to 3 carbon atoms
It is an acid ester ion. ].

The compound represented by the formula (II) and / or the compound represented by the general formula (III) is disclosed in
No. 230001, paragraphs 0008 to 0020, etc.

The liquid detergent composition of the present invention comprises the component (b), preferably the compound represented by the formula (II) and / or (III), in an amount of 0.05 to 15% by weight, more preferably 0.05 to 15% by weight. ~
The content of 10% by weight, particularly 0.1 to 5% by weight, is preferable in view of the softening effect on clothing.

The total amount of the components (a) and (b) of the present invention is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, particularly preferably 0.2 to 20% by weight in the composition. ~
10% by weight, and the weight ratio of component (a) / component (b) is 1/5 to 5/1, more preferably 1/3 to 3/1, and even more preferably 1
/ 2 to 2/1, especially 1 / 1.2 to 1.2 / 1, more particularly about 1/1 is preferred in view of the softening effect on clothing, especially cotton products.

<Other Components> In the present invention, a surfactant which is conventionally known to be incorporated into a liquid detergent composition can be used. In order to enhance detergency, it is preferable to use an anionic surfactant or a nonionic surfactant as a main surfactant. When used in combination with a cationic surfactant to further enhance flexibility, a nonionic surfactant is preferably used as the main surfactant.

As the anionic surfactant, a compound having 10 carbon atoms
Alkali metal salts such as linear alkyl benzene sulfonates having an alkyl chain of from 18 to 18, alkyl sulfates, polyoxyalkylene alkyl ether sulfates, and alpha sulfo fatty acid alkyl (eg, methyl) ester salts are preferred, and are derived from tallow or coconut May be added in small amounts.

As the counter ion of the anionic surfactant, an alkali earth metal such as magnesium and / or an alkanolamine such as mono, di, triethanolamine and the like are used in addition to the alkali metal such as sodium and potassium. In particular, the use of alkanolamine is preferable since the liquid stability is improved. In that case, the content of the anionic surfactant in the composition is 5 to 50% by weight, particularly 10% by weight.
~ 50% by weight is preferred.

As the nonionic surfactant, the following (1)
~ (4) can be used. (1) having an alkyl group derived from a linear primary alcohol or a linear secondary alcohol having an average carbon number of 8 to 20 or an alkyl group or an alkenyl group derived from a branched alcohol, and ethylene oxide (hereinafter referred to as EO); 1 to 2 on average
Polyoxyethylene alkyl or alkenyl ether to which 0 mol has been added. (2) Polyoxy having an alkyl group or an alkenyl group having an average carbon number of 8 to 20, and having an average of 1 to 15 mol of EO and an average of 1 to 5 mol of propylene oxide (hereinafter referred to as PO). Alkylene alkyl or alkenyl ether. In this case, EO and PO may be either random addition or block addition. (3) An alkyl polysaccharide surfactant represented by the following general formula (IV). _{^{R 10 - (OR 11) i}} G j (IV) : wherein, R ¹⁰ is a straight or branched chain alkyl group having 8 to 18 carbon atoms, an alkenyl group, or alkylphenyl group, R ¹¹
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, i is a number having an average value of 0 to 6, and j is a number having an average value of 1 to 10. (4) Fatty acid alkanolamides and polyhydroxy fatty acid amides.

In particular, the polyoxyalkylene alkyl ether (1) or (2) is preferable from the viewpoint of oily soil detergency. Further, the content of the nonionic surfactant in the composition is preferably 5 to 50% by weight, particularly preferably 10 to 50% by weight.

In order to further improve the flexibility of clothing, etc., a cationic surfactant such as a mono-long-chain alkyl quaternary ammonium salt is added to the composition in an amount of 0.5 to 10% by weight, especially 1 to 5% by weight. It is preferable that the content be contained by weight. In terms of the effect of improving flexibility, the long-chain alkyl group has 12 to 22 carbon atoms, particularly 1
Long-chain alkyltrimethylammonium salts having 4 to 20 alkyl groups are preferred. The counter ion of the cationic surfactant includes a halogen ion, CH ₃ SO ₄ ⁻ , and C ₂ H ₅ S
O ₄ ^-, CH ₃ COO ^- or HCOO ^- are preferred. In order to further increase the flexibility, the cationic surfactant is anionic surfactant, cationic surfactant / anionic surfactant = 3/1 to 1/2, further 2/1 to 1/2. , Especially 1.
It is preferable to mix them in a molar ratio of 2/1 to 1 / 1.2.

As other surfactants, amphoteric surfactants may be blended in view of the stability of the liquid and the ability to clean mud. As the amphoteric surfactant, alkylcarbobetaine, alkylsulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine type betaine, alkylimidazoline type betaine and the like can be blended. The amphoteric surfactant is preferably contained in the composition in an amount of 1 to 20% by weight.

Further, the following components can be added to the cleaning composition of the present invention. Hydroxides of alkali metals, silicates, carbonates such as sodium carbonate, and alkali agents such as alkanolamines 0.01 to 10% by weight; alcohols such as ethanol; glycols such as ethylene glycol and propylene glycol; Toluenesulfonic acid, benzoate (which also has an effect as a preservative) and a thinning and solubilizing agent such as urea 0.01 to 30% by weight; phase adjustment of polyoxyalkylene benzyl ether, polyoxyalkylene phenyl ether and the like 0.01 to 10% by weight of nitrile triacetate, ethylenediaminetetraacetate, iminodiacetate, diethylenetriaminepentaacetate, glycol etherdiaminetetraacetate, hydroxyethyliminodiacetate and triethylene Aminopolyacetates such as tetramine hexaacetate, malonic acid 0.1 to 20% by weight of metal ion scavengers such as salts of succinic acid, diglycolic acid, malic acid, tartaric acid and citric acid; polyacrylic acid, polymaleic acid, carboxymethylcellulose, polyethylene glycol having an average molecular weight of 5,000 or more, anhydrous Maleic acid-acrylic acid copolymer, maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-isobutylene copolymer, maleic anhydride-vinyl acetate copolymer,
Naphthalene sulfonate formalin condensate, and claims 1 to 21 of JP-A-59-62614.
(From line 3 to column 4, line 14) 0.01 to 10% by weight of a redeposition inhibitor and dispersant such as a polymer; 0.01 to 10% by weight of a color transfer inhibitor such as polyvinylpyrrolidone; Bleach such as sodium borate 0.01 to 10
% By weight; tetraacetylethylenediamine,
Nos. 316700 and (I-2), (I-3) and (I-3)
-4), 0.01 to 10% by weight of a bleaching activator such as a bleaching activator represented by (I-5), (I-6) or (I-7); amylase, protease, lipase, cellulase, etc. 0.001 to 2% by weight of an enzyme; 0.001 to 2% by weight of an enzyme stabilizer such as calcium chloride, calcium sulfate, formic acid, boric acid (boron compound); Tinopearl CBS (manufactured by Ciba Geigy) or Whitetex SA ( (Sumitomo Chemical Co., Ltd.)
0.001 to 1% by weight of a fluorescent dye such as silica; defoaming agent such as silicone other than the component (a) 0.01 to 2% by weight; butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium hydrogen sulfite 0.01 to 2% by weight of an antioxidant; a bluing agent; a fragrance; an antimicrobial preservative;

The liquid detergent composition of the present invention comprises the above (a)
(B) It consists of a component, an optional component, and the balance of water. The pH of the liquid detergent composition of the present invention is preferably 7.5 to 9 (25 ° C), and the pH is preferably adjusted with an alkali agent or an acid agent. Examples of the alkaline agent include monoethanolamine, diethanolamine, triethanolamine, methyl monoethanolamine, dimethylethanolamine,
Alkanolamines such as 3-aminopropanol, sodium hydroxide, potassium hydroxide and the like, sodium silicate,
Inorganic salts such as sodium carbonate can be used, and one or more selected from monoethanolamine, sodium hydroxide, and potassium hydroxide are particularly preferable. As the acid agent, one or more selected from sulfuric acid, hydrochloric acid, phosphoric acid, a fatty acid having 1 to 12 carbon atoms, and an alkyl sulfuric acid having 1 to 3 carbon atoms are preferable.

[0025]

EXAMPLES Liquid detergent compositions shown in Table 1 were prepared, and the following softening effects and color care (prevention of fading) effects were evaluated using the obtained compositions. Table 1 shows the results.

[Evaluation of softening effect] (1-1) Preparation of pre-treated cloth Automatic two-tub washing machine (Toshiba Ginga 3.6 VH-360S)
1) was prepared, 40 L of tap water was poured into the washing tub, and a cotton towel and cotton Melias underwear were mixed into the washing tank so that the total weight would be 2.0 kg. In addition, compact type powder detergent (Attack, Kao Corporation) is added according to the standard usage amount,
Washed for 10 minutes, dewatered for 1 minute, rinsed with running water for 8 minutes (water volume of 15 L / min), and dried in a dryer. This washing cycle is 5
This was repeated twice to obtain a pre-treated cloth.

(1-2) Evaluation Method 30 L of tap water is poured into the washing tub of the washing machine, and two cotton towels and three cotton Melias non-wearing undergarments among the pretreatment cloths for evaluating flexibility are put. Further, the liquid detergent composition of Table 1 was added to 2
0 mL was added, and washing was performed for 10 minutes. Then dehydrate for 1 minute,
Rinse with 30 L of tap water for 5 minutes x 2 times. Finally dehydrate for 1 minute, air dry indoors, 20 ℃ / 65% R
The sample was allowed to stand in a constant temperature and humidity room of H for one day.

(1-3) Softening Effect Judgment Criteria A total of five cotton towels and three cotton Melias non-wearing undergarments were rated as follows by comparing the unwashed products with the hand. Significantly softer than unwashed items; +2 points Softer than unwashed items; +1 point Same as unwashed items; 0 points A score of 0 or more was given by five skilled panelists, and the average total score of a total of five clothes judged The softening effect was compared.

[Evaluation of Fading Prevention Effect] (2-1) Test Cloth As a test cloth, cotton broad 2023 cloth was used as a dye Cibacr.
on Blue F-GFN (manufactured by Ciba-Geigy) Prepared several pieces of a cloth dyed with a 5% aqueous solution cut to 6 cm x 6 cm,
A test cloth was used.

(2-2) Cleaning Conditions A two-tub washing machine (Toshiba Galaxy 3.6 VH-360S1) was prepared, 40 L of 20 ° C. tap water was put into the washing tub, and 1.4 kg of cotton An unworn undergarment and a 0.6 kg cotton / polyester blend unworn undergarment shirt are placed. In addition, one sheet of five test cloths for evaluation sewn on a 30 cm × 30 cm cotton cloth is prepared, placed in a washing tub, and 26.67 mL of the liquid detergent composition shown in Table 1 is further put therein and washed normally for 10 minutes. . After that, dehydrate for 1 minute and repeat rinsing twice for 4 minutes. After that, it is dehydrated for 5 minutes and air-dried indoors. This step was defined as one step, and cumulative cleaning was performed five times.

(2-3) Colorimetry Method Colorimetry is performed using a color difference meter (Nippon Denshoku Industries Co., Ltd .: ND (F) -300A).
Was used to measure the L value, a value, and b value of the test cloth, and the ΔE value was calculated from the average value of the five test cloths by the following equation. Δ
The smaller the E value, the less discoloration due to cumulative washing. ΔE = ｛(ΔL) ² + (Δa) ² + (Δb) ² ｝ ^1/2 ΔL; [L value of test cloth after cleaning (average value)] − [L value of test cloth before cleaning (average value) )] Δa; [a value (average value) of test cloth after cleaning] − [a value (average value) of test cloth before cleaning] Δb; [b value (average value) of test cloth after cleaning] − [B value (average value) of test cloth before washing]

[0032]

[Table 1]

The components used in Table 1 are shown below. Compound a-1: a compound having the following structure in the general formula (I). [R: CH ₃ , R ⁵ : CH ₃ , A: (A)-(CH ₂ ) ₃ -NH-CO-CH ₂ -O
_{- (C 2 H 4 O)} 5 -C 12 H 25 and, (ii) - a mixture of (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 ], compound a-2: Structure The following compounds of the general formula (I). [R: CH ₃ , R ⁵ : CH ₃ , A: (A)-(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] Compound a-3: a compound having the following structure in formula (I). [R: CH ₃ , R ⁵ : CH ₃ , A: (A)-(CH ₂ ) ₃ -NH-CO-CH ₂ -O
_{- (C 2 H 4 O)} 5 -C 12 H 25 and, _{(d) - (CH 2) 3 -NH} -CO-CH 2 -O- (C
Mixture of _{2 H 4 O) 5 -C 14} H 29, ( a) / (d) = 7/3 (molar _{ratio), B :-( CH 2) 3} -O- (C 2 H 4 O) 10 - CH ₃ , l = 200, m
= 14, n = 8] Compound b-1: a compound having the following structure in formula (II). [R ⁴ : an alkyl group having 17 and 15 carbon atoms mixed (17/15 carbon atoms = 60/40), R ⁵ is an ethylene group, X is a —COO— group, and R ⁶ is R ⁴ —X—R ⁵ -group, R ⁷ ,
R ⁸ is a methyl group, Y ⁻ is a chloride ion] Compound b-2: a compound having the following structure in general formula (III). [R ⁴ : an alkyl group in which C 17 and C 15 are mixed (C 17 / C 15 = 60/40), R ⁵ is an ethylene group, X is a —COO— group, and R ⁶ is R ⁴ —CONH—C ₃ H ₆ −
Group, R ⁷ is a methyl group] Compound b-3: a compound having the following structure in general formula (III). [R ⁴ : an alkyl group having 17 and 15 carbon atoms mixed (17/15 carbon atoms = 60/40), R ⁵ is a propylene group, X is a —CONH— group, R ⁶ is a hydroxyethyl group, R ⁷ Is a methyl group] Nonionic surfactant 1: straight-chain first having 10 to 14 carbon atoms
Non-ionic surfactant 2: straight-chain first having 10 to 14 carbon atoms obtained by randomly adding 8 mol of EO and 2 mol of PO on average to a secondary alcohol.
7 moles of EO and 2 moles of PO on average
Non-ionic surfactant 3: straight chain second having 10 to 14 carbon atoms in which EO is added in blocks in the order of 3 mol on average.
Non-ionic surfactant 4: straight-chain primary having 10 to 14 carbon atoms
Tertiary alcohol with an average of 12 moles of EO added Cationic surfactant: monoalkyltrimethylammonium chloride having 16 to 18 carbon atoms (16 to 18 carbon atoms)
LAS-S agent: linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms. ES: sodium polyoxyethylene alkyl ether sulfate (alkyl carbon number 12, average number of moles of EO added 3) fatty acid : Coconut oil fatty acid having 12 to 14 carbon atoms-High molecular compound: diisobutylene maleic anhydride copolymer, average molecular weight 5000-Polyethylene glycol phenyl ether: polyoxyethylene monophenyl ether (EO average addition mole number 3)-Enzyme : Durazyme 16.0L (Protease, Novozyme) ・ Fluorescent dye: Tinopearl CBS-X (Ciba Specialty Chemicals)

[0034]

Industrial Applicability The liquid detergent composition of the present invention has an excellent softening effect on cotton clothing and an excellent color care effect.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 17/08 C11D 17/08 D06L 1/12 D06L 1/12 (72) Inventor Toshio Miyake Wakayama, Wakayama Minato 1334 Kao Research Laboratory F-term (reference) 4H003 AB03 AB19 AB31 AC08 AC09 AC11 AC23 AE05 AE06 AE07 BA12 DA01 EA12 EB02 EB04 EB14 EB32 EB37 ED02 FA14 FA22 4J035 BA02 CA062 CA071 CA082 CA18N CA181 GB01

Claims (2)

[Claims] 1. A silicone derivative represented by the following general formula (I): (b) a hydrocarbon group having 8 to 36 carbon atoms
A liquid detergent composition comprising at least one quaternary ammonium salt having at least one tertiary amine and at least one tertiary amine having at least one hydrocarbon group having 8 to 36 carbon atoms or an acid salt thereof. Embedded image [Wherein l = 100 to 600, and m and n are 1: m =
100: 1 to 10: 1, and m: n = 1: 10 to 10:
It is a number that becomes 1. R is an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an alkoxy group, and R ¹ is ¹ to 4 carbon atoms.
4 alkyl groups, each of which may be different. A is a group represented by the following (A) or a group represented by the following (A) and (B). In the latter case, the proportion of (B) in A is 50 mol% or less. Embedded image (Where a = 2-6, b = 2-6, R ² is a hydrogen atom or an alkyl group having 1-4 carbon atoms, p = 1-6, q = 1-2
0, r = 0~20, R ³ is an alkyl group having 1 to 18 carbon atoms), the _{B - (CH 2) a -O-} (C 2 H 4 O) s - (C 3 H 6 O) t - R
^{2 ′} or R ² (where R ^{2 ′} is an alkyl group having 1 to 10 carbon atoms, s = 1 to 20, t = 0 to 20). When -C ₂ H ₄ O- and -C ₃ H ₆ O- are present in the formula (I), block addition or random addition may be performed. ] 2. The weight ratio of (a) / (b) is 1/5 to 5 /
The liquid detergent composition according to claim 1, which is 1.