JP2009155612A - Detergent composition for clothing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition for clothing having higher detergency. <P>SOLUTION: The detergent composition for clothing includes: (a) glyceryl monoether or 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 selected from sulfate ester salts expressed by general formula (II): R<SP>1</SP>-O-SO<SB>3</SB>M and sulfate ester salts expressed by general formula (III): R<SP>1</SP>-O-(EO)<SB>m</SB>-(AO)<SB>l</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 formulae (II) and (III), R<SP>1</SP>represents a 6-22C hydrocarbon group; EO represents an oxyethylene group; AO represents a specific oxyalkylene group; m is an integer from 1 to 10; l 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, non-ionic surfactants such as glycerin monoalkyl ethers and polyglycerin monoalkyl ethers mainly derived from plant-derived natural fats and oils are incorporated into detergents. This 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, an object of the present invention is to provide a detergent composition for clothing having higher detergency using glyceryl monoether or polyglyceryl monoether (hereinafter also referred to as glyceryl monoether) having a specific degree of glycerin condensation. That is.

  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 is represented by (a) glyceryl monoether or polyglyceryl monoether represented by general formula (I) [hereinafter referred to as component (a)], and (b) represented by general formulas (II) to (III). A laundry detergent composition comprising a sulfate ester salt (hereinafter referred to as component (b)), wherein component (a) is a plurality of different glycerin condensation degrees n of 3 to 5 in general formula (I) The present invention relates to a laundry detergent composition comprising a compound.
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—SO ₃ M (II)
R ¹ —O— (EO) _m — (AO) ₁ —SO ₃ M (III)
Wherein R ¹ is a hydrocarbon group having 6 to 22 carbon atoms, EO is an oxyethylene group, AO is an oxyalkylene group containing at least one of an oxyethylene group, an oxypropylene group and an oxybutylene group, and m is 1 10 represents an integer of 1 to 10, l represents 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 detergency 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.

  In the component (a), R in the general formula (I) is an alkyl group having 12 and / or 14 carbon atoms, and the total ratio of polyglyceryl monoethers having a glycerin condensation degree n of 3 to 5 is as follows: It is preferable that it is 40 mass% or more with respect to the compound whose condensation degree n of glycerol in General formula (I) is 1-7, More preferably, it is 50 mass% or more, More preferably, it is 60 mass% or more, more More preferably, it is 70 mass% or more, Most preferably, it is 80 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. The component (a) contains a plurality of compounds having different degrees of condensation of glycerin n in the general formula (I), and it contains two or more compounds, particularly 3 or more, different compounds of n from the viewpoint of washing performance at a low temperature. To preferred. 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 2 or more types and all 3 types (n = 3, 4, 5) are included among those having a condensation degree n of glycerol of 3 to 5 in the component (a). 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, It is preferable that 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 glycerin condensation degree n is 3 to 5 is 40% by mass or more. Furthermore, it is preferable to contain a plurality of compounds having different n selected from these compounds (a-1) and (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, 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 glycerin condensation of 3 to 5, 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 selected from a sulfate ester salt represented by the following general formula (II) and a sulfate ester salt represented by the general formula (III). The compound of the general formula (II) includes an alkyl sulfate ester salt, and the compound of the general formula (III) includes an alkyl ether sulfate salt.
R ¹ —O—SO ₃ M (II)
R ¹ —O— (EO) _m — (AO) ₁ —SO ₃ M (III)
Wherein R ¹ is a hydrocarbon group having 6 to 22 carbon atoms, EO is an oxyethylene group, AO is an oxyalkylene group containing at least one of an oxyethylene group, an oxypropylene group and an oxybutylene group, and m is 1 10 represents an integer of 1 to 10, l represents 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 formulas (II) and (III) 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. preferable. 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.

  The oxyalkylene group represented by (AO) in the general formula (III) is an oxyalkylene group containing at least one of an oxyethylene group, an oxypropylene group, and an oxybutylene group, and a combination of two or more thereof. Can be used.

The compound of the general formula (III) has a structure in which EO is bonded to R ¹ —O—, and when AO contains two or more oxyalkylene groups, either block addition or random addition may be used. When AO is only EO, the compound of general formula (III) is an ethylene oxide adduct of R ¹ —O— (EO) _{m + 1} -SO ₃ M.

  M in the general formula (III) is the number of added moles of (EO) and is an integer of 1 to 10, preferably from an integer of 1 to 5 from the viewpoint of production efficiency and washing performance during production. Yes, more preferably an integer of 1 to 3.

  Moreover, l in general formula (III) is the added mole number of (AO), and is an integer of 0-10 from viewpoints of detergency. The preferred number of l varies depending on the value of m.

  Further, M in the general formulas (II) and (III) is a cationic 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 production method of component (b) represented by general formulas (II) and (III) is not particularly limited. For example, in the case of producing the compound of the general formula (II), a method of sulfating an alcohol having a hydrocarbon group having 6 to 22 carbon atoms and then neutralizing it is referred to as “step (A)” below. To do. ].

Moreover, when manufacturing the compound of general formula (III), it can manufacture by the method containing the following process (X)-(Z).
Step (X): Step of adding ethylene oxide having an average number of moles of 0 or more and 10 or less to 1 mole of alcohol having a hydrocarbon group having 6 to 22 carbon atoms (Y): obtained in the above step (X) Step (Z) of obtaining an alkoxylate by adding an alkylene oxide containing at least one of ethylene oxide, propylene oxide, and butylene oxide in an average number of moles of 0 to 10 to the obtained ethylene oxide adduct: The step of sulfating and then neutralizing the alkoxylate obtained in 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 the general formula (i) is a sulfate ester salt represented by the general formula (II), and the compound of the general formula (iv) is a sulfate ester salt represented by the general formula (III).
R ¹ —O—SO ₃ M (i)
R ¹ —O— (EO) _x —SO ₃ M (ii)
R ¹ —O— (AO) _y —SO ₃ M (iii)
R ¹ —O— (EO) _z — (AO) _{z ′} —SO ₃ M (iv)

In general formula (ii) ~ (iv) in the x, y, z, z 'is an integer of 1 or more, respectively, R ¹ and M have the general formula (II), and R ¹ in (III) Same as M.

  As the hydrocarbon group of the alcohol in the step (A) and the step (X), an alkyl group having 8 to 16 carbon atoms is preferable, and an alkyl group having 10 to 14 carbon atoms is more preferable, from the viewpoint of versatility and handleability. An alkyl group having 12 to 14 carbon atoms is particularly preferable. 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 ethylene oxide in process (X) is the quantity from which the average added mole number of ethylene oxide with respect to 1 mol of said alcohol becomes larger than 0 and 10 or less.

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

  The steps (A) and (X) to (Y) can be performed by a conventionally known method. That is, the reaction vessel is charged with alcohol or ethylene oxide adduct and 0.5 to 1 mol% of KOH or the like as a catalyst with respect to the alcohol or ethylene oxide adduct, heated and dehydrated, at a temperature of 130 to 160 ° C. Each can be produced by addition reaction of a predetermined amount of ethylene oxide or 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. 7, p127-p138 (1966), Z. Kristallogr., 129, p396. -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) is within 20% by mass, the tendency of the cleaning performance to be impaired due to the component (e) itself acting as a stain can be suppressed.

  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 can contain a fatty acid salt as component (g). When the fatty acid salt of component (g) is used in combination, when component (g) combines with the hardness component in the wash water to form a metal soap, component (a) is finer than a general surfactant. Since it is dispersed, the defoaming effect tends to increase. Therefore, the compounding quantity of surfactant can be reduced. The ratio of component (a) + (b) to component (g) is preferably 1000/1 to 1/10, more preferably 100/1 to 1 by mass ratio [(a) + (b)] / (g). 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 from the viewpoint of detergency at a low temperature (for example, 5 ° C.) and solubility of the detergent. The amount of the anionic surfactant other than the component (g) is 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, particularly 20% by mass or more with respect to the component (b). preferable.

  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 mol 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] 0.0, preferably 11.0 to 14.5] is preferred for the purpose of enhancing the 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 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 the component (a) in combination with a nonionic surfactant other than the component (a) from the viewpoints of detergency at a low temperature (for example, 5 ° C.) and solubility of the detergent. The compounding amount of the activator is 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more with respect to 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. As a result, it is possible to suppress dust scattering properties and to improve 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) in the composition is 0.1 to 15% by mass, more preferably 1 to 10% by mass, and 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 shown in Table 1, powder detergent compositions for clothing shown in Table 1 were prepared. Moreover, the detergent composition for liquid clothes shown in Table 2 was prepared using the following compounding component and the component of Table 2. About each, the detergency was evaluated by the following method. The results are shown in Tables 1 and 2.

[1] Compounding component <AS>
The AS used sodium tetradecyl sulfate prepared from Calcoal 2098 manufactured by Kao Corporation. The alkyl chain length of AS was C12 / C14 = 2/98 (mass ratio).

<AES>
For AES, sodium polyoxyethylene tetradecyl ether sulfate prepared from Calcoal 4098 manufactured by Kao Corporation was used. The alkyl chain length of AES was C12 / C14 = 2/98 (mass ratio), and the average added mole number of ethylene oxide (hereinafter referred to as EO) was 1. In the AES, the ratio of the compound having an EO addition mole number of 1 or more was 55.8% by mass.

<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 glycidol conversion rate was 99.9% or more, lauryl alcohol 6.0 mass%, and the content of polyglycerin was 2.2 mass%. 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.

  Further, the following components (a1) to (a2) were separated from the product by column separation, and the molecular weight was measured by mass spectrum. As a result of quantifying the glycerin condensation degree 1 compound and the glycerin condensation degree 2 compound in the product (lauryl polyglyceryl ether) by gas chromatography using these as standard products, 12.2% by mass of the glycerin condensation degree 1 compound, glycerin condensation It was confirmed that 11.4% by mass of the compound of degree 2 was contained.

Glyceryl alkyl ether (a1): molecular weight 220 or more and less than 300 (corresponding to glycerin condensation degree 1)
Glyceryl alkyl ether (a2): molecular weight of 300 to less than 360 (corresponding to glycerin condensation degree 2)

<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 EO average added mole number was 6.

<Polymer>
Polyacrylic acid (weight 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 20 ° 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 20 ° 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, “anionic surfactant” is a mass% of an anionic surfactant, and is a value obtained by “mass% of AS + mass% of AES + mass% of LAS”. The “agent” is the mass% of the nonionic surfactant, and is a 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) a glyceryl monoether or polyglyceryl monoether represented by general formula (I) [hereinafter referred to as component (a)], and (b) a sulfate ester salt represented by general formulas (II) to (III) [ Hereinafter, the detergent composition for clothing containing the component (b)], wherein the component (a) includes a plurality of different compounds having a degree of condensation n of glycerol of 3 to 5 in the general formula (I). A detergent composition for clothing.
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—SO ₃ M (II)
R ¹ —O— (EO) _m — (AO) ₁ —SO ₃ M (III)
Wherein R ¹ is a hydrocarbon group having 6 to 22 carbon atoms, EO is an oxyethylene group, AO is an oxyalkylene group containing at least one of an oxyethylene group, an oxypropylene group and an oxybutylene group, and m is 1 10 represents an integer of 1 to 10, l represents 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.) 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).