JP2005154505A - Detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition which is excellent in softening effect, reduces friction between clothes after washing, prevents entanglement of clothes after washing, reduces wrinkles on clothes after drying and is excellent in cloth-caring effect. <P>SOLUTION: The detergent composition contains a polyoxyalkylene alkyl (or alkenyl) ether (a) having a 16-20C alkyl or alkenyl group and an average addition molar number of alkylene oxide of ≤10 and has a surfactant equivalent value described by JIS K3362:1998 within a specific range. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a cleaning composition, and more particularly to a cleaning composition that can be gently washed without damaging clothing.

Conventionally, liquid detergents have a soft image on clothes, and therefore liquid detergents having a softening effect on clothes have been developed for some time. For example, Patent Document 1 describes that a detergent containing amino-modified silicone or a derivative thereof has an excellent softening effect or an excellent felt shrinkage preventing effect. Patent Document 2 discloses a specific amino-modified silicone derivative and a specific HLB value as a liquid detergent composition that exhibits a good shrinkage prevention effect, penetrability, and texture imparting effect, and has a good storage stability. A liquid detergent composition containing a surfactant containing a nonionic surfactant is disclosed.
Furthermore, in addition to the softening effect, a technique for imparting a color care effect for preventing clothing from fading due to repeated washing has also been proposed. For example, Patent Document 3 discloses (a) a specific amino-modified silicone derivative and (b) a specific quaternary ammonium salt as a liquid detergent composition having an excellent softening effect on cotton clothing and an excellent color care effect. And a liquid detergent composition containing at least one selected from tertiary amines or acid salts thereof.
In addition, clothes are subjected to mechanical force such as rubbing and pulling by washing, and as washing is repeated, damage such as fluffing and tightness occurs. For this reason, for example, Patent Document 4 reports a method using a specific organic functionalized polydialkylsiloxane for the purpose of softening clothing, preventing static charge, and preventing wrinkles.
JP-A-9-67594 Japanese Patent Laid-Open No. 10-60480 JP 2002-249799 A Japanese Patent Laid-Open No. 60-215099

  However, while maintaining an excellent softening effect, it is possible to reduce friction between clothes after washing, to prevent tangling of clothes after washing (to facilitate removal from the washing machine), after drying No cleaning composition has yet been found that can reduce wrinkles in clothing and that it has excellent fabric care effects. Therefore, the subject of this invention is providing the cleaning composition excellent in these effects.

  The present invention is a polyoxyalkylene alkyl (or alkenyl) ether (a) [hereinafter referred to as component (a) having an alkyl group or alkenyl group having 16 to 20 carbon atoms, and having an average addition mole number of alkylene oxide of 10 or less. ], And a surfactant composition according to JIS K3362: 1998 is 15 to 55% by mass.

  The present invention also provides a polyoxyalkylene alkyl (or alkenyl) ether (a) having an alkyl group or alkenyl group having 16 to 20 carbon atoms and an average addition mole number of alkylene oxide of 10 or less, a water-soluble surfactant. (X) and a method for producing a liquid detergent composition containing water and having a surfactant equivalent of 15 to 55% by mass described in JIS K3362: 1998, wherein (a) and water are mixed The present invention relates to a production method having a step of preparing a mixture containing (a) and (X) at a mass ratio of (a) :( X) = 2: 3 to 1:50.

  According to the present invention, it has an excellent softening effect, can reduce friction between clothes after washing, can suppress entanglement of clothes after washing (makes easy removal from a washing machine), and drying A detergent composition satisfying that the wrinkles of the subsequent garments can be reduced and that the fabric care effect is excellent (clothes damage can be reduced) is obtained. Therefore, the cleaning composition of the present invention is suitable for clothing.

<(A) component>
The polyoxyalkylene alkyl (or alkenyl) ether as the component (a) is an alcohol having an alkyl group or alkenyl group having 16 to 20 carbon atoms and an average number of moles of alkylene oxide (hereinafter referred to as AO) of 10 or less, preferably Is a nonionic surfactant added at 8 or less. The lower limit of the average added mole number of AO is 1 or more. Here, the alkyl group or alkenyl group of the alcohol may be linear or branched, and may be a mixture of different carbon numbers.

  AO preferably has 2 to 4 carbon atoms, and examples thereof include ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), and butylene oxide. Among them, EO and / or PO are preferable, and it is particularly preferable that EO accounts for 50 to 100 mol%, more preferably 75 to 100 mol%, and particularly 100 mol% in all AO. In addition, the AO average addition mole number in (a) component can be measured as a weight average using LC-MAS etc.

  Further, the HLB (Griffin method) of the component (a) is preferably 6 to 14, more preferably 8 to 13, and particularly preferably 9 to 12.

<(B) component>
The cleaning composition of the present invention is represented by (b1) an amine represented by the following general formula (b1) or an acid salt thereof (hereinafter referred to as the (b1) component), and (b2) represented by the following general formula (b2). It is preferable to contain a soft base (b) [component (b)] selected from quaternary ammonium salts [hereinafter referred to as component (b2)] from the viewpoint of maintaining an excellent softening effect.

[Wherein, R ^1b is an alkyl or alkenyl group having 14 to 22 carbon atoms, R ^2b is an alkylene group having 1 to 5 carbon atoms, X is —COO—, —CONR ^5b —, —OCO—, It is a group selected from —NR ^5b CO—. Here, R ^5b is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. R ^3b and R ^4b are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ^1b —X—R ^2b —. ]

[Wherein, R ^6b is a hydrocarbon group such as an alkyl group or an alkenyl group having 8 to 22 carbon atoms, or a benzyl group. When R ^6b is a hydrocarbon group, the hydrocarbon group may be linear or branched, saturated or unsaturated, and optionally substituted with a hydroxyl group or the like. May be included. R ^6b may have a linking group such as an ester group, an amide group or an ether group in its chain. R ^7b is a hydrocarbon group such as an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, an alkyl group having 8 to 22 carbon atoms or an alkenyl group, or a benzyl group. When R ^7b is a hydrocarbon group, the hydrocarbon group may be linear or branched, may be saturated or unsaturated, and may optionally contain a substituent. Further, the hydrocarbon group R ^7b may have a linking group in its chain. R ^8b and R ^9b are each an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group. X ⁻ is a halogen ion such as a chlorine ion or a counter ion such as an alkyl sulfate ion. ]

  Specific examples of the component (b1) include laurylamidopropyldimethylamine, myristylamidopropyldimethylamine, palmitylamidepropyldimethylamine, stearylamidopropyldimethylamine, behenylamidopropyldimethylamine, oleylamidopropyldimethylamine, palmitylamide Aliphatic amidoalkyl tertiary amines such as propyldiethanolamine and stearylamidopropyldiethanolamine and their salts, aliphatic ester alkyl tertiary amines such as palmitate ester propyldimethylamine, stearate ester propyldimethylamine and their salts Among these, myristylamidopropyldimethylamine, palmitylamidopropyldimethylamine, stearylamide propylene Dimethylamine, behenyl dimethylamine, oleyl amidopropyl dimethylamine, and salts thereof preferably, particularly stearyl amidopropyl dimethylamine and salts thereof are preferred.

  Specific examples of the component (b2) include lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, coconut alkyltrimethylammonium chloride, cetyltrimethylammonium chloride, beef tallow alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, stearyldimethylbenzylammonium chloride, stearyldihydroxy. Ethylmethylammonium chloride, N-lauroylamidopropyl-N′-trimethylammonium chloride, N-myristoylamidopropyl-N′-trimethylammonium chloride, distearyldimethylammonium chloride, dimyristyldimethylammonium chloride, dioctyldimethylammonium chloride De, didecyl dimethyl ammonium chloride, such as dilauryl dimethyl ammonium chloride. Of these, beef tallow alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, and dimyristyldimethylammonium chloride are preferable in the present invention.

<(C) component>
The cleaning composition of the present invention preferably contains a silicone derivative (c) represented by the following general formula (c) from the viewpoint of reducing wrinkles.

[Wherein, l = 100 to 600, and m and n are numbers such that l: m = 100: 1 to 10: 1 and m: n = 1: 10 to 10: 1. R is an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an alkoxy group, and R ^1c 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 (A) and (B). In the latter case, the ratio of (B) in A is 50 mol% or less.

(Where a = 2 to 6, b = 2 to 6, R ^2c 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 ^3c is an alkyl group having 1 to 18 carbon atoms), B is — (CH ₂ ) _a —O— (C ₂ H ₄ O) _s — (C ₃ H ₆ O) _t —R ^2′c or R ^2c (here R ^2′c represents 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 (c), block addition or random addition may be used. ]

The structure of the general formula (c) of the component (c) is l = 100 to 400, l: m = 60: 1 to 10: 1, m: n = 1: 5 to 5: 1 in terms of the softening effect. , R and R ^1c are methyl groups, 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 ^2c is a hydrogen atom, p = 1 to 3, q = 1 to 15, r = 0 to 10, R ^3c is an alkyl group having 6 to 16 carbon atoms, and B is — (CH ₂ ) _a −. O— (C ₂ H ₄ O) _s — (C ₃ H ₆ O) _t —R ^2′c or R ^2c (where R ^2′c is a methyl group, s = 5 to 20, t = 0 to 10) Are preferred. In addition, when -C ₂ H ₄ O- and -C ₃ H ₆ O- are present in the general formula (c), block addition or random addition may be used, but block addition is preferable in terms of blending stability. .

<(D) component>
The cleaning composition of the present invention has a polyoxyalkylene alkyl (or alkenyl) ether (d) [(C) having an alkyl group or an alkenyl group having 8 to 14 carbon atoms and an average addition mole number of alkylene oxide of 10 to 22. d) Component] is preferable in terms of high detergency. As the component (d), a nonionic surfactant represented by the general formula (d1) is preferable.

^R1d- T-[( ^R2dO ) _j- H] _k (d1)
[Wherein R ^1d is an alkyl group or alkenyl group having an average carbon number of 8 to 14, preferably 10 to 14, more preferably 12, R ^2d is an alkylene group having 2 or 3 carbon atoms, preferably Ethylene group. j is a number from 10 to 22. T is —O—, —CON— or —N—. When T is —O—, k is 1, and when T is —CON— or —N—, k is 2. ]

  Specific examples of the compound represented by the general formula (d1) include the following compounds.

R ^1d —O— (C ₂ H ₄ O) _m —H
[Wherein R ^1d represents the above-mentioned meaning. m is a number from 10 to 22. ]

^{_{R 1d -O- (C 2 H 4}} O) n1 / (C 3 H 6 O) n2 -H
[Wherein R ^1d represents the above-mentioned meaning. n ₁ and n ₂ are each independently a number greater than 0, and the sum of n ₁ and n ₂ is 10-22. EO and PO may be random or block adducts, and the addition order of EO and PO is not particularly limited. ]

[Wherein R ^1d represents the above-mentioned meaning. p ₁ and p ₂ are each greater than 0, preferably a number from 1 to 10, q ₁ and q ₂ are each a number from 0 to 3, and p ₁ + p ₂ + q ₁ + q ₂ is from 10 to 22. Is a number. EO and PO may be random or block adducts. ]

  Among these nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ethers having an average of 10 to 22 moles of EO added to an alcohol having an alkyl or alkenyl group having an average carbon number of 8 to 14, and an average carbon number of Polyoxyalkylene alkyl (or alkenyl) ether obtained by adding 7 to 20 mol of EO and 1 to 3 mol of PO on average to alcohol having 8 to 14 alkyl groups or alkenyl groups (EO and PO are either random addition or block addition) The order of addition of EO and PO is not particularly limited, but the total number of moles of EO and PO added is preferably 10 to 22.), the alkyl group having 8 to 14 carbon atoms, and the average addition of EO Polyoxyethylene alkyl ether having a mole number of 10 to 16 is particularly preferred. In addition, the AO average addition mole number in (d) component can be measured as a weight average using LC-MAS etc.

  Further, the HLB (Griffin method) of the component (d) is preferably 14 to 18, more preferably 14.5 to 17, and particularly preferably 15 to 16.

<Cleaning agent composition>
The content of the component (a) in the cleaning composition of the present invention is 0.5 to 10% by mass, more preferably 0.5 to 7.5% by mass, and particularly 0.5 to 5% by mass. It is preferable in terms of stability.

  The mass ratio of the component (a) to the component (d) is (a) :( d) = 1: 1 to 1:30, further 1: 2 to 1:20, particularly 1: 5 to 1:13. It is preferable in terms of cleaning performance.

  It is stable that the content of the component (b) in the cleaning composition of the present invention is 0.1 to 10% by mass, further 0.2 to 7.5% by mass, particularly 0.5 to 3% by mass. From the viewpoint of flexibility and softening effect.

  The content of the component (c) in the cleaning composition of the present invention is 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly 0.5 to 3% by mass. It is preferable in terms of wrinkle reduction.

  The content of the component (d) in the cleaning composition of the present invention is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass from the viewpoint of cleaning performance.

  In the cleaning composition of the present invention, the amount corresponding to the surfactant described in JIS K3362: 1998 is 15 to 55% by mass, preferably 20 to 50% by mass, more preferably 30 to 45% by mass. In the total surfactant in the composition, the ratio of the component (a) is preferably 1 to 20% by mass, and more preferably 3 to 15% by mass.

  In the detergent composition of the present invention, surfactants other than the components (a), (b), and (d), for example, anionic surfactants, amphoteric surfactants, other nonionic surfactants, etc. Can be blended.

  Examples of the anionic surfactant that can be used in the present invention include the following (i) to (iv). The content of the anionic surfactant in the composition is preferably 0 to 20% by mass, particularly preferably 5 to 15% by mass.

(I) Alkyl (or alkenyl) benzene sulfonate having an alkyl group or alkenyl group having an average carbon number of 10 to 20 (ii) An average of 1 mole of alcohol having an alkyl or alkenyl group having an average carbon number of 10 to 20 Polyoxyethylene alkyl (or alkenyl) ether sulfate added with 0.5 to 6 mol of EO (iii) Average alkyl group having 10 to 20 carbon atoms or alkyl (or alkenyl) sulfate (iv) average C8-20 fatty acid salt

  Further, as counter ions of these anionic surfactants, alkali metals such as sodium and potassium, alkaline earth metals such as magnesium, alkanolamines such as mono, di, and triethanolamine, ammonium, and the like can be used. Sodium, potassium and monoethanolamine are preferred.

  Moreover, you may mix | blend an amphoteric surfactant from the point of stability of a liquid, and mud dirt cleaning property. As the amphoteric surfactant, alkylcarbobetaine, alkylsulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine type betaine, alkylimidazoline type betaine and the like can be blended. The content of the amphoteric surfactant in the composition is preferably 0 to 5% by mass.

  Examples of other nonionic surfactants include alkyl polysaccharide surfactants represented by the following general formula, fatty acid alkanolamides, polyhydroxy fatty acid amides, etc., and inclusion of these other nonionic surfactants in the composition The amount is preferably 0 to 5% by mass.

R ¹⁰ − (OR ¹¹ ) _i G _j
[Wherein R ¹⁰ is a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkylphenyl group, R ¹¹ is an alkylene group having 2 to 4 carbon atoms, and G is a group having 5 or 6 carbon atoms. Residues derived from reducing sugars, i is an average value of 0-6, and j is an average value of 1-10. ]

  Furthermore, the following components can be mix | blended with the cleaning composition of this invention in the following range, respectively.

(I) Alkali metal hydroxide, silicate, carbonate such as sodium carbonate, and alkali agent such as alkanolamine 0.01 to 10% by mass
(Ii) Alcohols such as ethanol, glycols such as ethylene glycol and propylene glycol, paratoluenesulfonic acid, benzoate (also has an effect as a preservative), and a thickener and solubilizer such as urea. 01-30% by mass
(Iii) Phase adjusters such as polyoxyalkylene benzyl ether and polyoxyalkylene phenyl ether and detergency improvers 0.01 to 10% by mass
(Iv) Aminopolyacetates such as nitrilotriacetic acid, ethylenediaminetetraacetate, iminodiacetate, diethylenetriaminepentaacetate, glycol etherdiaminetetraacetate, hydroxyethyliminodiacetate and triethylenetetraminehexaacetate, malonic acid 0.1 to 20% by mass of a metal ion scavenger such as succinic acid, malic acid, diglycolic acid, tartaric acid and citric acid
(V) Polyacrylic acid, polymaleic acid, carboxymethyl cellulose, polyethylene glycol having a weight average molecular weight of 5000 or more, maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-vinyl acetate copolymer Recontamination preventing agents such as polymers, naphthalene sulfonate formalin condensates, and polymers described in claims 1 to 21 (page 1, column 3, line 5 to page 3, column 4, line 14) of JP-A-59-62614; Dispersant 0.01 to 10% by mass
(Vi) 0.01-10% by mass of a color transfer inhibitor such as polyvinylpyrrolidone
(Vii) Bleaching agent such as sodium percarbonate or sodium perborate 0.01 to 10% by mass
(Viii) Tetraacetylethylenediamine, 0.01-10% by mass of a bleach activator such as bleach activators represented by general formulas (I-2) to (I-7) of JP-A-6-316700
(Ix) 0.001 to 2% by mass of enzymes such as amylase, protease, lipase and cellulase
(X) 0.001 to 2% by mass of an enzyme stabilizer such as calcium chloride, calcium sulfate, formic acid or boric acid (boron compound)
(Xi) 0.001 to 1% by mass of a fluorescent dye such as Chino Pearl CBS (manufactured by Ciba Specialty Chemicals) or Whiteex SA (manufactured by Sumitomo Chemical Co., Ltd.)
(Xii) 0.01-2% by mass of an antifoaming agent such as silica and silicone other than component (c)
(Xiii) 0.01-2% by mass of an antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium bisulfite
(Xiv) Bluening agent (xv) Fragrance (xvi) Antibacterial preservative

  The cleaning composition of the present invention comprises the above component (a) and optional components, and the balance of water, but is a liquid composition having a pH of 6 to 11, and more preferably 7 to 9.5 at 20 ° C. preferable. The viscosity of the cleaning composition of the present invention at 20 ° C. is preferably 50 to 500 mPa · s, more preferably 75 to 300 mPa · s, and particularly preferably 100 to 250 mPa · s.

<Method for producing cleaning composition>
The cleaning composition of the present invention comprises (a) the component and the water-soluble surfactant (X) [hereinafter referred to as the (X) component] (a) :( a) before mixing the component (a) with water. X) = 2: 3 to 1:50 by a production method having a step of preparing a mixture containing the component (a), component (X) and water, and the surface activity described in JIS K3362: 1998 It can be produced as a liquid detergent composition having an agent equivalent of 15 to 55% by mass. By using this production method, gelation of the component (a) can be suppressed. Water may be added to the mixture containing the component (a) and the component (X), or conversely, the mixture may be added to water. Further, the component (a) and the component (X) may be added to water while being mixed using, for example, a static mixer (manufactured by Noritake Co., Ltd.).

  In this case, as the component (X), one or more of the component (d), the anionic surfactant and the amphoteric surfactant described above can be appropriately selected. In addition, in terms of solubility of the mixture containing the component (a) and the component (X) in water, polyethylene glycol having a weight average molecular weight of 100 to 10,000 is added to the mixture containing the component (a) and the component (X). 4 to 12% by mass, more preferably 7 to 12% by mass.

<Production Example 1>
In Table 1, the liquid detergent composition of Example 1 was produced by the following method. Average of 6 moles of EO added to primary alcohol with 18 carbon atoms (nonionic surfactant A) 5 parts by weight, average of EO to alkyl group linear secondary alcohol mixed with 12 and 13 carbon atoms 7 moles added (non-ionic surfactant F) 20 parts by mass, primary alcohol having a linear alkyl group with 12 carbons, EO averaged 8 moles, PO averaged 2 moles, randomly added (Nonionic surfactant I) A mixed solution of 10 parts by mass was prepared, and 51 parts by mass of water was added and mixed uniformly while stirring. 2 parts by mass of ethanol, 5 parts by mass of propylene glycol, 3 parts by mass of phenyl glycol, and 5 parts by mass of monoethanolamine were added and mixed uniformly. Phenoxypolyethylene glycol-acrylic acid-maleic acid copolymer synthesized by the method of Synthesis Example 1 on page 4, paragraph 0020 of JP-A-10-60476 (weight average molecular weight 10,000, solid content 51.2% by mass, 3 parts by mass, 1 part by mass of fatty acid, and 0.5 parts by mass of enzyme were added. The amount of the surfactant equivalent (JIS K3362: 1998) of the obtained liquid cleaning composition was 42%.

<Production Example 2>
In Table 2, the liquid detergent composition of Example 6 was produced by the following method. An average of 9 mol of EO added to a linear primary alcohol containing 90% by mass or more of an alkenyl group having 18 carbon atoms and one unsaturated bond (nonionic surfactant C), 4 parts by mass, carbon number 15 parts by mass of non-ionic surfactant F having an average of 7 moles of EO added to an alkyl group linear secondary alcohol mixed with 12 and 13 and a primary alkyl group having 12 linear alkyl groups 15 parts by mass of alcohol obtained by adding 13 moles of EO on average (nonionic surfactant H) are uniformly mixed. A mixture of 8 parts by mass of ethanol and 5 parts by mass of p-toluenesulfonic acid was mixed with 3 parts by mass of amidopropyldimethylamine stearate (amine 1), and the mixture was homogenized. Then, 57 parts by mass of water was added with stirring. It was. The pH of this liquid detergent composition was measured, and adjusted to a pH of 9.5 at 20 ° C. using a 48% sodium hydroxide solution. The surfactant equivalent (JIS K3362: 1998) of the obtained liquid cleaning composition was 36.3 mass%.

<Production Example 3>
In Table 3, the liquid detergent composition of Example 7 was produced by the following method. EO is added to a primary alcohol having a straight chain alkyl group having 12 carbon atoms (nonionic surfactant H) obtained by adding an average of 13 moles of EO to a primary alcohol having a straight chain alkyl group having 12 carbon atoms. A 20: 5: 1.5 (mass ratio) mixture of an average of 8 moles, an average of 2 moles of PO, and a random addition (nonionic surfactant I) and polyethylene glycol (weight average molecular weight 2000) was prepared. 25 parts by mass of a mixture of this nonionic surfactant and polyethylene glycol, and 3 parts by mass of an average of 6 moles of EO added to a linear primary alcohol having 18 carbon atoms (nonionic surfactant A) While supplying a mixture such that the flow rate ratio of the mixture: nonionic surfactant A is in the range of 5: 1 to 10: 1 and mixing using a static mixer (manufactured by Noritake Co., Ltd.), 51.5 mass of water Added continuously to the part. 7 parts by mass of butyl carbitol, 10 parts by mass of sodium polyoxyethylene alkyl ether sulfate (12 alkyl carbons, 3 average EO addition moles, ES in the table) and 2 parts by mass of silicone A were added thereto. The surfactant equivalent (JIS K3362: 1998) of the obtained liquid detergent composition was 40.5 mass%.

<Production Example 4>
In Table 4, the liquid detergent composition of Example 10 was produced by the following method. 52.5 parts by mass of water was mixed with 5 parts by mass of butyl carbitol, 1 part by mass of p-toluenesulfonic acid, and 2 parts by mass of ethanol. 20 parts by mass of an average of 13 moles of EO added to a linear primary alcohol having 12 alkyl atoms (nonionic surfactant H) and 2 parts by mass of polyethylene glycol (weight average molecular weight 2000) Was added with stirring at a constant flow rate. At that time, an average of 7 moles of EO added to a linear primary alcohol of an alkyl group (carbon number 16 / carbon number 18 = 70/30, mass ratio) in which carbon numbers 16 and 18 are mixed (nonionic interface) Using a static mixer (manufactured by Noritake Co., Ltd.), supplying 3 parts by mass of activator B so that the flow rate ratio is in the range of 4: 1 to 15: 1 of the mixture: nonionic surfactant B Added continuously with mixing. To this, 10 parts by mass of linear alkylbenzene sulfonic acid (in the table, LAS), a phenoxypolyethyleneglycol-acrylic acid-maleic acid copolymer synthesized by the method of Synthesis Example 1 on page 4, paragraph 0020 of JP-A-10-60476 2 parts by weight (weight average molecular weight 10,000, solid content 51.2% by mass), 0.5 part by mass of citric acid, and 1 part by mass of stearamide amidopropyldimethylamine (amine 1) were added with stirring. The pH of this liquid detergent composition was measured and adjusted with a 48% aqueous sodium hydroxide solution so that the pH at 20 ° C. was 7.5, and 2 parts by mass of silicone A was added thereto. The surfactant equivalent (JIS K3362: 1998) of the obtained liquid cleaning composition was 37.8 mass%.

Examples 1-3 and Comparative Examples 1-3
The following evaluation was performed using the liquid detergent composition of Table 1. The results are shown in Table 1.

<Evaluation>
(1) Evaluation of softening effect (1-1) Adjustment of pretreatment cloth Cotton towel is set so that the washing water volume of the fully automatic washing machine (Toshiba, AW-D802VP) is set to 45L, and the total amount is 2.25kg. , Put cotton Melias unweared underwear. Further, a compact type powder detergent (Attack, Kao Co., Ltd.) was added according to the standard usage amount, washed for 8 minutes, dehydrated for 3 minutes, rinsed twice, dehydrated for 3 minutes, and dried with a drier. This washing cycle was repeated 5 times to obtain a pretreated fabric.

(1-2) Evaluation method Set the amount of washing water to 28L with the above washing machine, and put 2 cotton towels and 3 cotton underwear for cotton melias out of the pretreatment cloth for flexibility evaluation. In addition, 23.3 mL of the liquid detergent composition shown in Table 1 was added, washed for 8 minutes, dehydrated for 3 minutes, rinsed twice, dehydrated for 3 minutes, naturally dried indoors, and placed in a constant temperature and humidity room at 20 ° C and 65% RH. Let stand for 10 hours.

(1-3) Judgment criteria for softening effect A total of 5 cotton towels and 3 cotton underwears were scored as follows by comparing the unwashed product with the touch.
2 points; 1 point that is considerably softer than unwashed products; 0 point that is softer than unwashed products; no difference from unwashed products

  The above scores were performed by five skilled panelists, and the total score of five sheets determined by each person was averaged to compare the softening effect.

(2) Evaluation of frictional force reduction effect (2-1) Preparation of pre-treated cloth 5L of water is put in a jar, and 12 moles of EO is added on average to a non-ionic surfactant (12 primary carbon linear alcohol). After adding 0.5 g of the mixture, 1 kg of cotton satin cloth and acrylic jersey cloth are added. After immersing for 10 minutes, rinse with running water for 5 minutes, dehydrate for 1 minute in the dewatering tank of an automatic 2-tank washing machine (Toshiba Galaxy 3.6VH-360S1), and dry naturally in the room.

(2-2) Evaluation of frictional force reduction effect Using a surface property tester (HEIDON 14DR), evaluation is performed using the pretreatment cloth adjusted in (2-1). An aqueous solution of 0.83 mL / L of the liquid detergent composition shown in Table 1 is sprayed evenly over the whole so that the moisture content of the cloth prepared in (2-1) is 40%. The surface of the prepared cloth was moved with the same kind of cloth wetted with a moisture content of 40%, and the coefficient of friction was measured for each of the cotton cloth and the acrylic cloth using the surface property tester.

(2-3) Criteria for judging the effect of reducing friction With respect to cotton satin cloth and acrylic jersey cloth, the static friction coefficient was measured three times, and the average value was compared with Comparative Example 1 to give the following score.
A: Friction coefficient is considerably smaller than Comparative Example 1 (difference is 0.1 or more)
○: Friction coefficient is small compared to Comparative Example 1 (difference is more than 0 and less than 0.1)
Δ: Friction coefficient is not different from Comparative Example 1 ×: Friction coefficient is larger than Comparative Example 1

(3) Wrinkle evaluation method for clothing (3-1) Wrinkle evaluation for clothing Set the washing water volume of a fully automatic washing machine (Toshiba, AW-D802VP) to 45 L, and 10 unwashed and unworn cotton T-shirts (about 2. 2 kg). The washing machine was charged with 37.5 mL of the liquid detergent composition shown in Table 1, followed by washing for 8 minutes for washing, 3 minutes for dehydration, twice for rinsing and 6 minutes for dehydration, and repeated washing 5 times without drying. After the fifth wash, the lid was left unopened for 1 hour, then removed from the washing machine, held on both shoulders, shaken once, hung on a hanger, and dried at 20 ° C. and 65% RH. After drying for 12 hours, wrinkles on the entire back of the T-shirt were determined.

(3-2) Criteria for Wrinkles Judgment was made by comparing the clothes washed in Comparative Example 1 with five panelists and scoring according to the following criteria.
◎: Compared to Comparative Example 1, all five people are judged to have less wrinkles ○: Compared to Comparative Example 1, 3 to 4 people are judged to have less wrinkles Δ: Compared to Comparative Example 1, 3 or more people have no difference And judgment X: Compared with Comparative Example 1, it is judged that three or more people have many wrinkles.

(4) Cloth sag evaluation method (4-1) Cloth sewage performance evaluation method The cloth sag performance evaluation method of the washing machine performance evaluation standard (1998) of the Japan Electrical Manufacturers' Association Washing Machine Technical Committee was used. A fully automatic washing machine (Toshiba AW-D802VP) was prepared and put so that the mass of the clothes was 4.2 kg. The water level was set at 62 L, and the liquid detergent composition shown in Table 1 was placed in a 51.7 mL washing machine, washed for 8 minutes, twice for rinsing and 6 minutes for dehydration.

(4-2) Crushing criteria for cloth garments Judgment is performed by testing three panelists five times each, and the laundry loosening rate (%) described in the washing machine performance evaluation criteria (the larger the value, the more cloth garments are garbled). It calculated and evaluated by the reference | standard shown below from the average value of three persons.
A: The laundry unraveling rate was significantly lower than the laundry unraveling rate of Comparative Example 1 (the difference was 20% or more).
○: The laundry unraveling rate was lower than the laundry unraveling rate of Comparative Example 1 (the difference was less than 20%).
Δ: The laundry unraveling rate was almost the same as the laundry unraveling rate of Comparative Example 1.
X: The laundry unraveling rate exceeded the laundry unraveling rate of Comparative Example 1.

(5) Fabric care (MA test cloth)
(5-1) Preparation of pretreatment cloth The washing water amount of a fully automatic washing machine (Toshiba, AW-D802VP) was set to 45 L, and 10 pieces of cotton T-shirts (about 2.2 kg) were put into this. Further, a compact type powder detergent (Attack, Kao Co., Ltd.) was added according to the standard usage amount, washed for 8 minutes, dehydrated for 3 minutes, rinsed twice, dehydrated for 3 minutes, and dried with a drier. This washing cycle was repeated 5 times to obtain a pretreated fabric.

(5-2) Fabric care test (MA test cloth)
Among the T-shirts of the pretreated cloth, four fabrics were placed on Testfabrics, Inc. MA (Machine Action) test cloth manufactured by the company was sewn with a sewing machine. The MA test cloth is according to Frants Saras; "The mechanical action in washing machines. MA-test peices instruction and application." (1982).

  A total automatic washing machine (Toshiba, AW-D802VP) set the washing water volume to 45L, total of 4 T-shirts sewn with the MA test cloth and 6 cotton T-shirts of the same type without the MA test cloth sewn Ten sheets (about 2.2 kg) were put. Put 37.5mL of the liquid detergent composition shown in Table 1 into the washing machine, wash for 8 minutes, dehydrate for 3 minutes, rinse twice, dehydrate for 6 minutes, and dry the MA test cloth from the T-shirt without drying. The number of removed and frayed yarns was measured.

(5-3) Criteria for evaluating fabric care Evaluation was made by determining the average value of the frayed yarns of the four MA test fabrics and comparing the average value of the number of frayed yarns of the MA test fabric washed in Comparative Example 1. Scoring was based on the following criteria.
A: The number of frayed yarns is considerably smaller than that of Comparative Example 1 (the difference is within 15 / sheet)
○: The number of frayed yarns is smaller than that of Comparative Example 1. Δ: The number of frayed yarns is substantially the same as that of Comparative Example 1. ×: The number of frayed yarns is larger than that of Comparative Example 1.

Examples 4-6 and Comparative Examples 4-6
Evaluation similar to Example 1 etc. was performed using the liquid detergent composition of Table 2. However, the reference was Comparative Example 4. The results are shown in Table 2.

Examples 7-8 and Comparative Example 7
Evaluation similar to Example 1 etc. was performed using the liquid detergent composition of Table 3. However, the reference was Comparative Example 7. The results are shown in Table 3.

Examples 9 to 11 and Comparative Example 8
Evaluation similar to Example 1 etc. was performed using the liquid cleaning composition of Table 4. However, the reference was Comparative Example 8. The results are shown in Table 4.

(Note) The components in the above table are as follows.
Nonionic surfactant A: straight chain primary alcohol having 18 carbon atoms with an average of 6 moles of EO added nonionic surfactant B: alkyl group having 16 and 18 carbon atoms mixed (16 carbon atoms) / 7 carbon atoms with an average of 7 mol of EO added to a linear primary alcohol having 18 carbon atoms = 70/30).
Nonionic surfactant C: A product obtained by adding an average of 9 mol of EO to a linear primary alcohol containing 90% by mass or more of an alkenyl group having 18 carbon atoms and one unsaturated bond.
Nonionic surfactant D: 18 primary carbon primary alcohol with an average of 18 moles of EO added Nonionic surfactant E; alkyl group having 16 and 18 carbon atoms (16 carbon atoms) / Average carbon number 18 = 70/30, mass ratio) linear primary alcohol added with 13 mol of EO on average.
Nonionic surfactant F: A compound obtained by adding an average of 7 moles of EO to an alkyl group linear secondary alcohol mixed with 12 and 13 carbon atoms.
Nonionic surfactant G: An average of 6 moles of EO added to a linear primary alcohol having 12 alkyl atoms.
Nonionic surfactant H: An average of 13 moles of EO added to a linear primary alcohol having 12 alkyl atoms.
Nonionic surfactant I: A linear primary alcohol having 12 carbon atoms in which EO is added in an average of 8 mol and PO in an average of 2 mol is randomly added.
-Nonionic surfactant J: 12 moles of carbon atoms mixed with 12 and 14 carbon atoms (carbon number 12 / carbon number 14 = 70/30, mass ratio) is an alkyl group linear primary alcohol with an average of 8 moles of EO Added one.
-LAS-S agent; linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms-ES; sodium polyoxyethylene alkyl ether sulfate ester (12 alkyl carbon atoms, 3 average EO addition moles)
Fatty acid: C12-14 coconut oil fatty acid / cationic surfactant A: alkyl group mixed with 16 carbon atoms and 18 carbon atoms (16 carbon atoms / 18 carbon atoms = 70/30, mass ratio) Monoalkyltrimethylammonium chloride / cationic surfactant B; dialkyldimethylammonium chloride / amine 1 having an alkyl group having 16 and 18 carbon atoms (carbon number 16 / carbon number 18 = 70/30, mass ratio); Stearylamidopropyldimethylamine polyethylene glycol; weight average molecular weight 2000
High molecular copolymer: Phenoxypolyethylene glycol-acrylic acid-maleic acid copolymer synthesized by the method of Synthesis Example 1 on page 4, paragraph 0020 of JP-A-10-60476 (weight average molecular weight 10,000, solid content 51. 2% by mass)
Silicone A; R and R ^1c in the general formula (c) are methyl groups, A; (I)-(CH ₂ ) ₃ —NH—CO—CH ₂ —O— (C ₂ H ₄ O) ₅ —C ₁₂ H ₂₅ and (b)-(CH ₂ ) ₃ —NH ₂ mixed, (b) / (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 B: R and R ^1c in the general formula (c) are methyl groups, A; (I)-(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 C; R and R ^1c in the general formula (c) are methyl groups, A; (I)-(CH ₂ ) ₃ —NH—CO—CH ₂ —O— (C ₂ H ₄ O) ₅ —C ₁₂ H ₂₅ and (d)-(CH ₂ ) ₃ —NHCO—CH ₂ —O— (C ₂ H ₄ O) ₅ —C ₁₄ H ₂₉ mixed, (I) / (D) = 7/3 ( Molar ratio), B; — (CH ₂ ) ₃ —O— (C ₂ H ₄ O) ₁₀ —CH ₃ , l = 200, m = 14, n = 8
・ Enzyme: Durazyme 16.0L (protease, Novozyme)

Claims (12)

A polyoxyalkylene alkyl (or alkenyl) ether (a) having an alkyl group or alkenyl group having 16 to 20 carbon atoms and an average addition mole number of alkylene oxide of 10 or less, and a surface activity described in JIS K3362: 1998 The detergent composition whose agent equivalent is 15-55 mass%. (B1) Contains a flexible base (b) selected from amines represented by the following general formula (b1) or acid salts thereof, and (b2) quaternary ammonium salts represented by the following general formula (b2). The cleaning composition according to claim 1.

[Wherein, R ^1b is an alkyl or alkenyl group having 14 to 22 carbon atoms, R ^2b is an alkylene group having 1 to 5 carbon atoms, X is —COO—, —CONR ^5b —, —OCO—, It is a group selected from —NR ^5b CO—. Here, R ^5b is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. R ^3b and R ^4b are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ^1b —X—R ^2b —. ]

[Wherein R ^6b represents a hydrocarbon group having 8 to 22 carbon atoms or a benzyl group. When R ^6b is a hydrocarbon group, this hydrocarbon group may be linear or branched, may be saturated or unsaturated, and may optionally contain a substituent. Further, the hydrocarbon group R ^6b may have a linking group in its chain. R ^7b is an alkyl group having 1 to 3 carbon atoms, a hydrocarbon group having 8 to 22 carbon atoms, or a benzyl group. When R ^7b is a hydrocarbon group, the hydrocarbon group may be linear or branched, may be saturated or unsaturated, and may optionally contain a substituent. Further, the hydrocarbon group R ^7b may have a linking group in its chain. R ^8b and R ^9b are each an alkyl group having 1 to 3 carbon atoms. X ⁻ is a counter ion. ] The cleaning composition according to claim 2, comprising 0.1 to 10% by mass of (b). The cleaning composition of Claim 1 or 2 containing the silicone derivative (c) represented by the following general formula (c).

[Wherein, l = 100 to 600, and m and n are numbers such that l: m = 100: 1 to 10: 1 and m: n = 1: 10 to 10: 1. R is an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an alkoxy group, and R ^1c 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 (A) and (B). In the latter case, the ratio of (B) in A is 50 mol% or less.

(Where a = 2 to 6, b = 2 to 6, R ^2c 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 ^3c is an alkyl group having 1 to 18 carbon atoms), B is — (CH ₂ ) _a —O— (C ₂ H ₄ O) _s — (C ₃ H ₆ O) _t —R ^2′c or R ^2c (here R ^2′c represents 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 (c), block addition or random addition may be used. ] The cleaning composition of Claim 4 which contains 0.1-10 mass% of (c). The cleaning composition according to any one of claims 1 to 5, comprising (a) in an amount of 0.5 to 10% by mass. The polyoxyalkylene alkyl (or alkenyl) ether (d) having an alkyl group or alkenyl group having 8 to 14 carbon atoms and an average addition mole number of alkylene oxide of 10 to 22 is contained. The cleaning composition according to 1. The cleaning composition according to claim 7, wherein the mass ratio of (a) to (d) is (a) :( d) = 1: 1 to 1:30. The cleaning composition according to any one of claims 1 to 8, further comprising water and having a liquid shape. Polyoxyalkylene alkyl (or alkenyl) ether (a) having an alkyl group or alkenyl group having 16 to 20 carbon atoms and an average addition mole number of alkylene oxide of 10 or less, water-soluble surfactant (X), and water In which a surfactant equivalent according to JIS K3362: 1998 is 15 to 55% by mass, wherein (a) and (a) are mixed before water is mixed. The manufacturing method which has the process of preparing the mixture which contains (X) by the mass ratio of (a) :( X) = 2: 3 to 1:50. At least a part of (X) is a polyoxyalkylene alkyl (or alkenyl) ether (d) having an alkyl group or alkenyl group having 8 to 14 carbon atoms and having an average addition mole number of alkylene oxide of 10 to 22. The manufacturing method of Claim 10. The manufacturing method of Claim 10 or 11 which contains 4-12 mass% of polyethyleneglycol of the weight average molecular weights 100-10,000 in the said mixture.