JP5495641B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition.

  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 detergent, there is a problem that when the concentration of a surfactant as a washing component is increased (for example, 50% by mass or more), thickening or gelation occurs and the usability is remarkably 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. In addition, in such a high-concentration surfactant system, a method for obtaining a low-viscosity composition by adding a large amount of a solvent, a solubilizing agent, or the like is generally known, but the composition is water when diluted with water, particularly cold water. When diluted, the diluted composition forms a liquid crystal, causing poor solubility, and when the surfactant concentration is increased, the composition is likely to solidify during low-temperature storage. There was a problem with sex.

  Patent Documents 1 to 3 describe concentrated liquid detergent compositions containing specific nonionic surfactants, but have problems in stability at low temperatures and solubility in cold water. Also, when a concentrated liquid detergent composition is applied directly to stain stains or wrinkle stains, the penetration into the fibers may be hindered due to increased viscosity due to the surfactant concentration, etc. When the liquid crystal is produced in the fiber and gelation occurs, there is a concern that the cleaning effect cannot be sufficiently exhibited. In particular, in the case of the concentrated type, when the entire amount used for coating is used because the amount used once is reduced, it does not flow out of the fiber and the designed detergency cannot be obtained.

  Patent Document 4 describes a concentrated liquid detergent composition in which a nonionic surfactant obtained by adding ethylene oxide or propylene oxide to a higher alcohol and a specific solvent are blended. Similarly, as a preferable nonionic surfactant in the text and examples, an ethylene oxide / propylene oxide block type nonionic surfactant in which ethylene oxide is added and then propylene oxide is described. Nonionic surfactants have higher liquid crystal and crystal suppression effects than ordinary ethylene oxide type nonionic surfactants, but their effects are insufficient, and they do not completely solve the stability at low temperatures and the solubility in cold water. It was. Patent Document 5 discloses an ethylene oxide / propylene oxide / ethylene oxide block type nonionic surfactant and anion having a specific molecular weight or less, in which ethylene oxide is first added to higher alcohol, propylene oxide is added, and then ethylene oxide is added again. Even when the surfactant is mixed with water at a high concentration, a surfactant composition having a viscosity of 300 cps or less is disclosed. Patent Document 6 discloses a nonionic interface of an ethylene oxide / propylene oxide / ethylene oxide block type. A technology that can achieve excellent sebum dirt cleaning properties by using a nonionic surfactant obtained by adding ethylene oxide to a secondary alcohol and an alkanolamine as an activator has been disclosed, but contains a high concentration surfactant. When applying and using liquid cleaning agents No consideration is given to a point.

JP 2008-7705 A JP 2008-7706 A JP 2008-7707 A JP-A-8-157867 International Publication No. 98/24865 Pamphlet JP 11-2441092 A

  An object of the present invention is to provide a liquid detergent containing a high-concentration surfactant, which does not gel or thicken when diluted with water, and can exhibit excellent detergency when applied. It is to provide.

The present invention is a liquid detergent composition containing the following components (a) to (d), wherein the total content of the components (a), (b) and (c) is (a) + ( b) + (c) = 50 to 90% by mass, and the total mass ratio of the component (a) and the component (b) to the component (c) is [(a) + (b)] / (c) = It is related with the liquid detergent composition which is 25/75-90/10.
(A) component: 15-75 mass% of nonionic surfactant represented by the following general formula (1)
R ^1a (CO) ₁ O — [(C ₂ H ₄ O) _m / (AO) _n ] R ^2a (1)
[Wherein, R ^1a is a chain hydrocarbon group having 8 to 22 carbon atoms, and R ^2a is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. l is a number of 0 or 1, and when l = 0, R ^2a is a hydrogen atom. AO is an oxyalkylene group having 3 to 5 carbon atoms. m and n are average addition mole numbers, m is a number of 14-50, and n is a number of 1-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]
(B) Component: (b) Nonionic surfactant represented by the general formula (2) 0.5 to 10% by mass
R ^1b O (C ₂ H ₄ O) _x H (2)
[R ^1b is a hydrocarbon group having 8 to 22 carbon atoms, and x is an average added mole number, which is a number of 2 to 8. ]
(C) Component: Anionic surfactant.
(D) Component: 5-40 mass% of water miscible organic solvent

  According to the present invention, there is provided a liquid detergent composition that contains a high concentration of a surfactant that does not gel when diluted with water and that has excellent detergency when applied to a textile product. Is done.

  The liquid detergent composition of the present invention will be described. The liquid detergent composition of this invention contains (a) component, (b) component, and (c) component as main surfactant. These specific two kinds of nonionic surfactants and anionic surfactants are contained in a specific ratio and at a high concentration, and further, a water-miscible organic solvent as component (d) is contained.

<(A) component>
In the general formula (1) of the component (a), R ^1a is a hydrocarbon group having 8 to 22 carbon atoms, preferably a hydrocarbon group having 8 to 18 carbon atoms, and more preferably 8 to 16 carbon atoms. R ^1a is preferably a linear hydrocarbon group. The hydrocarbon group for R ^1a is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. R ^1a is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. The carbon atom of R ^1a 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 (1) is not particularly limited, but when l = 0, R ^2a is a hydrogen atom, and an addition reaction of ethylene oxide with an alcohol having 8 to 22 carbon atoms, Or it can obtain by carrying out addition reaction of ethylene oxide and C3-C5 alkylene oxide.

When l = 1, R ^2a 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 alkylene oxide and ethylene oxide having 3 to 5 carbon atoms to alcohol (R ^2a -OH) or at the same time 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. Further, it can also be produced by a method of adding an alkylene oxide to an esterified product of fatty acid and alcohol (R ^1a COOR ^2a ) between the esters using a specific catalyst (see Japanese Patent Application Laid-Open No. 4-279552). it can.

  In the general formula (1), m is the average number of moles of ethylene oxide or oxyethylene groups after the addition reaction, and m is preferably 16 or more, more preferably 18 or more in terms of rinsing properties and washing performance. The upper limit is preferably 30 or less, more preferably 25 or less. n is an average addition mole number of the oxyalkylene group after the addition reaction represented by alkylene oxide having 3 to 5 carbon atoms or AO, and the lower limit is 1 or more, preferably 2 or more from the viewpoint of washing performance, and the upper limit. Is 5 or less, preferably 4 or less, more preferably 3 or less.

  The oxyalkylene group, which is AO in the general formula (1), has a methyl branched structure, an ethyl branched structure, or a propyl branched structure when obtained by an 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, in particular, AO is an oxypropylene group, the average addition mole number n of oxypropylene group is 2 to 4, particularly 2 to 3, and the average addition mole number m of oxyethylene group is 16 It is preferable to use a compound having an addition of ˜30, more preferably 18 to 25 mol, because a liquid detergent composition having excellent rinsing properties and detergency can be obtained.

The component (a) is preferably a compound of l = 0 in the general formula (1). By the way, in the case of a structure in which AO is present at a position close to R ^1a O—, since AO is a hydrophobic group, the structure becomes similar to a structure in which a chain hydrocarbon group as R ^1a is extended to be hydrophobic. Shows a tendency to increase. In the present invention, in the general formula (1), the proportion of the compound which is R ^1a O—C ₂ H ₄ O— (when 1 = 0) is 75 mol% in the compound constituting the component (a). In addition, it is preferably 80 mol% or more (the upper limit is 100 mol% or less). Such a compound can also be obtained by removing unreacted alcohol. In the present invention, particularly by adding 6 mol or more, particularly 8 mol or more of ethylene oxide to 1 mol of R ^1a OH, The requirement can be achieved. This rule may be applied to general formulas (1-2), (1-4), and (1-5) described later.

The component (a) is 1 = 0 in the general formula (1) and satisfies the condition of R ^1a O—C ₂ H ₄ O—, and the terminal is further —C ₂ H ₄ O—H. Is more preferable than the case of -AO-H, which is an oxyalkylene group having 3 to 5 carbon atoms of the hydrophobic group, and in this case, the compound having a structure of -C ₂ H ₄ O-H at the end. Is more preferably 70 mol% or more, and more preferably 80 mol% or more (the upper limit is 100 mol% or less). Such a compound is produced by first adding ethylene oxide under the above-mentioned conditions in the production of the general formula (1), or after adding ethylene oxide, removing unreacted alcohol, and then carbon which is the source of AO. It can be obtained by performing an addition reaction step of several to 5 alkylene oxides, preferably propylene oxide, and finally adding only ethylene oxide in an amount of 6 mol or more, particularly 8 mol or more. This rule may be applied to general formula (1-5) described later. Note that the ratio of R ^1a O—C ₂ H ₄ O— or —C ₂ H ₄ O—H can be determined by quantitative measurement using C ¹³ -NMR.

  The compound of the general formula (1) of the present invention may be a compound of the following general formulas (1-1) to (1-5).

In the general formula (1-1), “/” represents a random relationship between the oxyethylene group (hereinafter sometimes referred to as EO) which is the C ₂ H ₄ O group of the component (a) of the present invention and the AO group. It means that either a bond or a block bond may be used. Moreover, n of AO may be divided as a plurality of block bodies. The compounds represented by the general formulas (1-1) to (1-5) can be prepared by considering the reaction ratio and reaction sequence of alkylene oxide with respect to R ^1a OH or R ^2a OH.
R ^1a (CO) ₁ O— (AO) _n — (EO) _m R ^2a (1-1)
R ^1a (CO) ₁ O— (EO) _m — (AO) _n R ^2a (1-2)
^R1a (CO) _lO -[(EO) _m1. (AO) _n ]-(EO) _m2 ^R2a (1-3)
_{^{R 1a (CO) l O- (}} EO) m1 - [(AO) n · (EO) m2] R 2a (1-4)
_{^{R 1a (CO) l O- (}} EO) m1 - (AO) n - (EO) m2 R 2a (1-5)
[Wherein, R ^1a , R ^2a , l, m, n, EO and AO have the above-mentioned meanings, and m1 and m2 are average added mole numbers, and m = m1 + m2. “·” Indicates a random bond. ]

In the present invention, compounds of the general formulas (1-2), (1-4) and (1-5), wherein l = 0 and R ^2a is a hydrogen atom are more preferred, and in particular, the general formula Most preferred is a compound of (1-5) wherein l = 0 and R ^2a is a hydrogen atom.

The component (a) of the present invention is preferably a nonionic surfactant obtained by the following production requirements. That is, after adding m1 mole of ethylene oxide per mole of a compound represented by R ^1a —OH (R ^1a is a hydrocarbon group having 8 to 22 carbon atoms, preferably the same as the above R ^1a ), A nonionic surfactant obtained by adding n2 mol of alkylene oxide of ˜5 and then adding m2 mol of ethylene oxide, wherein m1 is a number from 3 to 50, preferably 7 to 30, more preferably 8 N is a number from 1 to 5, preferably a number from 1 to 3, and m1 and m2 are in total m1 + m2 = 14-50, preferably 16-30, more preferably 18-25. It is a non-ionic surfactant that is a number. Although m2 can be calculated | required from said m1 and m1 + m2, m2 becomes like this. Preferably m2 is the number of 3-30, More preferably, it is the number of 7-25 or more, Preferably it is the number of 8-20. In the present invention, it is particularly preferable that AO is not bonded to the terminal and R ^1a , and m1 and m2 are m1 / (m1 + m2) = 0.2 to 0.8, preferably 0.3 to 0.7. . In this case, R ^1a , m1, m2 and n have the same meaning as in the general formula (1-5).

Regarding the production of the component (a), examples of the catalyst used for alkoxylation of R ^1a —OH or R ^2a —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 8 to 22 carbon atoms (compound represented by R ^1a —OH), and then purged with nitrogen, at 100 to 110 ° C. and 1 to 7 kPa. Dehydration is performed for 30 minutes to 1 hour. Next, ethylene oxide is added at 100 to 170 ° C. and 0.3 to 0.6 MPa, and then alkylene oxide having 3 to 5 carbon atoms, preferably propylene oxide under the conditions of 100 to 150 ° C. and 0.3 to 0.7 MPa. After adding ethylene oxide again under the conditions of 100 to 170 ° C. and 0.3 to 0.7 MPa, the medium was added with the added potassium hydroxide and an equimolar amount of acid agent (acetic acid, lactic acid, glycolic acid, etc.). Obtained by summing. In addition, the usage-amount of each ethylene oxide and a C3-C5 alkylene oxide is selected according to the number-of-moles of raw material alcohol so that the conditions of the average value of m and n in a composition may be satisfy | filled.

  The liquid detergent composition of the present invention satisfies the quantitative relationship with the component (b) and the component (c), and then the component (a) is 15 to 75% by mass, further 25 to 60% by mass, and more It is preferable to contain 35-50 mass%.

<(B) component>
In the general formula (2) of the component (b), R ^1b is a hydrocarbon group having 8 to 22 carbon atoms, preferably a hydrocarbon group having 8 to 18 carbon atoms, and more preferably 8 to 16 carbon atoms. R ^1b is preferably a linear hydrocarbon group. The hydrocarbon group for R ^1b is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. R ^1b is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. In the nonionic surfactant of the general formula (2), the carbon atom of R ^1b bonded to the oxygen atom is preferably a second carbon atom. For the production of a nonionic surfactant in which the carbon atom of R ^1b bonded to the oxygen atom is a secondary carbon atom, ethylene oxide is added to a secondary alcohol, or ethylene oxide is reacted with a 1-olefin or an inner olefin, A method of reacting polyethylene glycol with olefin or a known production method by introducing a hydroxyl group into n-paraffin and adding ethylene oxide can be used.

  The average added mole number x of the oxyethylene group is 2 to 8, preferably 2 to 7.5, and most preferably 2.5 to 4.

  The component (b) is usually obtained as a mixture containing unreacted alcohol. Since unreacted alcohol affects the problem of odor and the storage stability of the composition, it is preferably reduced by distillation or the like. In the present invention, the proportion of the unreacted alcohol, that is, the alcohol having a hydrocarbon group having 8 to 22 carbon atoms, is preferably 5% by mass or less, more preferably 3% by mass or less, relative to the component (b). .5% by mass or less is most preferable. Moreover, it is preferable that the ratio of unreacted alcohol, ie, the alcohol which has a C8-C22 hydrocarbon group, is 5 mass% or less with respect to the sum total of (a) component and (b) component, and 3 mass%. The following is more preferable, and 0.5% by mass or less is most preferable. However, the lower limit is considered after considering the environment such as the energy required for the distillation process.

  Other known impurities derived from the component (a) and the component (b) or conceivable by those skilled in the art may be mixed as long as the effect is not impaired.

  The liquid detergent composition of the present invention contains the component (b) in an amount of 0.5 to 10% by mass, preferably 0.5 to 5% by mass, more preferably 0.8 to 3% by mass.

<(C) component>

  In the present invention, the combined use of the anionic surfactant of the component (c) together with the component (a) and the component (b) is important from the viewpoint of detergency and prevention of gelation or viscosity increase upon dilution. It is a requirement. Since the component (a) originally defined in the present invention is highly hydrophilic, the detergency is lower than that of conventional nonionic surfactants. However, excellent cleaning is achieved by using the component (c) at a specific ratio together with the component (b). Demonstrate sex.

  In the liquid detergent composition of the present invention, the content of the component (c) satisfies the ratio described later from the relationship between the components (a) and (b). The component (c) suppresses formation of a liquid crystal phase upon dilution by using the component (a) and the component (b) at a specific ratio, together with the effect as a cleaning component. The reason for this is not clear, but by mixing the molecules of component (c) between the molecules of component (a), the alignment of surfactant molecules is suppressed from the electrical repulsion of the anionic group of component (c). As a result, liquid crystal and crystal formation are expected to be suppressed.

  As the anionic surfactant, for example, the following (c1) to (c5) can be used, and (c1), (c2), and (c4) are preferable in terms of cleaning performance, stability, and solubility, and ( It is more preferable to contain c1).

(C1) Alkylbenzenesulfonate having an alkyl group having an average carbon number of 10 to 20.
(C2) having an alkyl group derived from a linear primary alcohol or linear secondary alcohol having an average carbon number of 10 to 20 or a branched alcohol, and having an average addition mole number of an oxyalkylene group of 1 to 5. The polyoxyalkylene alkyl ether sulfate ester salt (c3) having an average carbon number of 10 to 10, which contains an oxyethylene group as the oxyalkylene group and may contain an oxypropylene group in the range of an average addition mole number of 0.2 to 2 moles. An alkyl or alkenyl sulfate ester salt having 20 alkyl groups or alkenyl groups.
(C4) Fatty acid salt having an average carbon number of 8 to 20.
(C5) having an alkyl group derived from a straight-chain primary alcohol or straight-chain secondary alcohol having 10 to 20 carbon atoms or a branched alcohol, and having an average addition mole number of an oxyalkylene group of 1 to 5 A polyoxyalkylene alkyl ether carboxylate which contains an oxyethylene group as an oxyalkylene group and may contain an oxypropylene group in an average addition mole number range of 0.2 to 2 mol.

  Examples of the salt constituting the component (c) include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. In particular, alkanolamine salts from the viewpoint of stability. It is preferable that The anionic surfactant may be added in an acid form in the liquid detergent and neutralized with alkali in the system. In the present invention, the component (c) is preferably an alkanolamine salt or an acid form and neutralized with an alkanolamine [alkanolamine used as an alkali agent for the component (e) described later] in the system. Metal-type counter ions such as alkaline earth metals and the like may be contained through the production process of component (a) or as a salt of a sequestering agent or other anionic compound, but it is rare. Preferably, it is substantially 5% by mass or less, and particularly preferably 3% by mass or less.

  In the liquid detergent composition of the present invention, from the viewpoint of detergency, the total content of the components (a), (b) and (c) is (a) + (b) + (c) = 50 to 90 mass%, preferably 55-80 mass%, particularly preferably 60-70 mass%. In addition, since the mass of the anionic surfactant of the component (c) varies depending on the molecular weight of the salt, in the present invention, the mass when the acid type, that is, the counter ion is assumed to be a hydrogen atom ion, is not a salt. ) The mass of the component.

  In the liquid detergent composition of the present invention, the total mass ratio of the component (a) and the component (b) to the component (c) [(a) + ( b)] / (c) is 25/75 to 90/10, preferably 50/50 to 85/15, and more preferably 60/40 to 80/20. From the viewpoint of the general formula cleaning power, the proportions of the component (a) and the component (b) and the component (c) are equal to or higher than the lower limit value and are equal to or lower than the upper limit value from the viewpoint of suppressing gelation formation by water.

<(D) component>
The liquid detergent composition of the present invention contains (d) a water-miscible organic solvent in order to suppress the formation of a crystal phase or a liquid crystal phase. The water-miscible organic solvent referred to in the present invention refers to a solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C., that is, a solvent having a degree of dissolution of 50 g / L or more.

  (D) Content of a component is 5-40 mass% in a composition from the point of stability and solubility, and 10-35 mass% is preferable.

  As the component (d), a water-miscible organic solvent having a hydroxyl group and / or an ether group is preferable.

  Examples of the water-miscible organic solvent include (d1) alkanols such as ethanol, 1-propanol, 2-propanol and 1-butanol, (d2) glycols such as propylene glycol, butylene glycol and hexylene glycol, and (d3) diethylene glycol. , Glycols such as triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, (d4) 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 Rumonomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerol ether, 2-methylglycerol ether, 1,3-dimethylglycerol ether, 1-ethylglycerol ether, 1,3- Alkyl ethers such as diethyl glyceryl ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, diethylene glycol monobutyl ether (butoxy diglycol), (d5) 2 -Phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monomer having an average molecular weight of about 480 Phenyl ether, 2-benzyloxy ethanol, aromatic ethers such as diethylene glycol monobenzyl ether, and the like.

  The component (d) is effective as a viscosity modifier and a gelation inhibitor of the composition, and the above (d1) alkanols, (d2) glycols, (d4) alkyl ethers, (d5) aromatic ethers It is preferable to use at least one selected from the group consisting of (d2) glycols, (d4) alkyl ethers, and (d5) aromatic ethers. Is preferred.

  In the present invention, in order to increase the surfactant concentration, the total mass ratio of the component (a), the component (b), and the component (c) to the component (d) is preferably [(a) + (b ) + (C)] / (d) is 90/10 to 65/35, more preferably 85/15 to 70/30, and most preferably 80/20 to 70/30. When the upper limit is exceeded, a liquid crystal phase is formed upon dilution with water, so that a measurement error tends to occur.

<(E) component>
The liquid detergent composition of the present invention preferably contains an alkanolamine having 1 to 3 alkanol groups having 2 to 4 carbon atoms as the component (e). The alkanol is preferably a hydroxyethyl group. Other than the alkanol group is a hydrogen atom, but it may be an alkyl group having 1 to 5 carbon atoms, particularly a methyl group. 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.

  (E) A component can be used as a pH adjuster mentioned later. Moreover, you may mix | blend as a salt with respect to above-mentioned (c) component.

  The liquid detergent composition of the present invention preferably contains 0.5 to 8% by mass, more preferably 1 to 7% by mass of the alkanolamine as the component (e). In addition, alkanolamine can also be mix | blended as counter ions, such as the salt of (c) component, and those amounts are also included as (e) component.

<Component (f)>
The liquid detergent composition of the present invention contains water as the component (f). Water is preferably contained in the composition in an amount of 5 to 30% by mass, more preferably 7 to 20% by mass, and particularly preferably 8 to 15% by mass. It is preferable to use water that does not affect the composition, such as ion exchange water.

  The liquid detergent composition of the present invention is the sum of the contents of the components (a) to (f), that is, the components (a) + (b) + (c) + (d) + (e) + (f) However, it is preferably 90% by mass or more, more preferably 95% by mass or more.

<Other ingredients>
[(G) component]
The liquid detergent composition of the present invention contains a surfactant other than the component (a), the component (b) and the component (c) [hereinafter referred to as the component (g)] within a range not impairing the effects of the present invention. be able to. Examples of the component (g) include the following (g1) to (g3).
(G1) Nonionic surfactants that do not fall under component (a).
For example, the following (g1-1) and (g1-2) are mentioned.
(G1-1) A polysaccharide surfactant represented by the following general formula.
_{^{R 1g - (OR 2g) y}} G z
[Wherein R ^1g is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, R ^2g is an alkylene group having 2 to 4 carbon atoms, and G is derived from a reducing sugar having 5 or 6 carbon atoms. Residue, y is the number of average values 0-6, z is the number of average values 1-10. ]
(G1-2) Fatty acid alkanolamide, polyhydroxy fatty acid amide.
(G2) Cationic surfactant.
For example, it is a primary to tertiary amine having a long-chain alkyl group (excluding the alkanolamine described above), and preferably has 8 to 8 carbon atoms which may have an ether bond, an ester bond or an amide bond in the middle. Mention may be made, for example, of cationic surfactants having one or two 22 alkyl groups, the remainder being 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 8 to 22 carbon atoms and a tertiary amine having one long-chain alkyl group having 8 to 22 carbon atoms are preferable.
(G3) Amphoteric surfactant For example, sulfobetaine or carbobetaine having an alkyl group having 10 to 18 carbon atoms can be mentioned.

  (G) Content in the case of containing a component, Preferably it is 0.5-10 mass% in a composition. Or in all the surfactants, and further in (a) + (b) + (c) + (g), it is 20% by mass or less, preferably 10% by mass or less, and most preferably 5% by mass or less. In addition, compounds other than this constituent requirement generated during the production process of each component may be included. They may be mixed in consideration of this effect and production economy. In addition, the nonionic surfactant (g1) in the component (g) is combined with the components (a) and (b) as [(a) + (b) + (g1)] / (c). It is preferable to fall within the range of the mass ratio of [(a) + (b)] / (c). Similarly, for the component (d), [(a) + (b) + (c) + (g1)] / (d) is changed to the above [(a) + (b) + (c)] / ( It is preferable to be in the numerical range of d). For the quaternary ammonium salt, the mass excluding the counter anion is the mass of the quaternary ammonium salt, and for the tertiary amine, hydrogen atoms other than organic groups are substituted among the groups bonded to the nitrogen atom. The mass of the resulting structure is defined as the mass of the tertiary amine.

[(H) component]
The liquid detergent composition of the present invention preferably has a low content of a chelating agent [hereinafter referred to as component (h)]. As the chelating agent of component (h), known ones used for liquid detergents can be used.
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 (b) 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 blending ratio of the component (h) in the composition is 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less when it is regarded as the acid type. The component (h) is an optional component, but an organic acid such as acetic acid, lactic acid or glycolic acid is used as a neutralizing agent for the base catalyst used in the addition reaction of the alkylene oxide of the component (a) or component (b). It is generally used. Accordingly, it can be considered that the liquid detergent composition of the present invention is also mixed. Therefore, the lower limit is not less than the mixing amount derived from the component (a) and the component (b), specifically 0.02% by mass or more, particularly 0.05% by mass or more.

[Other ingredients]
Furthermore, the components shown in the following (i) to (x) can be blended with 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) Enzymes such as cellulase, amylase, pectinase, protease, lipase (iv) Boron compound, calcium ion source (calcium ion supply compound), bihydroxy compound, formic acid, etc. Enzyme Stabilizers (v) Fluorescent dyes such as Tinopearl CBS ( Antioxidants such as fluorescent dyes (vi) butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium bisulfite, which are commercially available under the trade name of Ciba Specialty Chemicals and Whitetex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.) (Vii) Solubilizers such as paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, benzoate (also effective as a preservative) (viii) polyethylene glycol having an average molecular weight of about 200, and an average molecular weight of about 400 Polyalkylene glycol-based anti-gelling polymers such as polyethylene glycol and polypropylene glycol having an average molecular weight of about 2000 (ix) Paraffins such as octane, decane, dodecane and tridecane, olefins such as decene and dodecene, methylene chloride, 1,1 , 1-tric Alkyl halides such as Roetan, water-immiscible organic solvent such as terpenes, such as D- limonene.
(X) Other antifoaming agents such as pigments, fragrances, antibacterial preservatives, and 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 recontamination inhibitor and the dispersant (i) is preferably 0.01 to 2% by mass. The content of the color transfer inhibitor (ii) is preferably 0.01 to 2% by mass. The content of the enzyme (iii) is preferably 0.001 to 2% by mass. The content of the enzyme stabilizer (iv) is preferably 0.001 to 2% by mass. The content of the fluorescent dye (v) is preferably 0.001 to 1% by mass. The content of the antioxidant (vi) is preferably 0.01 to 2% by mass. The solubilizer of (vii) is preferably 0.1 to 2% by mass. The polyalkylene glycol-based anti-gelling polymer (viii) is preferably 0.01 to 2%. The water immiscible organic solvent (ix) is preferably 0.001 to 2% by mass. The other components of (x) can be blended, for example, at a known concentration.

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

  The liquid detergent composition of the present invention has a pH of 20 ° C. of preferably 6 to 11, more preferably 7.5 to 10, and most preferably 8 to 10. The pH is a pH measured at 20 ° C. described in JIS K3362: 1998.

  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. (D) 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 suitable for textile products such as clothing, bedding, and fabrics.

The liquid detergent composition of Table 1 was prepared and evaluated as follows.
<Evaluation method>
(1) Evaluation of coating detergency The heel stain test cloth was selected from those collected by cutting and collecting the heel portion of a cotton / polyester blended shirt worn for 3 days. The selected wrinkle stain test cloths were cut in half and sewed one by one on a 30 cm × 30 cm cotton cloth (hereinafter referred to as wrinkles), and 5 sets (10 sheets in total) were prepared for each test sample. The half-cut 5 sheets were used for the liquid detergent composition (test sample) to be evaluated, and the other 5 sheets were used for the reference detergent.

  Cotton underwear was put into the washing tub of a vertical fully automatic washing machine (AW-80VC; manufactured by Toshiba) (the total weight of the cotton underwear and 10 pieces of scissors was 2.35 kg) ) Next, 15.67 g of the liquid detergent composition in the table was weighed, and 3 g of each was applied to the heel portions of the five heel pieces, and the heel pieces were put in a washing tub. The remaining detergent, 0.67 g, was placed in the washing tub as it was. These were washed under the conditions of a water volume of 47 L (water temperature: 10 ° C., hardness: 4 ° DH, bath ratio: 20) and standard course (12 minutes for washing, twice for rinsing, 6 minutes for dehydration). After washing, the wrinkle stain test cloth was removed from the cotton cloth and then naturally dried in a room at 20 ° C. and a humidity of 65 RH. The wrinkle stain test cloth 5 was evaluated by the following methods.

10 expert panelists compared the wrinkle stain test cloth (5 sheets) after washing with a pair of wrinkle stain test cloths (5 sheets) washed under the same conditions using a standard detergent under a white light. Was judged from the following criteria based on comprehensive removal of dirt. If all 5 sets have better dirt removal from the test sample, the maximum is 5 points per person.
1 point: Good stain removal compared to the standard detergent 0 point: Equivalent to the standard detergent -1 point: Bad stain removal compared to the standard detergent Average score of 10 panelists was determined and used as an evaluation point for stain removal. It can be judged that dirt removal is excellent with an evaluation score of 4 or more.
○: Evaluation point 4 points or more Δ: Evaluation point −4 points or more and less than 4 points ×: Evaluation point less than −4 points The reference detergent was Comparative Product 4.

(2) Solubility model evaluation Liquid detergent composition and ion-exchanged water [(mass of liquid detergent composition) / (mass of liquid detergent composition + mass of ion-exchanged water) × 100 = 5 After preparing a total of 19 samples mixed in increments of 5% by mass so as to be 95% by mass, and standing at 10 ° C. for 1 day, the viscosity of this sample at 10 ° C. was measured under the following conditions: The determination was made according to the following criteria, which is a solubility model test in water at 10 ° C.
Measuring instrument Tokyo Keiki Co., Ltd. digital B type viscometer (model number; DV MB)
Measurement conditions 60 r / min 60 seconds ○: The viscosity of all the samples is less than 1500 mPa · s. This means that the liquid is not thickened due to liquid crystal formation or crystal formation at the time of dilution with cold water, and can be judged to be excellent in solubility.
X: Some samples have a viscosity of 1500 mPa · s or more. This means that thickening may occur due to liquid crystal formation or crystal formation upon dilution with cold water, and it is determined that the solubility is poor.

(Note) The components in the table are as follows. In the table, (a′-1) to (a′-3) are also regarded as the component (a) and the structures and quantity ratios are shown. In the following, EO is ethylene oxide and PO is propylene oxide.
(A-1): R ^1a in the general formula (1) is a linear alkyl group having 10 to 14 carbon atoms, l is 0, AO is an oxypropylene group, m is 20, n is 2, and R ^2a is H. A non-ionic surfactant having a block arrangement in which R ^1a O— is bonded in the order of EO and PO (20 mol of EO per mol of primary linear alcohol having 10 to 14 carbon atoms and 2 mol of PO on average) (Sequential block addition. R ^1a OH content is less than 0.05% by mass.)
(A-2): R ^1a in the general formula (1-5) is a linear alkyl group having 10 to 14 carbon atoms, l is 0, AO is an oxypropylene group, m1 is 10, n is 2, and m2 is 10 , R ^2a is H, and R ^1a O— is a non-ionic surfactant having a block arrangement in which EO, PO and EO are bonded in this order (10 to 10 EO per mole of primary linear alcohol having 10 to 14 carbon atoms) (Mole, PO 2 mol, EO 10 mol in block order. R ^1a OH content is less than 0.05% by mass.)
(A-3): R ^1a in the general formula (1-1) is a primary linear alkyl group having 11 carbon atoms, 1 is 1, AO is an oxypropylene group, m is 1.5, n is 15, R Nonionic surfactant having a block arrangement in which ^2a is CH ₃ and R ^1a is bound to CO in the order of PO and EO

(A′-1): R ^1a in the general formula (1) is a linear alkyl group having 10 to 14 carbon atoms, 1 is 0, m is 10, n is 0, and R ^2a is H. Agent (10 moles of EO added per mole of primary linear alcohol having 10 to 14 carbon atoms. R ^1a OH content is 0.67% by mass)
(A′-2): R ^1a in the general formula (1) is a linear alkyl group having 10 to 14 carbon atoms, 1 is 0, m is 10, n is 2, and R ^2a is H. Agent (10 mol of EO and 2 mol of PO added per mol of primary linear alcohol having 10 to 14 carbon atoms. R ^1a OH content is less than 0.05% by mass)
(A′-3): R ^1a in the general formula (1-5) is a linear alkyl group having 10 to 14 carbon atoms, l is 0, AO is an oxypropylene group, m1 is 5, n is 2, and m2 is 5, R ^2a is H, and R ^1a O— is a non-ionic surfactant having a block arrangement in which EO, PO and EO are bonded in this order (EO is added per mole of primary linear alcohol having 10 to 14 carbon atoms) (5 mol, PO 2 mol, EO 5 mol block added in this order. R ^1a OH content is less than 0.05% by mass.)

(B-1) Nonionic surface activity in which R ^1b is a linear alkyl group having 12 to 14 carbon atoms bonded to an oxygen atom and a second carbon atom, and x is 3 in the general formula (2) Agent (Three moles of EO added per mole of secondary linear alcohol having 12 to 14 carbon atoms, and then unreacted alcohol was removed by distillation. R ^1b OH content was 0.28% by mass.)
(B-2) Nonionic surface activity in which R ^1b is a linear alkyl group having 12 to 14 carbon atoms bonded to an oxygen atom and a second carbon atom, and x is 5 in the general formula (2) Agent [one obtained by further adding 2 mol of ethylene oxide to the nonionic surfactant of (b-1). R ^1b OH content is 0.25% by mass. ]

(C-1): C10-14 linear alkylbenzene sulfonic acid (c-2): LUNAC L-55 (trade name) (coconut oil fatty acid; manufactured by Kao Corporation)
(D-1): Butoxy diglycol (also called diethylene glycol monobutyl ether or butyl carbitol)
(D-2): Propylene glycol

Claims (5)

It is a liquid detergent composition containing the following (a)-(d) component, Comprising: The sum total of content of (a) component, (b) component, and (c) component is (a) + (b) + ( c) = 50 to 90% by mass, and the total mass ratio of the component (a) and the component (b) to the component (c) is [(a) + (b)] / (c) = 50/50 A liquid detergent composition that is 85/15 .
(A) component: 15-75 mass% of nonionic surfactant represented by the following general formula (1)
R ^1a (CO) ₁ O — [(C ₂ H ₄ O) _m / (AO) _n ] R ^2a (1)
[Wherein, R ^1a is a chain hydrocarbon group having 8 to 22 carbon atoms, and R ^2a is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. l is a number of 0 or 1, and when l = 0, R ^2a is a hydrogen atom. AO is an oxyalkylene group having 3 to 5 carbon atoms. m and n are average addition mole numbers, m is a number of 14-50, and n is a number of 1-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]
(B) Component: (b) Nonionic surfactant represented by the general formula (2) 0.5 to 10% by mass
R ^1b O (C ₂ H ₄ O) _x H (2)
[R ^1b is a hydrocarbon group having 8 to 22 carbon atoms, and x is an average added mole number, which is a number of 2 to 8. ]
Component (c): an anionic surfactant component (d): water-miscible organic solvent 5 to 40 mass% The component (a) is a nonionic surfactant in which the carbon atom of R ^1a bonded to the oxygen atom in the general formula (1) is the first carbon atom, and the component (b) is oxygen in the general formula (2). The liquid detergent composition according to claim 1, which is a nonionic surfactant in which the carbon atom of R ^1b bonded to the atom is a second carbon atom. Compound (a) is a compound in which l in general formula (1) is 0, and in the compound constituting component (a), the oxyalkylene group bonded to R ^1a O— is an oxyethylene group The liquid detergent composition according to claim 1 or 2, wherein the ratio of is at least 75 mol%.   The liquid detergent in any one of Claims 1-3 whose ratio of the alcohol which has a C8-C22 hydrocarbon group is 5 mass% or less with respect to the sum total of (a) component and (b) component. Composition.   The liquid detergent composition in any one of Claims 1-4 whose viscosity in 20 degreeC is 10-500 mPa * s.