JP2011201996A - Liquid detergent composition for clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition that has excellent detergency and low-temperature storage stability and does not impair finishing properties of clothing, wherein the detergent composition contains a high-concentration surfactant.SOLUTION: The liquid detergent composition comprises (a) 30-75 mass% of a surfactant composed of a nonionic surfactant containing 7-22C hydrocarbon groups or the nonionic surfactant containing 7-22C hydrocarbon groups and an anionic surfactant and/or a cationic surfactant and (b) a compound represented by general formula (1): HO-(CHO)-(AO)-(CHO)-(AO)-(CHO)-H (wherein AO is 3-5C alkyleneoxy; "-" shows that CHO and AO are block-bonded; a, b, c, o and p are each an average addition molar number, b=3-20, c=3-20, a+b+c=5-30, o=1-5, p=1-5 and o+p=2-6) and having a number-average molecular weight of 200-2,000.

Description

  The present invention relates to a liquid detergent composition for clothing that is excellent in washing performance and stability at low temperatures and does not impair the finish of fibers. Here, the term “for clothing” means not only clothing but also a textile product to be washed with water as a general laundry.

  In recent years, environmental awareness has increased, and there is a strong demand for the appearance of cleaning agents that have a low environmental impact. So-called concentrated type cleaning agents with higher cleaning component concentrations than conventional cleaning agents reduce the size of the cleaning agent itself, reduce the amount of container resin, reduce transportation costs, reduce waste after use, etc. It is thought that it is very effective for reducing.

  However, in a normal liquid cleaning agent, when the concentration of a surfactant as a cleaning component is increased, there is a problem that thickening or gelation occurs and the usability is significantly impaired. This is because an increase in the concentration of the surfactant forms a remarkably high phase such as liquid crystal or crystal in the composition. Furthermore, when clothing is washed with a liquid detergent containing a high concentration of nonionic surfactant to which ethylene oxide has been added, the finish of the clothing is impaired due to the influence of the surfactant adsorbed on the fibers in the washing process. .

  It is known that a polyalkylene glycol compound is blended in a cleaning agent. For example, Patent Documents 1 to 3 disclose, as an arbitrary component conventionally known to be blended in a liquid cleaning agent, a molecular weight of 200 to several. Thousands of polyalkylene glycols have been disclosed, but specific examples are polypropylene glycol and polyethylene glycol.

  Patent Document 4 discloses a polyalkylene glycol compound having a specific structure having a low-foaming property and excellent detergency and having a number average molecular weight of 350 to 30,000. This compound has a structure containing an alkyleneoxy group having 4 or more carbon atoms at the terminal.

  Patent Document 5 discloses that a polyoxyalkylene glycol having a number average molecular weight of 4000 or more can be used as an organic builder having a specific solubility parameter.

  Patent Document 6 discloses a liquid detergent excellent in stability in which a polyalkylene oxide adduct of a polyhydric alcohol having an average molecular weight of 300 to 4000 is blended.

  On the other hand, as a high-concentration type liquid cleaning agent, Patent Document 7 discloses that a higher alcohol is added with ethylene oxide (hereinafter also referred to as EO) and propylene oxide (hereinafter also referred to as PO). A concentrated liquid detergent composition containing an ionic surfactant and a specific solvent is described. As a preferred nonionic surfactant in the text and examples, an EO / PO block type nonionic surfactant in which EO is added and then PO is described is described. Such a type of nonion has higher liquid crystal and crystal suppression effect than a normal EO type nonionic surfactant, but its effect is insufficient and the stability at low temperature has not been completely solved.

  Patent Document 8 discloses a low-foaming detergent containing a polymerization type nonionic surfactant of ethylene oxide and propylene oxide. However, when used in a concentrated liquid detergent, there is no effect on stability at low temperatures. It was enough.

JP 2009-138056 A JP 2009-173700 A JP 2001-152200 A Japanese Patent Laid-Open No. 7-292098 JP 2002-53897 A JP-A-6-17095 JP-A-8-157867 JP 2008-156521 A

  An object of the present invention is to provide a liquid cleaning composition for clothing containing a high concentration of a surfactant, which is excellent in cleaning power and low-temperature storage stability and does not impair the finish of clothing. It is.

The present invention relates to a liquid detergent composition containing the following component (a) and component (b), wherein the content of component (a) is 30 to 75% by mass.
(A) Component: A surfactant which is the following (a1) component or a combination of the following (a1) component and one or more selected from the following (a2) component and the following (a3) component.
(A1) component: nonionic surfactant (a2) component: anionic surfactant (a3) component: cationic surfactant (b) component: number average molecular weight represented by the following general formula (1) 200 to 200 compounds of _{2000 HO- (C 2 H 4 O} ) a - (AO) o - (C 2 H 4 O) b - (AO) p - (C 2 H 4 O) c -H (1)
(In the formula, AO represents an alkyleneoxy group having 3 to 5 carbon atoms, and “-” indicates that a C ₂ H ₄ O group and an AO group are bonded to each other. A, b, c, o, p Is the average number of moles added, b = 3-20, c = 3-20, a + b + c = 5-30, o = 1-5, p = 1-5, o + p = 2-6.

  The composition of the present invention exhibits a high detergency despite having a high concentration of a surfactant as a cleaning component, is excellent in storage stability at low temperatures, and is excellent in the finish of clothing. is there. The composition of the present invention is suitable as a liquid cleaning composition for clothing.

<(A) component>
The component (a) of the present invention is the component (a1), or the component (a1), the component (a2) and / or the component (a3). That is, the surfactant is a surfactant of the component (a1) or a combination of (a1) and one or more selected from the components (a2) and (a3), and is at least (a1) ) Component-containing surfactant.

  In terms of detergency such as mud dirt, it is preferable to use the anionic surfactant of component (a2) together with the nonionic surfactant of component (a1). For improving the finish of clothing, (a3) The component cationic surfactant is preferably used together with the component (a1) nonionic surfactant.

  As the nonionic surfactant of component (a1), (a1-1) an aliphatic alcohol having 8 to 22 carbon atoms in the alkyl group, a fatty acid and fatty acid alkyl ester having 7 to 21 carbon atoms in the alkyl group, and an alkyl group A compound obtained by adding an alkylene oxide such as EO or PO to a compound having one or more unshared electron pairs such as an aliphatic amine having 8 to 20 carbon atoms according to a conventional method, (a1-2) sugar Examples thereof include those having a derived polyol as a hydrophilic group, (a1-3) amine oxide, and (a1-4) fatty acid amides. Among these, the nonionic surfactant represented by the general formula (2) is preferable, and a high detergency can be obtained against the collar and cuff dirt.

_{^{R 1 (CO) l O -}} [(C 2 H 4 O) m / (AO) n] R 2 (2)
[Wherein, R ¹ is a chain hydrocarbon group having 7 to 22 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. AO is an alkyleneoxy group having 3 to 5 carbon atoms. l is a number of 0 or 1. m and n are average added mole numbers, m is a number of 8-30, and n is a number of 0-5. However, when l = 0, m is 12 to 30, and R ² is a hydrogen atom. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]

In the general formula (2), R ¹ is a hydrocarbon group having 7 to 22 carbon atoms, preferably a hydrocarbon group having 7 to 18 carbon atoms, and more preferably 7 to 16 carbon atoms. R ¹ is preferably a linear hydrocarbon group. The hydrocarbon group for R ¹ is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. R ¹ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. The R ¹ carbon atom bonded to the oxygen atom or carbonyl carbon is preferably the first carbon atom from the viewpoint of detergency, and is preferably a compound derived from a primary alcohol.

The method for obtaining the compound of the general formula (2) is not particularly limited, but when l = 0, R ² is a hydrogen atom, and an addition reaction of ethylene oxide with an alcohol having 8 to 22 carbon atoms, or It can be obtained by addition reaction of ethylene oxide and C3-C5 alkylene oxide.

When l = 1, R ² is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. Such a compound is obtained by sequentially adding or reacting an alcohol (R ² —OH) with a C 3-5 alkylene oxide and ethylene oxide to form an adduct, which is then esterified with a fatty acid or a fatty acid ester, respectively. It can be obtained by a method of producing by an oxidization reaction or transesterification, or by sequentially adding an alkylene oxide to a fatty acid or simultaneously adding it to form an adduct, and then reacting this with an alkyl halide. It can also be produced by a method in which an alkylene oxide is subjected to an addition reaction between an ester and an esterified product of fatty acid and alcohol (R ¹ COOR ² ) using a specific catalyst (see Japanese Patent Application Laid-Open No. 4-279552). it can.

  M in the general formula (2) is an average addition mole number of ethyleneoxy groups, and is a number of 8 to 30, preferably 9 to 25, particularly preferably 10 to 20. m is 10 or more when l = 0. n is the average number of added moles of an alkyleneoxy group having 3 to 5 carbon atoms, and the lower limit is 0 or more, preferably 1 or more, and the upper limit is 5 or less, preferably 4 or less in terms of cleaning performance. More preferably, it is 3 or less.

  The alkyleneoxy group which is AO in the general formula (2) has a methyl branched structure, an ethyl branched structure, or a propyl branched structure when obtained by addition reaction of alkylene oxide. AO is preferably an oxypropylene group obtained by addition reaction of propylene oxide (hereinafter sometimes referred to as PO).

  In the present invention, as the nonionic surfactant of the general formula (2), AO is a propyleneoxy group, the average added mole number n of the propyleneoxy group is 2 to 4, particularly 2 to 3, and It is more preferable to use a compound having an average addition mole number m of ethyleneoxy groups of 8 to 30, more preferably 9 to 25 moles because a liquid detergent composition having excellent rinsing properties and detergency can be obtained.

Regarding the production of the nonionic surfactant of the general formula (2), examples of the catalyst used for alkoxylation of R ¹ —OH or R ² —OH include a base catalyst and an acid catalyst. Of these, a base catalyst is preferably used from the viewpoint of cost, and sodium hydroxide or potassium hydroxide, particularly potassium hydroxide is most preferably used as the base.

An example of production conditions when potassium hydroxide is used as a catalyst is shown below. First, potassium hydroxide was charged into a raw material saturated or unsaturated higher alcohol having 7 to 22 carbon atoms (compound represented by R ¹ —OH), followed by nitrogen substitution, and at 100 to 110 ° C. and 1 to 7 kPa. After dehydration for 30 minutes to 1 hour and addition of alkylene oxide at 100 to 170 ° C. and 0.3 to 0.6 MPa, the added potassium hydroxide and an equimolar amount of acid agent (acetic acid, lactic acid, glycolic acid) Etc.). In addition, the usage-amount of an alkylene oxide is selected according to the number-of-moles of raw material alcohol so that the conditions of m and n of General formula (2) may be satisfy | filled.

  As the anionic surfactant of component (a2), alkylbenzene sulfonate, alkyl sulfate ester salt, polyoxyalkylene alkyl or alkenyl ether sulfate ester salt, α-olefin sulfonate salt, α-sulfo fatty acid salt or methyl ether thereof , Polyoxyalkylene alkyl or alkenyl ether carboxylate, fatty acid salt, amino acid type surfactant, N-acyl amino acid type surfactant and the like. Particularly, an alkylbenzene sulfonate having a linear alkyl group having 10 to 14 carbon atoms, an alkyl sulfate ester salt having 10 to 18 carbon atoms, an polyoxypropylene having an average of 0.2 to 3 moles of ethyleneoxy groups and any polyoxypropylene Ethylene (polyoxypropylene) alkyl ether sulfates and alkyl or alkenyl fatty acid salts having 10 to 18 carbon atoms are preferred.

  The counter ion of the anionic surfactant is preferably an alkali metal such as sodium or potassium, an alkaline earth metal such as magnesium, or an amine such as monoethanolamine, diethanolamine, or triethanolamine, because the liquid stability is particularly improved. Alkanolamine is preferred. Moreover, an anionic surfactant may be mix | blended in a composition with an acid form, and you may neutralize with the alkali agent (alkanolamine etc.) added separately. The mass when neutralized with an alkaline agent is calculated not as a salt but as an acid, and the alkaline agent is handled as the component (d) described later.

  The liquid detergent composition of the present invention can contain a cationic surfactant as the component (a3) as the component (a) in order to improve the finish of the fiber. Examples of the cationic surfactant include primary to tertiary amines having a long chain alkyl group (excluding alkanolamines described later) and quaternary ammonium salts having a long chain alkyl group. As a group bonded to a nitrogen atom, one or two alkyl groups having 6 to 22 carbon atoms which may have an ether bond, an ester bond or an amide bond in the middle are present, and the remainder is a hydrogen atom or carbon number 4 The amine which is the alkyl group which may have the following hydroxy groups, and the alkyl group having 6 to 22 carbon atoms which may have an ether bond, an ester bond or an amide bond in the middle as the group bonded to the nitrogen atom And quaternary ammonium salts which are alkyl groups which may have a hydrogen atom or a hydroxy group having 4 or less carbon atoms. In the present invention, a quaternary ammonium type surfactant having one long-chain alkyl group having 6 to 22 carbon atoms and a tertiary amine having one long-chain alkyl group having 6 to 22 carbon atoms are preferable. Among these, a quaternary ammonium salt type surfactant represented by the following general formula (3) is preferable as the surfactant.

[In the formula, R ³ is a hydrocarbon group having 6 to 22 carbon atoms, preferably a linear or branched chain, particularly a linear alkyl group or an alkenyl group, and — (A′O) _s — in R ³ May be included. A′O is an ethyleneoxy group and / or a propyleneoxy group, and s represents an average added mole number of A′O and is 0.1 to 10. R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 3 carbon atoms, a benzyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X is a halogen atom, CH ₃ SO ₄ or CH ₃ CH ₂ SO ₄ . ]

In the quaternary ammonium salt of the general formula (3), the carbon number of R ³ is preferably 8 to 20, more preferably 10 to 18, and most preferably 10 to 16. R ⁴ , R ⁵ and R ⁶ are each preferably a methyl group or an ethyl group, and more preferably a methyl group.

As the cationic surfactant, for example, the following (a3-1) to (a3-4) can be used, but (a3-1) and (a3-3) are preferable in terms of cleaning performance, stability and flexibility. More preferably, the carbon number of R ³ is preferably 8 to 20, more preferably 10 to 18, and most preferably 10 to 14. In the case of containing (a3-1), it is most preferable in terms of washing performance and finish of clothing to occupy 50% by mass or more, particularly 60% by mass in the component (a3).

  Further, it is not necessary that all of the cationic surfactant of the component (a3) is a compound of the above general formula (3), and a quaternary ammonium salt or amine salt having another structure may be used.

(A3-1): A trialkylammonium salt in which R ³ is a linear alkyl group having an average carbon number of 6 to 22 and R ^{4 to} R ⁶ are an alkyl group having 1 to 3 carbon atoms.
(A3-2): a trialkylammonium salt in which R ³ is a branched alkyl group having an average carbon number of 6 to 22 and R ^{4 to} R ⁶ are an alkyl group having 1 to 3 carbon atoms.
(A3-3): an ammonium salt in which R ³ is a linear alkyl group having 6 to 22 average carbon atoms, R ⁴ is a benzyl group, and R ⁵ and R ⁶ are alkyl groups having 1 to 3 carbon atoms .
(A3-4): R ³ is a straight chain alkyl group having an average carbon number of 6 to 22, R ³ includes — (A′O) _s —, s is 1 to 5, and R ⁴ to An ammonium salt in which R ⁶ is an alkyl group having 1 to 3 carbon atoms.

  In the liquid detergent composition of the present invention, the content of the component (a), and further the total content of the components (a1) and (a2) is 30 to 75% by mass, and 35% from the viewpoint of detergency. % Or more is preferable, and 40 mass% or more is more preferable. The upper limit is 75% by mass or less, preferably 70% by mass or less, and more preferably 65% by mass or less from the viewpoint of the storage stability of the liquid detergent composition. The above range definition includes the case where the component (a2) and / or the component (a3) is 0% by mass.

  In the liquid detergent composition of the present invention, from the viewpoint of detergency and flexibility, when the component (a3) is contained, the component (a2) is preferably contained together with the component (a1) as the component (a).

  In the present invention, a surfactant other than the component (a) may be blended to such an extent that this effect is not impaired, and examples thereof include amphoteric surfactants. However, in the present invention, it is preferable that the surfactant substantially consists of the components (a1) to (a3).

<(B) component>
The component (b) of the present invention is a compound represented by the following general formula (1), and has a specific block addition structure and is characterized in that both ends are hydrophilic ethyleneoxy groups.
_{HO- (C 2 H 4 O)} a - (AO) o - (C 2 H 4 O) b - (AO) p - (C 2 H 4 O) c -H (1)
(In the formula, AO represents an alkyleneoxy group having 3 to 5 carbon atoms, and “-” indicates that a C ₂ H ₄ O group and an AO group are bonded to each other. A, b, c, o, p Is the average number of moles added, b = 3-20, c = 3-20, a + b + c = 5-30, o = 1-5, p = 1-5, o + p = 2-6.

  General formula (1) AO shows a C3-C5 alkyleneoxy group, and it is especially preferable that it is a propyleneoxy group. a, b, c, o, and p are average added mole numbers, b is 3-20 independently, Preferably it is 4-18, More preferably, it is 5-15. a + b + c is 5 to 30, preferably 7 to 25, and more preferably 10 to 20. b is preferably larger than a. Further, b is preferably larger than c. Each of a and c is not 0, and can be selected from the range of 0.1 to 10 so as to satisfy the above requirements.

  The component (b) is, for example, in the production method described in the component (a1), using an average b mole of polyethylene glycol instead of the higher alcohol, and 2-6 moles of propylene oxide, preferably 2 It is obtained by adding 4 mol, sufficiently aging and then adding 2- (30-b) mol, preferably 3- (25-b) mol of ethylene oxide again. In addition, b is synonymous with the numerical value shown by General formula (1). The component (b) has a number average molecular weight of 200 to 2000, preferably 300 to 1500, and more preferably 400 to 1200. The concentration and number average molecular weight of the component (b) in the reaction product obtained by the above method can be confirmed by an HPLC method (high performance liquid chromatography method) using an ODS reverse phase column. As a developing medium, a solvent mixed with methanol / water = 85/15 (volume% ratio) is used, and the number average molecular weight is PEG, POLYMER LABORATIES LTD with number average molecular weights of 174, 600, 1470, 7100 as standard products. A calibration curve is created from the peak area obtained by using the above method. On the other hand, the concentration of component (b) can be calculated by creating a calibration curve from the peak area when the concentration is changed using PEG appropriately selected from the above.

  In the liquid detergent composition of the present invention, the content of the component (b) is 0.01 to 3% by mass for the storage stability of the liquid detergent composition at low temperatures and the suppression of liquid crystal formation by cold water. 0.05-2 mass% is still more preferable, and 0.1-1.5 mass% is more preferable. In addition, (b) component distinguishes from the above-mentioned (a1) component and the below-mentioned (c) component, and is mix | blended separately.

  In the liquid detergent composition of the present invention, the total content of the component (a) and the component (b), that is, (a1) + (a2) + (a3) + (b) In order to exhibit property, it is preferable that it is 40-90 mass%, 40-80 mass% is preferable, and 40-70 mass% is especially preferable.

<(C) component>
The liquid detergent composition of the present invention preferably contains a water-miscible organic solvent other than the component (b) as the component (c) from the viewpoint of storage stability at low temperatures. The content of the component (c) is preferably 5 to 40% by mass in the composition, more preferably 6 to 35% by mass, and still more preferably 8 to 25% by mass. From the viewpoint of low temperature stability, the mass ratio (a) / (c) of the component (a) to the component (c), that is, [(a1) + (a2) + (a3)] / (c), Preferably, the mass ratio [(a1) + (a2)] / (c) of the sum of the components (a1) and (a2) and the component (c) is preferably 90/10 to 50/50, and 90/10 -60/30 is more preferable, and 85 / 15-60 / 30 is still more preferable.

  As the component (c), a water-miscible organic solvent having a hydroxyl group and / or an ether group is preferable in terms of cleaning performance and stability.

  Examples of the water-miscible organic solvent include (c1) alkanols such as ethanol, 1-propanol, 2-propanol, and 1-butanol, and (c2) 2 to 2 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol. 6 alkylene glycols, glycerin, (c3) diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, or alkylene having 2 to 4 carbon atoms such as polyethylene glycol or polypropylene glycol having a weight average molecular weight of 400 to 4000 Polyalkylene glycols composed of glycol units, (c4) 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, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, or 1-ethoxy-2 A (poly) alkylene glycol (mono or di) alkyl ether comprising (poly) alkylene glycol having 2 to 4 carbon atoms such as propanol and an alkanol having 1 to 5 carbon atoms, (c5) 1-methylglycerin ether 2-methylglycerol ether, 1,3-dimethylglycerol ether, 1-ethylglycerol ether, 1,3-diethylglycerol Alkyl, glyceryl ethers having 1 to 8 carbon atoms such as ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, (c6) 2- Having an alkylene glycol unit having 2 to 3 carbon atoms such as phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, 2-benzyloxyethanol, diethylene glycol monobenzyl ether ( And aromatic ethers of poly) alkylene glycols.

  The component (c) is effective as a viscosity modifier and a gelation inhibitor of the composition, and one or more selected from the above categories (c1) to (c6) are used. It is preferable to use a solvent selected from the above (c1) alkanols, (c2) glycols, (c4) alkyl ethers, and (c6) aromatic ethers, and more specifically, ethanol, propylene glycol, diethylene glycol. By using one or more solvents selected from monobutyl ether, 2-phenoxyethanol, diethylene glycol monophenyl ether and triethylene glycol monophenyl ether, in particular, two or more solvents can be used to effectively adjust the viscosity of the composition and suppress gelation. It is more preferable because it is possible. Aromatic ethers obtained by reacting ethylene oxide with an aromatic compound having a hydroxy group can be used as a mixture having different numbers of moles of ethyleneoxy group added, but unreacted products to which ethylene oxide has not been added are removed. It is desirable to use it.

<Other ingredients>
[Component (d)]
An alkaline agent [hereinafter referred to as component (d)] can be blended in the liquid detergent composition of the present invention. Examples of the alkali agent include alkanolamines having 1 to 3 alkanol groups having 2 to 4 carbon atoms in general alkanols in addition to alkali metal hydroxides, alkali metal carbonates, and the like. . Of these, the alkanol is preferably a hydroxyethyl group. Other than the alkanol group is a hydrogen atom, but even a methyl group can be used as an alkali agent. As alkanolamine, 2-aminoethanol, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanol Alkanolamines such as amine and isopropanolamine mixtures (mono, di and tri mixtures) can be mentioned. In the present invention, monoethanolamine and triethanolamine are most preferred.

  (D) A component can be used as a pH adjuster mentioned later. Moreover, you may mix | blend as a counter salt when anionic surfactant is contained in above-described (a) component.

  The liquid detergent composition of the present invention preferably contains 0.1 to 8% by mass, more preferably 0.2 to 7% by mass of component (d). Among these, it is more preferable to use alkanolamine as the component (d).

Hereinafter, other components that can be further used in the present invention are shown (component (e)).
The liquid detergent composition of the present invention can contain a chelating agent [hereinafter referred to as component (e)]. As the chelating agent of component (e), known ones used for liquid detergents can be used, for example,
Aminopolyacetic acid or salts thereof such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid,
Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid and the like, or salts thereof,
Examples thereof include aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and alkali metal or lower amine salts thereof. In the present invention, the alkanolamine mentioned in the component (d) is preferably used as a salt, and may be a salt blended with an acid and neutralized with an alkali agent in the system.

  The mixing ratio of the component (e) in the composition is 0.1 to 5% by mass, preferably 0.1 to 4% by mass, and more preferably 0.1 to 3% by mass when regarded as the acid type. It is.

[Component (f)]
Furthermore, the components shown in the following (i) to (xii) can be added to the liquid detergent composition of the present invention to such an extent that the effects of the present invention are not impaired.
(I) 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 (ii) Color transfer inhibitor such as polyvinylpyrrolidone (iii) Bleaching agent such as hydrogen peroxide, sodium percarbonate or sodium perborate (iv) Tetraacetylethylenediamine, general formula (I- Bleach activators such as bleach activators represented by 2) to (I-7) (v) cellulase, amylase Enzymes such as pectinase, protease, lipase (vi) Boron compounds, calcium ion sources (calcium ion supply compounds), bihydroxy compounds, formic acid and other enzyme stabilizers (vii) fluorescent dyes such as Tinopearl CBS (trade name, Ciba Fluorescent dyes (viii) butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium bisulfite, which are commercially available as Specialty Chemicals) and Whiteex SA (trade name, manufactured by Sumitomo Chemical Co.) Solubilizers such as toluene sulfonic acid, cumene sulfonic acid, meta-xylene sulfonic acid, benzoate (also effective as preservative) (x) paraffins such as octane, decane, dodecane, tridecane, decene, dodecene, etc. Olefin, methylene chloride, 1,1,1 Alkyl halides such as trichloroethane, water-immiscible organic solvent such as terpenes, such as D- limonene.
(Xi) Other antifoaming agents such as pigments, fragrances, antibacterial preservatives, silicones

  Although the density | concentration as a parameter | index at the time of mix | blending the said arbitrary component in the liquid detergent composition of this invention below is shown, it adjusts suitably to such an extent that this effect is not impaired, and excludes when it is not suitable for a mixing | blending. The content of the anti-staining agent and dispersant (i) is preferably 0.01 to 10% by mass. The content of the color transfer inhibitor (ii) is preferably 0.01 to 10% by mass. The content of the bleaching agent (iii) is preferably 0.01 to 10% by mass. The content of the bleach activator (vi) is preferably 0.01 to 10% by mass. The content of the enzyme (v) is preferably 0.001 to 2% by mass. The content of the enzyme stabilizer (vi) is preferably 0.001 to 2% by mass. The content of the fluorescent dye (vii) is preferably 0.001 to 1% by mass. The content of the antioxidant (viii) is preferably 0.01 to 2% by mass. The solubilizer of (ix) is preferably 0.1 to 2% by mass. The water immiscible organic solvent (x) is preferably 0.001 to 2% by mass. The other components of (xi) can be blended at a known concentration, for example.

  Of the above-mentioned optional components, (ix) and (x) affect the stability of the liquid detergent composition, so particular attention must be paid to their formulation.

  The pH of the composition of the present invention (7.2 of JIS Z 8802) is preferably 5 to 11, particularly 6 to 10 (25 ° C.) from the viewpoint of cleaning performance and stability.

  The viscosity at 20 ° C. of the liquid detergent composition of the present invention is preferably 10 to 500 mPa · s, more preferably 50 to 400 mPa · s, and still more preferably 100 to 300 mPa · s in terms of ease of handling. (C) It is preferable to adjust so that it may become such a range with a component and a solubilizing agent.

  In the present invention, the viscosity is measured with a B-type viscometer. Select a rotor that matches the viscosity. It rotates at a rotational speed of 60 r / min, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the liquid detergent composition or diluent.

  The liquid detergent composition of the present invention is filled in a container, for example, a plastic container including a measuring cap and a bottle, to form a liquid detergent article in a container, preferably a liquid detergent article for clothes in a container. Can do. As a material of the bottle, plastics such as polypropylene (PP), polyethylene terephthalate (PET), high density polyethylene (HDPE), medium density polyethylene (MDPE), vinyl chloride (PVC) can be used. The container for filling the liquid detergent composition of the present invention is a plastic container having a container for containing a liquid detergent composition, from the viewpoint of suppressing deformation under reduced pressure due to a decrease in the internal pressure of the plastic material molding container, The container is preferably a plastic container having a flexural modulus (JIS K7171) of 2000 MPa or more, preferably 5000 MPa or less, more preferably 3000 MPa or less, and a wall thickness of 0.3 to 1.5 mm. A bottle that satisfies such a flexural modulus and thickness is used. As a reason for the container deformation, the liquid detergent composition of the present invention is presumed to dissolve oxygen present in the space in the bottle because the surfactant is blended at a high concentration. Since light transmission promotes the solubility of oxygen in a liquid detergent composition containing a surfactant, especially a nonionic surfactant, it is preferable to use a light-shielding bottle in the present invention. The dissolution of oxygen in the liquid detergent composition of the present invention is preferably 15% or less for the wavelength because the light transmittance is greatly affected by light in the wavelength range of 600 nm to 700 nm. In order to improve the light shielding property, titanium oxide or carbon black can be added to the plastic constituting the container.

  Further, as an article filled in a refill container, the liquid detergent composition of the present invention is enclosed in a bag-like container formed by laminating a flexible laminated resin film from the viewpoint of storage stability. Is preferred.

  In addition, a nozzle part with a dispensing channel is provided in a part of the upper edge of the bag body, laser processing, score processing, etc. are performed, and the nozzle upper part edge is opened by hand to form the nozzle part discharge port What can be made is preferable from the viewpoint of ease of use, and as a bag shape, a standing pouch type bag is easy to handle and is a preferable type.

  As the film forming the bag, a flexible single layer resin film can be used, but a laminated resin film is generally used. As the base layer of the laminated resin film, stretched nylon film (ONy), polyethylene terephthalate (PET), stretched polypropylene (OPP), as the sealant layer, unstretched polypropylene (CPP), linear low density polyethylene (LLDPE), high Examples thereof include high density polyethylene (HDPE), low density polyethylene (LDPE), and aluminum vapor-deposited polyethylene terephthalate (VM-PET), ceramic vapor-deposited polyethylene terephthalate, and aluminum foil as the barrier layer.

  In particular, the laminated resin film is preferably composed of three or more layers, and preferably has a structure in which printing ink (ink layer) is not interposed between the intermediate layer and the innermost layer. In view of production aptitude, drop strength, openability and packaging material cost, PET (preferably 9 to 25 μm in thickness) / [ink layer from outer layer (layer farthest from the layer in contact with the liquid detergent composition) + Adhesive layer] / ONy (preferably a thickness of 15 to 25 μm) / adhesive layer / LLDPE (preferably a thickness of 60 to 200 μm) is most preferable.

  The components shown in Table 1 were mixed to obtain compositions of the present invention and comparative products. The following evaluations were performed using the obtained compositions. The results are shown in Table 1. Table 2 shows formulation examples of the liquid detergent composition of the present invention.

<Detergency evaluation method>
(1) Detergency evaluation (1-1) Preparation method of cocoon pieces 衿 As a soil test cloth, the ones with the same degree of soiling were selected from those collected by cutting the heel part of a cotton / polyester blended shirt worn for 3 days. . The selected wrinkle stain test cloth is cut in half and sewed one by one on a 30 cm x 30 cm cotton cloth (hereinafter referred to as a scissors piece). This is a set of 6 liquid detergent compositions shown in Table 1 (12 sheets in total). ) Prepared. One half of the half was used for the liquid detergent composition of the present invention or the comparative product, and the other six were used for the index detergent for determining the cleaning power.

(1-2) Washing water adjustment method The water used for washing is calcium chloride · dihydrate 25.14 g and magnesium chloride · 6 water so that the hardness component is calcium / magnesium = 8/2 (mass ratio). 400 ° DH hard water obtained by dissolving 8.70 g of the Japanese product in 2966.13 g of ion exchange water was used, diluted with ion exchange water when used in the detergency test, and adjusted to 4 ° DH.

(1-3) Determination Method For the washing test, water adjusted by the above method was used using a washing machine (NA-FV8001; manufactured by Panasonic). Detergency was determined by 10 panelists (male in their 30s). Cleaning of 6 pieces of scissors cleaned with the liquid detergent composition of Table 1 and 6 pieces of scissors cleaned in the same manner except that the detergent was replaced with the indicator detergent described in JIS K 3362: 1998 The degree was judged visually. Judge which pair of pieces is superior in detergency and use the liquid detergent composition for evaluation when the detergency is superior as “+1” point. The case where the detergency is excellent is defined as “−1” point (the total evaluation point per panelist is in the range of “+6” to “−6”). Each panel was evaluated by 10 panelists, and the detergency was evaluated by the total of the 10 panelists. When the total score is +5 to -5, it can be judged that the cleaning power of the evaluation detergent and the index detergent is equivalent, and when it is +6 or more, it can be judged that the evaluation detergent has better cleaning power, and when it is -6 or less, the evaluation is evaluated. It can be judged that the detergent is inferior in cleaning power.

(2) Evaluation of low-temperature storage stability After filling a 50 mL sample bottle (No. 6 wide-mouthed standard bottle, glass, cylindrical shape with a diameter of 40 mm and a height of 80 mm) with 40 mL of the liquid detergent composition, capping it, It left still for 20 days in a 0 degreeC thermostat. The stability of the composition was determined by visually observing the appearance and following criteria.
A: A uniform liquid phase in which no liquid crystal or crystals are formed, and the liquid stability is excellent.
X: Liquid crystal formation, crystal formation, separation, or precipitation is observed.

(3) Evaluation of finishing properties 4.5 g of nonionic surfactant (Emulgen 108; Kao Corporation), which is a general cleaning component, is preliminarily dissolved in 50 mL of ion-exchanged water to prepare a detergent solution and diluted 1000 times Thus, a commercially available cotton towel (100% cotton) was washed (Panasonic fully automatic washing machine NA-F60E, water volume 45 L, bath ratio 20, water temperature 20 ° C., washing course is a standard course). This operation was repeated three times in total, and then dried under the conditions of 20 ° C. and 45% RH to obtain an evaluation towel.

Using the evaluation towel prepared by the above-described method, washing is performed with the detergent composition of the present invention or comparative product (Panasonic fully automatic washing machine: NA-F60E, standard course, water amount setting 45 L, bath ratio) 20, water temperature 20 ° C., water hardness 4 ° DH, detergent usage 0.5 g; using the input of a washing machine), softness of cotton towels treated with a reference composition (Attack Biogel; Kao Corporation) Based on the above, the softness of the cotton towel treated with the cleaning composition described in Table 1 was determined by 10 panelists (10 women in their 20s to 40s) according to the following criteria, and the average score was determined. When the average score is +0.3 or more, it is soft compared to the standard that can be judged to be more flexible than the standard .... Softness equivalent to the one-point standard .... Compared to the zero-point standard. It's hard ...- 1 point

(Note) The components in the table are as follows.
(A) Component (a1-1): R ¹ in the general formula (2) is a linear alkyl group having 10 to 14 carbon atoms, l is 0, m is 12, n is 0, and R ² is a hydrogen atom. Nonionic surfactant (a1-2): R ¹ in the general formula (2) is a linear alkyl group having 10 to 14 carbon atoms, l is 0, m is 18, n is 2, and R ² is a hydrogen atom. Yes, after adding 9 mol of EO on average, nonionic surfactant (a1-3) in which PO was added in the order of 2 mol of PO and 9 mol of EO: R ¹ in the general formula (2) is the carbon number Nonionic surfactant (a1-4) wherein 11 is a linear alkyl group, 1 is 1, m is 15, n is 0, and R ² is CH ₃ : R ¹ in the general formula (2) has 10 carbon atoms to 14 linear alkyl group, l is 0, m is 10, n is 2, R ² is a hydrogen atom, block of EO after an average 7 moles added 2 moles of PO, in the order of 3 moles of EO Nonionic surfactants were added

(A2-1): alkylbenzenesulfonic acid having a linear alkyl group having 10 to 14 carbon atoms (a2-2): sodium polyoxyethylene alkyl ether sulfate (linear alkyl having 10 to 14 carbon atoms, EO average addition mole number) 3)
(A2-3): LUNAC L-55 (trade name; C10-C18 coconut oil fatty acid; manufactured by Kao Corporation)

Linear alkyl (carbon number 12) trimethylammonium chloride (a3-1-2); linear alkyl (carbon number 16) trimethylammonium chloride (a3-3-1); linear alkyl ( 12-16 carbon atoms) benzyldimethylammonium chloride

(B) Component (b-1): a compound in which a in formula (1) is 5, b is 10, c is 5, o is 1 and p is 1 (number average molecular weight of about 1000)
(B-2): a compound in which a in formula (1) is 2, b is 10, c is 1, o is 1 and p is 1 (number average molecular weight of about 580)

(C) Component (c-1): Diethylene glycol monobutyl ether (c-2): Propylene glycol (c-3): Triethylene glycol monophenyl ether (c-4): Ethanol

(D) Component (d-1): Monoethanolamine (d-2): Diethanolamine

(E) Component (e-1): Citric acid

(Other (f) component)
(F-1): Polymer (1): Polymer compound synthesized by the method of Synthesis Example 1 on page 4, paragraph 0020 of JP-A-10-60476 (f-2): Enzyme: Everase 16.0L-EX ( Product name) (Protease, manufactured by Novozyme)
(F-3): Dye (1): Green No. 202

Claims (4)

The liquid detergent composition which contains the following (a) component and (b) component, and content of (a) component is 30-75 mass%.
(A) Component: A surfactant which is the following (a1) component or a combination of the following (a1) component and one or more selected from the following (a2) component and the following (a3) component.
(A1) component: nonionic surfactant (a2) component: anionic surfactant (a3) component: cationic surfactant (b) component: number average molecular weight represented by the following general formula (1) 200 to 200 compounds of _{2000 HO- (C 2 H 4 O} ) a - (AO) o - (C 2 H 4 O) b - (AO) p - (C 2 H 4 O) c -H (1)
(In the formula, AO represents an alkyleneoxy group having 3 to 5 carbon atoms, and “-” indicates that a C ₂ H ₄ O group and an AO group are bonded to each other. A, b, c, o, p Is the average number of moles added, b = 3-20, c = 3-20, a + b + c = 5-30, o = 1-5, p = 1-5, o + p = 2-6. The liquid detergent composition according to claim 1, wherein the component (a1) is a nonionic surfactant represented by the following general formula (2).
_{^{R 1 (CO) l O -}} [(C 2 H 4 O) m / (AO) n] R 2 (2)
[Wherein, R ¹ is a chain hydrocarbon group having 7 to 22 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. AO is an alkyleneoxy group having 3 to 5 carbon atoms. l is a number of 0 or 1. m and n are average added mole numbers, m is a number of 8-30, and n is a number of 0-5. However, when l = 0, m is 12 to 30, and R ² is a hydrogen atom. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ] The liquid detergent composition according to claim 1 or 2, wherein the component (a3) is a cationic surfactant represented by the following general formula (3).

[Wherein, R ³ is a hydrocarbon group having 6 to 22 carbon atoms, and R ( ³ ) may include — (A′O) _s −]. A′O is an ethyleneoxy group and / or a propyleneoxy group, and s represents an average added mole number of A′O and is 0.1 to 10. R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 3 carbon atoms, a benzyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X is a halogen atom, CH ₃ SO ₄ or CH ₃ CH ₂ SO ₄ . ]   The liquid cleaning composition in any one of Claims 1-3 which contains water miscible organic solvents other than (b) component as (c) component.