JP4727281B2 - Liquid detergent composition for clothing - Google Patents

Description

  The present invention relates to a liquid cleaning composition for clothing.

  In recent years, consumer expectations regarding liquid detergents for washing have increased awareness of high cleaning performance against sebum stains and washing clothes without damaging them (care effects for clothes, etc.). This is one of the issues of cleaning agents.

  For example, a combination of a nonionic surfactant and a specific ratio of cationic surfactant / anionic surfactant provides a high level of cleaning performance against sebum soil and a liquid softening agent with an excellent softening effect. Has been proposed (Patent Document 1). In addition, a liquid detergent that combines a nonionic surfactant and an amino-modified silicone as an agent that suppresses tangling of clothes during washing has also been developed (Patent Document 2).

Therefore, there has been a demand for a technique that achieves both high cleaning performance against sebum dirt and solid particle dirt, prevention of recontamination of dirt, and suppression of clothing damage during washing.
JP-A-11-217585 JP 2002-249799 A

  However, the combination of surfactants in Patent Document 1 is insufficient in the performance of cleaning sebum dirt and solid particles, and the ability to prevent re-contamination of dirt, and the softening effect after washing and drying is recognized. The effect of washing clothes without damaging them (the effect of suppressing tangling of clothes during washing) was insufficient. Moreover, although the liquid cleaning agent of patent document 2 has the high cleaning effect with respect to sebum dirt, the softening effect, and the effect which suppresses the entanglement of the clothing at the time of washing, the improvement effect of the solid-contamination dirt and dirt re-contamination prevention performance Was not enough. Accordingly, there has been a demand for a technique that can satisfy all of the high cleaning performance against sebum dirt and solid particle dirt, the ability to prevent re-contamination of dirt, and the suppression of damage to clothes during washing.

  An object of the present invention is to provide a liquid detergent composition for clothing having high cleaning performance, an effect of washing without damaging clothes (care effect), and an improved anti-contamination property.

The present invention is 10 to 30 average mole number of added (a) ethylene oxide, polyoxyalkylene alkyl ether having a carbon number of 8 to 14 alkyl group [hereinafter referred to as component (a)] and 5 to 55 mass%, (b) an average number of moles added is 1 to 20 ethylene oxide, polyoxyalkylene alkyl ether having a carbon number of 16 to 20 alkyl group [hereinafter referred to as component (b)] 0.5 a 10% by mass , and (c) a constitutional unit derived from the compound (c1) represented by the following general formula (c1) and a constitutional unit derived from the compound (c2) represented by the following general formula (c2) A copolymer (hereinafter referred to as the component (c)) of 0.1 to 0.1 % by mass of the total of the structural units (c1) and the structural units (c2), including the unit (c2). 10% by mass , (a This relates to a liquid detergent composition for clothing , wherein the mass ratio of the component (b) to the component (b) is (a) / (b) = 95/5 to 50/50 .

[In formula, R < ₁ > -R < ₄ > is the hydrogen atom which may be same or different, a C1-C30 alkyl group, a phenyl group, or a carboxy group, or its salt. However, at least one of R _{1 to} R ₄ is a carboxy group or a salt thereof. ]

[Wherein, R _{5 to} R ₈ are the same or different, a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a phenyl group,

_{-O-R 9, -COO-R} 9, or -OCO-R _9. However, not all of R _{5 to} R ₈ are hydrogen atoms. R ₉ is an alkyl group having 1 to 30 carbon atoms or a phenyl group. ]

  ADVANTAGE OF THE INVENTION According to this invention, the liquid cleaning composition for clothes excellent in the washing | cleaning performance, the effect (care effect) which wash | cleans clothes without damaging, and the recontamination prevention property is provided.

<(A) component>
The component (a) of the present invention is a polyoxyalkylene having an average added mole number of C2-3 alkylene oxide (hereinafter referred to as AO) of 10-30 and an alkyl group of 8-14 carbon atoms. Alkylene alkyl ether. AO is ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter referred to as PO), and preferably includes EO. When both EO and PO are included, either random addition or block addition may be used. The average added mole number of AO is preferably 10-22. The alkyl group of component (a) may be linear or branched, and may be primary, secondary, or tertiary. In addition, although (a) component can also contain AO other than C2-C3 AO, C2-C3 AO is 80-100 mol% in all AO, Furthermore, 90-100 mol%. It is preferable.

<(B) component>
The component (b) of the present invention is a polyoxyalkylene alkyl ether having an average addition mole number of AO having 2 to 3 carbon atoms of 1 to 20 and an alkyl group having 16 to 20 carbon atoms. AO is EO and PO, and preferably contains EO. When both EO and PO are included, either random addition or block addition may be used. The average added mole number of AO is preferably 1-20, particularly 1-15. The alkyl group as component (b) may be linear or branched, and may be primary, secondary or tertiary.

<(C) component>
The component (c) of the present invention is derived from the structural unit (c1) derived from the compound (c1) represented by the general formula (c1) and the compound (c2) represented by the general formula (c2). The copolymer is a copolymer including the structural unit (c2), and the total of the structural unit (c1) and the structural unit (c2) is 80% by mass or more, preferably 90% by mass or more. The copolymer is a copolymer of a compound (c1) which is a polymerizable unsaturated carboxylic acid or a salt thereof and a compound (c2) which is a polymerizable unsaturated hydrocarbon. The component (c) may be a salt obtained by using a polymerizable unsaturated carboxylic acid and neutralizing part or all after copolymerization. Moreover, when the compound (c1) has a plurality of carboxy groups, it may be an anhydride. The structural unit (c1) and the structural unit (c2) may be either introduced by a corresponding compound at the time of copolymerization or later introduced into the copolymer.

  In the production of the component (c), monomers other than the compound (c1) and the compound (c2) can be used, but the total of the compound (c1) and the compound (c2) is 80 mass in all monomers. % Or more, and preferably 90% by mass or more. The molar ratio of the structural unit (c1) to the structural unit (c2) is preferably (c1) / (c2) = 10/90 to 90/10, more preferably 20/80 to 80/20, The molar ratio of the compound (c1) to the compound (c2) is preferably within this range.

  Compound (c1) is a vinyl monomer having a carboxy group or a salt thereof. Examples of the monomer include (meth) acrylic acid [(meth) acrylic acid means acrylic acid, methacrylic acid or a mixture thereof] and salts thereof, styrene carboxylic acid and salts thereof, maleic monomer [anhydride Maleic acid, maleic acid, maleic acid monoester, and maleic acid monoamide or a mixture of two or more thereof] and salts thereof, itaconic acid and salts thereof, and the like. Can be used.

  Moreover, as a compound (c2), the monomer chosen from the following monomer group (c2-1)-(c2-6) is mentioned preferably.

(C2-1) Vinyl ethers having 1 to 22 carbon atoms, unsubstituted or substituted, saturated or unsaturated alkyl groups or aralkyl groups. Examples thereof include methyl vinyl ether, ethyl vinyl ether, 4-hydroxybutyl vinyl ether, phenyl vinyl ether, lauryl vinyl ether, myristyl vinyl ether, palmityl vinyl ether, stearyl vinyl ether and the like.

(C2-2) (meth) acrylic acid esters having an unsubstituted or substituted, saturated or unsaturated alkyl group or aralkyl group having 1 to 7 carbon atoms. Examples include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and the like.

(C2-3) Styrenes. For example, styrene, 4-ethylstyrene, α-methylstyrene and the like are preferable.

(C2-4) Vinyl esters. For example, vinyl acetate and vinyl caproate are preferable.

(C2-5) (meth) acrylic acid ester having a saturated or unsaturated alkyl group or aralkyl group having 8 to 30, preferably 12 to 22 carbon atoms. Examples include decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, and the like.

(C2-6) Alkenes having 3 to 30 carbon atoms such as butene, hexene, pentene, octene, nonene, decene, dodecene and the like can be mentioned.

  As the compound (c2), styrene, 4-ethylstyrene, and α-methylstyrene are preferable.

  (C) A component can contain the structural unit derived from monomers other than a compound (c1) and a compound (c2). Examples of other monomers include the following.

(X1) A vinyl monomer having a sulfonic acid group or a salt thereof. Examples of the monomer include 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamido-2-alkyl (1 to 4 carbon atoms) propanesulfonic acid, vinyl Examples thereof include sulfonic acid monomers such as sulfonic acid and styrene sulfonic acid, and one or more selected from these can be used.

(X2) A vinyl monomer having a phosphoric acid group or a phosphonic acid group or a salt thereof. Examples of the monomer include (meth) acryloyloxyalkyl (C1-4) phosphoric acid, vinylphosphonic acid and the like.

(X3) Substituted (meth) acrylamides which are unsubstituted or have a saturated or unsaturated alkyl group or aralkyl group having 1 to 12 carbon atoms on nitrogen. For example, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-t-butyl (meth) acrylamide, (meth) acryloylmorpholine, 2 -(N, N-dimethylamino) ethyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N- Butoxymethyl (meth) acrylamide and the like are preferable.

(X4) N-vinyl aliphatic amides. For example, N-vinylpyrrolidone, N-vinylacetamide, N-vinylformamide and the like are preferable.

(X5) Alkylene oxides. For example, ethylene oxide and propylene oxide are preferable.

(X6) Cyclic imino ethers. For example, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline and the like are preferable.

(X7) A monomer used in the production of polyamides such as N-methylvalerolactams.

(X8) Monomers used for the production of polyaddition products such as polyurethane, such as polyethylene glycol, hexamethylene diisocyanate, and N-methyl-diethanolamine or 1,4-butanediol.

(X9) Substituted (meth) acrylamide having 1 or 2 saturated or unsaturated alkyl group or aralkyl group having 8 to 30 carbon atoms, preferably 12 to 22 carbon atoms bonded to nitrogen. For example, N-lauryl (meth) acrylamide, N-dioctyl (meth) acrylamide, etc. are mentioned.

(X10) A monomer used for the production of polyesters composed of a dihydric alcohol and a divalent carboxylic acid. Examples thereof include polyethylene glycol and terephthalic acid, or 1,4-butanediol and succinic acid.

  Examples of salts of these compounds (c1) and other monomers include alkali metals, alkaline earth metals, ammonium, alkyl or alkenyl ammonium having 1 to 22 carbon atoms, alkyl or alkenyl substituted pyridinium having 1 to 22 carbon atoms, Examples include alkanol ammonium having 1 to 22 carbon atoms or basic amino acid, and alkali metal salts such as sodium and potassium are preferable.

  (C) The molecular weight of a component is 3000-8 million in a weight average molecular weight, Furthermore, 3000-1 million are preferable. This weight average molecular weight is measured using gel permeation chromatography (GPC), and the average molecular weight is determined in terms of polyethylene glycol (PEG).

  The liquid detergent composition for clothes of the present invention preferably contains 5 to 55% by mass, further 5 to 40% by mass, and further 10 to 20% by mass of component (a) in terms of cleaning performance. Moreover, it is clothing care effect to contain (b) component 0.5-55 mass%, further 0.5-10 mass%, further 0.5-7.5 mass%, and also 0.5-5 mass%. From the viewpoint of blending stability. Moreover, it is preferable from the point of recontamination prevention property to contain (c) component 0.1-10 mass%, further 0.1-7.5 mass%, and also 0.1-5 mass%.

  The content of the surfactant in the liquid detergent composition for clothing of the present invention is preferably 5.5 to 65% by mass, and more preferably 7 to 40% by mass. In the total surfactant, the total mass ratio [[(a) + (b)] / total surfactant] of the component (a) and the component (b) is 0.055 to 0.55, It is preferable that it is 07-0.3.

  Moreover, in the liquid detergent composition for clothes of this invention, mass ratio of (a) component and (b) component is (a) / (b) = 95 / 5-50 / 50, Furthermore, 93 / 7- 80/20 is preferable in terms of cleaning performance and clothing care effect.

  The liquid detergent composition for clothing of the present invention contains (d) an amine represented by the following general formula (d1) or an acid salt thereof (hereinafter referred to as “component (d)”) to reduce the friction of synthetic fibers, and to fade It is preferable in terms of prevention and softening.

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

  The content of the component (d) in the composition is preferably 0.1 to 5% by mass, more preferably 0.1 to 2% by mass. Specific examples of the component (d) 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, stearylamidopropyl Methylamine, behenyl dimethylamine, oleyl amidopropyl dimethylamine, and salts thereof preferably, particularly stearyl amidopropyl dimethylamine and salts thereof are preferred.

  Moreover, in the liquid detergent composition for clothes of this invention, mass ratio of (c) component and (d) component is (c) / (d) = 99 / 1-30 / 70, Furthermore, 80 / 20- A ratio of 40/60 is preferable from the standpoint of preventing recontamination and flexibility.

  The liquid detergent composition for clothing of the present invention may contain other surfactants such as an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and other nonionic surfactants. it can.

  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 (III) with 0.5 to 6 moles of EO added Average alkyl group having 10 to 20 carbon atoms or alkyl (or alkenyl) sulfate (IV) having an alkenyl group 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.

  Moreover, as a cationic surfactant, mono long-chain alkyl (C8-C22 is preferable) quaternary ammonium salt is mentioned. Specific examples include lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palm alkyltrimethylammonium chloride, cetyltrimethylammonium chloride, beef tallow alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, stearyldimethylbenzylammonium chloride, stearyldihydroxyethylmethylammonium chloride, N-lauroylamidopropyl-N′-trimethylammonium chloride, N-myristoylamidopropyl-N′-trimethylammonium chloride, distearyldimethylammonium chloride, dimyristyldimethylammonium chloride, dioctyldimethylammonium chloride, didecyl Ammonium chloride, etc. dilauryl dimethyl ammonium chloride. Of these, beef tallow alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, and dimyristyldimethylammonium chloride are preferable in the present invention. Further, a quaternary ammonium salt in which the composition of the long chain alkyl group is a mixed composition having 16 and 18 carbon atoms is also preferable.

  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 liquid cleaning composition for clothes of this invention in the following range, respectively.

(I) Alkali metal hydroxides, silicates, carbonates such as sodium carbonate, and 2-aminoethanol, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, Alkaline agents such as diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanolamine, alkanolamines such as isopropanolamine mixture (mixture of mono, di, and tri), etc. 0.01 to 10% by mass

(Ii) (ii-1) alkanols such as ethanol, 1-propanol, 2-propanol, 1-butanol, (ii-2) glycols such as propylene glycol, butylene glycol, hexylene glycol, (ii-3) Polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, dipropylene glycol, tripropylene glycol, polypropylene glycol having an average molecular weight of about 2000, (ii- 4) Diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl Ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerol ether, 2-methylglycerol ether, 1 , 3-dimethylglycerin ether, 1-ethylglycerin ether, 1,3-diethylglycerin ether, triethylglycerin ether, 1-pentylglyceryl ether, 2-pentylglyceryl ether, 1-octylglyceryl ether, 2-ethylhexylglyceryl ether, diethylene glycol Alkyl ethers such as monobutyl ether, (ii-5) 2-phenoxyethanol, diethylene glycol monophenyl ether, Water miscibility of poly (ethylene glycol monophenyl ether), polyethylene glycol monophenyl ether having an average molecular weight of about 480, 2-benzyloxyethanol, diethylene glycol monobenzyl ether, polyoxyalkylene benzyl ether, polyoxyalkylene phenyl ether, and other aromatic ethers 0.1-15% by mass of organic solvent. These also have functions as a thickener, a solubilizer, a phase adjuster, a detergency improver and the like.

(Iii) Paratoluenesulfonic acid, benzoate (also has an effect as a preservative), and a thinning agent and solubilizer such as urea 0.01 to 30% 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, carboxymethylcellulose, polyethylene glycol having a weight average molecular weight of 5000 or more, naphthalene sulfonate formalin condensate, and claims 1-21 of JP 59-62614 (column 3, page 1) 5 to 3 pages, 4 columns, 14 lines) recontamination preventives and dispersants such as polymers described in 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 preservatives

  The liquid detergent composition for clothing of the present invention comprises the above components (a) to (c) and optional components, and the remaining water, but the pH at 20 ° C. is 6 to 11, and further 7 to 9.5. A liquid composition is preferred.

  Moreover, the viscosity at 20 ° C. of the liquid detergent composition for clothing of the present invention is preferably 50 to 500 mPa · s, more preferably 75 to 300 mPa · s, and particularly preferably 100 to 250 mPa · s.

  The liquid cleaning composition shown in Table 1 was prepared, and the following cleaning power, recontamination prevention property, and fabric care effect were evaluated using the obtained composition. The results are shown in Table 1.

(1) Detergency evaluation (preparation of collar red cloth)
A collar lining cloth described in JIS K3362: 1998 is prepared.
(Cleaning conditions and evaluation method)
The detergency of the liquid detergent composition shown in Table 1 and the index detergent for determining detergency was compared in accordance with the method for evaluating the detergency of a synthetic detergent for clothing described in JIS K 3362: 1998. The use concentration of the liquid detergent composition shown in Table 1 was 1.33 g / L.
The determination of the cleaning power was “◎” when it was better than the index detergent, “◯” when it was equivalent to the index detergent, and “x” when it was inferior to the index detergent.

(2) Recontamination prevention property White cotton cloth (gold cloth 2003 cloth) was cut into 10 cm × 10 cm to form a set of five sheets. To 1 liter of the detergent aqueous solution for evaluation, kanuma red soil for gardening was added, and the test was conducted with a targotometer under the following conditions.
<Experimental conditions>
Cleaning time: 10 minutes Cleaning agent concentration: 0.08% by mass
Water hardness: 4 ° DH
Water temperature: 20 ° C
Rinsing: Rinsing with running water at 20 ° C for 5 minutes

The anti-recontamination ability was determined by measuring the reflectance at 460 nm of the raw cloth (white cloth) before washing and the contaminated cloth after the test with a self-recording colorimeter (manufactured by Shimadzu Corporation), and obtaining the re-contamination prevention ratio by the following formula.
Recontamination prevention rate (%) = (reflectance after test / reflectance of base fabric) × 100
The determination of recontamination prevention was “◎” when it was better than the index detergent, “◯” when it was equivalent to the index detergent, and “x” when it was inferior to the index detergent.

(3) Fabric care effect (MA test cloth)
(3-1) Preparation of pre-treatment cloth Prepare a fully automatic washing machine (Toshiba, AW-D802VP), set the amount of washing water to 45L, and put a total of 2 cotton T-shirts (about 2.2kg) into this. It was. 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.

(3-2) Fabric care test (MA test fabric)
Among the T-shirts of the pretreated cloth, 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).

  Prepare a fully automatic washing machine (Toshiba, AW-D802VP), set the amount of washing water to 45 L, and put a total of 10 cotton T-shirts (about 2.2 kg) including T-shirts sewn with the MA test cloth. It was. Put 37.5 mL of the 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.

(3-3) Criteria for evaluating fabric care Evaluation is made by determining the average value of the frayed yarns of the four MA test cloths and comparing the average value of the number of frayed yarns of the MA test cloth 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 15 pieces / sheet or more ).
○: 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.

The components in the table are as follows. The “adjusted amount” of sodium hydroxide is an amount that adjusts the pH (20 ° C.) of the composition to 6 to 11.
Nonionic surfactant a1: An average of 13 moles of EO added to a linear primary alcohol having an alkyl group having 12 carbon atoms. Nonionic surfactant a2: an alkyl group having 12, 13, 14 carbon atoms. Mixture (12 alkyl groups / 13 alkyl groups / 14 alkyl groups = 20/50/30, mass ratio) linear secondary alcohol added with an average of 7 mol of EO Ionic surfactant a3: A linear primary alcohol having an alkyl group of 12 carbon atoms, with an average of 8 mol of EO and an average of 2 mol of PO, non-ionic surfactant b1: 18 carbon atoms An average of 6 moles of EO added to a linear primary alcohol having an alkyl group. Nonionic surfactant b2: mixed of 16 and 18 alkyl groups (16 alkyl groups / 18 carbon atoms) Alkyl group = 70/30, mass ratio) linear primary alcohol with an average of 7 mol of EO added non-ionic surfactant b3: linear chain 1 containing 90% by mass or more of alkenyl groups having 18 carbon atoms Copolymer c1: maleic anhydride-diisobutylene copolymer (maleic anhydride / diisobutylene = 50/50, molar ratio, weight average molecular weight 5000)
Copolymer c2: Amylene-maleic anhydride copolymer sodium salt (amylene / maleic anhydride = 50/50, molar ratio, weight average molecular weight 15000)
Polyacrylic acid: weight average molecular weight 10,000, sodium salt Amine 1: stearylamidopropyldimethylamine Cationic surfactant 1: mono long chain alkyltrimethylammonium chloride, long chain alkyl group is alkyl having 16 and 18 carbon atoms Groups are mixed (alkyl group having 16 carbon atoms / alkyl group having 18 carbon atoms = 70/30, mass ratio).
Cationic surfactant 2: Di long chain alkyldimethylammonium chloride and long chain alkyl group are both mixed alkyl groups having 16 and 18 carbon atoms (alkyl group having 16 carbon atoms / alkyl group having 18 carbon atoms = 70). / 30, mass ratio)
Anionic surfactant 1: Alkylbenzenesulfonic acid having a linear alkyl group having 10 to 14 carbon atoms Anionic surfactant 2: Polyoxyethylene alkyl ether sodium sulfate ester (EO average addition mole number 2.5, alkyl Group carbon number 12)
Anionic surfactant 3: coconut oil fatty acid having an alkyl group having 12 to 14 carbon atomsEnzyme: Durizer Im 16.0 L (protease, Novozyme)
・ Fluorescent dye: Chino Pearl CBS-X (Nippon Ciba-Geigy Co., Ltd.)

Claims (3)

(A) 5 to 55% by mass of polyoxyalkylene alkyl ether having an average addition mole number of ethylene oxide of 10 to 30 and an alkyl group having 8 to 14 carbon atoms, (b) average addition mole number of ethylene oxide 1 to 20 and 0.5 to 10% by mass of a polyoxyalkylene alkyl ether having an alkyl group with 16 to 20 carbon atoms , ( c) a compound (c1) represented by the following general formula (c1) The structural unit (c1) and the structural unit (c2) derived from the compound (c2) represented by the following general formula (c2) are included, and among the structural units, the structural unit (c1) and the structural unit (c2) ) 0.1 to 10% by mass of a copolymer having a total of 80% by mass or more , and (d) an amine represented by the following general formula (d1) or an acid salt thereof, The mass ratio of the component (b) is ( ) / (B) = 95 / 5~50 a / 50, laundry liquid detergent compositions.

[In formula, R < ₁ > -R < ₄ > is the hydrogen atom which may be same or different, a C1-C30 alkyl group, a phenyl group, or a carboxy group, or its salt. However, at least one of R _{1 to} R ₄ is a carboxy group or a salt thereof. ]

[Wherein, R _{5 to} R ₈ are the same or different, a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a phenyl group,

_{-O-R 9, -COO-R} 9, or -OCO-R _9. However, not all of R _{5 to} R ₈ are hydrogen atoms. R ₉ is an alkyl group having 1 to 30 carbon atoms or a phenyl group. ]

[Wherein, R ^1d is an alkyl or alkenyl group having 14 to 22 carbon atoms, R ^2d is an alkylene group having 1 to 5 carbon atoms, X is —COO—, —CONR ^5d —, —OCO—, It is a group selected from —NR ^5d CO—. Here, R ^5d is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. R ^3d and R ^4d are the same or different alkyl group having 1 to 3 carbon atoms or hydroxyalkyl group, or R ^1d —X—R ^2d —. ] A surfactant is contained in an amount of 5 to 60% by mass, and the total mass ratio [[(a) + (b)] / total surfactant] of the components (a) and (b) is 0 in all surfactants. a is claim 1 laundry liquid detergent composition according .055～0.55. The liquid cleaning composition for clothing according to claim 1 or 2 , wherein the mass ratio of the component (c) and the component (d) is (c) / (d) = 99/1 to 70/30.