WO2011007778A1 - Liquid detergent composition for clothes - Google Patents

Liquid detergent composition for clothes Download PDF

Info

Publication number
WO2011007778A1
WO2011007778A1 PCT/JP2010/061841 JP2010061841W WO2011007778A1 WO 2011007778 A1 WO2011007778 A1 WO 2011007778A1 JP 2010061841 W JP2010061841 W JP 2010061841W WO 2011007778 A1 WO2011007778 A1 WO 2011007778A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
mass
detergent composition
liquid detergent
group
Prior art date
Application number
PCT/JP2010/061841
Other languages
French (fr)
Japanese (ja)
Inventor
剛 寺林
亮 兵藤
知佳 小林
行裕 金子
祥子 藤井
Original Assignee
ライオン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ライオン株式会社 filed Critical ライオン株式会社
Priority to CN201080033750.9A priority Critical patent/CN102471741B/en
Priority to KR1020127002822A priority patent/KR101726898B1/en
Publication of WO2011007778A1 publication Critical patent/WO2011007778A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers

Definitions

  • the present invention relates to a liquid detergent composition for clothing.
  • nonionic surfactants primary alcohol ethoxylates and the like are used.
  • Alcohol alkoxylates have been used.
  • surfactants form alcohols, which are typical nonionic surfactants, in a high concentration region, forming high-viscosity high-order association structures such as lyotropic liquid crystals such as hexagonal liquid crystals and lamellar liquid crystals.
  • lyotropic liquid crystals such as hexagonal liquid crystals and lamellar liquid crystals.
  • an ethoxylate also forms a highly viscous liquid crystal phase in a considerably wide concentration range in a high concentration system having a concentration of 40% by mass or more.
  • the alcohol alkoxylate since the alcohol alkoxylate has a large gelation region, the liquid fluidity and stability are lowered as the concentration is increased, and it is difficult to obtain a concentrated detergent containing 40% or more.
  • the dissolution rate is slow when it is put into the washing bath at the time of washing. Especially when washing is performed with cold water, gel-like deposits are formed on the clothing at the end of washing. Prone to problems such as remaining. In order to solve such problems, a method of blending a hydrotrope agent or the like is known in order to improve liquid fluidity, stability and dissolution rate.
  • Patent Documents 4 to 5 describe cleaning agents containing flexibility-imparting components such as long-chain amines and cationic surfactants. A composition is disclosed.
  • JP 2000-186295 A Japanese Patent Laid-Open No. 2002-180087 JP 2000-144178 A JP 2003-206500 A JP 2005-23123 A
  • a detergent composition containing a fatty acid alkyl ester alkoxylate as described above at a high concentration may impair the comfort of the washed clothes.
  • This problem is particularly noticeable in the case of hemp clothing, for example, the merit of hemp clothing is impaired, such as a feeling of firmness and coolness when worn.
  • the present invention has been made in view of the above circumstances, and contains a nonionic surfactant in a high concentration and stability, is excellent in solubility and washing performance during washing, and is used for washed clothes, particularly hemp clothes.
  • An object of the present invention is to provide a liquid detergent composition for clothing having good comfort.
  • an object of the present invention is to provide a liquid cleaning composition for clothing that can clean hemp clothing.
  • a first aspect of the present invention for solving the above problems is 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.
  • R 2 represents an alkylene group having 2 to 4 carbon atoms,
  • R 3 represents an alkyl group having 1 to 3 carbon atoms, and
  • m represents an average added mole number and is 5 to 25.
  • nonionic surfactant (A) represented by the formula: R 4 —O (R 5 O) n H [wherein R 4 is a hydrocarbon group having 10 to 22 carbon atoms, and R 5 is carbon An alkylene group having a number of 2 to 4, and n represents an average addition mole number and is 5 to 25.
  • the total amount of the component (A) and the component (B) is 40 to 75% by mass with respect to the total mass of the liquid detergent composition, and the component (A)
  • the liquid detergent composition for clothing according to the first aspect which is 3 to 25% by mass relative to the mass.
  • R 6 —N (R 7 ) (R 8 ) [wherein R 6 is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group, and 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 having 2 to 4 carbon atoms. And p represents an average added mole number and is 1 to 25. ].
  • the liquid cleaning composition for clothes as described in the 2nd aspect containing the compound (C) selected from the group which consists of a tertiary amine compound represented by these, and its salt.
  • a fourth aspect is further in laundry detergent composition according to the second embodiment containing the anionic surfactants having an SO 3 group or SO 4 group (D) and / or enzyme (F) is there.
  • the detergent composition for clothing according to the third aspect wherein the blending amount of the component (C) is 0.1 to 10% by mass with respect to the total mass of the liquid detergent composition. It is.
  • a sixth aspect is the garment cleaning composition according to the fourth aspect, wherein the blending amount of the component (D) is 1 to 10% by mass relative to the total mass of the liquid cleaning composition.
  • the detergent composition for clothing according to the fourth aspect wherein the blending amount of the component (F) is 0.1 to 3% by mass with respect to the total mass of the liquid detergent composition It is.
  • R 6 —N (R 7 ) (R 8 ) [wherein R 6 is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group, and 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 having 2 to 4 carbon atoms. And p represents an average added mole number and is 1 to 25. ].
  • the total amount of component A) and component (B) is 10 to 65% by mass relative to the total mass of the liquid detergent composition, and the combination of component (A) and component (B)
  • a liquid for clothing that has excellent detergency, anti-recontamination performance and flexibility imparting performance, has good liquid stability, and can wash clothing, particularly hemp clothing, without impairing comfort.
  • a cleaning composition can be provided.
  • a liquid detergent composition for clothes that contains a high concentration and stability of nonionic surfactants, has excellent solubility and washing performance during washing, and is comfortable to wear washed clothes, especially hemp clothes. it can.
  • the liquid detergent composition for clothing in the first aspect of the present invention contains the following components (A), (B), and (E). .
  • the liquid cleaning composition for clothing in the second aspect of the present invention contains the following components (A), (B), and (E).
  • the liquid cleaning composition for clothing in the third aspect and the fifth aspect of the present invention contains the following components (A), (B), (E) and (C).
  • the liquid detergent composition for clothing according to the fourth, sixth and seventh aspects of the present invention contains the following components (A), (B) and (D) to (F): .
  • the liquid detergent composition for clothing in the eighth and ninth aspects of the present invention contains the following components (A) to (E).
  • the component (A) is a nonionic surfactant represented by R 1 —CO (OR 2 ) m OR 3 .
  • 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, the detergency and gelation resistance are excellent.
  • the alkyl group and alkenyl group preferably have 10 to 13 carbon atoms, more preferably 11 to 13 carbon atoms. Each of the alkyl group and the alkenyl group is preferably linear or branched.
  • R 1 examples include C 9 H 19 , C 10 H 21 , C 11 H 23 , C 12 H 25 , C 13 H 27 , C 13 H 25 and the like. Of these, 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, preferably an ethylene group or a propylene group. A plurality of R 2 in the formula may be the same or different. That is, as the alkylene group for R 2 , only one type may be used alone, or a plurality of types may be combined.
  • the addition method of ethylene oxide and propylene oxide may be, for example, random addition. After adding ethylene oxide, after adding propylene oxide, or after adding propylene oxide, Block addition in which ethylene oxide is added or ethylene oxide is added, followed by propylene oxide and further ethylene oxide may be used.
  • at least one R 2 is an ethylene group because foaming during washing is good and inexpensive.
  • R 3 is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.
  • m represents the average number of moles of alkylene oxide added and is 5 to 25. When m is within the above range, the cleaning power, particularly the cleaning power against sebum dirt is improved.
  • m is preferably 5 to 20, and more preferably 12 to 18.
  • m is 5 to 25, particularly preferably 12 to 21, of which the average added mole number of propylene oxide is 0 to 5, 0 to 3 are particularly preferable.
  • the average added mole number of propylene oxide exceeds 5, detergency, initial appearance and stability as a liquid detergent are deteriorated.
  • Specific examples of the component (A) include fatty acid alkyl ethoxylates, adducts of fatty acid alkyl esters with ethylene oxide and propylene oxide, and the like.
  • fatty acid methyl ester ethoxylates and adducts of fatty acid methyl esters of ethylene oxide and propylene oxide are preferred, and lauric acid methyl ethoxylate, myristic acid methyl ester ethoxylate, and coconut fatty acid methyl ester ethoxylate are more preferred.
  • the average added mole number of alkylene oxide is most preferably 15.
  • the narrow ratio indicating the proportion of the distribution of alkylene oxide adducts having different numbers of added moles of alkylene oxide is preferably 20% by mass or more, and the upper limit is substantially 80% by mass or less. It is preferable that The narrow ratio is more preferably 20 to 50% by mass, and more preferably 30 to 45% by mass in order to improve storage stability. The higher the narrow rate, the better the cleaning power. Moreover, when the said narrow rate is 20 mass% or more, especially 30 mass% or more, it will become easy to obtain the liquid detergent composition with few raw material odors of surfactant.
  • the “narrow ratio” in the present specification means that represented by the following formula (S) indicating the distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide.
  • n max represents the number of added moles of alkylene oxide of the alkylene oxide adduct most present in the entire alkylene oxide adduct.
  • i represents the number of added moles of alkylene oxide.
  • Yi represents the proportion (% by mass) of the alkylene oxide adduct having an added mole number of alkylene oxides i present in the entire alkylene oxide adduct.
  • the narrow rate can be controlled by, for example, the method for producing the component (A).
  • the method for producing the component (A) is not particularly limited. For example, a method of addition polymerization of an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP 2000-2000A).
  • Such a surface-modified composite metal oxide catalyst include, specifically, metal ions (Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 1) that have been surface-modified with a metal hydroxide or the like. 3+ , Sc 3+ , La 3+ , Mn 2+, etc.) and a hydrotalcite calcined catalyst whose surface has been modified by a composite metal oxide catalyst such as magnesium oxide or a metal hydroxide and / or metal alkoxide is there.
  • the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is changed to metal hydroxide with respect to 100 parts by mass of the composite metal oxide.
  • the ratio of the product and / or metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.
  • the component (A) only one type may be used alone, or a plurality of types may be used in combination.
  • 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) with an average addition mole number n.
  • R 4 is a hydrocarbon group having 10 to 22 carbon atoms. When the carbon number is 10 or more, the detergency against sebum stains is improved, and when it is 22 or less, the solubility and liquid stability as the liquid detergent composition are improved.
  • the hydrocarbon group preferably has 10 to 20 carbon atoms, and more preferably 10 to 18 carbon atoms.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group (a hydrocarbon group having no aromaticity).
  • the said hydrocarbon group may have an unsaturated bond and does not need to have it.
  • the hydrocarbon group is preferably linear or branched.
  • R 4 may be a single chain length or a mixture of a plurality of chain lengths.
  • R 4 is derived from a raw material alcohol (R 4 —OH), and examples of the alcohol include alcohols derived from natural fats and oils such as coconut oil, palm oil, and beef 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.
  • a plurality of R 5 in the formula may be the same or different. That is, as the alkylene group for R 5 , only one type may be used alone, or a plurality of types may be combined.
  • the addition method of ethylene oxide and propylene oxide may be, for example, random addition. After adding ethylene oxide, after adding propylene oxide, or after adding propylene oxide, Block addition in which ethylene oxide is added or ethylene oxide is added, followed by propylene oxide and further ethylene oxide may be used.
  • R 5 is at least one ethylene group because foaming during washing is good and inexpensive.
  • n represents the average number of added moles of alkylene oxide, and is 5 to 25. When n is within the above range, an excellent detergency against sebum dirt is exhibited. Further, when n is 5 or more, it is possible to further prevent odor degradation. On the other hand, when n exceeds 25, HLB (Hydrophile-Lipophile Balance) becomes too high, and the detergency against sebum dirt decreases.
  • n is preferably 5 to 20, more preferably 8 to 18, and particularly preferably 10 to 16.
  • n is 5 to 25, preferably 8 to 22, particularly preferably 10 to 19, and of these, the average added mole number of propylene oxide is 0 to 5 0 to 4 are preferable, and 0 to 3 are particularly preferable.
  • the average added mole number of propylene oxide exceeds 5, detergency, initial appearance and stability as a liquid detergent are deteriorated.
  • the addition mole number distribution of the alkylene oxide is not particularly limited.
  • the distribution varies depending on the reaction method during the production of the component (B).
  • a general alkali catalyst such as sodium hydroxide or potassium hydroxide.
  • specific alkoxylation such as magnesium oxide added with metal ions such as Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , Mn 2+, etc. described in JP-B-6-15038
  • the distribution tends to be relatively narrow.
  • the component (B) those derived from primary alcohol, manufactured by Shell: trade name Neodol (C12 / C13), manufactured by Sasol: Safol23 (C12 / C13), etc., 12 and Examples include those obtained by adding ethylene oxide equivalent to 15 mol, and those manufactured by P & G: natural alcohols such as trade names CO-1214 and CO-1270 to which 9, 12 and 15 mol equivalent ethylene oxide are added.
  • Specific examples of those derived from secondary alcohols are those obtained by adding 9, 12, and 15 moles of ethylene oxide to secondary alcohols having 12 to 14 carbon atoms (Nippon Shokubai Co., Ltd., Softanol 90 120 and 150).
  • the component (B) may be used alone or in combination of two or more.
  • the component (A) and the component (B) are blended mainly for the purpose of imparting detergency to the liquid detergent composition of the present invention.
  • the blending amount of the component (A) is preferably 2 to 67.5% by mass, and 4.5 to 56% by mass with respect to the total mass of the liquid detergent composition. More preferred is 8 to 42% by mass.
  • the blending amount of the component (B) is preferably 1 to 60% by mass, more preferably 1.5 to 49% by mass, and further preferably 2 to 36% by mass with respect to the total mass of the liquid detergent composition. preferable.
  • the total amount of the component (A) and the component (B) is 10 to 75 with respect to the total mass of the liquid detergent composition. It is necessary to be mass%.
  • the total amount is preferably 15 to 70% by mass, and more preferably 20 to 65% by mass.
  • a high detergency can be given to the liquid detergent composition.
  • gelation tends to occur, and the stability as a liquid detergent composition is lowered.
  • the ratio of (B) is too high, the viscosity of the composition becomes high, and the usability deteriorates, such as being difficult to pour into a measuring cup.
  • gelation occurs, the fluidity and stability of the liquid detergent composition are reduced, and the clothes after washing are not comfortable to wear.
  • the ratio of (A) is too high, there will be little elasticity of the clothes after washing, and it will be inferior to comfort.
  • the blending amount of the component (A) is preferably 8 to 67.5% by mass with respect to the total mass of the liquid detergent composition in the second to seventh aspects of the present invention. 5 to 56% by mass is more preferable, and 20 to 42% by mass is more preferable.
  • the blending amount of component (B) is preferably 4 to 60% by mass, more preferably 9 to 49% by mass, and still more preferably 15 to 36% by mass with respect to the total mass of the liquid detergent composition.
  • the total amount of the component (A) and the component (B) is 40 to 75% by mass with respect to the total mass of the liquid detergent composition. is necessary.
  • the total amount is preferably 45 to 70% by mass, and more preferably 50 to 65% by mass.
  • the ratio of (B) is too high, gelation occurs, so that the liquid fluidity and stability as the liquid detergent composition are lowered, and the clothes after washing are not comfortable to wear, for example.
  • the blending amount of the component (A) is preferably 2 to 58.5% by mass, and 4.5 to 48% with respect to the total mass of the liquid detergent composition. % By mass is more preferable, and 8 to 38.5% by mass is even more preferable.
  • the blending amount of the component (B) is preferably 1 to 52% by mass, more preferably 1.5 to 42% by mass, and further preferably 2 to 33% by mass with respect to the total mass of the liquid detergent composition. preferable.
  • the total amount of the component (A) and the component (B) is the total mass of the liquid detergent composition.
  • it should be 10 to 65% by mass.
  • the total amount is preferably 15 to 60% by mass, and more preferably 20 to 55% by mass.
  • a high detergency can be given to the liquid detergent composition.
  • it exceeds 65% by mass gelation is likely to occur, and the (C) component and (D) component cannot be blended stably, and the stability as a liquid detergent composition is lowered.
  • the ratio of (B) is too high, the viscosity of the composition becomes high, and the usability deteriorates, such as being difficult to pour into a measuring cup. Moreover, there exists a possibility that gelatinization may arise or the comfort of the clothes after washing
  • That the blending ratio of the component (A) and the component (B) contributes particularly to an improvement in finishing feeling for clothing made of hard fibers such as hemp.
  • the reason is considered as follows.
  • the nonionic surfactant remaining in the clothes after washing gives hardness (squeak feeling). Since the component (A) is superior to the component (B) in rinsing properties, the component (A) hardly remains in the clothes after washing.
  • the surfactant hardly remains, so that the finish feeling for clothing made of hard fibers such as hemp is inferior, and an appropriate feeling of comfort is impaired.
  • the component (B) when used as a liquid detergent composition, the amount of the component (B) remaining in the clothes after washing is relatively large and hard (squeaks). Therefore, it is presumed that by using the component (B) and the component (A) in combination at a specific ratio, the residual amount falls within an appropriate range and decreases, resulting in an appropriate finish feeling. Therefore, the liquid detergent composition of the present invention is particularly useful for apparel using hemp. Hemp is excellent in hygroscopicity, and the fiber surface is hard, so it gives a cool feeling when touching the skin and is suitable for spring and summer clothing.
  • the component (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.
  • Component (C) is blended mainly for the purpose of imparting flexibility imparting performance to clothing such as cotton, polyester, and acrylic to the liquid detergent composition of the present invention.
  • R 6 is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group.
  • the carbon number is preferably 7-25.
  • carbon number contained in a coupling group is not contained in carbon number of a hydrocarbon group.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group.
  • the said hydrocarbon group may have an unsaturated bond and does not need to have it.
  • the hydrocarbon group is preferably linear or branched.
  • “the hydrocarbon group has a linking group” means that the 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—), an ether group (—O—), and the like.
  • 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 has 2 to 4 carbon atoms. And p represents an average added mole number and is 1 to 25.
  • the alkyl group, hydroxyalkyl group (alkanol group) in R 7 and R 8, and the alkylene group in R 9 may each be linear or branched.
  • 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) pH , (C 3 H 6 O) pH, and the like. Of these, CH 3 , C 2 H 5 , CH 2 OH, C 2 H 5 OH, (C 2 H 4 O) pH , and (C 3 H 6 O) pH are preferable, and CH 3 is more preferable.
  • R 8 examples 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) pH , (C 3 H 6 O) pH, and the like.
  • CH 3 , C 2 H 5 , CH 2 OH, C 2 H 5 OH, (C 2 H 4 O) pH , and (C 3 H 6 O) pH are preferable, and CH 3 is more preferable.
  • R 9 is preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.
  • the tertiary amine compound represented by R 6 —N (R 7 ) (R 8 ) may be used as it is or as a salt.
  • Specific examples of the salt include an acid salt obtained by neutralizing the tertiary amine compound with an acid.
  • 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, cumenesulfonic acid, and the like. Two or more types may be used in combination.
  • the component (C) is particularly preferably at least one selected from the group consisting of tertiary amine compounds represented by the following general formula (c-1) or (c-2) and salts thereof.
  • 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 the same as defined above.
  • the hydrocarbon group in R 61 is a hydrocarbon group having 7 to 23 carbon atoms, and the carbon number is preferably 7 to 21.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group.
  • the said hydrocarbon group may have an unsaturated bond and does not need to have it.
  • the hydrocarbon group is preferably linear or branched.
  • the alkylene group for R 62 may be linear or branched.
  • 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 the same as defined above.
  • the hydrocarbon group in R 63 is a hydrocarbon group having 11 to 23 carbon atoms, and the carbon number is preferably 12 to 20.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group.
  • the said hydrocarbon group may have an unsaturated bond and does not need to have it.
  • the hydrocarbon group is preferably linear or branched.
  • the alkylene group for R 64 may be linear or branched.
  • tertiary amine compound represented by the formula (c-1) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid.
  • Long chain aliphatic amide dialkyl tertiary amines such as dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide Long chain aliphatic amide dialkanol tertiary amines, and the like.
  • tertiary amine compound represented by the formula (c-2) include aliphatic ester dialkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine. Among these, a tertiary amine compound represented by the formula (c-1) or a salt thereof is preferable.
  • tertiary amine compound represented by the formula (c-1) or (c-2) and a salt thereof specific examples of the tertiary amine compound that can be used as the component (C) include lauryl dimethylamine, myristyl dimethylamine. , Palm alkyl dimethylamine, palmityl dimethylamine, beef tallow alkyl dimethylamine, hardened beef tallow alkyl dimethylamine, stearyl dimethylamine, stearyl diethanolamine, polyoxyethylene hardened beef tallow alkylamine (product name: ETHOMEEN HT / 14) Etc.).
  • (C) A commercially available thing may be used for a component and you may synthesize
  • the method for producing the component (C) is explained by taking a long-chain aliphatic amidoalkyl tertiary amine such as a tertiary amine compound represented by the formula (c-1) as an example.
  • Derivatives fatty acid lower alkyl esters, animal / vegetable oils and fats, etc.
  • dialkyl (or alkanol) aminoalkylamine are subjected to a condensation reaction, and then unreacted dialkyl (or alkanol) aminoalkylamine is reduced in pressure or nitrogen blown.
  • the target compound is obtained by distilling off.
  • caprylic acid capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid
  • specific examples include corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oils or animal oil fatty acids, or methyl esters, ethyl esters, glycerides, etc.
  • 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 alone or in combination of two or more.
  • Specific examples of the dialkyl (or alkanol) aminoalkylamine include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, and among them, dimethylaminopropylamine is particularly preferable.
  • the amount of the dialkyl (or alkanol) aminoalkylamine used in the production of the long-chain aliphatic amidoalkyl tertiary amine is preferably 0.9 to 2.0 times the molar amount of the fatty acid or its derivative, 1.0 to A 1.5-fold mole is particularly preferred.
  • the reaction temperature is usually 100 to 220 ° C, preferably 150 to 200 ° C. If the reaction temperature is less than 100 ° C., the reaction becomes too slow, and if it exceeds 220 ° C., the resulting tertiary amine may be markedly colored.
  • the production conditions other than those described above for the long-chain aliphatic amidoalkyl tertiary amine can be appropriately changed.
  • the pressure during the reaction may be normal pressure or reduced pressure, and may be introduced by blowing an inert gas such as nitrogen during the reaction.
  • an inert gas such as nitrogen during the reaction.
  • acid catalysts such as sulfuric acid and p-toluenesulfonic acid
  • alkaline catalysts such as sodium methylate, caustic potash and caustic soda can be used for a short time at a low reaction temperature.
  • the reaction can proceed efficiently.
  • the obtained tertiary amine is a long-chain amine having a high melting point, it is preferably molded into a flake shape or a pellet shape after the reaction in order to improve handling properties, or in an organic solvent such as ethanol. It is preferable to dissolve and make it liquid.
  • Specific examples of commercially available component (C) include Kachinal MPAS-R manufactured by Toho Chemical Co., Ltd.
  • the component (C) only one type may be used alone, or a plurality of types may be used in combination.
  • the blending amount of the component (C) is 0.1 to 10% by mass, and 0.5 to 5% by mass with respect to the total mass of the liquid detergent composition. preferable.
  • the content of the component (C) is 0.1% by mass or more, sufficient flexibility imparting performance can be obtained.
  • flexibility provision property corresponding to it is not seen, but it becomes economically disadvantageous.
  • the component (D) is an anionic surfactant having a SO 3 group or a SO 4 group.
  • the component (D) is blended mainly for the purpose of imparting anti-recontamination performance to the liquid detergent composition of the present invention. (D) It does not specifically limit as a component, A well-known thing can be utilized.
  • component (D) examples include linear alkylbenzene sulfonic acid or a salt thereof; ⁇ -olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; And alkane sulfonate having a group; ⁇ -sulfo fatty acid ester salt and the like.
  • these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
  • the linear alkylbenzenesulfonic acid or a salt thereof preferably has 8 to 16 carbon atoms, and particularly preferably has 10 to 14 carbon atoms, in the linear alkyl group.
  • the ⁇ -olefin sulfonate those having 10 to 20 carbon atoms are preferable.
  • the alkyl sulfate ester salt preferably has 10 to 20 carbon atoms.
  • the alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average of 1 to 10 moles of ethylene oxide added (ie, Polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferred.
  • the carbon number of the alkanesulfonate is 10 to 20, preferably 14 to 17, and the secondary alkanesulfonate is particularly preferable.
  • the ⁇ -sulfo fatty acid ester salt preferably has 10 to 20 carbon atoms.
  • Component (D) is, among the above, at least one selected from the group consisting of linear alkylbenzene sulfonic acids or salts thereof, alkane sulfonates, polyoxyethylene alkyl ether sulfates, and ⁇ -olefin sulfonates. Species are preferred. Specific examples of component (D) include sodium linear alkylbenzene sulfonate, sodium secondary alkane sulfonate, sodium polyoxyethylene alkyl ether sulfate, and the like. Of these, sodium linear alkylbenzene sulfonate is preferred.
  • the amount of component (D) in the liquid detergent composition is 1 to 10% by mass relative to the total mass of the liquid detergent composition. It is preferably 1 to 5% by mass, more preferably 2 to 5% by mass. If content of (D) component is 1 mass% or more, cleaning performance, especially coating cleaning power will improve. Moreover, if content of (D) component is 10 mass% or less, the liquid stability of this composition will improve. In the eighth and ninth aspects of the present invention, the blending amount of the component (D) in the liquid detergent composition is 1 to 20% by mass with respect to the total mass of the liquid detergent composition. 1 to 10% by mass is preferable. If the content of the component (D) is 1% by mass or more, sufficient recontamination prevention performance can be obtained. Moreover, if content of (D) component is 20 mass% or less, the liquid stability of this composition will improve.
  • Component (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 represents an average added mole number and is 1 to 5. ]
  • Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
  • 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, and diethylene glycol. Examples thereof include monomethyl ether.
  • monohydric alcohols and polyhydric alcohols are preferable, and ethanol and propylene glycol are particularly preferable because of their mild odor and availability of raw materials.
  • the component (E) may be used alone or in combination of two or more.
  • the amount of component (E) is 3 to 25% by mass, preferably 3 to 20% by mass, preferably 4 to 15%, based on the total mass of the liquid detergent composition. More preferably, it is more preferably 5 to 12% by mass. If content of (E) component is 3 mass% or more, the liquid fluidity
  • the first aspect of the liquid detergent composition of the present invention comprises the components (A), (B) and (E) as essential components, and the components (A), (B) and (E) It may be comprised only from this, and you may contain components other than (A), (B) and (E) component, etc. as needed. It does not specifically limit as said other component,
  • the component normally used for the liquid cleaning composition for garments can be contained.
  • the liquid detergent composition of the present invention preferably further contains water in view of ease of preparation of the liquid detergent composition, solubility in water as the detergent composition, storage stability, and the like.
  • the water content is preferably 0 to 86% by mass, more preferably 20 to 80% by mass, based on the total mass of the liquid detergent composition. preferable.
  • the eighth and ninth aspects of the liquid detergent composition of the present invention comprise the components (A) to (E) as essential components, and are composed of only the components (A) to (E). If necessary, it may contain components other than the components (A) to (E). It does not specifically limit as said other component,
  • the component normally used for the liquid cleaning composition for garments can be contained.
  • the liquid detergent composition of the present invention preferably further contains water in view of ease of preparation of the liquid detergent composition, solubility in water as the detergent composition, storage stability, and the like.
  • the water content is preferably 0 to 86% by mass, more preferably 20 to 80% by mass, based on the total mass of the liquid detergent composition. preferable.
  • the 4th aspect of the liquid cleaning composition of this invention contains the said (A), (B), (D), and (E) component, and also contains (F) component.
  • a component is not specifically limited, The enzyme currently mix
  • the component (F) include protease, amylase, lipase, cellulase, mannanase and the like. Among these, one or more enzymes selected from the group consisting of protease, amylase, and lipase are preferable because of the excellent effects described above.
  • component (F) as proteases, trade names such as Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type EX, Everse L 2.5e, Ultrase L Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, trade names available from Genencor Corporation, such as Perfect L, Perfect OX, Properase L, etc.
  • amylases trade names such as Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, trade names available from Genencore Co., Ltd. And trade name DB-250 available from Seikagaku Corporation.
  • lipase examples include trade names Lipex 100L and Lipolase 100L, which are available from Novozymes as lipase preparations.
  • the cellulase include trade names Endolase 5000L, Celluzyme 0.4L, Carzyme 4500L and the like which are available from Novozymes as cellulase preparations.
  • mannanase include Mannaway 4L, which is a mannanase preparation available from Novozymes.
  • a particularly preferred component (F) in the present invention is a protease.
  • a protease is a protease.
  • trade names are Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L, Everase Ultra 16L, Liquidase 2.5L, and Liquidase UltraL2.5.
  • Everase 16L, Savinase 16L, Coronase 48L are preferred.
  • a component may be used individually by 1 type and may use 2 or more types together.
  • the content of the component (F) is preferably 0.1 to 3% by mass with respect to the total mass of the liquid detergent composition, 0.1 to 1 More preferably, it is mass%. If content of (F) component is 0.1 mass% or more, the detergency with respect to various dirt (especially the detergency with respect to oily dirt, such as sebum dirt) will fully improve. Moreover, if content of (F) component is 3 mass% or less, it will be easy to obtain the detergency with respect to various stain
  • the liquid detergent composition of the present invention preferably further contains water in view of ease of preparation of the liquid detergent composition, solubility in water as the detergent composition, storage stability, and the like.
  • the content of water is preferably 0 to 57% by mass and more preferably 25 to 46% by mass with respect to the total mass of the liquid detergent composition. preferable.
  • the liquid cleaning composition of this invention can contain surfactant other than (A) component, (B) component, and (D) component.
  • surfactant include a nonionic surfactant other than the components (A) and (B), an anionic surfactant other than the component (D), a cationic surfactant, an amphoteric surfactant, and the like. Is mentioned.
  • nonionic surfactants other than the component (A) and the component (B) include alkylphenols, alkylene oxide adducts such as higher fatty acids or higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acids Alkanolamide, polyhydric alcohol fatty acid ester or alkylene oxide adduct thereof, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, Examples include alkyl glycosides.
  • anionic surfactants other than the component (D) include higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, acylaminocarboxylic acids.
  • Phosphate type anionic surface activity such as carboxylic acid type such as salt, alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkylphenyl phosphate salt, glycerin fatty acid ester monophosphate ester salt Agents and the like.
  • Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salt cationic surfactants.
  • Examples of amphoteric surfactants include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, phosphoric acid type amphoteric surfactant. Is mentioned.
  • the solubilizer can be contained, for example, in an amount of 0.01 to 15% by mass. Further, for example, 0.1 to 20% by mass of a metal ion sequestering agent such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid or citric acid can be contained.
  • an antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium hydrogen sulfite can be contained, for example, in an amount of 0.01 to 2% by mass.
  • an antiseptic such as Caisson CG (trade name) manufactured by Rohm and House may be included, for example, in an amount of 0.001 to 1% by mass.
  • texture improvers for the purpose of improving detergency and stability, texture improvers, flexibility imparting agents, alkanols such as monoethanolamine, diethanolamine, triethanolamine, N-methyl-diethanolamine, N, N-dimethylmonoethanolamine, etc.
  • Alkali builders such as amines, pH adjusters, hydrotropes, fluorescent agents, enzymes, dye transfer inhibitors, anti-staining agents that do not fall under component (D) (for example, polyvinyl pyrrolidone, carboxymethyl cellulose, etc.), pearl agents, soil Release agents and the like can be included.
  • Flexibility agents include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenine.
  • Long chain aliphatic amide alkyl tertiary amines such as acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide or salts thereof; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide, and the like.
  • dimethylaminopropylamide stearate 1 to 5% by mass of dimethylaminopropylamide stearate can be contained.
  • the texture improver include FZ-3707, FZ-3504, BY16-205, FZ-3760, FZ-3705, BY16-209, FZ-3710, SF8417, BY16-849, BY16 manufactured by Toray Dow Corning Co., Ltd.
  • flavoring agents coloring agents, emulsifying agents, extracts of natural products, and the like can also be included for the purpose of improving the added value of goods.
  • a flavoring agent a fragrance composition described in JP-A-2002-146399 and JP-A-2009-108248 can be used, and a preferable blending amount is 0.1 to 2 mass. %.
  • General-purpose dyes 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 Turquoise P-GR (all are trade names) For example, about 0.00005 to 0.005 mass%.
  • the emulsion examples include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is preferably used.
  • a polystyrene emulsion manufactured by Seiden Chemical Co., Ltd. (trade name) Cybinol RPX-196 PE-3, solid content 40% by mass) and the like can be contained in an amount of 0.01 to 0.5% by mass.
  • extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou,
  • 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 can be adjusted with a pH adjuster.
  • the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide, alkanolamine and ammonia.
  • a pH adjuster may be used individually by 1 type, and may use 2 or more types together.
  • an inorganic acid preferably hydrochloric acid or sulfuric acid
  • potassium hydroxide can be further added for fine adjustment of pH.
  • the pH of the liquid detergent composition (controlled at 25 ° C.) indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.
  • the liquid detergent composition of the present invention can be produced based on a conventional method, for example, by mixing the above-described 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 for using the liquid detergent composition for clothing. That is, a method in which the liquid detergent composition is poured into water together with the laundry at the time of washing, a method in which the liquid detergent composition is directly applied to mud dirt or sebum dirt, a liquid detergent composition previously dissolved in water and clothing. And the like. Also preferred is a method in which the liquid detergent composition is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a normal laundry solution. In that case, the usage-amount of the liquid cleaning composition of this invention can be made smaller than the usage-amount of the conventional liquid cleaning composition.
  • Examples 1 to 19 and Comparative Examples 1 to 13> A liquid detergent composition having the composition shown in Table 1 was prepared by the following procedure.
  • (A) component, (B) component, and (E) component were put into a 500 mL beaker, and it fully stirred with the magnetic stirrer (made by MITAMURA KOGYO INC.).
  • the magnetic stirrer made by MITAMURA KOGYO INC.
  • purified water was added so that the total amount became 98 parts by mass, and further stirred.
  • the sebum detergency was evaluated by the following procedure. 10 sheets of acrylic jersey cloth rubbed with sebum on the face and cut into 20cm square size and 4 pieces of commercially available T-shirts (100% cotton, manufactured by BVD Corp.) ("CW-C30A1 type" manufactured by Mitsubishi Electric Corporation). Next, 20 g of a liquid detergent composition is added to about 30 L of tap water at 25 ° C., washed with a standard water flow (10 minutes), dehydrated (1 minute), and rinsed with a standard water flow (repeat twice for 5 minutes each) ) And dehydration (1 minute) were sequentially performed.
  • 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 The cleaning rate is less than 55%.
  • washing time rinsing, dehydration, and water volume (set to a low water level, water volume of about 12 L), no adjustment was made and the standard course setting of the washing machine was used.
  • the cloth subjected to the above washing treatment was left in a constant temperature and humidity room at 25 ° C. and humidity 65% RH.
  • panelists 5 people wear them at room temperature of 28 ° C, and compared the feeling when they touched the skin (comfort) with a control cloth (a new shirt that has not been washed). Scored according to criteria. 1 point: There is no firmness compared to the control cloth, or there is a noticeable gore and is not very comfortable to wear.
  • the flexibility was evaluated by the following procedure. Into a two-tank washing machine (CW-C30A1 type, manufactured by Mitsubishi Electric Corporation), 30 L of tap water and 10 g of a liquid detergent composition are placed, and there are five acrylic jersey cloths cut into a 20 cm square size and a commercial T Six shirts (100% cotton, manufactured by BVD Co., Ltd.) were put in, washed for 10 minutes, dehydrated for 1 minute, rinsed for 5 minutes, and dehydrated for 1 minute. The tap water used was adjusted to a temperature of 25 ° C. The acrylic jersey cloth treated in the washing operation was shade-dried and dried for 12 hours.
  • CW-C30A1 type manufactured by Mitsubishi Electric Corporation
  • the dried acrylic jersey cloth was left in a constant temperature and humidity room at 25 ° C. and 65% RH for 2 days. This was used as a test cloth, and its softness was compared with a control cloth by panelists (5 persons) and scored according to the following criteria.
  • a control fabric a nonionic surfactant (alcohol ethoxylate (b-1 in Table 1) obtained by adding an average of 15 moles of ethylene oxide per mole to a natural alcohol CO-1270 manufactured by P & G)
  • An acrylic jersey cloth treated by the same washing operation as described above was used as a composition. 1 point: Equivalent to the control cloth. 2 points: Slightly softer than the control cloth. 3 points: Softer than the control cloth. 4 points: considerably softer than the control cloth.
  • 5 points Very softer than the control fabric. From the average value of the scoring results of five panelists, flexibility was evaluated according to the following criteria. :: 4 points or more, ⁇ : flat 3.5 points or more and less than 4 points, ⁇ : 3 points or more and less than 3.5 points, ⁇ : less than 3 points.
  • the recontamination prevention property was evaluated by the following procedure.
  • a washing bath of Terg-O-Tometer manufactured by UNITED STATES TESTING
  • 900 mL of tap water and 0.3 g of cleaning solution were added and stirred at 120 rpm for 3 minutes, and then one piece of oil stain cloth (5 ⁇ 5 cm), red soil One paste cloth (5 ⁇ 5 cm) and two white polyester tropical cloths (5 ⁇ 5 cm) were added and washed for 10 minutes (25 ° C.).
  • the cleaning solution was removed by emptying the colander, and the test cloth (oil soil cloth, red soil soil cloth, white polyester tropical cloth) was dehydrated for 1 minute in a dewatering tank of a 2-tank washing machine. Further, it was rinsed for 3 minutes in a Terg-O-Tometer bath containing 900 mL of tap water, and the test cloth was dehydrated for 1 minute in a dewatering tank of a 2-tank washing machine (CW-C30A1 type, manufactured by Mitsubishi Electric Corporation). Similarly, after repeating the operations of rinsing (3 minutes) and dehydration (1 minute), the white polyester tropical cloth was dried to measure the reflectance, and the difference from the reflectance before washing was determined as the degree of recontamination ( ⁇ Z).
  • ⁇ Z is 3 or less
  • O ⁇ Z is more than 3 and 6 or less
  • ⁇ ⁇ Z is more than 6 and 9 or less
  • X ⁇ Z is more than 9.
  • the liquid detergent composition of the present invention had good liquid stability and good results in both initial appearance and storage stability. In addition, good results were obtained in a well-balanced manner with respect to all evaluation items of sebum detergency, comfort of the washed garment, flexibility, and anti-recontamination property.
  • the comparative example 1 which mix
  • the comparative example 3 which does not mix
  • Example 6 Comparative Example 7 in which A + B was 68% by mass, and Comparative Example 9 in which B / A was 86/14, the initial appearance was poor, and subsequent evaluation could not be performed.
  • Comparative Example 4 in which component (C) is not blended and Comparative Example 12 in which D / C is 12/1 are poor in flexibility
  • Comparative Example 5 in which component (D) is not blended is recontamination preventing property
  • Comparative Example 8 having a D / C of 0.67 / 1 was poor in re-contamination prevention property, and inferior in flexibility and storage stability.
  • the comparative example 10 whose A + B is 6 mass% had low sebum detergency, and the comfort was also poor.
  • blend (A) component was inferior in sebum cleaning power, comfort, and a softness
  • Liquid detergent compositions having the compositions shown in Tables 2 to 3 were prepared by the following procedure.
  • (A) component, (B) component, and (E) component were put into a 500 mL beaker, and it fully stirred with the magnetic stirrer (made by MITAMURA KOGYO INC.).
  • component (D), component (F), common additive component) and stirring purified water was added so that the total amount became 98 parts by mass, and further stirred.
  • pH adjuster sodium hydroxide or sulfuric acid
  • Tables 2 to 3 show the total ratio (A + B) (mass%) of the components (A) and (B) in the liquid detergent composition, and the blending amounts of the components (A) and (B). The ratio (B / A) is also shown. The following evaluation was performed about the obtained liquid detergent composition. The results are also shown in Tables 2-3.
  • X Precipitation or gelation was observed, and the appearance did not become transparent and uniform even when immersed in a hot water bath at 40 ° C. for 1 hour.
  • ⁇ Measurement of dissolution rate and evaluation of solubility Put 300 mL of ion exchange water at 25 ° C. into a 500 mL beaker, stir (500 rpm) using a magnetic stirrer (MITAMURA KOGYO INC.), And drop 0.1 mL of the liquid detergent composition using a poly dropper. The time until the liquid detergent composition was completely dissolved (dissolution time) was measured visually. From the measured dissolution time, the solubility of each liquid detergent composition was evaluated according to the following criteria. A: Less than 50 seconds. ⁇ : 50 seconds to less than 100 seconds. ⁇ : 100 seconds to less than 150 seconds. X: 150 seconds or more.
  • the sebum detergency was evaluated by the following procedure. 10 pieces of cotton cloth (cotton plain weave cloth, 100 count) rubbed with sebum on the face and cut into a 20 cm square size and a commercially available T-shirt (100% cotton, manufactured by BVD Corporation) 4 The sheet was put into an electric washing machine (“CW-C30A1 type” manufactured by Mitsubishi Electric Corporation). Next, a liquid detergent composition is added at a rate of 10 mL to about 30 L of tap water at 25 ° C., washed with a standard water flow (10 minutes), dehydrated (1 minute), and rinsed with a standard water flow (repeated twice).
  • a washing operation was sequentially performed for 5 minutes each and dehydration (1 minute).
  • the cotton cloth not rubbed with sebum stain was used as an uncontaminated cloth, the cotton cloth before the cleaning treatment was used as the contamination cloth, and the cotton cloth after the cleaning treatment was used as the cleaning cloth.
  • the Z value (reflectance) was measured with a spectroscopic color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., “SE2000”), and the cleaning rate (%) was calculated according to the following formula (II). ) was calculated.
  • 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%.
  • This cotton cloth with curry stains was cut into 10 cm ⁇ 10 cm, and this was used as a contaminated cloth.
  • 0.1 g of the liquid detergent composition that had been stored at 25 ° C. for 24 hours was applied to the six soiled cloths and left for 5 minutes. Thereafter, the contaminated cloth was put into a Terg-O-Tometer (manufactured by UNITED STATES TESTING), 0.9 L of 25 ° C. tap water (hardness 3DH) was added, and the mixture was stirred at 120 rpm for 10 minutes. (Mitsubishi Electric Corporation, 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 stain was used as an uncontaminated cloth, and the contaminated cloth after the cleaning treatment was used as a cleaning cloth.
  • the Z value was measured in the same manner as the evaluation of the sebum detergency, and the washing rate (%) was calculated. From the obtained washing rate (%) (average value of 6 sheets subjected to washing at the same time), the coating washing power of the liquid detergent composition against curry stains was evaluated according to the following criteria.
  • ⁇ The cleaning rate is 35% or more and less than 40%.
  • ⁇ The cleaning rate is 30% or more and less than 35%.
  • X The cleaning rate is less than 30%.
  • the liquid detergent composition of the present invention had good initial appearance and storage stability even when a nonionic surfactant was blended at a high concentration. Also, the dissolution rate was fast and the solubility at the time of washing was excellent. Also, various cleaning performances were good, and Examples 41 to 56, in which both the component (D) and the component (F) were blended, were excellent. In addition, the comfort of the washed clothing was good. On the other hand, Comparative Example 14 with 30% by mass of A + B had a low sebum detergency.
  • Comparative Example 15 in which A + B is 78% by mass
  • Comparative Examples 16 to 17 in which the blending amount of the component (E) is 2% by mass or less
  • Comparative Example 18 in which the component (A) is not blended
  • Comparative Example 19 in which a fatty acid methyl ester ethoxylate not corresponding to the component was blended and Comparative Example 20 having a B / A of 84/16 had poor initial appearance and storage stability, and the dissolution rate was also slow.
  • Comparative Example 21 having a B / A of 7/93 was inferior in the comfort of the washed clothing.
  • symbol in Tables 1-3 shows the following.
  • (A-2): C 11 H 23 CO (OCH 2 CH 2 ) m OCH 3 , m average 15, narrow ratio 33% by mass, synthetic product.
  • (A-3): a mixture of C 11 H 23 CO (OCH 2 CH 2 ) m OCH 3 and C 13 H 27 CO (OCH 2 CH 2 ) m OCH 3 in a mass ratio of 8/2, m average 15 , Narrow ratio 45% by mass, synthetic product.
  • (A-4): C 11 H 23 CO (OCH 2 CH 2 ) m OCH 3 and C 13 H 27 CO (OCH 2 CH 2 ) m OCH 3 in a mass ratio of 8/2, m average 15 , Narrow rate 60% by mass, synthetic product.
  • (A-5 (comparative product)): C 17 H 33 CO (OCH 2 CH 2 ) m OCH 3 , m average 9, narrow ratio 65% by mass, synthetic product.
  • Synthesis of (a-1) Synthesis was performed according to Production Example 1 in the examples described in JP-A No. 2000-144179. That is, alumina hydroxide and magnesium hydroxide having a chemical composition of 2.5 MgO.Al 2 O 3 .nH 2 O (trade name: Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) at 600 ° C.
  • reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added, respectively, and the catalyst was filtered off to obtain (a-1).
  • the amount of alkali added to the catalyst was adjusted so that the narrow ratio of (a-1) was 33% by mass.
  • Synthesis of (a-2) Instead 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 so that the narrow ratio was 33% by mass.
  • (A-2) was produced in the same manner as the synthesis method of (a-1).
  • Synthesis of (a-4) was produced in the same manner as the synthesis method (a-1) except that the amount of alkali added to the catalyst was adjusted so that the narrow ratio was 65% by mass.
  • Synthesis of (a-5) instead of 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester, 350 g of oleic acid methyl ester was used, 468 g of ethylene oxide was introduced, and the amount of alkali added to the catalyst was adjusted so that the narrow ratio was 65% by mass. (A-5) was produced in the same manner as in the synthesis method of (a-1).
  • ⁇ (B) component> (B-1): An average of 15 moles of ethylene oxide added to natural alcohol CO-1270 (trade name) manufactured by P & G. (B-2): An average of 15 moles of ethylene oxide added to natural alcohol CO-1214 (trade name) manufactured by P & G. (B-3): An average of 12 moles of ethylene oxide added to natural alcohol CO-1270 (trade name) manufactured by P & G. (B-4): An average of 9 moles of ethylene oxide added to natural alcohol CO-1270 (trade name) manufactured by P & G. (B-5): Softanol 120 (trade name, polyoxyethylene alkyl ether (C12-14 secondary alcohol), manufactured by Nippon Shokubai Co., Ltd.).
  • Nonionic surfactant obtained by block addition of 8 mol of ethylene oxide, 2 mol of propylene oxide, and 8 mol of ethylene oxide in this order to natural alcohol (C12 / C14 7/3).
  • Synthesis of (b-2) Synthesis was performed in the same manner as (b-1) except that 224.4 g of natural alcohol CO-1214 manufactured by P & G was used instead of natural alcohol CO-1270.
  • Synthesis of (b-3) This compound was synthesized in the same manner as (b-1) except that 610.2 g of ethylene oxide was used.
  • Synthesis of (b-4) This compound was synthesized in the same manner as (b-1) except that 457.2 g of ethylene oxide was used.
  • Synthesis of (b-6) Synthesis was performed in the same manner as in (a-1) except that 704 g of ethylene oxide and 130 g of propylene oxide (gaseous) were used instead of 820.4 g of ethylene oxide.
  • C-2) C 17 H 35 CONH (CH 2 ) 3 N (CH 3 ) 2 , amidopropyldimethylamine stearate; synthetic product.
  • C-2 was synthesized by the following procedure.
  • a 1 liter four-necked flask equipped with a flow condenser was charged with 360 g of stearic acid (molecular weight 284) and heated to 80 ° C. to melt the stearic acid.
  • the temperature was raised to 150 ° C., and 123 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to stearic acid: 0.95) was added dropwise over 1 hour.
  • the temperature was raised to 185 ° C. over 1 hour, and 45 g of dimethylaminopropylamine was added dropwise over 1 hour.
  • the temperature was maintained at 185 to 190 ° C. and aged for 7 hours to distill off by-product water out of the system. Further, while maintaining the temperature at 170 to 190 ° C., the pressure was reduced (4.0 kPa) and the mixture was allowed to stand for 1 hour to distill off unreacted dimethylaminopropylamine to obtain (c-2).
  • D-1 Rypon LH-200 (trade name, linear alkylbenzene sulfonic acid (LAS), carbon number 10-14, average molecular weight 322, manufactured by Lion Corporation).
  • D-2) HOSTAPUR SAS30A (trade name, secondary sodium alkanesulfonate (SAS), manufactured by Clariant Japan).
  • D-3) sodium polyoxyethylene alkyl ether sulfate (AES) (synthetic product, carbon number 12-13, average addition mole number of EO 2 mol, raw alcohol: Neodol 23 (trade name, manufactured by Shell Chemicals)) .
  • AES sodium polyoxyethylene alkyl ether sulfate
  • Neodol 23 alcohol [trade name, manufactured by Shell Chemicals; C12, 13 alcohol (mixture of alcohol ratio of carbon 12 and alcohol of carbon number 1/1), branching ratio 20% by mass 400 g and potassium hydroxide catalyst 0.8 g were charged, the inside of the autoclave was purged with nitrogen, and the temperature was increased while stirring. Thereafter, 272 g of ethylene oxide was introduced while maintaining a temperature of 180 ° C. and a pressure of 0.3 mPa, to obtain a reaction product having an average added mole number of ethylene oxide of 2.
  • E-1 Ethanol (trade name, specific alcohol 95 degree synthesis, manufactured by Nippon Alcohol Sales Co., Ltd.).
  • E-2) Propylene glycol (manufactured by BASF).
  • F-1 Evalase 16L TypeEX (trade name, protease, manufactured by Novozymes)
  • F-2 Recanase Ultra 2.5XL (trade name, protease, manufactured by Novozymes).
  • F-3) Leipex 100L (trade name, lipase, manufactured by Novozymes).
  • F-4) Stainzyme 12L (trade name, amylase, manufactured by Novozymes).
  • ⁇ Common additive component c> Sodium benzoate: 0.5% by mass Citric acid: 0.1% by mass Paratoluenesulfonic acid: 3% by mass Coconut fatty acid: 1.0% by mass Fragrance: 1.75% by mass Green No. 3: 0.0001% by mass Water (purified water): Balance (amount to make the total amount of the liquid detergent composition 100% by mass)
  • Sodium benzoate manufactured by Toagosei Co., Ltd., trade name “Sodium benzoate”.
  • Citric acid trade name “Liquid Citric Acid”, manufactured by Yushi Co., Ltd.
  • Paratoluenesulfonic acid Kyowa Hakko Kogyo Co., Ltd., trade name “PTS acid”.
  • coconut fatty acid NOF Corporation, trade name “Zushi fatty acid”.
  • Polyethylene glycol Product name “PEG # 1000”, manufactured by Lion Corporation.
  • Dibutylhydroxytoluene Sumitomo Chemical Co., Ltd., trade name “SUMILZER BHT-R”.
  • Monoethanolamine manufactured by Nippon Shokubai Co., Ltd.
  • Perfume Perfume component a described in JP-A-2009-108248.
  • Green No. 3 (pigment): Product name “Green No. 3” manufactured by Sakai Kasei Co., Ltd.
  • the details of sodium hydroxide and sulfuric acid used as pH adjusters are as follows. Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd. Sulfuric acid: Toho Zinc Co., Ltd.
  • Sodium benzoate manufactured by Toagosei Co., Ltd., trade name “Sodium benzoate”.
  • Citric acid trade name “Liquid Citric Acid”, manufactured by Yushi Co., Ltd. Palmitic acid: Nippon Oil & Fat Co., Ltd., trade name “NAA-160”.
  • Paratoluenesulfonic acid Kyowa Hakko Kogyo Co., Ltd., trade name “PTS acid”.
  • Polyethylene glycol Product name “PEG # 1000-L60” manufactured by Lion Corporation.
  • Dibutylhydroxytoluene Sumitomo Chemical Co., Ltd., trade name “SUMILZER BHT-R”.
  • Monoethanolamine manufactured by Nippon Shokubai Co., Ltd. Fragrance A fragrance composition A described in Tables 11 to 18 of Japanese Patent Application No. 2002-146399.
  • Green No. 3 (pigment): Product name “Green No. 3” manufactured by Sakai Kasei Co., Ltd.
  • the details of sodium hydroxide and sulfuric acid used as pH adjusters are as follows. Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd. Sulfuric acid: Toho Zinc Co., Ltd.
  • a liquid for clothing that has excellent detergency, anti-recontamination performance and flexibility imparting performance, has good liquid stability, and can wash clothing, particularly hemp clothing, without impairing comfort.
  • a cleaning composition can be provided.
  • a liquid detergent composition for clothes that contains a high concentration and stability of nonionic surfactants, has excellent solubility and washing performance during washing, and is comfortable to wear washed clothes, especially hemp clothes. it can.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Disclosed is a liquid detergent composition for clothes, which comprises a nonionic surfactant (A) represented by the following formula: R1-CO(OR2)mOR3, a nonionic surfactant (B) represented by the following formula: R4-O(R5O)nH, and a solvent (E) selected from the group consisting of a monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms and a glycol ether solvent represented by the following formula: R6-(OR7)kOH. The liquid detergent composition for clothes can contain a nonionic surfactant at a high concentration and stably, has solubility upon washing, excellent washing performance, anti-soil-redeposition performance, softness-imparting performance and good liquid stability, and can wash clothes, particularly linen clothes, without imparting wear comfort of the clothes.

Description

衣料用液体洗浄剤組成物Liquid detergent composition for clothing
　本発明は、衣料用液体洗浄剤組成物に関する。 The present invention relates to a liquid detergent composition for clothing.
　近年、地球環境にやさしい製品の開発、販売の重要性がいっそう増しており、日用品分野でも地球環境に配慮した商品が求められている。
そのような中、物流におけるエネルギー削減やゴミの減量が期待されることから、洗浄剤組成物を収容する容器の小型化が進んでいる。それに伴い、少ない洗剤量で高い洗浄性能を発現する洗浄剤組成物が求められている。たとえば界面活性剤を主基剤とする液体洗浄剤組成物の場合、界面活性剤濃度を高めた濃縮洗剤が求められる。たとえば衣料用洗浄剤組成物の場合、使用量の低減等のため、洗浄力の向上が求められる。
　衣料用の液体洗浄剤組成物としては、非イオン性界面活性剤を主基剤とするものが広く用いられており、従来、非イオン性界面活性剤としては、第１級アルコールエトキシレート等のアルコールアルコキシレートが用いられていた。
　しかし、一般に、界面活性剤は高濃度の領域において、ヘキサゴナル液晶、ラメラ液晶に代表されるリオトロピック液晶などの高粘度の高次会合構造を形成し、典型的な非イオン性界面活性剤であるアルコールエトキシレートも、その濃度が４０質量％以上の高濃度系では、かなり広範な濃度領域で高粘度の液晶相を形成することが知られている。このように、アルコールアルコキシレートは、そのゲル化領域が大きいために、濃度が高くなるにつれて液流動性と安定性が低下し、４０％以上配合した濃縮洗剤とすることは困難である。また、アルコールアルコキシレートを高濃度に含むと、洗濯時に洗濯浴中に投入された際の溶解速度が遅く、特に低温の水で洗濯した場合には、洗濯終了時に衣類にゲル状の付着物が残るなどの不具合を生じやすい。
　このような問題に対し、液流動性と安定性及び溶解速度の向上のために、ハイドロトロープ剤などを配合する方法が知られている。しかし、より高濃度の濃縮洗剤とするためには、洗浄剤組成物中のほとんどをアルコールエトキシレートとハイドロトロープ剤とする必要があり、酵素やキレート剤などの機能成分を配合することが困難となる。ハイドロトロープ剤は、溶解性改善効果はあるものの洗浄性能には全く影響しないことから、上記組成では充分な洗浄性能は得られない。
　一方、脂肪酸アルキルエステルアルコキシレートは、そのゲル化領域が小さいことが知られており、特定の脂肪酸アルキルエステルアルコキシレートを高濃度に配合した洗浄剤組成物も提案されている（たとえば特許文献１～３参照）。　　
　また、家庭用の電気洗濯機でも、省エネ、節水、節電といった技術をキーとして、地球環境に配慮した新型機種が相次いで発売されている。これらの洗濯機では、洗い方（機械力）を工夫しより少ないエネルギーでの洗濯を可能としたり、より少ない水量での洗濯を可能としている。しかし、このような洗い方では、衣料にかかる負荷が大きく、洗濯後に仕上がり感が悪くなる。そのため、洗濯後に良好な仕上がり感を付与できる衣料用洗剤に対する要求が高まっており、たとえば特許文献４～５には、長鎖アミンや陽イオン性界面活性剤などの柔軟性付与成分を含む洗浄剤組成物が開示されている。
　また、最近では、洗濯機の大型化、節水型洗濯機の普及により、より水が少ない条件で、衣料を詰め込んで洗濯する場合が多くなっている。しかし、このような条件で洗濯した場合、洗濯によって落とされた汚れが再び衣料に付着し、洗濯後の衣料がくすんでくるといった再汚染の問題を生じやすい。このような問題に対し、洗浄剤組成物に直鎖アルキルベンゼンスルホン酸塩などの陰イオン性界面活性剤を配合すると、再汚染防止効果が得られることが知られている。 In recent years, the importance of development and sales of products that are friendly to the global environment has increased, and products that are friendly to the global environment are also demanded in the daily necessities field.
Under such circumstances, since the reduction of energy and the amount of waste in logistics are expected, miniaturization of containers for storing the cleaning composition is progressing. Accordingly, there is a demand for a cleaning composition that exhibits high cleaning performance with a small amount of detergent. For example, in the case of a liquid detergent composition having a surfactant as a main base, a concentrated detergent having an increased surfactant concentration is required. For example, in the case of a cleaning composition for clothing, an improvement in cleaning power is required to reduce the amount used.
As liquid detergent compositions for clothing, those based on nonionic surfactants are widely used. Conventionally, as nonionic surfactants, primary alcohol ethoxylates and the like are used. Alcohol alkoxylates have been used.
However, in general, surfactants form alcohols, which are typical nonionic surfactants, in a high concentration region, forming high-viscosity high-order association structures such as lyotropic liquid crystals such as hexagonal liquid crystals and lamellar liquid crystals. It is known that an ethoxylate also forms a highly viscous liquid crystal phase in a considerably wide concentration range in a high concentration system having a concentration of 40% by mass or more. Thus, since the alcohol alkoxylate has a large gelation region, the liquid fluidity and stability are lowered as the concentration is increased, and it is difficult to obtain a concentrated detergent containing 40% or more. In addition, when alcohol alkoxylate is contained at a high concentration, the dissolution rate is slow when it is put into the washing bath at the time of washing. Especially when washing is performed with cold water, gel-like deposits are formed on the clothing at the end of washing. Prone to problems such as remaining.
In order to solve such problems, a method of blending a hydrotrope agent or the like is known in order to improve liquid fluidity, stability and dissolution rate. However, in order to obtain a concentrated detergent with a higher concentration, it is necessary to use alcohol ethoxylate and hydrotrope for most of the detergent composition, and it is difficult to mix functional components such as enzymes and chelating agents. Become. Although the hydrotrope agent has the effect of improving the solubility, it does not affect the cleaning performance at all. Therefore, sufficient cleaning performance cannot be obtained with the above composition.
On the other hand, fatty acid alkyl ester alkoxylates are known to have a small gelling region, and cleaning compositions containing specific fatty acid alkyl ester alkoxylates at high concentrations have also been proposed (for example, Patent Documents 1 to 4). 3).
In addition, new types of household electric washing machines that are friendly to the global environment have been put on the market one after another using technologies such as energy saving, water saving, and power saving as keys. In these washing machines, the washing method (mechanical force) is devised so that washing with less energy is possible, or washing with a smaller amount of water is possible. However, in such a washing method, the load applied to the clothing is large, and the finished feeling becomes worse after washing. Therefore, there is an increasing demand for detergents for clothing that can give a good finish feeling after washing. For example, Patent Documents 4 to 5 describe cleaning agents containing flexibility-imparting components such as long-chain amines and cationic surfactants. A composition is disclosed.
In recent years, with the increase in size of washing machines and the spread of water-saving washing machines, there are many cases where clothes are stuffed and washed under conditions of less water. However, when washing is performed under such conditions, the stains removed by washing again adhere to the clothing, and the problem of re-contamination is likely to occur. In order to solve such a problem, it is known that an anti-staining effect can be obtained when an anionic surfactant such as a linear alkylbenzene sulfonate is added to the cleaning composition.
特開２０００－１８６２９５号公報JP 2000-186295 A 特開２００２－１８００８７号公報Japanese Patent Laid-Open No. 2002-180087 特開２０００－１４４１７８号公報JP 2000-144178 A 特開２００３－２０６５００号公報JP 2003-206500 A 特開２００５－２３１２３号公報JP 2005-23123 A
しかしながら、液体洗浄剤組成物に長鎖アミン、陽イオン性界面活性剤等の柔軟性付与成分と、再汚染防止のために用いられる陰イオン性界面活性剤の両成分を配合した場合、柔軟性付与性能や再汚染防止性能が充分に発揮されなかったり、液体洗浄剤組成物の保存安定性が低下することがある。これは、両成分間の静電気的な相互作用により沈殿を生じやすいためと考えられる。
　一方、液体洗浄剤組成物の主基剤として非イオン性界面活性剤である脂肪酸メチルエステルエトキシレートを用いた場合、比較的このような問題が生じにくい。しかしながら、上記のような脂肪酸アルキルエステルアルコキシレートを高濃度に配合した洗浄剤組成物は、洗浄した衣料の着心地を損なうことがある。この問題は特に麻製衣料の場合に顕著であり、たとえば着用時のハリ感、冷感など、麻製衣料のメリットが損なわれてしまう。
本発明は、上記事情に鑑みてなされたものであって、非イオン性界面活性剤を高濃度かつ安定に含み、洗浄時における溶解性及び洗浄性能に優れ、洗浄した衣料、特に麻製衣料の着心地も良好な衣料用液体洗浄剤組成物を提供することを目的とする。
　本発明は、上記事情に鑑みてなされたものであって、優れた洗浄力、再汚染防止性能及び柔軟性付与性能を有し、液安定性が良好で、しかも着心地を損なうことなく衣料、特に麻製衣料を洗浄できる衣料用液体洗浄剤組成物を提供することを目的とする。 However, when both a softening component such as a long chain amine and a cationic surfactant and an anionic surfactant used to prevent recontamination are blended in the liquid detergent composition, the flexibility The imparting performance and the recontamination preventing performance may not be sufficiently exhibited, or the storage stability of the liquid detergent composition may be lowered. This is presumably because precipitation is likely to occur due to electrostatic interaction between the two components.
On the other hand, when fatty acid methyl ester ethoxylate, which is a nonionic surfactant, is used as the main base of the liquid detergent composition, such problems are relatively unlikely to occur. However, a detergent composition containing a fatty acid alkyl ester alkoxylate as described above at a high concentration may impair the comfort of the washed clothes. This problem is particularly noticeable in the case of hemp clothing, for example, the merit of hemp clothing is impaired, such as a feeling of firmness and coolness when worn.
The present invention has been made in view of the above circumstances, and contains a nonionic surfactant in a high concentration and stability, is excellent in solubility and washing performance during washing, and is used for washed clothes, particularly hemp clothes. An object of the present invention is to provide a liquid detergent composition for clothing having good comfort.
The present invention has been made in view of the above circumstances, has excellent cleaning power, anti-recontamination performance and flexibility imparting performance, good liquid stability, and without impairing comfort, In particular, an object of the present invention is to provide a liquid cleaning composition for clothing that can clean hemp clothing.
　本発明者らは、鋭意検討を重ねた結果、特定の非イオン性界面活性剤と、特定溶剤とを配合することにより上記課題が解決されることを見出し、本発明を完成した。
　上記課題を解決する本発明の第一の態様は、Ｒ１－ＣＯ（ＯＲ２）ｍＯＲ３［式中、Ｒ１は炭素数９～１３のアルキル基又は炭素数９～１３のアルケニル基であり、Ｒ２は炭素数２～４のアルキレン基であり、Ｒ３は炭素数１～３のアルキル基であり、ｍは平均付加モル数を表し５～２５である。］で表される非イオン性界面活性剤（Ａ）と、Ｒ４－Ｏ（Ｒ５Ｏ）ｎＨ［式中、Ｒ４は炭素数１０～２２の炭化水素基であり、Ｒ５は炭素数２～４のアルキレン基であり、ｎは平均付加モル数を表し５～２５である。］で表される非イオン性界面活性剤（Ｂ）と、炭素数２～４の一価アルコール、炭素数２～４の多価アルコール及びＲ１１－（ＯＲ１２）ｋＯＨ［式中、Ｒ１１は炭素数１～６のアルキル基又はフェニル基であり、Ｒ１２は炭素数２～４のアルキレン基であり、ｋは平均付加モル数を表し１～５である。］で表されるグリコールエーテル系溶剤からなる群から選択される溶剤（Ｅ）とを含有する衣料用液体洗浄剤組成物である。
第二の態様は、前記（Ａ）成分及び前記（Ｂ）成分の配合量の合計が、前記液体洗浄剤組成物の総質量に対し、４０～７５質量％であり、前記（Ａ）成分と前記（Ｂ）成分との配合比率（質量比）が（Ｂ）／（Ａ）＝８０／２０～１０／９０であり、前記（Ｅ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、３～２５質量％である第一の態様に記載の衣料用液体洗浄剤組成物である。
第三の態様は、さらに、Ｒ６－Ｎ（Ｒ７）（Ｒ８）［式中、Ｒ６は連結基を有していてもよい炭素数７～２７の炭化水素基であり、Ｒ７及びＲ８はそれぞれ独立して、炭素数１～４のアルキル基、炭素数１～４のヒドロキシアルキル基、又は（Ｒ９Ｏ）ｐＨ［式中、Ｒ９は炭素数２～４のアルキレン基であり、ｐは平均付加モル数を表し１～２５である。］で表される基である。］で表される３級アミン化合物及びその塩からなる群から選択される化合物（Ｃ）を含有する第二の態様に記載の衣料用液体洗浄剤組成物である。
第四の態様は、さらに、ＳＯ３基又はＳＯ４基を有する陰イオン性界面活性剤（Ｄ）及び／又は酵素（Ｆ）を含有する第二の態様に記載の衣料用洗浄剤組成物である。
第五の態様は、前記（Ｃ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、０．１～１０質量％である第三の態様に記載の衣料用洗浄剤組成物である。
第六の態様は、前記（Ｄ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、１～１０質量％である第四の態様に記載の衣料用洗浄剤組成物である。
第七の態様は、前記（Ｆ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、０．１～３質量％である第四の態様に記載の衣料用洗浄剤組成物である。
第八の態様は、さらに、Ｒ６－Ｎ（Ｒ７）（Ｒ８）［式中、Ｒ６は連結基を有していてもよい炭素数７～２７の炭化水素基であり、Ｒ７及びＲ８はそれぞれ独立して、炭素数１～４のアルキル基、炭素数１～４のヒドロキシアルキル基、又は（Ｒ９Ｏ）ｐＨ［式中、Ｒ９は炭素数２～４のアルキレン基であり、ｐは平均付加モル数を表し１～２５である。］で表される基である。］で表される３級アミン化合物及びその塩からなる群から選択される化合物（Ｃ）と、ＳＯ３基又はＳＯ４基を有する陰イオン性界面活性剤（Ｄ）とを含有し、前記（Ａ）成分及び前記（Ｂ）成分の配合量の合計が、前記液体洗浄剤組成物の総質量に対し、１０～６５質量％であり、前記（Ａ）成分と前記（Ｂ）成分との配合比率（質量比）が（Ｂ）／（Ａ）＝８０／２０～１０／９０であり、前記（Ｃ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、０．１～１０質量％であり、前記（Ｄ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、１～２０質量％であり、前記（Ｃ）成分と前記（Ｄ）成分との配合比率（質量比）が（Ｄ）／（Ｃ）＝１／１～１０／１であり、前記（Ｅ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、３～２０質量％である第一の態様に記載の衣料用液体洗浄剤組成物である。
第九の態様は、前記（Ａ）成分と前記（Ｂ）成分との配合比率（質量比）が（Ｂ）／（Ａ）＝７０／３０～２０／８０である第八の実施態様に記載の衣料用液体洗浄剤組成物である。 As a result of intensive studies, the present inventors have found that the above problem can be solved by blending a specific nonionic surfactant and a specific solvent, and have completed the present invention.
A first aspect of the present invention for solving the above problems is 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. R 2 represents an alkylene group having 2 to 4 carbon atoms, R 3 represents an alkyl group having 1 to 3 carbon atoms, and m represents an average added mole number and is 5 to 25. And a nonionic surfactant (A) represented by the formula: R 4 —O (R 5 O) n H [wherein R 4 is a hydrocarbon group having 10 to 22 carbon atoms, and R 5 is carbon An alkylene group having a number of 2 to 4, and n represents an average addition mole number and is 5 to 25. A nonionic surfactant (B) represented by the formula: 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 added mole number and is 1 to 5. ] The liquid cleaning composition for clothes containing the solvent (E) selected from the group which consists of a glycol ether solvent represented by these.
In a second aspect, the total amount of the component (A) and the component (B) is 40 to 75% by mass with respect to the total mass of the liquid detergent composition, and the component (A) The blending ratio (mass ratio) with the component (B) is (B) / (A) = 80/20 to 10/90, and the blending amount of the component (E) is the total amount of the liquid detergent composition. The liquid detergent composition for clothing according to the first aspect, which is 3 to 25% by mass relative to the mass.
In the third aspect, R 6 —N (R 7 ) (R 8 ) [wherein R 6 is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group, and 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 having 2 to 4 carbon atoms. And p represents an average added mole number and is 1 to 25. ]. ] The liquid cleaning composition for clothes as described in the 2nd aspect containing the compound (C) selected from the group which consists of a tertiary amine compound represented by these, and its salt.
A fourth aspect is further in laundry detergent composition according to the second embodiment containing the anionic surfactants having an SO 3 group or SO 4 group (D) and / or enzyme (F) is there.
In a fifth aspect, the detergent composition for clothing according to the third aspect, wherein the blending amount of the component (C) is 0.1 to 10% by mass with respect to the total mass of the liquid detergent composition. It is.
A sixth aspect is the garment cleaning composition according to the fourth aspect, wherein the blending amount of the component (D) is 1 to 10% by mass relative to the total mass of the liquid cleaning composition. .
In a seventh aspect, the detergent composition for clothing according to the fourth aspect, wherein the blending amount of the component (F) is 0.1 to 3% by mass with respect to the total mass of the liquid detergent composition It is.
In the eighth aspect, R 6 —N (R 7 ) (R 8 ) [wherein R 6 is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group, and 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 having 2 to 4 carbon atoms. And p represents an average added mole number and is 1 to 25. ]. A compound (C) selected from the group consisting of a tertiary amine compound represented by the following formula: and an anionic surfactant (D) having a SO 3 group or a SO 4 group, The total amount of component A) and component (B) is 10 to 65% by mass relative to the total mass of the liquid detergent composition, and the combination of component (A) and component (B) The ratio (mass ratio) is (B) / (A) = 80/20 to 10/90, and the blending amount of the component (C) is from 0.1 to the total mass of the liquid detergent composition. 10% by mass, and the blending amount of the component (D) is 1 to 20% by mass with respect to the total mass of the liquid detergent composition, and the blending of the component (C) and the component (D) The ratio (mass ratio) is (D) / (C) = 1/1 to 10/1, and the amount of the component (E) is the liquid detergent composition Based on the total weight of a laundry liquid detergent composition according to the first aspect is 3 to 20 mass%.
A ninth aspect is the eighth aspect, wherein the blending ratio (mass ratio) of the component (A) and the component (B) is (B) / (A) = 70/30 to 20/80. This is a liquid detergent composition for clothing.
　本発明によれば、優れた洗浄力、再汚染防止性能及び柔軟性付与性能を有し、液安定性が良好で、しかも着心地を損なうことなく衣料、特に麻製衣料を洗浄できる衣料用液体洗浄剤組成物を提供できる。
また、非イオン性界面活性剤を高濃度かつ安定に含み、洗浄時における溶解性及び洗浄性能に優れ、洗浄した衣料、特に麻製衣料の着心地も良好な衣料用液体洗浄剤組成物を提供できる。 According to the present invention, a liquid for clothing that has excellent detergency, anti-recontamination performance and flexibility imparting performance, has good liquid stability, and can wash clothing, particularly hemp clothing, without impairing comfort. A cleaning composition can be provided.
Also provided is a liquid detergent composition for clothes that contains a high concentration and stability of nonionic surfactants, has excellent solubility and washing performance during washing, and is comfortable to wear washed clothes, especially hemp clothes. it can.
　本発明の第一の態様における衣料用液体洗浄剤組成物（以下、液体洗浄剤組成物ということがある。）は、以下に示す（Ａ）、（Ｂ）、及び（Ｅ）成分を含有する。
本発明の第二の態様における衣料用液体洗浄剤組成物は、以下に示す（Ａ）、（Ｂ）、及び（Ｅ）成分を含有する。
本発明の第三の態様及び第五の態様における衣料用液体洗浄剤組成物は、以下に示す（Ａ）、（Ｂ）、（Ｅ）及び（Ｃ）成分を含有する。
本発明の第四の態様、第六の態様及び第七の態様における衣料用液体洗浄剤組成物は、以下に示す（Ａ）、（Ｂ）、及び（Ｄ）～（Ｆ）成分を含有する。
本発明の第八の態様及び第九の態様における衣料用液体洗浄剤組成物は、以下に示す（Ａ）～（Ｅ）成分を含有する。 The liquid detergent composition for clothing in the first aspect of the present invention (hereinafter sometimes referred to as “liquid detergent composition”) contains the following components (A), (B), and (E). .
The liquid cleaning composition for clothing in the second aspect of the present invention contains the following components (A), (B), and (E).
The liquid cleaning composition for clothing in the third aspect and the fifth aspect of the present invention contains the following components (A), (B), (E) and (C).
The liquid detergent composition for clothing according to the fourth, sixth and seventh aspects of the present invention contains the following components (A), (B) and (D) to (F): .
The liquid detergent composition for clothing in the eighth and ninth aspects of the present invention contains the following components (A) to (E).
＜（Ａ）成分＞
　（Ａ）成分は、Ｒ１－ＣＯ（ＯＲ２）ｍＯＲ３で表される非イオン性界面活性剤である。
　式中、Ｒ１は炭素数９～１３のアルキル基又は炭素数９～１３のアルケニル基である。炭素数が上記範囲内であることにより、洗浄力やゲル化防止性に優れる。前記アルキル基及びアルケニル基の炭素数は、それぞれ、１０～１３であることが好ましく、１１～１３であることがより好ましい。
　前記アルキル基及びアルケニル基は、それぞれ、直鎖状又は分岐鎖状であることが好ましい。Ｒ１の具体例としては、Ｃ９Ｈ１９，Ｃ１０Ｈ２１，Ｃ１１Ｈ２３，Ｃ１２Ｈ２５，Ｃ１３Ｈ２７，Ｃ１３Ｈ２５などが挙げられる。なかでもＣ９Ｈ１９，Ｃ１１Ｈ２３，Ｃ１３Ｈ２７が好ましく、Ｃ１１Ｈ２３，Ｃ１３Ｈ２７がより好ましい。
　Ｒ２は炭素数２～４のアルキレン基であり、エチレン基又はプロピレン基が好ましい。式中の複数のＲ２はそれぞれ同じであってもよく異なってもよい。すなわち、Ｒ２のアルキレン基として、１種類のみを単独で用いてもよく、複数種組み合わせてもよい。たとえばエチレン基とプロピレン基を含む場合、エチレンオキサイドとプロピレンオキサイドの付加方法は、例えばランダム付加であってもよく、エチレンオキサイドを付加した後、プロピレンオキサイドを付加する、またはプロピレンオキサイドを付加した後、エチレンオキサイドを付加する、あるいはエチレンオキサイドを付加した後、プロピレンオキサイドを付加しさらにエチレンオキサイドを付加するブロック付加でもよい。
　上記のなかでも、洗浄時の泡立ちが良く、安価であることから、少なくとも１つのＲ２がエチレン基であることが好ましい。
　Ｒ３は炭素数１～３のアルキル基であり、メチル基が好ましい。
　ｍはアルキレンオキサイドの平均付加モル数を表し、５～２５である。ｍが前記範囲内であることで、洗浄力、特に皮脂汚れに対する洗浄力が向上する。また、洗浄剤組成物の溶解性が向上する。エチレンオキサイド付加体である場合、ｍは５～２０が好ましく、１２～１８がより好ましい。
エチレンオキサイドとプロピレンオキサイドとを組み合わせた付加体である場合、ｍは５～２５、特に好ましくは１２～２１であり、このうちプロピレンオキサイドの平均付加モル数は０～５であり、０～４が好ましく、０～３が特に好ましい。プロピレンオキサイドの平均付加モル数が５を超えると、洗浄力、液体洗剤としての初期外観と安定性が悪くなる。
（Ａ）成分の具体例としては、脂肪酸アルキルエトキシレート、脂肪酸アルキルエステルのエチレンオキサイドとプロピレンオキサイドの付加物などが挙げられる。なかでも脂肪酸メチルエステルエトキシレート、脂肪酸メチルエステルのエチレンオキサイドとプロピレンオキサイドの付加物が好ましく、ラウリン酸メチルエトキシレート、ミリスチン酸メチルエステルエトキシレート、ヤシ脂肪酸メチルエステルエトキシレートがより好ましい。ここで、アルキレンオキサイドの平均付加モル数が、１５であることが最も好ましい。 <(A) component>
The component (A) is a nonionic surfactant represented by R 1 —CO (OR 2 ) m OR 3 .
In the formula, 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, the detergency and gelation resistance are excellent. The alkyl group and alkenyl group preferably have 10 to 13 carbon atoms, more preferably 11 to 13 carbon atoms.
Each of the alkyl group and the alkenyl group is preferably linear or branched. 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 , C 13 H 25 and the like. Of these, 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, preferably an ethylene group or a propylene group. A plurality of R 2 in the formula may be the same or different. That is, as the alkylene group for R 2 , only one type may be used alone, or a plurality of types may be combined. For example, when an ethylene group and a propylene group are included, the addition method of ethylene oxide and propylene oxide may be, for example, random addition. After adding ethylene oxide, after adding propylene oxide, or after adding propylene oxide, Block addition in which ethylene oxide is added or ethylene oxide is added, followed by propylene oxide and further ethylene oxide may be used.
Among the above, it is preferable that at least one R 2 is an ethylene group because foaming during washing is good and inexpensive.
R 3 is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.
m represents the average number of moles of alkylene oxide added and is 5 to 25. When m is within the above range, the cleaning power, particularly the cleaning power against sebum dirt is improved. Moreover, the solubility of a cleaning composition improves. In the case of an ethylene oxide adduct, m is preferably 5 to 20, and more preferably 12 to 18.
When the adduct is a combination of ethylene oxide and propylene oxide, m is 5 to 25, particularly preferably 12 to 21, of which the average added mole number of propylene oxide is 0 to 5, 0 to 3 are particularly preferable. When the average added mole number of propylene oxide exceeds 5, detergency, initial appearance and stability as a liquid detergent are deteriorated.
Specific examples of the component (A) include fatty acid alkyl ethoxylates, adducts of fatty acid alkyl esters with ethylene oxide and propylene oxide, and the like. Of these, fatty acid methyl ester ethoxylates and adducts of fatty acid methyl esters of ethylene oxide and propylene oxide are preferred, and lauric acid methyl ethoxylate, myristic acid methyl ester ethoxylate, and coconut fatty acid methyl ester ethoxylate are more preferred. Here, the average added mole number of alkylene oxide is most preferably 15.
　（Ａ）成分において、アルキレンオキサイドの付加モル数が異なるアルキレンオキサイド付加体の分布の割合を示すナロー率は、２０質量％以上であることが好ましく、上限値としては実質的には８０質量％以下であることが好ましい。当前記ナロー率は、２０～５０質量％であることがより好ましく、保存安定性が向上するため、３０～４５質量％がさらに好ましい。
　前記ナロー率は高いほど、良好な洗浄力が得られる。また、当該ナロー率が２０質量％以上、特に３０質量％以上であると、界面活性剤の原料臭気の少ない液体洗浄剤組成物が得られやすくなる。これは、（Ａ）成分の製造後、（Ａ）成分と共存する（Ａ）成分の原料である脂肪酸エステルと前記式中のｍが１又は２のアルキレンオキサイド付加体が少なくなるためである。
　ここで、本明細書において「ナロー率」とは、アルキレンオキサイドの付加モル数が異なるアルキレンオキサイド付加体の分布の割合を示す下記の数式（Ｓ）で表されるものを意味する。 In the component (A), the narrow ratio indicating the proportion of the distribution of alkylene oxide adducts having different numbers of added moles of alkylene oxide is preferably 20% by mass or more, and the upper limit is substantially 80% by mass or less. It is preferable that The narrow ratio is more preferably 20 to 50% by mass, and more preferably 30 to 45% by mass in order to improve storage stability.
The higher the narrow rate, the better the cleaning power. Moreover, when the said narrow rate is 20 mass% or more, especially 30 mass% or more, it will become easy to obtain the liquid detergent composition with few raw material odors of 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 1 or 2 in the above formula are reduced.
Here, the “narrow ratio” in the present specification means that represented by the following formula (S) indicating the distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide.
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　式（Ｓ）中、ｎｍａｘは、全体のアルキレンオキサイド付加体中に最も多く存在するアルキレンオキサイド付加体のアルキレンオキサイドの付加モル数を示す。
　ｉはアルキレンオキサイドの付加モル数を示す。
　Ｙｉは全体のアルキレンオキサイド付加体中に存在するアルキレンオキサイドの付加モル数がｉであるアルキレンオキサイド付加体の割合（質量％）を示す。
　前記ナロー率は、例えば前記（Ａ）成分の製造方法等によって制御することができる。
　（Ａ）成分の製造方法としては、特に限定されるものではないが、例えば表面改質された複合金属酸化物触媒を用いて、脂肪酸アルキルエステルにアルキレンオキサイドを付加重合させる方法（特開２０００－１４４１７９号公報参照）により容易に製造することができる。
　かかる表面改質された複合金属酸化物触媒の好適なものとしては、具体的には、金属水酸化物等により表面改質された金属イオン（Ａｌ３＋、Ｇａ３＋、Ｉｎ３＋、Ｔｌ３＋、Ｃｏ３＋、Ｓｃ３＋、Ｌａ３＋、Ｍｎ２＋等）が添加された酸化マグネシウム等の複合金属酸化物触媒や金属水酸化物及び／又は金属アルコキシド等により表面改質されたハイドロタルサイトの焼成物触媒である。
　また、前記複合金属酸化物触媒の表面改質においては、複合金属酸化物と、金属水酸化物及び／又は金属アルコキシドとの混合割合を、複合金属酸化物１００質量部に対して、金属水酸化物及び／又は金属アルコキシドの割合を０．５～１０質量部とすることが好ましく、１～５質量部とすることがより好ましい。
　本発明の液体洗浄剤組成物において、（Ａ）成分は、一種類のみを単独で用いてもよく、複数種類を組み合わせて使用してもよい。 In the formula (S), n max represents the number of added moles of alkylene oxide of the alkylene oxide adduct most present in the entire alkylene oxide adduct.
i represents the number of added moles of alkylene oxide.
Yi represents the proportion (% by mass) of the alkylene oxide adduct having an added mole number of alkylene oxides i present in the entire alkylene oxide adduct.
The narrow rate can be controlled by, for example, the method for producing the component (A).
The method for producing the component (A) is not particularly limited. For example, a method of addition polymerization of an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP 2000-2000A). 144194179)).
Specific examples of such a surface-modified composite metal oxide catalyst include, specifically, metal ions (Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 1) that have been surface-modified with a metal hydroxide or the like. 3+ , Sc 3+ , La 3+ , Mn 2+, etc.) and a hydrotalcite calcined catalyst whose surface has been modified by a composite metal oxide catalyst such as magnesium oxide or a metal hydroxide and / or metal alkoxide is there.
In the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is changed to metal hydroxide with respect to 100 parts by mass of the composite metal oxide. The ratio of the product and / or metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.
In the liquid detergent composition of the present invention, as the component (A), only one type may be used alone, or a plurality of types may be used in combination.
＜（Ｂ）成分＞
　（Ｂ）成分は、Ｒ４－Ｏ（Ｒ５Ｏ）ｎＨで表される非イオン性界面活性剤である。
　（Ｂ）成分は、アルコール（Ｒ４－ＯＨ）に炭素数２～４の酸化アルキレンが平均付加モル数ｎにて付加したアルコールアルコキシレートである。
　式中、Ｒ４は炭素数１０～２２の炭化水素基である。炭素数が１０以上であることで皮脂汚れに対する洗浄力が向上し、２２以下であることで液体洗浄剤組成物としての溶解性と液安定性が向上する。前記炭化水素基の炭素数は、１０～２０が好ましく、１０～１８がより好ましい。前記炭化水素基は、脂肪族炭化水素基（芳香族性を有さない炭化水素基）であることが好ましい。前記炭化水素基は、不飽和結合を有してよく、有さなくてもよい。前記炭化水素基は、直鎖状又は分岐鎖状であることが好ましい。
　Ｒ４は、単一鎖長であってもよく、複数の鎖長の混合物であってもよい。
　Ｒ４は原料のアルコール（Ｒ４－ＯＨ）に由来し、前記アルコールとしては、ヤシ油、パーム油、牛脂などの天然油脂由来のアルコールや石油由来の合成アルコールが挙げられる。 <(B) component>
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) with an average addition mole number n.
In the formula, R 4 is a hydrocarbon group having 10 to 22 carbon atoms. When the carbon number is 10 or more, the detergency against sebum stains is improved, and when it is 22 or less, the solubility and liquid stability as the liquid detergent composition are improved. The hydrocarbon group preferably has 10 to 20 carbon atoms, and more preferably 10 to 18 carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group (a hydrocarbon group having no aromaticity). The said hydrocarbon group may have an unsaturated bond and does not need to have it. The hydrocarbon group is preferably linear or branched.
R 4 may be a single chain length or a mixture of a plurality of chain lengths.
R 4 is derived from a raw material alcohol (R 4 —OH), and examples of the alcohol include alcohols derived from natural fats and oils such as coconut oil, palm oil, and beef tallow, and synthetic alcohols derived from petroleum.
　Ｒ５は炭素数２～４のアルキレン基であり、エチレン基又はプロピレン基が好ましい。式中の複数のＲ５はそれぞれ同じであってもよく異なってもよい。すなわち、Ｒ５のアルキレン基として、１種類のみを単独で用いてもよく、複数種組み合わせてもよい。たとえばエチレン基とプロピレン基を含む場合、エチレンオキサイドとプロピレンオキサイドの付加方法は、例えばランダム付加であってもよく、エチレンオキサイドを付加した後、プロピレンオキサイドを付加する、またはプロピレンオキサイドを付加した後、エチレンオキサイドを付加する、あるいはエチレンオキサイドを付加した後、プロピレンオキサイドを付加しさらにエチレンオキサイドを付加するブロック付加でもよい。
　上記のなかでも、洗浄時の泡立ちが良く、安価であることから、Ｒ５が少なくとも１つのエチレン基であることが好ましい。
　ｎはアルキレンオキサイドの平均付加モル数を表し、５～２５である。ｎが前記範囲内であると、皮脂汚れに対し優れた洗浄力を示す。また、ｎが５以上であると、さらに、臭気の劣化を防ぐこともできる。一方、ｎが２５を超えると、ＨＬＢ（Hydrophile-Lipophile Balance）が高くなりすぎて皮脂汚れに対する洗浄力が低下する。エチレンオキサイド付加体の場合、ｎは５～２０が好ましく、８～１８がより好ましく、１０～１６が特に好ましい。
エチレンオキサイドとプロピレンオキサイドとを組み合わせた付加体の場合、ｎは５～２５、好ましくは８～２２、特に好ましくは１０～１９であり、このうちプロピレンオキサイドの平均付加モル数は０～５であり、０～４が好ましく、０～３が特に好ましい。プロピレンオキサイドの平均付加モル数が５を超えると、洗浄力、液体洗剤としての初期外観と安定性が悪くなる。 R 5 is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group. A plurality of R 5 in the formula may be the same or different. That is, as the alkylene group for R 5 , only one type may be used alone, or a plurality of types may be combined. For example, when an ethylene group and a propylene group are included, the addition method of ethylene oxide and propylene oxide may be, for example, random addition. After adding ethylene oxide, after adding propylene oxide, or after adding propylene oxide, Block addition in which ethylene oxide is added or ethylene oxide is added, followed by propylene oxide and further ethylene oxide may be used.
Among these, it is preferable that R 5 is at least one ethylene group because foaming during washing is good and inexpensive.
n represents the average number of added moles of alkylene oxide, and is 5 to 25. When n is within the above range, an excellent detergency against sebum dirt is exhibited. Further, when n is 5 or more, it is possible to further prevent odor degradation. On the other hand, when n exceeds 25, HLB (Hydrophile-Lipophile Balance) becomes too high, and the detergency against sebum dirt decreases. In the case of an ethylene oxide adduct, n is preferably 5 to 20, more preferably 8 to 18, and particularly preferably 10 to 16.
In the case of an adduct in which ethylene oxide and propylene oxide are combined, n is 5 to 25, preferably 8 to 22, particularly preferably 10 to 19, and of these, the average added mole number of propylene oxide is 0 to 5 0 to 4 are preferable, and 0 to 3 are particularly preferable. When the average added mole number of propylene oxide exceeds 5, detergency, initial appearance and stability as a liquid detergent are deteriorated.
　（Ｂ）成分において、アルキレンオキサイドの付加モル数分布は特に限定されない。前記分布は、（Ｂ）成分の製造時の反応方法によって変動し、例えば、一般的な水酸化ナトリウムや水酸化カリウムなどのアルカリ触媒を用いて酸化エチレンを疎水性原料に付加させた際には、比較的広い分布となる傾向にある。また、特公平６－１５０３８号公報に記載のＡｌ３＋、Ｇａ３＋、Ｉｎ３＋、Ｔｌ３＋、Ｃｏ３＋、Ｓｃ３＋、Ｌａ３＋、Ｍｎ２＋等の金属イオンを添加した酸化マグネシウム等の特定のアルコキシル化触媒を用いて酸化エチレンを疎水基原料に付加させた際には、比較的狭い分布となる傾向にある。 In the component (B), the addition mole number distribution of the alkylene oxide is not particularly limited. The distribution varies depending on the reaction method during the production of the component (B). For example, when ethylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. , Tend to have a relatively wide distribution. Also, specific alkoxylation such as magnesium oxide added with metal ions such as Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , Mn 2+, etc. described in JP-B-6-15038 When ethylene oxide is added to a hydrophobic group raw material using a catalyst, the distribution tends to be relatively narrow.
　（Ｂ）成分の具体例としては、第１級アルコール由来のものとして、Ｓｈｅｌｌ製：商品名Ｎｅｏｄｏｌ（Ｃ１２／Ｃ１３）、Ｓａｓｏｌ製：Ｓａｆｏｌ２３（Ｃ１２／Ｃ１３）等のアルコールに対して、１２及び、１５モル相当の酸化エチレンを付加したもの、Ｐ＆Ｇ社製：商品名ＣＯ－１２１４やＣＯ－１２７０等の天然アルコールに９、１２及び、１５モル相当の酸化エチレンを付加したものなどが挙げられる。また、第２級アルコール由来のものの具体例としては、炭素数１２～１４の第２級アルコールに９、１２及び、１５モル相当の酸化エチレンを付加したもの（日本触媒（株）製、ソフタノール９０、１２０及び、１５０）などが挙げられる。
　本発明の液体洗浄剤組成物において、（Ｂ）成分は、一種類のみを単独で用いてもよく、複数種類を組み合わせて使用してもよい。 As specific examples of the component (B), those derived from primary alcohol, manufactured by Shell: trade name Neodol (C12 / C13), manufactured by Sasol: Safol23 (C12 / C13), etc., 12 and Examples include those obtained by adding ethylene oxide equivalent to 15 mol, and those manufactured by P & G: natural alcohols such as trade names CO-1214 and CO-1270 to which 9, 12 and 15 mol equivalent ethylene oxide are added. Specific examples of those derived from secondary alcohols are those obtained by adding 9, 12, and 15 moles of ethylene oxide to secondary alcohols having 12 to 14 carbon atoms (Nippon Shokubai Co., Ltd., Softanol 90 120 and 150).
In the liquid detergent composition of the present invention, the component (B) may be used alone or in combination of two or more.
　上記（Ａ）成分及び（Ｂ）成分は、本発明の液体洗浄剤組成物へ洗浄力を付与することを主目的として配合される。
これらのうち、第一の態様において、（Ａ）成分の配合量は、前記液体洗浄剤組成物の総質量に対して、２～６７．５質量％が好ましく、４．５～５６質量％がより好ましく、８～４２質量％がさらに好ましい。
　また、（Ｂ）成分の配合量は、前記液体洗浄剤組成物の総質量に対して、１～６０質量％が好ましく、１．５～４９質量％がより好ましく、２～３６質量％がさらに好ましい。
　ただし、第一の態様において、本発明の液体洗浄剤組成物においては、（Ａ）成分及び（Ｂ）成分の配合量の合計が、前記液体洗浄剤組成物の総質量に対し、１０～７５質量％であることが必要である。前記合計量は、１５～７０質量％が好ましく、２０～６５質量％がより好ましい。前記合計が１０質量％以上であると、液体洗浄剤組成物に高い洗浄力を与えることができる。一方、７５質量％を超えると、ゲル化が生じやすく、液体洗浄剤組成物としての安定性が低下する。
また、本発明の第一の態様において、液体洗浄剤組成物中、（Ａ）成分と（Ｂ）成分との配合比率（質量比）は、（Ｂ）／（Ａ）＝８０／２０～１０／９０であり、７０／３０～２０／８０が好ましく、６０／４０～２０／８０がより好ましい。（Ｂ）の比率が高すぎると、組成物の粘度が高くなって、計量カップに注ぎにくいなど、使用性が悪くなる。また、ゲル化を生じるため液体洗浄剤組成物としての液流動性と安定性が低下し、また、洗濯後の衣料にゴワツキがあるなど、着心地に劣る。
一方、（Ａ）の比率が高すぎると、洗濯後の衣料のハリ感が少なく、着心地に劣る。
また、（Ａ）成分の配合量は、本発明の第二の態様ないし第七の態様において、前記液体洗浄剤組成物の総質量に対して、８～６７．５質量％が好ましく、１３．５～５６質量％がより好ましく、２０～４２質量％がさらに好ましい。
（Ｂ）成分の配合量は、前記液体洗浄剤組成物の総質量に対して、４～６０質量％が好ましく、９～４９質量％がより好ましく、１５～３６質量％がさらに好ましい。ただし、本発明の液体洗浄剤組成物においては、（Ａ）成分及び（Ｂ）成分の配合量の合計が、前記液体洗浄剤組成物の総質量に対し、４０～７５質量％であることが必要である。前記合計量は、４５～７０質量％が好ましく、５０～６５質量％がより好ましい。前記合計が４０質量％以上であると、液体洗浄剤組成物に高い洗浄性能を与えることができる。一方、７５質量％を超えると、ゲル化が生じやすく、液体洗浄剤組成物としての安定性が低下する。
また、本発明の第二の態様ないし第七の態様において、液体洗浄剤組成物中、（Ａ）成分と（Ｂ）成分との配合比率（質量比）は、（Ｂ）／（Ａ）＝８０／２０～１０／９０であり、７０／３０～２０／８０が好ましく、６０／４０～２０／８０がより好ましい。（Ｂ）の比率が高すぎると、ゲル化を生じるため液体洗浄剤組成物としての液流動性と安定性が低下し、また、洗濯後の衣料にゴワツキがあるなど、着心地に劣る。また、（Ａ）の比率が高すぎると、洗濯後の衣料のハリ感が少なく、着心地に劣る。
　また、第八の態様及び第九の態様において、（Ａ）成分の配合量は、前記液体洗浄剤組成物の総質量に対して、２～５８．５質量％が好ましく、４．５～４８質量％がより好ましく、８～３８．５質量％がさらに好ましい。
　また、（Ｂ）成分の配合量は、前記液体洗浄剤組成物の総質量に対して、１～５２質量％が好ましく、１．５～４２質量％がより好ましく、２～３３質量％がさらに好ましい。
　ただし、第八の態様及び第九の態様において、本発明の液体洗浄剤組成物においては、（Ａ）成分及び（Ｂ）成分の配合量の合計が、前記液体洗浄剤組成物の総質量に対し、１０～６５質量％であることが必要である。前記合計量は、１５～６０質量％が好ましく、２０～５５質量％がより好ましい。前記合計が１０質量％以上であると、液体洗浄剤組成物に高い洗浄力を与えることができる。一方、６５質量％を超えると、ゲル化が生じやすく、また、（Ｃ）成分や（Ｄ）成分を安定に配合できず、液体洗浄剤組成物としての安定性が低下する。
また、本発明の液体洗浄剤組成物中、（Ａ）成分と（Ｂ）成分との配合比率（質量比）は、（Ｂ）／（Ａ）＝８０／２０～１０／９０であり、７０／３０～２０／８０が好ましく、６０／４０～２５／７５がより好ましい。（Ｂ）の比率が高すぎると、組成物の粘度が高くなって、計量カップに注ぎにくいなど、使用性が悪くなる。また、ゲル化が生じたり、洗浄後の衣料の着心地が悪くなるおそれもある。
一方、（Ａ）の比率が高すぎると、洗濯後の衣料、特に麻製衣料のハリ感が少なく、着心地に劣る。 The component (A) and the component (B) are blended mainly for the purpose of imparting detergency to the liquid detergent composition of the present invention.
Among these, in the first embodiment, the blending amount of the component (A) is preferably 2 to 67.5% by mass, and 4.5 to 56% by mass with respect to the total mass of the liquid detergent composition. More preferred is 8 to 42% by mass.
The blending amount of the component (B) is preferably 1 to 60% by mass, more preferably 1.5 to 49% by mass, and further preferably 2 to 36% by mass with respect to the total mass of the liquid detergent composition. preferable.
However, in the first aspect, in the liquid detergent composition of the present invention, the total amount of the component (A) and the component (B) is 10 to 75 with respect to the total mass of the liquid detergent composition. It is necessary to be mass%. The total amount is preferably 15 to 70% by mass, and more preferably 20 to 65% by mass. When the total is 10% by mass or more, a high detergency can be given to the liquid detergent composition. On the other hand, when it exceeds 75% by mass, gelation tends to occur, and the stability as a liquid detergent composition is lowered.
In the first embodiment 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. When the ratio of (B) is too high, the viscosity of the composition becomes high, and the usability deteriorates, such as being difficult to pour into a measuring cup. In addition, since gelation occurs, the fluidity and stability of the liquid detergent composition are reduced, and the clothes after washing are not comfortable to wear.
On the other hand, if the ratio of (A) is too high, there will be little elasticity of the clothes after washing, and it will be inferior to comfort.
The blending amount of the component (A) is preferably 8 to 67.5% by mass with respect to the total mass of the liquid detergent composition in the second to seventh aspects of the present invention. 5 to 56% by mass is more preferable, and 20 to 42% by mass is more preferable.
The blending amount of component (B) is preferably 4 to 60% by mass, more preferably 9 to 49% by mass, and still more preferably 15 to 36% by 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 component (A) and the component (B) is 40 to 75% by mass with respect to the total mass of the liquid detergent composition. is necessary. The total amount is preferably 45 to 70% by mass, and more preferably 50 to 65% by mass. When the total is 40% by mass or more, high cleaning performance can be imparted to the liquid detergent composition. On the other hand, when it exceeds 75% by mass, gelation tends to occur, and the stability as a liquid detergent composition is lowered.
In the second aspect to the seventh aspect of the present invention, in the liquid detergent composition, the blending ratio (mass ratio) of the component (A) and the component (B) is (B) / (A) = 80/20 to 10/90, preferably 70/30 to 20/80, and more preferably 60/40 to 20/80. When the ratio of (B) is too high, gelation occurs, so that the liquid fluidity and stability as the liquid detergent composition are lowered, and the clothes after washing are not comfortable to wear, for example. Moreover, when the ratio of (A) is too high, there is little elasticity of the clothes after washing, and it is inferior to comfort.
In the eighth and ninth aspects, the blending amount of the component (A) is preferably 2 to 58.5% by mass, and 4.5 to 48% with respect to the total mass of the liquid detergent composition. % By mass is more preferable, and 8 to 38.5% by mass is even more preferable.
The blending amount of the component (B) is preferably 1 to 52% by mass, more preferably 1.5 to 42% by mass, and further preferably 2 to 33% by mass with respect to the total mass of the liquid detergent composition. preferable.
However, in the eighth aspect and the ninth aspect, in the liquid detergent composition of the present invention, the total amount of the component (A) and the component (B) is the total mass of the liquid detergent composition. On the other hand, it should be 10 to 65% by mass. The total amount is preferably 15 to 60% by mass, and more preferably 20 to 55% by mass. When the total 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 is likely to occur, and the (C) component and (D) component cannot be blended stably, and the stability as a liquid detergent composition is lowered.
In the liquid detergent composition of the present invention, the blending ratio (mass ratio) of the component (A) and the component (B) is (B) / (A) = 80/20 to 10/90, 70 / 30 to 20/80 is preferable, and 60/40 to 25/75 is more preferable. When the ratio of (B) is too high, the viscosity of the composition becomes high, and the usability deteriorates, such as being difficult to pour into a measuring cup. Moreover, there exists a possibility that gelatinization may arise or the comfort of the clothes after washing | cleaning may worsen.
On the other hand, if the ratio of (A) is too high, the clothes after washing, particularly hemp clothes, are less elastic and inferior in comfort.
　（Ａ）成分と（Ｂ）成分との配合比率が上記範囲内であることは、特に、麻のような硬い繊維からなる衣料に対する仕上がり感の向上に寄与する。
　その理由としては以下のことが考えられる。
　洗濯後の衣料に残留した非イオン性界面活性剤は、硬さ（きしみ感）を与える。（Ａ）成分は、（Ｂ）成分に比べて、すすぎ性に優れるために、洗濯後の衣料に（Ａ）成分はほとんど残留しない。（Ａ）成分単独で液体洗浄剤組成物とした場合、界面活性剤はほとんど残留しないため、麻のような硬い繊維からなる衣料に対する仕上がり感に劣り、適度な着心地感が損なわれる。一方、（Ｂ）成分単独で液体洗浄剤組成物とした場合、洗濯後の衣料に残留する（Ｂ）成分量は比較的多く、硬く（きしむ）なる。そのため、（Ｂ）成分と（Ａ）成分とを特定比率で併用することで、残留量が適度な範囲内となり、少なくなるため、適度な仕上がり感となると推測される。
　したがって、本発明の液体洗浄剤組成物は、特に、麻を用いた衣料用としての有用性が高い。麻は吸湿性に優れ、さらに繊維表面が硬いため、肌に触れたときに冷感を与え、春夏物衣料に適する。 That the blending ratio of the component (A) and the component (B) is within the above range contributes particularly to an improvement in finishing feeling for clothing made of hard fibers such as hemp.
The reason is considered as follows.
The nonionic surfactant remaining in the clothes after washing gives hardness (squeak feeling). Since the component (A) is superior to the component (B) in rinsing properties, the component (A) hardly remains in the clothes after washing. When the component (A) alone is used as a liquid detergent composition, the surfactant hardly remains, so that the finish feeling for clothing made of hard fibers such as hemp is inferior, and an appropriate feeling of comfort is impaired. On the other hand, when the component (B) is used as a liquid detergent composition, the amount of the component (B) remaining in the clothes after washing is relatively large and hard (squeaks). Therefore, it is presumed that by using the component (B) and the component (A) in combination at a specific ratio, the residual amount falls within an appropriate range and decreases, resulting in an appropriate finish feeling.
Therefore, the liquid detergent composition of the present invention is particularly useful for apparel using hemp. Hemp is excellent in hygroscopicity, and the fiber surface is hard, so it gives a cool feeling when touching the skin and is suitable for spring and summer clothing.
＜（Ｃ）成分＞
　（Ｃ）成分は、Ｒ６－Ｎ（Ｒ７）（Ｒ８）で表される３級アミン化合物及びその塩からなる群から選択される化合物である。
　（Ｃ）成分は、綿、ポリエステル、アクリルなどの衣類への柔軟性付与性能を本発明の液体洗浄剤組成物に付与することを主目的に配合される。
　式中、Ｒ６は連結基を有していてもよい炭素数７～２７の炭化水素基である。前記炭素数は、７～２５が好ましい。なお、前記炭化水素基が連結基を有する場合、連結基に含まれる炭素数は、炭化水素基の炭素数には含まれない。
　前記炭化水素基は、脂肪族炭化水素基であることが好ましい。前記炭化水素基は、不飽和結合を有してよく、有さなくてもよい。前記炭化水素基は、直鎖状又は分岐鎖状であることが好ましい。
　ここで、炭化水素基が「連結基を有する」とは、炭化水素基中の炭素原子間に連結基が介在していることを意味する。
　前記炭化水素基が有していてもよい連結基としては、アミド基（－ＣＯ－ＮＨ－）、エステル基（－ＣＯ－Ｏ－）、エーテル基（－Ｏ－）等が挙げられる。
　Ｒ７及びＲ８はそれぞれ独立して、炭素数１～４のアルキル基、炭素数１～４のヒドロキシアルキル基、又は（Ｒ９Ｏ）ｐＨ［式中、Ｒ９は炭素数２～４のアルキレン基であり、ｐは平均付加モル数を表し１～２５である。］で表される基である。
　Ｒ７及びＲ８におけるアルキル基、ヒドロキシアルキル基（アルカノール基）、Ｒ９におけるアルキレン基は、それぞれ、直鎖状であってもよく、分岐鎖状であってもよい。
Ｒ７の具体例としては、ＣＨ３，Ｃ２Ｈ５，Ｃ３Ｈ７，Ｃ４Ｈ９，ＣＨ２ＯＨ，Ｃ２Ｈ５ＯＨ，Ｃ３Ｈ７ＯＨ，Ｃ４Ｈ９ＯＨ，（Ｃ２Ｈ４Ｏ）ｐＨ，（Ｃ３Ｈ６Ｏ）ｐＨなどが挙げられる。なかでもＣＨ３，Ｃ２Ｈ５，ＣＨ２ＯＨ，Ｃ２Ｈ５ＯＨ，（Ｃ２Ｈ４Ｏ）ｐＨ，（Ｃ３Ｈ６Ｏ）ｐＨが好ましく、ＣＨ３がより好ましい。
Ｒ８の具体例としては、ＣＨ３，Ｃ２Ｈ５，Ｃ３Ｈ７，Ｃ４Ｈ９，ＣＨ２ＯＨ，Ｃ２Ｈ５ＯＨ，Ｃ３Ｈ７ＯＨ，Ｃ４Ｈ９ＯＨ，（Ｃ２Ｈ４Ｏ）ｐＨ，（Ｃ３Ｈ６Ｏ）ｐＨなどが挙げられる。なかでもＣＨ３，Ｃ２Ｈ５，ＣＨ２ＯＨ，Ｃ２Ｈ５ＯＨ，（Ｃ２Ｈ４Ｏ）ｐＨ，（Ｃ３Ｈ６Ｏ）ｐＨが好ましく、ＣＨ３がより好ましい。
　Ｒ９としては、エチレン基又はプロピレン基が好ましく、エチレン基が特に好ましい。 <(C) component>
The component (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.
Component (C) is blended mainly for the purpose of imparting flexibility imparting performance to clothing such as cotton, polyester, and acrylic to the liquid detergent composition of the present invention.
In the formula, R 6 is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group. The carbon number is preferably 7-25. In addition, when the said hydrocarbon group has a coupling group, carbon number contained in a coupling group is not contained in carbon number of a hydrocarbon group.
The hydrocarbon group is preferably an aliphatic hydrocarbon group. The said hydrocarbon group may have an unsaturated bond and does not need to have it. The hydrocarbon group is preferably linear or branched.
Here, “the hydrocarbon group has a linking group” means that the 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—), an ether group (—O—), and the like.
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 has 2 to 4 carbon atoms. And p represents an average added mole number and is 1 to 25. ].
The alkyl group, hydroxyalkyl group (alkanol group) in R 7 and R 8, and the alkylene group in R 9 may each be linear or branched.
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) pH , (C 3 H 6 O) pH, and the like. Of these, CH 3 , C 2 H 5 , CH 2 OH, C 2 H 5 OH, (C 2 H 4 O) pH , and (C 3 H 6 O) pH 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) pH , (C 3 H 6 O) pH, and the like. Of these, CH 3 , C 2 H 5 , CH 2 OH, C 2 H 5 OH, (C 2 H 4 O) pH , and (C 3 H 6 O) pH are preferable, and CH 3 is more preferable.
R 9 is preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.
　前記Ｒ６－Ｎ（Ｒ７）（Ｒ８）で表される３級アミン化合物は、そのまま使用してもよく、塩として用いてもよい。前記塩としては、前記３級アミン化合物を酸で中和した酸塩等が具体的に挙げられる。中和に用いる酸としては、例えば、塩酸、硫酸、硝酸、リン酸、グリコール酸、乳酸、クエン酸、ポリアクリル酸、パラトルエンスルホン酸、クメンスルホン酸等が挙げられ、これらは１種を単独で用いても２種以上を併用してもよい。 The tertiary amine compound represented by R 6 —N (R 7 ) (R 8 ) may be used as it is or as a salt. Specific examples of the salt include an acid salt obtained by neutralizing the tertiary amine compound with an acid. 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, cumenesulfonic acid, and the like. Two or more types may be used in combination.
　（Ｃ）成分としては、特に、下記一般式（ｃ－１）又は（ｃ－２）で表される３級アミン化合物及びその塩からなる群から選択される少なくとも１種が好ましい。 The component (C) is particularly preferably at least one selected from the group consisting of tertiary amine compounds represented by the following general formula (c-1) or (c-2) and salts thereof.
Figure JPOXMLDOC01-appb-C000002
 ［式中、Ｒ６１は炭素数７～２３の炭化水素基であり、Ｒ６２は炭素数１～４のアルキレン基であり、Ｒ７及びＲ８はそれぞれ前記と同じである。］
Figure JPOXMLDOC01-appb-C000002
 [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 the same as defined above. ]
　式中、Ｒ６１における炭化水素基は、炭素数７～２３の炭化水素基であり、前記炭素数は、７～２１が好ましい。前記炭化水素基は、脂肪族炭化水素基であることが好ましい。前記炭化水素基は、不飽和結合を有してよく、有さなくてもよい。前記炭化水素基は、直鎖状又は分岐鎖状であることが好ましい。
　Ｒ６２におけるアルキレン基は、直鎖状であってもよく、分岐鎖状であってもよい。 In the formula, the hydrocarbon group in R 61 is a hydrocarbon group having 7 to 23 carbon atoms, and the carbon number is preferably 7 to 21. The hydrocarbon group is preferably an aliphatic hydrocarbon group. The said hydrocarbon group may have an unsaturated bond and does not need to have it. The hydrocarbon group is preferably linear or branched.
The alkylene group for R 62 may be linear or branched.
Figure JPOXMLDOC01-appb-C000003
 ［式中、Ｒ６３は炭素数１１～２３の炭化水素基であり、Ｒ６４は炭素数１～４のアルキレン基であり、Ｒ７及びＲ８はそれぞれ前記と同じである。］
Figure JPOXMLDOC01-appb-C000003
 [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. ]
　式中、Ｒ６３における炭化水素基は、炭素数１１～２３の炭化水素基であり、前記炭素数は、１２～２０が好ましい。前記炭化水素基は、脂肪族炭化水素基であることが好ましい。前記炭化水素基は、不飽和結合を有してよく、有さなくてもよい。前記炭化水素基は、直鎖状又は分岐鎖状であることが好ましい。
　Ｒ６４におけるアルキレン基は、直鎖状であってもよく、分岐鎖状であってもよい。 In the formula, the hydrocarbon group in R 63 is a hydrocarbon group having 11 to 23 carbon atoms, and the carbon number is preferably 12 to 20. The hydrocarbon group is preferably an aliphatic hydrocarbon group. The said hydrocarbon group may have an unsaturated bond and does not need to have it. The hydrocarbon group is preferably linear or branched.
The alkylene group for R 64 may be linear or branched.
　式（ｃ－１）で表される３級アミン化合物の具体例としては、カプリル酸ジメチルアミノプロピルアミド、カプリン酸ジメチルアミノプロピルアミド、ラウリン酸ジメチルアミノプロピルアミド、ミリスチン酸ジメチルアミノプロピルアミド、パルミチン酸ジメチルアミノプロピルアミド、ステアリン酸ジメチルアミノプロピルアミド、ベヘニン酸ジメチルアミノプロピルアミド、オレイン酸ジメチルアミノプロピルアミドなどの長鎖脂肪族アミドジアルキル３級アミン；パルミチン酸ジエタノールアミノプロピルアミド、ステアリン酸ジエタノールアミノプロピルアミドなどの長鎖脂肪族アミドジアルカノール３級アミン；等が挙げられる。
　式（ｃ－２）で表される３級アミン化合物の具体例としては、パルミテートエステルプロピルジメチルアミン、ステアレートエステルプロピルジメチルアミン等の脂肪族エステルジアルキル３級アミン等が挙げられる。
　これらの中でも、式（ｃ－１）で表される３級アミン化合物又はその塩が好ましく、カプリル酸ジメチルアミノプロピルアミド、カプリン酸ジメチルアミノプロピルアミド、ラウリン酸ジメチルアミノプロピルアミド、ミリスチン酸ジメチルアミノプロピルアミド、パルミチン酸ジメチルアミノプロピルアミド、ステアリン酸ジメチルアミノプロピルアミド、ベヘニン酸ジメチルアミノプロピルアミド、オレイン酸ジメチルアミノプロピルアミド又はその塩が特に好ましい。 Specific examples of the tertiary amine compound represented by the formula (c-1) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid. Long chain aliphatic amide dialkyl tertiary amines such as dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide Long chain aliphatic amide dialkanol tertiary amines, and the like.
Specific examples of the tertiary amine compound represented by the formula (c-2) include aliphatic ester dialkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine.
Among these, a tertiary amine compound represented by the formula (c-1) or a salt thereof is preferable. Caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropyl Amides, dimethylaminopropylamide palmitate, dimethylaminopropylamide stearate, dimethylaminopropylamide behenate, dimethylaminopropylamide oleate or salts thereof are particularly preferred.
　式（ｃ－１）又は（ｃ－２）で表される３級アミン化合物及びその塩以外に、（Ｃ）成分として使用できる３級アミン化合物の具体例としては、ラウリルジメチルアミン、ミリスチルジメチルアミン、ヤシアルキルジメチルアミン、パルミチルジメチルアミン、牛脂アルキルジメチルアミン、硬化牛脂アルキルジメチルアミン、ステアリルジメチルアミン、ステアリルジエタノールアミン、ポリオキシエチレン硬化牛脂アルキルアミン（ライオンアクゾ（株）製　商品名：ＥＴＨＯＭＥＥＮ　ＨＴ／１４等）等が挙げられる。 In addition to the tertiary amine compound represented by the formula (c-1) or (c-2) and a salt thereof, specific examples of the tertiary amine compound that can be used as the component (C) include lauryl dimethylamine, myristyl dimethylamine. , Palm alkyl dimethylamine, palmityl dimethylamine, beef tallow alkyl dimethylamine, hardened beef tallow alkyl dimethylamine, stearyl dimethylamine, stearyl diethanolamine, polyoxyethylene hardened beef tallow alkylamine (product name: ETHOMEEN HT / 14) Etc.).
　（Ｃ）成分は、市販のものを用いてもよく、公知の方法により合成してもよい。
　たとえば（Ｃ）成分の製造方法を、前記式（ｃ－１）で表される３級アミン化合物のような長鎖脂肪族アミドアルキル３級アミンを例に挙げて説明すると、例えば、脂肪酸又は脂肪酸誘導体（脂肪酸低級アルキルエステル、動・植物性油脂等）と、ジアルキル（又はアルカノール）アミノアルキルアミンとを縮合反応させ、その後、未反応のジアルキル（又はアルカノール）アミノアルキルアミンを減圧又は窒素ブローにて留去することにより目的の化合物が得られる。
　ここで、脂肪酸又は脂肪酸誘導体としては、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、ベヘニン酸、エルカ酸、１２－ヒドロキシステアリン酸、ヤシ油脂肪酸、綿実油脂肪酸、とうもろこし油脂肪酸、牛脂脂肪酸、パーム核油脂肪酸、大豆油脂肪酸、アマニ油脂肪酸、ひまし油脂肪酸、オリーブ油脂肪酸等の植物油又は動物油脂肪酸等、又は、これらのメチルエステル、エチルエステル、グリセライド等が具体的に挙げられ、中でも、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、ベヘニン酸等が特に好ましい。これら脂肪酸又は脂肪酸誘導体は、１種を単独で用いても２種以上を併用しても良い。
　ジアルキル（又はアルカノール）アミノアルキルアミンとしては、ジメチルアミノプロピルアミン、ジメチルアミノエチルアミン、ジエチルアミノプロピルアミン、ジエチルアミノエチルアミン等が具体的に挙げられ、中でも、ジメチルアミノプロピルアミンが特に好ましい。
　長鎖脂肪族アミドアルキル３級アミンを製造する際のジアルキル（又はアルカノール）アミノアルキルアミンの使用量は、脂肪酸又はその誘導体に対し、０．９～２．０倍モルが好ましく、１．０～１．５倍モルが特に好ましい。反応温度は、通常１００～２２０℃であり、好ましくは１５０～２００℃である。反応温度が１００℃未満では反応が遅くなりすぎ、２２０℃超では得られる３級アミンの着色が顕著となる恐おそれがある。
　長鎖脂肪族アミドアルキル３級アミンの上記以外の製造条件は適宜変更可能であり、反応時の圧力は常圧でも減圧でも良く、反応時に窒素等の不活性ガスを吹き込むことにより導入することも可能である。
　また、脂肪酸を用いる場合は、硫酸、ｐ－トルエンスルホン酸等の酸触媒、脂肪酸誘導体を用いる場合は、ナトリウムメチラート、苛性カリ、苛性ソーダ等のアルカリ触媒を用いることで、低い反応温度で短時間により効率良く反応を進行させることができる。また、得られる３級アミンが、融点が高い長鎖アミンの場合には、ハンドリング性を向上させるため、反応後、フレーク状又はペレット状に成形することが好ましく、又は、エタノール等の有機溶媒に溶解し液状にすることが好ましい。
　市販の（Ｃ）成分の具体例として、東邦化学（株）製カチナールＭＰＡＳ－Ｒ等が挙げられる。 (C) A commercially available thing may be used for a component and you may synthesize | combine by a well-known method.
For example, the method for producing the component (C) is explained by taking a long-chain aliphatic amidoalkyl tertiary amine such as a tertiary amine compound represented by the formula (c-1) as an example. Derivatives (fatty acid lower alkyl esters, animal / vegetable oils and fats, etc.) and dialkyl (or alkanol) aminoalkylamine are subjected to a condensation reaction, and then unreacted dialkyl (or alkanol) aminoalkylamine is reduced in pressure or nitrogen blown. The target compound is obtained by distilling off.
Here, as the fatty acid or fatty acid derivative, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid, Specific examples include corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oils or animal oil fatty acids, or methyl esters, ethyl esters, glycerides, etc. 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 alone or in combination of two or more.
Specific examples of the dialkyl (or alkanol) aminoalkylamine include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, and among them, dimethylaminopropylamine is particularly preferable.
The amount of the dialkyl (or alkanol) aminoalkylamine used in the production of the long-chain aliphatic amidoalkyl tertiary amine is preferably 0.9 to 2.0 times the molar amount of the fatty acid or its derivative, 1.0 to A 1.5-fold mole is particularly preferred. The reaction temperature is usually 100 to 220 ° C, preferably 150 to 200 ° C. If the reaction temperature is less than 100 ° C., the reaction becomes too slow, and if it exceeds 220 ° C., the resulting tertiary amine may be markedly colored.
The production conditions other than those described above for the long-chain aliphatic amidoalkyl tertiary amine can be appropriately changed. The pressure during the reaction may be normal pressure or reduced pressure, and may be introduced by blowing an inert gas such as nitrogen during the reaction. Is possible.
In addition, when using fatty acids, acid catalysts such as sulfuric acid and p-toluenesulfonic acid, and when using fatty acid derivatives, alkaline catalysts such as sodium methylate, caustic potash and caustic soda can be used for a short time at a low reaction temperature. The reaction can proceed efficiently. Further, when the obtained tertiary amine is a long-chain amine having a high melting point, it is preferably molded into a flake shape or a pellet shape after the reaction in order to improve handling properties, or in an organic solvent such as ethanol. It is preferable to dissolve and make it liquid.
Specific examples of commercially available component (C) include Kachinal MPAS-R manufactured by Toho Chemical Co., Ltd.
　（Ｃ）成分は、一種類のみを単独で用いてもよく、複数種類を組み合わせて使用してもよい。
　本発明の液体洗浄剤組成物中、（Ｃ）成分の配合量は、前記液体洗浄剤組成物の総質量に対して、０．１～１０質量％であり、０．５～５質量％が好ましい。（Ｃ）成分の含有量が０．１質量％以上であれば、充分な柔軟性付与性能が得られる。また、（Ｃ）成分を１０質量％より多く配合しても、それに見合う柔軟性付与性能の向上効果は見られず、経済的にも不利となる。 As the component (C), only one type 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 0.1 to 10% by mass, and 0.5 to 5% by mass with respect to the total mass of the liquid detergent composition. preferable. When the content of the component (C) is 0.1% by mass or more, sufficient flexibility imparting performance can be obtained. Moreover, even if it mixes more than (C) component more than 10 mass%, the improvement effect of the softness | flexibility provision property corresponding to it is not seen, but it becomes economically disadvantageous.
＜（Ｄ）成分＞
　（Ｄ）成分は、ＳＯ３基又はＳＯ４基を有する陰イオン性界面活性剤である。
　（Ｄ）成分は、本発明の液体洗浄剤組成物へ再汚染防止性能を付与することを主目的に配合される。
　（Ｄ）成分としては、特に限定されず、公知のものを利用できる。
　（Ｄ）成分の具体例としては、直鎖アルキルベンゼンスルホン酸又はその塩；α－オレフィンスルホン酸塩；直鎖又は分岐鎖のアルキル硫酸エステル塩；アルキルエーテル硫酸エステル塩又はアルケニルエーテル硫酸エステル塩；アルキル基を有するアルカンスルホン酸塩；α－スルホ脂肪酸エステル塩などが挙げられる。
　これらの塩としては、ナトリウム、カリウムなどのアルカリ金属塩、マグネシウムなどのアルカリ土類金属塩、モノエタノールアミン、ジエタノールアミンなどのアルカノールアミン塩等が挙げられる。
　上記のうち、直鎖アルキルベンゼンスルホン酸又はその塩としては、直鎖アルキル基の炭素数が８～１６のものが好ましく、炭素数１０～１４のものが特に好ましい。
　α－オレフィンスルホン酸塩としては、炭素数１０～２０のものが好ましい。
　アルキル硫酸エステル塩としては、炭素数１０～２０のものが好ましい。
　アルキルエーテル硫酸エステル塩又はアルケニルエーテル硫酸エステル塩としては、炭素数１０～２０の直鎖又は分岐鎖のアルキル基もしくはアルケニル基を有し、平均１～１０モルの酸化エチレンを付加したもの（すなわち、ポリオキシエチレンアルキルエーテル硫酸エステル塩又はポリオキシエチレンアルケニルエーテル硫酸エステル塩）が好ましい。
　アルカンスルホン酸塩の炭素数は１０～２０、好ましくは１４～１７であり、２級アルカンスルホン酸塩が特に好ましい。
　α－スルホ脂肪酸エステル塩としては、炭素数１０～２０のものが好ましい。
　これらの（Ｄ）成分は市場において容易に入手することができる。また、公知の方法により合成してもよい。
　（Ｄ）成分としては、上記のなかでも、直鎖アルキルベンゼンスルホン酸又はその塩、アルカンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、及びα－オレフィンスルホン酸塩からなる群から選択される少なくとも１種が好ましい。
（Ｄ）成分の具体例としては、直鎖アルキルベンゼンスルホン酸ナトリウム、セカンダリーアルカンスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウムなどが挙げられる。なかでも直鎖アルキルベンゼンスルホン酸ナトリウムが好ましい。 <(D) component>
The component (D) is an anionic surfactant having a SO 3 group or a SO 4 group.
The component (D) is blended mainly for the purpose of imparting anti-recontamination performance to the liquid detergent composition of the present invention.
(D) It does not specifically limit as a component, A well-known thing can be utilized.
Specific examples of the component (D) include linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; And alkane sulfonate having a group; α-sulfo fatty acid ester salt and the like.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
Of the above, the linear alkylbenzenesulfonic acid or a salt thereof preferably has 8 to 16 carbon atoms, and particularly preferably has 10 to 14 carbon atoms, in the linear alkyl group.
As the α-olefin sulfonate, those having 10 to 20 carbon atoms are preferable.
The alkyl sulfate ester salt preferably has 10 to 20 carbon atoms.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average of 1 to 10 moles of ethylene oxide added (ie, Polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferred.
The carbon number of the alkanesulfonate is 10 to 20, preferably 14 to 17, and the secondary alkanesulfonate is particularly preferable.
The α-sulfo fatty acid ester salt preferably has 10 to 20 carbon atoms.
These components (D) can be easily obtained in the market. Moreover, you may synthesize | combine by a well-known method.
Component (D) is, among the above, at least one selected from the group consisting of linear alkylbenzene sulfonic acids or salts thereof, alkane sulfonates, polyoxyethylene alkyl ether sulfates, and α-olefin sulfonates. Species are preferred.
Specific examples of component (D) include sodium linear alkylbenzene sulfonate, sodium secondary alkane sulfonate, sodium polyoxyethylene alkyl ether sulfate, and the like. Of these, sodium linear alkylbenzene sulfonate is preferred.
　（Ｄ）成分は、一種類のみを単独で用いてもよく、複数種類を組み合わせて使用してもよい。
　本発明の第四の態様及び第六の態様において、液体洗浄剤組成物中、（Ｄ）成分の配合量は、前記液体洗浄剤組成物の総質量に対して、１～１０質量％であることが好ましく、１～５質量％であることがより好ましく、２～５質量％であることがさらに好ましい。（Ｄ）成分の含有量が１質量％以上であれば、洗浄性能、特に塗布洗浄力が向上する。また、（Ｄ）成分の含有量が１０質量％以下であれば、本組成物の液安定性が向上する。
本発明の第八の態様及び第九の態様において、液体洗浄剤組成物中、（Ｄ）成分の配合量は、前記液体洗浄剤組成物の総質量に対して、１～２０質量％であり、１～１０質量％が好ましい。（Ｄ）成分の含有量が１質量％以上であれば、充分な再汚染防止性能が得られる。また、（Ｄ）成分の含有量が２０質量％以下であれば、本組成物の液安定性が向上する。 As the component (D), only one type may be used alone, or a plurality of types may be used in combination.
In the fourth and sixth aspects of the present invention, the amount of component (D) in the liquid detergent composition is 1 to 10% by mass relative to the total mass of the liquid detergent composition. It is preferably 1 to 5% by mass, more preferably 2 to 5% by mass. If content of (D) component is 1 mass% or more, cleaning performance, especially coating cleaning power will improve. Moreover, if content of (D) component is 10 mass% or less, the liquid stability of this composition will improve.
In the eighth and ninth aspects of the present invention, the blending amount of the component (D) in the liquid detergent composition is 1 to 20% by mass with respect to the total mass of the liquid detergent composition. 1 to 10% by mass is preferable. If the content of the component (D) is 1% by mass or more, sufficient recontamination prevention performance can be obtained. Moreover, if content of (D) component is 20 mass% or less, the liquid stability of this composition will improve.
　前記（Ｃ）成分と（Ｄ）成分とを特定比率で配合することにより、再汚染防止性能の向上と、衣料、特にアクリルやポリエステルなどの疎水性繊維からなる衣料に対する柔軟性付与性能の向上とを両立できる。
　本発明の液体洗浄剤組成物中、（Ｃ）成分と（Ｄ）成分の配合比率（質量比）は、（Ｄ）／（Ｃ）＝１／１～１０／１であり、１．０５／１～５／１が好ましい。（Ｄ）成分の比率が低すぎると、（Ｄ）成分による再汚染防止効果が充分に得られないだけでなく、液体洗浄剤組成物として安定配合できない。一方、（Ｃ）成分の比率が低すぎると、（Ｃ）成分による充分な柔軟性付与効果が得られない。
　上記効果を奏する理由については、おそらく、（Ｃ）成分と（Ｄ）成分とが洗浄時に水中で複合体を形成することによって柔軟付与成分である（Ｃ）成分の疎水性が高まり、特に疎水性の繊維表面に対し高い吸着性を示すようになったためと推察される。 By blending the component (C) and the component (D) at a specific ratio, the improvement in the re-contamination prevention performance and the improvement in the flexibility imparting performance on the clothing, particularly the clothing made of hydrophobic fibers such as acrylic and polyester Can be compatible.
In the liquid detergent composition of the present invention, the blending ratio (mass ratio) of the component (C) and the component (D) is (D) / (C) = 1/1 to 10/1, and 1.05 / 1 to 5/1 is preferred. If the ratio of the component (D) is too low, the effect of preventing recontamination by the component (D) cannot be sufficiently obtained, and the liquid detergent composition cannot be stably blended. On the other hand, when the ratio of the component (C) is too low, a sufficient flexibility imparting effect by the component (C) cannot be obtained.
The reason for the above effect is that the (C) component and the (D) component form a complex in water at the time of washing, so that the hydrophobicity of the (C) component, which is a softening component, is increased. This is presumed to be due to the high adsorptivity to the fiber surface.
＜（Ｅ）成分＞
　（Ｅ）成分は、炭素数２～４の一価アルコール、炭素数２～４の多価アルコール及びＲ１１－（ＯＲ１２）ｋＯＨ［式中、Ｒ１１は炭素数１～６のアルキル基又はフェニル基であり、Ｒ１２は炭素数２～４のアルキレン基であり、ｋは平均付加モル数を表し１～５である。］で表されるグリコールエーテル系溶剤で表されるグリコールエーテル系溶剤からなる群から選択される溶剤である。
　炭素数２～４の１価アルコールとしては、たとえば、エタノール、１－プロパノール、２－プロパノール、１－ブタノール等が挙げられる。
　炭素数２～４の多価アルコールとしては、エチレングリコール、プロピレングリコール、ブチレングリコール、グリセリン等が挙げられる。
　前記式Ｒ１１－（ＯＲ１２）ｋＯＨで表されるグリコールエーテル系溶剤としては、エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールモノフェニルエーテル、ジエチレングリコールモノメチルエーテル等が挙げられる。
　これらのなかでも、臭気の穏やかな点や原料の入手のしやすさから、一価アルコール、多価アルコールが好ましく、特にエタノール、プロピレングリコールが好ましい。
　本発明の液体洗浄剤組成物において、（Ｅ）成分は、一種類のみを単独で用いてもよく、複数種類を組み合わせて使用してもよい。 <(E) component>
Component (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 represents an average added mole number and is 1 to 5. ] A solvent 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, glycerin and the like.
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, and diethylene glycol. Examples thereof include monomethyl ether.
Among these, monohydric alcohols and polyhydric alcohols are preferable, and ethanol and propylene glycol are particularly preferable because of their mild odor and availability of raw materials.
In the liquid detergent composition of the present invention, the component (E) may be used alone or in combination of two or more.
　本発明の液体洗浄剤組成物中、（Ｅ）成分の配合量は、前記液体洗浄剤組成物の総質量に対し、３～２５質量％であり、３～２０質量％が好ましく、４～１５質量％がより好ましく、５～１２質量％がさらに好ましい。（Ｅ）成分の含有量が３質量％以上であれば、前記組成物の液流動性が良好となり、ゲル化せず、洗浄剤として使用できる。２５質量％より多く配合してもそれに見合う液流動性の改善効果は見られず、経済的にも不利になる。 In the liquid detergent composition of the present invention, the amount of component (E) is 3 to 25% by mass, preferably 3 to 20% by mass, preferably 4 to 15%, based on the total mass of the liquid detergent composition. More preferably, it is more preferably 5 to 12% by mass. If content of (E) component is 3 mass% or more, the liquid fluidity | liquidity of the said composition will become favorable, it does not gelatinize and can be used as a washing | cleaning agent. Even if blending more than 25% by mass, the liquid fluidity improvement effect corresponding to that is not seen, which is disadvantageous economically.
本発明の液体洗浄剤組成物の第一の態様は、上記（Ａ）、（Ｂ）及び（Ｅ）成分を必須の成分として含むものであり、（Ａ）、（Ｂ）及び（Ｅ）成分のみから構成されてもよく、必要に応じて、（Ａ）、（Ｂ）及び（Ｅ）成分以外の成分等を含有してもよい。前記他の成分としては、特に限定されず、衣料用液体洗浄剤組成物に通常用いられている成分を含有することができる。
　たとえば、本発明の液体洗浄剤組成物は、液体洗浄剤組成物の調製しやすさ、洗浄剤組成物としての水への溶解性や保存安定性等から、さらに、水を含むことが好ましい。本発明の液体洗浄剤組成物中、水の含有量は、前記液体洗浄剤組成物の総質量に対して、０～８６質量％であることが好ましく、２０～８０質量％であることがより好ましい。 The first aspect of the liquid detergent composition of the present invention comprises the components (A), (B) and (E) as essential components, and the components (A), (B) and (E) It may be comprised only from this, and you may contain components other than (A), (B) and (E) component, etc. as needed. It does not specifically limit as said other component, The component normally used for the liquid cleaning composition for garments can be contained.
For example, the liquid detergent composition of the present invention preferably further contains water in view of ease of preparation of the liquid detergent composition, solubility in water as the detergent composition, storage stability, and the like. In the liquid detergent composition of the present invention, the water content is preferably 0 to 86% by mass, more preferably 20 to 80% by mass, based on the total mass of the liquid detergent composition. preferable.
　本発明の液体洗浄剤組成物の第八の態様及び第九の態様は、上記（Ａ）～（Ｅ）成分を必須の成分として含むものであり、（Ａ）～（Ｅ）成分のみから構成されてもよく、必要に応じて、（Ａ）～（Ｅ）成分以外の成分等を含有してもよい。前記他の成分としては、特に限定されず、衣料用液体洗浄剤組成物に通常用いられている成分を含有することができる。
　たとえば、本発明の液体洗浄剤組成物は、液体洗浄剤組成物の調製しやすさ、洗浄剤組成物としての水への溶解性や保存安定性等から、さらに、水を含むことが好ましい。本発明の液体洗浄剤組成物中、水の含有量は、前記液体洗浄剤組成物の総質量に対して、０～８６質量％であることが好ましく、２０～８０質量％であることがより好ましい。 The eighth and ninth aspects of the liquid detergent composition of the present invention comprise the components (A) to (E) as essential components, and are composed of only the components (A) to (E). If necessary, it may contain components other than the components (A) to (E). It does not specifically limit as said other component, The component normally used for the liquid cleaning composition for garments can be contained.
For example, the liquid detergent composition of the present invention preferably further contains water in view of ease of preparation of the liquid detergent composition, solubility in water as the detergent composition, storage stability, and the like. In the liquid detergent composition of the present invention, the water content is preferably 0 to 86% by mass, more preferably 20 to 80% by mass, based on the total mass of the liquid detergent composition. preferable.
本発明の液体洗浄剤組成物の第四の態様は、上記（Ａ）、（Ｂ）、（Ｄ）、及び（Ｅ）を成分を含有し、さらに（Ｆ）成分を含有する。 The 4th aspect of the liquid cleaning composition of this invention contains the said (A), (B), (D), and (E) component, and also contains (F) component.
＜（Ｆ）成分＞
　（Ｆ）成分は、特に限定されず、従来、衣料用洗浄剤組成物等に配合されている酵素を使用できる。
　（Ｆ）成分としては、たとえば、プロテアーゼ、アミラーゼ、リパーゼ、セルラーゼ、マンナナーゼ等が挙げられる。これらの中でも、上記効果に優れることから、プロテアーゼ、アミラーゼ及びリパーゼからなる群から選択される１種以上の酵素が好ましい。 <(F) component>
(F) A component is not specifically limited, The enzyme currently mix | blended with the cleaning composition for clothing etc. can be used conventionally.
Examples of the component (F) include protease, amylase, lipase, cellulase, mannanase and the like. Among these, one or more enzymes selected from the group consisting of protease, amylase, and lipase are preferable because of the excellent effects described above.
　（Ｆ）成分の具体例としては、プロテアーゼとしては、プロテアーゼ製剤としてノボザイムズ社から入手できる商品名Ｓａｖｉｎａｓｅ１６Ｌ、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、ジェネンコア社から入手できる商品名Ｐｕｒａｆｅｃｔ　Ｌ、Ｐｕｒａｆｅｃｔ　ＯＸ，Ｐｒｏｐｅｒａｓｅ　Ｌ等が挙げられる。
　アミラーゼとしては、アミラーゼ製剤としてノボザイムズ社から入手できる商品名Ｔｅｒｍａｍｙｌ　３００Ｌ、Ｔｅｒｍａｍｙｌ　Ｕｌｔｒａ　３００Ｌ、Ｄｕｒａｍｙｌ　３００Ｌ、Ｓｔａｉｎｚｙｍｅ　１２Ｌ、Ｓｔａｉｎｚｙｍｅ　Ｐｌｕｓ　１２Ｌ、ジェネンコア社から入手できる商品名Ｍａｘａｍｙｌ、天野製薬社から入手できる商品名プルラナーゼアマノ、生化学工業社から入手できる商品名ＤＢ－２５０等が挙げられる。
　リパーゼとしては、リパーゼ製剤としてノボザイムズ社から入手できる商品名Ｌｉｐｅｘ　１００Ｌ、Ｌｉｐｏｌａｓｅ　１００Ｌ等が挙げられる。
　セルラーゼとして、セルラーゼ製剤としてノボザイムズ社から入手できる商品名Ｅｎｄｏｌａｓｅ　５０００Ｌ、Ｃｅｌｌｕｚｙｍｅ　０．４Ｌ、Ｃａｒｚｙｍｅ　４５００Ｌ等が挙げられる。
　マンナナーゼとして、マンナナーゼ製剤としてノボザイムズ社から入手できる商品名Ｍａｎｎａｗａｙ　４Ｌ等が挙げられる。 As specific examples of the component (F), as proteases, trade names such as Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type EX, Everse L 2.5e, Ultrase L Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, trade names available from Genencor Corporation, such as Perfect L, Perfect OX, Properase L, etc.
As amylases, trade names such as Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, trade names available from Genencore Co., Ltd. And trade name DB-250 available from Seikagaku Corporation.
Examples of the lipase include trade names Lipex 100L and Lipolase 100L, which are available from Novozymes as lipase preparations.
Examples of the cellulase include trade names Endolase 5000L, Celluzyme 0.4L, Carzyme 4500L and the like which are available from Novozymes as cellulase preparations.
Examples of mannanase include Mannaway 4L, which is a mannanase preparation available from Novozymes.
　本発明において特に好ましい（Ｆ）成分はプロテアーゼである。プロテアーゼとしては、上記の中でも、商品名Ｓａｖｉｎａｓｅ１６Ｌ、Ｓａｖｉｎａｓｅ　Ｕｌｔｒａ　１６Ｌ、Ｓａｖｉｎａｓｅ　Ｕｌｔｒａ　１６ＸＬ、Ｅｖｅｒｌａｓｅ　１６Ｌ、Ｅｖｅｒｌａｓｅ　Ｕｌｔｒａ　１６Ｌ、Ｌｉｑｕａｎａｓｅ　２．５Ｌ、Ｌｉｑｕａｎａｓｅ　Ｕｌｔｒａ　２．５Ｌ、Ｌｉｑｕａｎａｓｅ　Ｕｌｔｒａ　２．５ＸＬ、Ｃｏｒｏｎａｓｅ　４８Ｌが好ましく、特にＥｖｅｒｌａｓｅ　１６Ｌ、Ｓａｖｉｎａｓｅ　１６Ｌ、Ｃｏｒｏｎａｓｅ　４８Ｌが好ましい。 A particularly preferred component (F) in the present invention is a protease. Among the above-mentioned proteases, trade names are Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L, Everase Ultra 16L, Liquidase 2.5L, and Liquidase UltraL2.5. Everase 16L, Savinase 16L, Coronase 48L are preferred.
　（Ｆ）成分は、１種を単独で用いてもよく、２種以上を併用してもよい。
　本発明の液体洗浄剤組成物中、（Ｆ）成分の含有量は、前記液体洗浄剤組成物の総質量に対して、０．１～３質量％であることが好ましく、０．１～１質量％であることがより好ましい。（Ｆ）成分の含有量が０．１質量％以上であれば、各種汚れに対する洗浄力（特に皮脂汚れ等の油性汚れに対する洗浄力）が充分に向上する。また、（Ｆ）成分の含有量が３質量％以下であれば、各種汚れに対する洗浄力が充分に得られやすく、経済的にも有利となる。 (F) A component may be used individually by 1 type and may use 2 or more types together.
In the liquid detergent composition of the present invention, the content of the component (F) is preferably 0.1 to 3% by mass with respect to the total mass of the liquid detergent composition, 0.1 to 1 More preferably, it is mass%. If content of (F) component is 0.1 mass% or more, the detergency with respect to various dirt (especially the detergency with respect to oily dirt, such as sebum dirt) will fully improve. Moreover, if content of (F) component is 3 mass% or less, it will be easy to obtain the detergency with respect to various stain | pollution | contamination fully, and it will become economically advantageous.
　本発明の液体洗浄剤組成物の第二の態様ないし第七の態様は、必要に応じて、本発明の効果を損なわない範囲で、上記（Ａ）～（Ｆ）成分以外の他の成分を含有してもよい。前記他の成分としては、特に限定されず、衣料用液体洗浄剤組成物に通常用いられている成分を含有することができる。
　たとえば、本発明の液体洗浄剤組成物は、液体洗浄剤組成物の調製しやすさ、洗浄剤組成物としての水への溶解性や保存安定性等から、さらに、水を含むことが好ましい。本発明の液体洗浄剤組成物中、水の含有量は、前記液体洗浄剤組成物の総質量に対して、０～５７質量％であることが好ましく、２５～４６質量％であることがより好ましい。 In the second aspect to the seventh aspect of the liquid detergent composition of the present invention, other components than the above components (A) to (F) are added as necessary within the range not impairing the effects of the present invention. You may contain. It does not specifically limit as said other component, The component normally used for the liquid cleaning composition for garments can be contained.
For example, the liquid detergent composition of the present invention preferably further contains water in view of ease of preparation of the liquid detergent composition, solubility in water as the detergent composition, storage stability, and the like. In the liquid detergent composition of the present invention, the content of water is preferably 0 to 57% by mass and more preferably 25 to 46% by mass with respect to the total mass of the liquid detergent composition. preferable.
　また、本発明の液体洗浄剤組成物は、（Ａ）成分、（Ｂ）成分及び（Ｄ）成分以外の界面活性剤を含むことができる。
　前記界面活性剤としては、（Ａ）成分及び（Ｂ）成分以外の非イオン性界面活性剤、（Ｄ）成分以外の陰イオン性界面活性剤、陽イオン性界面活性剤、両性界面活性剤等が挙げられる。
　（Ａ）成分及び（Ｂ）成分以外の非イオン性界面活性剤の例としては、アルキルフェノール、高級脂肪酸又は高級アミン等のアルキレンオキサイド付加体、ポリオキシエチレンポリオキシプロピレンブロックコポリマー、脂肪酸アルカノールアミン、脂肪酸アルカノールアミド、多価アルコール脂肪酸エステル又はそのアルキレンオキサイド付加体、多価アルコール脂肪酸エーテル、アルキル（又はアルケニル）アミンオキサイド、硬化ヒマシ油のアルキレンオキサイド付加体、糖脂肪酸エステル、Ｎ－アルキルポリヒドロキシ脂肪酸アミド、アルキルグリコシド等が挙げられる。
　（Ｄ）成分以外の陰イオン性界面活性剤の例としては、高級脂肪酸塩、アルキルエーテルカルボン酸塩、ポリオキシアルキレンエーテルカルボン酸塩、アルキル（又はアルケニル）アミドエーテルカルボン酸塩、アシルアミノカルボン酸塩等のカルボン酸型、アルキルリン酸エステル塩、ポリオキシアルキレンアルキルリン酸エステル塩、ポリオキシアルキレンアルキルフェニルリン酸エステル塩、グリセリン脂肪酸エステルモノリン酸エステル塩等のリン酸エステル型陰イオン性界面活性剤等が挙げられる。
　陽イオン性界面活性剤の例としては、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルベンジルジメチルアンモニウム塩、アルキルピリジニウム塩の陽イオン性界面活性剤等が挙げられる。
　両性界面活性剤の例としては、アルキルベタイン型、アルキルアミドベタイン型、イミダゾリン型、アルキルアミノスルホン型、アルキルアミノカルボン酸型、アルキルアミドカルボン酸型、アミドアミノ酸型、リン酸型両性界面活性剤等が挙げられる。 Moreover, the liquid cleaning composition of this invention can contain surfactant other than (A) component, (B) component, and (D) component.
Examples of the surfactant include a nonionic surfactant other than the components (A) and (B), an anionic surfactant other than the component (D), a cationic surfactant, an amphoteric surfactant, and the like. Is mentioned.
Examples of nonionic surfactants other than the component (A) and the component (B) include alkylphenols, alkylene oxide adducts such as higher fatty acids or higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acids Alkanolamide, polyhydric alcohol fatty acid ester or alkylene oxide adduct thereof, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, Examples include alkyl glycosides.
Examples of anionic surfactants other than the component (D) include higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, acylaminocarboxylic acids. Phosphate type anionic surface activity such as carboxylic acid type such as salt, alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkylphenyl phosphate salt, glycerin fatty acid ester monophosphate ester salt Agents and the like.
Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salt cationic surfactants.
Examples of amphoteric surfactants include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, phosphoric acid type amphoteric surfactant. Is mentioned.
　また、トリエチレングリコール、テトラエチレングリコール、平均分子量約２００～５０００のポリエチレングリコールなどのグリコール類、パラトルエンスルホン酸、安息香酸塩（防腐剤としての効果もある）、尿素等の減粘剤及び可溶化剤を、例えば０．０１～１５質量％含むことができる。
　また、マロン酸、コハク酸、リンゴ酸、ジグリコール酸、酒石酸、クエン酸等の金属イオン疎捕捉剤を、例えば０．１～２０質量％含むことができる。
　また、ブチルヒドロキシトルエン、ジスチレン化クレゾール、亜硫酸ナトリウム及び亜硫酸水素ナトリウム等の酸化防止剤を、例えば０．０１～２質量％含むことができる。
　また、ローム・アンド・ハウス社製ケーソンＣＧ（商品名）等の防腐剤を、例えば０．００１～１質量％含むことができる。 In addition, triethylene glycol, tetraethylene glycol, glycols such as polyethylene glycol having an average molecular weight of about 200 to 5000, paratoluenesulfonic acid, benzoate (also has an effect as a preservative), a viscosity reducing agent such as urea and the like. The solubilizer can be contained, for example, in an amount of 0.01 to 15% by mass.
Further, for example, 0.1 to 20% by mass of a metal ion sequestering agent such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid or citric acid can be contained.
Further, an antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium hydrogen sulfite can be contained, for example, in an amount of 0.01 to 2% by mass.
Further, an antiseptic such as Caisson CG (trade name) manufactured by Rohm and House may be included, for example, in an amount of 0.001 to 1% by mass.
　また、洗浄力向上や安定性向上等を目的として、風合い向上剤、柔軟性付与剤、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ－メチル－ジエタノールアミン、Ｎ，Ｎ－ジメチルモノエタノールアミン等のアルカノールアミン等のアルカリビルダー、ｐＨ調整剤、ハイドロトロープ剤、蛍光剤、酵素、移染防止剤、前記（Ｄ）成分に該当しない再汚染防止剤（例えばポリビニルピロリドン、カルボキシメチルセルロースなど）、パール剤、ソイルリリース剤等を含むことができる。
柔軟性付与剤としては、カプリル酸ジメチルアミノプロピルアミド、カプリン酸ジメチルアミノプロピルアミド、ラウリン酸ジメチルアミノプロピルアミド、ミリスチン酸ジメチルアミノプロピルアミド、パルミチン酸ジメチルアミノプロピルアミド、ステアリン酸ジメチルアミノプロピルアミド、ベヘニン酸ジメチルアミノプロピルアミド、オレイン酸ジメチルアミノプロピルアミド等の長鎖脂肪族アミドアルキル３級アミン又はこれらの塩；パルミチン酸ジエタノールアミノプロピルアミド、ステアリン酸ジエタノールアミノプロピルアミド等が挙げられる。例えば、ステアリン酸ジメチルアミノプロピルアミドを１～５質量％含むことができる。
　風合い向上剤としては、東レ・ダウコーニング（株）製のＦＺ－３７０７、ＦＺ－３５０４、ＢＹ１６－２０５、ＦＺ－３７６０、ＦＺ－３７０５、ＢＹ１６－２０９、ＦＺ－３７１０、ＳＦ８４１７、ＢＹ１６－８４９、ＢＹ１６－８５０、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－７００２、ＳＩＬＷＥＴ　Ｌ－７６０２、ＳＩＬＷＥＴ　Ｌ－７６０４、ＳＩＬＷＥＴ　ＦＺ－２１０４、ＳＩＬＷＥＴ　ＦＺ－２１２０、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、；信越化学工業（株）製のＸ－２０－８０１０Ｂ、ＫＦ３５２Ａ、ＫＦ６００８、ＫＦ６１５Ａ、ＫＦ６０１２、ＫＦ６０１６、ＫＦ６０１７；ＧＥ東芝シリコーン（株）製のＴＳＦ４４５０、ＴＳＦ４４５２、ＴＳＦ４４４５（以上、商品名）等の変性シリコーンを用いることができ、当該変性シリコーンは、液体洗浄剤組成物中、０．１～３質量％含むことができる。 Also, for the purpose of improving detergency and stability, texture improvers, flexibility imparting agents, alkanols such as monoethanolamine, diethanolamine, triethanolamine, N-methyl-diethanolamine, N, N-dimethylmonoethanolamine, etc. Alkali builders such as amines, pH adjusters, hydrotropes, fluorescent agents, enzymes, dye transfer inhibitors, anti-staining agents that do not fall under component (D) (for example, polyvinyl pyrrolidone, carboxymethyl cellulose, etc.), pearl agents, soil Release agents and the like can be included.
Flexibility agents include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenine. Long chain aliphatic amide alkyl tertiary amines such as acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide or salts thereof; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide, and the like. For example, 1 to 5% by mass of dimethylaminopropylamide stearate can be contained.
Examples of the texture improver include FZ-3707, FZ-3504, BY16-205, FZ-3760, FZ-3705, BY16-209, FZ-3710, SF8417, BY16-849, BY16 manufactured by Toray Dow Corning Co., Ltd. -850, 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-7002, SILWET L-7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SILWET FZ-2171 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-W09ZILS -F1-009-11, ABN SILWET FZ-F1-009-13, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-22-22, Modified silicones such as X-20-8010B, KF352A, KF6008, KF615A, KF6012, KF6016, KF6017 manufactured by Koshi Chemical Industry Co., Ltd .; TSF4450, TSF4452 and TSF4445 manufactured by GE Toshiba Silicone Co., Ltd. The modified silicone can be used in an amount of 0.1 to 3% by mass in the liquid detergent composition.
　上記の他、商品の付加価値向上等を目的として、着香剤、着色剤、乳濁化剤、天然物などのエキス等を含むこともできる。
　着香剤としては、代表的な例として、特開２００２－１４６３９９号公報や特開２００９－１０８２４８号公報に記載の香料組成物などが使用でき、好ましい配合量としては、０．１～２質量％である。
　着色剤としては、アシッドレッド１３８、Ｐｏｌａｒ　Ｒｅｄ　ＲＬＳ、アシッドイエロー２０３、アシッドブルー９、青色１号、青色２０５号、緑色３号、ターコイズＰ－ＧＲ（いずれも商品名）等の汎用の色素や顔料を、例えば０．００００５～０．００５質量％程度含むことができる。
　乳濁剤は、ポリスチレンエマルション、ポリ酢酸ビニルエマルジョン等が挙げられ、通常、固形分３０～５０質量％のエマルションが好適に用いられる。具体例としては、ポリスチレンエマルション（サイデン化学社製（商品名）サイビノールＲＰＸ－１９６　ＰＥ－３、固形分４０質量％）等を、０．０１～０．５質量％含むことができる。
　天然物などのエキスとしては、イヌエンジュ、ウワウルシ、エキナセア、コガネバナ、キハダ、オウレン、オールスパイス、オレガノ、エンジュ、カミツレ、スイカズラ、クララ、ケイガイ、ケイ、ゲッケイジュ、ホオノキ、ゴボウ、コンフリー、ジャショウ、ワレモコウ、シャクヤク、ショウガ、セイタカアワダチソウ、セイヨウニワトコ、セージ、ヤドリギ、ホソバオケラ、タイム、ハナスゲ、チョウジ、ウンシュウミカン、ティーツリー、バーベリー、ドクダミ、ナンテン、ニュウコウ、ヨロイグサ、シロガヤ、ボウフウ、オランダヒユ、ホップ、ホンシタン、マウンテングレープ、ムラサキタガヤサン、セイヨウヤマハッカ、ヒオウギ、ヤマジソ、ユーカリ、ラベンダー、ローズ、ローズマリー、バラン、スギ、ギレアドバルサムノキ、ハクセン、ホウキギ、ミチヤナギ、ジンギョウ、フウ、ツリガネニンジン、ヤマビシ、ヤブガラシ、カンゾウ、セイヨウオトギリソウなどの植物のエキスが挙げられ、これらを例えば、０～０．５質量％程度含むことができる。 In addition to the above, flavoring agents, coloring agents, emulsifying agents, extracts of natural products, and the like can also be included for the purpose of improving the added value of goods.
As a typical example of a flavoring agent, a fragrance composition described in JP-A-2002-146399 and JP-A-2009-108248 can be used, and a preferable blending amount is 0.1 to 2 mass. %.
General-purpose dyes 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 Turquoise P-GR (all are trade names) For example, about 0.00005 to 0.005 mass%.
Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is preferably used. As a specific example, a polystyrene emulsion (manufactured by Seiden Chemical Co., Ltd. (trade name) Cybinol RPX-196 PE-3, solid content 40% by mass) and the like can be contained in an amount of 0.01 to 0.5% by mass.
Examples of extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou, Liquidambar formosana, Adenophortriphylla, Yamabishi, cayratia japonica, licorice, include plant extracts such as St. John's wort, it can include, for example, about 0 to 0.5% by weight.
　本発明の液体洗浄剤組成物は、２５℃でのｐＨが４～９であることが好ましく、４～８であることがより好ましい。前記ｐＨが４～９であることにより、特に、液体洗浄剤組成物を長期間保存しても、経時安定性を良好に保つことができる。
　ｐＨはｐＨ調整剤により調整できる。ｐＨ調整剤としては、塩酸、硫酸、リン酸等の無機酸；多価カルボン酸類、ヒドロキシカルボン酸類等の有機酸；水酸化ナトリウム、水酸化カリウム、アルカノールアミン、アンモニア等が挙げられる。これらのなかでも、液体洗浄剤組成物の経時安定性の面から、硫酸、水酸化ナトリウム、水酸化カリウム、アルカノールアミンが好ましく、硫酸、水酸化ナトリウムが好ましい。
　ｐＨ調整剤は、１種を単独で用いてもよく、２種以上を併用してもよい。たとえば一定量の硫酸、水酸化ナトリウム等を添加することにより制御した場合、さらに、ｐＨの微調整用として無機酸（好ましくは塩酸、硫酸）又は水酸化カリウム等をさらに添加することができる。
　本明細書において、液体洗浄剤組成物（２５℃に調温）のｐＨは、ｐＨメーター（製品名：ＨＭ－３０Ｇ、東亜ディーケーケー（株）製）等により測定される値を示す。 The liquid detergent composition of the present invention preferably has a pH of 4 to 9 at 25 ° C., more preferably 4 to 8. When the pH is 4 to 9, it is 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 with a pH adjuster. Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide, alkanolamine and ammonia. Of these, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid and sodium hydroxide are preferable from the viewpoint of the temporal stability of the liquid detergent composition.
A pH adjuster may be used individually by 1 type, and may use 2 or more types together. For example, when controlled by adding a certain amount of sulfuric acid, sodium hydroxide or the like, an inorganic acid (preferably hydrochloric acid or sulfuric acid) or potassium hydroxide can be further added for fine adjustment of pH.
In the present specification, the pH of the liquid detergent composition (controlled at 25 ° C.) indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.
　本発明の液体洗浄剤組成物は、常法に基づいて製造することができ、たとえば上記各成分を混合することにより製造できる。このとき、液体媒体として水を添加することが好ましい。 The liquid detergent composition of the present invention can be produced based on a conventional method, for example, by mixing the above-described components. At this time, it is preferable to add water as a liquid medium.
　本発明の液体洗浄剤組成物は、衣料用液体洗浄剤組成物の通常の使用方法と同様の方法で使用できる。すなわち液体洗浄剤組成物を、洗濯時に洗濯物と一緒に水に投入する方法、液体洗浄剤組成物を泥汚れや皮脂汚れに直接塗布する方法、液体洗浄剤組成物を予め水に溶かして衣類を浸漬する方法等が挙げられる。また、液体洗浄剤組成物を洗濯物に塗布後、適宜放置し、その後、通常の洗濯液を用いて通常の洗濯を行う方法も好ましい。
その際、本発明の液体洗浄剤組成物の使用量は、従来の液体洗浄剤組成物の使用量よりも少なくすることができる。 The liquid detergent composition of the present invention can be used in the same manner as the usual method for using the liquid detergent composition for clothing. That is, a method in which the liquid detergent composition is poured into water together with the laundry at the time of washing, a method in which the liquid detergent composition is directly applied to mud dirt or sebum dirt, a liquid detergent composition previously dissolved in water and clothing. And the like. Also preferred is a method in which the liquid detergent composition is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a normal laundry solution.
In that case, the usage-amount of the liquid cleaning composition of this invention can be made smaller than the usage-amount of the conventional liquid cleaning composition.
　本発明について、実施例を示してさらに具体的に説明する。ただし本発明はこれらの限定されるものではない。
＜実施例１～１９、比較例１～１３＞
　表１に示す組成の液体洗浄剤組成物を下記の手順で調製した。
　５００ｍＬビーカーに（Ａ）成分、（Ｂ）成分及び（Ｅ）成分を入れ、マグネットスターラー（ＭＩＴＡＭＵＲＡ　ＫＯＧＹＯ　ＩＮＣ．製）で充分に攪拌した。続いて、その他の成分（（Ｃ）成分、（Ｄ）成分、共通添加成分）を加えて攪拌しながら、全体量が９８質量部になるように精製水を入れ、さらによく攪拌した。２５℃でのｐＨが７．０になるようにｐＨ調整剤（水酸化ナトリウム又は硫酸）を適量添加した後、全体量が１００質量部になるように精製水を加えて、液体洗浄剤組成物を得た。
　表１中、各成分の配合量の単位は「質量％」である。また、表１に、液体洗浄剤組成物中の（Ａ）成分及び（Ｂ）成分の合計の割合（Ａ＋Ｂ）（質量％）と、（Ａ）成分及び（Ｂ）成分の配合量の比（Ｂ／Ａ）と、（Ｃ）成分及び（Ｄ）成分の配合量の比（Ｄ／Ｃ）とを併記する。
　得られた液体洗浄剤組成物について、以下の評価を行った。その結果を表１に併記する。 The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these.
<Examples 1 to 19 and Comparative Examples 1 to 13>
A liquid detergent composition having the composition shown in Table 1 was prepared by the following procedure.
(A) component, (B) component, and (E) component were put into a 500 mL beaker, and it fully stirred with the magnetic stirrer (made by MITAMURA KOGYO INC.). Subsequently, while adding the other components (component (C), component (D), common additive component) and stirring, purified water was added so that the total amount became 98 parts by mass, and further stirred. After adding a suitable amount of pH adjusting agent (sodium hydroxide or sulfuric acid) so that the pH at 25 ° C. is 7.0, purified water is added so that the total amount becomes 100 parts by mass, and a liquid detergent composition Got.
In Table 1, the unit of the amount of each component is “% by mass”. Moreover, in Table 1, the ratio (A + B) (mass%) of the sum total of (A) component and (B) component in liquid cleaning composition, and ratio of the compounding quantity of (A) component and (B) component ( B / A) and the ratio (D / C) of the blending amounts of component (C) and component (D) are shown together.
The following evaluation was performed about the obtained liquid detergent composition. The results are also shown in Table 1.
＜初期外観の評価＞
　上記手順で調製した液体洗浄剤組成物５００ｇの入ったビーカー（容量５００ｍＬ）を斜めに傾けて、内容物約１００ｍＬを透明のガラス瓶（広口規格びんＰＳ－ＮＯ．１１）に取り出す操作を行った。
　このとき、ガラス瓶に取り出せた液体洗浄剤組成物を流動性あり、取り出せなかったものを流動性なしと判定した。
　また、ガラス瓶に取り出せた液体洗浄剤組成物の外観を目視にて観察した。
　それらの結果から、各液体洗浄剤組成物の初期外観を下記基準で評価した。
　○：流動性があり、かつ外観が透明均一である。
　×：流動性がない（ガラス瓶に取り出せない）。または、流動性はあるものの、外観に濁り、浮遊・沈殿物がある。 <Evaluation of initial appearance>
A beaker (capacity 500 mL) containing 500 g of the liquid detergent composition prepared by the above procedure was tilted, and about 100 mL of the contents were taken out into a transparent glass bottle (wide-mouth standard bottle PS-NO.11).
At this time, it was determined that the liquid detergent composition taken out into the glass bottle had fluidity, and the liquid detergent composition that could not be taken out had no fluidity.
Moreover, the external appearance of the liquid detergent composition taken out to the glass bottle was observed visually.
From these results, the initial appearance of each liquid detergent composition was evaluated according to the following criteria.
○: fluid and transparent and uniform in appearance.
X: No fluidity (cannot be taken out into a glass bottle) Or, although it has fluidity, it is turbid in appearance and has floating and sediment.
＜皮脂洗浄力の評価＞
　上記初期外観の評価にて流動性ありと判定された液体洗浄剤組成物について、下記の手順で皮脂洗浄力を評価した。
　顔面の皮脂汚れを擦り付けたアクリルジャージ布を２０ｃｍ角の大きさに裁断したものを１０枚と、市販のＴシャツ（綿１００％、Ｂ．Ｖ．Ｄ．社製）４枚とを電気洗濯機（三菱電機社製、「ＣＷ－Ｃ３０Ａ１型」）に投入した。
　ついで、２５℃の水道水約３０Ｌに対し、液体洗浄剤組成物を２０ｇ添加し、標準水流で洗浄（１０分）、脱水（１分）、標準水流でためすすぎ（２回繰り返しを各５分）、脱水（１分）、を順次行う洗浄操作を行った。
　皮脂汚れを擦り付けていないアクリルジャージ布を未汚染布、洗浄処理前のアクリルジャージ布を汚染布、洗浄処理後のアクリルジャージ布を洗浄布とした。未汚染布、汚染布、洗浄布それぞれについて、分光式色差計（日本電色工業社製、「ＳＥ２０００」）にてＺ値（反射率）を測定し、下記式（Ｉ）により洗浄率（％）を算出した。 <Evaluation of sebum detergency>
About the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the sebum detergency was evaluated by the following procedure.
10 sheets of acrylic jersey cloth rubbed with sebum on the face and cut into 20cm square size and 4 pieces of commercially available T-shirts (100% cotton, manufactured by BVD Corp.) ("CW-C30A1 type" manufactured by Mitsubishi Electric Corporation).
Next, 20 g of a liquid detergent composition is added to about 30 L of tap water at 25 ° C., washed with a standard water flow (10 minutes), dehydrated (1 minute), and rinsed with a standard water flow (repeat twice for 5 minutes each) ) And dehydration (1 minute) were sequentially performed.
An acrylic jersey cloth not rubbed with sebum stain was used as an uncontaminated cloth, an acrylic jersey cloth before the cleaning treatment was used as a contaminated cloth, and an acrylic jersey cloth after the cleaning treatment was used as a cleaning cloth. For each of unstained cloth, contaminated cloth and cleaning cloth, the Z value (reflectance) was measured with a spectroscopic color difference meter (“SE2000” manufactured by Nippon Denshoku Industries Co., Ltd.), and the cleaning rate (%) was calculated according to the following formula (I). ) Was calculated.
Figure JPOXMLDOC01-appb-M000004
Figure JPOXMLDOC01-appb-M000004
　求めた洗浄率（％）（同時に洗浄処理した１０枚の平均値）から、下記基準により液体洗浄剤組成物の皮脂汚れに対する洗浄力を評価した。
　◎：洗浄率が７５％以上。
　○：洗浄率が６５％以上７５％未満。
　△：洗浄率が５５％以上６５％未満。
　×：洗浄率が５５％未満。 From the determined washing rate (%) (average value of 10 sheets subjected to washing at the same time), the detergency of the liquid detergent composition against sebum stain was evaluated according to the following criteria.
A: The cleaning rate is 75% or more.
○: The cleaning rate is 65% or more and less than 75%.
Δ: The cleaning rate is 55% or more and less than 65%.
X: The cleaning rate is less than 55%.
＜洗濯後の衣類の着心地の評価＞
　上記初期外観の評価にて流動性ありと判定された液体洗浄剤組成物について、下記の手順で、洗濯後の衣類の着心地を評価した。
　全自動電気洗濯機（Ｈａｉｅｒ社製ＪＷ－Ｚ２３Ａ）に、市販のシャツ（麻１００％）１枚、及び市販の綿タオル（綿１００％）を投入した（綿タオルの投入量は全布質量が約８００ｇとなるように調整した）。そこに液体洗浄剤組成物５ｍＬを添加し、標準コースで洗浄、すすぎ、脱水を順次行う洗浄操作を行った。洗浄時間、すすぎ、脱水、水量（低水位に設定、水量約１２Ｌ）に関しては、一切調整せず、洗濯機の標準コース設定を使用した。
　洗濯終了後、上記の洗浄処理が施された布を２５℃、湿度６５％ＲＨの恒温恒湿室に放置した。１日後、室温２８℃の室内でパネリスト（５人）に着用してもらい、肌に触れたときの感触（着心地）を、対照布（洗濯処理をしていない新品シャツ）と比較し、下記基準により採点した。
　１点：対照布に比べてハリ感がないか、または顕著なゴワつきがあり、かなり着心地がよくない。
　２点：対照布に比べてハリ感が少ないか、または若干ゴワつきがあり、やや着心地がよくない。
　３点：対照布と同等の着心地。
　４点：対照布よりやや着心地がよい。
　５点：対照布よりかなり着心地がよい。
　パネリスト５人の採点結果の平均値から、下記基準により洗濯後の衣類の着心地を評価した。
　◎：４点以上、○：３．５点以上４点未満、△：３点以上３．５点未満、×：３点未満。 <Evaluation of clothes comfort after washing>
About the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the comfort of the clothes after washing was evaluated by the following procedure.
A fully-automatic electric washing machine (JW-Z23A manufactured by Haier) was charged with a commercially available shirt (100% of linen) and a commercially available cotton towel (100% cotton). Adjusted to be about 800 g). The liquid cleaning composition 5mL was added there, and the washing operation which performs washing | cleaning, a rinse, and spin-drying | dehydration in order by the standard course was performed. With regard to washing time, rinsing, dehydration, and water volume (set to a low water level, water volume of about 12 L), no adjustment was made and the standard course setting of the washing machine was used.
After the washing, the cloth subjected to the above washing treatment was left in a constant temperature and humidity room at 25 ° C. and humidity 65% RH. One day later, panelists (5 people) wear them at room temperature of 28 ° C, and compared the feeling when they touched the skin (comfort) with a control cloth (a new shirt that has not been washed). Scored according to criteria.
1 point: There is no firmness compared to the control cloth, or there is a noticeable gore and is not very comfortable to wear.
2 points: There is little elasticity compared to the control cloth, or there is a slight crease and it is slightly uncomfortable.
3 points: Same comfort as the control cloth.
4 points: A little more comfortable than the control cloth.
5 points: Very comfortable to wear than the control cloth.
From the average value of the scoring results of five panelists, the comfort of clothes after washing was evaluated according to the following criteria.
：: 4 points or more, ○: 3.5 points or more and less than 4 points, Δ: 3 points or more and less than 3.5 points, ×: less than 3 points.
＜柔軟性の評価＞
　上記初期外観の評価にて流動性ありと判定された液体洗浄剤組成物について、下記の手順で柔軟性（柔軟性付与効果）を評価した。
　二槽式洗濯機（三菱電機社製、ＣＷ－Ｃ３０Ａ１型）に、水道水３０Ｌ、液体洗浄剤組成物１０ｇを入れ、そこに、２０ｃｍ角の大きさに裁断したアクリルジャージ布５枚と市販Ｔシャツ（綿１００％、Ｂ．Ｖ．Ｄ．社製）６枚を投入し、１０分間洗浄した後、脱水１分、ためすすぎ５分、脱水１分を行った。用いた水道水の温度は２５℃になるよう調整を行った。前記洗浄操作で処理したアクリルジャージ布を陰干しして１２時間乾燥させた。乾燥させたアクリルジャージ布を、２５℃、６５％ＲＨの恒温恒湿室に２日間放置した。これを試験布とし、その柔らかさをパネリスト（５人）により対照布と比較し、下記基準により採点した。対照布としては、非イオン性界面活性剤（Ｐ＆Ｇ社製の天然アルコールＣＯ－１２７０に対し、１モル当たり平均１５モルの酸化エチレンを付加させたアルコールエトキシレート（表１中のｂ－１））の２０％水溶液を組成物として、上記と同じ洗浄操作で処理したアクリルジャージ布を用いた。
　１点：対照布と同等である。
　２点：対照布よりやや柔らかい。
　３点：対照布より柔らかい。
　４点：対照布よりかなり柔らかい。
　５点：対照布より非常に柔らかい。
　パネリスト５人の採点結果の平均値から、下記基準により柔軟性を評価した。
　◎：４点以上、○：平３．５点以上４点未満、△：３点以上３．５点未満、×：３点未満。 <Evaluation of flexibility>
About the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the flexibility (flexibility imparting effect) was evaluated by the following procedure.
Into a two-tank washing machine (CW-C30A1 type, manufactured by Mitsubishi Electric Corporation), 30 L of tap water and 10 g of a liquid detergent composition are placed, and there are five acrylic jersey cloths cut into a 20 cm square size and a commercial T Six shirts (100% cotton, manufactured by BVD Co., Ltd.) were put in, washed for 10 minutes, dehydrated for 1 minute, rinsed for 5 minutes, and dehydrated for 1 minute. The tap water used was adjusted to a temperature of 25 ° C. The acrylic jersey cloth treated in the washing operation was shade-dried and dried for 12 hours. The dried acrylic jersey cloth was left in a constant temperature and humidity room at 25 ° C. and 65% RH for 2 days. This was used as a test cloth, and its softness was compared with a control cloth by panelists (5 persons) and scored according to the following criteria. As a control fabric, a nonionic surfactant (alcohol ethoxylate (b-1 in Table 1) obtained by adding an average of 15 moles of ethylene oxide per mole to a natural alcohol CO-1270 manufactured by P & G) An acrylic jersey cloth treated by the same washing operation as described above was used as a composition.
1 point: Equivalent to the control cloth.
2 points: Slightly softer than the control cloth.
3 points: Softer than the control cloth.
4 points: considerably softer than the control cloth.
5 points: Very softer than the control fabric.
From the average value of the scoring results of five panelists, flexibility was evaluated according to the following criteria.
：: 4 points or more, ○: flat 3.5 points or more and less than 4 points, Δ: 3 points or more and less than 3.5 points, ×: less than 3 points.
＜再汚染防止性の評価＞
　上記初期外観の評価にて流動性ありと判定された液体洗浄剤組成物について、下記の手順で再汚染防止性を評価した。
　Ｔｅｒｇ－Ｏ－Ｔｏｍｅｔｅｒ（ＵＮＩＴＥＤ　ＳＴＡＴＥＳ　ＴＥＳＴＩＮＧ社製）の洗浄浴中に、水道水９００ｍＬ、洗浄液０．３ｇを入れ、１２０ｒｐｍで３分間攪拌した後、油汚垢布（５×５ｃｍ）１枚、赤土汚垢布（５×５ｃｍ）１枚、白色ポリエステルトロピカル布（５×５ｃｍ）２枚を入れ、１０分間洗浄した（２５℃）。その後、ザルに空けて洗浄液を除き、試験布（油汚垢布、赤土汚垢布、白色ポリエステルトロピカル布）を２槽式洗濯機の脱水槽で１分間脱水した。さらに、水道水９００ｍＬを入れたＴｅｒｇ－Ｏ－Ｔｏｍｅｔｅｒ浴中で３分間すすぎ、試験布を２槽式洗濯機（三菱電機社製、ＣＷ－Ｃ３０Ａ１型）の脱水槽で１分間脱水した。同様に、すすぎ（３分）、脱水（１分）の操作を繰り返した後、白色ポリエステルトロピカル布を乾燥させて反射率を測定し、洗浄前の反射率との差を再汚染度（ΔＺ）として算出した。ΔＺの値から、下記基準により再汚染防止性を評価した。
　◎：ΔＺが３以下、○：ΔＺが３超６以下、△：ΔＺが６超９以下、×：ΔＺが９超。 <Evaluation of recontamination prevention>
About the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the recontamination prevention property was evaluated by the following procedure.
In a washing bath of Terg-O-Tometer (manufactured by UNITED STATES TESTING), 900 mL of tap water and 0.3 g of cleaning solution were added and stirred at 120 rpm for 3 minutes, and then one piece of oil stain cloth (5 × 5 cm), red soil One paste cloth (5 × 5 cm) and two white polyester tropical cloths (5 × 5 cm) were added and washed for 10 minutes (25 ° C.). Thereafter, the cleaning solution was removed by emptying the colander, and the test cloth (oil soil cloth, red soil soil cloth, white polyester tropical cloth) was dehydrated for 1 minute in a dewatering tank of a 2-tank washing machine. Further, it was rinsed for 3 minutes in a Terg-O-Tometer bath containing 900 mL of tap water, and the test cloth was dehydrated for 1 minute in a dewatering tank of a 2-tank washing machine (CW-C30A1 type, manufactured by Mitsubishi Electric Corporation). Similarly, after repeating the operations of rinsing (3 minutes) and dehydration (1 minute), the white polyester tropical cloth was dried to measure the reflectance, and the difference from the reflectance before washing was determined as the degree of recontamination (ΔZ). Calculated as From the value of ΔZ, the anti-recontamination property was evaluated according to the following criteria.
A: ΔZ is 3 or less, O: ΔZ is more than 3 and 6 or less, Δ: ΔZ is more than 6 and 9 or less, and X: ΔZ is more than 9.
＜保存安定性の評価＞
　上記初期外観の評価にて流動性ありと判定された液体洗浄剤組成物について、下記の手順で保存安定性を評価した。
　液体洗浄剤組成物１００ｍＬを透明のガラス瓶（広口規格びんＰＳ－ＮＯ．１１）に取り、蓋を閉めて密封し、この状態で－５℃の恒温槽中に置いて１ヵ月保存した。その後、恒温槽から取り出し、それから１分以内に室温（２５℃）にて内容物の外観を目視で観察し下記基準により評価した。
　○：外観が透明均一であった。
　△：沈殿又はゲル化が認められたが、４０℃の湯浴に１時間浸すと外観が透明均一となった。
　×：沈殿又はゲル化が認められ、４０℃の湯浴に１時間浸しても外観が透明均一にならなかった。　 <Evaluation of storage stability>
The storage stability of the liquid detergent composition determined to have fluidity in the initial appearance evaluation was evaluated according to the following procedure.
100 mL of the liquid detergent composition was placed in a transparent glass bottle (wide-mouth standard bottle PS-NO.11), sealed with the lid closed, and placed in a thermostatic bath at −5 ° C. and stored for 1 month. Then, it took out from the thermostat, and the external appearance of the contents was observed visually at room temperature (25 degreeC) within 1 minute, and it evaluated by the following reference | standard.
○: Appearance was transparent and uniform.
Δ: Precipitation or gelation was observed, but the appearance became transparent and uniform when immersed in a 40 ° C. hot water bath for 1 hour.
X: Precipitation or gelation was observed, and the appearance did not become transparent and uniform even when immersed in a hot water bath at 40 ° C. for 1 hour.
　表１の結果に示すように、本発明の液体洗浄剤組成物は、液安定性が良好で、初期外観、保存安定性ともに良好な結果が得られた。また、皮脂洗浄力、洗浄した麻衣料の着心地、柔軟性、再汚染防止性の全ての評価項目でバランス良く、良好な結果が得られた。
　一方、本発明の（Ａ）成分に該当しない脂肪酸メチルエステルエトキシレートを配合した比較例１、（Ａ）成分を配合していない比較例３、（Ｅ）成分の配合量が２質量％の比較例６、Ａ＋Ｂが６８質量％の比較例７、Ｂ／Ａが８６／１４の比較例９は、それぞれ、初期外観が悪く、以降の評価ができなかった。また、（Ｂ）成分を配合していない比較例２、Ｂ／Ａが４／９６の比較例１１はそれぞれ洗浄した麻衣料の着心地に劣っていた。また、（Ｃ）成分を配合していない比較例４、Ｄ／Ｃが１２／１の比較例１２はそれぞれ柔軟性が悪く、（Ｄ）成分を配合していない比較例５は再汚染防止性が悪く、Ｄ／Ｃが０．６７／１の比較例８は、再汚染防止性が悪く、柔軟性、保存安定性も劣っていた。また、Ａ＋Ｂが６質量％の比較例１０は、皮脂洗浄力が低く、着心地も不良であった。また、（Ａ）成分を配合していない比較例１３は、Ａ＋Ｂの値が同じ実施例１３と比べて、皮脂洗浄力、着心地、柔軟性が劣っていた。 As shown in the results of Table 1, the liquid detergent composition of the present invention had good liquid stability and good results in both initial appearance and storage stability. In addition, good results were obtained in a well-balanced manner with respect to all evaluation items of sebum detergency, comfort of the washed garment, flexibility, and anti-recontamination property.
On the other hand, the comparative example 1 which mix | blended the fatty acid methyl ester ethoxylate which does not correspond to the (A) component of this invention, the comparative example 3 which does not mix | blend the (A) component, the comparison of the compounding quantity of (E) component being 2 mass% In Example 6, Comparative Example 7 in which A + B was 68% by mass, and Comparative Example 9 in which B / A was 86/14, the initial appearance was poor, and subsequent evaluation could not be performed. Moreover, the comparative example 2 which is not mix | blending (B) component, and the comparative example 11 whose B / A is 4/96 were inferior to the comfort of the washed garments, respectively. Further, Comparative Example 4 in which component (C) is not blended and Comparative Example 12 in which D / C is 12/1 are poor in flexibility, and Comparative Example 5 in which component (D) is not blended is recontamination preventing property. However, Comparative Example 8 having a D / C of 0.67 / 1 was poor in re-contamination prevention property, and inferior in flexibility and storage stability. Moreover, the comparative example 10 whose A + B is 6 mass% had low sebum detergency, and the comfort was also poor. Moreover, the comparative example 13 which does not mix | blend (A) component was inferior in sebum cleaning power, comfort, and a softness | flexibility compared with Example 13 with the same value of A + B.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　＜実施例２０～６２、比較例１４～２１＞
　表２～３に示す組成の液体洗浄剤組成物を下記の手順で調製した。
　５００ｍＬビーカーに（Ａ）成分、（Ｂ）成分及び（Ｅ）成分を入れ、マグネットスターラー（ＭＩＴＡＭＵＲＡ　ＫＯＧＹＯ　ＩＮＣ．製）で充分に攪拌した。続いて、その他の成分（（Ｄ）成分、（Ｆ）成分、共通添加成分）を加えて攪拌しながら、全体量が９８質量部になるように精製水を入れ、さらによく攪拌した。２５℃でのｐＨが７．０になるように、ｐＨ調整剤（水酸化ナトリウム又は硫酸）を適量添加した後、全体量が１００質量部になるように精製水を加えて、液体洗浄剤組成物を得た。
　表２～３中、各成分の配合量の単位は「質量％」である。また、表２～３に、液体洗浄剤組成物中の（Ａ）成分および（Ｂ）成分の合計の割合（Ａ＋Ｂ）（質量％）と、（Ａ）成分および（Ｂ）成分の配合量の比（Ｂ／Ａ）を併記する。
　得られた液体洗浄剤組成物について、以下の評価を行った。その結果を表２～３に併記する。 <Examples 20 to 62, Comparative Examples 14 to 21>
Liquid detergent compositions having the compositions shown in Tables 2 to 3 were prepared by the following procedure.
(A) component, (B) component, and (E) component were put into a 500 mL beaker, and it fully stirred with the magnetic stirrer (made by MITAMURA KOGYO INC.). Subsequently, while adding other components (component (D), component (F), common additive component) and stirring, purified water was added so that the total amount became 98 parts by mass, and further stirred. After adding an appropriate amount of pH adjuster (sodium hydroxide or sulfuric acid) so that the pH at 25 ° C. becomes 7.0, purified water is added so that the total amount becomes 100 parts by mass, and a liquid detergent composition I got a thing.
In Tables 2 to 3, the unit of the blending amount of each component is “mass%”. Tables 2 to 3 show the total ratio (A + B) (mass%) of the components (A) and (B) in the liquid detergent composition, and the blending amounts of the components (A) and (B). The ratio (B / A) is also shown.
The following evaluation was performed about the obtained liquid detergent composition. The results are also shown in Tables 2-3.
＜初期外観の評価＞
　上記手順で調製した液体洗浄剤組成物５００ｇの入ったビーカー（容量５００ｍＬ）を斜めに傾けて、内容物約１００ｍＬを透明のガラス瓶（広口規格びんＰＳ－ＮＯ．１１）に取り出す操作を行った。
　このとき、ガラス瓶に取り出せた液体洗浄剤組成物を流動性あり、取り出せなかったものを流動性なしと判定した。
　また、ガラス瓶に取り出せた液体洗浄剤組成物の外観を目視にて観察した。
　それらの結果から、各液体洗浄剤組成物の初期外観を下記基準で評価した。
　○：流動性があり、かつ外観が透明均一である。
　×：流動性がない（ガラス瓶に取り出せない）。または、流動性はあるものの、外観に濁り、浮遊・沈殿物がある。 <Evaluation of initial appearance>
A beaker (capacity 500 mL) containing 500 g of the liquid detergent composition prepared by the above procedure was tilted, and about 100 mL of the contents were taken out into a transparent glass bottle (wide-mouth standard bottle PS-NO.11).
At this time, it was determined that the liquid detergent composition taken out into the glass bottle had fluidity, and the liquid detergent composition that could not be taken out had no fluidity.
Moreover, the external appearance of the liquid detergent composition taken out to the glass bottle was observed visually.
From these results, the initial appearance of each liquid detergent composition was evaluated according to the following criteria.
○: fluid and transparent and uniform in appearance.
X: No fluidity (cannot be taken out into a glass bottle) Or, although it has fluidity, it is turbid in appearance and has floating and sediment.
＜保存安定性の評価＞
　液体洗浄剤組成物１００ｍＬを透明のガラス瓶（広口規格びんＰＳ－ＮＯ．１１）に取り、蓋を閉めて密封し、この状態で－５℃の恒温槽中に置いて１ヵ月保存した。その後、恒温槽から取り出し、それから１分以内に室温（２５℃）にて内容物の外観を目視で観察し下記基準により評価した。
　○：外観が透明均一であった。
　△：沈殿またはゲル化が認められたが、４０℃の湯浴に１時間浸すと外観が透明均一となった。
　×：沈殿またはゲル化が認められ、４０℃の湯浴に１時間浸しても外観が透明均一にならなかった。 <Evaluation of storage stability>
100 mL of the liquid detergent composition was placed in a transparent glass bottle (wide-mouth standard bottle PS-NO.11), sealed with the lid closed, and placed in a thermostatic bath at −5 ° C. and stored for 1 month. Then, it took out from the thermostat, and the external appearance of the contents was observed visually at room temperature (25 degreeC) within 1 minute, and it evaluated by the following reference | standard.
○: Appearance was transparent and uniform.
Δ: Precipitation or gelation was observed, but the appearance became transparent and uniform when immersed in a 40 ° C. hot water bath for 1 hour.
X: Precipitation or gelation was observed, and the appearance did not become transparent and uniform even when immersed in a hot water bath at 40 ° C. for 1 hour.
＜溶解速度の測定および溶解性の評価＞
　５００ｍＬビーカーに２５℃のイオン交換水３００ｍＬを入れ、マグネットスターラー（ＭＩＴＡＭＵＲＡ　ＫＯＧＹＯ　ＩＮＣ．）を用いて攪拌（５００ｒｐｍ）しつつ、そこに、ポリスポイトを用いて液体洗浄剤組成物０．１ｍＬを滴下し、液体洗浄剤組成物が完全に溶解するまでの時間（溶解時間）を目視にて測定した。
　測定した溶解時間から、各液体洗浄剤組成物の溶解性を下記基準により評価した。
　◎：５０秒未満。
　○：５０秒～１００秒未満。
　△：１００秒～１５０秒未満。
　×：１５０秒以上。 <Measurement of dissolution rate and evaluation of solubility>
Put 300 mL of ion exchange water at 25 ° C. into a 500 mL beaker, stir (500 rpm) using a magnetic stirrer (MITAMURA KOGYO INC.), And drop 0.1 mL of the liquid detergent composition using a poly dropper. The time until the liquid detergent composition was completely dissolved (dissolution time) was measured visually.
From the measured dissolution time, the solubility of each liquid detergent composition was evaluated according to the following criteria.
A: Less than 50 seconds.
○: 50 seconds to less than 100 seconds.
Δ: 100 seconds to less than 150 seconds.
X: 150 seconds or more.
＜皮脂洗浄力の評価＞
　上記初期外観の評価にて流動性ありと判定された液体洗浄剤組成物について、下記の手順で皮脂洗浄力を評価した。
　顔面の皮脂汚れを擦り付けた綿布（綿平織り布、１００番手）を２０ｃｍ角の大きさに裁断したものを１０枚と、市販のＴシャツ（綿１００％、Ｂ．Ｖ．Ｄ．社製）４枚とを電気洗濯機（三菱電機社製、「ＣＷ－Ｃ３０Ａ１型」）に投入した。
　ついで、２５℃の水道水約３０Ｌに対し、液体洗浄剤組成物を１０ｍＬの割合で添加し、標準水流で洗浄（１０分）、脱水（１分）、標準水流でためすすぎ（２回繰り返しを各５分）、脱水（１分）、を順次行う洗浄操作を行った。
　皮脂汚れを擦り付けていない綿布を未汚染布、洗浄処理前の綿布を汚染布、洗浄処理後の綿布を洗浄布とした。未汚染布、汚染布、洗浄布それぞれについて、分光式色差計（日本電色工業社製、「ＳＥ２０００」）にてＺ値（反射率）を測定し、下記式（ＩＩ）により洗浄率（％）を算出した。 <Evaluation of sebum detergency>
About the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the sebum detergency was evaluated by the following procedure.
10 pieces of cotton cloth (cotton plain weave cloth, 100 count) rubbed with sebum on the face and cut into a 20 cm square size and a commercially available T-shirt (100% cotton, manufactured by BVD Corporation) 4 The sheet was put into an electric washing machine (“CW-C30A1 type” manufactured by Mitsubishi Electric Corporation).
Next, a liquid detergent composition is added at a rate of 10 mL to about 30 L of tap water at 25 ° C., washed with a standard water flow (10 minutes), dehydrated (1 minute), and rinsed with a standard water flow (repeated twice). A washing operation was sequentially performed for 5 minutes each and dehydration (1 minute).
The cotton cloth not rubbed with sebum stain was used as an uncontaminated cloth, the cotton cloth before the cleaning treatment was used as the contamination cloth, and the cotton cloth after the cleaning treatment was used as the cleaning cloth. For each of the unstained cloth, the contaminated cloth, and the cleaning cloth, the Z value (reflectance) was measured with a spectroscopic color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., “SE2000”), and the cleaning rate (%) was calculated according to the following formula (II). ) Was calculated.
Figure JPOXMLDOC01-appb-M000006
Figure JPOXMLDOC01-appb-M000006
　求めた洗浄率（％）（同時に洗浄処理した１０枚の平均値）から、下記基準により液体洗浄剤組成物の皮脂汚れに対する洗浄力を評価した。
　◎：洗浄率が７０％以上。
　○：洗浄率が６０％以上７０％未満。
　△：洗浄率が５０％以上６０％未満。
　×：洗浄率が５０％未満。 From the determined washing rate (%) (average value of 10 sheets subjected to washing at the same time), the detergency of the liquid detergent composition against sebum stain was evaluated according to the following criteria.
A: The cleaning rate is 70% or more.
○: The cleaning rate is 60% or more and less than 70%.
Δ: The cleaning rate is 50% or more and less than 60%.
X: The cleaning rate is less than 50%.
＜カレー汚れに対する塗布洗浄力の評価＞
　２５℃で示される液粘度で塗布した際の洗浄力を評価するため、上記初期外観の評価にて流動性ありと判定された液体洗浄剤組成物のうち、実施例４１～６２の液体洗浄剤組成物を２５℃で２４時間保存し、前記保存後の液体洗浄剤組成物について、下記の手順でカレー汚れに対する皮脂洗浄力を評価した。
　ボンカレーゴールド中辛口（商品名、大塚食品社製）をガーゼでろ過し、これをステンレスバットに開けた。その中に綿布（綿平織り布、１００番手）を約１時間浸漬した後、ブラッシングして過剰に付着した汚れを脱落させ、一夜風乾した。このカレー汚れが付着した綿布を１０ｃｍ×１０ｃｍに裁断し、これを汚染布とした。
　前記汚染布６枚に、２５℃で２４時間保存後の液体洗浄剤組成物０．１ｇを塗布し、５分間放置した。その後、前記汚染布をＴｅｒｇ－Ｏ－Ｔｏｍｅｔｅｒ（ＵＮＩＴＥＤ　ＳＴＡＴＥＳ　ＴＥＳＴＩＮＧ社製）に投入し、２５℃水道水（硬度３ＤＨ）０．９Ｌを入れ、１２０ｒｐｍで１０分間撹拌した後、二槽式洗濯機（三菱電機社製、ＣＷ－Ｃ３０Ａ１型）に移し、１分間脱水した。その後、１分間流水ですすぎ、１分間脱水をした後、風乾した。
　カレー汚れ付着前の綿布を未汚染布、洗浄処理後の汚染布を洗浄布とした。未汚染布、汚染布（洗浄処理前）、洗浄布それぞれについて、前記皮脂洗浄力の評価と同様にしてＺ値を測定し、洗浄率（％）を算出した。
　求めた洗浄率（％）（同時に洗浄処理した６枚の平均値）から、下記基準により液体洗浄剤組成物のカレー汚れに対する塗布洗浄力を評価した。
　◎：洗浄率が４０％以上。
　○：洗浄率が３５％以上４０％未満。
　△：洗浄率が３０％以上３５％未満。
　×：洗浄率が３０％未満。 <Evaluation of coating cleaning power against curry stains>
Of the liquid detergent compositions determined to have fluidity in the initial appearance evaluation described above, the liquid detergents of Examples 41 to 62 were evaluated in order to evaluate the detergency when applied at a liquid viscosity indicated at 25 ° C. The composition was stored at 25 ° C. for 24 hours, and the liquid detergent composition after the storage was evaluated for sebum cleaning power against curry stains by the following procedure.
Bon Curry Gold medium dry (trade name, manufactured by Otsuka Foods Co., Ltd.) was filtered with gauze and opened into a stainless steel bat. A cotton cloth (cotton plain weave cloth, No. 100) was immersed therein for about 1 hour, then brushed to remove excessively adhered dirt and air-dried overnight. This cotton cloth with curry stains was cut into 10 cm × 10 cm, and this was used as a contaminated cloth.
0.1 g of the liquid detergent composition that had been stored at 25 ° C. for 24 hours was applied to the six soiled cloths and left for 5 minutes. Thereafter, the contaminated cloth was put into a Terg-O-Tometer (manufactured by UNITED STATES TESTING), 0.9 L of 25 ° C. tap water (hardness 3DH) was added, and the mixture was stirred at 120 rpm for 10 minutes. (Mitsubishi Electric Corporation, 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 stain was used as an uncontaminated cloth, and the contaminated cloth after the cleaning treatment was used as a cleaning cloth. For each of the uncontaminated cloth, the contaminated cloth (before the washing treatment), and the washing cloth, the Z value was measured in the same manner as the evaluation of the sebum detergency, and the washing rate (%) was calculated.
From the obtained washing rate (%) (average value of 6 sheets subjected to washing at the same time), the coating washing power of the liquid detergent composition against curry stains was evaluated according to the following criteria.
A: The cleaning rate is 40% or more.
○: The cleaning rate is 35% or more and less than 40%.
Δ: The cleaning rate is 30% or more and less than 35%.
X: The cleaning rate is less than 30%.
＜洗濯後の衣類の着心地評価＞
　全自動電気洗濯機（Ｈａｉｅｒ社製ＪＷ－Ｚ２３Ａ）に、市販のシャツ（麻１００％）１枚、及び市販の綿タオル（綿１００％）を投入した（綿タオルの投入量は全布質量が約８００ｇとなるように調整した）。そこに、上記初期外観の評価にて流動性ありと判定された液体洗浄剤組成物５ｍＬを添加し、標準コースで洗浄、すすぎ、脱水を順次行う洗浄操作を行った。洗浄時間、すすぎ、脱水、水量（低水位に設定、水量約１２Ｌ）に関しては、一切調整せず、洗濯機の標準コース設定を使用した。洗濯終了後、上記の洗浄処理が施された布を２５℃、湿度６５％ＲＨの恒温恒湿室に放置した。
　１日後、室温２８℃の室内でパネリスト（５人）に着用してもらい、肌に触れたときの感触（着心地）を、対照布（洗濯処理をしていない新品シャツ）と比較し、下記基準により採点した。
　１点：対照布に比べてハリ感がないか、または顕著なゴワつきがあり、かなり着心地がよくない。
　２点：対照布に比べてハリ感が少ないか、または若干ゴワつきがあり、やや着心地がよくない。
　３点：対照布と同等の着心地。
　４点：対照布よりやや着心地がよい。
　５点：対照布よりかなり着心地がよい。
　パネリスト５人の採点結果の平均値から、下記基準により洗濯後の衣類の着心地を評価した。
　　◎：４点以上、○：３．５点以上４点未満、△：３点以上３．５点未満、×：３点未満。 <Evaluation of comfort of clothes after washing>
A fully-automatic electric washing machine (JW-Z23A manufactured by Haier) was charged with a commercially available shirt (100% of linen) and a commercially available cotton towel (100% cotton). Adjusted to be about 800 g). Thereto was added 5 mL of a liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, and a cleaning operation was sequentially performed for washing, rinsing and dehydration in a standard course. With regard to washing time, rinsing, dehydration, and water volume (set to a low water level, water volume of about 12 L), no adjustment was made and the standard course setting of the washing machine was used. After the washing, the cloth subjected to the above washing treatment was left in a constant temperature and humidity room at 25 ° C. and humidity 65% RH.
One day later, panelists (5 people) wear them at room temperature of 28 ° C, and compared the feeling when they touched the skin (comfort) with a control cloth (a new shirt that has not been washed). Scored according to criteria.
1 point: There is no firmness compared to the control cloth, or there is a noticeable gore and is not very comfortable to wear.
2 points: There is little elasticity compared to the control cloth, or there is a slight crease and it is slightly uncomfortable.
3 points: Same comfort as the control cloth.
4 points: A little more comfortable than the control cloth.
5 points: Very comfortable to wear than the control cloth.
From the average value of the scoring results of five panelists, the comfort of clothes after washing was evaluated according to the following criteria.
：: 4 points or more, ○: 3.5 points or more and less than 4 points, Δ: 3 points or more and less than 3.5 points, ×: less than 3 points.
　表２～３の結果に示すように、本発明の液体洗浄剤組成物は、非イオン性界面活性剤を高濃度に配合しても初期外観や保存安定性が良好であった。また、溶解速度も速く、洗浄時における溶解性に優れていた。また、各種洗浄性能も良好で、特に（Ｄ）成分および（Ｆ）成分の両方を配合した実施例４１～５６が優れていた。また、洗浄した麻衣料の着心地も良好であった。
　一方、Ａ＋Ｂが３０質量％の比較例１４は皮脂洗浄力が低かった。また、Ａ＋Ｂが７８質量％の比較例１５、（Ｅ）成分の配合量が２質量％以下の比較例１６～１７、（Ａ）成分を配合していない比較例１８、本発明の（Ａ）成分に該当しない脂肪酸メチルエステルエトキシレートを配合した比較例１９、Ｂ／Ａが８４／１６の比較例２０は、それぞれ、初期外観や保存安定性が悪く、溶解速度も遅かった。さらに、Ｂ／Ａが７／９３の比較例２１は、洗浄した麻衣料の着心地に劣っていた。 As shown in the results of 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 blended at a high concentration. Also, the dissolution rate was fast and the solubility at the time of washing was excellent. Also, various cleaning performances were good, and Examples 41 to 56, in which both the component (D) and the component (F) were blended, were excellent. In addition, the comfort of the washed clothing was good.
On the other hand, Comparative Example 14 with 30% by mass of A + B had a low sebum detergency. Further, Comparative Example 15 in which A + B is 78% by mass, Comparative Examples 16 to 17 in which the blending amount of the component (E) is 2% by mass or less, Comparative Example 18 in which the component (A) is not blended, (A) of the present invention Comparative Example 19 in which a fatty acid methyl ester ethoxylate not corresponding to the component was blended and Comparative Example 20 having a B / A of 84/16 had poor initial appearance and storage stability, and the dissolution rate was also slow. Further, Comparative Example 21 having a B / A of 7/93 was inferior in the comfort of the washed clothing.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表１～３中の各符号は以下のものを示す。
＜（Ａ）成分＞
　（ａ－１）：Ｃ１１Ｈ２３ＣＯ（ＯＣＨ２ＣＨ２）ｍＯＣＨ３とＣ１３Ｈ２７ＣＯ（ＯＣＨ２ＣＨ２）ｍＯＣＨ３との質量比で８／２の混合物、ｍ＝平均１５、ナロー率３３質量％、合成品。
　（ａ－２）：Ｃ１１Ｈ２３ＣＯ（ＯＣＨ２ＣＨ２）ｍＯＣＨ３、ｍ＝平均１５、ナロー率３３質量％、合成品。
　（ａ－３）：Ｃ１１Ｈ２３ＣＯ（ＯＣＨ２ＣＨ２）ｍＯＣＨ３とＣ１３Ｈ２７ＣＯ（ＯＣＨ２ＣＨ２）ｍＯＣＨ３との質量比で８／２の混合物、ｍ＝平均１５、ナロー率４５質量％、合成品。
　（ａ－４）：Ｃ１１Ｈ２３ＣＯ（ＯＣＨ２ＣＨ２）ｍＯＣＨ３とＣ１３Ｈ２７ＣＯ（ＯＣＨ２ＣＨ２）ｍＯＣＨ３との質量比で８／２の混合物、ｍ＝平均１５、ナロー率６０質量％、合成品。
　（ａ－５（比較品））：Ｃ１７Ｈ３３ＣＯ（ＯＣＨ２ＣＨ２）ｍＯＣＨ３、ｍ＝平均９、ナロー率６５質量％、合成品。
（ａ－６）：Ｃ１１Ｈ２３ＣＯ（ＯＣＨ２ＣＨ（ＣＨ３））ｎ（ＯＣＨ２ＣＨ２）ｍＯＣＨ３とＣ１３Ｈ２７ＣＯ（ＯＣＨ２ＣＨ（ＣＨ３））ｎ（ＯＣＨ２ＣＨ２）ｍＯＣＨ３との質量比で８／２の混合物、ｍ＝平均１５、ｎ＝平均１（ランダム）、ナロー率３７質量％、合成品。 Each code | symbol in Tables 1-3 shows the following.
<(A) component>
(A-1): a mixture of C 11 H 23 CO (OCH 2 CH 2 ) m OCH 3 and C 13 H 27 CO (OCH 2 CH 2 ) m OCH 3 in a mass ratio of 8/2, m = average 15 , Narrow ratio 33% by mass, synthetic product.
(A-2): C 11 H 23 CO (OCH 2 CH 2 ) m OCH 3 , m = average 15, narrow ratio 33% by mass, synthetic product.
(A-3): a mixture of C 11 H 23 CO (OCH 2 CH 2 ) m OCH 3 and C 13 H 27 CO (OCH 2 CH 2 ) m OCH 3 in a mass ratio of 8/2, m = average 15 , Narrow ratio 45% by mass, synthetic product.
(A-4): C 11 H 23 CO (OCH 2 CH 2 ) m OCH 3 and C 13 H 27 CO (OCH 2 CH 2 ) m OCH 3 in a mass ratio of 8/2, m = average 15 , Narrow rate 60% by mass, synthetic product.
(A-5 (comparative product)): C 17 H 33 CO (OCH 2 CH 2 ) m OCH 3 , m = average 9, narrow ratio 65% by mass, synthetic product.
(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 a mass ratio of m OCH 3 8/2, m = average 15, n = average 1 (random), narrow ratio 37 wt%, the composition.
　前記（ａ－１）～（ａ－６）のナロー率は下記の手順で測定した。
　下記測定条件により、酸化エチレンの付加モル数が異なる酸化エチレン付加体の分布を測定し、前記数式（Ｓ）によりナロー率（質量％）を算出した。［ＨＰＬＣによる酸化エチレン付加体の分布の測定条件］
　　装置：ＬＣ－６Ａ（（株）島津製作所製）、
　　検出器：ＳＰＤ－１０Ａ、
　　測定波長：２２０ｎｍ、
　　カラム：Ｚｏｒｂａｘ　Ｃ８（Ｄｕ　Ｐｏｎｔ（株）製）、
　　移動相：アセトニトリル／水＝６０／４０（体積比）、
　　流速：１ｍＬ／分、
　　温度：２０℃ The narrow ratios of (a-1) to (a-6) were measured by the following procedure.
Under the following measurement conditions, the distribution of ethylene oxide adducts having different numbers of moles of ethylene oxide was measured, and the narrow ratio (% by mass) was calculated from the above formula (S). [Conditions for measuring distribution of ethylene oxide adducts by HPLC]
Apparatus: LC-6A (manufactured by Shimadzu Corporation),
Detector: SPD-10A,
Measurement wavelength: 220 nm
Column: Zorbax C8 (manufactured by Du Pont)
Mobile phase: acetonitrile / water = 60/40 (volume ratio),
Flow rate: 1 mL / min,
Temperature: 20 ° C
　前記（ａ－１）～（ａ－６）はそれぞれ以下の手順で合成した。
　（ａ－１）の合成：
　特開２０００－１４４１７９号公報に記載の実施例における製造例１に準じて合成した。
　すなわち、化学組成が２．５ＭｇＯ・Ａｌ２Ｏ３・ｎＨ２Ｏである水酸化アルミナ・マグネシウム（協和化学工業（株）製、商品名：キョーワード３００）を、６００℃で１時間、窒素雰囲気下で焼成して得られた焼成水酸化アルミナ・マグネシウム（未改質）触媒２．２ｇと、０．５規定の水酸化カリウムエタノール溶液２．９ｍＬと、ラウリン酸メチルエステル２８０ｇ及びミリスチン酸メチルエステル７０ｇとを４リットルオートクレーブに仕込み、オートクレーブ内で触媒の改質を行った。次いで、オートクレーブ内を窒素で置換した後、昇温を行い、温度を１８０℃、圧力を３ａｔｍに維持しつつ、酸化エチレン１０５２ｇを導入し、撹拌しながら反応させた。さらに、反応液を８０℃に冷却し、水１５９ｇと、濾過助剤として活性白土及び珪藻土をそれぞれ５ｇ添加した後、触媒を濾別して、（ａ－１）を得た。
　触媒に対するアルカリ添加量は、（ａ－１）のナロー率が３３質量％となるように調節した。 The above (a-1) to (a-6) were synthesized by the following procedure.
Synthesis of (a-1):
Synthesis was performed according to Production Example 1 in the examples described in JP-A No. 2000-144179.
That is, alumina hydroxide and magnesium hydroxide having a chemical composition of 2.5 MgO.Al 2 O 3 .nH 2 O (trade name: Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) at 600 ° C. for 1 hour in a nitrogen atmosphere Calcined alumina hydroxide / magnesium (unmodified) catalyst 2.2 g obtained by calcining under pressure, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester and myristic acid methyl ester 70 g was charged into a 4 liter autoclave and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 1052 g of ethylene oxide was introduced and reacted while stirring. Further, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added, respectively, and the catalyst was filtered off to obtain (a-1).
The amount of alkali added to the catalyst was adjusted so that the narrow ratio of (a-1) was 33% by mass.
　（ａ－２）の合成：
　ラウリン酸メチルエステル２８０ｇ及びミリスチン酸メチルエステル７０ｇの代わりに、ラウリン酸メチルエステル３５０ｇを用い、酸化エチレン１０７９ｇを導入し、触媒に対するアルカリ添加量をナロー率が３３質量％となるように調整した以外は、上記（ａ－１）の合成方法と同様にして（ａ－２）を製造した。
　（ａ－３）の合成：
　触媒に対するアルカリ添加量をナロー率が４５質量％となるように調整した以外は、上記（ａ－１）の合成方法と同様にして（ａ－３）を製造した。
　（ａ－４）の合成：
　触媒に対するアルカリ添加量をナロー率が６５質量％となるように調整した以外は、上記（ａ－１）の合成方法と同様にして（ａ－４）を製造した。
　（ａ－５）の合成：
　ラウリン酸メチルエステル２８０ｇ及びミリスチン酸メチルエステル７０ｇの代わりに、オレイン酸メチルエステル３５０ｇを用い、酸化エチレン４６８ｇを導入し、触媒に対するアルカリ添加量をナロー率が６５質量％となるように調整した以外は、上記（ａ－１）の合成方法と同様にして（ａ－５）を製造した。
（ａ－６）の合成：
　ラウリン酸メチルエステル２８０ｇおよびミリスチン酸メチルエステル７０ｇを用い、酸化エチレン１０５２ｇおよびプロピレンオキサイド９３ｇを導入し、触媒に対するアルカリ添加量をナロー率が３７質量％となるように調整した以外は、上記（ａ－１）の合成方法と同様にして（ａ－６）を製造した。 Synthesis of (a-2):
Instead 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 so that the narrow ratio was 33% by mass. (A-2) was produced in the same manner as the synthesis method of (a-1).
Synthesis of (a-3):
(A-3) was produced in the same manner as the synthesis method (a-1) except that the amount of alkali added to the catalyst was adjusted so that the narrow ratio was 45% by mass.
Synthesis of (a-4):
(A-4) was produced in the same manner as the synthesis method (a-1) except that the amount of alkali added to the catalyst was adjusted so that the narrow ratio was 65% by mass.
Synthesis of (a-5):
Instead of 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester, 350 g of oleic acid methyl ester was used, 468 g of ethylene oxide was introduced, and the amount of alkali added to the catalyst was adjusted so that the narrow ratio was 65% by mass. (A-5) was produced in the same manner as in the synthesis method of (a-1).
Synthesis of (a-6):
Except that 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester were used, 1052 g of ethylene oxide and 93 g of propylene oxide were introduced, and the amount of alkali added to the catalyst was adjusted so that the narrow ratio was 37 mass%. (A-6) was produced in the same manner as in the synthesis method of 1).
＜（Ｂ）成分＞
　（ｂ－１）：Ｐ＆Ｇ社製の天然アルコールＣＯ－１２７０（商品名）に対して平均１５モル相当の酸化エチレンを付加したもの。
　（ｂ－２）：Ｐ＆Ｇ社製の天然アルコールＣＯ－１２１４（商品名）に対して平均１５モル相当の酸化エチレンを付加したもの。
　（ｂ－３）：Ｐ＆Ｇ社製の天然アルコールＣＯ－１２７０（商品名）に対して平均１２モル相当の酸化エチレンを付加したもの。
　（ｂ－４）：Ｐ＆Ｇ社製の天然アルコールＣＯ－１２７０（商品名）に対して平均９モル相当の酸化エチレンを付加したもの。
（ｂ－５）：ソフタノール１２０（商品名、ポリオキシエチレンアルキルエーテル（Ｃ１２～１４第２級アルコール）、日本触媒（株）製）。
（ｂ－６）：天然アルコール（Ｃ１２／Ｃ１４＝７／３）に、１６モルのエチレンオキサイドと２モルのプロピレンオキサイドをランダム付加させて得られた非イオン（ノニオン）界面活性剤
（ｂ－７）：天然アルコール（Ｃ１２／Ｃ１４＝７／３）に、８モルのエチレンオキサイド、２モルのプロピレンオキサイド、８モルのエチレンオキサイドの順にブロック付加させて得られたノニオン界面活性剤。 <(B) component>
(B-1): An average of 15 moles of ethylene oxide added to natural alcohol CO-1270 (trade name) manufactured by P & G.
(B-2): An average of 15 moles of ethylene oxide added to natural alcohol CO-1214 (trade name) manufactured by P & G.
(B-3): An average of 12 moles of ethylene oxide added to natural alcohol CO-1270 (trade name) manufactured by P & G.
(B-4): An average of 9 moles of ethylene oxide added to natural alcohol CO-1270 (trade name) manufactured by P & G.
(B-5): Softanol 120 (trade name, polyoxyethylene alkyl ether (C12-14 secondary alcohol), manufactured by Nippon Shokubai Co., Ltd.).
(B-6): Nonionic surfactant (b-7) obtained by random addition of 16 mol of ethylene oxide and 2 mol of propylene oxide to natural alcohol (C12 / C14 = 7/3) ): Nonionic surfactant obtained by block addition of 8 mol of ethylene oxide, 2 mol of propylene oxide, and 8 mol of ethylene oxide in this order to natural alcohol (C12 / C14 = 7/3).
　前記（ｂ－１）～（ｂ－４）、（ｂ－６）及び（ｂ－７）はそれぞれ以下の手順で合成した。
　（ｂ－１）の合成：
　Ｐ＆Ｇ社製の天然アルコールＣＯ－１２７０を２２４．４ｇ、３０％ＮａＯＨ水溶液２．０ｇを耐圧型反応容器中に採取し、容器内を窒素置換した。次に温度１００℃、圧力２．０ｋＰａ以下で３０分間脱水してから、温度を１６０℃まで昇温した。アルコールを攪拌しながら酸化エチレン（ガス状）７６０．４ｇを、吹き込み管を使って、反応温度が１８０℃を超えないように添加速度を調整しながらアルコールの液中に徐々に加えた。
　酸化エチレンの添加終了後、温度１８０℃、圧力０．３ＭＰａ以下で３０分間熟成した後、温度１８０℃、圧力６．０ｋＰａ以下で１０分間未反応の酸化エチレンを留去した。
　次に温度を１００℃以下まで冷却した後、反応物の１％水溶液のｐＨが約７になるように、７０％ｐ－トルエンスルホン酸を加えて中和し、（ｂ－１）を得た。 The above (b-1) to (b-4), (b-6) and (b-7) were synthesized by the following procedure.
Synthesis of (b-1):
224.4 g of natural alcohol CO-1270 manufactured by P & G Co. and 2.0 g of 30% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 760.4 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blow tube.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, to obtain (b-1). .
　（ｂ－２）の合成：
　天然アルコールＣＯ－１２７０の代わりにＰ＆Ｇ社製の天然アルコールＣＯ－１２１４を２２４．４ｇ用いた以外は、（ｂ－１）と同様に合成した。
　（ｂ－３）の合成：
　酸化エチレンを６１０．２ｇ用いた以外は、（ｂ－１）と同様に合成した。
　（ｂ－４）の合成：
　酸化エチレンを４５７．２ｇ用いた以外は、（ｂ－１）と同様に合成した。
（ｂ－６）の合成
　酸化エチレン８２０．４ｇの代わりに酸化エチレン７０４ｇおよび酸化プロピレン（ガス状）１３０ｇを用いた以外は、（ａ－１）と同様に合成した。
（ｂ－７）の合成：
Ｐ＆Ｇ社製の「ＣＯ－１２７０」２２４．４ｇと、３０質量％ＮａＯＨ水溶液２．０ｇとを耐圧型反応容器中に採取し、容器内を窒素置換した。次に温度１００℃、圧力２．０ｋＰａ以下で３０分間脱水してから、温度を１６０℃まで昇温した。アルコールを攪拌しながら酸化エチレン（ガス状）４０５ｇを吹き込み管を使って、反応温度が１８０℃を超えないように添加速度を調整しながらアルコールの液中に徐々に加えて反応させた。
添加終了後、温度１８０℃、圧力０．３ＭＰａ以下で３０分間熟成した後、さらにプロピレンオキサイド１３０ｇを吹き込み管を使って、反応温度が１８０℃を超えないように添加速度を調整しながら徐々に加えて反応させた。温度１８０℃、圧力０．３ＭＰａ以下で３０分間熟成した後、さらに酸化エチレン４０５ｇを反応させた。熟成後、未反応の酸化エチレンを留去した後、温度を１００℃以下まで冷却し、反応物の１質量％水溶液のｐＨが約７になるように、７０質量％ｐ－トルエンスルホン酸を加えて中和し、（ｂ－７）を得た。 Synthesis of (b-2):
Synthesis was performed in the same manner as (b-1) except that 224.4 g of natural alcohol CO-1214 manufactured by P & G was used instead of natural alcohol CO-1270.
Synthesis of (b-3):
This compound was synthesized in the same manner as (b-1) except that 610.2 g of ethylene oxide was used.
Synthesis of (b-4):
This compound was synthesized in the same manner as (b-1) except that 457.2 g of ethylene oxide was used.
Synthesis of (b-6) Synthesis was performed in the same manner as in (a-1) except that 704 g of ethylene oxide and 130 g of propylene oxide (gaseous) were used instead of 820.4 g of ethylene oxide.
Synthesis of (b-7):
224.4 g of “CO-1270” manufactured by P & G and 2.0 g of 30 mass% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 405 g of ethylene oxide (gaseous) was blown into the alcohol solution while gradually adjusting the rate of addition so that the reaction temperature did not exceed 180 ° C. using the tube.
After completion of the addition, after aging for 30 minutes at a temperature of 180 ° C. and a pressure of 0.3 MPa or less, 130 g of propylene oxide was gradually added using a blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. And reacted. After aging for 30 minutes at a temperature of 180 ° C. and a pressure of 0.3 MPa or less, 405 g of ethylene oxide was further reacted. After aging, unreacted ethylene oxide was distilled off, the temperature was cooled to 100 ° C. or less, and 70% by mass p-toluenesulfonic acid was added so that the pH of the 1% by mass aqueous solution of the reaction product was about 7. To obtain (b-7).
＜（Ｃ）成分＞
　（ｃ－１）：カチナールＭＰＡＳ－Ｒ（商品名、脂肪酸（Ｃ１６／Ｃ１８）ジメチルアミノプロピルアミド、ステアリン酸／パルミチン酸の質量比＝７／３）東邦化学（株）製）。
　（ｃ－２）：Ｃ１７Ｈ３５ＣＯＮＨ（ＣＨ２）３Ｎ（ＣＨ３）２、ステアリン酸アミドプロピルジメチルアミン；合成品。 <(C) component>
(C-1): Katchinal MPAS-R (trade name, fatty acid (C16 / C18) dimethylaminopropylamide, stearic acid / palmitic acid mass ratio = 7/3) manufactured by Toho Chemical Co., Ltd.
(C-2): C 17 H 35 CONH (CH 2 ) 3 N (CH 3 ) 2 , amidopropyldimethylamine stearate; synthetic product.
　前記（ｃ－２）は以下の手順で合成した。
　流冷却器を備えた１リットル四ツ口フラスコに、ステアリン酸３６０ｇ(分子量２８４)を仕込み、８０℃に加熱してステアリン酸を融解した。窒素置換を２回行った後、１５０℃に昇温し、ジメチルアミノプロピルアミン（分子量１０２）１２３ｇ（ステアリン酸に対するモル比：０．９５）を１時間かけて滴下した。次に、１５０～１６０℃で１時間保持した後、１時間かけて１８５℃に昇温し、更にジメチルアミノプロピルアミン４５ｇを１時間かけて滴下した。滴下終了後、１８５～１９０℃に保持し、７時間熟成して副生の水を系外に留去した。更に１７０～１９０℃に保持したまま減圧（４．０ｋＰａ）し、１時間放置することにより未反応のジメチルアミノプロピルアミンを留去することにより、（ｃ－２）を得た。 (C-2) was synthesized by the following procedure.
A 1 liter four-necked flask equipped with a flow condenser was charged with 360 g of stearic acid (molecular weight 284) and heated to 80 ° C. to melt the stearic acid. After performing nitrogen substitution twice, the temperature was raised to 150 ° C., and 123 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to stearic acid: 0.95) was added dropwise over 1 hour. Next, after maintaining at 150 to 160 ° C. for 1 hour, 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 temperature was maintained at 185 to 190 ° C. and aged for 7 hours to distill off by-product water out of the system. Further, while maintaining the temperature at 170 to 190 ° C., the pressure was reduced (4.0 kPa) and the mixture was allowed to stand for 1 hour to distill off unreacted dimethylaminopropylamine to obtain (c-2).
＜（Ｄ）成分＞
　（ｄ－１）：ライポンＬＨ－２００（商品名、直鎖アルキルベンゼンスルホン酸（ＬＡＳ）、炭素数１０～１４、平均分子量３２２、ライオン社製）。
　（ｄ－２）：ＨＯＳＴＡＰＵＲ　ＳＡＳ３０Ａ（商品名、セカンダリーアルカンスルホン酸ナトリウム（ＳＡＳ）、クラリアント・ジャパン社製）。
　（ｄ－３）：ポリオキシエチレンアルキルエーテル硫酸ナトリウム（ＡＥＳ）（合成品、炭素数１２～１３、ＥＯの平均付加モル数２モル、原料アルコール：ネオドール２３（商品名、シェルケミカルズ社製））。 <(D) component>
(D-1): Rypon LH-200 (trade name, linear alkylbenzene sulfonic acid (LAS), carbon number 10-14, average molecular weight 322, manufactured by Lion Corporation).
(D-2): HOSTAPUR SAS30A (trade name, secondary sodium alkanesulfonate (SAS), manufactured by Clariant Japan).
(D-3): sodium polyoxyethylene alkyl ether sulfate (AES) (synthetic product, carbon number 12-13, average addition mole number of EO 2 mol, raw alcohol: Neodol 23 (trade name, manufactured by Shell Chemicals)) .
　（ｄ－３）は以下の手順で合成した。
　４Ｌのオートクレーブ中に、Ｎｅｏｄｏｌ２３アルコール［商品名、シェルケミカルズ社製；Ｃ１２、１３アルコール（炭素数１２のアルコールと、炭素数１３のアルコールとの質量比１／１の混合物）、分岐率２０質量％］４００ｇと水酸化カリウム触媒０．８ｇとを仕込み、オートクレーブ内を窒素置換し、攪拌しながら昇温した。その後、温度１８０℃、圧力０．３ｍＰａに維持しながら酸化エチレン２７２ｇを導入し、酸化エチレンの平均付加モル数２の反応物を得た。
　次に、上記で得られたアルコールエトキシレート２８０ｇを、攪拌装置付の５００ｍＬフラスコにとり、窒素置換後、液体無水硫酸（サルファン）６７ｇを反応温度４０℃に保ちながらゆっくりと滴下した。滴下終了後、１時間攪拌を続け（硫酸化反応）、ポリオキシエチレンアルキルエーテル硫酸を得た。さらに、これを水酸化ナトリウム水溶液で中和することにより、（ｄ－３）を得た。 (D-3) was synthesized by the following procedure.
In a 4 L autoclave, Neodol 23 alcohol [trade name, manufactured by Shell Chemicals; C12, 13 alcohol (mixture of alcohol ratio of carbon 12 and alcohol of carbon number 1/1), branching ratio 20% by mass 400 g and potassium hydroxide catalyst 0.8 g were charged, the inside of the autoclave was purged with nitrogen, and the temperature was increased while stirring. Thereafter, 272 g of ethylene oxide was introduced while maintaining a temperature of 180 ° C. and a pressure of 0.3 mPa, to obtain a reaction product having an average added mole number of ethylene oxide of 2.
Next, 280 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 67 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Further, this was neutralized with an aqueous sodium hydroxide solution to obtain (d-3).
＜（Ｅ）成分＞
　（ｅ－１）：エタノール（日本アルコール販売（株）製　商品名、特定アルコール９５度合成）。
　（ｅ－２）：プロピレングリコール（ＢＡＳＦ社製）。 <(E) component>
(E-1): Ethanol (trade name, specific alcohol 95 degree synthesis, manufactured by Nippon Alcohol Sales Co., Ltd.).
(E-2): Propylene glycol (manufactured by BASF).
＜（Ｆ）成分＞
（ｆ－１）：エバラーゼ１６Ｌ　ＴｙｐｅＥＸ（商品名、プロテアーゼ、ノボザイムス社製）。
　（ｆ－２）：リカナーゼ　ウルトラ２．５ＸＬ（商品名、プロテアーゼ、ノボザイムス社製）。
　（ｆ－３）：ライペックス１００Ｌ（商品名、リパーゼ、ノボザイムス社製）。
　（ｆ－４）：ステインザイム１２Ｌ（商品名、アミラーゼ、ノボザイムス社製）。 <(F) component>
(F-1): Evalase 16L TypeEX (trade name, protease, manufactured by Novozymes)
(F-2): Recanase Ultra 2.5XL (trade name, protease, manufactured by Novozymes).
(F-3): Leipex 100L (trade name, lipase, manufactured by Novozymes).
(F-4): Stainzyme 12L (trade name, amylase, manufactured by Novozymes).
＜共通添加成分ａ＞
　安息香酸ナトリウム：０．５質量％、
　クエン酸：０．１５質量％、
　パラトルエンスルホン酸：４．０質量％、
　ヤシ脂肪酸：１．０質量％、
　ポリエチレングリコール：２．０質量％、
　ジブチルヒドロキシトルエン：０．０５質量％、
　モノエタノールアミン：１．８質量％、
　香料：１．４質量％、
　色素（緑３号）：０．０００１質量％、
　水（精製水）：バランス（液体洗浄剤組成物全体の量を１００質量％とするための量）。 <Common additive component a>
Sodium benzoate: 0.5% by mass
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,
Dibutylhydroxytoluene: 0.05% by mass,
Monoethanolamine: 1.8% by mass,
Fragrance: 1.4% by mass
Dye (Green No. 3): 0.0001% by mass,
Water (purified water): Balance (amount for making the total amount of the liquid detergent composition 100% by mass).
＜共通添加成分ｂ＞
　安息香酸ナトリウム：０．５質量％、
　クエン酸：０．１５質量％、
　パラトルエンスルホン酸：４．０質量％、
　パルミチン酸：０．１質量％、
　ポリエチレングリコール：２．０質量％、
　ジブチルヒドロキシトルエン：０．０５質量％、
　モノエタノールアミン：１．８質量％、
　香料：１．４質量％、
　緑３号：０．０００１質量％、
　水（精製水）：バランス（液体洗浄剤組成物全体の量を１００質量％とするための量）。 <Common additive component b>
Sodium benzoate: 0.5% by mass
Citric acid: 0.15% by mass,
Paratoluenesulfonic acid: 4.0% by mass,
Palmitic acid: 0.1% by mass,
Polyethylene glycol: 2.0% by mass,
Dibutylhydroxytoluene: 0.05% by mass,
Monoethanolamine: 1.8% by mass,
Fragrance: 1.4% by mass
Green No. 3: 0.0001% by mass,
Water (purified water): Balance (amount for making the total amount of the liquid detergent composition 100% by mass).
＜共通添加成分ｃ＞
安息香酸ナトリウム：０．５質量％
クエン酸：０．１質量％
パラトルエンスルホン酸：３質量％
ヤシ脂肪酸：１．０質量％
香料：１．７５質量％
緑３号：０．０００１質量％
水（精製水）：バランス（液体洗浄剤組成物全体の量を１００質量％とするための量） <Common additive component c>
Sodium benzoate: 0.5% by mass
Citric acid: 0.1% by mass
Paratoluenesulfonic acid: 3% by mass
Coconut fatty acid: 1.0% by mass
Fragrance: 1.75% by mass
Green No. 3: 0.0001% by mass
Water (purified water): Balance (amount to make the total amount of the liquid detergent composition 100% by mass)
＜共通添加成分ｄ＞
　安息香酸ナトリウム：１．８質量％、
　クエン酸：０．３質量％、
　パルミチン酸：０．１質量％、
　パラトルエンスルホン酸：１．０質量％、
　ポリエチレングリコール：１．０質量％、
　ジブチルヒドロキシトルエン：０．０５質量％、
　モノエタノールアミン：１．０質量％、
　香料：０．４質量％、
　緑３号：０．０００３質量％、
　水（精製水）：バランス（液体洗浄剤組成物全体の量を１００質量％とするための量）。 <Common additive component d>
Sodium benzoate: 1.8% by mass,
Citric acid: 0.3% by mass
Palmitic acid: 0.1% by mass,
Paratoluenesulfonic acid: 1.0% by mass,
Polyethylene glycol: 1.0% by mass,
Dibutylhydroxytoluene: 0.05% by mass,
Monoethanolamine: 1.0% by mass
Fragrance: 0.4% by mass
Green No. 3: 0.0003 mass%,
Water (purified water): Balance (amount for making the total amount of the liquid detergent composition 100% by mass).
　共通添加成分ａ、ｂ及びｃに含まれる各成分の詳細は以下の通りである。
　安息香酸ナトリウム：東亜合成製、商品名「安息香酸ナトリウム」。
　クエン酸：一方社油脂工業（株）製、商品名「液体クエン酸」。
　パラトルエンスルホン酸：協和発酵工業（株）製、商品名「ＰＴＳ酸」。
　ヤシ脂肪酸：日油株式会社、商品名「椰子脂肪酸」。
　ポリエチレングリコール：ライオン（株）製、商品名「ＰＥＧ＃１０００」。
　ジブチルヒドロキシトルエン：住友化学（株）製、商品名「ＳＵＭＩＬＺＥＲ　ＢＨＴ－Ｒ」。
　モノエタノールアミン：（株）日本触媒製。
　香料：特開２００９－１０８２４８記載の香料成分ａ。
　緑３号（色素）：癸巳化成（株）製、商品名「緑色３号」。
　また、ｐＨ調整剤として用いた水酸化ナトリウム及び硫酸の詳細は以下の通りである。
　水酸化ナトリウム：鶴見曹達（株）製。
　硫酸：東邦亜鉛（株）製。 Details of each component contained in the common additive components a, b and c are as follows.
Sodium benzoate: manufactured by Toagosei Co., Ltd., trade name “Sodium benzoate”.
Citric acid: trade name “Liquid Citric Acid”, manufactured by Yushi Co., Ltd.
Paratoluenesulfonic acid: Kyowa Hakko Kogyo Co., Ltd., trade name “PTS acid”.
Coconut fatty acid: NOF Corporation, trade name “Zushi fatty acid”.
Polyethylene glycol: Product name “PEG # 1000”, manufactured by Lion Corporation.
Dibutylhydroxytoluene: Sumitomo Chemical Co., Ltd., trade name “SUMILZER BHT-R”.
Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.
Perfume: Perfume component a described in JP-A-2009-108248.
Green No. 3 (pigment): Product name “Green No. 3” manufactured by Sakai Kasei Co., Ltd.
The details of sodium hydroxide and sulfuric acid used as pH adjusters are as follows.
Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.
Sulfuric acid: Toho Zinc Co., Ltd.
　共通添加成分ｄに含まれる各成分の詳細は以下の通りである。
　安息香酸ナトリウム：東亜合成製、商品名「安息香酸ナトリウム」。
　クエン酸：一方社油脂工業（株）製、商品名「液体クエン酸」。
　パルミチン酸：日本油脂（株）、商品名「ＮＡＡ－１６０」。
　パラトルエンスルホン酸：協和発酵工業（株）製、商品名「ＰＴＳ酸」。
　ポリエチレングリコール：ライオン（株）製、商品名「ＰＥＧ＃１０００－Ｌ６０」。
　ジブチルヒドロキシトルエン：住友化学（株）製、商品名「ＳＵＭＩＬＺＥＲ　ＢＨＴ－Ｒ」。
　モノエタノールアミン：（株）日本触媒製。
　香料　特願２００２－１４６３９９号公報の表１１～１８記載の香料組成物Ａ。
　緑３号（色素）：癸巳化成（株）製、商品名「緑色３号」。
　また、ｐＨ調整剤として用いた水酸化ナトリウム及び硫酸の詳細は以下の通りである。
　水酸化ナトリウム：鶴見曹達（株）製。
　硫酸：東邦亜鉛（株）製。 Details of each component included in the common additive component d are as follows.
Sodium benzoate: manufactured by Toagosei Co., Ltd., trade name “Sodium benzoate”.
Citric acid: trade name “Liquid Citric Acid”, manufactured by Yushi Co., Ltd.
Palmitic acid: Nippon Oil & Fat Co., Ltd., trade name “NAA-160”.
Paratoluenesulfonic acid: Kyowa Hakko Kogyo Co., Ltd., trade name “PTS acid”.
Polyethylene glycol: Product name “PEG # 1000-L60” manufactured by Lion Corporation.
Dibutylhydroxytoluene: Sumitomo Chemical Co., Ltd., trade name “SUMILZER BHT-R”.
Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.
Fragrance A fragrance composition A described in Tables 11 to 18 of Japanese Patent Application No. 2002-146399.
Green No. 3 (pigment): Product name “Green No. 3” manufactured by Sakai Kasei Co., Ltd.
The details of sodium hydroxide and sulfuric acid used as pH adjusters are as follows.
Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.
Sulfuric acid: Toho Zinc Co., Ltd.
本発明によれば、優れた洗浄力、再汚染防止性能及び柔軟性付与性能を有し、液安定性が良好で、しかも着心地を損なうことなく衣料、特に麻製衣料を洗浄できる衣料用液体洗浄剤組成物を提供できる。
また、非イオン性界面活性剤を高濃度かつ安定に含み、洗浄時における溶解性及び洗浄性能に優れ、洗浄した衣料、特に麻製衣料の着心地も良好な衣料用液体洗浄剤組成物を提供できる。 According to the present invention, a liquid for clothing that has excellent detergency, anti-recontamination performance and flexibility imparting performance, has good liquid stability, and can wash clothing, particularly hemp clothing, without impairing comfort. A cleaning composition can be provided.
Also provided is a liquid detergent composition for clothes that contains a high concentration and stability of nonionic surfactants, has excellent solubility and washing performance during washing, and is comfortable to wear washed clothes, especially hemp clothes. it can.

Claims (9)

  1. 　Ｒ１－ＣＯ（ＯＲ２）ｍＯＲ３［式中、Ｒ１は炭素数９～１３のアルキル基又は炭素数９～１３のアルケニル基であり、Ｒ２は炭素数２～４のアルキレン基であり、Ｒ３は炭素数１～３のアルキル基であり、ｍは平均付加モル数を表し５～２５である。］で表される非イオン性界面活性剤（Ａ）と、
    　Ｒ４－Ｏ（Ｒ５Ｏ）ｎＨ［式中、Ｒ４は炭素数１０～２２の炭化水素基であり、Ｒ５は炭素数２～４のアルキレン基であり、ｎは平均付加モル数を表し５～２５である。］で表される非イオン性界面活性剤（Ｂ）と、
    　　炭素数２～４の一価アルコール、炭素数２～４の多価アルコール及びＲ１１－（ＯＲ１２）ｋＯＨ［式中、Ｒ１１は炭素数１～６のアルキル基又はフェニル基であり、Ｒ１２は炭素数２～４のアルキレン基であり、ｋは平均付加モル数を表し１～５である。］で表されるグリコールエーテル系溶剤からなる群から選択される溶剤（Ｅ）とを含有する衣料用液体洗浄剤組成物。     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, and R 2 is an alkylene group having 2 to 4 carbon atoms] R 3 represents an alkyl group having 1 to 3 carbon atoms, and m represents an average added mole number and is 5 to 25. A nonionic surfactant (A) represented by
    R 4 —O (R 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 the average number of moles added. And 5 to 25. A nonionic surfactant (B) represented by
    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 represents an alkylene group having 2 to 4 carbon atoms, and k represents an average added mole number and is 1 to 5. ] The liquid cleaning composition for clothes containing the solvent (E) selected from the group which consists of a glycol ether solvent represented by these.
  2. 　前記（Ａ）成分及び前記（Ｂ）成分の配合量の合計が、前記液体洗浄剤組成物の総質量に対し、４０～７５質量％であり、前記（Ａ）成分と前記（Ｂ）成分との配合比率（質量比）が（Ｂ）／（Ａ）＝８０／２０～１０／９０であり、前記（Ｅ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、３～２５質量％である請求項１に記載の衣料用液体洗浄剤組成物。 The total amount of the component (A) and the component (B) is 40 to 75% by mass based on the total mass of the liquid detergent composition, and the component (A) and the component (B) The blending ratio (mass ratio) of (B) / (A) = 80/20 to 10/90, and the blending amount of the component (E) is 3 to 3 based on the total mass of the liquid detergent composition The liquid detergent composition for clothes according to claim 1, which is 25% by mass.
  3. さらに、Ｒ６－Ｎ（Ｒ７）（Ｒ８）［式中、Ｒ６は連結基を有していてもよい炭素数７～２７の炭化水素基であり、Ｒ７及びＲ８はそれぞれ独立して、炭素数１～４のアルキル基、炭素数１～４のヒドロキシアルキル基、又は（Ｒ９Ｏ）ｐＨ［式中、Ｒ９は炭素数２～４のアルキレン基であり、ｐは平均付加モル数を表し１～２５である。］で表される基である。］で表される３級アミン化合物及びその塩からなる群から選択される化合物（Ｃ）を含有する請求項２に記載の衣料用液体洗浄剤組成物である。 R 6 —N (R 7 ) (R 8 ) [wherein R 6 is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group, and R 7 and R 8 are each independently And 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, and p is The average added mole number is 1 to 25. ]. ] The liquid cleaning composition for clothes of Claim 2 containing the compound (C) selected from the group which consists of the tertiary amine compound represented by these, and its salt.
  4. 　さらに、ＳＯ３基又はＳＯ４基を有する陰イオン性界面活性剤（Ｄ）及び／又は酵素（Ｆ）を含有する請求項２に記載の衣料用洗浄剤組成物。 Further, SO 3 group or anionic surfactants having an SO 4 group (D) and / or enzyme (F) for clothes detergent composition according to claim 2 containing.
  5. 前記（Ｃ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、０．１～１０質量％である請求項３に記載の衣料用液体洗浄剤組成物。 The liquid detergent composition for clothes according to claim 3, wherein the blending amount of the component (C) is 0.1 to 10 mass% with respect to the total mass of the liquid detergent composition.
  6. 前記（Ｄ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、１～１０質量％である請求項４に記載の衣料用液体洗浄剤組成物。 The liquid detergent composition for clothes according to claim 4, wherein the blending amount of the component (D) is 1 to 10 mass% with respect to the total mass of the liquid detergent composition.
  7. 前記（Ｆ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、０．１～３質量％である請求項４に記載の衣料用液体洗浄剤組成物である。 The liquid detergent composition for clothes according to claim 4, wherein the blending amount of the component (F) is 0.1 to 3 mass% with respect to the total mass of the liquid detergent composition.
  8. 　　さらに、Ｒ６－Ｎ（Ｒ７）（Ｒ８）［式中、Ｒ６は連結基を有していてもよい炭素数７～２７の炭化水素基であり、Ｒ７及びＲ８はそれぞれ独立して、炭素数１～４のアルキル基、炭素数１～４のヒドロキシアルキル基、又は（Ｒ９Ｏ）ｐＨ［式中、Ｒ９は炭素数２～４のアルキレン基であり、ｐは平均付加モル数を表し１～２５である。］で表される基である。］で表される３級アミン化合物及びその塩からなる群から選択される化合物（Ｃ）と、
    　ＳＯ３基又はＳＯ４基を有する陰イオン性界面活性剤（Ｄ）とを含有し、
    　前記（Ａ）成分及び前記（Ｂ）成分の配合量の合計が前記液体洗浄剤組成物の総質量に対し、１０～６５質量％であり、前記（Ａ）成分と前記（Ｂ）成分との配合比率（質量比）が（Ｂ）／（Ａ）＝８０／２０～１０／９０であり、
    　前記（Ｃ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、０．１～１０質量％であり、前記（Ｄ）成分の配合量が１～２０質量％であり、前記（Ｃ）成分と前記（Ｄ）成分との配合比率（質量比）が（Ｄ）／（Ｃ）＝１／１～１０／１であり、
    　前記（Ｅ）成分の配合量が、前記液体洗浄剤組成物の総質量に対し、３～２０質量％である請求項１に記載の衣料用液体洗浄剤組成物。     R 6 —N (R 7 ) (R 8 ) [wherein R 6 is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group, and R 7 and R 8 are each independently And 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, and p is The average added mole number is 1 to 25. ]. A compound (C) selected from the group consisting of a tertiary amine compound represented by the formula:
    An anionic surfactant (D) having a SO 3 group or a SO 4 group,
    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 component (A) and the component (B) The blending ratio (mass ratio) is (B) / (A) = 80/20 to 10/90,
    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 amount of the component (D) is 1 to 20% by mass, The blending ratio (mass ratio) of the component (C) and the component (D) is (D) / (C) = 1/1 to 10/1,
    The liquid detergent composition for clothes according to claim 1, wherein the blending amount of the component (E) is 3 to 20 mass% with respect to the total mass of the liquid detergent composition.
  9. 　前記（Ａ）成分と前記（Ｂ）成分との配合比率（質量比）が（Ｂ）／（Ａ）＝７０／３０～２０／８０である請求項８に記載の衣料用液体洗浄剤組成物。 The liquid detergent composition for clothes according to claim 8, wherein a blending ratio (mass ratio) of the component (A) and the component (B) is (B) / (A) = 70/30 to 20/80. .
PCT/JP2010/061841 2009-07-17 2010-07-13 Liquid detergent composition for clothes WO2011007778A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201080033750.9A CN102471741B (en) 2009-07-17 2010-07-13 Liquid detergent composition for clothes
KR1020127002822A KR101726898B1 (en) 2009-07-17 2010-07-13 Liquid detergent composition for clothes

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2009169155 2009-07-17
JP2009-169155 2009-07-17
JP2009-179159 2009-07-31
JP2009179159 2009-07-31

Publications (1)

Publication Number Publication Date
WO2011007778A1 true WO2011007778A1 (en) 2011-01-20

Family

ID=43449385

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/061841 WO2011007778A1 (en) 2009-07-17 2010-07-13 Liquid detergent composition for clothes

Country Status (4)

Country Link
KR (1) KR101726898B1 (en)
CN (1) CN102471741B (en)
MY (1) MY160104A (en)
WO (1) WO2011007778A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011132271A (en) * 2009-12-22 2011-07-07 Kao Corp Liquid detergent composition for clothing
JP2012224652A (en) * 2011-04-14 2012-11-15 Lion Corp Liquid detergent
CN104450214A (en) * 2014-11-28 2015-03-25 青岛市市南区隆德中医药研究所 Efficient laundry detergent with bacterial inhibition and sterilization functions
KR20160148508A (en) 2014-04-24 2016-12-26 라이온 가부시키가이샤 Method for producing fatty acid aklyl ester alkoxylate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115873662A (en) * 2022-12-27 2023-03-31 高梵(浙江)信息技术有限公司 Velvet down jacket care washing liquid and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08311488A (en) * 1995-05-10 1996-11-26 Hoechst Ag Surfactant mixture
JP2000144178A (en) * 1998-11-10 2000-05-26 Lion Corp Detergent composition
JP2000186295A (en) * 1998-12-22 2000-07-04 Lion Corp Liquid detergent composition
JP2003206500A (en) * 2002-01-15 2003-07-22 Lion Corp Liquid detergent composition
JP2003238999A (en) * 2002-02-14 2003-08-27 Lion Corp Method for producing high concentration liquid detergent
JP2008024753A (en) * 2006-07-18 2008-02-07 Lion Corp Liquid detergent composition for clothing
JP2009144002A (en) * 2007-12-12 2009-07-02 Lion Corp Liquid detergent composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002180087A (en) 2000-12-07 2002-06-26 Lion Corp Nonionic detergent composition
JP4273853B2 (en) 2003-06-30 2009-06-03 ライオン株式会社 Liquid detergent composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08311488A (en) * 1995-05-10 1996-11-26 Hoechst Ag Surfactant mixture
JP2000144178A (en) * 1998-11-10 2000-05-26 Lion Corp Detergent composition
JP2000186295A (en) * 1998-12-22 2000-07-04 Lion Corp Liquid detergent composition
JP2003206500A (en) * 2002-01-15 2003-07-22 Lion Corp Liquid detergent composition
JP2003238999A (en) * 2002-02-14 2003-08-27 Lion Corp Method for producing high concentration liquid detergent
JP2008024753A (en) * 2006-07-18 2008-02-07 Lion Corp Liquid detergent composition for clothing
JP2009144002A (en) * 2007-12-12 2009-07-02 Lion Corp Liquid detergent composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011132271A (en) * 2009-12-22 2011-07-07 Kao Corp Liquid detergent composition for clothing
JP2012224652A (en) * 2011-04-14 2012-11-15 Lion Corp Liquid detergent
KR20160148508A (en) 2014-04-24 2016-12-26 라이온 가부시키가이샤 Method for producing fatty acid aklyl ester alkoxylate
CN104450214A (en) * 2014-11-28 2015-03-25 青岛市市南区隆德中医药研究所 Efficient laundry detergent with bacterial inhibition and sterilization functions

Also Published As

Publication number Publication date
KR101726898B1 (en) 2017-04-13
KR20120050988A (en) 2012-05-21
CN102471741B (en) 2014-10-08
CN102471741A (en) 2012-05-23
MY160104A (en) 2017-02-28

Similar Documents

Publication Publication Date Title
JP6086957B2 (en) Liquid cleaning agent
KR101791707B1 (en) Liquid detergent composition
JP5331332B2 (en) Liquid detergent composition
JP6335787B2 (en) Textile treatment agent and textile treatment method
JP5986887B2 (en) Liquid detergent for textile products
JP6275122B2 (en) Liquid cleaning agent
WO2015083800A1 (en) Liquid detergent
JPWO2018056197A1 (en) Liquid cleaner
JP5331412B2 (en) Liquid detergent composition
JP5586349B2 (en) Liquid detergent composition for clothing
JP2011137111A (en) Liquid detergent composition for clothing
WO2011007778A1 (en) Liquid detergent composition for clothes
JP5736131B2 (en) Liquid detergent composition for clothing
JP6188223B2 (en) Cleaning agent for textile products
JP5851323B2 (en) Liquid cleaning agent
JP2011137112A (en) Liquid detergent composition for clothes
JP6930850B2 (en) Liquid detergent composition
JP6945442B2 (en) Liquid detergent composition
JP2002167600A (en) Liquid detergent composition
JP2010059275A (en) Liquid detergent composition for clothing
JP5597371B2 (en) Liquid detergent composition for clothing
JP2013227386A (en) Liquid detergent
JP2013057011A (en) Liquid detergent composition for clothing
JP4991199B2 (en) Liquid detergent composition for clothing
WO2017022779A1 (en) Liquid detergent composition for clothes

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080033750.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10799836

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 12012500109

Country of ref document: PH

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 1201000120

Country of ref document: TH

ENP Entry into the national phase

Ref document number: 20127002822

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 10799836

Country of ref document: EP

Kind code of ref document: A1