HK1172053A1

HK1172053A1 - Liquid detergent composition

Info

Publication number: HK1172053A1
Application number: HK12112953.6A
Authority: HK
Inventors: Kobayashi Chika; Konta Hiroshi; Kaneko Yukihiro; Terabayashi Tsuyoshi
Original assignee: Lion Corporation
Priority date: 2009-10-15
Filing date: 2010-10-14
Publication date: 2013-04-12
Also published as: WO2011046170A1; JP5613677B2; CN102575195B; CN102575195A; JPWO2011046170A1; KR20120095884A; MY158741A; EP2489722A1; KR101791707B1; EP2489722A4

Abstract

The invention relates to a liquid detergent composition includes: a component (A) which includes a nonionic surfactant represented by the formula R 1 O(CH 2 CH 2 O) n H; a component (B) which includes at least one species of anionic surfactant selected from the group consisting of compounds represented by the formulas R 2 CH(SO 3 M 1 )COOR 3 and R 4 CH(SO 3 M 2 )CONHR 5 ; and a component (C) which includes at least two species of water-miscible solvents selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, butyl carbitol, phenoxy ethanol, and polyethylene glycol with an average molecular weight of 570 to 3800, wherein the total amount of the component (A) and the component (B) is in the range of 40 to 75 % by mass and the mass ratio of the amount of the component (B) with respect to the total amount of the component (A) and the component (B) satisfies component (B)/(component (A)+component (B)) =1/10 to 6/10. The invention can provide a liquid detergent composition which includes a surfactant at a high concentration and which has superior low-temperature preservation stability and superior low-temperature solubility and sebum detergency during washing.

Description

Liquid detergent composition

Technical Field

The present invention relates to liquid cleaning compositions.

The present application claims priority based on application No. 2009-238354, filed in japan on 10, 15, 2009, the contents of which are incorporated herein by reference.

Background

In recent years, the importance of development of environmental products has been increasing, and products taking care of the global environment have been pursued in the field of daily necessities such as laundry detergents. For example, containers for detergents are being developed toward miniaturization in order to reduce energy consumption in logistics and to reduce generation of garbage. Accordingly, a concentrated liquid detergent is required to exhibit a high sebum-cleaning ability with a small amount of detergent. In order to concentrate a liquid detergent, it is required that the detergent does not gel and does not reduce the washing ability against sebum even when diluted with water during washing. In particular, when sebum stains are applied directly, even at low temperatures (about 15 ℃) in winter, the solubility of the sebum stains is required to be such that the sebum stains do not adhere to clothes and remain.

In response to such a demand, liquid detergent compositions containing a nonionic surfactant or an anionic surfactant as a main matrix have been widely used.

For example, patent document 1 discloses a liquid detergent composition using a combination of a primary alcohol polyoxyethylene ether and a secondary alcohol polyoxyethylene ether to which ethylene oxide and propylene oxide are added as a nonionic surfactant.

Patent document 2 discloses a surfactant composition that is easily used in a liquid detergent composition, and the surfactant composition contains 35 to 80 mass% of an α -sulfofatty acid alkyl ester and an alcohol having 6 to 22 carbon atoms as an anionic surfactant.

Further, a liquid detergent composition using a primary alcohol polyoxyethylene ether as a nonionic surfactant has been attracting attention because of its high sebum-cleaning ability and excellent cost and versatility.

However, it is generally known that a surfactant tends to form a highly viscous higher-order association structure such as a hexagonal liquid crystal in a high concentration region, and when a primary alcohol polyoxyethylene ether is used, a highly viscous liquid crystal phase (liquid crystalline phase) is formed in a very wide concentration region when the concentration thereof is as high as 40 mass% or more. Such a primary alcohol polyoxyethylene ether has a wide highly viscous region, and therefore tends to be highly viscous with increasing concentration, and it is difficult to prepare a concentrated liquid detergent composition containing 40 mass% or more of the above components.

Further, when a high concentration of primary alcohol polyoxyethylene ether is contained, the solubility is liable to be lowered when added to a washing solution, and particularly, when the washing is carried out at a low temperature in winter, there is a tendency that a gel-like adhesive substance is liable to remain on the clothes after the completion of washing.

In response to such a situation, a method of improving solubility by mixing a hydrotrope is known.

However, in order to obtain a liquid detergent composition having excellent solubility even at a higher concentration, it is necessary to use a primary alcohol polyoxyethylene ether and a hydrotrope in the composition, but functional components such as enzymes and chelating agents necessary for detergents cannot be sufficiently mixed.

The following are known as liquid detergent compositions containing a mixture of primary alcohol polyoxyethylene ethers.

Patent document 3 discloses a high-concentration anionic surfactant aqueous slurry containing a high-concentration anionic surfactant and containing a primary alcohol polyoxyethylene ether, 50 to 80 mass% of an anionic surfactant (an α -sulfo fatty acid ester salt or the like), and polyethylene glycol having an average molecular weight of 200 to 800 in order to suppress an increase in viscosity with time.

Patent document 4 discloses a liquid detergent composition for clothing, which contains a primary alcohol polyoxyethylene ether and a polyoxyalkylene amine in order to exhibit high cleaning performance at a low concentration.

Patent document 5 discloses a liquid detergent composition using a combination of a primary alcohol polyoxyethylene ether and an anionic surfactant such as an alkylbenzene sulfonate (LAS) or an alkyl polyoxyethylene ether sulfate (AES).

Patent documents 6 and 7 disclose liquid concentrated detergent compositions containing an anionic surfactant such as a primary alcohol polyoxyethylene ether, a sulfone compound of an α -sulfofatty acid derivative or a polyalkylene glycol monomethyl ether unsaturated fatty acid ester, or a salt thereof.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. Hei 11-241092

Patent document 2: japanese patent laid-open No. 2008-94942

Patent document 3: japanese patent laid-open No. 2001-288500

Patent document 4: japanese patent laid-open No. 2005-171195

Patent document 5: japanese patent laid-open No. 9-176685

Patent document 6: japanese patent laid-open No. 8-269485

Patent document 7: japanese patent laid-open No. 9-78092

Disclosure of Invention

Problems to be solved by the invention

However, the liquid cleanser composition using the liquid cleanser composition described in patent document 1 and the surfactant composition described in patent document 2 is insufficient in cleaning performance (sebum cleaning ability) against sebum stains.

In addition, although the high-concentration anionic surfactant aqueous slurry described in patent document 3 has improved fluidity when containing an anionic surfactant at a high concentration (50% by mass or more), it is not satisfactory in terms of storage stability at low temperature (about 5 ℃), low-temperature solubility (about 15 ℃), and cleansing ability for sebum.

The liquid detergent composition for clothing described in patent document 4 is highly viscous and thick when stored at low temperatures.

The liquid detergent composition described in patent document 5 contains 30 mass% or more of LAS or AES, but protection of the global environment is not considered.

The liquid concentrated cleaning agent compositions described in patent documents 6 and 7 are not satisfactory in terms of price and versatility because they are expensive to synthesize anionic surfactants. In addition, it is also poor in biodegradability.

In view of the above circumstances, the present invention has been made to provide a liquid detergent composition which contains a surfactant at a high concentration and has excellent low-temperature storage stability, and which is excellent in low-temperature solubility and sebum-cleaning ability during cleaning.

Means for solving the problems

The present inventors have made extensive studies and as a result, have found that by mixing specific amounts of a primary alcohol polyoxyethylene ether and a specific anionic surfactant and using a specific 2 or more types of a hydrotrope, the surfactant can be blended at a high concentration without lowering the low-temperature solubility while suppressing the occurrence of high thickening. Further, it has been found that functional components such as an enzyme and a chelating agent can be sufficiently mixed without mixing a large amount of a hydrotrope because the solubility at low temperature can be maintained, and the present invention has been completed.

Namely, the liquid detergent composition of the present invention is characterized by containing

(A) The components: a nonionic surfactant represented by the following general formula (1),

(B) The components: at least 1 anionic surfactant selected from the group consisting of compounds represented by the following general formulae (2) and (3),

(C) The components: at least 2 aqueous mixed solvents selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, butyl carbitol, phenoxyethanol, and polyethylene glycol having an average molecular weight of 570-3800;

the total content of the component (A) and the component (B) is 40 to 75 mass%,

and the mass ratio of the component (B) to the total of the contents of the component (A) and the component (B) is as follows: (B) component/{ (A) component + (B) component } -, 1/10-6/10.

R¹O(CH₂CH₂O)_nH …(1)

R²CH(SO₃M¹)COOR³ …(2)

R⁴CH(SO₃M²)CONHR⁵ …(3)

In the formulae (1) to (3), R¹Is a linear alkyl group having 10 to 22 carbon atoms, R²Is a linear or branched alkyl group having 9 to 14 carbon atoms or a linear or branched alkenyl group having 9 to 16 carbon atoms, R³Is a straight chain or branched alkyl group having 1 to 3 carbon atoms, R⁴Is a linear or branched alkyl group having 9 to 14 carbon atoms or a linear or branched alkenyl group having 9 to 16 carbon atoms, R⁵Is hydrogen or a straight-chain or branched alkyl group having 1 to 3 carbon atoms and having a hydroxyl group, M¹And M²Can be respectively phase-connectedAnd (b) an alkali metal, an alkaline earth metal, a protonated primary-tertiary amine having 1 to 6 total carbon atoms which may have hydroxyl groups, or ammonium, and n represents an average molar number of ethylene oxide added and is 5 to 20.

The liquid detergent composition according to the present invention is characterized in that the component (C) contains at least ethanol.

The liquid cleanser composition of the present invention is characterized in that the component (C) contains at least ethanol and polyethylene glycol having an average molecular weight of 570 to 1050.

The liquid detergent composition according to the present invention is characterized in that,

the content of the component (A) is 20-60 mass%, the content of the component (B) is 4-45 mass%, and the content of the component (C) is 2-20 mass%.

the mass ratio of the component (B) to the total content of the components (A) and (B) in the preceding paragraph is: (B) component/{ (A) component + (B) component } -, 2/10-5/10.

ADVANTAGEOUS EFFECTS OF INVENTION

The liquid detergent composition of the present invention contains a surfactant at a high concentration, has good low-temperature storage stability, and is excellent in low-temperature solubility and sebum-cleaning ability during washing.

Detailed Description

Hereinafter, the present invention will be described in detail.

The liquid detergent composition of the present invention contains the following components (a) to (C).

< ingredient (A) >

(A) The component (A) is a nonionic surfactant represented by the following general formula (1).

R¹O(CH₂CH₂O)_nH …(1)

In the formula (1), R1 is a linear alkyl group having 10 to 22 carbon atoms. The alkyl group is linear, which improves the cleaning property. The alkyl group having 10 or more carbon atoms can improve sebum detergency, and the alkyl group having 22 or less carbon atoms can improve low-temperature storage stability and low-temperature solubility during washing.

The number of carbon atoms of the alkyl group is preferably 10 to 20, more preferably 10 to 18.

R¹Derived from the starting alcohol (R)¹-OH), as said alcohols there may be mentioned: higher primary alcohols, higher fatty acids, and higher fatty acid amides, and the like.

As R¹Specific examples of the alkyl group of (1) include: decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, stearyl, eicosyl, and the like.

n represents the average molar number of addition of ethylene oxide. n is 5 to 20, preferably 8 to 18, and particularly preferably 10 to 16. When n is within the above range, sebum-cleaning ability can be improved.

In the component (A), the distribution of the number of moles of ethylene oxide added is not particularly limited. The distribution of the number of moles added varies depending on the reaction method in producing the component (A). For example, when ethylene oxide is added to a hydrophobic raw material using a basic catalyst such as sodium hydroxide or potassium hydroxide, the distribution tends to be wide. Further, Al described in Japanese patent publication No. 6-15038 is added³⁺、Ga³⁺、In³⁺、Tl³⁺、Co³⁺、Sc³⁺、La³⁺And Mn²⁺Specific alkoxylation catalysts such as magnesium oxide with metal particles tend to have a narrow distribution when ethylene oxide is added to the hydrophobic base material.

Specific examples of the component (A) include those obtained by adding ethylene oxide to a natural alcohol such as "CO-1214" or "CO-1270" available from P & G such that the average number of moles added is 12 moles or 15 moles.

(A) The component (b) may be used alone or in combination of 2 or more.

< ingredient (B) >

(B) Component (b) is at least 1 anionic surfactant selected from the group consisting of compounds represented by the following general formulae (2) and (3).

R²CH(SO₃M¹)COOR³ …(2)

R⁴CH(SO₃M²)CONHR⁵ …(3)

In the formula (2), R²Is a linear or branched alkyl group having 9 to 14 carbon atoms or a linear or branched alkenyl group having 9 to 16 carbon atoms. The alkyl group having 9 or more carbon atoms can improve sebum-cleansing ability, and the alkyl group having 14 or less carbon atoms can suppress precipitation during low-temperature storage.

The number of carbon atoms of the alkyl group is preferably 10 to 14, more preferably 10 to 12, from the viewpoint of sebum cleansing ability and prevention of viscosity increase at low temperatures. On the other hand, the number of carbon atoms of the alkenyl group is preferably 10 to 16, more preferably 10 to 12.

R³Is a linear or branched alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 or more carbon atoms can suppress precipitation during low-temperature storage, and having 3 or less carbon atoms can improve low-temperature solubility during washing.

The number of carbon atoms in the alkyl group is preferably 1 to 2.

M¹Represents a counter ion, with R²CH(COOR³)SO₃The salts which together form a water-soluble salt are alkali metals, alkaline earth metals, protonated primary to tertiary amines of 1 to 6 total carbon atoms which may have hydroxyl groups, or ammonium. The alkali metal and alkaline earthThe metalloid can exist as a cation with R²CH(COOR³)SO₃The number of atoms in combination varies with the valency of the cation.

Examples of the alkali metal include sodium and potassium, and examples of the alkaline earth metal include calcium.

The protonated primary to tertiary amines having 1 to 6 total carbon atoms may or may not have a hydroxyl group, but preferably have a hydroxyl group in view of good low-temperature solubility in washing. Examples of such primary to tertiary amines include aliphatic alcohol amines, and specific examples thereof include: monoethanolamine, diethanolamine, and triethanolamine, and the like.

As M¹Sodium, monoethanolamine, and triethanolamine are preferred.

Examples of the compound represented by the general formula (2) include α -sulfo fatty acid ester salts (MES). Specific examples thereof include: alpha-sulfolauric acid methyl ester monoethanolamine salt, alpha-sulfolauric acid methyl ester sodium salt, alpha-sulfopalmitic acid methyl ester monoethanolamine salt, and the like.

The compound represented by the general formula (2) may be used alone or in combination of 2 or more.

In the formula (3), R⁴Is a linear or branched alkyl group having 9 to 14 carbon atoms or a linear or branched alkenyl group having 9 to 16 carbon atoms. The alkyl group having 9 or more carbon atoms can improve sebum-cleansing ability, and the alkyl group having 14 or less carbon atoms can suppress precipitation during low-temperature storage.

The number of carbon atoms of the alkyl group is preferably 10 to 14, more preferably 12 to 14, from the viewpoint of sebum-cleaning ability and prevention of viscosity increase at low temperatures. On the other hand, the number of carbon atoms of the alkenyl group is preferably 10 to 16, more preferably 12 to 16.

In addition, R²And R⁴May be the same or different.

As R²Specific examples of the alkyl group of (1) include: nonyl, sec-nonyl,Decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl, and the like.

As R²Specific examples of the alkenyl group of (1) include: nonene, decene, undecenyl, dodecenyl, tetradecenyl, and the like.

As R⁴Specific examples of the alkyl group of (1) include: nonyl, secondary nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl and the like.

As R⁴Specific examples of the alkenyl group of (1) include: nonene, decene, undecenyl, dodecenyl, tetradecenyl, and the like.

R⁵Is hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group. The alkyl group having 1 or more carbon atoms can suppress precipitation during low-temperature storage, and having 3 or less carbon atoms can improve low-temperature solubility during washing.

The number of carbon atoms in the alkyl group is preferably 2 to 3.

The alkyl group may have 1 or more hydroxyl groups, but preferably has a hydroxyl group in view of good low-temperature solubility during washing. The linear alkyl group is more excellent in low-temperature storage stability than the branched alkyl group.

M²Represents a counter ion, with R⁴CH(CONHR⁵)SO₃The salts which together form a water-soluble salt are alkali metals, alkaline earth metals, protonated primary to tertiary amines of 1 to 6 total carbon atoms which may have hydroxyl groups, or ammonium. The alkali metal and alkaline earth metal may be present as cations with R⁴CH(CONHR⁵)SO₃The number of atoms in combination varies with the valency of the cation.

The protonated primary to tertiary amines, which may have 1 to 6 total carbon atoms of the hydroxyl group, may or may not have a hydroxyl group, but preferably have a hydroxyl group in view of good low-temperature solubility during washing. Examples of such primary to tertiary amines include aliphatic alcohol amines, and specific examples thereof include: monoethanolamine, diethanolamine, and triethanolamine, and the like.

As M²Sodium, monoethanolamine, and triethanolamine are preferred.

In addition, M¹And M²May be the same or different.

Examples of the compound represented by the general formula (3) include derivatives of α -sulfo fatty acid ester salts. Specific examples include: sodium salt of α -sulfolauric monoethanolamide, sodium salt of α -sulfolauric isopropanolamide, and the like.

The compound represented by the general formula (3) may be used alone or in combination of 2 or more.

The component (B) may be a compound represented by the general formula (2), a compound represented by the general formula (3), or a combination thereof, but a compound represented by the general formula (3) is particularly preferable. The compound represented by the general formula (3) has a heavier molecular structure (i.e., a larger steric hindrance) than the compound represented by the general formula (2). Since the larger the steric hindrance, the more likely it is to hinder the formation of a liquid crystal phase, the viscosity increase can be suppressed even if the surfactant is contained at a high concentration.

The main purpose of mixing the component (a) is to impart cleaning power (particularly sebum cleaning power) to the liquid cleanser composition of the present invention. On the other hand, component (B) also has an effect of inhibiting the formation of a liquid crystal phase, and is excellent in solubility in water because it is a salt. Therefore, the liquid cleanser composition of the present invention can contain a surfactant at a high concentration and has excellent sebum-cleansing ability because the increase in viscosity is suppressed by using the component (a) and the component (B) in combination. Further, since gel is not easily formed even when diluted with water during washing, excellent sebum-cleaning ability can be effectively exhibited.

However, when the component (a) is contained and the component (B) is not contained, the liquid detergent composition is gelled and is not easily dissolved in water when being put into a washing machine or the like, and thus sufficient sebum-cleaning ability may not be exhibited.

Further, if the component (B) is contained at a high concentration without containing the component (a), the component (B) is not easily dissolved in water, precipitates are easily generated, and the low-temperature storage stability and the solubility are both lowered. The reduced solubility is particularly apparent in winter when low temperature water is used.

(A) The content of the component (b) is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 45% by mass based on 100% by mass of the liquid detergent composition. (A) When the content of the component (b) is 20% by mass or more, a high sebum-cleaning ability can be imparted to the liquid cleanser composition. On the other hand, when the content of the component (a) is 60% by mass or less, the solubility and the low-temperature storage stability of the liquid detergent composition can be maintained well.

On the other hand, the content of the component (B) is preferably 4 to 45% by mass, more preferably 9 to 40% by mass, and particularly preferably 10 to 35% by mass, based on 100% by mass of the liquid detergent composition. (B) When the content of the component (c) is 4% by mass or more, the increase in viscosity at low temperature can be suppressed, and thus the liquid detergent composition can be provided with storage stability (particularly low-temperature storage stability) and solubility. On the other hand, when the content of component (B) is 45% by mass or less, the sebum-cleaning ability of the liquid cleanser composition can be satisfactorily maintained.

The total content of the component (A) and the component (B) in the liquid detergent composition of the present invention is 40 to 75% by mass based on 100% by mass of the liquid detergent composition. The total content is preferably 45 to 70% by mass, more preferably 50 to 65% by mass. When the total content is 40% by mass or more, the liquid cleansing composition can be provided with sebum cleansing ability, and can sufficiently exhibit the function as a concentrated liquid cleansing agent. On the other hand, if the total content is 75% by mass or less, the low-temperature storage stability of the liquid detergent composition can be maintained well.

Further, the mass ratio of the component (B) to the total content of the components (a) and (B) is: (B) component/{ (A) component + (B) component } -1/10 to 6/10, preferably 2/10 to 5/10, and more preferably 2/10 to 4/10. When the mass ratio of the component (B) is within the above range relative to the total content of the components (a) and (B), the liquid cleansing composition can be provided with low-temperature storage stability, low-temperature solubility, and sebum cleansing ability. (B) If the ratio of the component(s) is too low, the low-temperature solubility of the liquid detergent composition decreases. On the other hand, if the ratio of the component (B) is too high, the sebum-cleaning ability of the liquid cleanser composition is lowered.

Even if the mass ratio of the component (B) satisfies the above range with respect to the total content of the components (a) and (B), the fluidity and the low-temperature solubility are deteriorated if the total content of the components (a) and (B) exceeds 75% by mass.

< ingredient (C) >

(C) The component (A) is at least 2 aqueous mixed solvents selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, butyl carbitol, phenoxyethanol, and polyethylene glycol with average molecular weight of 570-3800.

(C) The component (a) is a hydrotrope which imparts low-temperature storage stability and low-temperature solubility to the liquid detergent composition, but when 1 of the above solvents is used alone, the liquid detergent composition is difficult to dissolve in water. The proportion of the component (C) can be increased to improve the solubility of the liquid detergent composition, but the increased amount tends to reduce the proportion of the surfactant, or to make it difficult to mix functional components such as an enzyme and a chelating agent.

However, in the present invention, since 2 or more of the above-mentioned solvents are used in combination as the component (C), the solubility of the liquid detergent composition can be imparted without unnecessarily increasing the proportion of the component (C). Further, since it is not necessary to increase the proportion of the component (C), a sufficient amount of the functional component can be mixed without decreasing the proportion of the surfactant.

The combination of the solvents used as component (C) is not particularly limited, and it is preferable to use at least ethanol from the viewpoint of easy prevention of formation of a liquid crystal phase and easy inhibition of bacterial growth. Further, the use of ethanol further improves the low-temperature solubility and the low-temperature storage stability.

It is preferable to use 1 or more of methanol, ethanol, propanol, butanol and phenoxyethanol which are monohydric alcohols in combination with 1 or more of ethylene glycol, propylene glycol, butylene glycol, butyl carbitol and polyethylene glycol which are polyhydric alcohols.

Among monohydric alcohols, phenoxyethanol is preferred in addition to ethanol.

On the other hand, ethylene glycol, polyethylene glycol and propylene glycol are preferable among the polyhydric alcohols, and polyethylene glycol having an average molecular weight of 570 to 3800 is preferable in terms of suppressing viscosity increase, further improving low-temperature solubility and low-temperature storage stability of the liquid cleanser composition, and stably dissolving optional components described later. The average molecular weight of the polyethylene glycol is 570-3800, more preferably 570-1050, and particularly preferably 950-1050.

The average molecular weight is an average molecular weight described in the ministry of medicine and foreign products Standard 2006 in Japan, and polyethylene glycols having an average molecular weight of 570 to 3800 include polyethylene glycol 600 (average molecular weight of 570 to 630), polyethylene glycol 1000 (average molecular weight of 950 to 1050), polyethylene glycol 2000 (average molecular weight of 1850 to 2150), and polyethylene glycol 4000 (average molecular weight of 2600 to 3800). Depending on the commercial product, there may be instances where # is added between polyethylene glycol and the number, such as polyethylene glycol # 1000.

The component (C) is preferably a combination of ethanol and polyethylene glycol having an average molecular weight of 570 to 1050, and particularly preferably a combination of ethanol and polyethylene glycol having an average molecular weight of 950 to 1050.

(C) The content of the component (B) is preferably 2 to 20% by mass, more preferably 2 to 15% by mass, based on 100% by mass of the liquid detergent composition. (C) When the content of the component (b) is 2% by mass or more, the liquid detergent composition can be provided with low-temperature storage stability and low-temperature solubility. On the other hand, if the content of component (C) is 20% by mass or less, a sufficient amount of any component can be mixed into the liquid detergent composition.

When ethanol is used as component (C), the content thereof is preferably 3 to 10% by mass based on 100% by mass of the liquid detergent composition. When polyethylene glycol is used as the component (C), the content thereof is preferably 2 to 8% by mass based on 100% by mass of the liquid detergent composition.

< optional Components >

The liquid detergent composition of the present invention contains the above-mentioned components (a) to (C) as essential components, may be composed of only the components (a) to (C), and may be mixed with water as an optional component, a surfactant other than the components (a) to (B), other components, and the like as necessary within the range not impairing the effects of the present invention.

(Water)

The liquid detergent composition of the present invention is preferably aqueous in view of ease of preparation, storage stability and solubility in water.

The content of water is preferably 15 to 50% by mass, more preferably 20 to 45% by mass, based on 100% by mass of the liquid detergent composition.

(other surfactants)

As other surfactants, there may be mentioned: (A) nonionic surfactants other than component (a), anionic surfactants other than component (B), cationic surfactants, and amphoteric surfactants.

Examples of the nonionic surfactant other than the component (a) include: alkylphenol, alkenyl oxide adducts of higher fatty acids or higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid aliphatic alcohol amines, fatty acid fatty alcohol amides, polyol fatty acid esters or alkenyl oxide adducts thereof, polyol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkenyl oxide adducts of cured castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides.

Examples of the anionic surfactant other than component (B) include: linear alkyl benzene sulfonic acid or a salt thereof, an α -olefin sulfonate, a linear or branched alkyl sulfate, an alkyl ether sulfate or an alkenyl ether sulfate, an alkyl sulfonate having an alkyl group, a higher fatty acid salt, an alkyl ether carboxylate, a polyoxyalkylene ether carboxylate, an alkyl (or alkenyl) amide ether carboxylate, a carboxylic acid type such as an acylamino carboxylate, an alkyl phosphate, a polyoxyalkylene alkylphenyl phosphate, a phosphate type anionic surfactant such as a glycerin fatty acid ester monophosphate, and the like.

Examples of the cationic surfactant include: and cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts.

As the amphoteric surfactant, there may be mentioned: alkyl betaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamide carboxylic acid type, amidoamino acid type, phosphoric acid type amphoteric surfactants, and the like.

< other ingredients >

The liquid detergent composition of the present invention may contain an enzyme that is generally used in a liquid detergent for clothing, from the viewpoint of further improving the cleaning performance.

Examples of the enzyme include: trade names "リカナ - ゼ (Liquanase)", "サビナ - ゼ (Savinase)", "アルカラ - ゼ (Alcalase)", "エバラ - ゼ (Everlase)", "カンナ - ゼ (Kannase)", and "エスペラ - ゼ (Espeperaze)", manufactured by Novozymes (ノボザイムズ); trade name "API 21" manufactured by showa electrician (ltd.); trade names "マタサタ - ゼ (Maxtaze)", "マクサカル (Maxacal)", "ピユラフエクト (Purafect)", "マクサペム", and "プロペラ - ゼ (Properase)" manufactured by GENENCOR (ジエネンコア); trade name "KAP" manufactured by Kao corporation; the trade names "プロテア - ゼ K-14" and "K-16" described in Japanese patent laid-open No. 5-25492; ノボザイムズ, trade name "タ - マミル (Termamyl)", "デュラミル (Duramyl)", "ステインザイム (Stainzyme)", "プロモザイム (Promozyme) 200L"; ジエネンコア, trade name "マキサミル (Maxamamyl)"; trade name "プルラナ - ゼアマノ" manufactured by Tianye エンザイム (strain); "DB-250 (pullulanase derived from Aerogenes ATCC 9621: crude product or crystalline product)" available from Biochemical industry Co., Ltd.; ノボザイムズ, trade names "リポラ - ゼ", "リポラ - ゼウルトラ", "ライペツクズ", and "ライペツクス 100L"; and a commercially available lipase (lipase preparation) such as "リポサム" trade name manufactured by Showa Denko K.K.

The enzyme content is preferably 0.1 to 3% by mass based on 100% by mass of the liquid detergent composition. When the content of the enzyme is 0.1% by mass or more, the cleaning ability against various stains (particularly, the cleaning ability against oily stains such as sebum stains) is improved. When the content of the enzyme is 3% by mass or less, sufficient cleaning ability against various stains can be easily obtained, and the enzyme is advantageous from the economical viewpoint.

The liquid detergent composition of the present invention may further contain, for example, 0.01 to 15% by mass of a viscosity reducing agent such as p-toluenesulfonic acid, a benzoate (also having an effect as a preservative), urea, and a solubilizer.

Further, for example, 0.1 to 20 mass% of a metal ion chelating agent such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, or citric acid may be contained.

Further, for example, 0.01 to 2 mass% of an antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite, or sodium bisulfite may be contained.

Further, for example, 0.001 to 1% by mass of a preservative such as ロ - ム, アンド and ハウス, trade name "ケ - ソン CG".

The liquid detergent composition of the present invention may further contain a softness imparting agent, a texture improving agent, an alkali builder such as aliphatic alcohol amine, a pH adjuster, a hydrotrope other than the component (C), a fluorescent agent, a migration inhibitor, a recontamination inhibitor, a pearling agent, a detergent, and the like, for the purpose of improving the cleaning performance, stability, and the like.

Examples of the agents for imparting pliability include: long-chain aliphatic amidoalkyl tertiary amines such as capric acid dimethylaminopropyl amide, lauric acid dimethylaminopropyl amide, myristic acid dimethylaminopropyl amide, palmitic acid dimethylaminopropyl amide, stearic acid dimethylaminopropyl amide, behenic acid dimethylaminopropyl amide, and oleic acid dimethylaminopropyl amide, or salts thereof; palmitic acid diethanolaminopropylamide; and stearic acid diethanolaminopropylamide and the like. For example, 1 to 5 mass% of stearic acid dimethylaminopropylamide may be contained.

As hand-feeling enhancers, there may be used, for example: trade names "CF 1188 HV", "SH 3748", "SH 3794", "SH 3772M", "SH 3775M", "SF 8410", "SH 8700", "BY 22-008", "BY 22-012", "SILWET L-7001", "SILWET L-7002", "SILWET L-7602", "SILWET L-7604", "SILWET Z-2104", "SILWET FZ-2120", "SILWET FZ-2161", "SILWET FZ-2162", "SILWEZ-2164", "SILWET FZ-2171", "ABN SILWET FZ-F1-009-01", and "ABN WETFZ-1-009-02", "ABN FZ-F1-009-03", "ABN WET FZ-F-1-SILT-36009-24" manufactured BY Chinese gall, "ABN SILWET FZ-F1-009-11", "ABN SILWET FZ-F1-009-13", "ABN SILWET FZ-F1-009-54", "ABN SILWET FZ-22-22"; trade names "X-20-8010B", "KF 352A", "KF 6008", "KF 615A", "KF 6012", "KF 6016", and "KF 6017", manufactured by shin-Etsu chemical Co., Ltd.; and polyether-modified silicones such as "TSF 4450", "TSF 4452" and "TSF 4445" under the trade names of GE Toshiba シリコ - ン. The polyether modified organic silicon is contained in the liquid cleaning agent composition by 0.1-3 mass%.

In addition to the above, a flavor enhancer, a coloring agent, an opacifying agent, a natural substance, and the like may be added to increase the added value of the product.

As the odorant, a perfume composition described in Japanese patent laid-open No. 2002-146399 and the like can be used, and the amount to be mixed is preferably 0.1 to 1% by mass.

The coloring agent may contain, for example, about 0.00005 to 0.005 mass% of a common coloring matter or pigment such as "acid red 138", "polar red RLS", "acid yellow 203", "acid blue 9", "blue No. 1", "blue No. 205", "Green No. 3", and "タ - コイズ P-GR" (trade names).

Examples of opacifying agents include: as the polystyrene latex, polyvinyl acetate emulsion, etc., in general, a latex having a solid content of 30 to 50 mass% can be suitably used. Specifically, the resin composition may contain 0.01 to 0.5 mass% of a polystyrene latex (product name of サイデン chemical Co., Ltd. "サイビノ - ル RPX-196 PE-3", solid content 40 mass%), or the like.

Examples of extracts of natural substances include: maackia amurensis, bearberry, echinacea purpurea, scutellaria baicalensis, phellodendron amurense, goldthread root, allspice, origanum vulgaris, sophora japonica, chamomile, honeysuckle, sophora flavescens, schizonepeta, vitex negundo, bay tree, magnolia officinalis, burdock, comfrey, cnidium monnieri, sanguisorba, peony, ginger, solidago canadensis, elderberry, sage, loranthus parasiticus, rhizoma atractylodis, senecio, rhizoma anemarrhenae, clove, satsuma mandarin orange and tea plant, berberis thunbergii, houttuynia cordata, nandina domestica, frankincense, radix angelicae, cogongrass rhizome, divaricate saposhnikovia root, fructus psoraleae, hops, rosewood, vitis amurensis, sabia japonica, sabal, eucalyptus, lavender, rose, rosemary, cymbidium, japanese cedar, ganmarigold, dictamnus dasycarpus, dictamnus, polygonum aviculare, gentiana macrophylla, sweetgum tree, adenophora stricta, pedicellus litsea, cayratia japonica, liquorice, saint john's wort herb and the like, and about 0-0.5 mass% of the substances can be contained.

< Properties >

The cleaning agent composition of the present invention preferably has a pH of 4 to 9, more preferably 4 to 8, at 25 ℃. When the pH is within the above range, particularly, the liquid detergent composition can be stored for a long period of time while maintaining good stability with time.

The pH of the liquid cleaner composition may be adjusted with a pH adjuster. Examples of the pH adjuster include: inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as polycarboxylic acids and hydroxycarboxylic acids; sodium hydroxide; potassium hydroxide; an aliphatic alcohol amine; and ammonia and the like. Among these, sulfuric acid, sodium hydroxide, potassium hydroxide, and aliphatic alcohol amine are preferable in view of the stability of the liquid detergent composition over time. These pH regulators can be used in 1 or more than 2.

In addition, in order to finely adjust the pH of the liquid detergent composition, an inorganic acid (preferably hydrochloric acid or sulfuric acid) or potassium hydroxide may be further added.

In the present invention, the pH of the liquid detergent composition (temperature-adjusted at 25 ℃) is a value measured by a pH meter (product name "HM-30G" manufactured by Toyo デイ - ケ - ケ (Ltd.).

The viscosity of the cleaning agent composition of the present invention at 25 ℃ is preferably 40 to 150 mPas, more preferably 50 to 130 mPas.

In particular, since the amount (amount) of the concentrated liquid detergent to be metered is small, it is difficult to meter the required amount of the liquid detergent when the viscosity is not suitable. However, if the viscosity is 40mPa · s or more, appropriate viscosity can be maintained, and therefore, the workability is good and an appropriate amount can be easily measured. On the other hand, when the viscosity is 150 mPas or less, gelation of the liquid detergent composition can be suppressed particularly when the liquid detergent composition is poured from a detergent inlet of a washing machine at low temperature.

The viscosity of the liquid cleaner composition can be measured as follows.

First, the measurement sample was heated to 25 ℃ in a thermostatic bath set to 25 ℃. Subsequently, the sample heated to 25 ℃ was placed in a type B VISCOMETER (product name "VICOMETER MODEL DVM-B" manufactured by Tokyo counter Co., Ltd.) and the rotor No.2 to 4 was rotated at 60rpm/min, and the viscosity was measured for 60 seconds.

< production of liquid detergent composition >

The liquid detergent composition of the present invention can be produced by a conventional method. For example, the composition can be produced by mixing the above components (A) to (C) and, if necessary, optional components. At this time, water is preferably added.

The liquid detergent composition of the present invention thus obtained can be used in the same manner as that generally used for liquid detergents for clothing. Namely, there can be mentioned: the liquid detergent composition of the present invention (the product of the present invention), a method of putting the liquid detergent composition into water together with laundry at the time of washing, a method of directly applying the product of the present invention to soil stains or sebum stains, a method of dissolving the product of the present invention in water in advance and then soaking clothes, and the like. Further, a method is also preferable in which the product of the present invention is applied to a laundry, and then the product is allowed to stand as appropriate, and thereafter, a normal washing is performed using a normal washing liquid.

The liquid detergent composition of the present invention described above contains the components (A) to (C). (A) The component (A) is a surfactant raw material in consideration of the global environment, namely a nonionic surfactant which is a natural oil raw material and has excellent biodegradability (particularly sebum washing ability) after processing and is excellent in price and raw material supply. On the other hand, component (B) is an anionic surfactant and has an effect of inhibiting the formation of a liquid crystal phase, and the liquid crystal phase is easily formed when the concentration of the surfactant is high. Therefore, by using the component (a) and the component (B) in combination as a surfactant, an increase in viscosity is suppressed, and therefore, a surfactant can be contained at a high concentration, and the sebum cleansing ability is excellent. Further, the detergent composition does not easily form a gel even when diluted with water during washing, and can effectively exhibit excellent sebum-cleaning ability.

Further, the liquid detergent composition of the present invention contains the component (C), and therefore, it is excellent in low-temperature storage stability and low-temperature solubility.

Since the liquid detergent has viscosity, if the low-temperature storage stability is poor, the viscosity increases to a level higher than the desired viscosity, and handling becomes difficult when the detergent is taken out from a container. This tendency is particularly noticeable in winter.

However, since the liquid detergent composition of the present invention has excellent low-temperature storage stability, it can maintain appropriate viscosity even in a low-temperature environment such as winter, and thus can be handled easily.

In addition, in particular in winter, the detergent residual components that are not dissolved adhere to the laundry, but since the liquid detergent composition of the present invention has excellent solubility at low temperature, the detergent residual components that are not dissolved do not easily adhere to the laundry.

Examples

The present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

< raw materials used >)

As the component (a), the following compounds were used.

A-1: natural alcohol "CO-1270" (alcohol having 12 carbon atoms/alcohol having 14 carbon atoms) manufactured by P & G, 70% by mass/30% by mass, linear chain ratio 100%, and intermediate chain branching ratio 0%), ethylene oxide was added so that the average molar number of addition was 15 mol (purity 90%).

A-2: natural alcohol "CO-1214" (alcohol having 12 carbon atoms/alcohol having 14 carbon atoms) manufactured by P & G, 71 mass%/29 mass%, linear chain ratio 100%, and intermediate chain branching ratio 0%), ethylene oxide was added so that the average molar number of addition was 15 mol (purity 90%).

A-3: ethylene oxide was added to a natural alcohol "CO-1270" manufactured by P & G such that the average molar number of addition was 12 mol (purity: 90%).

A-4: ethylene oxide was added to a natural alcohol "CO-1214" manufactured by P & G such that the average molar number of addition was 9 mol (purity: 90%).

The above-mentioned a-1 to a-4 were synthesized in the following manner, respectively.

(Synthesis of a-1)

224.4G of a natural alcohol "CO-1270" manufactured by P & G and 2.0G of a 30 mass% aqueous sodium hydroxide solution were charged into a pressure-resistant reaction vessel as raw material alcohols, and the inside of the vessel was purged with nitrogen. Then, the inside of the container was dehydrated for 30 minutes while maintaining the temperature at 100 ℃ and the pressure at 1.5 to 2.0kPa, and then the temperature was raised to 160 ℃. While stirring the natural alcohol, 760.4 ethylene oxide (in the form of gas) was gradually added to the natural alcohol solution by using a blowing tube so that the reaction temperature did not exceed 180 ℃ while adjusting the addition rate.

After the addition of ethylene oxide, the mixture is aged for 30 minutes while maintaining the temperature of 180 ℃ and the pressure of 0.2 to 0.3MPa in the vessel, and then the pressure in the vessel is reduced to 5.5 to 6.0kPa, and the unreacted ethylene oxide is removed by distillation for 10 minutes.

Subsequently, the temperature in the vessel was reduced to 80 to 100 ℃, and then 70 mass% of p-toluenesulfonic acid was added to neutralize the reaction solution so that the pH of a1 mass% aqueous solution of the reactant was about 7, thereby obtaining a-1.

(Synthesis of a-2)

A-2 was obtained in the same manner as in a-1 except that 224.4G of the natural alcohol "CO-1214" manufactured by P & G was used as the raw material alcohol and the amount of ethylene oxide was changed to 760.6G.

(Synthesis of a-3)

A-3 was obtained in the same manner as in a-1, except that the amount of ethylene oxide was changed to 610.2 g.

(Synthesis of a-4)

A-4 was obtained in the same manner as in a-1 except that 224.4G of the natural alcohol "CO-1214" manufactured by P & G was used as the raw material alcohol and the amount of ethylene oxide was 457.2G.

As the nonionic surfactant other than the component (a), the following compounds were used. The nonionic surfactant is described as the "component (a').

A-5: polyoxyethylene lauryl ether and an average 3-mole adduct of EO (ethylene oxide) (product name "EMALEX 703", manufactured by Japan エマルジヨン (Ltd.) (purity 100%).

A-6: polyoxyethylene lauryl ether and an adduct of EO (ethylene oxide) of 25mol on average (product name "EMALEX 725" manufactured by Japan エマルジヨン, Ltd.) (purity 100%).

·a-7：C₁₂H₂₅O(CH₂CH₂O)₁₀(CH₂CH(CH₃) O) H, (purity 100%).

·a-8：C₁₄H₂₉O(CH₂CH₂O)₇(CH₂CH(CH₃)O)(CH₂CH₂O)₃H. (purity 100%).

A-9: polyoxyethylene (15) tallowalkylamine (a composition of tallowalkyl group: 1 mass% of an alkyl group having 12 carbon atoms, 3 mass% of an alkyl group having 14 carbon atoms, 31 mass% of an alkyl group having 16 carbon atoms, 20 mass% of an alkyl group having 18 carbon atoms, 1 mass% of an alkyl group having 20 carbon atoms, and 44 mass% of an alkenyl group having 18 carbon atoms), and an average 15 mol adduct of EO (product of ライオンアクゾ, trade name "エソミン T/25") (purity 100%).

The above a-7 and a-8 were synthesized in the following manner, respectively.

(Synthesis of a-7)

1026g of an alcohol "コノ - ル 20P" manufactured by Nippon Japan as a raw material alcohol was charged in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Then, the inside of the container was dehydrated for 30 minutes while maintaining the temperature at 100 ℃ and the pressure at 1.5 to 2.0kPa, and then the temperature was raised to 140 ℃. 2063g of ethylene oxide (gaseous) was slowly added to the alcohol solution while stirring the alcohol, while adjusting the speed so that the reaction temperature did not exceed 180 ℃.

Then, after the temperature in the vessel was decreased to 80 to 100 ℃, 1231g of the crude reaction product was taken out from the vessel and the temperature in the vessel was increased to 120 ℃. While stirring the remaining reaction mixture, 173g of propylene oxide (gaseous) was slowly added to the reaction mixture while adjusting the speed so that the reaction temperature did not exceed 125 ℃.

After the addition of propylene oxide, the mixture was aged for 2 hours while maintaining the temperature in the vessel at 120 ℃ and the pressure at 0.25 to 0.30MPa, and then the pressure in the vessel was reduced to 5.5 to 6.0kPa, and the unreacted propylene oxide was removed by distillation for 10 minutes to obtain a-7.

(Synthesis of a-8)

A pressure-resistant reaction vessel was charged with 1004g of an alcohol "コノ - ル 1495" manufactured by Nisshinoki Co., Ltd., and 10.0g of potassium hydroxide as raw material alcohols, and the interior of the vessel was purged with nitrogen gas. Then, the inside of the container was dehydrated for 30 minutes while maintaining the temperature at 100 ℃ and the pressure at 1.5 to 2.0kPa, and then the temperature was raised to 140 ℃. 1444g of ethylene oxide (in the form of a gas) was slowly added to the alcohol solution with a speed adjusted so that the reaction temperature did not exceed 180 ℃ by using a blowing tube while stirring the alcohol.

Subsequently, the temperature in the vessel was reduced to 80 to 100 ℃, and then 1463g of the crude reactant was taken out from the vessel, and the temperature in the vessel was increased to 120 ℃. While stirring the remaining reaction product, 110g of propylene oxide (gaseous) was gradually added to the reaction product with the speed adjusted so as not to exceed 125 ℃.

After the addition of propylene oxide, the mixture is aged for 2 hours while maintaining the temperature in the vessel at 120 ℃ and the pressure at 0.2 to 0.3MPa, and then the pressure in the vessel is reduced to 5.5 to 6.0kPa, and the unreacted propylene oxide is removed by distillation for 10 minutes.

Subsequently, the temperature in the vessel was raised to 140 ℃ and 251g of ethylene oxide (gaseous) was gradually added to the reaction mixture with the rate adjusted so as not to exceed 180 ℃ while stirring the remaining reaction mixture with a blowing tube.

After the addition of ethylene oxide, the mixture was aged for 30 minutes while maintaining the temperature in the vessel at 180 ℃ and the pressure at 0.2 to 0.3MPa, and then the pressure in the vessel was reduced to 5.5 to 6.0kPa, and the unreacted ethylene oxide was removed by distillation for 10 minutes to obtain a-8.

As the component (B), the following compounds were used.

·b-1：C₁₀H₂₁CH(SO₃NH₃CH₂CH₂OH)COOCH₃And (purity 100%).

·b-2：C₁₀H₂₁CH(SO₃Na)COOCH₃And (purity 100%).

·b-3：C₁₄H₂₉CH(SO₃NH₃CH₂CH₂OH)COOCH₃And (purity 100%).

·b-4：C₁₀H₂₁CH(SO₃Na)CONHCH₂CH₂OH, (purity 100%).

·b-5：C₁₀H₂₁CH(SO₃Na)CONHCH₂CH(OH)CH₃And (purity 100%).

The above-mentioned b-1 to b-5 were synthesized in the following manner, respectively.

(Synthesis of b-1)

In a 1L4 neck flask equipped with a thermometer, a stirrer, a dropping funnel and a calcium chloride tube for drying, 54g (0.25mol) of methyl laurate and 540g of carbon tetrachloride were charged, and 24g (0.3mol) of sulfuric anhydride was dropped while maintaining the reaction temperature at 10 to 15 ℃. After the completion of the dropping, the mixture was stirred under reflux for 3 hours.

Then, the reaction solvent (carbon tetrachloride) was distilled off in a water bath at 50 ℃ using an evaporator, and then 500mL of methanol was added thereto, followed by stirring under reflux for 20 minutes. Thereafter, the reaction solution was adjusted to pH7 with a 0.5mol/L aqueous solution of monoethanolamine. Subsequently, the reaction solvent (methanol) was distilled off under reduced pressure. At this time, water was distilled off while adding isopropyl alcohol azeotropically due to foaming.

The residue (crude product) was dissolved in a mixed solution of ethanol and water (volume ratio: ethanol/water: 9/1) by heating to 50 to 60 ℃ to remove insoluble matter. Then, the filtrate was cooled to 5 ℃ and recrystallized, and the precipitate was separated by filtration and dried under vacuum to obtain 58g of α -sulfolauric acid methyl ester monoethanolamine salt (b-1). Furthermore, b-1 is a compound corresponding to the above general formula (2).

(Synthesis of b-2)

Alpha-methyl sulfolaurate sodium salt (b-2) was obtained in the same manner as in b-1, except that a 20 mass% aqueous sodium hydroxide solution was used in place of the 0.5mol/L aqueous monoethanolamine solution and the pH was adjusted to 7. Further, b-2 is a compound corresponding to the above general formula (2).

(Synthesis of b-3)

Alpha-sulfopalmitic acid methyl ester monoethanolamine salt (b-3) was obtained in the same manner as in b-1, except that 68g (0.25mol) of methyl palmitate was used instead of 54g (0.25mol) of methyl laurate. Further, b-3 is a compound corresponding to the above general formula (2).

(Synthesis of b-4)

A300 mL one-mouth eggplant type flask equipped with a Dean-Stark apparatus and a stirrer was charged with 20g (63.2mmol) of methyl α -sulfolaurate sodium salt and 150mL of toluene, and dehydrated under reflux for 1 hour.

Then, the reaction mixture was cooled to room temperature, the Dean-Stark apparatus was removed, and a Dimroth condenser tube was attached. The reaction solution was charged with 4.05g (66.4mmoL) of 2-aminoethanol and 342mg (6.3mmoL) of sodium methoxide and stirred at 90 ℃ for 4 hours. Then, the mixture was cooled to room temperature, 1.3mL of a 5N aqueous hydrochloric acid solution was added, and the solvent (toluene) was completely distilled off while azeotroping with isopropanol to obtain a solid crude product.

The obtained crude product was dissolved in a mixed solution of methanol and water (volume ratio: methanol/water: 9/1) by heating to 50 to 60 ℃, recrystallized at-20 ℃, and the precipitate was separated by filtration. The residue was dissolved again in a mixed solution of methanol and water at 50 to 60 ℃ and then recrystallized at-20 ℃, and the precipitate was separated by filtration and dried under vacuum to obtain 15.44g of b-4.

The obtained b-4(15mg) was dissolved in 0.5mL of heavy water¹H-NMR (270MHz, manufactured by Japan Electron デ - タム, product name "FTNMRSYSTEMJNM-EX 270") was measured at a measurement temperature of 25 ℃. The chemical shift when the heavy water peak was set to 4.75ppm as a reference was δ 0.73(br,3H) δ 1.15(br, 16H), δ 1.88(br, 2H), δ 3.24(m, 1H), δ 3.33(m, 1H), 3.58(br, 3H). From these results, it was confirmed that the obtained b-4 was α -sulfolauric acid monoethanolamide sodium salt. Furthermore, b-4 is a compound corresponding to the above general formula (3).

(Synthesis of b-5)

A solid crude product was obtained in the same manner as in b-4 except that 4.98g (66.4mmol) of 3-amino-2-propanol was used in place of 4.05g (66.4mmol) of 2-aminoethanol.

The obtained crude product was extracted with chloroform and a mixed solution of methanol and water (volume ratio: chloroform/methanol/water: 1/1/8), the aqueous layer was separated, the solvent (mixed solution) was distilled off under reduced pressure while azeotroping with isopropyl alcohol, and the mixture was dried under vacuum to obtain 18.9 b-5.

The obtained b-5(15mg) was dissolved in 0.5mL of heavy water¹H-NMR (270MHz, manufactured by Japan Electron デ - タム, product name "FTNMRSYSTEMJNM-EX 270") was measured at a measurement temperature of 25 ℃. Chemical shifts when the peak value of heavy water was 4.75ppm were defined as δ 0.71(br, 3H), δ 1.05-1.15(m + br, 19H), δ 1.87(br, 2H), δ 3.18(br, 2H), 3.60(br, 1H), and δ 3.82(br, 1H). From these results, it was confirmed that the obtained b-5 was α -sulfolauric acid isopropanolamide sodium salt. Further, b-5 is a compound corresponding to the above-mentioned general formula (3).

As the anionic surfactant other than the component (B), the following compounds were used. The anionic surfactant is described as a "(B') component".

B-6: sodium polyoxyethylene Alkyl Ether Sulfate (AES) (product of シエルケミカルズ, alcohol "ネオド - ル 23" (20% branching ratio, mixture of C12 alcohol and C13 alcohol at a mass ratio of 1: 1), and ethylene oxide added so that the average molar number of addition is 2 mol (purity 66.3)).

The above b-6 was synthesized by the following methods, respectively.

A4L autoclave was charged with 400g of "Neodol 23" manufactured by シエルケミカルズ as a raw material alcohol and 0.8g of potassium hydroxide as a catalyst, and the temperature of the autoclave was raised under stirring while changing the pressure to nitrogen. Then, while maintaining the temperature at 180 ℃ and the pressure at 0.3MPa, 272g of ethylene oxide was introduced to obtain a reaction product (alcohol ethoxylate) having an average molar number of addition of 2 of ethylene oxide.

Then, 280g of the alcohol ethoxylate obtained above was charged into a 500mL flask equipped with a stirrer, nitrogen gas was introduced, and 67g of liquid anhydride sulfuric acid (サルフアン) was slowly added dropwise while maintaining the reaction temperature at 40 ℃. After completion of the dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Further, this was neutralized with an aqueous solution of sodium hydroxide to give sodium polyoxyethylene alkyl ether sulfate (b-6).

As the component (C), the following compounds were used.

C-1: ethanol (product name "specific アルコ - ル 95 degree synthetic", manufactured by Nippon アルコ - ル, Co., Ltd.) (purity 95%).

C-2: propylene glycol (manufactured by BASF) (purity 100%).

C-3: methanol (pure chemical) (purity 100%).

C-4: butanol (product name: 1- ブタノ - ル, manufactured by Tokyo Kasei K.K.) (purity: 100%).

C-5: phenoxyethanol (product name "ethylene glycol monophenyl ether" manufactured by Tokyo Kasei K.K.) (purity 100%).

C-6: butyl carbitol (product name "ジエチレンゲリコ - ルモノブチルゲリコ - ル" manufactured by Tokyo Kasei K.K.) (purity 100%).

C-7: propanol (product name "1- プロパノ - ル" manufactured by Tokyo Kabushiki Kaisha) (purity: 100%).

C-8: ethylene glycol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (purity 100%).

C-9: butanediol (product name "1, 3- ブタンジオ - ル" manufactured by Tokyo Kabushiki Kaisha Co., Ltd.) (purity: 100%).

C-10: polyethylene glycol (trade name "PEG # 1000-L60" manufactured by ライオン K., average molecular weight: 950-1050) (purity 60%).

C-11: polyethylene glycol (trade name "PEG # 600" manufactured by ライオン K., average molecular weight 570-630) (purity 60%)

As component (C), the following reagents were used.

Sodium benzoate: manufactured by Toyo Seiya, trade name "benzoic acid ナトリウム" (purity 100%).

Citric acid: manufactured by Tokusan oil & fat industries, , trade name "liquid クエン acid" (purity 50%).

Palmitic acid: manufactured by Nippon fat and oil Co., Ltd., trade name "NAA-160" (purity 100%).

P-toluenesulfonic acid: prepared by kyowa and fermentation キリン (strain), and has a trade name of "PTS acid" (purity 70%).

Liquid protease: ノボザイム, trade name "リカナ - ゼウルトラ 2.5.5 XL" (purity 100%).

Dibutylhydroxytoluene: manufactured by Sumitomo chemical Co., Ltd., trade name "SUMILZERBHT-R" (purity 100%).

Monoethanolamine: manufactured by Japan catalyst (purity 75%).

Flavor: perfume composition A (purity 100%) described in tables 11 to 18 of Japanese patent laid-open No. 2002-146399.

Green No. 3 (pigment): kaihua was manufactured by Kabushiji Kaisha, under the trade name " color No. 3" (purity 100%).

The amounts of the respective components used for preparing the liquid detergent composition are shown in table 1. The numerical values in table 1 are amounts in terms of purity. The term "balance" refers to the amount of water mixed in the liquid detergent composition in order to adjust the total amount of all components contained in the liquid detergent composition to 100% by mass.

[ Table 1]

< measurement and evaluation method >)

< measurement of viscosity >

The beaker containing 100g of the liquid detergent composition was placed in a thermostatic bath at 25 ℃ and heated for 1 hour. The heated liquid detergent composition was charged into a viscometer of type B (product name "VISCOMETER MODEL DVM-B", manufactured by Tokyo counter Co., Ltd.), and the rotor was rotated at 60rpm/min with a rotor No.2 or 3, and the viscosity was measured for 60 seconds. In comparative example 3, the rotor No.4 was used, and the rotation was started at a rotor rotation speed of 60rpm/min, and the viscosity was measured for a measurement time of 60 seconds.

< evaluation of initial appearance >

The beaker containing 100g of the liquid detergent composition was tilted, and the appearance at the tilt was visually observed, and the initial appearance was evaluated according to the following criteria.

A: has fluidity.

B: it has no fluidity.

< evaluation of storage stability at Low temperature >

100mL of the liquid detergent composition was put into a clear glass bottle (Wide-mouth Standard bottle PS-NO.11), and the bottle was closed with a cap. In this state, the sample was left at room temperature (25 ℃) for 1 month, and this was used as a room-temperature storage sample.

Further, 100mL of the liquid detergent composition was put into a transparent glass bottle, and the bottle was sealed with a cap. The mixture was placed in a 5 ℃ thermostat at that state for 1 month. Thereafter, the reaction mixture was taken out of the thermostatic bath and left at room temperature (25 ℃ C.) for 1 hour. The appearance and viscosity of the solution of the contents after leaving the vessel were visually observed, and the low-temperature retention stability was evaluated according to the following criteria.

A: the appearance was transparent and uniform, and the liquid viscosity was the same as that of the sample kept at room temperature.

B: no precipitated material was found in the clear and uniform appearance, but the liquid viscosity was slightly increased from that of the room-temperature-maintained sample to a level that was not problematic.

C: precipitation and/or high degree of viscosification was found.

< evaluation of solubility at Low temperature >

300mL of ion-exchanged water at 15 ℃ was charged into a 500mL beaker, and 0.1g of the liquid detergent composition was added dropwise to the beaker using a burette while stirring the beaker with a magnetic stirrer (MITAMURAKOGYO INC.) at a rotation speed of 500 rpm/min. The time until the liquid detergent composition was completely dissolved (dissolution time) was measured, and the low-temperature solubility was evaluated according to the following criteria.

A: the dissolution time is less than 50 seconds.

B: the dissolution time is more than 50 seconds and less than 100 seconds.

C: the dissolution time is more than 100 seconds.

< evaluation of sebum-cleaning ability >

Cotton cloth (cotton plain cloth, No. 100) with sebum stain on face removed was cut into 10 pieces of 20cm squares, and put into an electric washing machine (model CW-C30A1, Mitsubishi electric machine) together with 4 pieces of commercially available T-shirt (cotton 100%, manufactured by B.V.D.).

Next, about 30L of a liquid detergent composition was added to 25 ℃ tap water at a ratio of 10mL, and the cleaning operation was performed in this order by washing with a standard water flow (10 minutes), dehydrating (1 minute), rinsing with a standard water flow (repeated 2 times), and dehydrating (1 minute).

The cotton cloth without wiping sebum stain is used as non-stained cloth, the cotton cloth before cleaning is used as stained cloth, and the cotton cloth after cleaning is used as cleaning cloth.

The reflectance of each of the non-stained cloth, the stained cloth, and the washed cloth was measured by a spectroscopic colorimeter ("SE 2000", manufactured by japan electric color industries), and the washing rate (%) was calculated according to the following formula (I).

Cleaning ratio (%) { (K/S of soiled cloth-K/S of cleaned cloth)/(K/S of soiled cloth-K/S of unsoiled cloth) } × 100

…(I)

In the formula (I), "K/S" is (1-R/100)2/(2R/100) (wherein R represents the reflectance (%) of an uncontaminated cloth, a soiled cloth, or a cleaned cloth).

The cleaning rate (%) of 10 soiled cloths was calculated, and the sebum cleaning rate was evaluated according to the following criteria using the average value.

A: the average value of the cleaning rate is more than 70%.

B: the average value of the cleaning rate is more than 50% and less than 70%.

C: the average value of the washing rate was less than 50%.

< examples 1 to 48 and comparative examples 1 to 14 >)

Each ingredient was put into a 500mL beaker according to the composition shown in tables 2 to 5, and sufficiently stirred with a magnetic stirrer (MITAMURAKOGYO INC.). Then, arbitrary components (excluding pure water) were added in the amounts shown in table 1, and pure water was added while stirring to make the total amount 98 mass%, and further stirring was performed. An appropriate amount of a pH adjuster (sodium hydroxide or sulfuric acid) was added to adjust the pH at 25 ℃ to 7.0, and then pure water was added to make the total amount to 100% by mass, to obtain a liquid detergent composition.

The obtained liquid detergent composition was subjected to various measurements and evaluations. The results are shown in tables 2 to 5.

In tables 2 to 5, the unit of the amount to be mixed is mass%, and any component is represented by a purity equivalent.

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

As is clear from tables 2 to 4, the liquid detergent compositions obtained in the respective examples contained a high concentration of the surfactant without increasing the viscosity. These liquid cleansing compositions also have good low-temperature storage stability, and excellent low-temperature solubility and sebum cleansing ability during cleansing.

In particular, when the proportion of the component (A) in the surfactant is larger than that in examples 1 to 8, the sebum cleansing ability tends to be improved, and when the proportion of the component (B) is larger than that in examples, the low-temperature solubility tends to be improved. Further, when the compound represented by the above general formula (3) is used as the component (B), the increase in viscosity is suppressed and the low-temperature storage stability is excellent as compared with the case of using the compound represented by the general formula (2).

In comparative examples 9 to 14, the concentrations of the surfactants (i.e., the total content of the component (a) and the component (B)) in the liquid cleanser compositions were high, and the sebum cleansing ability tended to be improved. When the compound represented by the general formula (3) is used as the component (B), the storage stability at low temperature is excellent.

In comparison between example 7 and example 15, when the compound represented by the above general formula (3) was used as the component (B), the low-temperature storage stability was more excellent than when the compound represented by the general formula (2) was used as the component (B).

In comparative examples 3 and 16, R of the compound represented by the above general formula (2) was used as the component (B)²When the number of carbon atoms of (2) is 10, sebum-cleaning ability is more excellent.

In comparative examples 7 and 17, component (B) used was a compound represented by the above general formula (3) wherein R was⁵Is straight chain CH₂CH₂When OH is used, a branched CH is used₂CH(OH)CH₃The compound (4) has more excellent low-temperature storage stability than the compound (3).

Comparing examples 3 with 18 to 19, example 3 having a large ethanol content is more excellent in low-temperature solubility.

Comparing examples 7 and 20, example 7 having a large ethanol content is more excellent in low-temperature storage stability.

In comparative examples 21 to 36, when the compound represented by the general formula (3) was used as the component (B), the storage stability at low temperature was more excellent. The same tendency was observed when 2 kinds of solvents or 3 kinds of solvents were used as the component (C).

In examples 3, 7 and 21 to 36 and 37 to 42, when a solvent other than ethanol and/or polyethylene glycol is used as the component (C), the thickening property, the low-temperature solubility and the low-temperature storage stability tend to be lowered.

In comparative examples 7, 43 and 44, the content of polyethylene glycol as the component (C) was in the range of 2 to 8%, and good results were obtained in terms of both low-temperature solubility and low-temperature storage stability.

In comparative examples 7 and 45, the low-temperature storage stability was more excellent when polyethylene glycol 1000 having an average molecular weight of 950 to 1050 was used as component (C) than when polyethylene glycol 600 having an average molecular weight of 570 to 630 was used.

In comparative examples 3 and 7 and 46 to 51, compounds (a-1 and a-2) in which the average molar number of addition of polyethylene oxide (n) was 15 were used as the component (a), and the low-temperature solubility and sebum-cleansing ability were more excellent than those obtained when compounds (a-3 and a-4) in which n was 12 and 9 were used. When the compound represented by the general formula (3) is used as the component (B), the storage stability at low temperature is more excellent.

On the other hand, as is clear from Table 5, comparative example 1 containing no component (B) had no fluidity and had poor initial appearance. In addition, the adhesive tends to be highly viscous and thick, and has low-temperature storage stability and low-temperature solubility. In particular, when a liquid cleansing composition is put into the container, gel is easily formed, so that the liquid cleansing composition is hardly dissolved in water, and as a result, sebum cleansing ability is also lowered.

In comparative example 2 containing no component (a), the sebum cleansing ability was low. Further, since the component (B) is contained at a high concentration, precipitates are hardly formed in water, and the low-temperature storage stability and the low-temperature solubility are also low.

In comparative examples 3 and 4 in which 1 solvent was used as component (C), the low-temperature storage stability, low-temperature solubility, and sebum-cleansing ability were low. In particular, comparative example 3, which contained no ethanol, had a poor initial appearance.

In comparative examples 5 and 6 in which component (A') was used in place of component (A), although the effect of component (B) suppressed high viscosity at room temperature, gel was likely to be generated when diluted with water, and low-temperature solubility and sebum cleansing ability were reduced. In particular, in comparative example 6 in which a-6 was used in place of component (A), high viscosity and thickening were likely to occur at low temperatures, and the low-temperature storage stability was also low.

In comparative example 7 in which component (B') was used in place of component (B), high viscosity and thickening were likely to occur, and low-temperature storage stability and low-temperature solubility were low. In particular, when a liquid cleansing composition is put into the container, the liquid cleansing composition is gelled and therefore hardly dissolved in water, and as a result, the sebum-cleansing ability is also lowered.

In comparative examples 8 to 10 in which component (A') was used instead of component (B), the adhesive was liable to be highly viscous, and low-temperature storage stability and low-temperature solubility were low.

In comparative example 11 in which the total content of component (a) and component (B) was 35 mass%, the sebum-cleansing ability was low.

In comparative example 12 in which the total content of component (a) and component (B) was 80 mass%, high viscosity and thickening were likely to occur, and low-temperature storage stability was low. Further, the initial appearance was poor, and the low-temperature solubility was also low.

In comparative example 13 in which the mass ratio of component (B) is 0.5/10 with respect to the total content of component (A) and component (B), the low-temperature storage stability and the low-temperature solubility were low.

In comparative example 14 in which the mass ratio of component (B) is 7/10 based on the total content of components (a) and (B), the low-temperature storage stability and the sebum cleansing ability were low.

Industrial applicability

The liquid detergent composition of the present invention contains a high concentration of a surfactant, has good low-temperature storage stability, and is excellent in low-temperature solubility and sebum-cleaning ability during washing, and therefore, can be used as a detergent for clothes and the like.

Claims

1. A liquid detergent composition characterized by containing

(B) The components: at least 1 kind of anionic surfactant selected from the group consisting of compounds represented by the following general formulae (2) and (3),

the total content of the component (A) and the component (B) is 40-75 mass%;

and the mass ratio of the component (B) to the total of the contents of the component (A) and the component (B) is as follows: (B) component/{ (A) component + (B) component } = 1/10-6/10;

the content of the component (A) is 20-60 mass%, the content of the component (B) is 4-45 mass%,

the content of the component (C) is 2 to 20 mass%,

R¹O(CH₂CH₂O)_nH…(1)

R²CH(SO₃M¹)COOR³…(2)

R⁴CH(SO₃M²)CONHR⁵…(3)

in the formulae (1) to (3), R¹Is a linear alkyl group having 10 to 22 carbon atoms;

R²is a linear or branched alkyl group having 9 to 14 carbon atoms or a linear or branched alkenyl group having 9 to 16 carbon atoms;

R³is a straight chain or branched alkyl group having 1 to 3 carbon atoms;

R⁴is a linear or branched alkyl group having 9 to 14 carbon atoms or a linear or branched alkenyl group having 9 to 16 carbon atoms;

R⁵is hydrogen or a straight-chain or branched alkyl group having 1 to 3 carbon atoms and optionally having a hydroxyl group;

M¹and M²Respectively, the same or different, and is an alkali metal, an alkaline earth metal, a protonated primary amine, secondary amine, tertiary amine, or ammonium having 1 to 6 total carbon atoms with or without a hydroxyl group;

n represents an average addition mole number of ethylene oxide and is 5 to 20.

2. The liquid detergent composition as claimed in claim 1, wherein,

the component (C) contains at least ethanol.

3. The liquid detergent composition as claimed in claim 1 or 2, wherein,

the component (C) at least contains ethanol and polyethylene glycol with the average molecular weight of 570-1050.

4. The liquid detergent composition as claimed in claim 1 or 2, wherein,

the mass ratio of the component (B) to the total content of the component (A) and the component (B) is as follows: (B) component/{ (A) component + (B) component } = 2/10 to 5/10.

5. A liquid detergent composition as claimed in claim 3, wherein,

6. The liquid detergent composition according to claim 1 or 2, wherein the component (C) is at least two aqueous miscible solvents selected from the group consisting of ethanol, propylene glycol, methanol, butanol, phenoxyethanol, butyl carbitol, propanol, ethylene glycol, butanediol, polyethylene glycol having an average molecular weight of 950 to 1050, and polyethylene glycol 600 having an average molecular weight of 570 to 630.

7. The liquid detergent composition according to claim 1 or 2, wherein the component (C) is at least 1 monohydric alcohol selected from the group consisting of methanol, ethanol, propanol, butanol, and phenoxyethanol; and at least 1 polyol selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, butyl carbitol, polyethylene glycol having an average molecular weight of 950-1050, and polyethylene glycol 600 having an average molecular weight of 570-630.