WO2012137642A1 - Liquid detergent - Google Patents
Liquid detergent Download PDFInfo
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- WO2012137642A1 WO2012137642A1 PCT/JP2012/058126 JP2012058126W WO2012137642A1 WO 2012137642 A1 WO2012137642 A1 WO 2012137642A1 JP 2012058126 W JP2012058126 W JP 2012058126W WO 2012137642 A1 WO2012137642 A1 WO 2012137642A1
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Classifications
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- 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
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- 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
- C11D3/26—Organic compounds containing nitrogen
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- 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
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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- 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
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- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/08—Liquid soap, e.g. for dispensers; capsuled
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- 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
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- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
- C11D3/323—Amides; Substituted amides urea or derivatives thereof
-
- 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
- C11D3/40—Dyes ; Pigments
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- 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
Definitions
- the present invention relates to a liquid detergent containing urea.
- This application claims priority based on Japanese Patent Application No. 2011-081768 filed in Japan on April 1, 2011, the contents of which are incorporated herein by reference.
- the composition of the liquid cleaning agent is a so-called “concentrated type” that contains a high concentration of surfactant and can be washed with half the amount of conventional use per wash. Compositions have been developed.
- the liquid detergent having a high surfactant content has a problem that the usability deteriorates with the passage of time, particularly because the liquid detergent itself tends to gel on the liquid surface. If the liquid cleaning agent is gelled, it becomes difficult to measure the liquid cleaning agent in the cap (that is, metering), and the ability to discharge the cap from the cap to the inlet of the washing machine also deteriorates. For this reason, in addition to a high detergency, the concentrated liquid detergent is required to maintain fluidity without causing gelation or the like with time and to have good liquidity. On the other hand, a concentrated liquid cleaning agent using a specific polyoxyethylene fatty acid methyl ester as a surfactant is disclosed (see Patent Documents 1 and 2).
- the liquid cleaning agent is colored by coloring it, and the cap is made transparent so that the amount of liquid cleaning agent collected in the cap can be easily understood and measured. .
- the object to be washed (the object to be cleaned) to which the liquid cleaning agent is applied is left for a whole day or night, or the rinsing is insufficient.
- pigments are likely to be dyed on an object to be washed.
- the present invention has been made in view of the above circumstances, and in a concentrated liquid detergent containing a pigment, the liquid detergent has a high detergency and has suppressed dye dyeing on an object to be washed. The issue is to provide.
- the surfactant (A) is 40% by mass or more, the dye (B) is 150 ppm (mass basis) or less, and urea or its derivative (C) is 0.5 to 12% by mass.
- a liquid detergent containing in the liquid detergent of the first aspect, is a nonionic surfactant represented by the following general formulas (a1) to (a3): It is a liquid detergent containing at least one selected surfactant.
- R 1 is a linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms
- R 2 is an alkylene group having 2 to 4 carbon atoms
- R 3 is carbon
- R 4 is a hydrocarbon group having 10 to 22 carbon atoms
- R 5 represents an alkylene group having 2 to 4 carbon atoms
- t represents an average number of repetitions of R 5 O, and is an integer of 5 to 20
- R 6 represents an alkyl having 10 to 16 carbon atoms
- p represents the average number of repetitions of EO
- q represents the average number of repetitions of PO
- r represents the average number of repetitions of EO
- p, q, r are p> 1, r ⁇ 0 , 0 ⁇ q ⁇ 3, and
- a third aspect of the present invention is a liquid detergent further comprising an organic solvent (D) represented by the following general formula (d1) in the liquid detergent of the first or second aspect.
- R 7 represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms; m represents an average repeat number of PO, n represents an average repeat number of EO, and m represents an integer of 0 to 2] N is an integer of 0 to 3 and 1 ⁇ m + n ⁇ 5; EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]
- liquid cleaning agent that has high detergency and suppresses dye dyeing on an object to be washed in a concentrated liquid cleaning agent containing a dye.
- the liquid detergent of the present invention contains 40% by mass or more of the surfactant (A), 150 ppm (mass basis) or less of the dye (B), and 0.5 to 12% by mass of urea or its derivative (C). To do.
- these three components may be referred to as (A) component, (B) component, and (C) component, respectively.
- surfactant (A) As surfactant (A), nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, and other surfactants usually used in liquid detergents for clothing are blended. Can do.
- Nonionic surfactant Preferred examples of the nonionic surfactant include surfactants represented by the following general formulas (a1) to (a3), and polyoxyalkylene alkyl ethers.
- R 1 is a linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms
- R 2 is an alkylene group having 2 to 4 carbon atoms
- R 3 is carbon An alkyl group having a number of 1 to 4, and s represents an average number of repetitions of OR 2 and is an integer of 5 to 30.
- R 1 is a linear or branched alkyl group having 5 to 21 carbon atoms, or a linear or branched alkenyl group having 5 to 21 carbon atoms.
- the number of carbon atoms of the alkyl group and alkenyl group in R 1 is preferably 9 to 13 carbon atoms, more preferably 11 to 13 carbon atoms, respectively, from the viewpoint of improving detergency and storage stability.
- Specific examples of the alkyl group include C 11 H 23 , C 13 H 27 , and the like.
- Specific examples of the alkenyl group include C 11 H 21 , C 13 H 25 , and the like.
- R 2 is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group.
- (OR 2 ) s may be a single oxyalkylene group repeating structure, or two or more oxyalkylene groups may be mixed. When two or more kinds of oxyalkylene groups are mixed, the oxyalkylene groups may be added in a block shape or may be added in a random shape.
- R 3 is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
- s represents an average number of repetitions of OR 2 and is an integer of 5 to 30. From the viewpoint of improving the detergency and liquid stability of the liquid detergent (especially stability at low temperatures, etc.), s is preferably 12-18.
- a narrow ratio indicating a distribution ratio of compounds having different OR 2 repeating numbers is 20% by mass or more.
- the upper limit of the narrow ratio is preferably substantially 80% by mass or less. That is, the narrow ratio is preferably 20 to 80% by mass, more preferably 20 to 60% by mass, and further preferably 30 to 45% by mass. As the narrow ratio is higher, better detergency can be obtained. However, if it is too high, the temporal stability at low temperatures may be lowered.
- the “narrow ratio” refers to a value represented by the following mathematical formula (S).
- S max represents the number of added moles of alkylene oxide of the alkylene oxide adduct most frequently present in the whole component represented by the formula (a1).
- 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 oxide present in the whole component represented by the formula (a1).
- the narrow rate can be controlled by the method for producing the component represented by the formula (a1).
- the method for producing the component represented by the formula (a1) is not particularly limited, and as an example, a method of adding an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (special feature). (See Japanese Laid-Open Patent Publication No. 2000-144179).
- Such a surface-modified composite metal oxide catalyst specifically, metal ions (Al 3+ , Ga 3+ , In 3+ , Tl 3+ , surface-modified with a metal hydroxide or the like, A composite metal oxide catalyst such as magnesium oxide to which Co 3+ , Sc 3+ , La 3+ , Mn 2+, etc.) are added; and at least one compound selected from the group consisting of metal hydroxides, metal alkoxides, etc. Examples thereof include a calcined product catalyst of modified hydrotalcite.
- a mixing ratio of the composite metal oxide and at least one compound selected from the group consisting of a metal hydroxide and a metal alkoxide is used.
- the ratio of at least one compound selected from the group consisting of metal hydroxides and metal alkoxides to 100 parts by mass is preferably 0.5 to 10 parts by mass, and preferably 1 to 5 parts by mass. Is more preferable.
- R 4 represents a hydrocarbon group having 10 to 22 carbon atoms
- R 5 represents an alkylene group having 2 to 4 carbon atoms
- t represents an average number of repeating R 5 O
- 5 to It is an integer of 20.
- R 4 has 10 to 22, preferably 10 to 20, more preferably 10 to 18 carbon atoms.
- the hydrocarbon group for R 4 may be linear or branched, and may have an unsaturated bond. Specific examples of the hydrocarbon group for R 4 include C 10 H 21 , C 12 H 25 , C 14 H 29 , C 16 H 33 , C 18 H 37 , C 20 H 41 , and the like.
- the component represented by the formula (a2) may be a component having a single chain length or a mixture of components having a plurality of chain lengths.
- R 5 is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group.
- R 5 O) t may be a single oxyalkylene group repeating structure, or two or more oxyalkylene groups may be mixed. When two or more kinds of oxyalkylene groups are mixed, the oxyalkylene groups may be added in a block shape or may be added in a random shape.
- t represents an average number of repetitions of R 5 O and is an integer of 5 to 20, preferably an integer of 8 to 18, more preferably an integer of 10 to 16.
- t exceeds 20, the HLB becomes too high and disadvantageous for the sebum cleaning, so that the cleaning function tends to deteriorate.
- t is 5 or more, it becomes easy to prevent odor deterioration.
- t is in the range of 10 to 16, it exhibits a high detergency against sebum dirt.
- the addition mole number distribution of R 5 O varies depending on the reaction method during the production of the component represented by the formula (a2), and is not particularly limited.
- a general alkali catalyst such as sodium hydroxide or potassium hydroxide
- the added mole number distribution of R 5 O tends to be a relatively wide distribution.
- 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 added mole number distribution of R 5 O tends to be a relatively narrow distribution.
- Neodol manufactured by Shell mixture of alcohol having 12 carbon atoms and alcohol having 13 carbon atoms: hereinafter may be referred to as C12 / C13
- R 6 represents an alkyl group or alkenyl group having 10 to 16 carbon atoms
- p represents the average number of repetitions of EO
- q represents the average number of repetitions of PO
- r represents the average number of repetitions of EO.
- EO represents an oxyethylene group
- PO represents an oxypropylene group
- EO and PO in (EO) p / (PO) q may be mixed and arranged.
- the alkyl group or alkenyl group in R 6 has 10 to 16 carbon atoms, and preferably 10 to 14 carbon atoms.
- the alkyl group and alkenyl group of R 6 may be linear or branched. Specific examples of the linear or branched alkyl group include C 10 H 21 , C 12 H 25 , C 14 H 29 , and the like. Specific examples of the linear or branched alkenyl group include C 10 H 19 , C 12 H 23 , C 14 H 27 , and the like.
- r is r ⁇ 0, preferably r ⁇ 1.
- the ratio of EO and PO is preferably a ratio represented by q / (p + r) of 0.1 to 0.5, more preferably 0.1 to 0.3. is there.
- the ratio represented by q / (p + r) is equal to or greater than the lower limit value, bubbles are not excessively formed and foaming is optimized.
- the ratio represented by q / (p + r) is not more than the upper limit value, an appropriate viscosity is easily obtained, and gelation is easily suppressed.
- biodegradability improves because q is 3 or less. Only one of EO and PO in (EO) p / (PO) q may exist, or they may be mixed and arranged. In (EO) p / (PO) q, EO and PO may be added randomly, or may be added in blocks.
- the component represented by the formula (a3) can be synthesized by a known method. As an example, after addition reaction of ethylene oxide and propylene oxide in this order to alcohol derived from natural fats and oils or after mixed addition of ethylene oxide and propylene oxide (random addition), ethylene oxide is added again by adding ethylene oxide and propylene oxide.
- the component represented by the formula (a3) can be synthesized.
- polyoxyalkylene alkyl ether an average of 3 to 30 mol, preferably 5 to 20 mol, of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms.
- Polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether (alcohol alkoxylate) may be mentioned.
- polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether are preferable.
- the aliphatic alcohol used here include primary alcohols and secondary alcohols.
- the alkyl group of the aliphatic alcohol may have a branched chain.
- a primary alcohol is preferable.
- Anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, secondary alkane sulfonate, polyoxyethylene alkyl ether sulfate, ⁇ -olefin sulfonate, ⁇ -sulfo fatty acid ester salt, polyoxyethylene alkyl Examples include ether carboxylates.
- Specific examples of the anionic surfactant include a linear alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 16 carbon atoms (preferably 10 to 14 carbon atoms); an alkyl group having 10 to 20 carbon atoms.
- LAS linear alkylbenzene sulfonate
- Alkyl sulfate Polyalkylene having an alkyl group having 10 to 20 carbon atoms (preferably 10 to 14 carbon atoms) and having an average addition mole number of ethylene oxide of 1 to 10 (preferably an average addition mole number of 1 to 4).
- Oxyethylene alkyl ether sulfate AES
- AOS ⁇ -olefin sulfonate
- SAS Secondary alkanesulfonate
- ⁇ -sulfo fatty acid methyl ester salt having an alkyl group having 10 to 20 carbon atoms ( ⁇ -SF); It has 0 alkyl group, a polyoxyethylene alkyl error of average addition mole number of 1 to 10 ethylene oxide - Terukarubon acid salts, and the like preferably.
- these salts include alkali metal salts such as sodium salts and potassium salts; alkanolamine salts such as monoethanolamine salts and diethanolamine salts, and alkali metal salts are preferred.
- polyoxyethylene alkyl ether sulfate when the addition mole number of ethylene oxide of the ethylene oxide adduct most present on the mass basis in all ethylene oxide adducts constituting the polyoxyethylene alkyl ether sulfate is “nlmax”, Polyoxyethylene alkyl ether sulfates in which the total proportion of ethylene oxide adducts with the number of moles of ethylene oxide added (nlmax-1), nlmax, and (nlmax + 1) is 55% by mass or more based on the total ethylene oxide adduct Polyoxyethylene alkyl ether sulfate in the range of 55 to 80% by mass is more preferable. Within the above range, the fluidity of the polyoxyethylene alkyl ether sulfate is increased and the manufacturability is improved.
- alkylbenzene sulfonate alkylbenzene sulfonate, polyoxyethylene alkyl ether sulfate, and secondary alkane sulfonate are preferable because of good anti-recontamination property; alkylbenzene sulfonic acid Salts and polyoxyethylene alkyl ether sulfates are more preferred; alkyl benzene sulfonates are particularly preferred.
- Examples of the cationic surfactant include alkylamine salts and alkyl quaternary ammonium salts.
- Examples of amphoteric surfactants include carboxylic acid type amphoteric surfactants (amino type and betaine type), sulfate ester type amphoteric surfactants, sulfonic acid type amphoteric surfactants, and phosphate ester type amphoteric surfactants. It is done.
- Examples of other surfactants include natural surfactants, protein hydrolyzate derivatives, polymer surfactants, surfactants containing titanium / silicon, and fluorocarbon surfactants.
- a component may be used individually by 1 type and may use 2 or more types together.
- a nonionic surfactant and an anionic surfactant as the component (A).
- the component (A) preferably contains 50% by mass or more of the nonionic surfactant relative to the component (A), more preferably contains 80% by mass or more of the nonionic surfactant. It is more preferable to contain 90% by mass or more of the ionic surfactant, and the nonionic surfactant may be 100% by mass.
- the nonionic surfactant contains at least one nonionic surfactant selected from the nonionic surfactants represented by the general formulas (a1) to (a3) because of its high detergency. Is preferred.
- an antiionic surfactant is used in combination with a nonionic surfactant because the antifouling property of preventing dirt from adhering to the washing object again in the washing liquid is increased. Is preferred.
- the content of the component (A) in the liquid detergent is 40% by mass or more, preferably 40 to 70% by mass, and preferably 45 to 65% by mass with respect to the total mass of the liquid detergent. More preferred.
- the content of the component (A) is 40% by mass or more with respect to the total mass of the liquid detergent, the effect of the present invention is remarkably exhibited. In addition, good detergency can be obtained.
- the effectiveness (commercial value) as a concentrated liquid cleaning agent is increased.
- the content of the component (A) is preferably 70% by mass or less, more preferably 65% by mass or less, with respect to the total mass of the liquid detergent, the gelation of the liquid detergent on the liquid surface with time Etc. are less likely to occur, and a film is less likely to be formed on the liquid surface.
- the content of the anionic surfactant is preferably 1 to 10% by mass, more preferably 1 to 5% by mass with respect to the total mass of the liquid detergent. Preferably, 2 to 5% by mass is more preferable.
- the content of the anionic surfactant is 10% by mass or less with respect to the total mass of the liquid detergent, the liquid detergent itself is difficult to gel and a film is formed on the liquid surface of the liquid detergent. It becomes difficult. Further, the coating cleaning power is improved satisfactorily.
- the content of the anionic surfactant is 1% by mass or more based on the total mass of the liquid detergent, the recontamination preventing property is further improved.
- the dye (B) is not particularly limited, and is an acid dye, basic dye, cationic dye, mordant (oil-soluble) dye, vat dye, naphthol dye (azo dye), reactive dye (reactive dye), disperse dye, An oxidation dye etc. are mentioned.
- the structure of each dye is described in the “Legal Handbook” (edited by Japan Cosmetic Industry Association).
- a dye having a maximum absorption wavelength at 400 to 700 nm is preferable, and a dye having a maximum absorption wavelength at 500 to 700 nm is more preferable because the effects of the present invention are remarkably easily exhibited.
- a blue to green dye having a maximum absorption wavelength at 590 to 650 nm is particularly preferable.
- Specific examples of the dye (B) include the following blue dyes and green dyes.
- Blue dye C.I. I. Acid Blue 5, C.I. I. Acid Blue 9, C.I. I. Acid Blue 74, C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 63, C.I. I. Diverse Blue1, C.I. I. Diverse Blue 3, C.I. I. Diverse Blue 5, C.I. I. Diverse Blue 6, C.I. I. Diverse Blue 7, C.I. I. Diverse Blue 26, C.I. I. Diverse Blue 27, C.I. I. Diverse Blue 54, C.I. I. Diverse Blue 55, C.I. I. Diverse Blue 56, C.I.
- Solvent (oil-soluble) dyes dyes that are chemically modified with a water-soluble polymer such as polyethylene glycol or polypropylene glycol at the end of the chromophore structure to increase water solubility. But you can. Specific examples include trade names such as Liquid Blue Blue and Liquid Blue BL manufactured by Milliken.
- Green dye C.I. I. Acid Green1, C.I. I. Acid Green 3, C.I. I. Acid Green 5, C.I. I. Acid Green 25, C.I. I. Food Blue2, C.I. I. Food Green 3, C.I. I. Solvent Green 3, C.I. I. Food Green 3, C.I. I. Solvent Green 7, C.I. I. Solvent Green et al.
- a component may be used individually by 1 type and may use 2 or more types together.
- the content of the component (B) in the liquid detergent is 1 ppm (mass basis) or more and 150 ppm (mass basis) with respect to the total mass of the liquid detergent, from the dyeing property to the washing object and the liquid color degree by blending. (Mass basis) or less (0.015 mass% or less), preferably 1 to 100 ppm (mass basis) (0.0001 to 0.01 mass%), preferably 3 to 50 ppm (mass basis) (0.0003 to 0.003). (005% by mass) is more preferable. If the content of the component (B) is less than the lower limit, the liquid detergent liquid may not be sufficiently colored. On the other hand, when the content of the component (B) exceeds the upper limit value, dye dyeing to the object to be washed may not be suppressed.
- urea or its derivative (C) examples include urea [CO (NH 2 ) 2 ], urea double salt, and other urea derivatives.
- urea double salt examples include HNO 3 ⁇ CO (NH 2 ) 2 , H 3 PO 4 ⁇ CO (NH 2 ) 2 , H 2 C 2 O 4 ⁇ 2CO (NH 2 ) 2 , Ca (NO 3 ) 2 ⁇ 4CO.
- the “urea derivative” includes a compound having a structure represented by the following general formula (c1). Among the urea derivatives, preferred are compounds represented by the general formula (c1-1).
- R a is a methyl group, an ethyl group, or a hydroxyalkyl group having 1 to 2 carbon atoms.
- R b , R c and R d are each independently a hydrogen atom, a methyl group or an ethyl group.
- Examples of the compound represented by the formula (c1-1) include 1,3-dimethylurea, N- (2-hydroxyethyl) urea and the like.
- the component (C) one type may be used alone, or two or more types may be used in combination.
- the content of the component (C) in the liquid detergent is preferably 0.5 to 12% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 8% with respect to the total mass of the liquid detergent. % By mass.
- the content of the component (C) is less than the lower limit, dyeing of the object to be washed may not be sufficiently suppressed.
- the content of the component (C) exceeds the upper limit value, ammonia tends to be generated as a decomposition product after storage, and odor may be a problem as a liquid detergent product.
- the affinity to dirt is likely to be reduced, there is a possibility that the coating cleaning power is reduced.
- the mixing ratio of the component (A) and the component (C) is preferably 30 or less in terms of mass ratio represented by (A) / (C), and is 6 to 15. More preferably, it is more preferably 9-11.
- mass ratio represented by (A) / (C) is less than or equal to the upper limit value, dyeing of the article to be washed is easily suppressed.
- mass ratio represented by (A) / (C) is less than the lower limit, the coating cleaning power may be reduced.
- “mass ratio represented by (A) / (C)” represents the ratio (mass ratio) of the content of component (A) to the content of component (C) in the liquid detergent. .
- the liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of preparation of the liquid detergent, solubility in water when used, and the like.
- the content of water in the liquid detergent is preferably 15 to 45% by mass, more preferably 25 to 40% by mass with respect to the total mass of the liquid detergent. If the water content is at least the lower limit, the liquid stability of the liquid detergent with time will be better, and if it is not more than the upper limit, the liquid viscosity will be reasonably low, which is good from the viewpoint of usability. .
- the liquid detergent of the present invention preferably further contains an organic solvent (D) represented by the following general formula (d1) (hereinafter also referred to as “component (D)”).
- component (D) an organic solvent represented by the following general formula (d1)
- the component (D) is also effective as a viscosity modifier for the liquid detergent and a gelation inhibitor.
- R 7 represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms; m represents an average number of repetitions of PO; n represents an average number of repetitions of EO; , N is an integer of 0 to 3, and 1 ⁇ m + n ⁇ 5; EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged.
- R 7 is a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms.
- the alkyl group for R 7 may be linear or branched. Specific examples of the linear and branched alkyl groups include CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , and the like. Only one of EO and PO in (EO) n / (PO) m may exist, or they may be mixed and arranged. In (EO) n / (PO) m, EO and PO may be added randomly, or may be added in blocks.
- alkanols such as ethanol, 1-propanol, 2-propanol, 1-butanol (D1); ethylene glycol, propylene glycol, copolymers of ethylene glycol and propylene glycol, diethylene glycol, triethylene glycol , Alkylene glycol (D2) such as dipropylene glycol; diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monobutyl ether Alkylene glycols having 2 to 3 carbon atoms such as Consisting of units of the (poly) alkylene glycol and the alkanol of 1 to 4 carbon atoms (poly) alkylene glycol (mono- or di-) alkyl ether (D3), and the like.
- D1 alkano
- a component may be used individually by 1 type and may use 2 or more types together.
- the component (D) it is preferable to use at least one organic solvent selected from the group consisting of the above (D1) to (D3), and two or more organic solvents selected from the above group are used. It is more preferable to use a combination of solvents. By using a combination of two or more organic solvents, it is easy to obtain the effects of adjusting the viscosity of the liquid detergent and suppressing gelation.
- the content of the component (D) in the liquid detergent is preferably 5 to 20% by mass, more preferably 5 to 18% by mass, and further preferably 5 to 15% by mass with respect to the total mass of the liquid detergent. It is.
- the content of the component (D) is less than the lower limit, it is difficult to obtain an appropriate viscosity, and the liquid cleaning agent is likely to be solidified when applied to an object to be cleaned.
- the content of the component (D) exceeds the upper limit value, there is a risk that an odor derived from the component (D) may be generated, and it is not preferable in terms of cost.
- liquid cleaning agent of the present invention other components other than the components described above may be blended as necessary within a range not impairing the effects of the present invention.
- the other components are not particularly limited, and components usually used in a liquid detergent composition for clothing can be blended, and specific examples include the following components.
- the liquid detergent of the present invention may contain alkanolamine for the purpose of improving the appearance stability.
- the alkanolamine is a component that can serve as a counter ion for the anionic surfactant, and the white turbidity that tends to be generated by blending the anionic surfactant It serves to suppress and improve appearance stability. Therefore, in the liquid cleaning agent of the present invention, it is preferable that the surfactant (A) contains an anionic surfactant and further contains an alkanolamine.
- an alkanolamine that acts as a counter ion for an anionic surfactant is preferable; an alkanolamine having an alkyl group having 1 to 3 carbon atoms is preferable; an alkanolamine having an alkyl group having 1 to 2 carbon atoms is more preferable.
- monoethanolamine, diethanolamine, and triethanolamine are more preferred.
- An alkanolamine may be used individually by 1 type, and may use 2 or more types together.
- the content of alkanolamine in the liquid detergent is preferably 0.1 to 3% by mass, more preferably 0.5 to 3% by mass, and still more preferably 0.5% by mass with respect to the total mass of the liquid detergent. ⁇ 2% by weight.
- the liquid detergent of the present invention includes enzymes (proteases, lipases, cellulases, etc.), organic solvents other than component (D), and thickeners (long-chain fatty acid alkylamides) for the purpose of improving washing performance and blending stability. Etc.), texture improvers, pH adjusters, preservatives, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, soil release agents, and the like.
- As the pH adjuster sulfuric acid, sodium hydroxide, potassium hydroxide and the like are preferable from the viewpoint of liquid stability.
- a flavoring agent, an emulsifying agent, etc. can also be mix
- the fragrance compositions A, B, C, D and the like described in Tables 11 to 18 of JP-A No. 2002-146399 can be used.
- the content of the flavoring agent is preferably 0.1 to 1% by mass relative to the total mass of the liquid detergent.
- the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is preferably used. Specific examples include polystyrene emulsion (manufactured by Seiden Chemical Co., Ltd., “Cybinol RPX-196 PE-3”, solid content 40% by mass).
- the content of the emulsifying agent is preferably 0.01 to 0.5% by mass relative to the total mass of the liquid detergent.
- the pH of the liquid detergent of the present invention is preferably 5 to 10 at 25 ° C., more preferably 5 to 9.5, and still more preferably 5 to 9.
- the pH is particularly preferably 6-9.
- the pH of the liquid detergent is equal to or higher than the lower limit value, good detergency is easily maintained when the liquid detergent is stored for a long time.
- the pH is less than the upper limit value, dyeing of the object to be washed is more easily suppressed.
- the liquid stability is easily maintained well.
- the pH of the liquid detergent (controlled at 25 ° C.) is a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation).
- the liquid cleaning agent of the present invention is a liquid cleaning agent that has a high detergency and suppresses dye dyeing to an object to be washed in a concentrated liquid cleaning agent containing a pigment.
- a concentrated liquid cleaning agent containing a pigment the object to be washed (the object to be cleaned) to which the liquid cleaning agent is applied is left for a while or is rinsed once with a drum-type washing machine or the like.
- it is broken (that is, when rinsing is insufficient)
- the likelihood of this dyeing on the object to be washed varies depending on the composition of the liquid detergent, the type of clothing (fiber), the temperature, and the water temperature. For example, dyeing is more likely to occur at lower temperature conditions or depending on the type of organic solvent, the more hydrophobic fibers (such as polyester fibers).
- the reason why pigments are dyed on the object to be washed is that the high concentration surfactant and the object to be washed are in contact with each other for a long time, or the surfactant is partially applied to the object to be washed due to insufficient rinsing. The surfactant may permeate the clothing (fiber) too much, and the pigment will be adsorbed deeply into the clothing (fiber).
- urea or a derivative thereof (C) is contained together with 40% by mass or more of the surfactant with respect to the total mass of the liquid cleaning agent and the dye. While component (C) is a highly hydrophilic substance, its interaction with the surfactant is strong due to its structural characteristics, so component (C) is around the surfactant molecule in the formulation.
- the liquid detergent of the present invention by containing the component (C), in particular, an anionic surfactant that suppresses recontamination, and an alkanolamine that can be a counter ion of the anionic surfactant, the yellowing of the liquid color, which is likely to occur when using together, is also suppressed, and the appearance stability is kept good.
- the liquid cleaning agent of the present invention exhibits a high cleaning effect with a small amount of cleaning agent used.
- the liquid detergent of the present invention is particularly suitable for clothing, and is a liquid detergent that contains a pigment and is suitable for a composition having a high surfactant concentration (concentrated composition).
- a liquid detergent containing a surfactant (A), a dye (B), urea or a derivative thereof (C), and an organic solvent (D), with respect to the total mass of the liquid detergent is 40 to 70% by mass
- the component (B) is 1 to 150 ppm (mass basis)
- Examples thereof include liquid detergents in which the component (C) is 0.5 to 12% by mass, the component (D) is 5 to 20% by mass, and the total amount of the components does not exceed 100% by mass.
- the component (A) is 40 to 70% by mass
- the component (B) is 1 to 150 ppm (mass basis)
- the component (C) is 0.5 to 12% by mass
- the water is 15 to 45% by mass
- the total amount of the components is 100% by mass.
- a liquid detergent containing a surfactant (A), a dye (B), urea or a derivative thereof (C), an organic solvent (D), and water wherein the total mass of the liquid detergent Whereas
- the component (A) is 40 to 70% by mass
- the component (B) is 1 to 150 ppm (mass basis)
- the component (C) is 0.5 to 12% by mass
- Examples thereof include liquid detergents in which the component (D) is 5 to 20% by mass, the water is 15 to 45% by mass, and the total amount of each component does not exceed 100% by mass.
- compositions of the liquid detergents in each example are shown in Tables 1 to 3.
- the raw materials used in this example are as follows.
- A-1 C 11 H 23 CO— (OC 2 H 4 ) 15 —OCH 3 , narrow ratio 33% by mass; synthetic product.
- A-1 was produced by a method based on the method described in JP-A-2002-144179. That is, alumina hydroxide / magnesium hydroxide (trade name Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical composition of 2.5 MgO.Al 2 O 3 .nH 2 O is fired at 600 ° C. for 1 hour in a nitrogen atmosphere.
- A-2 Mixture of C 11 H 23 CO— (OC 2 H 4 ) 15 —OCH 3 and C 13 H 27 CO— (OC 2 H 4 ) 15 —OCH 3 in a mass ratio of 8/2, narrow ratio 33% by mass; synthetic product.
- A-2 was synthesized in the same manner as A-1, except that instead of 350 g of lauric acid methyl ester, a mixture of 280 g of lauric acid methyl ester and 70 g of myristic acid was used and 1052 g of ethylene oxide was introduced. Manufactured with.
- A-3 A nonionic surfactant in which an average of 9 moles of ethylene oxide, an average of 2 moles of propylene oxide, and an average of 9 moles of ethylene oxide are added in block order to a primary alcohol having 10 to 14 carbon atoms.
- A-5 Polyoxyethylene alkyl (C12-13) ether.
- A-6 linear alkyl (carbon number 10 to 14) benzenesulfonic acid [manufactured by Lion Corporation, trade name Rypon LH-200 (LAS-H pure content 96 mass%)].
- A-7 AES-Na, sodium polyoxyethylene alkyl ether sulfate having 12 to 13 carbon atoms (average addition mole number of ethylene oxide 2), synthetic product (raw alcohol is trade name Neodol 23, manufactured by Shell).
- A-8 Natural alcohol (trade name CO-1214 manufactured by P & G) with 12 mole equivalent of ethylene oxide added [LMAO (C12 / 14-15EO)], synthetic product.
- the synthesis was performed as follows. 861.2 g of a trade name “CO-1214” 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. Next, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution.
- reaction temperature might not exceed 180 degreeC using the blowing tube.
- aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
- 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, and LMAO (C12 / 14 -15EO).
- B-1 C.I. I. Food Green 3, Green No. 3, manufactured by Sakai Kasei Co., Ltd .; maximum absorption wavelength 610 nm.
- B-2 Liquid Blue Blue, manufactured by Milliken Co .; maximum absorption wavelengths of 595 nm and 645 nm.
- B-3 C.I. I. Solvent Blue 63, Blue No. 403, manufactured by Sakai Kasei Co., Ltd .; maximum absorption wavelengths of 600 nm and 645 nm.
- MEA Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.) 100% by mass pure.
- DEA 100% by mass of diethanolamine (manufactured by Nippon Shokubai Co., Ltd.)
- Polyethylene glycol manufactured by Lion Chemical Co., Ltd., trade name “PEG # 1000-L60”, polymerization degree 20.
- Enzyme Protease, trade name “Everlase 16L TYPE EX”, manufactured by Novozymes.
- Citric acid manufactured by Fuso Chemical Industries, Ltd., 100% pure content.
- pH adjuster KOH (Asahi Glass Co., Ltd.) and sulfuric acid (Toho Zinc Co., Ltd.). Ion exchange water.
- liquid detergents of each example were produced by the following production methods (when there are blank blending components in the table, the blending components are Not blended).
- the content of the compounding component indicates a pure equivalent amount.
- only content of (B) component is displayed by "ppm" (mass basis).
- the “balance” indicating the water content indicates a blending amount adjusted so that the total amount of the liquid cleaning agent as the final preparation is 100% by mass.
- the “appropriate amount” indicating the content of the pH adjusting agent indicates an amount blended for adjusting the pH (25 ° C.) of the liquid cleaning agent to the pH shown in the table.
- Mass ratio: (A) / (C) represents the ratio (mass ratio) of the content of component (A) to the content of component (C) in the liquid detergent.
- Examples 1 to 19, Comparative Examples 1 to 3, Reference Example 1 In a 500 mL beaker, the component (D) of the content (mass%) shown in the table, polyethylene glycol, MEA or DEA, and A-6 or A-7 were added and stirred (in the table, If there is a blank compounding component, the compounding component is not blended). Subsequently, (C) component aqueous solution (concentration 50 mass%) and citric acid aqueous solution (concentration 50 mass%) which respectively dissolved (C) component and citric acid in water were added and stirred. Subsequently, it adjusted so that pH (25 degreeC) of a solution might become the value shown in a table
- the coating cleaning power was evaluated by measuring the reflectance (Z value) using a reflectance meter (spectral color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.) before and after cleaning. %).
- Washing rate (%) (Z value of contaminated cloth after washing ⁇ Z value of contaminated cloth before washing) / (Z value of raw cloth ⁇ Z value of contaminated cloth before washing) ⁇ 100
- raw fabric refers to cotton knitted fabric that has not been subjected to contamination treatment in the preparation of the above-mentioned contaminated fabric.
- the cleaning rate (%) of 5 contaminated cloths was calculated, the average value thereof was determined, and the coating cleaning power was evaluated based on the following evaluation criteria.
- the washing course was set at a washing time of 10 minutes, designated once for rinsing and dehydration for 8 minutes.
- the above operations in the case of cotton towels) were performed under the conditions of summer and winter.
- an evaluation sample (cotton) coated with 5 g of a liquid detergent was left at a temperature of 25 ° C. for 12 hours, and water adjusted to 25 ° C. during washing was used.
- an evaluation sample (cotton) coated with 5 g of a liquid detergent was left at a temperature of 5 ° C. for 12 hours, and water adjusted to 5 ° C. during washing was used.
- a polyester (PE) jersey (Tanigami Shoten) was cut into 5 cm ⁇ 5 cm, and used as a sample for evaluation (PE) (0.2 g by mass).
- 2 g of the standard amount (15 g) of liquid detergent used for 4 kg of laundry was applied to the evaluation sample (PE) and allowed to stand for 12 hours.
- the sample for evaluation (PE) coated with 5 g of detergent and a cotton skin shirt as a charge cloth are put into a washing machine so as to be 4 kg in total, and the remaining liquid detergent is added, and the same as the above washing conditions. Laundry was performed under conditions. The above operation (in the case of PE) was performed only under the same summer conditions as described above.
- the present invention is extremely industrially useful because it can provide a liquid cleaning agent that has a high detergency and suppresses dye dyeing to an object to be washed in a concentrated liquid cleaning agent containing a pigment.
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Abstract
Description
本願は、2011年4月1日に、日本に出願された特願2011-081768号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a liquid detergent containing urea.
This application claims priority based on Japanese Patent Application No. 2011-081768 filed in Japan on April 1, 2011, the contents of which are incorporated herein by reference.
液体洗浄剤については、「液体洗浄剤入り容器を手で持つと重い」、「店から持ち帰るのが大変」、「すぐに使い切ってしまう」等の消費者の不満が存在している。
一方、洗浄剤分野においては、環境負荷に対する意識の高まりから、洗浄剤の洗濯1回当たりの使用量を低減すること、洗浄剤が収容される容器のサイズを小型化して樹脂廃棄量を削減すること等が求められている。
このような不満、要望に対して、液体洗浄剤の組成としては、高濃度の界面活性剤を含有し、洗濯1回当たり従来の半分の使用量で洗濯が可能な、いわゆる「濃縮タイプ」の組成物が開発されている。 Recently, as a detergent used for laundry at home, it has features that are different from powder detergents (for example, there is no undissolved, you can enjoy fragrance, etc.), and the price is affordable, so the demand for liquid detergents has increased. ing.
With regard to liquid detergents, there are consumer complaints such as "It is heavy to hold a container with liquid detergent by hand", "It is difficult to take home from a store", "It will be used up quickly".
On the other hand, in the field of cleaning agents, due to heightened awareness of environmental impact, the amount of cleaning agent used per wash is reduced, and the size of the container in which the cleaning agent is stored is reduced to reduce the amount of resin waste. That is required.
In response to such dissatisfaction and demand, the composition of the liquid cleaning agent is a so-called “concentrated type” that contains a high concentration of surfactant and can be washed with half the amount of conventional use per wash. Compositions have been developed.
これに対して、界面活性剤として特定のポリオキシエチレン脂肪酸メチルエステルを用いた、濃縮タイプの液体洗浄剤が開示されている(特許文献1、2参照)。 The liquid detergent having a high surfactant content has a problem that the usability deteriorates with the passage of time, particularly because the liquid detergent itself tends to gel on the liquid surface. If the liquid cleaning agent is gelled, it becomes difficult to measure the liquid cleaning agent in the cap (that is, metering), and the ability to discharge the cap from the cap to the inlet of the washing machine also deteriorates. For this reason, in addition to a high detergency, the concentrated liquid detergent is required to maintain fluidity without causing gelation or the like with time and to have good liquidity.
On the other hand, a concentrated liquid cleaning agent using a specific polyoxyethylene fatty acid methyl ester as a surfactant is disclosed (see Patent Documents 1 and 2).
こうした問題に対し、色素を配合して液体洗浄剤を着色し、さらにキャップを透明にすることで、液体洗浄剤のキャップへの採取量を分かりやすくし、計量しやすくする工夫が施されている。 Also, when measuring the liquid detergent into the cap, in the case of a liquid with a colorless and transparent appearance, it is difficult to collate with the scale of the cap, so the amount of liquid measured in the cap is likely to be too much or too little than the predetermined amount. . In particular, in the case of a concentrated liquid cleaning agent, it is important to accurately measure and use the cap because it can be used in a smaller amount than in the past.
In order to solve these problems, the liquid cleaning agent is colored by coloring it, and the cap is made transparent so that the amount of liquid cleaning agent collected in the cap can be easily understood and measured. .
本発明は、上記事情に鑑みてなされたものであり、色素を含有する濃縮タイプの液体洗浄剤において、高い洗浄力を有すると共に、被洗物への色素染着が抑制された液体洗浄剤を提供することを課題とする。 However, in a concentrated liquid cleaning agent containing a pigment, the object to be washed (the object to be cleaned) to which the liquid cleaning agent is applied is left for a whole day or night, or the rinsing is insufficient. There is a problem that pigments are likely to be dyed on an object to be washed.
The present invention has been made in view of the above circumstances, and in a concentrated liquid detergent containing a pigment, the liquid detergent has a high detergency and has suppressed dye dyeing on an object to be washed. The issue is to provide.
本発明の第2の態様は、前記第1の態様の液体洗浄剤において、前記界面活性剤(A)が、下記の一般式(a1)~(a3)で表される非イオン界面活性剤から選択される少なくとも一種の界面活性剤を含む液体洗浄剤である。 As a result of intensive studies, the present inventors provide the following means in order to solve the above problems. That is, in the first aspect of the present invention, the surfactant (A) is 40% by mass or more, the dye (B) is 150 ppm (mass basis) or less, and urea or its derivative (C) is 0.5 to 12% by mass. And a liquid detergent containing
According to a second aspect of the present invention, in the liquid detergent of the first aspect, the surfactant (A) is a nonionic surfactant represented by the following general formulas (a1) to (a3): It is a liquid detergent containing at least one selected surfactant.
以下、これらの3成分をそれぞれ(A)成分、(B)成分、(C)成分ということがある。 The liquid detergent of the present invention contains 40% by mass or more of the surfactant (A), 150 ppm (mass basis) or less of the dye (B), and 0.5 to 12% by mass of urea or its derivative (C). To do.
Hereinafter, these three components may be referred to as (A) component, (B) component, and (C) component, respectively.
界面活性剤(A)としては、非イオン界面活性剤、陰イオン界面活性剤、陽イオン界面活性剤、両性界面活性剤等、衣料用の液体洗浄剤に通常用いられる界面活性剤を配合することができる。 [Surfactant (A)]
As surfactant (A), nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, and other surfactants usually used in liquid detergents for clothing are blended. Can do.
非イオン界面活性剤としては、下記の一般式(a1)~(a3)で表される界面活性剤、及びポリオキシアルキレンアルキルエーテルが好適に挙げられる。 (Nonionic surfactant)
Preferred examples of the nonionic surfactant include surfactants represented by the following general formulas (a1) to (a3), and polyoxyalkylene alkyl ethers.
R1におけるアルキル基、及びアルケニル基の炭素数は、洗浄力向上や保存安定性の点から、それぞれ炭素数9~13であることが好ましく、それぞれ炭素数11~13であることがより好ましい。
前記アルキル基として、具体的には、C11H23、C13H27、等が挙げられる。
前記アルケニル基として、具体的には、C11H21、C13H25、等が挙げられる。
R2は、炭素数2~4のアルキレン基であり、炭素数2~3のアルキレン基であることが好ましく、エチレン基であることがより好ましい。また、(OR2)sは、一種単独のオキシアルキレン基の繰返し構造であってもよく、二種以上のオキシアルキレン基が混在していてもよい。二種以上のオキシアルキレン基が混在している場合、オキシアルキレン基はブロック状に付加していてもよく、ランダム状に付加していてもよい。
R3は、炭素数1~4のアルキル基であり、好ましくはメチル基である。 In the formula (a1), R 1 is a linear or branched alkyl group having 5 to 21 carbon atoms, or a linear or branched alkenyl group having 5 to 21 carbon atoms.
The number of carbon atoms of the alkyl group and alkenyl group in R 1 is preferably 9 to 13 carbon atoms, more preferably 11 to 13 carbon atoms, respectively, from the viewpoint of improving detergency and storage stability.
Specific examples of the alkyl group include C 11 H 23 , C 13 H 27 , and the like.
Specific examples of the alkenyl group include C 11 H 21 , C 13 H 25 , and the like.
R 2 is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group. In addition, (OR 2 ) s may be a single oxyalkylene group repeating structure, or two or more oxyalkylene groups may be mixed. When two or more kinds of oxyalkylene groups are mixed, the oxyalkylene groups may be added in a block shape or may be added in a random shape.
R 3 is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
本明細書において「ナロー率」とは、下記の数式(S)で表される値をいう。 In the component represented by the formula (a1), it is preferable that a narrow ratio indicating a distribution ratio of compounds having different OR 2 repeating numbers is 20% by mass or more. The upper limit of the narrow ratio is preferably substantially 80% by mass or less. That is, the narrow ratio is preferably 20 to 80% by mass, more preferably 20 to 60% by mass, and further preferably 30 to 45% by mass. As the narrow ratio is higher, better detergency can be obtained. However, if it is too high, the temporal stability at low temperatures may be lowered.
In this specification, the “narrow ratio” refers to a value represented by the following mathematical formula (S).
iはアルキレンオキシドの付加モル数を示す。Yiは、前記式(a1)で表される成分全体の中に存在するアルキレンオキシドの付加モル数がiであるアルキレンオキシド付加体の割合(質量%)を示す。
前記ナロー率は、前記式(a1)で表される成分の製造方法等によって制御することができる。 In the formula (S), S max represents the number of added moles of alkylene oxide of the alkylene oxide adduct most frequently present in the whole component represented by the formula (a1).
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 oxide present in the whole component represented by the formula (a1).
The narrow rate can be controlled by the method for producing the component represented by the formula (a1).
かかる表面改質された複合金属酸化物触媒の好適な例としては、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;金属水酸化物及び金属アルコキシド等からなる群から選択される少なくとも1種の化合物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等が挙げられる。 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、金属水酸化物及び金属アルコキシドからなる群から選択される少なくとも1種の化合物との混合割合を、複合金属酸化物100質量部に対して、金属水酸化物及び金属アルコキシドからなる群から選択される少なくとも1種の化合物の割合を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。 The method for producing the component represented by the formula (a1) is not particularly limited, and as an example, a method of adding an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (special feature). (See Japanese Laid-Open Patent Publication No. 2000-144179).
As a suitable example of such a surface-modified composite metal oxide catalyst, specifically, metal ions (Al 3+ , Ga 3+ , In 3+ , Tl 3+ , surface-modified with a metal hydroxide or the like, A composite metal oxide catalyst such as magnesium oxide to which Co 3+ , Sc 3+ , La 3+ , Mn 2+, etc.) are added; and at least one compound selected from the group consisting of metal hydroxides, metal alkoxides, etc. Examples thereof include a calcined product catalyst of modified hydrotalcite. In the surface modification of the composite metal oxide catalyst, a mixing ratio of the composite metal oxide and at least one compound selected from the group consisting of a metal hydroxide and a metal alkoxide is used. The ratio of at least one compound selected from the group consisting of metal hydroxides and metal alkoxides to 100 parts by mass is preferably 0.5 to 10 parts by mass, and preferably 1 to 5 parts by mass. Is more preferable.
前記式(a2)で表される成分は、単一の鎖長からなる成分でもよく、複数の鎖長を持つ成分の混合物でもよい。前記式(a2)で表される成分を合成する際の原料としては、ヤシ油、パーム油、牛脂等の天然油脂由来のアルコール;石油由来の合成アルコール等が使用できる。
前記式(a2)中、R5は、炭素数2~4のアルキレン基であり、炭素数2~3のアルキレン基であることが好ましく、エチレン基であることがより好ましい。また、(R5O)tは、一種単独のオキシアルキレン基の繰返し構造であってもよく、二種以上のオキシアルキレン基が混在していてもよい。二種以上のオキシアルキレン基が混在している場合、オキシアルキレン基はブロック状に付加していてもよく、ランダム状に付加していてもよい。 In the formula (a2), R 4 has 10 to 22, preferably 10 to 20, more preferably 10 to 18 carbon atoms. The hydrocarbon group for R 4 may be linear or branched, and may have an unsaturated bond. Specific examples of the hydrocarbon group for R 4 include C 10 H 21 , C 12 H 25 , C 14 H 29 , C 16 H 33 , C 18 H 37 , C 20 H 41 , and the like.
The component represented by the formula (a2) may be a component having a single chain length or a mixture of components having a plurality of chain lengths. As raw materials for synthesizing the component represented by the formula (a2), alcohols derived from natural fats and oils such as palm oil, palm oil and beef tallow; synthetic alcohols derived from petroleum and the like can be used.
In the formula (a2), R 5 is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group. (R 5 O) t may be a single oxyalkylene group repeating structure, or two or more oxyalkylene groups may be mixed. When two or more kinds of oxyalkylene groups are mixed, the oxyalkylene groups may be added in a block shape or may be added in a random shape.
前記直鎖状または分岐鎖状のアルキル基として、具体的には、C10H21、C12H25、C14H29、等が挙げられる。
前記直鎖状または分岐鎖状のアルケニル基として、具体的には、C10H19、C12H23、C14H27、等が挙げられる。 前記式(a3)中、rは、r≧0であり、好ましくはr≧1である。p+r=10~30であり、好ましくはp+r=14~20である。
前記式(a3)中、EOとPOとの比率は、q/(p+r)で表される比が0.1~0.5であることが好ましく、より好ましくは0.1~0.3である。q/(p+r)で表される比が下限値以上であると、泡が立ちすぎず、泡立ちの適正化が図られる。q/(p+r)で表される比が上限値以下であると、適度な粘度が得られやすくなり、ゲル化が抑制されやすい。また、qが3以下であることにより、生分解性が向上する。
(EO)p/(PO)qにおけるEOとPOとは、いずれか一方のみが存在していてもよく、混在して配列してもよい。(EO)p/(PO)qは、EOとPOとがランダム状に付加していてもよく、ブロック状に付加していてもよい。 In the formula (a3), the alkyl group or alkenyl group in R 6 has 10 to 16 carbon atoms, and preferably 10 to 14 carbon atoms. The alkyl group and alkenyl group of R 6 may be linear or branched.
Specific examples of the linear or branched alkyl group include C 10 H 21 , C 12 H 25 , C 14 H 29 , and the like.
Specific examples of the linear or branched alkenyl group include C 10 H 19 , C 12 H 23 , C 14 H 27 , and the like. In the formula (a3), r is r ≧ 0, preferably r ≧ 1. p + r = 10 to 30, preferably p + r = 14 to 20.
In the formula (a3), the ratio of EO and PO is preferably a ratio represented by q / (p + r) of 0.1 to 0.5, more preferably 0.1 to 0.3. is there. When the ratio represented by q / (p + r) is equal to or greater than the lower limit value, bubbles are not excessively formed and foaming is optimized. When the ratio represented by q / (p + r) is not more than the upper limit value, an appropriate viscosity is easily obtained, and gelation is easily suppressed. Moreover, biodegradability improves because q is 3 or less.
Only one of EO and PO in (EO) p / (PO) q may exist, or they may be mixed and arranged. In (EO) p / (PO) q, EO and PO may be added randomly, or may be added in blocks.
ここで使用される脂肪族アルコールとしては、第1級アルコール、又は第2級アルコールが挙げられる。脂肪族アルコールのアルキル基は、分岐鎖を有していてもよい。脂肪族アルコールとしては、第1級アルコールが好ましい。 As the polyoxyalkylene alkyl ether, an average of 3 to 30 mol, preferably 5 to 20 mol, of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether (alcohol alkoxylate) may be mentioned. Among these, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether are preferable.
Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group of the aliphatic alcohol may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
陰イオン界面活性剤としては、アルキルベンゼンスルホン酸塩、アルキル硫酸塩、二級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、α-オレフィンスルホン酸塩、α-スルホ脂肪酸エステル塩、ポリオキシエチレンアルキルエーテルカルボン酸塩等が挙げられる。
陰イオン界面活性剤として具体的には、炭素数8~16(好ましくは炭素数10~14)のアルキル基を有する直鎖アルキルベンゼンスルホン酸塩(LAS);炭素数10~20のアルキル基を有するアルキル硫酸塩(AS);炭素数10~20(好ましくは炭素数10~14)のアルキル基を有し、エチレンオキシドの平均付加モル数1~10(好ましくは平均付加モル数1~4)のポリオキシエチレンアルキルエーテル硫酸塩(AES);炭素数10~20のアルキル基を有するα-オレフィンスルホン酸塩(AOS);炭素数10~20(好ましくは炭素数10~14)のアルキル基を有する二級アルカンスルホン酸塩(SAS);炭素数10~20のアルキル基を有するα-スルホ脂肪酸メチルエステル塩(α-SF);炭素数10~20のアルキル基を有し、エチレンオキシドの平均付加モル数1~10のポリオキシエチレンアルキルエ-テルカルボン酸塩等が好適に挙げられる。
これらの塩としては、ナトリウム塩、カリウム塩等のアルカリ金属塩;モノエタノールアミン塩、ジエタノールアミン塩等のアルカノールアミン塩等が挙げられ、アルカリ金属塩が好ましい。 (Anionic surfactant)
Anionic surfactants include alkylbenzene sulfonate, alkyl sulfate, secondary alkane sulfonate, polyoxyethylene alkyl ether sulfate, α-olefin sulfonate, α-sulfo fatty acid ester salt, polyoxyethylene alkyl Examples include ether carboxylates.
Specific examples of the anionic surfactant include a linear alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 16 carbon atoms (preferably 10 to 14 carbon atoms); an alkyl group having 10 to 20 carbon atoms. Alkyl sulfate (AS): Polyalkylene having an alkyl group having 10 to 20 carbon atoms (preferably 10 to 14 carbon atoms) and having an average addition mole number of ethylene oxide of 1 to 10 (preferably an average addition mole number of 1 to 4). Oxyethylene alkyl ether sulfate (AES); α-olefin sulfonate (AOS) having an alkyl group having 10 to 20 carbon atoms; two having an alkyl group having 10 to 20 carbon atoms (preferably 10 to 14 carbon atoms) Secondary alkanesulfonate (SAS); α-sulfo fatty acid methyl ester salt having an alkyl group having 10 to 20 carbon atoms (α-SF); It has 0 alkyl group, a polyoxyethylene alkyl error of average addition mole number of 1 to 10 ethylene oxide - Terukarubon acid salts, and the like preferably.
Examples of these salts include alkali metal salts such as sodium salts and potassium salts; alkanolamine salts such as monoethanolamine salts and diethanolamine salts, and alkali metal salts are preferred.
両性界面活性剤としては、カルボン酸型両性界面活性剤(アミノ型、及びベタイン型)、硫酸エステル型両性界面活性剤、スルホン酸型両性界面活性剤、リン酸エステル型両性界面活性剤等が挙げられる。
また、その他の界面活性剤としては、天然界面活性剤、タンパク質加水分解物の誘導体、高分子界面活性剤、チタン・ケイ素を含む界面活性剤、フッ化炭素系界面活性剤等も挙げられる。 Examples of the cationic surfactant include alkylamine salts and alkyl quaternary ammonium salts.
Examples of amphoteric surfactants include carboxylic acid type amphoteric surfactants (amino type and betaine type), sulfate ester type amphoteric surfactants, sulfonic acid type amphoteric surfactants, and phosphate ester type amphoteric surfactants. It is done.
Examples of other surfactants include natural surfactants, protein hydrolyzate derivatives, polymer surfactants, surfactants containing titanium / silicon, and fluorocarbon surfactants.
上記のなかでも、(A)成分としては、非イオン界面活性剤、及び陰イオン界面活性剤を用いることが好ましい。
特に、(A)成分中に、非イオン界面活性剤を(A)成分に対して50質量%以上含有することが好ましく、非イオン界面活性剤を80質量%以上含有することがより好ましく、非イオン界面活性剤を90質量%以上含有することがさらに好ましく、非イオン界面活性剤が100質量%であってもよい。
非イオン界面活性剤を用いることにより、高濃度の界面活性剤を含有してもゲル化等を起こさず、良好な保存安定性を示す濃縮タイプの液体洗浄剤が得られやすい。加えて、濃縮タイプの液体洗浄剤であることにより、液体洗浄剤を被洗物に塗布して使用する際、優れた塗布洗浄力が得られる。
非イオン界面活性剤としては、洗浄力が高いことから、前記の一般式(a1)~(a3)で表される非イオン界面活性剤から選択される少なくとも一種の非イオン界面活性剤を含むことが好ましい。
また、(A)成分としては、汚れが洗濯液中で再度被洗物に付着するのを防止する再汚染防止性が高まることから、非イオン界面活性剤と共に陰イオン界面活性剤を併用することが好ましい。 (A) A component may be used individually by 1 type and may use 2 or more types together.
Among the above, it is preferable to use a nonionic surfactant and an anionic surfactant as the component (A).
In particular, the component (A) preferably contains 50% by mass or more of the nonionic surfactant relative to the component (A), more preferably contains 80% by mass or more of the nonionic surfactant. It is more preferable to contain 90% by mass or more of the ionic surfactant, and the nonionic surfactant may be 100% by mass.
By using a nonionic surfactant, it is easy to obtain a concentrated liquid cleaning agent that does not cause gelation even if it contains a high concentration of surfactant and exhibits good storage stability. In addition, when the liquid cleaning agent is a concentrated type liquid cleaning agent, an excellent application cleaning power can be obtained when the liquid cleaning agent is applied to an object to be cleaned.
The nonionic surfactant contains at least one nonionic surfactant selected from the nonionic surfactants represented by the general formulas (a1) to (a3) because of its high detergency. Is preferred.
In addition, as the component (A), an antiionic surfactant is used in combination with a nonionic surfactant because the antifouling property of preventing dirt from adhering to the washing object again in the washing liquid is increased. Is preferred.
(A)成分の含有量が液体洗浄剤の総質量に対して40質量%以上であると、本発明の効果が顕著に発揮される。また、良好な洗浄力が得られる。加えて、高濃度の界面活性剤を含有することから、濃縮タイプの液体洗浄剤としての有効性(商品価値)が高くなる。
(A)成分の含有量が、液体洗浄剤の総質量に対して、好ましくは70質量%以下、より好ましくは65質量%以下であると、経時に伴う液表面での液体洗浄剤のゲル化等が起きにくくなって、液表面において皮膜が形成されにくくなる。 The content of the component (A) in the liquid detergent is 40% by mass or more, preferably 40 to 70% by mass, and preferably 45 to 65% by mass with respect to the total mass of the liquid detergent. More preferred.
When the content of the component (A) is 40% by mass or more with respect to the total mass of the liquid detergent, the effect of the present invention is remarkably exhibited. In addition, good detergency can be obtained. In addition, since it contains a high-concentration surfactant, the effectiveness (commercial value) as a concentrated liquid cleaning agent is increased.
When the content of the component (A) is preferably 70% by mass or less, more preferably 65% by mass or less, with respect to the total mass of the liquid detergent, the gelation of the liquid detergent on the liquid surface with time Etc. are less likely to occur, and a film is less likely to be formed on the liquid surface.
陰イオン界面活性剤の含有量が、液体洗浄剤の総質量に対して10質量%以下であると、液体洗浄剤の液表面において、前記液体洗浄剤自体がゲル化しにくくなって皮膜が形成されにくくなる。また、塗布洗浄力が良好に向上する。陰イオン界面活性剤の含有量が、液体洗浄剤の総質量に対して1質量%以上であると、再汚染防止性がより向上する。 When an anionic surfactant is used in combination with a nonionic surfactant, the content of the anionic surfactant is preferably 1 to 10% by mass, more preferably 1 to 5% by mass with respect to the total mass of the liquid detergent. Preferably, 2 to 5% by mass is more preferable.
When the content of the anionic surfactant is 10% by mass or less with respect to the total mass of the liquid detergent, the liquid detergent itself is difficult to gel and a film is formed on the liquid surface of the liquid detergent. It becomes difficult. Further, the coating cleaning power is improved satisfactorily. When the content of the anionic surfactant is 1% by mass or more based on the total mass of the liquid detergent, the recontamination preventing property is further improved.
色素(B)は、特に限定されず、酸性染料、塩基性染料、カチオン染料、媒染(油溶性)染料、建染染料、ナフトール染料(アゾ染料)、反応染料(反応性染料)、分散染料、酸化染料等が挙げられる。各染料の構造は「法定色素ハンドブック」(日本化粧品工業連絡会編)に記載されている。
上記のなかでも、(B)成分としては、本発明の効果が顕著に発揮されやすいことから、400~700nmに最大吸収波長を有する色素が好ましく、500~700nmに最大吸収波長を有する色素がより好ましく、590~650nmに最大吸収波長を有する青~緑色の色素が特に好ましい。
色素(B)として具体的には、以下に示す青色系染料、緑色系染料が例示される。 [Dye (B)]
The dye (B) is not particularly limited, and is an acid dye, basic dye, cationic dye, mordant (oil-soluble) dye, vat dye, naphthol dye (azo dye), reactive dye (reactive dye), disperse dye, An oxidation dye etc. are mentioned. The structure of each dye is described in the “Legal Handbook” (edited by Japan Cosmetic Industry Association).
Among the above, as the component (B), a dye having a maximum absorption wavelength at 400 to 700 nm is preferable, and a dye having a maximum absorption wavelength at 500 to 700 nm is more preferable because the effects of the present invention are remarkably easily exhibited. A blue to green dye having a maximum absorption wavelength at 590 to 650 nm is particularly preferable.
Specific examples of the dye (B) include the following blue dyes and green dyes.
Blue81、C.I.Diperse Blue87、C.I.Diperse Blue90、C.I.Diperse Blue91、C.I.Diperse Blue97、C.I.Diperse Blue98、C.I.Diperse Blue99、C.I.Diperse Blue103、C.I.Diperse Blue104、C.I.Diperse Blue105、C.I.Basic Blue7、C.I.Vat Blue1、C.I.Vat Blue6、C.I.Pigment Blue15等。
また、上記のなかでSolvent系(油溶性)色素に対して、発色団の構造の末端にポリエチレングリコールやポリプロピレングリコール等の水溶性高分子を化学的に修飾して水溶性を増すようにした色素でもよい。具体的には、ミリケン社製のLiquitint Blue HP、Liquitint Blue BL等の商品名が挙げられる。 Blue dye: C.I. I. Acid Blue 5, C.I. I. Acid Blue 9, C.I. I. Acid Blue 74, C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 63, C.I. I. Diverse Blue1, C.I. I. Diverse Blue 3, C.I. I. Diverse Blue 5, C.I. I. Diverse Blue 6, C.I. I. Diverse Blue 7, C.I. I. Diverse Blue 26, C.I. I. Diverse Blue 27, C.I. I. Diverse Blue 54, C.I. I. Diverse Blue 55, C.I. I. Diverse Blue 56, C.I. I. Diverse Blue 60, C.I. I. Diverse Blue 61, C.I. I. Diverse Blue 62, C.I. I. Diperse Blue 64, C.I. I. Diverse Blue 72, C.I. I. Diverse Blue 73, C.I. I. Diverse
Blue 81, C.I. I. Diverse Blue87, C.I. I. Diverse Blue90, C.I. I. Diverse Blue 91, C.I. I. Diverse Blue 97, C.I. I. Diverse Blue 98, C.I. I. Diverse Blue99, C.I. I. Diverse Blue 103, C.I. I. Diverse Blue 104, C.I. I. Diverse Blue 105, C.I. I. Basic Blue 7, C.I. I. Vat Blue1, C.I. I. Vat Blue 6, C.I. I. Pigment Blue 15 etc.
Also, among the above-described Solvent (oil-soluble) dyes, dyes that are chemically modified with a water-soluble polymer such as polyethylene glycol or polypropylene glycol at the end of the chromophore structure to increase water solubility. But you can. Specific examples include trade names such as Liquid Blue Blue and Liquid Blue BL manufactured by Milliken.
Blue2、C.I.Food Green3、C.I.Solvent Green3、C.I.Food Green3、C.I.Solvent Green7、C.I.Solvent Green等。 Green dye: C.I. I. Acid Green1, C.I. I. Acid Green 3, C.I. I. Acid Green 5, C.I. I. Acid Green 25, C.I. I. Food
Blue2, C.I. I. Food Green 3, C.I. I. Solvent Green 3, C.I. I. Food Green 3, C.I. I. Solvent Green 7, C.I. I. Solvent Green et al.
液体洗浄剤中の(B)成分の含有量は、被洗物への染着性、及び配合による液色度合いから、液体洗浄剤の総質量に対して、1ppm(質量基準)以上、150ppm(質量基準)以下(0.015質量%以下)であり、1~100ppm(質量基準)(0.0001~0.01質量%)が好ましく、3~50ppm(質量基準)(0.0003~0.005質量%)がより好ましい。
(B)成分の含有量が下限値未満では、液体洗浄剤の液に色が充分に着かない場合がある。一方、(B)成分の含有量が上限値を超えると、被洗物への色素染着を抑制しきれない場合がある。 (B) A component may be used individually by 1 type and may use 2 or more types together.
The content of the component (B) in the liquid detergent is 1 ppm (mass basis) or more and 150 ppm (mass basis) with respect to the total mass of the liquid detergent, from the dyeing property to the washing object and the liquid color degree by blending. (Mass basis) or less (0.015 mass% or less), preferably 1 to 100 ppm (mass basis) (0.0001 to 0.01 mass%), preferably 3 to 50 ppm (mass basis) (0.0003 to 0.003). (005% by mass) is more preferable.
If the content of the component (B) is less than the lower limit, the liquid detergent liquid may not be sufficiently colored. On the other hand, when the content of the component (B) exceeds the upper limit value, dye dyeing to the object to be washed may not be suppressed.
尿素又はその誘導体(C)としては、尿素[CO(NH2)2]、尿素複塩、及びこれ以外の尿素の誘導体が挙げられる。
尿素複塩としては、HNO3・CO(NH2)2、H3PO4・CO(NH2)2、H2C2O4・2CO(NH2)2、Ca(NO3)2・4CO(NH2)2、CaSO4・4CO(NH2)2、Mg(NO3)2・CO(NH2)2・2H2O、CaSO4・(5~6)4CO(NH2)2・2H2O等を用いることができる。 [Urea or its derivative (C)]
Examples of urea or its derivative (C) include urea [CO (NH 2 ) 2 ], urea double salt, and other urea derivatives.
Examples of the urea double salt include HNO 3 · CO (NH 2 ) 2 , H 3 PO 4 · CO (NH 2 ) 2 , H 2 C 2 O 4 · 2CO (NH 2 ) 2 , Ca (NO 3 ) 2 · 4CO. (NH 2 ) 2 , CaSO 4 · 4CO (NH 2 ) 2 , Mg (NO 3 ) 2 · CO (NH 2 ) 2 · 2H 2 O, CaSO 4 · (5 to 6) 4CO (NH 2 ) 2 · 2H 2 O or the like can be used.
前記式(c1-1)で表される化合物としては、1,3-ジメチル尿素、N-(2-ヒドロキシエチル)尿素等が挙げられる。 In the formula (c1-1), R a is a methyl group, an ethyl group, or a hydroxyalkyl group having 1 to 2 carbon atoms. R b , R c and R d are each independently a hydrogen atom, a methyl group or an ethyl group.
Examples of the compound represented by the formula (c1-1) include 1,3-dimethylurea, N- (2-hydroxyethyl) urea and the like.
液体洗浄剤中の(C)成分の含有量は、液体洗浄剤の総質量に対して0.5~12質量%が好ましく、より好ましくは1~10質量%であり、さらに好ましくは1~8質量%である。
(C)成分の含有量が下限値未満では、被洗物への色素染着を充分に抑制しきれない場合がある。一方、(C)成分の含有量が上限値を超えると、保存後に分解物としてアンモニアが発生しやすくなり、液体洗浄剤製品としてにおいが問題となることがある。また、汚れへの親和性が低下しやすくなるために塗布洗浄力が低下するおそれがある。 As the component (C), one type may be used alone, or two or more types may be used in combination.
The content of the component (C) in the liquid detergent is preferably 0.5 to 12% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 8% with respect to the total mass of the liquid detergent. % By mass.
When the content of the component (C) is less than the lower limit, dyeing of the object to be washed may not be sufficiently suppressed. On the other hand, when the content of the component (C) exceeds the upper limit value, ammonia tends to be generated as a decomposition product after storage, and odor may be a problem as a liquid detergent product. Moreover, since the affinity to dirt is likely to be reduced, there is a possibility that the coating cleaning power is reduced.
(A)/(C)で表される質量比が上限値以下であると、被洗物への色素染着が抑制されやすくなる。一方、(A)/(C)で表される質量比が下限値未満であると、塗布洗浄力が低下するおそれがある。
本発明において「(A)/(C)で表される質量比」とは、液体洗浄剤中の(C)成分の含有量に対する、(A)成分の含有量の割合(質量比)を表す。 In the liquid detergent of the present invention, the mixing ratio of the component (A) and the component (C) is preferably 30 or less in terms of mass ratio represented by (A) / (C), and is 6 to 15. More preferably, it is more preferably 9-11.
When the mass ratio represented by (A) / (C) is less than or equal to the upper limit value, dyeing of the article to be washed is easily suppressed. On the other hand, when the mass ratio represented by (A) / (C) is less than the lower limit, the coating cleaning power may be reduced.
In the present invention, “mass ratio represented by (A) / (C)” represents the ratio (mass ratio) of the content of component (A) to the content of component (C) in the liquid detergent. .
本発明の液体洗浄剤は、液体洗浄剤の調製のしやすさ、使用する際の水への溶解性等の観点から、溶媒として水を含有することが好ましい。
液体洗浄剤中の水の含有量は、液体洗浄剤の総質量に対して15~45質量%が好ましく、25~40質量%がより好ましい。
水の含有量が下限値以上であると、経時に伴う液体洗浄剤の液安定性がより良好となり、上限値以下であれば、液粘度が適度に低くなり、使用性の観点から良好である。 [Solvent: Water]
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of preparation of the liquid detergent, solubility in water when used, and the like.
The content of water in the liquid detergent is preferably 15 to 45% by mass, more preferably 25 to 40% by mass with respect to the total mass of the liquid detergent.
If the water content is at least the lower limit, the liquid stability of the liquid detergent with time will be better, and if it is not more than the upper limit, the liquid viscosity will be reasonably low, which is good from the viewpoint of usability. .
本発明の液体洗浄剤においては、下記一般式(d1)で表される有機溶剤(D)(以下「(D)成分」ともいう)をさらに含有することが好ましい。(D)成分を含有することにより、塗布洗浄力(特に油汚れやマジック汚れに対する洗浄力)が高まり、加えて、特に低温下(冬場想定)での被洗物への色素染着がより抑制されやすくなる。また、(D)成分は、前記液体洗浄剤の粘度調整剤、及びゲル化抑制剤としても有効である。 [Organic solvent (D)]
The liquid detergent of the present invention preferably further contains an organic solvent (D) represented by the following general formula (d1) (hereinafter also referred to as “component (D)”). By containing the component (D), the coating cleaning power (especially the cleaning power against oil stains and magic stains) is increased, and in addition, dyeing of objects to be washed is further suppressed, especially at low temperatures (assumed in winter). It becomes easy to be done. The component (D) is also effective as a viscosity modifier for the liquid detergent and a gelation inhibitor.
前記直鎖状及び分岐鎖状アルキル基として、具体的には、CH3、C2H5、C3H7、C4H9、等が挙げられる。 (EO)n/(PO)mにおけるEOとPOとは、いずれか一方のみが存在していてもよく、混在して配列してもよい。(EO)n/(PO)mは、EOとPOとがランダム状に付加していてもよく、ブロック状に付加していてもよい。 In the formula (d1), R 7 is a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms. The alkyl group for R 7 may be linear or branched.
Specific examples of the linear and branched alkyl groups include CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , and the like. Only one of EO and PO in (EO) n / (PO) m may exist, or they may be mixed and arranged. In (EO) n / (PO) m, EO and PO may be added randomly, or may be added in blocks.
上記のなかでも、(D)成分としては、上記の(D1)~(D3)からなる群より選択される少なくとも一種の有機溶剤を用いることが好ましく、前記群より選択される二種以上の有機溶剤を組み合わせて用いることがより好ましい。二種以上の有機溶剤を組み合わせて用いることにより、液体洗浄剤の粘度調整、及びゲル化抑制の効果が得られやすくなる。
液体洗浄剤中の(D)成分の含有量は、液体洗浄剤の総質量に対して5~20質量%が好ましく、より好ましくは5~18質量%であり、さらに好ましくは5~15質量%である。
(D)成分の含有量が下限値未満では、適切な粘度が得られにくく、被洗物に塗布した場合に液体洗浄剤が固まりやすくなる。一方、(D)成分の含有量が上限値を超えると、(D)成分由来の臭気が生じるおそれがあり、また、コストの点でも好ましくない。 (D) A component may be used individually by 1 type and may use 2 or more types together.
Among these, as the component (D), it is preferable to use at least one organic solvent selected from the group consisting of the above (D1) to (D3), and two or more organic solvents selected from the above group are used. It is more preferable to use a combination of solvents. By using a combination of two or more organic solvents, it is easy to obtain the effects of adjusting the viscosity of the liquid detergent and suppressing gelation.
The content of the component (D) in the liquid detergent is preferably 5 to 20% by mass, more preferably 5 to 18% by mass, and further preferably 5 to 15% by mass with respect to the total mass of the liquid detergent. It is.
When the content of the component (D) is less than the lower limit, it is difficult to obtain an appropriate viscosity, and the liquid cleaning agent is likely to be solidified when applied to an object to be cleaned. On the other hand, when the content of the component (D) exceeds the upper limit value, there is a risk that an odor derived from the component (D) may be generated, and it is not preferable in terms of cost.
本発明の液体洗浄剤には、本発明の効果を損なわない範囲で必要に応じて、上述した成分以外のその他の成分を配合してもよい。
その他の成分としては、特に限定されず、衣料用の液体洗浄剤組成物に通常用いられる成分を配合することができ、具体的には以下に示す成分が挙げられる。 [Other ingredients]
In the liquid cleaning agent of the present invention, other components other than the components described above may be blended as necessary within a range not impairing the effects of the present invention.
The other components are not particularly limited, and components usually used in a liquid detergent composition for clothing can be blended, and specific examples include the following components.
特に、界面活性剤(A)として陰イオン界面活性剤を配合する場合、アルカノールアミンは、陰イオン界面活性剤の対イオンとなり得る成分であり、陰イオン界面活性剤の配合によって生じやすい白濁等を抑制し、外観安定性を向上させる役割を果たす。したがって、本発明の液体洗浄剤においては、前記界面活性剤(A)が陰イオン界面活性剤を含むと共に、アルカノールアミンをさらに含有することが好ましい。
アルカノールアミンとしては、陰イオン界面活性剤の対イオンとして作用するアルカノールアミンが好ましく;炭素数1~3のアルキル基を有するアルカノールアミンが好ましく;炭素数1~2のアルキル基を有するアルカノールアミンがより好ましく;モノエタノールアミン、ジエタノールアミン、及びトリエタノールアミンがさらに好ましい。
アルカノールアミンは、1種を単独で用いてもよく、2種以上を併用してもよい。
液体洗浄剤中のアルカノールアミンの含有量は、液体洗浄剤の総質量に対して0.1~3質量%が好ましく、より好ましくは0.5~3質量%であり、さらに好ましくは0.5~2質量%である。
アルカノールアミンの含有量が液体洗浄剤の総質量に対して0.1質量%以上であれば、本組成物の外観安定性を向上させる効果が得られやすい。また、アルカノールアミンの含有量が液体洗浄剤の総質量に対して3質量%以下であれば、アルカノールアミンの酸素吸収によって容器が凹む現象の発生が抑制されやすい。 The liquid detergent of the present invention may contain alkanolamine for the purpose of improving the appearance stability.
In particular, when an anionic surfactant is blended as the surfactant (A), the alkanolamine is a component that can serve as a counter ion for the anionic surfactant, and the white turbidity that tends to be generated by blending the anionic surfactant It serves to suppress and improve appearance stability. Therefore, in the liquid cleaning agent of the present invention, it is preferable that the surfactant (A) contains an anionic surfactant and further contains an alkanolamine.
As the alkanolamine, an alkanolamine that acts as a counter ion for an anionic surfactant is preferable; an alkanolamine having an alkyl group having 1 to 3 carbon atoms is preferable; an alkanolamine having an alkyl group having 1 to 2 carbon atoms is more preferable. Preferably; monoethanolamine, diethanolamine, and triethanolamine are more preferred.
An alkanolamine may be used individually by 1 type, and may use 2 or more types together.
The content of alkanolamine in the liquid detergent is preferably 0.1 to 3% by mass, more preferably 0.5 to 3% by mass, and still more preferably 0.5% by mass with respect to the total mass of the liquid detergent. ~ 2% by weight.
If content of alkanolamine is 0.1 mass% or more with respect to the total mass of a liquid detergent, the effect which improves the external appearance stability of this composition will be easy to be acquired. Further, when the content of alkanolamine is 3% by mass or less with respect to the total mass of the liquid detergent, the occurrence of the phenomenon that the container is recessed due to oxygen absorption of alkanolamine is easily suppressed.
pH調整剤としては、液安定性の面から、硫酸、水酸化ナトリウム、水酸化カリウム等が好ましい。
さらに、本発明の液体洗浄剤には、商品の付加価値向上等を目的として、着香剤、乳濁化剤等を配合することもできる。
着香剤としては、特開2002-146399号公報の表11~18に記載の香料組成物A、B、C、D等を使用できる。着香剤の含有量は、液体洗浄剤の総質量に対して0.1~1質量%が好ましい。
乳濁化剤としては、ポリスチレンエマルジョン、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%のエマルジ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ジョン(サイデン化学社製、「サイビノールRPX-196 PE-3」、固形分40質量%)等が挙げられる。乳濁化剤の含有量は、液体洗浄剤の総質量に対して0.01~0.5質量%が好ましい。 The liquid detergent of the present invention includes enzymes (proteases, lipases, cellulases, etc.), organic solvents other than component (D), and thickeners (long-chain fatty acid alkylamides) for the purpose of improving washing performance and blending stability. Etc.), texture improvers, pH adjusters, preservatives, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, soil release agents, and the like.
As the pH adjuster, sulfuric acid, sodium hydroxide, potassium hydroxide and the like are preferable from the viewpoint of liquid stability.
Furthermore, a flavoring agent, an emulsifying agent, etc. can also be mix | blended with the liquid cleaning agent of this invention for the purpose of the added value improvement of goods, etc.
As the flavoring agent, the fragrance compositions A, B, C, D and the like described in Tables 11 to 18 of JP-A No. 2002-146399 can be used. The content of the flavoring agent is preferably 0.1 to 1% by mass relative to the total mass of the liquid detergent.
Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is preferably used. Specific examples include polystyrene emulsion (manufactured by Seiden Chemical Co., Ltd., “Cybinol RPX-196 PE-3”, solid content 40% by mass). The content of the emulsifying agent is preferably 0.01 to 0.5% by mass relative to the total mass of the liquid detergent.
液体洗浄剤のpHが下限値以上であると、液体洗浄剤を長期保存した際、良好な洗浄力が維持されやすい。前記pHが上限値未満であると、被洗物への色素染着がより抑制されやすくなる。液安定性についても良好に維持されやすい。
本発明において、液体洗浄剤(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 pH of the liquid detergent of the present invention is preferably 5 to 10 at 25 ° C., more preferably 5 to 9.5, and still more preferably 5 to 9. The pH is particularly preferably 6-9.
When the pH of the liquid detergent is equal to or higher than the lower limit value, good detergency is easily maintained when the liquid detergent is stored for a long time. When the pH is less than the upper limit value, dyeing of the object to be washed is more easily suppressed. The liquid stability is easily maintained well.
In the present invention, the pH of the liquid detergent (controlled at 25 ° C.) is a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation).
色素を含有する濃縮タイプの液体洗浄剤においては、前記液体洗浄剤が塗布された洗濯対象物(被洗物)がしばらく放置されたり、又は、ドラム式洗濯機等による濯ぎ1回の洗濯が行われた場合(即ち、濯ぎが不充分な場合)等に、被洗物に色素が染着しやすいという問題がある。
この被洗物への色素染着は、液体洗浄剤の組成、衣類(繊維)の種類、気温、及び水温の影響によって、その起こりやすさが変化する。例えば低温条件になるほど、又は、有機溶剤の種類によっては疎水性繊維(ポリエステル繊維等)ほど、色素染着が起こりやすい。
被洗物に色素が染着する原因としては、高濃度の界面活性剤と被洗物とが長い時間接触していたり、濯ぎが不充分なために界面活性剤が被洗物に部分的に残存していたりすることで、界面活性剤が衣類(繊維)に浸透しすぎること、これに伴って色素が衣類(繊維)の深くに吸着することで、被洗物に色素が染着しやすくなっていること、が考えられる。
また、温度条件、及び放置時間によっては、液体洗浄剤中の水分や溶剤が蒸発して、組成物がゲル化することで、洗浄の際に、液体洗浄剤が水に充分に溶解できない。このため、高濃度の界面活性剤と被洗物が長い時間接触するような状態になることで、被洗物に色素が染着しやすくなっていること、が考えられる。
本発明の液体洗浄剤においては、液体洗浄剤の総質量に対して40質量%以上の界面活性剤と、色素と共に、尿素又はその誘導体(C)を含有する。(C)成分は、親水性が強い物質である一方、それ自体の構造の特性により、界面活性剤との相互作用が強いため、(C)成分は、製剤中で界面活性剤の分子の周りに存在しやすいと考えられる。これにより、塗布洗浄時には、(C)成分の存在により、界面活性剤の衣類への吸着や浸透が抑制され、疎水性の繊維と界面活性剤との相互作用も抑えられる。これらの結果、本発明の効果が得られると推測される。
本発明の液体洗浄剤によれば、液体洗浄剤が塗布された被洗物がしばらく放置されたり、濯ぎが不充分であったりした場合でも、被洗物への色素染着が抑制される。 The liquid cleaning agent of the present invention is a liquid cleaning agent that has a high detergency and suppresses dye dyeing to an object to be washed in a concentrated liquid cleaning agent containing a pigment.
In a concentrated liquid cleaning agent containing a pigment, the object to be washed (the object to be cleaned) to which the liquid cleaning agent is applied is left for a while or is rinsed once with a drum-type washing machine or the like. In the case where it is broken (that is, when rinsing is insufficient), there is a problem that the dye tends to be dyed on the object to be washed.
The likelihood of this dyeing on the object to be washed varies depending on the composition of the liquid detergent, the type of clothing (fiber), the temperature, and the water temperature. For example, dyeing is more likely to occur at lower temperature conditions or depending on the type of organic solvent, the more hydrophobic fibers (such as polyester fibers).
The reason why pigments are dyed on the object to be washed is that the high concentration surfactant and the object to be washed are in contact with each other for a long time, or the surfactant is partially applied to the object to be washed due to insufficient rinsing. The surfactant may permeate the clothing (fiber) too much, and the pigment will be adsorbed deeply into the clothing (fiber). It is possible that
Further, depending on the temperature condition and the standing time, moisture and solvent in the liquid detergent evaporate and the composition gels, so that the liquid detergent cannot be sufficiently dissolved in water at the time of washing. For this reason, it can be considered that the dye is easily dyed on the object to be cleaned by bringing the high concentration surfactant into contact with the object to be cleaned for a long time.
In the liquid cleaning agent of the present invention, urea or a derivative thereof (C) is contained together with 40% by mass or more of the surfactant with respect to the total mass of the liquid cleaning agent and the dye. While component (C) is a highly hydrophilic substance, its interaction with the surfactant is strong due to its structural characteristics, so component (C) is around the surfactant molecule in the formulation. It is thought that it exists easily. Thereby, at the time of application | coating washing | cleaning, adsorption | suction and osmosis | permeation to the clothing of surfactant are suppressed by presence of (C) component, and interaction with a hydrophobic fiber and surfactant is also suppressed. As a result, it is estimated that the effects of the present invention can be obtained.
According to the liquid cleaning agent of the present invention, even when the object to be cleaned to which the liquid cleaner is applied is left for a while or the rinsing is insufficient, dyeing of the object to be cleaned is suppressed.
本発明の液体洗浄剤は、少ない洗浄剤使用量で高い洗浄効果を発現する。
本発明の液体洗浄剤は、特に衣料用として好適であり、色素を含有すると共に界面活性剤濃度の高い組成(濃縮組成)に適した液体洗浄剤である。 In addition, according to the liquid detergent of the present invention, by containing the component (C), in particular, an anionic surfactant that suppresses recontamination, and an alkanolamine that can be a counter ion of the anionic surfactant, The yellowing of the liquid color, which is likely to occur when using together, is also suppressed, and the appearance stability is kept good.
The liquid cleaning agent of the present invention exhibits a high cleaning effect with a small amount of cleaning agent used.
The liquid detergent of the present invention is particularly suitable for clothing, and is a liquid detergent that contains a pigment and is suitable for a composition having a high surfactant concentration (concentrated composition).
界面活性剤(A)と、色素(B)と、尿素又はその誘導体(C)と、有機溶剤(D)と、を含有する液体洗浄剤であって、前記液体洗浄剤の総質量に対し、
前記(A)成分が40~70質量%、
前記(B)成分が1~150ppm(質量基準)、
前記(C)成分が0.5~12質量%、及び
前記(D)成分が5~20質量%であり、かつ
前記各成分の合計量が100質量%を超えない液体洗浄剤が挙げられる。 As one aspect of the liquid cleaning agent of the present invention,
A liquid detergent containing a surfactant (A), a dye (B), urea or a derivative thereof (C), and an organic solvent (D), with respect to the total mass of the liquid detergent,
The component (A) is 40 to 70% by mass,
The component (B) is 1 to 150 ppm (mass basis),
Examples thereof include liquid detergents in which the component (C) is 0.5 to 12% by mass, the component (D) is 5 to 20% by mass, and the total amount of the components does not exceed 100% by mass.
界面活性剤(A)と、色素(B)と、尿素又はその誘導体(C)と、水と、を含有する液体洗浄剤であって、前記液体洗浄剤の総質量に対し、
前記(A)成分が40~70質量%、
前記(B)成分が1~150ppm(質量基準)、前記(C)成分が0.5~12質量%、及び
前記水が15~45質量%であり、かつ
前記各成分の合計量が100質量%を超えない液体洗浄剤が挙げられる。 As other aspects of the liquid detergent of the present invention,
A liquid detergent containing a surfactant (A), a dye (B), urea or a derivative thereof (C), and water, with respect to the total mass of the liquid detergent,
The component (A) is 40 to 70% by mass,
The component (B) is 1 to 150 ppm (mass basis), the component (C) is 0.5 to 12% by mass, the water is 15 to 45% by mass, and the total amount of the components is 100% by mass. % Liquid detergents not exceeding%.
界面活性剤(A)と、色素(B)と、尿素又はその誘導体(C)と、有機溶剤(D)と、水と、を含有する液体洗浄剤であって、前記液体洗浄剤の総質量に対し、
前記(A)成分が40~70質量%、
前記(B)成分が1~150ppm(質量基準)、
前記(C)成分が0.5~12質量%、
前記(D)成分が5~20質量%、及び
前記水が15~45質量%であり、かつ
前記各成分の合計量が100質量%を超えない液体洗浄剤が挙げられる。 As other aspects of the liquid detergent of the present invention,
A liquid detergent containing a surfactant (A), a dye (B), urea or a derivative thereof (C), an organic solvent (D), and water, wherein the total mass of the liquid detergent Whereas
The component (A) is 40 to 70% by mass,
The component (B) is 1 to 150 ppm (mass basis),
The component (C) is 0.5 to 12% by mass,
Examples thereof include liquid detergents in which the component (D) is 5 to 20% by mass, the water is 15 to 45% by mass, and the total amount of each component does not exceed 100% by mass.
本実施例において使用した原料は下記の通りである。 The compositions of the liquid detergents in each example are shown in Tables 1 to 3.
The raw materials used in this example are as follows.
A-1:C11H23CO-(OC2H4)15-OCH3、ナロー率33質量%;合成品。A-1は、特開2002-144179号公報に記載の方法に準拠した方法で製造した。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(商品名キョーワード300、協和化学工業社製)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・マグネシウム触媒(未改質)2.2gと、表面改質剤として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350gとを4リットルオートクレーブに仕込み、前記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に昇温し、温度180℃、圧力3×105Paに維持しながら、エチレンオキシド1079gを導入して撹拌しながら反応させた。
次いで、反応液を80℃まで冷却し、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、触媒を濾過して目的物であるA-1を得た。 [Surfactant (A)]
A-1: C 11 H 23 CO— (OC 2 H 4 ) 15 —OCH 3 , narrow ratio 33% by mass; synthetic product. A-1 was produced by a method based on the method described in JP-A-2002-144179. That is, alumina hydroxide / magnesium hydroxide (trade name Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical composition of 2.5 MgO.Al 2 O 3 .nH 2 O is fired at 600 ° C. for 1 hour in a nitrogen atmosphere. 4 g of calcined alumina hydroxide / magnesium catalyst (unmodified) obtained as described above, 2.9 mL of 0.5N potassium hydroxide ethanol solution as a surface modifier, and 350 g of lauric acid methyl ester A liter autoclave was charged, and the catalyst was reformed in the autoclave. Next, after replacing the inside of the autoclave with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure of 3 × 10 5 Pa, 1079 g of ethylene oxide was introduced and reacted while stirring.
Next, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth were added as filter aids, respectively, and the catalyst was filtered to obtain A-1 as the target product.
ただし、A-2は、前記A-1の合成において、ラウリン酸メチルエステル350gの代わりに、ラウリン酸メチルエステル280gとミリスチン酸70gの混合物を用い、エチレンオキシド1052gを導入した以外は、同様の合成方法で製造した。 A-2: Mixture of C 11 H 23 CO— (OC 2 H 4 ) 15 —OCH 3 and C 13 H 27 CO— (OC 2 H 4 ) 15 —OCH 3 in a mass ratio of 8/2, narrow ratio 33% by mass; synthetic product.
However, A-2 was synthesized in the same manner as A-1, except that instead of 350 g of lauric acid methyl ester, a mixture of 280 g of lauric acid methyl ester and 70 g of myristic acid was used and 1052 g of ethylene oxide was introduced. Manufactured with.
A-7:AES-Na、炭素数12~13ポリオキシエチレンアルキルエーテル硫酸ナトリウム(エチレンオキシドの平均付加モル数2)、合成品(原料アルコールは商品名ネオドール23、シェル社製)。 A-6: linear alkyl (carbon number 10 to 14) benzenesulfonic acid [manufactured by Lion Corporation, trade name Rypon LH-200 (LAS-H pure content 96 mass%)].
A-7: AES-Na, sodium polyoxyethylene alkyl ether sulfate having 12 to 13 carbon atoms (average addition mole number of ethylene oxide 2), synthetic product (raw alcohol is trade name Neodol 23, manufactured by Shell).
P&G社製の商品名「CO-1214」861.2g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分間脱水した後、温度を160℃まで昇温した。次いで、反応液を撹拌しながら、エチレンオキシド(ガス状)760.6gを反応液中に徐々に加えた。このとき、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節しながら加えた。エチレンオキシドの添加終了後、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、未反応のエチレンオキシドを留去した。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、LMAO(C12/14-15EO)を得た。 A-8: Natural alcohol (trade name CO-1214 manufactured by P & G) with 12 mole equivalent of ethylene oxide added [LMAO (C12 / 14-15EO)], synthetic product. The synthesis was performed as follows.
861.2 g of a trade name “CO-1214” 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. Next, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, it added, adjusting the addition rate so that reaction temperature might not exceed 180 degreeC using the blowing 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 then 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% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, and LMAO (C12 / 14 -15EO).
B-1:C.I.Food Green3、緑色3号、辰巳化成株式会社製;最大吸収波長610nm。
B-2:Liquitint Blue HP、ミリケン株式会社製;最大吸収波長595nm、645nm。
B-3:C.I.Solvent Blue63、青色403号、辰巳化成株式会社製;最大吸収波長600nm、645nm。 [Dye (B)]
B-1: C.I. I. Food Green 3, Green No. 3, manufactured by Sakai Kasei Co., Ltd .; maximum absorption wavelength 610 nm.
B-2: Liquid Blue Blue, manufactured by Milliken Co .; maximum absorption wavelengths of 595 nm and 645 nm.
B-3: C.I. I. Solvent Blue 63, Blue No. 403, manufactured by Sakai Kasei Co., Ltd .; maximum absorption wavelengths of 600 nm and 645 nm.
C-1:尿素、試薬、純正化学(株)製。
C-2:1,3-ジメチル尿素、試薬、東京化成工業(株)製。 [Urea (C)]
C-1: Urea, reagent, manufactured by Junsei Chemical Co., Ltd.
C-2: 1,3-dimethylurea, reagent, manufactured by Tokyo Chemical Industry Co., Ltd.
D-1:1,2-プロパンジオール(商品名プロピレングリコール、昭和電工株式会社製)純分100質量%。一般式(d1)におけるR7=ヒドロキシ基、m=1、n=0。
D-2:ブチルカルビトール(商品名ブチルジグリコール、日本乳化剤株式会社製)純分100質量%。一般式(d1)におけるR7=エチル基、m=0、n=3。
D-3:エタノール(商品名 特定アルコール95度合成アルコール、日本アルコール販売(株)製)。一般式(d1)におけるR7=水素原子、m=0、n=1。 [Organic solvent (D) represented by general formula (d1)]
D-1: 1,2-propanediol (trade name: propylene glycol, manufactured by Showa Denko KK) 100% by mass pure. R 7 in formula (d1) = hydroxy group, m = 1, n = 0.
D-2: Butyl carbitol (trade name butyl diglycol, manufactured by Nippon Emulsifier Co., Ltd.) 100% by mass pure. R 7 in the general formula (d1) = ethyl group, m = 0, n = 3.
D-3: Ethanol (trade name: specified alcohol 95 degree synthetic alcohol, manufactured by Nippon Alcohol Sales Co., Ltd.) In the general formula (d1), R 7 = hydrogen atom, m = 0, n = 1.
MEA:モノエタノールアミン(株式会社日本触媒製)純分100質量%。
DEA:ジエタノールアミン(株式会社日本触媒製)純分100質量%。
ポリエチレングリコール:(株)ライオン化学製、商品名「PEG#1000-L60」、重合度20。
酵素:プロテアーゼ、商品名「Everlase 16L TYPE EX」、ノボザイムス製。
クエン酸:扶桑化学工業(株)製、純分100質量%。
pH調整剤:KOH(旭硝子(株)製)と硫酸(東邦亜鉛(株)製)。
イオン交換水。 [Other ingredients]
MEA: Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.) 100% by mass pure.
DEA: 100% by mass of diethanolamine (manufactured by Nippon Shokubai Co., Ltd.)
Polyethylene glycol: manufactured by Lion Chemical Co., Ltd., trade name “PEG # 1000-L60”, polymerization degree 20.
Enzyme: Protease, trade name “Everlase 16L TYPE EX”, manufactured by Novozymes.
Citric acid: manufactured by Fuso Chemical Industries, Ltd., 100% pure content.
pH adjuster: KOH (Asahi Glass Co., Ltd.) and sulfuric acid (Toho Zinc Co., Ltd.).
Ion exchange water.
表1~3に示す組成の配合成分、含有量(質量%)に従い、下記の製造方法により各例の液体洗浄剤をそれぞれ製造した(表中、空欄の配合成分がある場合、その配合成分は配合しない)。
表中、配合成分の含有量は純分換算量を示す。なお、(B)成分の含有量のみ「ppm」(質量基準)で表示している。
水の含有量を示す「バランス」とは、最終調製物である液体洗浄剤の総量が100質量%になるように調整した配合量を示す。
pH調整剤の含有量を示す「適量」とは、液体洗浄剤のpH(25℃)を表に示すpHに調整するために配合した量を示す。
「質量比:(A)/(C)」は、液体洗浄剤中の(C)成分の含有量に対する、(A)成分の含有量の割合(質量比)を表す。 <Example of manufacturing liquid detergent>
According to the blending components and contents (mass%) of the compositions shown in Tables 1 to 3, liquid detergents of each example were produced by the following production methods (when there are blank blending components in the table, the blending components are Not blended).
In the table, the content of the compounding component indicates a pure equivalent amount. In addition, only content of (B) component is displayed by "ppm" (mass basis).
The “balance” indicating the water content indicates a blending amount adjusted so that the total amount of the liquid cleaning agent as the final preparation is 100% by mass.
The “appropriate amount” indicating the content of the pH adjusting agent indicates an amount blended for adjusting the pH (25 ° C.) of the liquid cleaning agent to the pH shown in the table.
“Mass ratio: (A) / (C)” represents the ratio (mass ratio) of the content of component (A) to the content of component (C) in the liquid detergent.
500mLのビーカーに、それぞれ表に示す含有量(質量%)の(D)成分と、ポリエチレングリコールと、MEA又はDEAと、A-6又はA-7とを加えて撹拌した(なお、表中、空欄の配合成分がある場合、その配合成分は配合しない)。次いで、(C)成分とクエン酸をそれぞれ水に溶解した(C)成分水溶液(濃度50質量%)とクエン酸水溶液(濃度50質量%)を加えて撹拌した。
次いで、pH調整剤を用いて、溶液のpH(25℃)が表に示す値となるように調整した。
次いで、残りの(A)成分を加えて撹拌した。次いで、酵素を加えて撹拌し、次に、(B)成分を水に溶解した色素水溶液(色素濃度1000ppm)を、所定の濃度になるように添加して撹拌した。その後、最終調製物の総量が100質量%になるようにイオン交換水を加えることにより、各例の液体洗浄剤をそれぞれ得た。
溶液のpH(25℃)は、pHメーター(製品名:HM-30G、東亜ディーケーケー(株)製)を用い、25℃に調温した溶液に、前記pHメーターの電極を入れ、2分後の値を読み取ることにより測定した。 (Examples 1 to 19, Comparative Examples 1 to 3, Reference Example 1)
In a 500 mL beaker, the component (D) of the content (mass%) shown in the table, polyethylene glycol, MEA or DEA, and A-6 or A-7 were added and stirred (in the table, If there is a blank compounding component, the compounding component is not blended). Subsequently, (C) component aqueous solution (concentration 50 mass%) and citric acid aqueous solution (concentration 50 mass%) which respectively dissolved (C) component and citric acid in water were added and stirred.
Subsequently, it adjusted so that pH (25 degreeC) of a solution might become the value shown in a table | surface using the pH adjuster.
Next, the remaining component (A) was added and stirred. Next, the enzyme was added and stirred, and then, an aqueous dye solution (dye concentration 1000 ppm) in which the component (B) was dissolved in water was added and stirred to a predetermined concentration. Thereafter, ion-exchanged water was added so that the total amount of the final preparation was 100% by mass, thereby obtaining each of the liquid cleaning agents in each example.
The pH of the solution (25 ° C.) was measured by adding the pH meter electrode to the solution adjusted to 25 ° C. using a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) It was measured by reading the value.
各例の液体洗浄剤について、以下に示す評価方法により「塗布洗浄力」、「衣類への色素染着性」及び「外観安定性」の評価をそれぞれ行った。その結果を表1~3に併記した。 <Evaluation of liquid detergent>
With respect to the liquid cleaning agents of the respective examples, “application cleaning power”, “dyeing property to clothes”, and “appearance stability” were evaluated by the following evaluation methods. The results are also shown in Tables 1 to 3.
汚染布の調製:
綿メリヤス(5cm×5cm)を、油性マジック(マジックインキ/ゴクホソ M700-T1)で均一にインクが行き渡るように円状(直径2cm)に黒く塗ったものを各例に付き5枚作製し、塗布洗浄力評価用の汚染布とした。 [Coating cleaning power]
Contaminated cloth preparation:
Five cotton knitted fabrics (5cm x 5cm) were applied in black with a circular shape (diameter 2cm) so that the ink was evenly distributed with oil-based magic (magic ink / Gokuhoso M700-T1). A contaminated cloth for detergency evaluation was used.
水30Lに対する標準使用量(濃縮タイプ10g/水30L、通常タイプ20g/水30mL)の液体洗浄剤を、前記汚染布5枚の1枚ずつに塗布した後、温度20℃下で5分間放置した。具体的には、汚染布1枚当たりの液体洗浄剤の塗布量を、実施例1~19、比較例1~3(濃縮タイプ)についてはそれぞれ0.3gとし、参考例1については0.6gとした。
その後、Terg-o-tometer(UNITED STATES TESTING社製)に、15℃の3°DH硬水900mLと、前記汚染布5枚と肌シャツ(LLサイズ、DVD社製)を細かく(3cm×3cm程度)裁断したものとを、浴比20倍となるように入れ、120rpm、15℃で10分間洗浄した。
(濯ぎ条件)
前記洗浄の後、1分間脱水し、その後、15℃の3°DH硬水900mLで、120rpm、15℃で3分間濯いだ。この脱水と濯ぎを2回繰り返した。
(乾燥条件)
2回目の濯ぎ後、1分間脱水し、その後、洗浄後汚染布を濾紙に1枚ずつ挟んでアイロンで乾燥した。 (Cleaning conditions)
After applying a standard amount of liquid detergent (concentrated type 10g / water 30L, normal type 20g / water 30mL) to 30L of water on each of the 5 contaminated cloths, the liquid detergent was left at a temperature of 20 ° C for 5 minutes. . Specifically, the application amount of the liquid cleaning agent per contaminated cloth is 0.3 g for each of Examples 1 to 19 and Comparative Examples 1 to 3 (concentrated type), and 0.6 g for Reference Example 1. It was.
After that, in Terg-o-meter (UNITED STATES TESTING), 15 mL of 3 ° DH hard water 900 mL, 5 sheets of contaminated cloth and skin shirt (LL size, DVD) are finely (about 3 cm x 3 cm) What was cut was put into a bath ratio of 20 times and washed at 120 rpm and 15 ° C. for 10 minutes.
(Rinsing conditions)
After the washing, it was dehydrated for 1 minute, and then rinsed with 900 mL of 15 ° C. 3 ° DH hard water at 120 rpm and 15 ° C. for 3 minutes. This dehydration and rinsing was repeated twice.
(Drying conditions)
After the second rinsing, it was dehydrated for 1 minute, and after washing, the soiled cloth was sandwiched between filter papers one by one and dried with an iron.
洗浄率(%)=(洗浄後の汚染布のZ値-洗浄前の汚染布のZ値)/(原布のZ値-洗浄前の汚染布のZ値)×100
式中、「原布」とは、上記汚染布の調製において、汚染処理を施していない綿メリヤスを示す。
各例について汚染布5枚の洗浄率(%)をそれぞれ算出し、それらの平均値を求め、下記評価基準に基づいて塗布洗浄力を評価した。◎、○、△を合格とした。
評価基準
◎:洗浄率(%)の平均値が15%以上であった。
○:洗浄率(%)の平均値が10%以上、15%未満であった。
△:洗浄率(%)の平均値が5%以上、10%未満であった。
×:洗浄率(%)の平均値が5%未満であった。 The coating cleaning power was evaluated by measuring the reflectance (Z value) using a reflectance meter (spectral color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.) before and after cleaning. %).
Washing rate (%) = (Z value of contaminated cloth after washing−Z value of contaminated cloth before washing) / (Z value of raw cloth−Z value of contaminated cloth before washing) × 100
In the formula, “raw fabric” refers to cotton knitted fabric that has not been subjected to contamination treatment in the preparation of the above-mentioned contaminated fabric.
For each example, the cleaning rate (%) of 5 contaminated cloths was calculated, the average value thereof was determined, and the coating cleaning power was evaluated based on the following evaluation criteria. ◎, ○, and △ were considered acceptable.
Evaluation criteria A: The average value of the cleaning rate (%) was 15% or more.
A: The average value of the cleaning rate (%) was 10% or more and less than 15%.
Δ: The average value of the cleaning rate (%) was 5% or more and less than 10%.
X: The average value of the cleaning rate (%) was less than 5%.
白の手拭き綿タオル(29cm×72cm)の長手方向の端部(厚くなっている所、縫い代部分)のみを切り出し、評価用試料(綿)とした(質量で5g分)。
次いで、洗濯物4kgに対する液体洗浄剤の標準使用量(15g)のうちの5g分の液体洗浄剤を、評価用試料(綿)に塗布して12時間放置した。
その後、洗剤5gを塗布した前記評価用試料(綿)と、チャージ布として綿肌シャツとを、合わせて4kgとなるように洗濯機に入れ、残りの液体洗浄剤を加えて洗濯を行った。
その際の洗濯条件を以下のように設定した。洗濯機には、東芝ドラム型洗濯機(製品名TW-4000VFL)を用いた。洗濯コースを、洗濯時間10分間、濯ぎ1回指定、脱水8分間とした。
以上の操作(綿タオルの場合)を、夏場想定と冬場想定の条件でそれぞれ行った。
夏場想定は、液体洗浄剤5gを塗布した評価用試料(綿)を、温度25℃下で12時間放置し、洗濯の際に25℃に調整した水を用いた。
冬場想定は、液体洗浄剤5gを塗布した評価用試料(綿)を、温度5℃下で12時間放置し、洗濯の際に5℃に調整した水を用いた。 [Evaluation of dyeing property to clothing]
Only a longitudinal end portion (thickened portion, seam allowance portion) of a white hand-wiped cotton towel (29 cm × 72 cm) was cut out and used as an evaluation sample (cotton) (5 g by mass).
Next, 5 g of the liquid detergent for standard usage (15 g) for 4 kg of laundry was applied to the evaluation sample (cotton) and left for 12 hours.
Thereafter, the sample for evaluation (cotton) coated with 5 g of detergent and a cotton skin shirt as a charge cloth were put together in a washing machine so as to be 4 kg, and the remaining liquid detergent was added for washing.
The washing conditions at that time were set as follows. A Toshiba drum type washing machine (product name TW-4000VFL) was used as the washing machine. The washing course was set at a washing time of 10 minutes, designated once for rinsing and dehydration for 8 minutes.
The above operations (in the case of cotton towels) were performed under the conditions of summer and winter.
Assuming summertime, an evaluation sample (cotton) coated with 5 g of a liquid detergent was left at a temperature of 25 ° C. for 12 hours, and water adjusted to 25 ° C. during washing was used.
Assuming winter season, an evaluation sample (cotton) coated with 5 g of a liquid detergent was left at a temperature of 5 ° C. for 12 hours, and water adjusted to 5 ° C. during washing was used.
次いで、洗濯物4kgに対する液体洗浄剤の標準使用量(15g)のうちの2g分の液体洗浄剤を、評価用試料(PE)に塗布して12時間放置した。
その後、洗剤5gを塗布した前記評価用試料(PE)と、チャージ布として綿肌シャツとを、合わせて4kgとなるように洗濯機に入れ、残りの液体洗浄剤を加え、上記洗濯条件と同じ条件にて洗濯を行った。
以上の操作(PEの場合)を、前記と同じ夏場想定の条件でのみ行った。 Further, a polyester (PE) jersey (Tanigami Shoten) was cut into 5 cm × 5 cm, and used as a sample for evaluation (PE) (0.2 g by mass).
Next, 2 g of the standard amount (15 g) of liquid detergent used for 4 kg of laundry was applied to the evaluation sample (PE) and allowed to stand for 12 hours.
Thereafter, the sample for evaluation (PE) coated with 5 g of detergent and a cotton skin shirt as a charge cloth are put into a washing machine so as to be 4 kg in total, and the remaining liquid detergent is added, and the same as the above washing conditions. Laundry was performed under conditions.
The above operation (in the case of PE) was performed only under the same summer conditions as described above.
評価基準
◎:洗濯後の評価用試料に色素染着が全く認められなかった。
○:洗濯後の評価用試料に色素染着がごくわずかに認められた。
△:洗濯後の評価用試料に色素染着が若干認められた。
×:洗濯後の評価用試料に色素染着が明らかに認められた。 Then, whether or not dyeing was observed on the evaluation sample (cotton) after washing and the evaluation sample (PE) was visually determined and evaluated based on the following evaluation criteria. ◎, ○, and △ were considered acceptable.
Evaluation criteria (double-circle): Dyeing | dye dyeing was not recognized at all in the sample for evaluation after washing.
○: Slight dyeing was observed in the evaluation sample after washing.
Δ: Some dyeing was observed in the evaluation sample after washing.
X: Dyeing was clearly recognized in the sample for evaluation after washing.
製造直後の各例の液体洗浄剤100gを円筒ガラス瓶(PS100)に入れ、蓋を閉めて密閉し、50℃下で30日間保管した。
そして、保管後の液体洗浄剤の外観(液色)の変化を目視で判定し、下記評価基準に基づいて評価した。◎、○を合格とした。
なお、保管により液体洗浄剤が黄変した場合、保管前(初期)に青色であったものは緑色に変色し、初期に緑色であったものは黄緑色に変色する。
評価基準
◎:初期と比較して、外観(液色)の変化が全く認められなかった。
○:初期に青色であったものは緑色に、初期に緑色であったものは黄緑色に、それぞれ変化したことが若干認められた。
×:初期に青色であったものは緑色に、初期に緑色であったものは黄緑色に、それぞれ変化したことがはっきり認められた。 [Appearance stability]
Immediately after production, 100 g of the liquid detergent of each example was placed in a cylindrical glass bottle (PS100), sealed with a lid, and stored at 50 ° C. for 30 days.
And the change of the external appearance (liquid color) of the liquid detergent after storage was judged visually, and it evaluated based on the following evaluation criteria. ◎ and ○ were accepted.
In addition, when the liquid detergent is yellowed by storage, the blue color before storage (initial) is changed to green, and the green color is initially changed to yellow-green.
Evaluation Criteria A: No change in appearance (liquid color) was observed compared to the initial value.
○: It was recognized that the blue color at the initial stage changed to green, and the green color at the initial stage changed to yellowish green.
X: It was clearly recognized that the initial blue color changed to green, and the initial green color changed to yellow-green.
Claims (3)
- 界面活性剤(A)を40質量%以上と、色素(B)150ppm(質量基準)以下と、尿素又はその誘導体(C)0.5~12質量%とを含有する液体洗浄剤。 Liquid detergent containing 40% by mass or more of surfactant (A), 150 ppm (mass basis) or less of dye (B), and 0.5 to 12% by mass of urea or its derivative (C).
- 前記界面活性剤(A)が、下記の一般式(a1)~(a3)で表される非イオン界面活性剤から選択される少なくとも一種の界面活性剤を含む、請求項1に記載の液体洗浄剤。
- 下記一般式(d1)で表される有機溶剤(D)をさらに含有する、請求項1又は請求項2記載の液体洗浄剤。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137022282A KR20140003569A (en) | 2011-04-01 | 2012-03-28 | Liquid detergent |
CN201280016756.4A CN103459579B (en) | 2011-04-01 | 2012-03-28 | Liquid washing agent |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-081768 | 2011-04-01 | ||
JP2011081768A JP5789394B2 (en) | 2011-04-01 | 2011-04-01 | Liquid cleaning agent |
Publications (1)
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WO2012137642A1 true WO2012137642A1 (en) | 2012-10-11 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2012/058126 WO2012137642A1 (en) | 2011-04-01 | 2012-03-28 | Liquid detergent |
Country Status (5)
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JP (1) | JP5789394B2 (en) |
KR (1) | KR20140003569A (en) |
CN (1) | CN103459579B (en) |
MY (1) | MY161693A (en) |
WO (1) | WO2012137642A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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JP5949822B2 (en) | 2014-03-28 | 2016-07-13 | 栗田工業株式会社 | Hardness measuring composition, hardness measuring reagent kit, hardness measuring method, and antifouling method in hardness measuring apparatus |
JP6274948B2 (en) * | 2014-04-04 | 2018-02-07 | 日本カーバイド工業株式会社 | Mold cleaning resin composition and mold cleaning method using the same |
JP6468738B2 (en) * | 2014-06-26 | 2019-02-13 | ライオン株式会社 | Liquid cleaning agent |
JP6681404B2 (en) * | 2015-09-03 | 2020-04-15 | ライオン株式会社 | Liquid detergent for clothing |
JP6598360B2 (en) * | 2015-09-03 | 2019-10-30 | ライオン株式会社 | Liquid detergent for clothing |
JP2017066394A (en) * | 2015-09-28 | 2017-04-06 | 三洋化成工業株式会社 | Detergent for clothing |
JP7004537B2 (en) * | 2016-09-30 | 2022-01-21 | ライオン株式会社 | Particle dispersion detergent composition |
JP6979831B2 (en) * | 2017-05-09 | 2021-12-15 | ライオン株式会社 | How to wash textiles and liquid cleaners |
JP6500148B1 (en) * | 2018-05-21 | 2019-04-10 | 第一工業製薬株式会社 | Surfactant and liquid detergent |
JP7462393B2 (en) * | 2018-09-07 | 2024-04-05 | ライオン株式会社 | How to wash textile products |
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JPS5811596A (en) * | 1981-04-03 | 1983-01-22 | ザ・プロクタ−・エンド・ギヤンブル・カンパニ− | Liquid detergent composition |
JPS60245698A (en) * | 1984-05-11 | 1985-12-05 | ユニリーバー・ナームローゼ・ベンノートシヤープ | Detergent composition |
JPS6191298A (en) * | 1984-10-09 | 1986-05-09 | コルゲート・パーモリブ・カンパニー | Soft detergent composition |
JPH05310542A (en) * | 1992-05-14 | 1993-11-22 | Kao Corp | Detergent composition |
JPH0711288A (en) * | 1993-06-25 | 1995-01-13 | Ajinomoto Co Inc | Liquid detergent composition |
JP2000144179A (en) * | 1998-11-10 | 2000-05-26 | Lion Corp | Detergent composition |
JP2002284670A (en) * | 2001-03-28 | 2002-10-03 | Shiseido Co Ltd | Remover of dyeing material |
JP2011021138A (en) * | 2009-07-17 | 2011-02-03 | Kao Corp | Cleaning agent composition |
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Publication number | Priority date | Publication date | Assignee | Title |
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AU573338B2 (en) * | 1984-05-11 | 1988-06-02 | Unilever Plc | Homogenous foaming liquid composition |
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2011
- 2011-04-01 JP JP2011081768A patent/JP5789394B2/en active Active
-
2012
- 2012-03-28 CN CN201280016756.4A patent/CN103459579B/en not_active Expired - Fee Related
- 2012-03-28 MY MYPI2013003551A patent/MY161693A/en unknown
- 2012-03-28 WO PCT/JP2012/058126 patent/WO2012137642A1/en active Application Filing
- 2012-03-28 KR KR1020137022282A patent/KR20140003569A/en not_active Application Discontinuation
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JPS5811596A (en) * | 1981-04-03 | 1983-01-22 | ザ・プロクタ−・エンド・ギヤンブル・カンパニ− | Liquid detergent composition |
JPS60245698A (en) * | 1984-05-11 | 1985-12-05 | ユニリーバー・ナームローゼ・ベンノートシヤープ | Detergent composition |
JPS6191298A (en) * | 1984-10-09 | 1986-05-09 | コルゲート・パーモリブ・カンパニー | Soft detergent composition |
JPH05310542A (en) * | 1992-05-14 | 1993-11-22 | Kao Corp | Detergent composition |
JPH0711288A (en) * | 1993-06-25 | 1995-01-13 | Ajinomoto Co Inc | Liquid detergent composition |
JP2000144179A (en) * | 1998-11-10 | 2000-05-26 | Lion Corp | Detergent composition |
JP2002284670A (en) * | 2001-03-28 | 2002-10-03 | Shiseido Co Ltd | Remover of dyeing material |
JP2011021138A (en) * | 2009-07-17 | 2011-02-03 | Kao Corp | Cleaning agent composition |
Also Published As
Publication number | Publication date |
---|---|
JP2012214653A (en) | 2012-11-08 |
KR20140003569A (en) | 2014-01-09 |
JP5789394B2 (en) | 2015-10-07 |
MY161693A (en) | 2017-05-15 |
CN103459579B (en) | 2016-04-20 |
CN103459579A (en) | 2013-12-18 |
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