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.

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