JP5270148B2 - Detergent composition for clothing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition for clothing having higher detergency even at low temperature. <P>SOLUTION: The detergent composition for clothing includes: (a) a glyceryl monoether or a polyglyceryl monoether expressed by general formula (I): R-O-(C<SB>3</SB>H<SB>6</SB>O<SB>2</SB>)<SB>n</SB>-H; and (b) a sulfate ester salt expressed by general formula (II): R<SP>1</SP>-O-(A<SP>1</SP>O)<SB>p</SB>-(AO)<SB>q</SB>-SO<SB>3</SB>M, wherein the component (a) has a specific compound distribution. In formula (I), R represents a 6-22C hydrocarbon group; and n is an integer representing a degree of glycerin condensation. In formula (II), R<SP>1</SP>represents a 6-22C hydrocarbon group; A<SP>1</SP>O represents an oxypropylene group and/or an oxybutylene group; AO represents a specific oxyalkylene group; p is an integer from 1 to 5; q is an integer from 0 to 10; and M represents an alkali metal or the like. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a laundry detergent composition.

In recent years, from the viewpoint of further improving detergency, blending nonionic surfactants such as glycerol monoalkyl ethers and polyglycerol monoalkyl ethers, which are mainly made from glycerin derived from plant-derived natural fats and oils, It is disclosed in Patent Documents 1-7.
JP 2001-49290 A JP 2001-49291 A JP 11-310792 A JP-A-4-506367 JP-A-7-500861 Japanese Patent Laid-Open No. 3-17496 JP 2006-348084 A

  However, these glyceryl monoethers or polyglyceryl monoethers are not always satisfactory in terms of detergency when used in a laundry detergent composition. Especially at low temperatures, they show high crystallinity, so the solubility in water is low, and the cleaning power tends to be inferior. As a result of intensive studies, it was found that the detergency was greatly influenced by the degree of condensation of glycerin groups and their distribution.

  That is, the problem of the present invention is that glyceryl monoether or polyglyceryl monoether having a specific degree of glycerin condensation (hereinafter also referred to as glyceryl monoether) has higher detergency, particularly high detergency at low temperatures. It is to provide a detergent composition for clothing.

  Further, from the viewpoint of carbon circulation such as an increase in carbon dioxide, a so-called carbon neutral component that does not increase carbon dioxide in the atmosphere is required. Among them, glyceryl monoether is promising from the viewpoint that it can be expected in the process of obtaining it.

The present invention comprises (a) glyceryl monoether or polyglyceryl monoether represented by general formula (I) [hereinafter referred to as component (a)], and (b) sulfate ester salt represented by general formula (II) [ Hereinafter referred to as component (b)], wherein the component (a) comprises a plurality of compounds having different degrees of condensation of glycerin n in the general formula (I) Related to things.
R—O— (C ₃ H ₆ O ₂ ) _n —H (I)
(In the formula, R is a hydrocarbon group having 6 to 22 carbon atoms, n is the degree of condensation of glycerin, and represents an integer.)
R ¹ —O— (A ₁ O) _p — (AO) _q —SO ₃ M (II)
(In the formula, R ¹ is a hydrocarbon group having 6 to 22 carbon atoms, A ¹ O is an oxypropylene group and / or oxybutylene group, and AO contains at least one of an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene group, p is an integer of 1 to 5, q is an integer of 0 to 10, M represents an alkali metal, an alkaline earth metal, NH ₄ or an alkanol ammonium group having 2 to 3 carbon atoms.)

  ADVANTAGE OF THE INVENTION According to this invention, the detergent composition for clothing which shows the outstanding cleaning power also on the washing | cleaning conditions at low temperature is provided.

<Component (a)>
Component (a) of the present invention is a glyceryl monoether in which one of the hydrogen atoms of a hydroxyl group in polyglycerol which is glycerin or its condensate is substituted with a hydrocarbon group having 6 to 22 carbon atoms to form an ether bond It is.

  The component (a) preferably contains 2 or more, particularly 3 or more compounds having a different glycerin condensation degree n in the general formula (I) from the viewpoint of washing performance at low temperatures. Especially, it is preferable that R is a C12 and / or C14 alkyl group, and the glycerin condensation degree n includes a plurality of compounds different from each other in a range of 3 to 5, and the total ratio is It is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more, and particularly preferably with respect to the total of compounds having a condensation degree n of 1 to 7. 80% by mass or more. From the viewpoint of washing performance at low temperatures, the upper limit of the ratio is preferably 99% by mass or less, 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less. Among the component (a), those in which R is an alkyl group having 12 and / or 14 carbon atoms and the condensation degree n of glycerol is 3 to 5 show the highest cleaning performance. However, even within this range, when the condensation degree n of glycerin consists of only one, it is easy to crystallize, so the solubility in water is particularly poor at low temperatures, and as a result, the detergency tends to decrease. On the other hand, when the component (a) contains a plurality of compounds having different glycerin condensation degrees n, crystallization is suppressed, so that high solubility is exhibited even at low temperatures, and as a result, good cleaning performance is obtained. Therefore, it is more preferable that all three types (n = 3, 4, 5) are included among those in which the degree of condensation n of glycerin in component (a) is 3-5. Furthermore, in the component (a), the ratio of the total of the polyglyceryl monoethers in which R is an alkyl group having 12 and / or 14 carbon atoms and the condensation degree n of glycerin is 3 to 5 is 99% by mass. In the case of the following, the solubility at a low temperature is remarkably improved, and as a result, the effect of greatly improving the cleaning performance can be obtained. In general, the lower the content, the better the solubility at low temperature, but at the same time the cleaning performance at normal temperature tends to be lowered, so an appropriate balance is required. Further, when the detergent composition is liquid, separation during storage can be suppressed, and the commercial value can be maintained even when stored for a long time.

  Component (a) of the present invention includes compound (a-1) in which R in general formula (I) in component (a) is an alkyl group having 12 carbons and glycerin condensation degree n is 3 to 5, The total ratio of the compound (a-2) in which R in the general formula (I) is an alkyl group having 14 carbon atoms and the condensation degree n of glycerol is 3 to 5 is 40% by mass or more. It is preferable to contain a plurality of compounds with different n selected from 1) and compound (a-2), particularly three compounds of n = 3, 4, and 5.

  From the viewpoint of detergency, the condensation degree n of glycerin, which is the raw material of component (a), is most preferably 4. Among glyceryl ethers having a condensation degree of 1 to 7, glyceryl monoether having a condensation degree n of 4 is used. The total ratio is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more.

  In the component (a), the ratio of glyceryl monoether or the like having a glycerin condensation degree n of 1 or 2 is preferably less than 50% by mass, and more preferably 35% by mass or less. Further, in the component (a), the content of glyceryl monoether having a glycerin condensation degree n of 1 is preferably less than 30% by mass, and more preferably 20% by mass or less.

  R in the general formula (I) may be linear, branched, saturated or unsaturated, and is preferably an alkyl group having 6 to 22, more preferably 12 to 14, particularly 12 carbon atoms. In the component (a), further, in the total of the compounds of general formula (I) having a glycerin condensation degree n of 1 to 7, R in the general formula (I) has 12 to 14 carbon atoms, particularly 12 carbon atoms. And the ratio of the compounds that are 14 alkyl groups is preferably 40% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and most preferably 95% or more.

The polyglycerin moiety to be condensed in the general formula (I) is labeled (C ₃ H ₆ O ₂ ) _n . However, this does not represent only the linear type, but includes a branched type and a random mixture of the linear type and the branched type. It is added that it is expressed in this way for convenience of expression.

  The mass ratio of the degree of condensation of glycerin constituting the component (a) [mass ratio in the component (a)] can be determined from area% of the gas chromatography (GC) method.

  The component (a) of the present invention can be obtained, for example, by reacting a predetermined amount of 2,3-epoxy-1-propanol (glycidol) with an alcohol having 6 to 22 carbon atoms in the presence of an alkali catalyst. Moreover, it can also manufacture by the method as described in Paragraphs 0007-0011 of Unexamined-Japanese-Patent No. 2000-160190.

  The binding mode of glycerin in component (a) is linear type (one in which glycerin is bonded at positions 1 and 3), branched type (one in which glycerin is bonded at positions 1, 2, and glycerin that is bonded at positions 1, 2 (2 Or the like, and glycerin is further bonded to the 1st and 3rd positions).

  In general, the glyceryl monoether such as component (a) is obtained as a mixture of compounds having different degrees of condensation. In the present invention, from the viewpoint of detergency, a plurality of compounds having different degrees of condensation of n of glycerol, preferably Since a compound having a glycerin condensation degree of 3 to 5 in a predetermined ratio is used, the reaction product can be purified by distillation or the like as necessary to obtain a compound having a condensation degree within this range.

<Component (b)>
Component (b) used in the present invention is a sulfate ester salt represented by the following general formula (II). The compound of the general formula (II) includes an alkyl ether sulfate ester salt.
R ¹ —O— (A ₁ O) _p — (AO) _q —SO ₃ M (II)
(In the formula, R ¹ is a hydrocarbon group having 6 to 22 carbon atoms, A ¹ O is an oxypropylene group and / or oxybutylene group, and AO contains at least one of an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene group, p is an integer of 1 to 5, q is an integer of 0 to 10, M represents an alkali metal, an alkaline earth metal, NH ₄ or an alkanol ammonium group having 2 to 3 carbon atoms.)

The hydrocarbon group as R ¹ in the general formula (II) is preferably an alkyl group having 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, and particularly preferably 12 to 14 carbon atoms. Furthermore, from the viewpoint of performance such as foaming power and emulsifying power and environmental aspects such as carbon neutral, a linear alkyl group, particularly a linear alkyl group derived from a natural fat or oil raw material is preferable.

Examples of the oxyalkylene group as A ¹ O in the general formula (II) include an oxyalkylene group containing at least one of an oxypropylene group and an oxybutylene group, and a combination of two or more thereof. A ¹ O preferably contains oxypropylene, and the group bonded to R ¹ —O— is preferably an oxypropylene group.

  In addition, as the oxyalkylene group which is AO in the general formula (II), an oxyethylene group (hereinafter also referred to as an EO group), an oxypropylene group (hereinafter also referred to as a PO group), An oxyalkylene group containing at least one oxybutylene group (hereinafter sometimes referred to as a BO group), and a combination of two or more of these can be used.

When the compound of the general formula (II) has a structure in which a PO group and / or a BO group is bonded to R ¹ —O—, and A ¹ O includes both oxyalkylene groups of the PO group and the BO group, Either block addition or random addition may be used. When A ¹ O and AO are both PO groups, the compound of the general formula (II) is a propylene oxide adduct of R ¹ —O— (PO) _{p + q} —SO ₃ M. Incidentally, R ¹ -O- in PO group, then the case of the structure in which the BO group is added R ¹ -O- (PO) _s - becomes (BO) _t -SO ₃ M propylene oxide, butylene oxide adduct of, s + t is When in the range of p, it can be regarded as a compound with q = 0. The same applies to a structure in which a BO group and then a PO group are added to R ¹ —O—.

P in the general formula (II) is the number of added moles of (A ¹ O), and is an integer of 1 to 5, but preferably an integer of 1 to 4 from the viewpoint of production efficiency and washing performance during production. And more preferably an integer of 1 to 3.

  Q in the general formula (II) is the number of added moles of (AO), and is an integer of 0 to 10 from the viewpoint of detergency and the like. The preferred number of q varies depending on the value of p.

  M in the general formula (II) is a cation group that forms a salt, and examples thereof include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkanol ammonium ions.

  Examples of the alkali metal for forming M include sodium, potassium, lithium and the like, examples of the alkaline earth metal include calcium, and examples of the alkanol ammonium ion include triethanolammonium ion. Among these, alkali metals such as sodium and potassium are preferable, and sodium is particularly preferable.

  The component (b) is preferably in the form of a powder from the viewpoint of handleability, but may be in the form of a hydrous paste or the like.

The manufacturing method of the component (b) represented by general formula (II) is not specifically limited. For example, it can be produced by a method including the following steps (X) to (Z).
Step (X): An alkylene oxide containing at least one of propylene oxide and butylene oxide is added in an average number of moles of more than 0 and not more than 5 to 1 mole of an alcohol having a hydrocarbon group having 6 to 22 carbon atoms. Step (Y): The alkylene oxide adduct obtained in the above step (X) contains an alkylene oxide containing at least one of ethylene oxide, propylene oxide, and butylene oxide in an average number of moles of 0 or more and 10 or less. Step (Z) for obtaining an alkoxylate by addition: Step for sulfating and then neutralizing the alkoxylate obtained in the above step (Y)

The reaction product obtained by the above method may be a mixture of compounds represented by the following general formulas (i) to (iv). Among these, the compound of general formula (ii), the compound of general formula (iii) (when AO is only PO group and / or BO) and the compound of general formula (iv) are represented by the general formula (II). It is a sulfate ester salt.
R ¹ —O—SO ₃ M (i)
R ¹ —O— (A ¹ O) _x —SO ₃ M (ii)
R ¹ —O— (AO) _y —SO ₃ M (iii)
R ¹ —O— (A ¹ O) _z — (AO) _{z ′} —SO ₃ M (iv)

In general formulas (ii) to (iv), x, y, z, and z ′ are each an integer of 1 or more, and R ¹ and M are the same as R ¹ and M in general formula (II). is there.

  As the hydrocarbon group of the alcohol in the step (X), an alkyl group having 8 to 16 carbon atoms is preferable, an alkyl group having 10 to 14 carbon atoms is more preferable, and an alkyl group having 12 to 14 carbon atoms is preferable from the viewpoints of versatility and handleability. Are particularly preferred. Furthermore, it is preferable that it is a linear alkyl group from a viewpoint of foaming power and emulsifying power performance.

  Moreover, the usage-amount of the alkylene oxide in process (X) is an quantity from which the average addition mole number of the alkylene oxide with respect to 1 mol of said alcohol becomes larger than 0 and 5 or less.

  The amount of alkylene oxide used in step (Y) is such that the average number of moles of alkylene oxide added to 1 mole of alkylene oxide adduct obtained in step (X) is 0 to 10 moles.

  The implementation of the steps (X) to (Y) can be performed by a conventionally known method. That is, the reaction vessel is charged with alcohol or alkylene oxide adduct, and 0.5 to 1 mol% of KOH or the like as a catalyst with respect to the alcohol or alkylene oxide adduct, and heated and dehydrated at a temperature of 130 to 160 ° C. It can be produced by addition reaction of a predetermined amount of alkylene oxide.

  Examples of the sulfation method in the step (Z) include a method using sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid, chlorosulfonic acid and the like. From the viewpoint of preventing generation of sulfur, a method of continuously supplying sulfur trioxide in a gaseous or liquid state simultaneously with the alkoxylate is preferable.

  There is no limitation on the neutralization method of the obtained sulfate, batch type that neutralizes while adding and stirring the sulfate in a predetermined amount of neutralizer, and supply the sulfate and neutralizer continuously into the pipe In addition, a continuous type that is neutralized with a stirring mixer can be employed. Examples of the neutralizing agent that can be used include an aqueous alkali metal solution, aqueous ammonia, and triethanolamine. An aqueous alkali metal solution is preferable, and sodium hydroxide is more preferable.

<Component (c)>
The detergent composition for clothing of the present invention can contain an alkaline agent [hereinafter also referred to as component (c)]. Examples of the component (c) include carbonates, bicarbonates, silicates, orthosilicates, metasilicates, crystalline silicates, phosphates and the like when the composition is in powder form. As the salt, alkali metal salts such as sodium salt and potassium salt are preferable. These alkaline agents can be used alone or as a mixture of two or more. Specific examples include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, sodium tetraborate, sodium pyrophosphate, sodium tripolyphosphate, and the like. Here, the crystalline silicate has a maximum pH of 11 or more in a dispersion dispersed in 0.1% by mass in ion-exchanged water at 20 ° C., and 5 ml or more in order to set the pH of 1 L of the dispersion to 10. It is an alkaline substance that requires a 0.1N-HCl aqueous solution, and is distinguished from the later-described component (d) zeolite (crystalline aluminosilicate). The crystalline silicate is preferably in the form of a layer, such as JP-A-7-89712, JP-A-60-227895, Phys.Chem.Glasses. -p404 (1969) etc. can be used. 0.42Na ₂ O · 0.14K crystalline silicate represented by _{2 O · SiO 2 · 0.03CaO ·} 0.0005MgO is preferably used. In addition, powdered and granular products are available from Hoechst under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ). When the composition is in a liquid form, the component (c) includes monoethanolamine, diethanolamine, triethanolamine, methylmonoethanolamine, dimethylethanolamine, alkanolamines such as 3-aminopropanol, Inorganic salts such as sodium hydroxide and potassium hydroxide, sodium silicate and sodium carbonate can be used, and at least one selected from monoethanolamine, sodium hydroxide and potassium hydroxide is particularly preferable.

  The pH of the laundry detergent composition of the present invention, when diluted with ion-exchanged water to a concentration of 0.1% by mass, is preferably pH 7 to 14, more preferably pH 8 to 12, most preferably pH 9 at 20 ° C. ~ 11.

<Component (d)>
The detergent composition for clothing of the present invention can contain (d) zeolite [hereinafter also referred to as component (d)]. Here, the zeolite of component (d) is a crystalline aluminosilicate, preferably a compound represented by the formula (d1), and more preferably a compound represented by (d2).

a (M ₂ O) · Al ₂ O ₃ · b (SiO ₂ ) · w (H ₂ O) (d1)
(In the formula, M represents an alkali metal atom, a, b, and w represent molar ratios of the respective components. Generally, 0.7 ≦ a ≦ 1.5, 0.8 ≦ b ≦ 6, and w is an arbitrary value. Represents a positive number.)
_{Na 2 O · Al 2 O 3} · n (SiO 2) · m (H 2 O) (d2)
(Here, n represents a number from 1.8 to 3, and m represents a number from 1 to 6.)

  Examples of the component (d) include synthetic zeolite represented by A-type, X-type, and P-type zeolite. The suitable average particle diameter of a component (d) is 0.1-10 micrometers.

<Component (e)>
The detergent composition of the present invention preferably contains an alcohol having 6 to 22 carbon atoms as the component (e). When component (e) is used in combination with component (a), there is a tendency to further suppress crystallization of component (a), so that the effect of improving the washing performance at low temperatures can be further enhanced. The amount of component (e) is 0.001 to 20% by mass, preferably 0.001 to 10% by mass, and more preferably 0.1 to 10% by mass with respect to component (a). When the content of the component (d) exceeds 20% by mass, the component (e) itself acts as a dirt, so that the cleaning performance tends to be impaired.

  Component (e) is preferably an alcohol having an alkyl group having 6 to 22 carbon atoms, and the alkyl group may be linear or branched, but 1-decanol, 1-dodecanol, and 1-tetradecanol are particularly preferable. .

<Component (f)>
The detergent composition of the present invention can contain one or more compounds selected from glycerin and polyglycerin as the component (f). Even when the component (f) is used in combination with the component (a), it tends to suppress the crystallization of the component (a), which is preferable from the viewpoint of improving the washing performance at a low temperature. Moreover, when the detergent composition of the present invention is a liquid, the viscosity of the detergent composition tends to decrease, so that the meterability can be improved. The amount of component (f) is 0.001 to 50% by weight, preferably 0.001 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly 1 to 5% by weight, based on component (a). Is preferred.

  Component (f) is preferably glycerin and / or polyglycerin, and in the case of polyglycerin, there is no particular limitation on the degree of condensation and the bonding mode. Examples of the degree of condensation of polyglycerol include 2 to 8. Either a chain or a ring may be used.

<Ingredient (g)>
The detergent composition of the present invention comprises (g-1) an alkyl sulfate ester salt having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms or polyoxyethylene alkyl (10 to 18 carbon atoms, preferably 12-14) One or more surfactants selected from ether sulfate ester salts [hereinafter also referred to as component (g-1)] and (g-2) fatty acid salts [hereinafter also referred to as component (g-2)]. Can be contained.

<Component (g-1)>
In the polyoxyethylene alkyl ether sulfate ester salt, the average added mole number of ethylene oxide is preferably 0.5 to 5.0. As the component (g-1), decyl sulfate ester salt, dodecyl sulfate ester salt, tetradecyl sulfate ester salt, polyoxyethylene decyl ether sulfate ester salt having an average addition mole number of ethylene oxide of 1 to 3, polyoxyethylene dodecyl ether sulfate Ester salts and polyoxyethylene tetradecyl ether sulfate ester salts are preferred. The counter ion of these salts is preferably sodium, potassium or ammonium.

<Component (g-2)>
In the detergent composition of the present invention, when a fatty acid salt is used in combination as the component (g-2), when the component (g-2) is combined with the hardness component in the wash water to form a metal soap, the component (a ) Is more finely dispersed than general surfactants, and therefore the defoaming effect tends to increase. Therefore, the compounding quantity of a fatty acid salt can be reduced. The ratio of the component (a) + (b) to the component (g-2) is preferably 1000/1 to 1/10, more preferably the mass ratio [(a) + (b)] / (g-2). 100/1 to 1/1, particularly preferably 50/1 to 2/1, most preferably 10/1 to 3/1. The component (g) is preferably a fatty acid salt having 12 to 22 carbon atoms, and specifically includes lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like. As a counter ion of these salts, sodium and potassium are preferable, and sodium is particularly preferable.

<Other ingredients>
The detergent composition for clothing of the present invention can contain a surfactant other than the component (a), the component (b), and the component (g). Examples of the surfactant other than the component (a), the component (b), and the component (g) include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants. Although a seed | species or a combination can be mentioned, Preferably it is an anionic surfactant and a nonionic surfactant.

  Examples of the anionic surfactant other than the component (b) and (g) include alkylbenzene sulfonate, α-sulfo fatty acid ester salt, paraffin sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, or α-sulfo fatty acid alkyl ester salts are preferred. In the present invention, in order to improve the washing performance at low temperature, the alkyl chain has 10 to 14, more preferably 12 to 14 linear alkylbenzene sulfonate or the alkyl chain has 12 to 18, more preferably 12 to 18 carbon atoms. 14-18 alpha-sulfo fatty acid ester salt can also be used together with a component (b). As a counter ion of these salts, alkali metal salts and amines are preferable, and sodium and / or potassium, monoethanolamine, and diethanolamine are particularly preferable.

  In the present invention, from the viewpoint of detergency, the compounding amount of the anionic surfactant other than the component (b) and the component (g) is 100% by mass or less, preferably 70% by mass or less with respect to the component (b). More preferably, it is 50% by mass or less, and particularly preferably 30% by mass or less.

  On the other hand, it is preferable to use an anionic surfactant other than the component (b) and the component (g) in combination with an anionic interface other than the component (b) from the viewpoint of further improving the low-temperature detergency and formulation. The blending amount of the activator is 1% by mass or more, preferably 2% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more with respect to the component (b).

  Nonionic surfactants other than component (a) include polyoxyalkylene alkyl (carbon number 8-20) ether, alkyl polyglycoside, polyoxyalkylene alkyl (carbon number 8-20) phenyl ether, polyoxyalkylene sorbitan Fatty acid (carbon number 8-22) ester, polyoxyalkylene glycol fatty acid (carbon number 8-22) ester, and polyoxyethylene polyoxypropylene block polymer are preferable. In particular, as a nonionic surfactant, 4 to 20 moles of alkylene oxide such as ethylene oxide or propylene oxide is added to an alcohol having 10 to 18 carbon atoms [HLB value (calculated by Griffin method) is 10.5 to 15. 0, preferably 11.0 to 14.5]. Polyoxyalkylene alkyl ethers are preferred for the purpose of enhancing cleaning performance.

  In the present invention, from the viewpoint of detergency, the blending amount of the nonionic surfactant other than the component (a) is 100% by mass or less, preferably 70% by mass or less, more preferably, relative to the component (a). It is preferably contained at 50% by mass or less, particularly 30% by mass or less.

  On the other hand, it is preferable to use a nonionic surfactant other than component (a) in combination from the viewpoint of further increasing the low-temperature detergency and formulation, and the amount of nonionic surfactant other than component (a) Is 1% by mass or more, preferably 2% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more based on the component (a).

  Moreover, the detergent composition for clothes of this invention can contain inorganic builders other than an organic builder, a component (c), and a component (d). Organic builders include carboxylates (aminocarboxylates, hydroxyaminocarboxylates, hydroxycarboxylates, cyclocarboxylates, maleic acid derivatives, oxalates, etc.), organic carboxylic acid (salt) polymers (acrylic acid) Polymer and copolymer, polyvalent carboxylic acid polymer and copolymer, glyoxylic acid polymer, polysaccharides and salts thereof, and the like. Of these, organic carboxylic acid (salt) polymers are preferred. In these builder salts, the counter ion is preferably an alkali metal salt or an amine, particularly sodium and / or potassium, monoethanolamine, or diethanolamine. These builders can be used alone or in combination of two or more.

  In particular, when the detergent composition of the present invention contains a carboxylic acid (salt) polymer, since the affinity with the component (a) is high, when the detergent composition is powdery, the water absorption of the polymer can be suppressed. it can. For this reason, it becomes possible to add a high amount of polymer while maintaining the caking resistance of the detergent particles, and an improvement in cleaning performance is recognized. Further, when the detergent composition is in a liquid state, the component (a) has an effect of suppressing the precipitation of the carboxylic acid (salt) polymer, so that the storage stability can be enhanced.

  The detergent composition for clothing of the present invention comprises a bleaching agent (percarbonate, perborate, bleach activator, etc.), a recontamination inhibitor (carboxymethylcellulose, etc.), a softening agent (dialkyl type quaternary ammonium salt). , Clay minerals, etc.), reducing agents (sulfites, etc.), fluorescent brighteners (biphenyl type, aminostilbene type, etc.), foam control agents (silicone, etc.), perfumes, enzymes (proteases, cellulases, pectinases, amylases, lipases, etc.) ) And the like can be contained.

  When the fluorescent whitening agent of biphenyl type or aminostilbenzene type is added to the detergent composition of the present invention, the solubility of the fluorescent whitening agent in the component (a) is small, so that the fluorescent whitening agent is a surfactant. The amount taken into the micelle is suppressed, and the washability of the fluorescent whitening agent to the laundry is improved. For this reason, the compounding quantity of a fluorescent whitening agent can be reduced. By the same mechanism, the amount of fragrance, especially cLogP of 3 or more, dissolved in the surfactant micelle decreases, so that the residual fragrance attached to the laundry is improved, and the fragrance tone during and after washing The change of can be reduced. Moreover, the adsorption | suction amount to the laundry of a silicone can be raised with the same mechanism.

  When an enzyme is blended in the detergent composition of the present invention, since the enzyme activity inhibition rate of component (a) is low, a decrease in enzyme activity during storage can be suppressed.

  Further, surface modification may be performed from the viewpoint of fluidity and caking resistance when the composition is in the form of particles. As the surface modifier, component (d) can be used, and in addition, silicate compounds such as calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate, metal Examples include soaps, fine powders such as powder surfactants, carboxymethylcellulose, polyethylene glycol, sodium polyacrylate, water-soluble polymers such as polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof, and fatty acids. More preferred are component (d) and crystalline silicate, and still more preferred is component (d).

  When the composition is in the form of particles, the combined use of component (a) and polyethylene glycol increases the fluidity in the granulation step, so that the generation of fine powder can be suppressed. Thereby, it becomes possible to suppress the scattering property of the powder and to improve the caking resistance.

<Detergent composition for clothing>
The detergent composition for clothing of the present invention preferably contains 1 to 80% by mass, further 3 to 40% by mass, particularly 5 to 20% by mass of the component (a). Moreover, it is preferable to contain a component (b) 1-80 mass%, 1.5-40 mass%, especially 2-20 mass%. Moreover, it is preferable to contain a component (c) 1-90 mass%, 5-50 mass%, especially 10-40 mass%. Moreover, it is preferable to contain a component (d) 1-90 mass%, 5-50 mass%, especially 10-40 mass%.

  In particular, the mass ratio of component (a) to component (b) affects the performance of the detergent composition. In particular, from the viewpoint of detergency, the mass ratio of component (a) to component (b) is preferably component (a) / component (b) = 5/95 to 95/5, more preferably 10/90 to 90/10, 25/75 to 75/25 is preferred.

  Moreover, it is preferable that a component (e) contains 0.001-20 mass% with respect to a component (a), Furthermore, 0.01-10 mass%, Especially 0.1-5 mass% is contained. The component (f) is contained in an amount of 0.001 to 50% by mass, further 0.01 to 20% by mass, further 0.01% to 10% by mass, and particularly 0.05 to 5% by mass with respect to the component (a). It is preferable to do.

  Further, the content of the surfactant other than the component (a) in the composition is preferably 0.1 to 50% by mass, more preferably 3 to 30% by mass, and particularly preferably 5 to 15% by mass. In particular, the content of the component (g-1) in the composition is 3 to 30% by mass, more preferably 5 to 20% by mass, and particularly 5 to 15% by mass in the composition of the component (g-2). The amount is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, particularly preferably 1 to 5% by mass.

  The ratio of the anionic surfactant in the surfactant is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass from the viewpoint of detergency.

  The garment detergent composition of the present invention is preferably in a powder form, and preferably has a bulk density of 300 to 1000 g / L, more preferably 500 to 900 g / L, and particularly preferably 600 to 800 g / L. Moreover, it is preferable that an average particle diameter is 150-3000 micrometers, 500-1500 micrometers, especially 600-1200 micrometers.

  Using the following blending components and the components of Table 1, the powdered laundry detergent composition shown in Table 1 is prepared, and using the components of Table 2, the liquid clothing detergent composition shown in Table 2 is prepared, Detergency was evaluated by the following method. The results are shown in Tables 1 and 2.

[1] Compounding ingredients <alkyl ether sulfate ester salt (b1)>
C12 linear alcohol (trade name: Calcoal 2098, manufactured by Kao Co., Ltd.) 2340 g and KOH 3.5 g were charged into an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device to 110 ° C. and 1.3 kPa. For 30 minutes. After dehydration, nitrogen substitution was performed, and after raising the temperature to 120 ° C., 1460 g of propylene oxide was charged. After addition reaction and aging at 120 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide was removed at 4.0 kPa. After removing unreacted propylene oxide, 3.8 g of acetic acid was added to the autoclave, and the mixture was stirred for 30 minutes at 80 ° C., and then extracted to obtain an alkoxylate having an average added mole number of propylene oxide of 2.0.

The obtained alkoxylate was sulfated in a falling thin film reactor (hereinafter referred to as FFR) using SO ₃ gas. The obtained sulfate was neutralized with an aqueous NaOH solution to obtain a composition containing a polyoxypropylene alkyl ether sulfate salt.

  As a result of GC analysis, the obtained composition contained 98% by mass of polyoxypropylene alkyl ether sulfate salt having a structure in which 1 mol or more of propylene oxide was added and 2% by mass of alkyl sulfate ester salt.

<Alkyl ether sulfate (b2)>
2340 g of alcohol having 12 carbon atoms (Kao Corporation, product name: Calcoal 2098) and 3.5 g of KOH were charged into an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, and 110 minutes at 110 ° C. and 1.3 kPa. Dehydration was performed. After dehydration, nitrogen substitution was performed, and after raising the temperature to 120 ° C., 511 g of propylene oxide was charged. After addition reaction and aging at 120 ° C., the temperature was raised to 145 ° C., and 1107 g of ethylene oxide was charged. After addition reaction and aging at 145 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide was removed at 4.0 kPa. After removal of unreacted ethylene oxide, 3.8 g of acetic acid was added to the autoclave and stirred at 80 ° C. for 30 minutes, then withdrawn, the average added mole number of propylene oxide was 0.7 mole, the average added mole of ethylene oxide An alkoxylate having a number of 2.0 mol was obtained.

The obtained alkoxylate was sulfated in a falling thin film reactor (hereinafter referred to as FFR) using SO ₃ gas. The obtained sulfate was neutralized with an aqueous NaOH solution to obtain an alkyl ether sulfate ester composition.

  As a result of GC and NMR analysis, the obtained composition contained 60% by mass of a sulfate ester salt having a structure in which 1 mol or more of propylene oxide was added.

<LAS>
For LAS, Neo-Perex G-15 manufactured by Kao Corporation was used.

<Glyceryl alkyl ether>
Lauryl alcohol 93.2 g (0.50 mol) and lanthanum triflate 2.94 g (0.0050 mol) were placed in a 300 mL four-necked flask and heated to 90 ° C. with stirring under a nitrogen stream. Next, 148.16 g (2.0 mol) of glycidol was added dropwise over 24 hours while maintaining the temperature, and stirring was continued for 2 hours to obtain 243.5 g of a reaction product. As a result of analyzing the obtained reaction product by gas chromatography, the conversion rate of glycidol was 99.9% or more and 6.0% by mass of lauryl alcohol. In the obtained lauryl polyglyceryl ether, the proportion of glycerin having a condensation degree n of 3 to 5 was 43.3% by mass relative to the total of those having n of 1 to 7. Therefore, it was confirmed that the product [glyceryl alkyl ether] contained a plurality of compounds having different degrees of condensation of glycerin n.

<AE>
As AE, polyoxyethylene alkyl ether manufactured by Kao Corporation was used. The alkyl chain length of AE was C12 / C14 = 72/28 (mass ratio), and the average number of moles of ethylene oxide added was 6.

<Polymer>
Polyacrylic acid (average molecular weight 15,000; measured by GPC, converted to polyethylene glycol)

<Zeolite>
As the zeolite, 4A-type zeolite having an average particle diameter of 3 μm manufactured by Tosoh Corporation was used.

[2] Evaluation method of detergency of powder detergent composition After dissolving 0.667 g of the detergent composition shown in Table 1 in 1 L of tap water, 5 spinach-contaminated cloths prepared as shown below were placed, and a targotometer Washing was performed at 5 ° C. (liquid temperature) for 10 minutes at 80 rpm. After rinsing sufficiently, it was dried and the washing rate was measured by the following formula.

Washing rate (%) = (reflectance after washing−reflectance before washing) / (reflectance of white cloth−reflectivity before washing) × 100

  The reflectance was measured with NDR-10DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

[3] Evaluation method of detergency of liquid detergent composition To 1 L of tap water, 0.833 g of the liquid detergent composition shown in Table 2 was added, and then 5 spinach-contaminated cloths prepared as shown below were added, and a targotometer Washing was performed at 5 ° C. (liquid temperature) for 10 minutes at 80 rpm. After rinsing sufficiently, it was dried and the washing rate was measured in the same manner as in the evaluation of the powder detergent composition.

<Preparation of spinach-contaminated cloth>
After commercially available spinach was pulverized with a mixer, the produced liquid portion was filtered off with a cotton cloth. 0.5 g of the obtained liquid was uniformly applied onto a 6 cm × 6 cm cotton gold cloth # 2023 and dried at 20 ° C. for 12 hours for the test.

(Note) In the case of the composition shown in Table 1, the anionic surfactant ratio is calculated by the following formula.
Anionic surfactant ratio (% by mass) = anionic surfactant / (anionic surfactant + nonionic surfactant) × 100
Here, the “anionic surfactant” is the mass% of the anionic surfactant, “the mass% of the alkyl ether sulfate ester salt (b1) + the mass% of the alkyl ether sulfate ester salt (b2) + LAS. The value obtained by “mass%”, “nonionic surfactant” is the mass% of nonionic surfactant, and is the value obtained by “mass% of glyceryl alkyl ether + mass% of AE”. Further, the “remainder” of sodium sulfate is an amount that makes the total mass ratio of the composition 100.

  In Table 2, “adjusted amount” of sodium hydroxide is an amount that makes the pH (20 ° C.) of the composition 9. The “remainder” of water is an amount that makes the total mass ratio of the composition 100.

Claims (5)

(A) glyceryl monoether or polyglyceryl monoether represented by general formula (I) [hereinafter referred to as component (a)], and (b) sulfate ester salt represented by general formula (II) [hereinafter referred to as component ( b)], and the component (a) comprises a plurality of compounds having different degrees of condensation n of glycerin in the general formula (I).
R—O— (C ₃ H ₆ O ₂ ) _n —H (I)
(In the formula, R is a hydrocarbon group having 6 to 22 carbon atoms, n is the degree of condensation of glycerin, and represents an integer.)
R ¹ —O— (A ₁ O) _p — (AO) _q —SO ₃ M (II)
(In the formula, R ¹ is a hydrocarbon group having 6 to 22 carbon atoms, A ¹ O is an oxypropylene group and / or oxybutylene group, and AO contains at least one of an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene group, p is an integer of 1 to 5, q is an integer of 0 to 10, M represents an alkali metal , NH ₄ or an alkanol ammonium group having 2 to 3 carbon atoms.) In the component (a), the ratio of the compound in which R in the general formula (I) is an alkyl group having 12 and / or 14 carbon atoms and the condensation degree n of glycerin is 3 to 5 is the general formula (I The detergent composition for clothes according to claim 1, which is 40% by mass or more based on the compound having a degree of condensation n of glycerol of 1) to 7). The detergent composition for clothes according to claim 1, wherein the proportion of the compound having a glycerin condensation degree n of 1 or 2 in the component (a) is less than 50% by mass. The detergent composition for clothing according to any one of claims 1 to 3, comprising 0.001 to 20% by mass of an alcohol having 6 to 22 carbon atoms with respect to the component (a). The detergent composition for clothing according to any one of claims 1 to 4, comprising 0.001 to 50 mass% of one or more compounds selected from glycerin and polyglycerin with respect to component (a).