JPH11315299A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in detergency for soil of clothes and softening effect on clothes by blending two specific nonionic surfactants, an alkylbenzene sulfonic acid (salt), a cationic surfactant and a fatty acid (salt) in a specific ratio. SOLUTION: (A) 5-50 wt.% of nonionic surfactants of formulae I and II, (B) 0.5-10 wt.% of an alkylbenzene sulfonic acid (salt) with the alkyl moiety having an average of 8-14 carbon atoms, (C) 0.1-10 wt.% of a cationic surfactant of formula III and (D) 0.5-5 wt.% of a fatty acid (salt) of formula IV are blended in a weight ratio satisfying (A)/[(B)+(C)+(D)]=8/1-2/1 and in a mole ratio satisfying (B)/(C)=2/1-1/2 and [(B)+(D)]/(C)=2/1-1/1. In the formulae, R<1> and R<2> are each a 8-20C alkyl or alkenyl; R<3> to R<5> are each H, a 1-20C alkyl or alkenyl; R<6> is H or methyl; and R<7> is a 7-19C alkyl or the like.

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 which is excellent in detergency against dirt such as clothes and softening effect on clothes.

[0002]

2. Description of the Related Art Since liquid detergents have a soft image on clothing, liquid detergents having a softening effect on clothing have been developed. Japanese Unexamined Patent Publication (Kokai) No. 57-105496 discloses an acidic liquid detergent composition comprising a specific nonionic surfactant, an anionic surfactant, a cationic surfactant and amine oxide. Is less satisfactory than weak alkaline heavy liquid detergent.
Further, JP-A-62-48796 discloses a liquid detergent composition comprising an anionic surfactant, a cationic surfactant and a nonionic surfactant, but dispersibility of stains on solid particles. About is not satisfactory. Further, Japanese Unexamined Patent Publication No. 9-255988 discloses a liquid detergent composition having a softening action. However, all of them are intended for a light detergent and have insufficient detergency. Absent. As described above, a liquid detergent composition containing a fabric softening base has problems in detergency and dispersibility of solid particle dirt, and a liquid detergent having a detergency at the level of a heavy detergent and a sufficient softening effect is required. Is desired.

[0003]

[Wherein R ¹ and R ² represent a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. p, q, r, m and n represent the average number of added moles, and are p>0, r>0, q=1 to 4, p+q+r=6 to 14 and p+r=5 to 12. Moreover, it is m=2-14 and n=0-2. ]

(B) Alkylbenzenesulfonic acid having an average carbon number of the alkyl portion of 8 to 14 and/or its salt 0.5 to 10% by weight (c) Cationic surfactant represented by the following formula (III):
1 to 10 wt% (X ^- as an amount which does not include a)

[0004]

[Chemical 2]

[Wherein R ³ , R ⁴ and R ⁵ are hydrogen atoms or an alkyl or alkenyl group having 1 to 20 carbon atoms, preferably 8 to 20 carbon atoms, R ⁶ is a hydrogen atom or a methyl group, and X ⁻ is a counter ion. Represents. (D) Fatty acid represented by the following formula (IV) and/or its salt
0.5 to 5% by weight (in the case of a salt, an amount not including a cation) R ⁷ COOH (IV) [wherein R ⁷ is a single product or a mixture of ⁷ to 19 saturated or unsaturated alkyl groups] , R ^{7 has} an average carbon number of 11 to 1
7 ]

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The nonionic surfactant represented by the formula (I) which is the component (a) of the present invention is an alcohol having a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, It can be obtained by adding ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO) to this product, and further adding EO to this product. As R ¹ in the formula (I), an alkyl group derived from a linear and/or branched primary alcohol and/or a linear secondary alcohol is preferable, and the average carbon number of R ¹ is more preferably 10 to 14. .. In the formula (I), p and r are preferably p≧r. Also,
The nonionic surfactant represented by formula (II) of the component (a) can be obtained by adding EO to an alcohol having a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, It can also be obtained by further adding PO to this product. R ² in formula (II) is preferably a secondary alkyl group having 8 to 16 carbon atoms, and particularly preferably 10 to 14 as the average carbon number of the alkyl group. Further, in the formula (II), m is more preferably 5 to 12, and n is more preferably 0 to 2. In the present invention, the nonionic surfactant of the formula (I) and the nonionic surfactant of the formula (II) are used together as the component (a).

The nonionic surfactants represented by the formulas (I) and (II) can be synthesized, for example, by a method of adding an alkylene oxide to a higher alcohol, that is, a method generally known as alkoxylation. You can The catalyst used in this reaction is, in addition to a base catalyst and an acid catalyst, MgO-ZnO and M described in JP-A-7-227540.
gO-SnO, MgO-TiO ₂ and MgO-SbO as well as similar Mg described in Japanese Patent Laid-Open No. 1-164437
A catalyst that gives a narrow alkylene oxide distribution such as a system catalyst can be used. Of these, a base catalyst is particularly preferable from the viewpoint of cost, and potassium hydroxide is most preferable as the base.

The component (b) of the present invention, such as alkylbenzene sulfonic acid and/or salt thereof, is, for example, Neoperex F25 manufactured by Kao Co., Ltd., and Dobs1 manufactured by Shell Co., Ltd.
02 and the like can be used. The alkyl part preferably has an average carbon number of 10 to 14.

The cationic surfactant represented by the above formula (III), which is the component (c) of the present invention, is added to the component (b) in a specific ratio to impart flexibility to clothes and the like. .. The component (c) is a compound in which R ³ , R ⁴ , R ⁵ , and R ⁶ are mono long-chain alkyltrimethyl (hereinafter abbreviated as mono).
And a compound in which R ³ , R ⁴ , R ⁵ , and R ^{6 are} dilong-chain alkyldimethyl (hereinafter abbreviated as di-form), the composition has a lower solution stability as the ratio of di-form to mono-form is lower. improves. Therefore, the weight ratio of the mono-form and the di-form is mono-form/di-form=20/1 or more, preferably 100/1 or more.
In formula (III), at least one of R ³ , R ⁴ and R ⁵ is preferably an alkyl group or an alkenyl group having 8 to 20 carbon atoms, and particularly preferably R ³ , R ⁴ , R ⁵ and R ⁶ are mono long-chain. It is a compound that is alkyl (8 to 20 carbon atoms) trimethyl. Further, in the formula (III), X ⁻ is a counter ion, and in addition to the halogen ion, it may be an anionic surfactant or an ion of toluenesulfonic acid or xylenesulfonic acid due to the equilibrium action in the system. The composition of the present invention contains the component (c) in an amount not including the weight of the counterion X ⁻ of 0.1 to 0.1.
10% by weight, preferably 0.4 to 10% by weight.
When X ^{− of the} component (c) is a halogen ion, the compounding amount including the halogen ion is preferably 0.5 to 10% by weight.

As the fatty acid and/or salt thereof as the component (d) of the present invention, natural fatty acids such as coconut oil fatty acid and beef tallow fatty acid can be used. For example, Kao Corporation
Lunack L-50, Lunack L-55, Lunack T
D-2, Lunak TH, etc. can be used.

In the present invention, (a)/[(b)+
The weight ratio of (c)+(d)] is the softening effect on clothing,
In terms of detergency and solution stability, it is 8/1 to 2/1, preferably 7/1 to 3/1, more preferably 6/1 to 4/1. The molar ratio of (b)/(c) is 2/1 to 1/2, preferably 3/2 to 2/3, and more preferably 4/, from the viewpoint of the softening effect on clothes and the anti-redeposition property. 3 to 3/4
Is. Further, the molar ratio of [(b)+(d)]/(c) is 2/in terms of the softening effect on clothes and the anti-redeposition property.
It is 1 to 1/1, preferably 3/2 to 1/1.

The liquid detergent composition of the present invention has a pH containing components (a), (b) and (d) in the production process.
It is preferable that it is produced by a method including a step of adding the aqueous solution of the component (c) to an aqueous solution of 9.0 or more from the viewpoints of recontamination resistance, detergency, and softening effect on clothes.

The composition of the present invention preferably further contains 0.1 to 5% by weight of a polycarboxylate polymer dispersant. Here, the polycarboxylate-based polymer dispersant is a polymer compound having a carboxyl group and/or a salt thereof in the polymer constituent unit and having a weight average molecular weight of 1,000 to 100,000, and at least 1 kg of the polymer compound. 1
It refers to those containing a molar carboxyl group and/or a salt thereof. The molecular weight can be measured by a gel permeation chromatography method (GPC method) using polyethylene glycol as a standard substance. Examples of the polymer dispersant include polymer compounds such as polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymer, polyaspartic acid, and carboxymethylcellulose, and salts thereof.
Polymers described in JP-A-9-62614, JP-A-7-53
The polymers described in Japanese Patent No. 993 can be used. Other,
Poise 521, Poise 530, Demol P, Demol EP, Demol ST, Seresh 100, manufactured by Kao Corporation
Seresh 200 or the like may be used. Further, the following anionic surfactants (1) to (2) can be used. (1) It has an alkyl group derived from a linear primary alcohol or a linear secondary alcohol having an average carbon number of 10 to 20 or an alkyl group derived from a branched alcohol system and has an average of 0.5 in one molecule.
Alkyl ether sulfate with addition of ~6 mol EO. (2) An alkyl or alkenyl sulfate having an alkyl group or an alkenyl group having an average carbon number of 10 to 20.

The counterion of these anionic surfactants is selected from the group consisting of cations such as sodium, potassium, magnesium, calcium and alkanolamines and mixtures thereof. It may be monomethyldiethanolamine or dimethylmonoethanolamine. When the anionic surfactant is blended, it may be blended in the detergent composition in an acid form, or may be neutralized with an alkali agent (alkanolamine etc.) separately added in the composition.

Further, the following nonionic surfactants (1) to (3) can also be used. (1) An alkyl polysaccharide surfactant represented by the following general formula (V). _{^{R 8 - (OR 9) x}} G y (V) wherein, R ⁸ is a linear or alkyl or alkenyl having 8 to 18 carbon atoms branched chain alkyl phenyl group, R ⁹ is C2-4 Alkylene group, G has 5 carbon atoms
Or a residue derived from a reducing sugar of 6, x represents a number having an average value of 0 to 6, and y represents a number having an average value of 1 to 10. ] (2) Fatty acid alkanolamide (3) Polyhydroxy fatty acid amide.

In addition, as the amphoteric surfactant, alkylcarbobetaine, alkylsulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine type betaine, alkylimidazoline type betaine and the like can be added.

The composition of the present invention contains at least one selected from toluenesulfonic acid and/or its salt and xylenesulfonic acid and/or its salt, preferably paratoluenesulfonic acid and/or its salt. By adding 10 to 10% by weight, in addition to the effect of reducing the viscosity and the effect of solubilizing, the freeze recovery property which does not cause phase separation or turbidity of the liquid when re-thawing after freezing is improved. In addition, this compounding quantity is an amount as an acid. Examples of these salts include alkali metal salts and alkanolamine salts.

Further, in the present invention, as an optional component, alkali metal hydroxides, silicates, carbonates and alkali agents such as alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alcohols such as ethanol and isopropanol. , Ethylene glycol, polyethylene glycol with a molecular weight of 200 or more,
Glycols such as propylene glycol, benzoates (also effective as preservatives) and viscosity reducing agents or solubilizers such as urea; Improving detergency and phase stability of polyoxyalkylene benzyl ether, polyoxyalkylene phenyl ether, etc. Agents: nitrilotriacetic acid salt, ethylenediaminetetraacetic acid salt, iminodiacetic acid salt, diethylenetriaminepentaacetic acid salt, glycol etherdiaminetetraacetic acid salt, hydroxyethyliminodiacetic acid salt, triethylenetetramine hexaacetic acid salt, malonic acid, succinic acid, Diglycolic acid, malic acid,
Metal ion scavengers such as tartaric acid, citric acid and salts thereof; polymers such as polyethylene glycol and polyvinyl alcohol having an average molecular weight of 5,000 or more; color transfer inhibitors such as polyvinylpyrrolidone; enzymes such as amylase, protease, lipase and cellulase; Calcium chloride,
Enzyme stabilizers such as calcium sulfate, formic acid and boric acid (boron compounds); fluorescent dyes such as Tinopearl CBS (manufactured by Ciba Geigy); softening agents such as amino-modified silicones or anti-shrinkage agents; defoaming agents such as silica and silicone. Agents; antioxidants such as dibutylhydroxytoluene, distyrenated cresol, sulfites, bisulfites; bluing agents: fragrances;
Antibacterial preservatives and the like can be mentioned.

[0019]

The liquid detergent composition of the present invention has both excellent detergency and softening effect.

[0020]

[Examples] Of the components shown in Table 1, components other than the cationic surfactant were mixed and the pH was adjusted to 10.
A composition of 5 was prepared. Then, a cationic surfactant was added, and NaOH was further added to adjust the pH of the liquid to 10.5 to prepare a liquid detergent composition. Each composition was evaluated for detergency and flexibility by the following methods. The results are shown in Table 1.

<Evaluation Method> (1) Detergency Evaluation Collar Staining Specimen Collar pieces of cotton/polyester blended shirts worn for 3 days were cut and collected. The second group of collar pieces from the other side was used for cleaning evaluation.

Washing conditions 40L in the washing tub of an automatic two-tub washing machine (Toshiba Galaxy 3.6)
Of tap water and 1.4 kg of cotton underwear and 0.6 kg of cotton/polyester blended shirt. Prepare a piece of 30×30 cm cotton cloth with five pieces of sewn collar pieces for cleaning evaluation, put it in a washing tub, and further put 26.67 mL of the liquid detergent composition shown in Table 1 and wash normally for 10 minutes. After that, dehydration for 1 minute, 15 L/m for 8 minutes
Rinse with running water. Then, it is dehydrated for 5 minutes and naturally dried in the room.

Criteria for Detergency of Detergency The detergency of collar stains was evaluated by one skilled panelist (hereinafter referred to as one experienced panelist) according to the following criteria. ○: Stain is removed and satisfactory level ▽; Stain is slightly left but satisfactory level △: Stain is slightly left and unsatisfactory level ×: Stain is not removed much and unsatisfactory level Reliability was confirmed by Scheffe's paired comparison method with 10 other panelists. In other words, among the collar stain test pieces judged by one skilled panelist, the test pieces with the adjacent results such as ○ and ▽, ▽ and △, △ and × were used as samples, and the other 10 panelists made a pair comparison of Scheffe. As a result of the test by the method, the judgment result of one skilled panelist was judged to be significant at the 95% confidence limit.

(2) Flexibility evaluation Preparation of pre-treated cloth 40 L in the washing tub of an automatic two-tub washing machine (Toshiba Galaxy 3.6)
Of tap water, and a total of 2.0 kg of cotton towels,
Mix with cotton knitted underwear and acrylic jersey. Further, a compact type powder detergent is added according to the standard amount of use, followed by washing for 10 minutes, dehydration for 1 minute, rinsing under running water for 8 minutes (1
5 L/min of water) and dried with a dryer. This washing cycle is repeated 5 times to obtain a pretreated cloth.

Flexibility evaluation An automatic two-tub type washing machine (Toshiba Galaxy 3.6) was prepared, and 35 L of tap water was put in the washing tub, and two cotton towels and cotton among the pretreatment cloths for flexibility evaluation were added to this. 2 pieces of knitted underwear,
Insert one acrylic jersey. Further, 23.33 mL of the liquid detergent composition shown in Table 1 is put therein and washed normally for 10 minutes. Then, dehydrate for 1 minute, and rinse with 35 L of tap water for 5 minutes×2 times. Finally, dehydrate for 3 minutes, let it air dry indoors,
The sample was left to stand in a thermo-hygrostat at 20°C/65%RH for 1 day.

Criteria for Flexibility Two cotton towels, two cotton knitted underwear and one acrylic jersey were evaluated as follows by comparing the unwashed product with the touch. Much softer than unwashed items; +2 points Softer than unwashed items; +1 point Same as unwashed items; 0 points or more were given by 5 trained panelists, and the average total score of 5 pieces of clothing judged And compared the flexibility.

[0027]

[Table 1]

(Note) Nonionic surfactant (1) A: An average of 5 moles of EO, an average of 2 moles of PO and an average of 3 moles of EO were added to a linear primary alcohol having 10 to 14 carbon atoms. Nonionic surface active agent (1) B: a linear primary alcohol having 10 to 14 carbon atoms added with an average of 7 moles of EO, an average of 2 moles of PO, and an average of 3 moles of EO. Activator (1) C: A linear primary alcohol having 10 to 14 carbon atoms with an average of 5 moles of EO, an average of 2 moles of PO, and an average of 5 moles of EO added ・Nonionic surfactant (2) D: average 10 moles of EO added to a linear secondary alcohol having 10 to 14 carbon atoms-nonionic surfactant (2) E: average 6 EO to linear secondary alcohol having 10 to 14 carbon atoms Mol, PO added with an average of 1 mol block Nonionic surfactant (2) F: EO averaged with 8 mol and PO added with an average of 1 mol block to a linear secondary alcohol having 10 to 14 carbon atoms Nonionic surfactant (2) G: EO having an average of 8 mol and PO having an average of 2 mol block added to a linear secondary alcohol having 10 to 14 carbon atoms. LAS-S agent: 10 alkyl carbon atoms. ~14 linear alkylbenzene sulfonic acid/fatty acid salt: 12 to 14 carbon atoms
Coconut oil fatty acid sodium salt-Cationic surfactant: Mono long-chain alkyltrimethylammonium chloride having 16 to 18 carbon atoms (ratio of 16 and 18 carbon atoms is 3/7)-Polycarboxylate-based polymer dispersant: Maleic anhydride diisobutylene copolymer, average molecular weight 5000-Polyethylene glycol phenyl ether: polyoxyethylene monophenyl ether (EO average 3 mol addition)-Enzyme: Durazyme 16.0L, protease (Novo Nordisk Bioindustry Co., Ltd.) ..

<Evaluation of Freezing Recovery> A liquid detergent composition having the composition shown in Table 2 was used as a wide-mouth standard bottle PS-No. 11 to 10
Insert 0 mL, fit the inner stopper, and seal with the outer lid to make a sample. This sample is TABAI ESPEC CO
RP. LOW TEMPARATURE CHAM made by
The sample is placed in PBER and stored at 20° C. for 12 hours and −20° C. for 12 hours as one cycle, and the state of the sample after 20 hours at 20° C. for 3 hours is visually observed. As a result, phase separation did not occur in any of them, and it was confirmed that these compositions have excellent freeze recovery properties. Table 2 shows the results of evaluation of detergency and flexibility as described above. In addition,
The components used in Table 2 are the same as those in Table 1.

[0030]

[Table 2]

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Claims (4)

[Claims] 1. A composition comprising the following components (a), (b), (c) and (d) in a weight ratio of (a)/[(b)+(c)+
(D)]=8/1 to 2/1, (b)/(c)= in molar ratio
2/1 to 1/2, and a molar ratio of [(b)+(d)]/
(C) A liquid detergent composition in which 2/1 to 1/1. (A) Two kinds of nonionic surfactants, a nonionic surfactant represented by the following general formula (I) and a nonionic surfactant represented by the following general formula (II): 5 to 50% by weight R ¹ _{O (EO) p (PO)} q (EO) r H (I) R 2 O (EO) m (PO) n H (II) [wherein R ¹ and R ² is a straight chain having 8 to 20 carbon atoms or It represents a branched alkyl group or alkenyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group. p, q,
r, m and n represent the average number of moles added, p>0, r>0,
q=1 to 4, p+q+r=6 to 14, p+r=5 to 12
Is. Moreover, it is m=2-14 and n=0-2. (B) Alkylbenzenesulfonic acid having an average carbon number of the alkyl portion of 8 to 14 and/or its salt 0.5 to 10% by weight (c) Cationic surfactant represented by the following formula (III):
1 to 10% by weight (the amount does not include X ⁻ ) [Wherein R ³ , R ⁴ , and R ⁵ are hydrogen atoms or 1 to 20 carbon atoms]
Is an alkyl group or an alkenyl group, R ⁶ is a hydrogen atom or a methyl group, and X ⁻ is a counter ion. (D) Fatty acid represented by the following formula (IV) and/or its salt
0.5 to 5% by weight (in the case of salt, a cation-free amount) R ⁷ COOH (IV) [wherein R ⁷ is a single product or a mixture of ⁷ to 19 saturated or unsaturated alkyl]. , R ^{7 has} an average carbon number of 11 to 1
7 ] 2. The liquid detergent composition according to claim 1, further comprising 0.1 to 5% by weight of a polycarboxylate-based polymer dispersant. 3. The liquid detergent composition according to claim 1, further comprising 0.1 to 10% by weight of at least one selected from toluenesulfonic acid and/or its salt and xylenesulfonic acid and/or its salt. object. 4. The component (c) is added to an aqueous solution containing the components (a), (b) and (d) according to claim 1 and having a pH of 9.0 or more.
A method for producing a liquid detergent composition, which comprises the step of adding the aqueous solution.