KR101726898B1 - Liquid detergent composition for clothes - Google Patents

Abstract

The present invention relates to a nonionic surfactant (A) represented by R ¹ -CO (OR ² ) _m OR ³ , a nonionic surfactant (B) represented by R ⁴ -O (R ⁵ O) _n H, (E) selected from the group consisting of monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, and glycol ether solvents represented by R ⁶ - (OR ⁷ ) _k OH. . INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a non-ionic surfactant which contains a nonionic surfactant at a high concentration and stably, has good solubility, good detergency at the time of cleaning, re-contamination prevention performance and flexibility imparting ability, good liquid stability, It is possible to provide a liquid detergent composition for clothes which can clean clothing, particularly clothes,

Description

[0001] LIQUID DETERGENT COMPOSITION FOR CLOTHES [0002]

The present invention relates to a liquid detergent composition for clothing.

In recent years, the importance of development and sales of mild products in the global environment has been increasing, and commodities that are considered in the global environment have been required in the daily necessities field.

Among them, reduction of energy in logistics and reduction of waste are expected, so that the container containing the detergent composition is being miniaturized. Accordingly, there is a demand for a detergent composition which exhibits high cleaning performance with a small detergent amount. For example, in the case of a liquid detergent composition containing a surfactant as a main component, a concentrated detergent with an increased surfactant concentration is required. For example, in the case of a detergent composition for clothes, the detergency is required to be improved because of the reduction in the amount used.

As a liquid detergent composition for clothing, it has been widely used to use a nonionic surfactant as a cycle agent, and alcoholic alkoxylates such as primary alcohol and ethoxylate are conventionally used as nonionic surfactants.

However, in general, the surfactant forms a high-viscosity, high-order association structure such as a hexagonal liquid crystal and a heliotropic liquid crystal typified by a lamellar liquid crystal in a high concentration range, and a typical nonionic surfactant It is known that alcohol ethoxylate forms a liquid crystal phase (liquid crystal phase) having a high viscosity in a considerably wide concentration range in a high concentration system having a concentration of 40% by mass or more. As described above, since the alcohol alkoxylate has a large gelation region, liquid fluidity (liquid flowability) and stability are lowered as the concentration is increased, and it is difficult to make a concentrated detergent containing 40% or more of alcohol alkoxylate. In addition, when the alcohol alkoxylate is contained at a high concentration, the dissolution rate when the laundry is put into the washing bath at the time of washing is low, and in particular, when the laundry is washed with low temperature water, It is easy to occur.

In order to improve the fluidity, stability and dissolution rate of such a problem, a method of compounding a hydrotrope agent or the like is known. However, in order to obtain a concentrated detergent at a higher concentration, it is necessary to use most of the detergent composition as an alcohol ethoxylate and a hydrotropic agent, and it becomes difficult to form a functional ingredient such as an enzyme or a kireate. The hydrotrope agent has an effect of improving the solubility, but does not affect the cleaning performance at all. Therefore, a sufficient cleaning performance can not be obtained with the above composition.

On the other hand, it is known that the fatty acid alkyl ester alkoxylate has a small gelation region, and a detergent composition in which a specific fatty acid alkyl ester alkoxylate is incorporated at a high concentration has also been proposed (see, for example, Patent Documents 1 to 3).

In addition, a new type of model conscious of the global environment is released successively in the electric washing machine of household use with the technology of energy conservation, water saving, and power saving. In these washing machines, the washing method (mechanical force) is devised so that washing with less energy is enabled or less washing is enabled. However, in such a washing method, such a load is large in the clothes and the feeling of finishing after laundry is deteriorated. For this reason, there is a growing demand for a detergent for clothes which can impart a good finish feeling after washing. For example, Patent Documents 4 to 5 disclose a detergent composition containing a long-chain amine and a positive ionic surfactant A detergent composition comprising a flexibility-imparting component is disclosed.

In recent years, there has been an increasing tendency to push the clothes by washing the clothes in a smaller amount of water by increasing the size of the washing machine and spreading the water-saving type washing machine. However, in the case of washing under such conditions, there is a tendency to cause a problem of re-contamination that garbage dropped by washing is attached to the clothes again, and the clothes after washing are dull. It is known that, when such an anionic surfactant such as a straight chain alkylbenzenesulfonate is blended with the detergent composition, the effect of preventing re-contamination can be obtained.

Patent Document 1: Japanese Patent Application Laid-Open No. 2000-186295 Patent Document 2: JP-A-2002-180087 Patent Document 3: Japanese Patent Application Laid-Open No. 2000-144178 Patent Document 4: JP-A-2003-206500 Patent Document 5: JP-A-2005-23123

However, when the liquid detergent composition is blended with both a flexibility imparting component such as a long chain amine and a cationic surfactant and both components of an anionic surfactant used for preventing re-contamination, flexibility imparting performance and re- Or the storage stability of the liquid detergent composition may be deteriorated. This is thought to be due to the fact that the precipitation tends to occur due to the electrostatic interaction between the two components.

On the other hand, when a fatty acid methyl ester ethoxylate is used as a cyclic agent of a liquid detergent composition, such a problem is relatively unlikely to occur. However, the detergent composition containing the fatty acid alkyl ester alkoxylate at a high concentration as described above may deteriorate the feeling of wearing of the washed clothes. This problem is particularly remarkable in the case of horseshoe (abrasive) clothes, for example, the merit of the horsetail garment such as a tight feeling at the time of wearing, a cold feeling, etc. is damaged.

Disclosure of the Invention The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a nonwoven fabric which is excellent in solubility and cleaning performance at the time of cleaning, contains a nonionic surfactant in a high concentration and stably, It is an object of the present invention to provide a detergent composition.

The present invention has been made in view of the above circumstances and has an object of providing a cleaning agent for clothes, particularly clothes for cleaning clothes, which has excellent washing power, re-contamination prevention performance and flexibility imparting performance, good liquid stability, And to provide a liquid detergent composition.

As a result of intensive studies, the present inventors have found that the above problems can be solved by blending a specific nonionic surfactant with a specific solvent, and have completed the present invention.

Embodiment of the first invention of the present application to solve the aforementioned problems ^{is, R 1 -CO (OR 2)} m OR 3 [ wherein, R ¹ is an alkenyl group having a carbon number of 9 to 13 carbon atoms or an alkyl group of 9 to 13, R ² is (A) represented by R ⁴ -O (R (2)) wherein R ³ is an alkyl group having 2 to 4 carbon atoms, R ³ is an alkyl group having 1 to 3 carbon atoms and m is an average addition mol number of from 5 to 25, ⁵ O) _n H wherein R ⁴ is a hydrocarbon group having 10 to 22 carbon atoms, R ⁵ is an alkylene group having 2 to 4 carbon atoms, and n is an average addition mol number of 5 to 25, A surfactant (B), a monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms, and R ¹¹ - (OR ¹² ) _k OH wherein R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ¹² is made as a glycol ether-based solvents represented by an alkylene group of a carbon number of 2 to 4, k represents an average addition mole number is 1 to 5; Which it is a liquid detergent composition for clothing containing a solvent (E) selected from the group.

The second embodiment is characterized in that the total amount of the component (A) and the component (B) is 40 to 75 mass% with respect to the total mass of the liquid detergent composition, (B) / (A) = 80/20 to 10/90, and the compounding amount of the component (E) is 3 to 25% by mass relative to the total mass of the liquid detergent composition, Is a liquid detergent composition for clothes according to the first aspect.

Form of the third, ^{also, R 6 -N (R 7)} (R 8) [ wherein, R ⁶ is a linking group which may have a good having 7 to 27 hydrocarbon group, R ⁷ and R ⁸ are each independently , An alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or (R ⁹ O) _p H wherein R ⁹ is an alkylene group having 2 to 4 carbon atoms, p is an average addition mole number of 1 to 25 And a compound (C) selected from the group consisting of a salt thereof. The liquid detergent composition according to the second aspect of the present invention is a liquid detergent composition according to the second aspect, further comprising a compound (C) selected from the group consisting of a tertiary amine compound represented by the formula

The fourth aspect is also the clothes detergent composition according to the second aspect, which further comprises an anionic surfactant (D) having an SO ₃ group or SO ₄ group and / or an enzyme (F).

The fifth aspect is the clothes detergent composition according to the third aspect, wherein the amount of the component (C) is 0.1 to 10% by mass with respect to the total mass of the liquid detergent composition.

The sixth aspect is the clothes detergent composition according to the fourth aspect, wherein the compounding amount of the component (D) is 1 to 10% by mass with respect to the total mass of the liquid detergent composition.

The seventh aspect is the clothes detergent composition according to the fourth aspect, wherein the compounding amount of the component (F) is 0.1 to 3% by mass with respect to the total mass of the liquid detergent composition.

Aspect of claim 8, ^{and, R 6 -N (R 7)} (R 8) [ wherein, R ⁶ is a linking group which may have a good having 7 to 27 hydrocarbon group, R ⁷ and R ⁸ are each independently , An alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or (R ⁹ O) _p H wherein R ⁹ is an alkylene group having 2 to 4 carbon atoms, p is an average addition mole number of 1 to 25 (C) selected from the group consisting of a tertiary amine compound represented by the general formula (1) and a salt thereof, and an anionic surfactant (D) having an SO ₃ group or a SO ₄ group, Wherein the total amount of the component (A) and the component (B) is 10 to 65% by mass with respect to the total mass of the liquid detergent composition, and the ratio of the component (A) (B) / (A) = 80/20 to 10/90, and the amount of the component (C) is 0.1 to 10% by mass, based on the total mass of the liquid detergent composition, (D) is contained in an amount of 1 to 20 mass% with respect to the total mass of the liquid detergent composition, and a mixing ratio (mass ratio) of the component (C) and the component (D) The liquid detergent composition according to the first aspect, wherein the amount of the component (E) is 3 to 20% by mass with respect to the total mass of the liquid detergent composition, to be.

The ninth aspect is the clothing according to the eighth embodiment, wherein the blending ratio (mass ratio) of the component (A) to the component (B) is (B) / (A) = 70/30 to 20/80 Liquid detergent composition.

According to the present invention, there is provided a liquid detergent composition for clothes, which has excellent detergency, re-contamination prevention performance and flexibility imparting performance, is excellent in liquid stability, and can clean clothes, particularly clothes, without impairing the feeling of wearing .

Further, it is possible to provide a liquid detergent composition for clothes which contains a nonionic surfactant at a high concentration and stably, is excellent in solubility and cleaning performance at the time of cleaning, and is excellent in the feeling of wearing clothes, especially clothes.

The liquid detergent composition for clothes (hereinafter sometimes referred to as a liquid detergent composition) in the first aspect of the present invention contains the components (A), (B) and (E) shown below.

The liquid detergent composition for clothes according to the second aspect of the present invention contains the following components (A), (B) and (E).

The liquid detergent composition for clothes according to the third and fifth aspects of the present invention contains the components (A), (B), (E) and (C) shown below.

The liquid detergent composition for clothes in the fourth, sixth and seventh aspects of the present invention contains the components (A), (B), and (D) to (F) shown below.

The liquid detergent composition for clothes in the eighth and ninth aspects of the present invention contains the following components (A) to (E).

≪ Component (A) >

The component (A) is a nonionic surfactant represented by R ¹ -CO (OR ² ) _m OR ³ .

Wherein R ¹ is an alkyl group having 9 to 13 carbon atoms or an alkenyl group having 9 to 13 carbon atoms. When the number of carbon atoms is within the above range, it is excellent in detergency and gelation resistance. The number of carbon atoms of the alkyl group and the alkenyl group is preferably 10 to 13, and more preferably 11 to 13.

The alkyl group and the alkenyl group are preferably linear (branched) or branched (branched), respectively. Specific examples of R ¹ include C ₉ H ₁₉ , C ₁₀ H ₂₁ , C ₁₁ H ₂₃ , C ₁₂ H ₂₅ , C ₁₃ H ₂₇ and C ₁₃ H ₂₅ . Among them, C ₉ H ₁₉ , C ₁₁ H ₂₃ and C ₁₃ H ₂₇ are preferable, and C ₁₁ H ₂₃ and C ₁₃ H ₂₇ are more preferable.

R ² is an alkylene group having 2 to 4 carbon atoms, and an ethylene group or a propylene group is preferable. The plurality of R ² in the formula may be the same or different. That is, as the alkylene group of R ² , only one type may be used alone, or a plurality of types may be used. For example, in the case of containing an ethylene group and a propylene group, for example, a method of adding ethylene oxide and propylene oxide may be, for example, a random addition, a method in which ethylene oxide is added and then propylene oxide is added or propylene oxide is added, A block portion in which ethylene oxide is added or ethylene oxide is added and then propylene oxide is added and ethylene oxide is added again may be used.

Among the above, it is preferable that at least one R ² is an ethylene group since the foaming period at the time of cleaning is good and it is inexpensive.

R ³ is an alkyl group having 1 to 3 carbon atoms, and a methyl group is preferable.

m represents an average addition mole number of the alkylene oxide, and is from 5 to 25. [ m is within the above range, the detergency against detergency, especially sebum dirt, is improved. In addition, the solubility of the detergent composition is improved. In the case of an ethylene oxide addition, m is preferably from 5 to 20, more preferably from 12 to 18.

M is preferably from 5 to 25, more preferably from 12 to 21, and the average addition mole number of propylene oxide is 0 to 5, preferably 0 to 4, more preferably 0 to 4, 3 is particularly preferable. When the average addition mole number of propylene oxide exceeds 5, detergency, initial appearance and stability as a liquid detergent deteriorate.

Specific examples of the component (A) include fatty acid alkyl ethoxylates and adducts of fatty acid alkyl esters of ethylene oxide and propylene oxide. Among them, fatty acid methyl ester ethoxylates and fatty acid methyl esters of ethylene oxide and propylene oxide adducts are preferable, and lauric acid methyl ethoxylate, myristic acid methyl ester ethoxylate and coconut fatty acid methyl ester ethoxylate are preferable. desirable. Here, the average addition mole number of the alkylene oxide is preferably 15.

In the component (A), the percentage of the distribution of the alkylene oxide adducts differing in the number of added moles of the alkylene oxide is preferably 20 mass% or more, and the upper limit is preferably 80 mass% or less . The above elongation percentage is more preferably from 20 to 50 mass% and further preferably from 30 to 45 mass% because the storage stability is improved.

The higher the elongation percentage, the better the cleaning performance can be obtained. Further, when the elongation percentage is 20 mass% or more, particularly 30 mass% or more, it is easy to obtain a liquid detergent composition having less raw material odor of the surfactant. This is because, after the production of the component (A), the fatty acid ester which is a raw material of the component (A) coexisting with the component (A) and the alkylene oxide adduct having m or 1 in the above formula become smaller.

Here, the "narrowing ratio" in the present specification means that the number of added moles of alkylene oxide is represented by the following formula (S) representing the ratio of the distribution of the alkylene oxide adducts.

[Equation 1]

In the formula (S), n _max represents the number of moles of the alkylene oxide added to the alkylene oxide adduct which is most present in the total alkylene oxide adduct.

i represents an addition mole number of the alkylene oxide.

And Yi represents the ratio (% by mass) of the alkylene oxide adduct having the addition mole number of the alkylene oxide present in the total alkylene oxide adduct.

The elongation percentage can be controlled by, for example, the method for producing the component (A).

The method for producing the component (A) is not particularly limited, and for example, a method in which a surface-modified composite metal oxide catalyst is used and an addition polymerization of an alkylene oxide to a fatty acid alkyl ester (Japanese Patent Application Laid-Open No. 2000-144179 ). ≪ / RTI >

As appropriate for these surface-modified mixed metal oxide catalysts, specifically, Al ^{+ 3,} the surface modification of the metal ions by metal hydroxide (Ga ^{+ 3,} In ^{+ 3,} Tl ^{+ 3,} Co ^{+ 3,} Sc ³⁺ , La ^{3 +} , Mn ^{2 +,} and the like), magnesium hydroxide and / or metal alkoxide, and the like.

In the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or the metal alkoxide is preferably set such that the ratio of the metal hydroxide and / or the metal alkoxide Is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass.

In the liquid detergent composition of the present invention, the component (A) may be used singly or in combination of a plurality of kinds.

≪ Component (B) >

The component (B) is a nonionic surfactant represented by R ⁴ -O (R ⁵ O) _n H.

The component (B) is an alcohol alkoxylate in which an alkylene oxide having 2 to 4 carbon atoms is added to an alcohol (R ⁴ -OH) in an average addition mole number n.

Wherein R ⁴ is a hydrocarbon group having 10 to 22 carbon atoms. When the number of carbon atoms is 10 or more, the detergency against the substrate is improved, and when it is 22 or less, the solubility and liquid stability of the liquid detergent composition are improved. The number of carbon atoms in the hydrocarbon group is preferably from 10 to 20, more preferably from 10 to 18. The hydrocarbon group is preferably an aliphatic hydrocarbon group (hydrocarbon group having no aromaticity). The hydrocarbon group may or may not have an unsaturated bond. The hydrocarbon group is preferably a straight chain or branched chain.

R ⁴ may be a single chain (chain length) or a mixture of plural chains.

R ⁴ is derived from an alcohol (R ⁴ -OH) as a raw material. Examples of the alcohol include alcohols derived from natural oils such as palm oil, palm oil and tallow, and synthetic alcohols derived from petroleum.

R ⁵ is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group. The plurality of R ⁵ in the formula may be the same or different. That is, as the alkylene group of R ⁵ , only one type may be used alone, or a plurality of types may be used. For example, in the case of containing an ethylene group and a propylene group, for example, a method of adding ethylene oxide and propylene oxide may be, for example, a random addition, a method in which ethylene oxide is added and then propylene oxide is added or propylene oxide is added, A block portion in which ethylene oxide is added or ethylene oxide is added and then propylene oxide is added and ethylene oxide is added again may be used.

Among them, R ⁵ is preferably at least one ethylene group since the foaming period during cleaning is good and low.

n represents an average addition mole number of the alkylene oxide, and is from 5 to 25. [ When n is within the above range, it exhibits excellent cleaning power against the object to be cleaned. Further, when n is 5 or more, it is possible to further prevent the deterioration of odor. On the other hand, when n exceeds 25, the HLB (Hydrophile-Lipophile Balance) becomes too high, and the cleaning power against the sebum is lowered. In the case of ethylene oxide adducts, n is preferably from 5 to 20, more preferably from 8 to 18, and particularly preferably from 10 to 16. In the case of an adduct obtained by combining ethylene oxide and propylene oxide, n is from 5 to 25, preferably from 8 to 22, particularly preferably from 10 to 19, the average addition mole number of propylene oxide is 0 to 5, To 4 is preferable, and 0 to 3 is particularly preferable. When the average addition mole number of propylene oxide exceeds 5, detergency, initial appearance and stability as a liquid detergent deteriorate.

In the component (B), the addition mole number distribution of the alkylene oxide is not particularly limited. The above distribution varies depending on the reaction method at the time of the production of the component (B), and when ethylene oxide is added to the hydrophobic raw material using an alkali catalyst such as common sodium hydroxide or potassium hydroxide, . In addition, Al ^{3 +} , Ga ^{3 +} , In ^{3 +} , and In ^{3 +} described in Japanese Patent Publication No. 6-15038, When ethylene oxide is added to a hydrophobic raw material by using a specific alkoxylation catalyst such as magnesium oxide added with a metal ion such as Tl ^{3 +} , Co ^{3 +} , Sc ^{3 +} , La ^{3 +} , Mn ^{2 +} , It tends to become a relatively narrow distribution.

Specific examples of the component (B) include those derived from primary alcohols and having 12 and 15 moles of oxides corresponding to an alcohol such as Neodol (C12 / C13) and Sasol: Safol23 (C12 / C13) Those obtained by adding ethylene, and those obtained by adding ethylene oxide equivalent to 9, 12, and 15 moles to a natural alcohol such as CO-1214 or CO-1270 under the trade names of P & G. Specific examples of secondary alcohols include those obtained by adding ethylene oxide equivalent to 9, 12, and 15 moles to a secondary alcohol having 12 to 14 carbon atoms (Soputanol 90, manufactured by Nippon Catalysts Co., Ltd.) 120, and 150).

In the liquid detergent composition of the present invention, the component (B) may be used singly or in combination of a plurality of kinds.

The component (A) and the component (B) are blended with a main purpose of imparting a cleaning force to the liquid detergent composition of the present invention.

In the first embodiment, the blending amount of the component (A) is preferably 2 to 67.5 mass%, more preferably 4.5 to 56 mass%, and more preferably 8 to 42 mass%, based on the total mass of the liquid detergent composition, % By mass is more preferable.

The blending amount of the component (B) is preferably from 1 to 60 mass%, more preferably from 1.5 to 49 mass%, and still more preferably from 2 to 36 mass%, based on the total mass of the liquid detergent composition.

However, in the first embodiment, in the liquid detergent composition of the present invention, the total amount of the component (A) and the component (B) should be 10 to 75% by mass relative to the total mass of the liquid detergent composition Do. The total amount is preferably 15 to 70 mass%, more preferably 20 to 65 mass%. When the total amount is 10% by mass or more, a high detergency can be given to the liquid detergent composition. On the other hand, if it exceeds 75% by mass, gelation tends to occur and stability as a liquid detergent composition deteriorates.

In the liquid detergent composition according to the first aspect of the present invention, the mixing ratio (mass ratio) of the component (A) to the component (B) is from 80/20 to 10/90 , Preferably 70/30 to 20/80, and more preferably 60/40 to 20/80. (B) is too high, the viscosity of the composition becomes high, which makes it difficult to be poured into the measuring cup, resulting in poor usability. Further, since gelation occurs, liquid fluidity and stability as a liquid detergent composition deteriorate, and further, the clothes after washing have stiffness, which makes them less comfortable to wear.

On the other hand, if the ratio of (A) is too high, the feeling of tightness of the garment after washing is small, and it is inferior to the feeling of wearing.

The blending amount of the component (A) is preferably 8 to 67.5 mass%, more preferably 13.5 to 56 mass%, based on the total mass of the liquid detergent composition in the second to seventh aspects of the present invention , More preferably from 20 to 42 mass%.

The blending amount of the component (B) is preferably from 4 to 60 mass%, more preferably from 9 to 49 mass%, and even more preferably from 15 to 36 mass% with respect to the total mass of the liquid detergent composition. However, in the liquid detergent composition of the present invention, the total amount of the components (A) and (B) should be 40 to 75% by mass with respect to the total mass of the liquid detergent composition. The total amount is preferably 45 to 70 mass%, more preferably 50 to 65 mass%. When the total amount is 40 mass% or more, a high cleaning performance can be given to the liquid detergent composition. On the other hand, if it exceeds 75% by mass, gelation tends to occur and stability as a liquid detergent composition deteriorates.

In the second to seventh aspects of the present invention, the blending ratio (mass ratio) of the component (A) and the component (B) in the liquid detergent composition is (B) / (A) = 80 / 20 to 10/90, preferably 70/30 to 20/80, and more preferably 60/40 to 20/80. (B) is too high, fluidity and stability of the liquid detergent composition as a liquid detergent composition deteriorate, and since the laundry after washing has stiffness, it is poor in wearing feeling. In addition, if the ratio of (A) is too high, the feeling of tightness of the garment after washing is small, and it is inferior to the feeling of wearing.

In the eighth and ninth aspects, the amount of the component (A) blended is preferably 2 to 58.5 mass%, more preferably 4.5 to 48 mass%, based on the total mass of the liquid detergent composition , More preferably from 8 to 38.5 mass%.

The blending amount of the component (B) is preferably 1 to 52 mass%, more preferably 1.5 to 42 mass%, and still more preferably 2 to 33 mass% with respect to the total mass of the liquid detergent composition.

However, in the liquid detergent compositions of the eighth and ninth aspects, the total amount of the component (A) and the component (B) is preferably from 10 to 65 Mass%. The total amount is preferably 15 to 60 mass%, more preferably 20 to 55 mass%. When the total amount is 10% by mass or more, a high detergency can be given to the liquid detergent composition. On the other hand, if it exceeds 65% by mass, gelation tends to occur, and the components (C) and (D) can not be stably mixed and the stability as a liquid detergent composition deteriorates.

(B) / (A) = 80/20 to 10/90, and the ratio of (A) to (B) in the liquid detergent composition of the present invention is 70/30 to 20 / 80 is preferable, and 60/40 to 25/75 is more preferable. (B) is too high, the viscosity of the composition becomes high, which makes it difficult to be poured into the measuring cup, resulting in poor usability. Further, gelation may occur or the feeling of wearing of the clothes after cleaning may deteriorate.

On the other hand, if the ratio of (A) is too high, the garment after washing, particularly the hemp garment, tends to be less taut and less comfortable to wear.

The blending ratio of the component (A) and the component (B) within the above range contributes to improvement of the finishing feeling particularly for a garment made of hard fibers such as hemp.

The reasons for this are as follows.

The nonionic surfactant remaining in the clothes after washing gives a hard (rough feeling). The component (A) is superior in rinsing property to the component (B), so that the component (A) hardly remains in the garment after washing. When the component (A) alone is used as a liquid detergent composition, since the surfactant hardly remains, it is inferior to the feeling of finishing for a garment made of hard fibers such as hemp, and the feeling of proper wearing feeling is impaired. On the other hand, when the component (B) is used alone as a liquid detergent composition, the amount of the component (B) remaining in the clothes after washing is relatively large and becomes hard (rough). Therefore, by using the component (B) and the component (A) at a specific ratio, it is presumed that the residual amount falls within a suitable range and becomes smaller, resulting in a proper finish feeling.

Therefore, the liquid detergent composition of the present invention is particularly useful for clothing using hemp. The hemp is excellent in hygroscopicity, and because the surface of the fiber is hard, it gives a cold sensation when it touches the skin, and is suitable for a spring clothing.

≪ Component (C) >

(C) is a compound selected from the group consisting of tertiary amine compounds represented by R ⁶ -N (R ⁷ ) (R ⁸ ) and salts thereof.

The component (C) is primarily blended with a liquid detergent composition of the present invention to impart flexibility to clothing such as cotton, polyester, and acrylic.

Wherein R < ⁶ > is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group. The carbon number is preferably 7 to 25. When the hydrocarbon group has a linking group, the number of carbon atoms contained in the linking group is not included in the number of carbon atoms of the hydrocarbon group.

The hydrocarbon group is preferably an aliphatic hydrocarbon group. The hydrocarbon group may or may not have an unsaturated bond. The hydrocarbon group is preferably a straight chain or branched chain.

Here, the term "having a linking group" means that a linking group is interposed between carbon atoms in the hydrocarbon group.

Examples of the linking group that the hydrocarbon group may have include an amide group (-CO-NH-), an ester group (-CO-O-), and an ether group (-O-).

R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or (R ⁹ O) _p H wherein R ⁹ is an alkylene group having 2 to 4 carbon atoms, p Represents an average addition mole number and is 1 to 25].

The alkyl group, hydroxyalkyl group (alkanol group) in R ⁷ and R ⁸ , and alkylene group in R ⁹ may be straight chain or branched chain.

Specific examples of R ⁷ include CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , CH ₂ OH, C ₂ H ₅ OH, C ₃ H ₇ OH, C ₄ H ₉ OH, (C ₂ H ₄ O) _p H, (C ₃ H ₆ O) _p H, and the like. Among them, CH ₃ , C ₂ H ₅ , CH ₂ OH, C ₂ H ₅ OH, (C ₂ H ₄ O) _p H and (C ₃ H ₆ O) _p H are preferable, and CH ₃ is more preferable.

Specific examples of R ⁸ include CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , CH ₂ OH, C ₂ H ₅ OH, C ₃ H ₇ OH, C ₄ H ₉ OH, (C ₂ H ₄ O) _p H, (C ₃ H ₆ O) _p H, and the like. Among them, CH ₃ , C ₂ H ₅ , CH ₂ OH, C ₂ H ₅ OH, (C ₂ H ₄ O) _p H and (C ₃ H ₆ O) _p H are preferable, and CH ₃ is more preferable.

As R ⁹ , an ethylene group or a propylene group is preferable, and an ethylene group is particularly preferable.

The tertiary amine compound represented by R ⁶ -N (R ⁷ ) (R ⁸ ) may be used as it is or may be used as a salt. Examples of the salt include acid salts in which the tertiary amine compound is neutralized with an acid, and the like. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, lactic acid, citric acid, polyacrylic acid, paratoluenesulfonic acid and cumenesulfonic acid. Two or more species may be used in combination.

As the component (C), at least one member selected from the group consisting of a tertiary amine compound represented by the following general formula (c-1) or (c-2) and salts thereof is particularly preferable.

[Chemical Formula 1]

Wherein R ⁶¹ is a hydrocarbon group having 7 to 23 carbon atoms, R ⁶² is an alkylene group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are each as defined above]

In the formula, the hydrocarbon group in R ⁶¹ is a hydrocarbon group having 7 to 23 carbon atoms, and the number of carbon atoms is preferably 7 to 21. The hydrocarbon group is preferably an aliphatic hydrocarbon group. The hydrocarbon group may or may not have an unsaturated bond. The hydrocarbon group is preferably a straight chain or branched chain.

The alkylene group for R ⁶² may be straight chain or branched chain.

(2)

Wherein R ⁶³ is a hydrocarbon group having 11 to 23 carbon atoms, R ⁶⁴ is an alkylene group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are the same as defined above,

In the formula, the hydrocarbon group in R ⁶³ is a hydrocarbon group having 11 to 23 carbon atoms, and the number of carbon atoms is preferably 12 to 20. The hydrocarbon group is preferably an aliphatic hydrocarbon group. The hydrocarbon group may or may not have an unsaturated bond. The hydrocarbon group is preferably a straight chain or branched chain.

The alkylene group for R ⁶⁴ may be straight chain or branched chain.

Specific examples of the tertiary amine compound represented by the formula (c-1) include dimethylaminopropylamide caprylate, dimethylaminopropylamide caprylate, dimethylaminopropylamide laurate, dimethylaminopropylamide myristate, palmitic acid Long-chain aliphatic amido dialkyl tertiary amines such as dimethylaminopropyl amide, stearic acid dimethylaminopropyl amide, behenic acid dimethylaminopropyl amide and oleic acid dimethylaminopropyl amide; Long-chain aliphatic amide dialkanol tertiary amines such as palmitic acid diethanol aminopropylamide and stearic acid diethanol aminopropylamide; And the like.

Specific examples of the tertiary amine compound represented by the formula (c-2)

Aliphatic ester dialkyl tertiary amines such as trimethylolpropyl dimethyl amine, palmitoyl ester propyl dimethyl amine and stearyl ester propyl dimethyl amine.

Among them, a tertiary amine compound represented by the formula (c-1) or a salt thereof is preferable, and dimethylaminopropylamide caprylate, dimethylaminopropylamide caprate, dimethylaminopropylamide laurate, myristic acid Particularly preferred are dimethylaminopropyl amide, dimethylaminopropylamide palmitate, dimethylaminopropylamide stearate, dimethylaminopropylamide behenate, and dimethylaminopropylamide oleate.

Specific examples of the tertiary amine compound which can be used as the component (C) in addition to the tertiary amine compound and the salt thereof represented by the formula (c-1) or (c-2) include lauryldimethylamine, myristyldimethylamine, (Trade name: ETHOMEENHT / L) manufactured by Lion Akzo Co., Ltd.), polyoxyethylene alkylamine, polyoxyethylene alkylamine, polyoxyethylene alkylamine, alkyldimethylamine, palmityldimethylamine, 14, etc.).

The component (C) may be commercially available or may be synthesized by a known method.

For example, a method for producing the component (C) will be described by taking as an example a long-chain aliphatic amidoalkyl tertiary amine such as a tertiary amine compound represented by the above formula (c-1) as a fatty acid or a fatty acid derivative (Or alkanol) aminoalkylamine is condensed with a dialkyl (or alkanol) aminoalkylamine, and then the unreacted dialkyl (or alkanol) aminoalkylamine is condensed or reduced with nitrogen or air The desired compound can be obtained by distillation.

Examples of the fatty acid or fatty acid derivative include caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12- hydroxystearic acid, palm oil fatty acid, cottonseed oil fatty acid, Methyl ester, ethyl ester, glyceride and the like of vegetable oil such as soybean oil, soybean oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid and olive oil fatty acid, Among them, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like are particularly preferable. These fatty acids or fatty acid derivatives may be used singly or in combination of two or more kinds.

Examples of dialkyl (or alkanol) aminoalkylamines include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine and the like. Among them, dimethylaminopropylamine is particularly preferable Do.

The amount of the dialkyl (or alkanol) aminoalkylamine to be used in preparing the long-chain aliphatic amidoalkyl tertiary amine is preferably 0.9 to 2.0 times (twice) the molar amount of the fatty acid or its derivative, more preferably 1.0 to 1.5 times desirable. The reaction temperature is usually from 100 to 220 占 폚, preferably from 150 to 200 占 폚. When the reaction temperature is less than 100 ° C, the reaction becomes too late, and when the reaction temperature is more than 220 ° C, the resulting tertiary amine may be remarkably colored.

The production conditions of the long-chain aliphatic amidoalkyl tertiary amine other than the above can be appropriately changed. The pressure during the reaction may be atmospheric pressure or reduced pressure, or may be introduced by blowing an inert gas such as nitrogen at the time of the reaction.

When an acid catalyst such as sulfuric acid or p-toluenesulfonic acid or a fatty acid derivative is used in the case of using a fatty acid, an alkali catalyst such as sodium methylate, caustic soda and caustic soda is used, The reaction can proceed more efficiently. When the obtained tertiary amine is a long-chain amine having a high melting point, it is preferable to form it into a flake or a pellet after the reaction in order to improve the handling property. Alternatively, it may be added to an organic solvent such as ethanol It is preferable to dissolve it into a liquid phase.

As a specific example of the commercially available component (C), Catheal PAS-R manufactured by Dongbang Chemical Co., Ltd. can be mentioned.

As the component (C), only one kind may be used alone, or a plurality of types may be used in combination.

In the liquid detergent composition of the present invention, the blending amount of the component (C) is preferably from 0.1 to 10 mass%, more preferably from 0.5 to 5 mass%, based on the total mass of the liquid detergent composition. When the content of the component (C) is 0.1% by mass or more, sufficient flexibility imparting performance can be obtained. Further, even if the component (C) is blended in an amount of more than 10% by mass, the effect of improving the flexibility imparting performance corresponding to the component (C) is not shown, which is economically disadvantageous.

≪ Component (D) >

The component (D) is an anionic surfactant having an SO ₃ group or a SO ₄ group.

The component (D) is primarily mixed with the liquid detergent composition of the present invention to impart re-contamination prevention performance.

The component (D) is not particularly limited, and known ones can be used.

Specific examples of the component (D) include straight-chain alkylbenzenesulfonic acid or a salt thereof; -olefin sulfonic acid salts; Straight-chain or branched-chain alkylsulfuric ester salts; Alkyl ether sulfuric acid ester salts or alkenyl ether sulfuric acid ester salts; An alkane sulfonate having an alkyl group; alpha -sulfo fatty acid ester salts, and the like.

Examples of salts thereof include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine and diethanolamine, and the like.

As the straight-chain alkylbenzenesulfonic acid or its salt, the straight-chain alkyl group preferably has 8 to 16 carbon atoms, particularly preferably 10 to 14 carbon atoms.

As the? -olefin sulfonic acid salt, those having 10 to 20 carbon atoms are preferable.

As the alkylsulfuric ester salt, those having 10 to 20 carbon atoms are preferable.

Examples of the alkyl ether sulfuric acid ester salt or alkenyl ether sulfuric acid ester salt include a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average of 1 to 10 moles of ethylene oxide added (that is, polyoxyethylene alkyl Ether sulfuric acid ester salt or polyoxyethylene alkenyl ether sulfuric acid ester salt) is preferable.

The number of carbon atoms of the alkane sulfonate is 10 to 20, preferably 14 to 17, and a secondary alkane sulfonate is particularly preferable.

As the? -sulfo fatty acid ester salt, those having 10 to 20 carbon atoms are preferable.

Such component (D) is readily available on the market. It may be synthesized by a known method.

As the component (D), at least one member selected from the group consisting of a straight-chain alkylbenzenesulfonic acid or a salt thereof, an alkanesulfonate, a polyoxyethylene alkyl ether sulfate, and an -olefin sulfonate is preferable.

Specific examples of the component (D) include a straight chain alkylbenzenesulfonic acid sodium salt, a secondary sodium alkanesulfonic acid salt, and a polyoxyethylene alkyl ether sulfate sodium salt. Among these, straight chain alkylbenzenesulfonic acid sodium is preferable.

As the component (D), only one kind may be used alone, or a plurality of types may be used in combination.

In the liquid detergent composition according to the fourth or sixth aspect of the present invention, the amount of the component (D) to be blended is preferably 1 to 10% by mass, more preferably 1 to 10% by mass with respect to the total mass of the liquid detergent composition, More preferably 5% by mass, and still more preferably 2% by mass to 5% by mass. When the content of the component (D) is 1% by mass or more, the cleaning performance, particularly the application cleaning power, is improved. When the content of the component (D) is 10 mass% or less, the liquid stability of the composition is improved.

In the liquid detergent composition according to the eighth or ninth aspect of the present invention, the amount of the component (D) to be blended is 1 to 20% by mass, preferably 1 to 10% by mass relative to the total mass of the liquid detergent composition, . When the content of the component (D) is 1% by mass or more, sufficient re-contamination prevention performance can be obtained. When the content of the component (D) is 20% by mass or less, the liquid stability of the composition is improved.

By blending the components (C) and (D) at a specific ratio, it is possible to improve the anti-fouling performance and to improve flexibility imparting performance to the clothing, particularly the clothing made of hydrophobic fibers such as acrylic or polyester .

(D) / (C) = 1/1 to 10/1, and 1.05 / 1 to 5/1, in the liquid detergent composition of the present invention, the mixing ratio (mass ratio) desirable. If the ratio of the component (D) is too low, the effect of preventing re-contamination by the component (D) is not sufficiently obtained, and the composition can not be stably mixed as a liquid detergent composition. On the other hand, if the proportion of the component (C) is too low, sufficient flexibility imparting effect by the component (C) can not be obtained.

Regarding the reason for achieving the above effect, it is presumed that the component (C) as the softening-imparting component has a high hydrophobicity and the hydrophobicity of the component (C) And it is presumed that the adsorbent of the present invention exhibits a high adsorption property.

≪ Component (E) >

(E) is a monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms, and R ¹¹ - (OR ¹² ) _k OH wherein R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ¹² Is an alkylene group having 2 to 4 carbon atoms, and k is an average addition molar number and is 1 to 5. The solvent is preferably selected from the group consisting of glycol ether solvents represented by glycol ether solvents.

Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.

Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, and glycerin.

Examples of the glycol ether solvent represented by the formula R ¹¹ - (OR ¹² ) _k OH include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether , Diethylene glycol monomethyl ether, and the like.

Of these, monohydric alcohols and polyhydric alcohols are preferable because of their mild odor and convenience of obtaining raw materials, and ethanol and propylene glycol are particularly preferable.

In the liquid detergent composition of the present invention, only one component (E) may be used alone, or a plurality of components may be used in combination.

In the liquid detergent composition of the present invention, the blending amount of the component (E) is preferably 3 to 25% by mass, more preferably 3 to 20% by mass, and more preferably 4 to 15% by mass with respect to the total mass of the liquid detergent composition , More preferably from 5 to 12 mass%. When the content of the component (E) is 3 mass% or more, the liquid fluidity of the composition becomes good and can be used as a detergent without gelation. Even when blended in an amount of more than 25% by mass, the effect of improving the fluidity of the liquid is not shown, which is economically disadvantageous.

The first aspect of the liquid detergent composition of the present invention comprises the above components (A), (B) and (E) as essential components and may be composed only of components (A), (B) And may contain components other than the components (A), (B) and (E), depending on the necessity. The other component is not particularly limited, and may contain a component that is usually used in a liquid detergent composition for clothes.

For example, the liquid detergent composition of the present invention preferably contains water from the viewpoints of ease of preparation of the liquid detergent composition, solubility in water and storage stability as a detergent composition, and the like. The content of water in the liquid detergent composition of the present invention is preferably 0 to 86 mass%, more preferably 20 to 80 mass%, based on the total mass of the liquid detergent composition.

The eighth and ninth aspects of the liquid detergent composition of the present invention include the above components (A) to (E) as essential components and may be composed of only components (A) to (E) (A) to (E), in addition to the components (A) to (E). The other component is not particularly limited, and may contain a component that is usually used in a liquid detergent composition for clothes.

For example, the liquid detergent composition of the present invention preferably further comprises water from the viewpoints of ease of preparation of the liquid detergent composition, solubility in water and storage stability as a detergent composition, and the like. The content of water in the liquid detergent composition of the present invention is preferably 0 to 86 mass%, more preferably 20 to 80 mass%, based on the total mass of the liquid detergent composition.

A fourth aspect of the liquid detergent composition of the present invention contains the above components (A), (B), (D), and (E) and further contains the component (F).

≪ Component (F) >

The component (F) is not particularly limited, and an enzyme conventionally mixed with a detergent composition for clothes or the like can be used.

Examples of the component (F) include protease, amylase, lipase, cellulase, mannanase and the like. Among them, at least one enzyme selected from the group consisting of protease, amylase and lipase is preferable as the above-mentioned effect.

Specific examples of the protease (F) include proteases such as Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, Purafect L, Purafect OX, and Properase L available from Genencor.

As the amylase, there can be used amylase preparations such as Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stain yme 12L, Stain yme Plus 12L available from Novozymes, Maxamyl available from Shinenko Co., DB-250 available from Biochemical Industry Co., Ltd., and the like.

Examples of the lipase include trade names Lipex 100L and Lipolase 100L available from Novozymes under the trade name of lipase.

Endolase 5000L, Cellu yme 0.4L, Car yme 4500L and the like available from Novozymes as a cellulase preparation as a cellulase.

Mannaway 4L, which is available as a mannanase and as a preparation and available from Novozymes.

Particularly preferred component (F) in the present invention is protease. Among the proteases mentioned above, Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L, Everlase Ultra 16L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL and Coronase 48L are preferable. Among them, Everlase 16L, Savinase 16L and Coronase 48L are preferable.

As the component (F), one kind may be used alone, or two or more kinds may be used in combination.

In the liquid detergent composition of the present invention, the content of the component (F) is preferably 0.1 to 3% by mass, more preferably 0.1 to 1% by mass with respect to the total mass of the liquid detergent composition. When the content of the component (F) is 0.1% by mass or more, the cleaning power against various kinds of dirt (in particular, cleaning power against oil dirt such as soil) is sufficiently improved. When the content of the component (F) is 3 mass% or less, a sufficient washing power against various kinds of dirt is easily obtained and it is economically advantageous.

The second to seventh aspects of the liquid detergent composition of the present invention may contain other components than the above components (A) to (F) within the range that does not impair the effect of the present invention good. The other component is not particularly limited, and may contain a component that is usually used in a liquid detergent composition for clothes.

For example, the liquid detergent composition of the present invention preferably further comprises water from the viewpoints of ease of preparation of the liquid detergent composition, solubility in water and storage stability as a detergent composition, and the like. The content of water in the liquid detergent composition of the present invention is preferably 0 to 57% by mass, more preferably 25 to 46% by mass with respect to the total mass of the liquid detergent composition.

Further, the liquid detergent composition of the present invention may contain a surfactant other than the component (A), the component (B) and the component (D).

Examples of the surfactant include nonionic surfactants other than the components (A) and (B), anionic surfactants other than the component (D), cationic surfactants, and amphoteric surfactants.

Examples of the nonionic surfactant other than the component (A) and the component (B) include alkylene oxide adducts such as alkylphenol, higher fatty acid or higher amine, polyoxyethylene polyoxypropylene block copolymer, fatty acid alkanolamine, fatty acid (Or alkenyl) amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkylpolyhydroxy fatty acid esters, fatty acid esters of polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, Amides, alkyl glycosides, and the like.

Examples of the anionic surfactant other than the component (D) include higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, acylaminocarboxylates Phosphoric ester type anionic surfactants such as carboxylic acid type, alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkylphenyl phosphoric acid ester salts and glycerin fatty acid ester monophosphate ester salts .

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

Examples of the amphoteric surfactant include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamide carboxylic acid type, amide amino acid type and phosphoric acid type amphoteric surfactant have.

Further, it is also possible to use a reducing agent such as glycols such as triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200 to 5,000, paratoluenesulfonic acid, benzoic acid salt (also as an antiseptic), urea, For example, 0.01 to 15% by mass.

The metal ion scavenger such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, and citric acid may be contained in an amount of, for example, 0.1 to 20 mass%.

The antioxidant such as butylhydroxytoluene, cresol disilene, sodium sulfite and sodium hydrogen sulfite may be contained in an amount of, for example, 0.01 to 2% by mass.

In addition, it may contain, for example, 0.001 to 1% by mass of a preservative such as Croma Song CG (trade name) manufactured by Rohm &

For the purpose of improving the detergency and improving the stability, a tackifier, a softening agent, a softening agent, an alkane such as monoethanolamine, diethanolamine, triethanolamine, N-methyl-diethanolamine and N, N-dimethylmonoethanolamine A pH adjuster, a hydrotrope agent, a fluorescent agent, an enzyme, a transfer agent, an anti-fouling agent not corresponding to the component (D) (for example, polyvinylpyrrolidone, carboxymethyl Cellulose, etc.), pearlescent agents, somale release agents, and the like.

Examples of the flexibility-imparting agent include dimethylaminopropylamide caprylate, dimethylaminopropylamide amide caprate, caproic acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristylic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, Long-chain aliphatic amidoalkyl tertiary amines such as dimethylaminopropylamide, ethylenediaminetetraacetic acid, and the like; Palmitic acid diethanol aminopropylamide, stearic acid diethanol aminopropylamide, and the like. For example, it may contain 1 to 5% by mass of dimethylaminopropylamide stearate.

FZ-3707, FZ-3504, BY16-205, FZ-3760, FZ-3705, BY16-209, FZ-3710, SF8417, BY16-849, BY16-850 (manufactured by Dow Corning Toray Co., , BY16-879B, BY16-892, FZ3501, FZ-3785, BY16-872, BY16-213, BY16-203, BY16-898, BY16-890, BY16-878, BY16-891, BY16-893, FZ-3789 , BY16-880, SF8428, FZ-3704, BY16-606, CF1188HV, SH3748, SH3794, SH3772M, SH3775M, SF8410, SH8700, BY22-008, BY22-012, SILWET L-7001, SILWET L- SILWET FZ-2161, SILWET FZ-2100, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1-009-01, ABN SILWET FZ -F1-009-02, ABN SILWET FZ-F1-009-03, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-009-09ABN SILWET FZ-F1-009-11, ABN SILWET FZ-F1 -009-13, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-22-22,; X-20-8010B, KF352A, KF6008, KF615A, KF6012, KF6016 and KF6017 of Shin-Etsu Chemical Co., Ltd.; Modified silicone such as TSF4450, TSF4452, TSF4445 (trade name, manufactured by GE Toshiba Silicone Co., Ltd.) can be used, and the modified silicone may be contained in an amount of 0.1 to 3 mass% in the liquid detergent composition.

In addition to the above, an extract such as a flavoring agent, a coloring agent, an emulsifying agent, and a natural product may be included for the purpose of improving the added value of the product.

As a typical example, a flavor composition described in Japanese Patent Application Laid-Open No. 2002-146399 or Japanese Patent Laid-Open No. 2009-108248 can be used as the flavor, and a preferable blending amount is 0.1 to 2 mass%.

Examples of the colorant include general-purpose pigments and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, and Tacos P- For example, about 0.00005 to 0.005 mass%.

Examples of the emulsifying agent include a polystyrene emulsion and a polyvinyl acetate emulsion. Usually, an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples thereof include 0.01 to 0.5% by mass of a polystyrene emulsion (Saibinol PX-196 PE-3 (trade name, manufactured by Saiden Chemical Industry Co., Ltd., solids content: 40% by mass)).

Examples of the extracts of natural products include, but are not limited to, elk trees, Uba urushii, Echinacea, golden, yellow, white, yellow, spice, oregano, fenugreek, camomile, Aegean, Peony, Ginger, Seaweed, Strawberry, Sage, Case, Creation, Time, Anemarrhena, Clove, Wenzhou Citrus, Tea Tree, Bayberry, Pomegranate, Rosemary, lavender, cedar, gilad adzuki bean tree, white line, chrysanthemum, mandarin orange, chrysanthemum, chrysanthemum, lily of the valley, And extracts of plants such as alfalfa, alfalfa, ginseng, alfalfa, alfalfa, licorice, and spinach, and these may be contained in an amount of, for example, about 0 to 0.5% by mass.

The liquid detergent composition of the present invention preferably has a pH of 4 to 9 at 25 ° C, more preferably 4 to 8. The pH of 4 to 9 makes it possible to maintain good stability over time even when the liquid detergent composition is stored for a long period of time.

The pH can be adjusted by 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, alkanolamine, ammonia, and the like. Of these, sulfuric acid, sodium hydroxide, potassium hydroxide and alkanolamine are preferable from the viewpoint of stability with time of the liquid detergent composition, and sulfuric acid and sodium hydroxide are preferable.

The pH adjusting agent may be used alone or in combination of two or more. For example, when controlling by adding a certain amount of sulfuric acid, sodium hydroxide or the like, an inorganic acid (preferably hydrochloric acid, sulfuric acid), potassium hydroxide or the like can be further added for fine adjustment of the pH.

In the present specification, the pH of the liquid detergent composition (temperature at 25 캜) shows a value measured by a pH meter (product name: HM-30G, manufactured by Dongdaikake K.K.).

The liquid detergent composition of the present invention can be produced by a routine method, for example, by mixing the above components. At this time, it is preferable to add water as a liquid medium.

The liquid detergent composition of the present invention can be used in the same manner as the usual method of using the liquid detergent composition for clothing. That is, a method of applying the liquid detergent composition to water together with the laundry at the time of washing, a method of directly applying the liquid detergent composition to the dirt dirt or sebum, a method of immersing the liquid detergent composition in water in advance to immerse the clothes, have. It is also preferable to apply the liquid detergent composition to the laundry, leave it properly, and then perform normal washing using a normal washing liquid.

At that time, the amount of the liquid detergent composition of the present invention to be used may be smaller than that of the conventional liquid detergent composition.

Example

The present invention will be described in more detail with reference to examples. However, the present invention is not limited to these.

≪ Examples 1 to 19, Comparative Examples 1 to 13 >

The liquid detergent compositions having the compositions shown in Table 1 were prepared in the following order.

(A), the component (B) and the component (E) were placed in a 500 mL beaker and sufficiently stirred with a magnet stirrer (MITAMURA KOGYO INC.). Subsequently, other components (component (C), component (D), and common added components) were added and purified water was added thereto while stirring the mixture in an amount of 98 parts by mass, and the mixture was stirred well. A proper amount of a pH adjusting agent (sodium hydroxide or sulfuric acid) was added so that the pH at 25 캜 was 7.0, and then purified water was added thereto so that the total amount was 100 mass parts, to obtain a liquid detergent composition.

In Table 1, the unit of the blending amount of each component is " mass% ". Table 1 also shows the ratio (B / B) of the total amount (A + B) (mass%) of the components (A) and (B) in the liquid detergent composition to the combined amounts of the components (A) (D / C) of the blending amount of the component (A), the component (C) and the component (D).

The obtained liquid detergent composition was evaluated as follows. The results are shown in Table 1.

<Evaluation of Initial Appearance>

The beaker (500 ml) containing 500 g of the liquid detergent composition prepared in the above procedure was tilted obliquely, and about 100 ml of the contents was taken out into a clear glass bottle (block standard bottle PS-NO. 11).

At this time, it was judged that the liquid detergent composition taken out of the glass bottle had fluidity and could not be taken out, and that there was no fluidity.

The appearance of the liquid detergent composition taken out of the glass bottle was visually observed.

From the results, the initial appearance of each liquid detergent composition was evaluated by the following criteria.

?: There is fluidity, and the appearance is transparent uniform.

X: No fluidity (can not be taken out of a glass bottle). Alternatively, there is fluidity, but the appearance is turbid, suspended or precipitated.

<Evaluation of sebum cleaning power>

With respect to the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the sebum cleaning power was evaluated in the following procedure.

10 pieces of a piece of acrylic jersey cloth which had been rubbed with sebum on the face in a size of 20 cm square and 4 pieces of a commercially available T-shirt (100% of cotton, manufactured by BVD) were placed in an electric washing machine (manufactured by Mitsubishi Electric Corporation, CW-C30A1 type &quot;).

Subsequently, 20 g of the liquid detergent composition was added to about 30 L of water at 25 DEG C, and the mixture was washed (10 minutes), dehydrated (1 minute), and rinsed with water 5 minutes), and dehydration (1 minute) were sequentially performed.

Acrylic jersey which did not rub sebum dirt was stained with Mio dye, Acrylic jar before dyed was contaminated, and Acrylic jar dyed after dyed was called dyed cloth. The Z value (reflectance) was measured by a spectrophotometer (SE2000, manufactured by Nippon Shokuhin Kogyo Co., Ltd.) with respect to each of Mio's dirt, contaminated cloth and cleaned cloth, and a cleaning rate (%) was calculated by the following formula (I).

[Equation 2]

Cleaning rate (%) = {(Z value of the contaminated cloth - Z value of the cleaning cloth) / (Z value of the contaminated cloth - Z value of the mio cloth)} x 100 (I)

The detergency of the liquid detergent composition against the substrate was evaluated from the obtained cleaning rate (%) (average value of ten sheets subjected to the cleaning treatment) by the following criteria.

◎: The cleaning rate is 75% or more.

○: The cleaning rate is 65% or more and less than 75%.

△: The cleaning rate is 55% or more and less than 65%.

X: Less than 55% cleaning rate.

&Lt; Evaluation of wearing comfort of clothes after washing &

With respect to the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the feeling of wearing of the clothes after washing was evaluated in the following order.

(100%) and a commercially available cotton towel (100% cotton) were fed into a fully automatic electric washing machine (JW-Z23A manufactured by Haier Co., Ltd.) (the amount of cotton towel to be fed was the total cloth mass About 800 g). 5 ml of the liquid detergent composition was added thereto, and a cleaning operation was performed in which cleaning, rinsing, and dehydration were performed sequentially with a standard course. Regarding the washing time, rinsing, dewatering, and water quantity (set at low water level, about 12 liter), the standard course setting of the washing machine was used without any adjustment.

After the completion of the washing, the bag having been subjected to the above-described washing treatment was allowed to stand in a constant temperature and humidity chamber at 25 DEG C and a humidity of 65% RH. One day later, the panelists (five persons) were worn in a room at a room temperature of 28 DEG C,

(Feeling of fit) when touching the skin was compared with a control cloth (new shirt not subjected to washing treatment) and scored according to the following criteria.

1 point: There is no feeling of tightness compared with the control pussy, or there is remarkable stiffness, and it is not very comfortable to wear.

2 points: There is little feeling of tightness or a little stiffness compared with the control pussy, and it is not comfortable to wear a little.

3 points: Wearing equivalent to the control cloth.

4 points: It is slightly better fit than the control cloth.

5 points: It is considerably better to wear than control foam.

From the average value of the scoring results of the panelists, the feeling of wearing of the clothes after washing was evaluated according to the following criteria.

⊚: not less than 4 points, ◯: not less than 3.5 points and less than 4 points, △: not less than 3 points and less than 3.5 points, and ∘: less than three points.

&Lt; Evaluation of flexibility &

With respect to the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the flexibility (flexibility imparting effect) was evaluated in the following procedure.

30 liters of tap water and 10 g of a liquid detergent composition were put into a 2-piece washing machine (CW-C30A1 made by Mitsubishi Electric Co., Ltd.), and 5 pieces of acrylic padded Zippo cut to a size of 20 cm and a commercially available T- Six companies were added and washed for 10 minutes, followed by dehydration for 1 minute, rinsing of the water for 5 minutes and dehydration for 1 minute. The temperature of the used tap water was adjusted to be 25 占 폚. The acrylic padded zippers treated with the above cleaning operation were dried in the shade and dried for 12 hours. The dried acrylic padded zippers were left in a constant temperature and humidity chamber at 25 DEG C and 65% RH for 2 days. This was used as a test strip, and its flexibility was compared with the control strip by the panelist (5 persons) and scored according to the following criteria. As a control, 20% aqueous solution of a nonionic surfactant (alcohol ethoxylate (b-1 in Table 1) obtained by adding 15 moles of ethylene oxide per mole of natural alcohol CO-1270 manufactured by P & G) , And the acrylic padded zippers treated by the above-described cleaning operation were used.

1 point: Equivalent to control.

2 points: It is a little more flexible than the control bubble.

3 points: It is more flexible than the control bubble.

4 points: It is considerably more flexible than the control bubble.

5 points: It is more flexible than the control bubble.

Flexibility was evaluated from the average value of the scoring results of the panelists by the following criteria.

?: At least 4 points,?: At least 5 points and less than 4 points,?: At least 3 points less than 3.5 points, and?: Less than 3 points.

<Assessment of re-contamination prevention>

With respect to the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the re-contamination prevention property was evaluated in the following procedure.

900 ml of tap water and 0.3 g of cleaning liquid were put in a lavage bath of Terg-O-Tometer (manufactured by UNITED STATES TESTING CO., LTD.) And stirred at 120 rpm for 3 minutes. Thereafter, one sheet of oil cloth (5 x 5 cm) One sheet of red soil cloth (5 × 5 cm) and two sheets of white polyester tropic cloth (5 × 5 cm) were placed in the bag and washed at 25 ° C. for 10 minutes. Thereafter, the cleaning liquid was removed from the bag, and the test pieces (Yuoguo, Kagaku Ogupo, white polyester tropic capsule) were dewatered for 1 minute in a dehydrating tank of a two-piece washing machine. Again, the rinse was rinsed in a Terg-O-Tometer bath containing 900 ml of tap water for 3 minutes, and the test pieces were dehydrated for 1 minute in a dehydrating tank of a 2-bath washing machine (CW-C30A1 made by Mitsubishi Electric). Likewise, after repeating the operations of rinsing (3 minutes) and dehydration (1 minute), the white polyester tropic bubble was dried to measure the reflectance, and the difference from the reflectance before cleaning was calculated as the re-contamination degree (? Z). From the value of? Z, the re-contamination prevention property was evaluated by the following criteria.

?: DELTA Z is 3 or more,?: DELTA Z is more than 3 and 6 or less,?: DELTA Z is 6 or more and 9 or less, X: DELTA Z is 9 or more.

<Evaluation of Storage Stability>

With respect to the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the storage stability was evaluated in the following procedure.

100 ml of the liquid detergent composition was taken in a transparent glass bottle (block standard size bottle PS-NO. 11), the lid was closed and sealed, and kept in a thermostat at -5 ° C for 1 month. Thereafter, the sample was taken out from the thermostatic chamber, and the appearance of the contents was visually observed at room temperature (25 DEG C) within 1 minute, and evaluated by the following criteria.

?: Appearance was transparent uniform.

?: Though precipitation or gelation was recognized, when it was immersed in a hot bath (hot water bath) of 40 ° C for 1 hour, the appearance became transparent uniform.

X: precipitation or gelation was observed, and the appearance was not transparent even when immersed in a hot water bath at 40 캜 for 1 hour.

As shown in the results of Table 1, the liquid detergent composition of the present invention had good liquid stability, good initial appearance, and good storage stability. In addition, good evaluation results were obtained in all evaluation items of sebum cleaning power, wearing comfort of the washed hemp garment (majeek), flexibility, and re-contamination prevention.

On the other hand, Comparative Example 1 in which the fatty acid methyl ester ethoxylate was not added to the component (A) of the present invention, Comparative Example 3 in which the component (A) was not added, and Comparative Example 3 in which the component (E) Example 6, Comparative Example 7 in which A + B was 68 mass%, and Comparative Example 9 in which B / A was 86/14 each had poor initial appearance and could not be evaluated subsequently. Further, Comparative Example 2 in which component (B) was not blended and Comparative Example 11 in which B / A was 4/96 were inferior to those of washed clothes. Comparative Example 4 in which component (C) was not blended and Comparative Example 12 in which D / C was 12/1 had poor flexibility. In Comparative Example 5 in which component (D) was not blended, In Comparative Example 8 in which the D / C ratio was 0.67 / 1, the re-contamination prevention property was poor, and flexibility and storage stability were also inferior. In Comparative Example 10 in which A + B was 6 mass%, the sebum cleaning power was low and the wearing comfort was poor. In Comparative Example 13 in which the component (A) was not blended, the sebum cleaning power, wearing feeling, and flexibility were inferior to those in Example 13 in which the value of A + B was the same.

[Table 1]

&Lt; Examples 20 to 62 and Comparative Examples 14 to 21 >

Liquid detergent compositions having the compositions shown in Tables 2 to 3 were prepared in the following order.

(A), the component (B) and the component (E) were placed in a 500 mL beaker and sufficiently stirred with a magnet stirrer (MITAMURA KOGYO INC.). Subsequently, other components (the component (D), the component (F), and the common addition component) were added, and while stirring, the purified water was added to the total amount of 98 parts by mass and stirred well. A proper amount of a pH adjusting agent (sodium hydroxide or sulfuric acid) was added so that the pH at 25 캜 was 7.0, and purified water was added thereto so that the total amount was 100 parts by weight, to obtain a liquid detergent composition.

In Tables 2 to 3, the unit of the blending amount of each component is &quot;% by mass &quot;. The ratio (A + B) (mass%) of the total amount of the component (A) and the component (B) in the liquid detergent composition to the compounding amount of the component (A) B / A).

The obtained liquid detergent composition was evaluated as follows. The results are shown in Tables 2 to 3.

<Evaluation of Initial Appearance>

The beaker (500 ml) containing 500 g of the liquid detergent composition prepared in the above procedure was tilted obliquely, and about 100 ml of the contents was taken out into a clear glass bottle (block standard bottle PS-NO. 11).

At this time, it was judged that the liquid detergent composition taken out of the glass bottle had fluidity and could not be taken out, and that there was no fluidity.

The appearance of the liquid detergent composition taken out of the glass bottle was visually observed.

From the results, the initial appearance of each liquid detergent composition was evaluated by the following criteria.

?: There is fluidity, and the appearance is transparent uniform.

X: No fluidity (can not be taken out of a glass bottle). Alternatively, there is fluidity, but the appearance is turbid, suspended or precipitated.

<Evaluation of Storage Stability>

100 ml of the liquid detergent composition was taken in a transparent glass bottle (block standard size bottle PS-NO. 11), the lid was closed and sealed, and kept in a thermostat at -5 ° C for 1 month. Thereafter, the sample was taken out from the thermostatic chamber, and the appearance of the contents was observed with naked eyes at room temperature (25 DEG C) within 1 minute and evaluated according to the following criteria.

?: Appearance was transparent uniform.

?: Though precipitation or gelation was recognized, when it was immersed in a hot water bath of 40 ° C for 1 hour, the appearance became transparent uniform.

X: precipitation or gelation was observed, and the appearance was not transparent uniform even if it was immersed in a hot water bath at 40 캜 for 1 hour.

<Measurement of dissolution rate and evaluation of solubility>

300 mL of ion-exchanged water at 25 캜 was placed in a 500 mL beaker, and 0.1 mL of the liquid detergent composition was dropped thereinto using a polystyrene while stirring (500 rpm) using a magnet steer (MITAMURA KOGYO INC.), The time until the liquid detergent composition completely dissolved (dissolution time) was visually measured.

From the dissolution time measured, the solubility of each liquid detergent composition was evaluated according to the following criteria.

◎: Less than 50 seconds.

?: Less than 50 seconds to less than 100 seconds.

?: Less than 100 seconds to less than 150 seconds.

×: more than 150 seconds.

<Evaluation of sebum cleaning power>

With respect to the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the sebum cleaning power was evaluated in the following procedure.

10 pieces of cotton cloths (cotton plain weave cloth, No. 100 cloth) that were rubbed on the face surface were cut into 20 cm square pieces, and a commercially available T-shirt (100% cotton, manufactured by BVD ) Were placed in an electric washing machine ("CW-C30A1" manufactured by Mitsubishi Electric Corporation).

Subsequently, a liquid detergent composition was added in a ratio of 10 mL to about 30 L of tap water at 25 DEG C, and washed with standard water (10 minutes), dehydrated (1 minute), water rinsed with standard water 5 minutes each), and dehydration (1 minute) sequentially.

The cotton cloth not rubbed with sebum dirt was called a dirty cotton cloth, the cotton cloth before the cleaning treatment was called a contaminated cloth, and the cotton cloth after the cleaning treatment was called a cleaning cloth. The Z value (reflectance) was measured by a spectroscopic colorimeter (SE2000, manufactured by Nippon Shokuhin Kogyo Co., Ltd.) with respect to each of Mio's dirt, contaminated cloth and cleaned cloth, and the cleaning rate (%) was calculated by the following formula (II).

[Equation 3]

Cleaning rate (%) = {(Z value of the contaminated cloth - Z value of the cleaning cloth) / (Z value of the contaminated cloth - Z value of the mio cloth)} x 100 (II)

The detergency of the liquid detergent composition against the substrate was evaluated from the obtained cleaning rate (%) (average value of ten sheets subjected to the cleaning treatment) by the following criteria.

◎: The cleaning rate is 70% or more.

○: The cleaning rate is 60% or more and less than 70%.

△: The cleaning rate is 50% or more and less than 60%.

X: The cleaning rate is less than 50%.

&Lt; Evaluation of application cleaning power against curry powder >

The liquid detergent compositions of Examples 41 to 62 were stored at 25 캜 for 24 hours among the liquid detergent compositions determined to have fluidity in the evaluation of the initial appearance in order to evaluate the detergency at the time of application at a liquid viscosity represented by 25 캜 , And the sebum cleaning power of the liquid detergent composition after the preservation was evaluated in the following procedure.

The curry powder Chinese medicinal herb (product name, manufactured by Otsuka Foods Co., Ltd.) was filtered with a gauze, and this was transferred to a stainless steel bat. The cotton fabric (cotton woven fabric No. 100) was immersed in the fabric for about 1 hour, and then the fabric was excessively removed by brushing, and the fabric was air-dried overnight. The cotton cloth adhered to the curry cloth was cut into a size of 10 cm x 10 cm, and this was used as a dirt cloth.

0.1 g of the liquid detergent composition after being stored at 25 DEG C for 24 hours was applied to the contaminated cloth 6 and left for 5 minutes. Thereafter, the dirt was introduced into a Terg-O-Tometer (manufactured by UNITED STATES TESTING CO., LTD.) And 0.9 L of tap water (hardness 3DH) at 25 캜 was added thereto. The mixture was stirred at 120 rpm for 10 minutes, CW-C30A1 type), and dehydrated for 1 minute. Thereafter, it was rinsed with running water for 1 minute, dehydrated for 1 minute, and then air-dried.

The cotton cloth before the curry dirt adhered was used as a cleaning cloth, and the dirt after the cleaning treatment was used as a cleaning cloth. The Z value was measured in the same manner as in the evaluation of the sebum cleaning power, and the cleaning rate (%) was calculated for each of the myo-dyed, contaminated (before the cleaning), and cleaning.

From the obtained cleaning rate (%) (the average value of six sheets treated at the same time), the applied cleaning power of the liquid detergent composition to the curry was evaluated by the following criteria.

◎: The cleaning rate is 40% or more.

○: The cleaning rate is 35% or more and less than 40%.

△: The cleaning rate is 30% or more and less than 35%.

X: Less than 30% cleaning rate.

&Lt; Evaluation of wearing comfort of clothes after washing &

One commercially available shirt (100% hemp) and a commercial cotton towel (100% cotton) were put in a fully automatic electric washing machine (JW-Z23A manufactured by Haier Co., Ltd.) (the amount of cotton towel was adjusted to be 800 g ). In the evaluation of the initial appearance, 5 ml of the liquid detergent composition determined to have fluidity was added thereto, and a cleaning operation was performed to sequentially perform cleaning, rinsing, and dehydration with a standard course. Regarding the washing time, rinsing, dewatering, and water quantity (set at low water level, about 12 liter), the standard course setting of the washing machine was used without any adjustment. After the completion of the washing, the bag having been subjected to the above-described washing treatment was allowed to stand in a constant temperature and humidity chamber at 25 DEG C and a humidity of 65% RH.

After 1 day, the panelists (five persons) were put in a room at a room temperature of 28 占 폚 to compare the feeling of touching the skin (comfort) with that of the control cloth (new shirt without washing treatment) Respectively.

1 point: There is no feeling of tightness compared with the control pussy, or there is remarkable stiffness, and it is not very comfortable to wear.

2 points: There is little feeling of tightness or a little stiffness compared with the control pussy, and it is not comfortable to wear a little.

3 points: Wearing equivalent to the control cloth.

4 points: It is slightly better fit than the control cloth.

5 points: It is considerably better to wear than control foam.

From the average value of the scoring results of the panelists, the feeling of wearing of the clothes after washing was evaluated according to the following criteria.

⊚: not less than 4 points, ◯: not less than 3.5 points and less than 4 points, △: not less than 3 points and less than 3.5 points, and ∘: less than three points.

As shown in Tables 2 to 3, the liquid detergent composition of the present invention had good initial appearance and storage stability even when a nonionic surfactant was added at a high concentration. In addition, the dissolution rate was fast, and the solubility at the time of washing was excellent. In addition, various cleaning performances were good, and in particular, Examples 41 to 56 in which both the component (D) and the component (F) were blended were excellent. In addition, the feeling of wearing comfort of washed clothes was good.

On the other hand, in Comparative Example 14 in which A + B was 30 mass%, sebum cleaning power was low. Comparative Example 15 in which A + B was 78 mass%, Comparative Examples 16 to 17 in which the amount of the component (E) was 2 mass% or less, Comparative Example 18 in which the component (A) was not added, Comparative Example 19 in which fatty acid methyl ester ethoxylate not corresponding to B / A was 84/16 and Comparative Example 20 in which B / A was 84/16 each had poor initial appearance and storage stability and a slow dissolution rate. Further, Comparative Example 21 in which B / A was 7/93 was inferior to the feeling of wearing of washed hemp clothing.

[Table 2]

[Table 3]

The symbols in Tables 1 to 3 indicate the following.

&Lt; Component (A) >

_{(a-1): C 11} H 23 CO (OCH 2 CH 2) m OCH 3 , and _{C 13 H 27 CO (OCH 2} CH 2) a mixture of 8/2 mass ratio between _m OCH _{3, m} = an average of 15, Me Yield: 33% by mass.

(a-2): C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) _m OCH ₃ , m = average 15, elongation: 33 mass%

_{(a-3): C 11} H 23 CO (OCH 2 CH 2) m OCH 3 , and _{C 13 H 27 CO (OCH 2} CH 2) a mixture of 8/2 mass ratio between _m OCH _{3, m} = an average of 15, Me 45% by mass, synthetic.

_{(a-4): C 11} H 23 CO (OCH 2 CH 2) m OCH 3 , and _{C 13 H 27 CO (OCH 2} CH 2) a mixture of 8/2 mass ratio between _m OCH _{3, m} = an average of 15, Me 60% by mass, synthetic.

(a-5 (comparative product)): C ₁₇ H ₃₃ CO (OCH ₂ CH ₂ ) _m OCH ₃ , m = average 9, narrowness 65 mass%

_{(a-6): C 11} H 23 CO (OCH 2 CH (CH 3)) n (OCH 2 CH 2) m OCH 3 , and _{C 13 H 27 CO (OCH 2} CH (CH 3)) n (OCH 2 CH ₂ ) a mixture of 8/2 by mass ratio with respect to _m OCH ₃ , m = average 15, n = mean 1 (random), narrowing ratio 37% by mass,

The elongation percentage of (a-1) to (a-6) was measured in the following order.

The distribution of the ethylene oxide adducts in which the number of added moles of ethylene oxide was different was measured under the following measurement conditions and the elongation percentage (% by mass) was calculated by the above formula (S). [Conditions for measuring the distribution of ethylene oxide adduct by HPLC]

Apparatus: LC-6A (manufactured by Shimadzu Corporation),

Detector: SPD-10A,

Measured wavelength: 220 nm,

Column: Zorbax C8 (manufactured by Du Pont Co., Ltd.),

Mobile phase: acetonitrile / water = 60/40 (volume ratio),

Flow rate: 1 ml / min,

Temperature: 20 ° C

The above-mentioned (a-1) to (a-6) were synthesized in the following order.

(a-1):

Was synthesized in accordance with Production Example 1 in the Examples described in Japanese Patent Application Laid-Open No. 2000-144179.

Namely, alumina-magnesium hydroxide (trade name: Kyowaido 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O was calcined at 600 ° C. for 1 hour under a nitrogen atmosphere 2.2 g of a calcined hydrous alumina-magnesium (unmodified) catalyst obtained, 2.9 ml of a 0.5-fold potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester were placed in a 4 liter autoclave , And the catalyst was reformed in an autoclave. Subsequently, the inside of the autoclave was replaced with nitrogen, and the temperature was raised. 1052 g of ethylene oxide was introduced while maintaining the temperature at 180 캜 and the pressure at 3 atm, and the reaction was carried out with stirring. The reaction solution was cooled to 80 占 폚, and 159 g of water and 5 g of active white clay and diatomaceous earth were added as filtration aids, respectively, and then the catalyst was filtered off to obtain (a-1).

The amount of alkali added to the catalyst was adjusted so that the narrowing ratio of (a-1) was 33 mass%.

(a-2):

In place of 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester, 350 g of lauric acid methyl ester was used, 1079 g of ethylene oxide was introduced, and the amount of alkali added to the catalyst was adjusted to 33% by mass (A-2) was prepared in the same manner as the synthesis method of the above (a-1).

(a-3):

(A-3) was prepared in the same manner as the synthesis method of the above-mentioned (a-1) except that the alkali addition amount to the catalyst was adjusted so that the narrowing ratio became 45 mass%.

(a-4):

(A-4) was prepared in the same manner as the synthesis method of the above (a-1) except that the amount of alkali added to the catalyst was adjusted so that the narrowing ratio became 65% by mass.

(a-5):

Except that 350 g of methyl oleate was used instead of 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester and 468 g of ethylene oxide was introduced and the amount of alkali added to the catalyst was adjusted to 65% (A-5) was prepared in the same manner as the synthesis method of (a-1).

(a-6):

Lauric acid methyl ester and 70 g of myristic acid methyl ester were used and 1052 g of ethylene oxide and 93 g of propylene oxide were introduced and the amount of alkali added to the catalyst was adjusted to 37 mass% -1), a compound (a-6) was prepared.

&Lt; Component (B) >

(b-1): Ethylene oxide equivalent to an average of 15 moles was added to natural alcohol CO-1270 (trade name) manufactured by P & G.

(b-2): Ethylene oxide equivalent to 15 moles on average was added to natural alcohol CO-1214 (trade name) manufactured by P & G.

(b-3): A product obtained by adding ethylene oxide equivalent to 12 moles on average to natural alcohol CO-1270 (trade name) manufactured by P & G.

(b-4): Ethylene oxide equivalent to an average of 9 moles was added to natural alcohol CO-1270 (trade name) manufactured by P & G.

(b-5): So Futanol 120 (trade name, polyoxyethylene alkyl ether (C12-14 secondary alcohol), manufactured by Nippon Catalysts Co., Ltd.).

(nonionic) surfactant obtained by randomly adding 16 moles of ethylene oxide and 2 moles of propylene oxide to a natural alcohol (C12 / C14 = 7/3)

(b-7): a nonionic surfactant obtained by block addition of natural alcohol (C12 / C14 = 7/3) in the order of 8 moles of ethylene oxide, 2 moles of propylene oxide and 8 moles of ethylene oxide.

The above-mentioned (b-1) to (b-4), (b-6) and (b-7) were synthesized in the following order.

(b-1):

224.4 g of a natural alcohol CO-1270 manufactured by P & G, and 2.0 g of a 30% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, dehydration was performed at a temperature of 100 占 폚 and a pressure of 2.0 kPa or lower for 30 minutes, and then the temperature was raised to 160 占 폚. While stirring the alcohol, 760.4 g of ethylene oxide (gaseous state) was gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 占 폚 using a blowing tube (blowing tube).

After completion of the addition of ethylene oxide, the reaction product was matured at a temperature of 180 DEG C and a pressure of 0.3 MPa or lower for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 DEG C and a pressure of 6.0 kPa or lower for 10 minutes.

Next, after the temperature was cooled to 100 ° C or lower, 70% p-toluenesulfonic acid was added to neutralize the reaction solution so that the pH of the 1% aqueous solution of the reaction solution became about 7 to obtain (b-1).

(b-2):

(B-1) except that 224.4 g of a natural alcohol CO-1214 manufactured by P & G was used instead of the natural alcohol CO-1270.

(b-3):

Synthesis was conducted in the same manner as in (b-1) except that 610.2 g of ethylene oxide was used.

(b-4):

Synthesis was conducted in the same manner as in (b-1) except that 457.2 g of ethylene oxide was used.

(b-6) Synthesis of

(A-1) except that 704 g of ethylene oxide and 130 g of propylene oxide (gaseous state) were used instead of 820.4 g of ethylene oxide.

(b-7):

4.4 g of &quot; CO-127022 &quot; manufactured by P & G and 2.0 g of a 30 mass% NaOH aqueous solution were taken in a pressure-resistant reaction vessel and the inside of the vessel was replaced with nitrogen. Next, dehydration was performed at a temperature of 100 占 폚 and a pressure of 2.0 kPa or lower for 30 minutes, and then the temperature was raised to 160 占 폚. While stirring the alcohol, 405 g of ethylene oxide (gaseous state) was slowly added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 캜 using a blowing tube.

After completion of the addition, the mixture was matured at a temperature of 180 ° C and a pressure of 0.3 MPa or less for 30 minutes. Thereafter, 130 g of propylene oxide was slowly added to the reaction mixture while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. After aging at a temperature of 180 ° C and a pressure of 0.3 MPa or less for 30 minutes, 405 g of ethylene oxide was again reacted. After the aging, unreacted ethylene oxide was distilled off, and the temperature was cooled to 100 DEG C or lower. 70 wt% p-toluenesulfonic acid was added to neutralize the solution so that the pH of the 1 mass% -7).

&Lt; Component (C) >

(mass ratio of fatty acid (C16 / C18) dimethylaminopropylamide, stearic acid / palmitic acid = 7/3) manufactured by Dongbang Chemical Co., Ltd. (c-1).

(c-2): C ₁₇ H ₃₅ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ , stearic acid amide propyldimethylamine; synthetic.

The above-mentioned (c-2) was synthesized in the following procedure.

360 g (molecular weight: 284) of stearic acid was placed in a 1 liter four-necked flask equipped with an oil cooler and heated at 80 DEG C to melt the stearic acid. After nitrogen purging was performed twice, the temperature was raised to 150 캜, and 123 g of dimethylaminopropylamine (molecular weight: 102) (molar ratio to stearic acid: 0.95) was added dropwise over 1 hour. Then, the temperature was maintained at 150 to 160 ° C for 1 hour, then the temperature was raised to 185 ° C over 1 hour, and 45 g of dimethylaminopropylamine was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was maintained at 185 to 190 ° C and aged for 7 hours to distill the by-product water out of the system. (4.0 kPa) while maintaining the temperature at 170 to 190 占 폚, and left standing for 1 hour to distill the unreacted dimethylaminopropylamine to obtain (c-2).

&Lt; Component (D) >

(d-1): Lysine LH-200 (trade name, straight chain alkylbenzenesulfonic acid (LAS), 10 to 14 carbon atoms, average molecular weight 322, manufactured by Lion Corporation).

(d-2): HOSTAPUR SAS30A (trade name, secondary sodium alkanesulfonate (SAS), Kurarianto Japan).

(trade name, Shell Chemical Injection). (d-3): Polyoxyethylene alkylether sodium sulfate (AES) (Synthesis, carbon number 12 to 13, average molar number of addition of 2 mol of EO, raw alcohol: neodol 23

(d-3) were synthesized in the following sequence.

In a 4 L autoclave, Neodol 23 alcohol [trade name, shell chemical injection; 400 g of C12, 13 alcohol (a mixture of alcohol having 12 carbon atoms and 1/13 of the mass ratio of the alcohol with carbon number 13, mass ratio of 20% by mass)] and 0.8 g of potassium hydroxide catalyst were placed, the autoclave was purged with nitrogen, Lt; / RTI &gt; Thereafter, 272 g of ethylene oxide was introduced while maintaining the temperature at 180 캜 and the pressure of 0.3 mPa to obtain a reaction product having an average addition number of moles of ethylene oxide of 2.

Next, 280 g of the alcohol ethoxylate obtained in the above was placed in 500 ml of Frasco equipped with a stirrer and after nitrogen replacement, 67 g of liquid sulfuric anhydride (sulphate) was slowly added dropwise while maintaining the reaction temperature at 40 占 폚. After completion of the dropwise addition, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Again, this was neutralized with an aqueous solution of sodium hydroxide to obtain (d-3).

&Lt; Component (E) >

(e-1): Ethanol (trade name, manufactured by Japan Alcohol Sales Co., Ltd., specific alcohol 95 degree synthesis).

(e-2): Propylene glycol (manufactured by BASF).

&Lt; Component (F) >

(f-1): EBARASE 16L TypeEX (trade name, protease, manufactured by NOVOJINES).

(f-2): Rikanase Ultra 2.5XL (trade name, protease, manufactured by NOVOJINES).

(f-3): Raifex 100L (trade name, Lipase, available from Novozymes).

(f-4): 12 g of Stainzime (trade name, Amylase, manufactured by Nobozafem).

<Common addition component a>

0.5% by mass sodium benzoate,

Citric acid: 0.15% by mass,

Paratoluenesulfonic acid: 4.0% by mass,

Coconut fatty acid: 1.0% by mass,

Polyethylene glycol: 2.0% by mass,

0.05% by mass of dibutylhydroxytoluene,

Monoethanolamine: 1.8% by mass,

Fragrance: 1.4% by mass,

Pigment (green No. 3): 0.0001% by mass,

Water (purified water): balance (amount to make the total amount of liquid detergent composition 100 mass%).

<Common addition component b>

0.5% by mass sodium benzoate,

Citric acid: 0.15% by mass,

Paratoluenesulfonic acid: 4.0% by mass,

0.1% by mass of palmitic acid,

Polyethylene glycol: 2.0% by mass,

0.05% by mass of dibutylhydroxytoluene,

Monoethanolamine: 1.8% by mass,

Fragrance: 1.4% by mass,

Green No. 3: 0.0001% by mass,

Water (purified water): balance (amount to make the total amount of liquid detergent composition 100 mass%).

<Common addition component c>

Sodium benzoate: 0.5 mass%

Citric acid: 0.1 mass%

Paratoluenesulfonic acid: 3 mass%

Coconut fatty acid: 1.0 mass%

Perfume: 1.75 mass%

Green No. 3: 0.0001 mass%

Water (purified water): Balance (amount to make the total amount of the liquid detergent composition 100% by mass)

<Common addition component d>

Sodium benzoate: 1.8% by mass,

Citric acid: 0.3% by mass,

0.1% by mass of palmitic acid,

Paratoluenesulfonic acid: 1.0% by mass,

Polyethylene glycol: 1.0% by mass,

0.05% by mass of dibutylhydroxytoluene,

Monoethanolamine: 1.0% by mass,

Fragrance: 0.4% by mass,

Green No. 3: 0.0003% by mass,

Water (purified water): balance (amount to make the total amount of liquid detergent composition 100 mass%).

Details of each component contained in the common addition components a, b and c are as follows.

Sodium benzoate: Synthesis agent of Donga, trade name "sodium benzoate".

Citric acid: Product name "Liquid citric acid", manufactured by ILVING INDUSTRIAL CO., LTD.

Paratoluenesulfonic acid: manufactured by Kyoei Fermentation Industry Co., Ltd., trade name "PTS acid".

Coconut fatty acid: trade name "palm fatty acid".

Polyethylene glycol: manufactured by Lion Corporation, trade name &quot; PEG # 1000 &quot;.

Dibutylhydroxytoluene: SUMILZER BHT-R, manufactured by Sumitomo Chemical Co., Ltd.

Monoethanolamine: Nippon Catalyst Co., Ltd.

Flavor: Japan Flavor 2009-108248 Flavor component of the base a.

Green No. 3 (coloring matter): manufactured by Sumitomo Chemical Co., Ltd., "Green No. 3".

Details of sodium hydroxide and sulfuric acid used as a pH adjuster are as follows.

Sodium hydroxide: manufactured by Tsuruomida Corporation.

Sulfuric acid: manufactured by Toho Zinc Co., Ltd.

Details of each component included in the common addition component d are as follows.

Sodium benzoate: Synthesis agent of Donga, trade name "sodium benzoate".

Citric acid: Product name "Liquid citric acid", manufactured by ILVING INDUSTRIAL CO., LTD.

Palmitic acid: NAA-160, trade name;

Paratoluenesulfonic acid: manufactured by Kyoei Fermentation Industry Co., Ltd., trade name "PTS acid".

Polyethylene glycol: trade name &quot; PEG # 1000-L60 &quot;

Dibutylhydroxytoluene: SUMILZER BHT-R, manufactured by Sumitomo Chemical Co., Ltd.

Monoethanolamine: Nippon Catalyst Co., Ltd.

Perfume The fragrance composition according to Tables 11 to 18 of JP-A-2002-146399.

Green No. 3 (coloring matter): manufactured by Sumitomo Chemical Co., Ltd., "Green No. 3".

Details of sodium hydroxide and sulfuric acid used as a pH adjuster are as follows.

Sodium hydroxide: manufactured by Tsuruomida Corporation.

Sulfuric acid: manufactured by Toho Zinc Co., Ltd.

(Industrial availability)

According to the present invention, there is provided a liquid detergent composition for clothes, which has excellent detergency, re-contamination prevention performance and flexibility imparting performance, is excellent in liquid stability, and can clean clothes, particularly clothes, without impairing the feeling of wearing .

Further, it is possible to provide a liquid detergent composition for clothes which contains a nonionic surfactant at a high concentration and stably, is excellent in solubility and cleaning performance at the time of cleaning, and is excellent in the feeling of wearing clothes, especially clothes.

Claims (9)

_{^{R 1 -CO (OR 2) m}} OR 3 [ wherein, R ¹ is an alkenyl group having a carbon number of 9 to 13 carbon atoms or an alkyl group of 9 to 13, R ² is an alkylene group of a carbon number of 2 to 4, R ³ is C 1 And m is an average addition mole number of from 5 to 25, and a nonionic surfactant (A) represented by the general formula
^{R 4 -O (R 5 O)} n H [ wherein, R ⁴ is a hydrocarbon group having a carbon number of 10 to 22, R ⁵ is an alkylene group of a carbon number of 2 to 4, n represents an average addition mole number is from 5 to 25 A nonionic surfactant (B) represented by the general formula
A polyhydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms, and R ¹¹ - (OR ¹² ) _k OH wherein R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ¹² is a group having 2 to 4 carbon atoms An alkylene group and k is an average addition mol number of 1 to 5, and the solvent (E) is selected from the group consisting of glycol ether solvents,
Wherein the total amount of the component (A) and the component (B) is 40 to 75 mass% with respect to the total mass of the liquid detergent composition and the mixing ratio of the component (A) (B) / (A) = 80/20 to 10/90, and the amount of the component (E) is 3 to 25% by mass with respect to the total mass of the liquid detergent composition,
, And the elongation percentage in the component (A) represented by the following formula (S) representing the proportion of the alkylene oxide adducts in which the number of added moles of the alkylene oxide (OR ² ) is different is from 20 to 45 mass% By weight of a liquid detergent composition.

[In the formula (S), n _max represents the number of moles of the alkylene oxide added to the alkylene oxide adduct which is most present in the total alkylene oxide adduct.
i represents an addition mole number of the alkylene oxide.
And Yi represents the ratio (% by mass) of the alkylene oxide adduct in which the addition mole number of the alkylene oxide present in the whole alkylene oxide adduct is i. delete The method according to claim 1,
(C) selected from the group consisting of tertiary amine compounds represented by the following general formula (c-1) or (c-2) and salts thereof: Detergent composition.

Wherein R ⁶¹ is a hydrocarbon group having 7 to 23 carbon atoms, R ⁶² is an alkylene group having 1 to 4 carbon atoms, R ⁷ and R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms A hydroxyalkyl group or a group represented by (R ⁹ O) _p H wherein R ⁹ is an alkylene group having 2 to 4 carbon atoms and p is an average addition mol number of 1 to 25.

Wherein R ⁶³ is a hydrocarbon group having 11 to 23 carbon atoms, R ⁶⁴ is an alkylene group having 1 to 4 carbon atoms, R ⁷ and R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms A hydroxyalkyl group or a group represented by (R ⁹ O) _p H wherein R ⁹ is an alkylene group having 2 to 4 carbon atoms and p is an average addition mol number of 1 to 25. The method according to claim 1,
The liquid detergent composition for clothes according to any one of claims ₁ to ₃ , further comprising an anionic surfactant (D) having an SO ₃ group or a SO ₄ group and / or an enzyme (F). The method of claim 3,
Wherein the compounding amount of the component (C) is 0.1 to 10% by mass relative to the total mass of the liquid detergent composition. 5. The method of claim 4,
The liquid detergent composition for clothing according to claim 1, wherein the compounding amount of the component (D) is 1 to 10% by mass with respect to the total mass of the liquid detergent composition. 5. The method of claim 4,
Wherein the compounding amount of the component (F) is 0.1 to 3 mass% with respect to the total mass of the liquid detergent composition. The method according to claim 1,
Further, at least one kind of compound (C) selected from the group consisting of tertiary amine compounds represented by the following general formula (c-1) or (c-2)
Anionic surfactant (D) having an SO ₃ group or SO ₄ group,
Wherein the compounding amount of the component (C) is from 0.1 to 10 mass% with respect to the total mass of the liquid detergent composition, the compounding amount of the component (D) is from 1 to 20 mass% (D) / (C) = 1/1 to 10/1, and the mixing ratio (mass ratio)
Wherein the compounding amount of the component (E) is 3 to 20% by mass with respect to the total mass of the liquid detergent composition.

Wherein R ⁶¹ is a hydrocarbon group having 7 to 23 carbon atoms, R ⁶² is an alkylene group having 1 to 4 carbon atoms, R ⁷ and R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms A hydroxyalkyl group or a group represented by (R ⁹ O) _p H wherein R ⁹ is an alkylene group having 2 to 4 carbon atoms and p is an average addition mol number of 1 to 25.

Wherein R ⁶³ is a hydrocarbon group having 11 to 23 carbon atoms, R ⁶⁴ is an alkylene group having 1 to 4 carbon atoms, R ⁷ and R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms A hydroxyalkyl group or a group represented by (R ⁹ O) _p H wherein R ⁹ is an alkylene group having 2 to 4 carbon atoms and p is an average addition mol number of 1 to 25. 9. The method of claim 8,
Wherein the ratio (mass ratio) of the component (A) to the component (B) is (B) / (A) = 70/30 to 20/80.