WO2014171476A1 - Détergent liquide - Google Patents

Détergent liquide Download PDF

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Publication number
WO2014171476A1
WO2014171476A1 PCT/JP2014/060809 JP2014060809W WO2014171476A1 WO 2014171476 A1 WO2014171476 A1 WO 2014171476A1 JP 2014060809 W JP2014060809 W JP 2014060809W WO 2014171476 A1 WO2014171476 A1 WO 2014171476A1
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WO
WIPO (PCT)
Prior art keywords
component
mass
group
compound
liquid detergent
Prior art date
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PCT/JP2014/060809
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English (en)
Japanese (ja)
Inventor
智貴 石塚
直也 田村
Original Assignee
ライオン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by ライオン株式会社 filed Critical ライオン株式会社
Priority to KR1020157025828A priority Critical patent/KR102182275B1/ko
Priority to JP2015512499A priority patent/JP6275122B2/ja
Publication of WO2014171476A1 publication Critical patent/WO2014171476A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • 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

Definitions

  • the present invention relates to a liquid cleaning agent.
  • This application claims priority based on Japanese Patent Application No. 2013-085808 for which it applied to Japan on April 16, 2013, and uses the content here.
  • Cleaning agents used for washing clothes and the like include powder types and liquid types.
  • the use ratio of liquid detergents has been increasing in that there are few concerns about undissolved residues and direct application to clothing and the like (see Patent Document 1).
  • the cleaning agent is required to have a high cleaning power against dirt adhering to clothes and the like.
  • high-load dirt for example, sebum dirt
  • high-load dirt containing a large amount of solids and oil is difficult to remove, and high detergency is required for such high-load dirt.
  • the liquid cleaning agent For dirt with a high load, it is considered effective to apply a liquid cleaning agent directly to the dirt.
  • the liquid cleaning agent has a high surfactant concentration (concentrated composition).
  • concentration concentration
  • the liquid detergent having a concentrated composition for example, a specific alkylene oxide adduct (nonionic surfactant) of 50 to 70% by mass with respect to the total mass of the liquid detergent, and a non-soap anionic surfactant 1 to 10
  • a liquid detergent containing mass% and a water-miscible organic solvent has been proposed (see Patent Document 2).
  • liquid detergent having a concentrated composition as described in Patent Document 2 easily penetrates into clothing, there is a problem that the liquid detergent is difficult to stay on the cloth and a sufficient coating cleaning power cannot be exhibited. For example, if the viscosity of the liquid cleaning agent is increased, the liquid cleaning agent tends to stay on the cloth.
  • liquid detergents with high viscosity have poor usability, such as poor fluidity, difficult to pour into caps, poor drainage from caps to the inlet of washing machines, and poor drainage from inlets.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid cleaning agent having excellent coating cleaning power and excellent usability.
  • a specific nonionic surfactant at least one component selected from the group consisting of a specific triglyceride component and a higher alcohol (for example, an alcohol having 6 to 18 carbon atoms), an anion It has been found that the above-mentioned problems can be solved by a liquid detergent that is used in combination with a surfactant and contains a surfactant at a high concentration.
  • the following (A) component, (B) component, and (C) component are contained, and the total content of all the surfactants is 45% by mass or more based on the total mass of the liquid detergent,
  • the liquid detergent which is 80% by mass or less:
  • a nonionic surfactant comprising at least one compound selected from: (B) component: at least one compound selected from the group consisting of a compound represented by the following general formula (b-1) and an alcohol having 6 to 18 carbon atoms; and
  • (C) component an anionic surfactant;
  • R 1 is a hydrocarbon group having 9 to 13 carbon atoms
  • R 2 is an alkylene group having 2 to 4 carbon atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms.
  • M is a number from 5 to 25 indicating the average number of repetitions of OR 2 ;
  • R 4 is a hydrocarbon group having 10 to 20 carbon atoms
  • EO is an oxyethylene group
  • PO is an oxypropylene group
  • s represents an average number of EO repeats of 5 to T is a number from 1 to 4 indicating the average number of repetitions of PO
  • [— (EO) s ⁇ (PO) t ⁇ ] is EO and PO
  • — (EO) s ⁇ (PO) t ⁇ means that they may be mixed and arranged regardless of the order. ;
  • R 1 is a hydrocarbon group having 10 to 20 carbon atoms;
  • a 1 O and A 2 O are each independently an oxyalkylene group having 2 to 4 carbon atoms;
  • p is A 1 O Q represents the average number of repetitions of A 2 O, p> 0, q> 0, and p + q is a number of 10 or more and less than 60;
  • the liquid cleaning agent of the present invention is excellent in coating cleaning power and is also excellent in usability.
  • the liquid detergent of this invention contains the following (A) component, (B) component, and (C) component.
  • the component (A) is a nonionic surfactant containing at least one compound selected from the group consisting of the following compound (A1), the following compound (A2) and the following compound (A4).
  • the component (A) is a component that imparts cleaning performance to the liquid cleaning agent of the present invention.
  • the component (A) is a nonionic surfactant (hereinafter referred to as “other nonion”). It may also be referred to as a “surfactant”.
  • the compound (A1) is a compound represented by the following general formula (a-1).
  • R 1 is a hydrocarbon group having 9 to 13 carbon atoms
  • R 2 is an alkylene group having 2 to 4 carbon atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms.
  • m is a number from 5 to 25 indicating the average number of repetitions of OR 2.
  • R 1 is a hydrocarbon group having 9 to 13 carbon atoms.
  • the hydrocarbon group may be linear or branched and may contain a cyclic structure.
  • R 1 is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
  • the hydrocarbon group has 9 to 13 carbon atoms, preferably 10 to 13 and more preferably 11 to 13. If carbon number is 9 or more, detergency will increase. On the other hand, if the number of carbon atoms is 13 or less, the liquid stability is improved, and particularly gelation is suppressed.
  • R 2 is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group.
  • the ethylene group means a structure represented by a structure of —CH 2 CH 2 —
  • the propylene group means a structure represented by —CH 2 CH 2 CH 2 .
  • the m OR 2 is, all may be the same or may be different. That is, the alkylene group in one molecule may be one type or a combination of two or more types. In particular, good foaming during cleaning, because it is inexpensive, it is preferable that the m OR 2 are all oxyethylene groups, or oxyethylene groups and oxypropylene groups are mixed.
  • the method for adding OR 2 is not particularly limited.
  • the addition method in the case where an oxyethylene group and an oxypropylene group are mixed may be random addition or block addition.
  • the block addition method include a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, a method of adding propylene oxide after adding ethylene oxide, and further adding ethylene oxide. Can be mentioned.
  • R 3 is an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.
  • R 3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. If the carbon number is 1 or more, precipitation during low-temperature storage is likely to be suppressed. On the other hand, if the carbon number is 4 or less, the solubility of the liquid cleaning agent in water under low temperature conditions is improved.
  • m is a number of 5 to 25 indicating the average number of repetitions of OR 2 groups (oxyalkylene group) (average addition mole number). If m is 5 or more, the detergency, particularly the detergency against sebum stains is improved. On the other hand, if m is 25 or less, the solubility of the liquid detergent in water is improved. If the m OR 2 are all oxyethylene groups, m is preferably 5-20, more preferably 12-18. Note that m may be an integer or may include a decimal. In m OR 2 , when oxyethylene group and oxypropylene group are mixed, m is preferably 12-21.
  • the average number of repeating oxypropylene groups is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, and even more preferably 1 or more and 3 or less.
  • the cleaning power and liquid stability as a liquid detergent may be reduced.
  • the “average number of repeating OR 2 groups (average number of added moles)” means the average number of moles of alkylene oxide added to 1 mole of the fatty acid ester used.
  • the “average number of added moles” in the present specification can be determined by, for example, NMR.
  • the narrow ratio indicating the distribution ratio of compounds (alkylene oxide adducts) having different OR 2 repeat numbers is preferably 20% by mass or more based on the total mass of the compound (A1). It is preferable that the upper limit of the narrow ratio is substantially 80% by mass or less. This narrow ratio is 20 to 80% by mass, more preferably 20 to 50% by mass, and further improves the liquid stability and the solubility in water, so that it is further 30 to 45% by mass. preferable. The higher the narrow rate, the easier it is to obtain good detergency. Further, when the narrow ratio is 20% by mass or more, particularly 30% by mass or more, a liquid cleaning agent with less raw material odor derived from the compound (A1) is easily obtained.
  • the “narrow ratio” refers to a value represented by the following mathematical formula (S), which indicates a distribution ratio of compounds having different OR 2 repeat numbers.
  • m max represents the number of repetitions of OR 2 of the compound (alkylene oxide adduct) which is most abundant in the entire compound (A1).
  • i represents the number of repetitions of OR 2 .
  • Yi is the ratio (wt%) to the total mass of the compounds repetition number of OR 2 is i present in the entire compound (A1) compounds of (alkylene oxide adducts) (A1).
  • the narrow rate can be controlled by, for example, the production method of the compound (A1).
  • the production method of the compound (A1) is not particularly limited.
  • a method of addition polymerization of an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst JP 2000-144179 A.
  • a surface-modified suitable composite metal oxide catalyst specifically, metal ions (Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , surface-modified with a metal hydroxide or the like are used.
  • the composite metal oxide catalyst such as magnesium oxide
  • the composite metal oxide catalyst such as magnesium oxide
  • the composite metal oxide is mixed with at least one component selected from the group consisting of metal hydroxide and metal alkoxide, and the composite metal oxide is used.
  • the ratio of at least one component selected from the group consisting of metal hydroxides and metal alkoxides to 100 parts by mass of the composite metal oxide is 0.5 to 10 parts by mass. It is preferably 1 to 5 parts by mass.
  • a compound (A1) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
  • the content of the compound (A1) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass.
  • the content of the compound (A1) is 1% by mass or more, good detergency can be obtained.
  • the content of the compound (A1) is 70% by mass or less, gelation with time will hardly occur.
  • Compound (A2) The compound (A2) is a compound represented by the following general formula (a-2).
  • R 4 represents a hydrocarbon group having 10 to 20 carbon atoms
  • EO represents an oxyethylene group
  • PO represents an oxypropylene group
  • s represents an average number of repetitions of EO.
  • T is a number from 1 to 4 indicating the average number of repetitions of PO;
  • [-(EO) s- (PO) t- ] is a formula in which EO and PO are represented by the formula-(EO) (Indicates that they may be mixed and arranged regardless of the order of s ⁇ (PO) t ⁇ ).
  • R 4 is a hydrocarbon group having 10 to 20 carbon atoms.
  • the hydrocarbon group may be linear or branched and may contain a cyclic structure.
  • R 4 is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group and a linear or branched alkenyl group.
  • the hydrocarbon group has 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, and more preferably 12 to 14 carbon atoms. If carbon number is 10 or more, detergency will increase. On the other hand, if the number of carbon atoms is 20 or less, the liquid stability is improved, and particularly gelation is suppressed.
  • Compound (A2) may be a mixture having a single chain length or a mixture having a plurality of chain lengths.
  • R 4 is derived from a raw material alcohol (R 4 —OH), and examples of the alcohol include alcohols derived from natural fats and oils such as coconut oil, palm oil, and beef tallow; synthetic alcohols derived from petroleum.
  • s is a number from 5 to 20 indicating the average number of repeating EO groups (oxyethylene groups) (average number of moles added). s may be an integer or may include a decimal number. When s is within the above range, the cleaning power, particularly the cleaning power against sebum dirt is improved. s is preferably 5 to 18.
  • t is a number from 1 to 4 indicating the average number of repeating PO groups (oxypropylene groups) (average number of moles added). t may be an integer or may include a decimal. If t is in the above range, gelation of the liquid detergent is likely to be suppressed, and good foamability is easily obtained at the time of rinsing. t is preferably 1 to 3.
  • average number of repeating EO groups (average number of added moles)” means the average number of moles of ethylene oxide to be added to 1 mole of alcohol used.
  • average number of repeating PO groups (average number of added moles) means the average number of moles of propylene oxide added to 1 mole of alcohol used.
  • [— (EO) s — (PO) t —] means that EO and PO may be mixed and arranged in the order of the left formula. That is, EO and PO may be added in a block shape or may be added in a random shape. Examples of the addition method when EO and PO are added in a block form include the addition methods exemplified above in the description of the compound (A1). In particular, a method of adding propylene oxide after adding ethylene oxide and further adding ethylene oxide is preferable because rinsing properties in washing in a fully automatic washing machine become better.
  • the addition mole number distribution of EO and PO is not particularly limited, and the addition mole number distribution can be controlled by the production method of the compound (A2) and the like.
  • a general alkali catalyst such as sodium hydroxide or potassium hydroxide
  • the distribution tends to be relatively wide.
  • specific alkoxyl 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
  • EO and PO are added to a hydrophobic raw material using an oxidization catalyst, there is a tendency that a relatively narrow addition mole number distribution is obtained.
  • a compound (A2) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
  • the content of the compound (A2) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. If the content of the compound (A2) is 1% by mass or more, good detergency can be obtained. On the other hand, when the content of the compound (A2) is 70% by mass or less, gelation with time is unlikely to occur.
  • the compound (A4) is a compound represented by the following general formula (a-4).
  • R 1 is a hydrocarbon group having 10 to 20 carbon atoms;
  • a 1 O and A 2 O are each independently an oxyalkylene group having 2 to 4 carbon atoms;
  • p is an average repeat of A 1 O Q represents the average number of repetitions of A 2 O, p> 0, q> 0, and
  • p + q is a number of 10 or more and less than 60.
  • R 1 is a hydrocarbon group having 10 to 20 carbon atoms. From the viewpoint of detergency, an alkyl group having 10 to 18 carbon atoms or an alkenyl group having 10 to 18 carbon atoms is preferable and may be linear or branched. When the carbon number of R 1 is 10 or more, the effect of preventing recontamination is enhanced and the cleaning power is improved. On the other hand, when the carbon number of R 1 is 20 or less, solubility in water is improved.
  • a 1 O and A 2 O are each independently an oxyalkylene group having 2 to 4 carbon atoms, preferably an oxyethylene group or an oxypropylene group.
  • a 1 O and A 2 O may be the same as or different from each other.
  • p represents the average number of repetitions of A 1 O
  • q represents the average number of repetitions of A 2 O
  • p and q each independently exceed 0.
  • p + q is a number of 10 or more and less than 60. When p + q is less than 10, it is difficult to obtain a cleaning effect.
  • p + q is 60 or more, as the molecular weight of the compound (A4) itself increases, the number of moles of the compound (A4) in the composition decreases at the same blending amount, so that the cleaning effect tends to decrease.
  • p + q is preferably 15 or more and 40 or less, more preferably 15 or more and 35 or less, because the cleaning power and the effect of preventing recontamination are further enhanced.
  • (A 1 O) p may be a repeating structure of only an oxyethylene group, a repeating structure of only an oxypropylene group, a repeating structure of only an oxybutylene group, or an oxyethylene group, an oxypropylene group, A mixed structure may be used. Among these, a repeating structure having only an oxyethylene group and a structure in which an oxyethylene group and an oxypropylene group are mixed are preferable, and a repeating structure having only an oxyethylene group is more preferable. In the case of a structure in which an oxyethylene group and an oxypropylene group are mixed, the oxyethylene group and the oxypropylene group may be repeated in a random manner or may be repeated in a block shape.
  • the total amount of oxyethylene groups in the compound (A4) is 60% by mass or more based on the total mass of all oxyalkylene groups in the compound (A4) from the viewpoint of solubility in water.
  • (A 2 O) q has the same meaning as (A 1 O) p, and preferred examples thereof are also the same.
  • a compound (A4) may be used individually by 1 type, and may use 2 or more types together.
  • the content of the compound (A4) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. If content of a compound (A4) is 1 mass% or more, the effect of preventing recontamination will increase and good detergency will be obtained. On the other hand, when the content of the compound (A4) is 70% by mass or less, it is preferable from the viewpoint that the fluidity of the liquid detergent is good, and the handling property during production is excellent.
  • the compound (A3) is a compound represented by the following general formula (a-3).
  • R 5 is a hydrocarbon group having 10 to 22 carbon atoms
  • EO is an oxyethylene group
  • n is a number of 5 to 20 indicating the average number of repetitions of EO.
  • R 5 is a hydrocarbon group having 10 to 22 carbon atoms.
  • the hydrocarbon group may be linear or branched and may contain a cyclic structure. Furthermore, the hydrocarbon group may have an unsaturated bond, and may be a mixture of a single chain length and a plurality of chain lengths.
  • R 5 is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
  • the hydrocarbon group has 10 to 22 carbon atoms, preferably 10 to 20, and more preferably 10 to 18. If the carbon number is 10 or more, the detergency is further improved.
  • R 5 is derived from a raw material alcohol (R 5 —OH).
  • the alcohol include alcohols derived from natural fats and oils such as palm oil, palm oil, and beef tallow, and petroleum-derived synthetic alcohols.
  • N is a number of 12 to 20 indicating the average number of repeating EO (oxyethylene group) (average number of added moles), preferably 12 to 18, and more preferably 12 to 16.
  • n may be an integer or may include a decimal. If n is 12 or more, a liquid detergent with little raw material odor derived from the compound (A3) is easily obtained. On the other hand, if n is 20 or less, it can suppress that HLB becomes high too much and can maintain the detergency with respect to sebum dirt favorably. In particular, when n is 12 to 16, it exhibits a high detergency against sebum dirt.
  • the addition mole number distribution of EO is not particularly limited, and the addition mole number distribution can be controlled by the production method of the compound (A3) and the like.
  • a general alkali catalyst such as sodium hydroxide or potassium hydroxide
  • the distribution tends to be relatively wide.
  • specific alkoxyl 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
  • EO is added to a hydrophobic raw material using a catalyst, it tends to have a relatively narrow addition mole number distribution.
  • the compound (A3) include a compound obtained by adding 12 and 15 moles of EO to an alcohol such as a product manufactured by Shell: trade name Neodol (C12 / C13) and a product manufactured by Sasol: Safol23 (C12 / C13).
  • Manufactured by P & G a compound obtained by adding 9, 12 and 15 moles of EO to natural alcohols such as trade names CO-1214 and CO-1270; 9, 12 and 12 to secondary alcohols having 12 to 14 carbon atoms; , Compounds having 15 moles of EO added (Nippon Shokubai Co., Ltd., Softanol 90, 120 and 150), and the like.
  • a compound (A3) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
  • nonionic surfactants examples include alkylpolyglucoside (APG), fatty acid diester (manufactured by Lion Corporation: trade name Lionon DT-600S), alkylamine oxide (Lion) Manufactured by Alomox DMC-W).
  • APG alkylpolyglucoside
  • fatty acid diester manufactured by Lion Corporation: trade name Lionon DT-600S
  • alkylamine oxide Lion
  • the content of the other nonionic surfactant is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. . If the content of other nonionic surfactant is 1% by mass or more, better detergency can be obtained. On the other hand, if the content of other nonionic surfactants is 70% by mass or less, gelation with time is less likely to occur.
  • the compound (A1) is preferable.
  • the compound (A1) is easier to mix with other components than the compound (A2) and the compound (A4) and is easy to concentrate. If it is a compound (A1), since a solvent is not required in the case of concentration, an aroma is hard to be impaired.
  • a compound (A3) in order to reduce the viscosity of a liquid detergent and to improve usability, it is preferable to use a compound (A3) together.
  • compound (A3) when compound (A3) is used in combination with said compound, compound (A1), compound ( In a molecular assembly composed of at least one compound selected from the group consisting of A2) and compound (A4) and compound (A3), the packing property between molecules is weakened, and the viscosity of the liquid detergent is reduced. Conceivable.
  • the “molecular assembly” means that at least one compound selected from the group consisting of the compound (A1), the compound (A2) and the compound (A4) and the compound (A3) are the temperature of the solution. It means an aggregate assembled by conditions such as pressure.
  • the mass ratio of the total of compound (A1) and compound (A2) to compound (A3) (total of compound (A1) and compound (A2) / compound (A3)) is preferably 0.02 to 4.5, 1.25 to 4 is more preferable, and 2 to 4 is more preferable. If the mass ratio is 0.02 or more, gelation with time is less likely to occur. On the other hand, if the mass ratio is 4.5 or less, the viscosity tends to be low, and the usability is likely to improve.
  • the component (B) is at least one compound selected from the group consisting of the following compound (B1) and higher alcohol (B2).
  • the compound (B1) is a compound (triglyceride component) represented by the following general formula (b-1).
  • Z 1 to Z 3 are each independently a hydrogen atom, a hydroxy group, or a carboxy group.
  • Z 1 to Z 3 may be the same or different.
  • the volume of the hydrophobic group becomes sufficiently bulky and the coating cleaning power is increased.
  • a + b, c + d, and e + f are each 19 or less, the risk of solidification due to an increase in the volume of the hydrophobic group portion is reduced.
  • Examples of the compound (B1) include a compound (B1-1) in which Z 1 to Z 3 are hydroxy groups, a compound (B1-2) in which Z 1 to Z 3 are hydrogen atoms, and the like.
  • a compound (B1) you may manufacture by a well-known method and can also use a commercial item.
  • Examples of the compound (B1-1) include “Caster Wax A Flakes” manufactured by NOF Corporation, and examples of the compound (B1-2) include “Palm Extremely Cured Oil A” manufactured by Shin Nippon Chemical Co., Ltd.
  • a compound (B1) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
  • the content of the compound (B1-1) is preferably 0.1 to 5% by mass, more preferably 0.1 to 2% by mass, with the total mass of the liquid detergent being 100% by mass, and 0.3 to 1% by mass is more preferable.
  • the content of the compound (B1-1) is 0.1% by mass or more, good detergency can be expressed.
  • the content of the compound (B1-1) is 5% by mass or less, the risk of causing solidification is reduced.
  • the content of the compound (B1-2) is preferably from 0.5 to 10% by mass, more preferably from 1 to 5% by mass, and more preferably from 2 to 4% by mass, when the total mass of the liquid detergent is 100% by mass. Further preferred. When the content of the compound (B1-2) is 0.5% by mass or more, good detergency can be expressed. On the other hand, when the content of the compound (B1-2) is 10% by mass or less, the risk of causing solidification is reduced.
  • the higher alcohol (B2) is a monohydric alcohol having 6 to 18 carbon atoms.
  • the higher the volume of the hydrophobic group portion the easier it is to form a structural liquid. Therefore, as the higher alcohol (B2), an alcohol having 12 or more carbon atoms is preferable, and among them, a branched alcohol is particularly preferable.
  • the number of carbon atoms is preferably 18 or less. If the higher alcohol (B2) has 18 or less carbon atoms, the liquid detergent containing the higher alcohol (B2) can form a structural liquid without causing solidification.
  • the “structural liquid” means a liquid having thixotropic properties.
  • the “thixotropic property” is a property exhibited by an intermediate substance between a plastic solid such as a gel and a non-Newtonian liquid such as a sol. Specifically, when the shear stress continues, the viscosity gradually decreases. It becomes a liquid, and when it is stationary, its viscosity gradually increases and finally becomes a solid.
  • the liquid detergent when the component (A) is included and the component (B) is not included, the liquid detergent is in a state of spherical micelles.
  • the critical packing parameter (CPP) relating the molecular structure of the surfactant and the self-assembled structure approaches 1, and the liquid changes to a thixotropic liquid.
  • Examples of the higher alcohol (B2) include “ISOFOL12” manufactured by SASOL.
  • a higher alcohol (B2) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
  • the content of the higher alcohol (B2) is preferably 1 to 7% by mass, more preferably 2 to 6% by mass, and further preferably 3 to 5% by mass, when the total mass of the liquid detergent is 100% by mass. . If the content of the higher alcohol (B2) is 1% by mass or more, good detergency can be expressed. On the other hand, when the content of the higher alcohol (B2) is 7% by mass or less, it becomes easier to form a structural liquid without causing solidification.
  • Component (C) is an anionic surfactant. It does not specifically limit as an anionic surfactant, A well-known anionic surfactant can be used. Specifically, linear alkylbenzene sulfonic acid or a salt thereof; ⁇ -olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; Examples include alkane sulfonates; ⁇ -sulfo fatty acid ester salts and the like. Examples of these salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanolamine salts such as monoethanolamine and diethanolamine.
  • the component (C) includes, for example, higher fatty acid salts having 10 to 20 carbon atoms, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates.
  • Carboxylic acid type anionic surfactants such as acylaminocarboxylates; alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkyl phenyl phosphate ester salts, glycerin fatty acid ester monophosphate ester salts, etc.
  • Examples include phosphate ester type anionic surfactants.
  • these salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanolamine salts such as monoethanolamine and diethanolamine.
  • the linear alkylbenzene sulfonic acid or a salt thereof is preferably a linear alkylbenzene sulfonic acid having 8 to 16 carbon atoms or a salt thereof, and a linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms or a salt thereof.
  • the salt is particularly preferred.
  • the ⁇ -olefin sulfonate is preferably an ⁇ -olefin sulfonate having 10 to 20 carbon atoms.
  • the alkyl sulfate ester salt is preferably an alkyl sulfate ester salt having 10 to 20 carbon atoms.
  • the alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched alkenyl group having 10 to 20 carbon atoms.
  • an alkyl ether sulfate ester salt or an alkenyl ether sulfate ester salt (that is, a polyoxyethylene alkyl ether sulfate ester salt or a polyoxyethylene alkenyl ether sulfate ester salt) to which ethylene oxide having an average repeating number of 1 to 10 mol is added is preferable. .
  • AES Alkyl (or alkenyl) ether sulfate ester salt
  • alkane sulfonate examples include alkane sulfonates having 10 to 20 carbon atoms, alkane sulfonates having 14 to 17 carbon atoms are preferable, and secondary alkane sulfonates are particularly preferable.
  • the ⁇ -sulfo fatty acid ester salt is preferably an ⁇ -sulfo fatty acid ester salt having 10 to 20 carbon atoms.
  • a linear alkylbenzene sulfonic acid or a salt thereof; an alkane sulfonate; a polyoxyethylene alkyl ether sulfate ester salt; an alkylene oxide having 2 to 4 carbon atoms; or an ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO 0.1 / 9.9 to 9.9 / 0.1), an average of 0.5 to 10 moles of linear chain having 10 to 20 carbon atoms (Or alkenyl) ether sulfate ester salt having a linear or branched alkyl group (or alkenyl group); ⁇ -olefin sulfonate, and higher fatty acid salt; and at least one anionic surface activity selected from the group consisting of Agents are preferred.
  • the liquid detergent of the present invention contains components that are usually used for liquid detergents within the range that does not impair the effects of the present invention. Can be blended. For example, the following components can be mentioned.
  • the liquid detergent of the present invention can contain a surfactant excluding the components (A) and (C) (hereinafter sometimes referred to as an optional surfactant).
  • Optional surfactants include cationic surfactants.
  • cationic surfactants include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, Long chain aliphatic amide alkyl tertiary amines such as behenic acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide or salts thereof; aliphatic ester alkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine Or salts thereof; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide, and the like.
  • cationic surfactants may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
  • dimethylaminopropylamide oleate or a salt thereof are also preferred.
  • cationic surfactant it can be appropriately selected from known cationic surfactants.
  • cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, and the like can be used.
  • the liquid cleaning agent of the present invention preferably contains water.
  • the water content is preferably 5 to 35% by mass, more preferably 20 to 35% by mass, when the total mass of the liquid detergent is 100% by mass.
  • the water content is 5% by mass or more, the liquid detergent is hardly gelled, and the fluidity and stability can be maintained well.
  • the component (A) and the component (B) can be contained in the liquid detergent within the optimum range, and a structural liquid can be easily formed.
  • the liquid cleaning agent of the present invention may contain a solvent.
  • a solvent the solvent conventionally mix
  • the solvent include alcohols such as ethanol, 1-propanol, 2-propanol, and 1-butanol; glycols such as propylene glycol, butylene glycol, and hexylene glycol; diethylene glycol, triethylene glycol, tetraethylene glycol, and average molecular weight.
  • Polyglycols such as polyethylene glycol having an average molecular weight of about 400, polyethylene glycol having an average molecular weight of about 400, polyethylene glycol having an average molecular weight of about 1000, and dipropylene glycol; alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and diethylene glycol dimethyl ether.
  • the total content of water and solvent is preferably 15 to 45% by mass, more preferably 25 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. When the total content of water and solvent is 15% by mass or more, the liquid detergent is hardly gelled, and fluidity and stability can be maintained well. On the other hand, if the total content of water and solvent is 45% by mass or less, the component (A) and the component (B) can be contained in the liquid detergent within the optimum range, and a structural liquid can be easily formed. .
  • the liquid detergent of the present invention may contain an inorganic salt, and is particularly preferably used in combination with the component (C). Since the inorganic salt can cancel the charge of the hydrophilic group of the component (C), it becomes easier to form a structural liquid.
  • the inorganic salt include sodium chloride, potassium chloride, sodium citrate, potassium nitrate, potassium sulfate and the like.
  • An inorganic salt may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
  • the content of the inorganic salt is preferably 0.2 to 1% by mass when the total mass of the liquid detergent is 100% by mass. If content of inorganic salt is 0.2 mass% or more, detergency will improve. On the other hand, if the content of the inorganic salt is 1% by mass or less, it is possible to suppress a reduction in detergency due to excess salt.
  • the liquid detergent of the present invention may contain particles that are hardly soluble in the components constituting the liquid detergent (that is, water-soluble particles and water-insoluble particles).
  • particles include a capsule containing a capsule fragrance and an active ingredient instead thereof, beads and a pearlescent agent for imparting specific product aesthetics, bentonite, carboxymethylcellulose (CMC), Laponite. S482, cluster dextrin, etc. are mentioned.
  • the liquid detergent of the invention may contain a cluster dextrin, and the residual fragrance can be further enhanced by containing the cluster dextrin.
  • Specific examples of cluster dextrin include “Cluster Dextrin” (registered trademark) manufactured by Glico Nutrition Foods, Inc. These particles may be used alone or in combination of two or more.
  • the content of at least one component selected from the group consisting of water-soluble particles and water-insoluble particles is preferably 0.05 to 5% by mass when the total mass of the liquid detergent is 100% by mass.
  • the liquid detergent of the present invention may contain urea or a derivative thereof, and is particularly preferably used in combination with the compound (A1).
  • urea or derivatives thereof include urea [CO (NH 2 ) 2 ], urea double salts, and other urea derivatives.
  • 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.
  • the “urea derivative” includes a compound having a partial structure represented by the following general formula (d-1).
  • the compound represented by the general formula (d-2) is a preferred compound.
  • 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, It is a methyl group or an ethyl group.
  • Examples of the compound represented by the formula (d-2) include 1,3-dimethylurea, N- (2-hydroxyethyl) urea and the like.
  • Urea may be used alone or in combination of two or more.
  • the content of urea in the liquid detergent is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% with respect to the total mass of the liquid detergent. % By mass. If the content exceeds the upper limit, ammonia tends to be generated as a decomposition product after storage, and odor may be a problem as a liquid detergent product.
  • the liquid detergent of the present invention may contain silicone. By containing silicone, it is possible to further improve rinsing properties and foam suppression during production.
  • silicone include polyether-modified silicone, amino-modified silicone, and the like. Among these, polyether-modified silicone is preferable.
  • the polyether-modified silicone is not particularly limited as long as it has a polyether group such as polyethylene oxide or polypropylene oxide as a functional group. In addition, other functional groups may be introduced as long as polyether groups such as polyethylene oxide and polypropylene oxide are introduced.
  • polyether-modified silicones include SH3772M, SH3775M, SH3749, SF8410, SH8700, BY22-008, SF8421, SILWET L-7001, SILWET L-7002, SILWET L- manufactured by Toray Dow Corning Co., Ltd.
  • SILWET FZ-2104 SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1-009, ABN SILWET FZ-F1-009-05, ABN SILWET FZ9-F1-00 ABN SILWET FZ-F1-009-54, ABN SILWET FZ-2222 (above, trade name); KF352A, KF6008, K manufactured by Shin-Etsu Chemical Co., Ltd. 615A, KF6016, KF6017 (trade names); GE Toshiba made Silicone Co., Ltd. TSF4450, TSF4452 (trade names), and the like.
  • silicone antifoaming agent examples include KM-7750, KM-90, KM-98, KS-538, KS-66, and KS-69 (above, trade names) manufactured by Shin-Etsu Chemical Co., Ltd. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the liquid cleaning agent of the present invention may contain other optional components that are acceptable as a liquid cleaning agent.
  • Other optional ingredients acceptable as liquid detergents include dispersion media, hydrotropes, detergency builders, stabilizers (eg, sodium benzoate, citric acid, citric acid, known in the liquid detergent art) Sodium, polyhydric alcohol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc.), alkali agent (eg, alkanolamine such as monoethanolamine, diethanolamine, triethanolamine, etc.), metal ion scavenger (eg, malonic acid, succinate) Acid, malic acid, diglycolic acid, tartaric acid, citric acid, or salts thereof), texture improver such as silicone, preservative, fluorescent agent, dye transfer inhibitor, pearl agent, antioxidant (for example, dibutylhydroxy) Toluene, distyrenated crezo , Sodium sulfite, sodium hydrogen sulfite),
  • the liquid detergent of this invention can contain the enzyme currently mix
  • the coating cleaning power is further improved.
  • enzyme refers to an enzyme preparation. Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase, cellulase and the like.
  • the protease is preferably a protease having serine, histidine, and aspartic acid in the molecule, such as serine protease.
  • protease include trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L Type 2.5, Eraase Ultra 16L, Esperase Ultra 16L, Esperase Ultra 16L, Esperase Ultra L 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L; trade names Purefect L, Perfect OX, Properase L, etc. available from Genencor.
  • amylase examples include trade names such as Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, and Stainzyme Plus 12L available from Genencore; Trade name pullulanase Amano; trade name DB-250 available from Seikagaku Corporation.
  • lipase examples include trade names Lipex 100L and Lipolase 100L available from Novozymes as lipase preparations.
  • cellulase examples include Carezyme 4500L (trade name, manufactured by Novozymes, reducing sugar production amount: 253.2 ⁇ M), Carezyme Premium 4500L (trade name, manufactured by Novozymes, reducing sugar production: 307.0 ⁇ M), Endolase Examples include endoglucanase preparations such as 5000L (trade name, manufactured by Novozymes, reducing sugar production: 187.0 ⁇ M), Cellclean 4500T (trade name, Novozymes, reducing sugar production: 120.6 ⁇ M), and the like.
  • carezyme 4500L and care enzyme premium 4500L are preferable, and carezyme premium 4500L is more preferable.
  • mannanase include Mannaway 4L, a trade name available from Novozymes as a mannanase preparation. These enzymes may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate. The content of the enzyme is preferably 0.1 to 3% by mass with respect to 100% by mass of the liquid detergent.
  • liquid detergents Another aspect of other optional ingredients that can be tolerated as liquid detergents includes stabilizers, cationic surfactants, pH adjusters, silicones, fragrances, water, alkaline agents, enzymes, urea, cluster dextrins, and dispersions It is preferably at least one component selected from the group consisting of media.
  • Total surfactant content The content of all the surfactants (hereinafter, also referred to as “total surfactant”) contained in the liquid detergent is 45% by mass or more when the total mass of the liquid detergent is 100% by mass. .
  • total surfactant content is 45% by mass or more, high cleaning performance can be imparted to the liquid cleaning agent and a structural liquid can be maintained.
  • the total surfactant content is preferably 51% by mass or more, more preferably more than 51% by mass, and particularly preferably 54% by mass or more.
  • 80 mass% or less is preferable, 70 mass% or less is more preferable, and 60 mass% or less is further more preferable.
  • the liquid detergent tends to gel, and the stability may decrease. That is, the content of the total surfactant is 45% by mass or more and 80% by mass or less, preferably 51% by mass or more and 80% by mass or less, and more than 51% by mass with respect to 100% by mass of the liquid detergent. 70 mass% or less is more preferable, and 54 mass% or more and 60 mass% or less are still more preferable.
  • total surfactant as used herein means the total content of the component (A), the component (C) and the surfactants included as optional components.
  • the content of the component (A) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass.
  • the content of the component (A) is 1% by mass or more, good detergency can be obtained.
  • the content of the component (A) is 70% by mass or less, gelation with time is unlikely to occur.
  • the content of the component (B) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 4% by mass when the total mass of the liquid detergent is 100% by mass. % Is more preferable. When the content of the component (B) is 0.1% by mass or more, good detergency can be expressed. On the other hand, if content of (B) component is 10 mass% or less, the risk of causing solidification will be reduced.
  • component (C) The content of component (C) is preferably 1 to 20% by mass, more preferably 3 to 18% by mass, and even more preferably 5 to 16% by mass, when the total mass of the liquid detergent is 100% by mass. If content of (C) component is 1 mass% or more, cleaning performance, especially coating cleaning power will improve. On the other hand, if content of (C) component is 20 mass% or less, liquid stability will improve.
  • the mass ratio of the component (A) to the component (B) is preferably 15 to 150, more preferably 37.5 to 110, and still more preferably 60 to 100.
  • the ratio of the component (B) is too high, gelation occurs, so that the fluidity and stability of the liquid detergent may be reduced.
  • the ratio of the component (B) is too low, the coating cleaning power is hardly improved.
  • the mass ratio of component (C) to component (A) is preferably 0.02 to 0.7, more preferably 0.06 to 0.5, and 0.1 to 0.3 is more preferable. If the ratio of the component (C) is too high, the detergency may be reduced. On the other hand, when the ratio of the component (C) is too low, protein cleaning power and recontamination are deteriorated.
  • the liquid detergent of the present invention preferably has a viscosity at 60 rpm of 50 to 1000 mPa ⁇ s at 25 ° C. using a B-type viscometer (manufactured by TOKIMEC, rotor No. 2 or 3), and 75 to 800 mPa ⁇ s. More preferably, it is more preferably 100 to 500 mPa ⁇ s. Further, the viscosity at 6 rpm measured by a B-type viscometer at 25 ° C. (manufactured by TOKIMEC, rotor No.
  • the TI value (viscosity at 6 rpm / viscosity at 60 rpm) represented by the ratio of the viscosity at 6 rpm to the viscosity at 60 rpm is preferably 2 or more.
  • the TI value is an index representing thixotropy, and the greater the TI value, the higher the thixotropy and the greater the difference in viscosity due to changes in shear rate.
  • the viscosity is defined as a value at 25 ° C. unless otherwise specified. That is, even if the value is outside the range specified in the present specification, it is included in the scope of the present invention as long as it is a viscosity value within the range specified in the present specification when corrected to a value at 25 ° C.
  • the liquid detergent of the present invention preferably has a pH of 6 to 9 at 25 ° C., more preferably 7 to 8.
  • the pH of the liquid detergent indicates a value measured by a pH meter (“HM-30G” manufactured by Toa DKK Corporation).
  • pH is defined as a value at 25 ° C. unless otherwise specified. That is, even if the pH value is outside the range specified in the present specification, it is included in the scope of the present invention as long as the pH value is within the range specified in the present specification when corrected to the pH value at 25 ° C. .
  • the pH of the liquid detergent of the present invention can be adjusted with a pH adjuster.
  • the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide, alkanolamine and ammonia.
  • sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid and sodium hydroxide are preferable from the viewpoint of the temporal stability of the liquid detergent.
  • a pH adjuster may be used individually by 1 type, and may use 2 or more types together. For example, when controlled by adding a certain amount of sulfuric acid, sodium hydroxide or the like, an inorganic acid (preferably hydrochloric acid or sulfuric acid) or potassium hydroxide can be further added for fine adjustment of pH.
  • the manufacturing method of the liquid detergent of this invention can be manufactured based on a conventional method. For example, after the component (A), the component (C), and an optional component as needed are dispersed in a part of water, the solution in which the component is dispersed is heated to the melting point of the component (B). Then, the component (B) heated to the melting point is added to the warmed solution. Then, it adjusts to arbitrary pH and adds the remainder of water, and obtains a liquid cleaning agent. At this time, it is preferable to start from blending the (A) component, the (C) component, and an optional component as necessary, in that gelation can be suppressed.
  • the liquid detergent of the present invention Dispersing the component (A), the component (C), and optionally other components in a part of water; Heating the solution in which the components are dispersed to the melting point of the component (B); Adding the component (B) heated to the melting point to the warmed solution; Adjusting the pH of the solution obtained by adding the component (B); and adding the remainder of the water to the pH adjusted solution;
  • cleaning liquid containing this is mentioned.
  • the liquid detergent of this invention can be used by the method similar to the normal usage method of the liquid detergent for clothes.
  • a method in which a liquid cleaning agent is poured into water together with the laundry during washing normal cleaning
  • a method in which the liquid cleaning agent is applied directly to dirt sites such as mud and sebum soil (application cleaning) application cleaning
  • a liquid cleaning agent for example, a method of pre-dissolving in water and immersing clothes (pickling washing) may be used.
  • a method of applying a liquid detergent to the laundry or immersing clothes in a diluted liquid of the liquid detergent and leaving it as it is, and then washing with a washing machine may be used.
  • the liquid cleaning agent of the present invention described above contains the component (A), the component (B), and the component (C), it has a high detergency against hydrophobic dirt and further forms a structural liquid. Therefore, the liquid detergent of the present invention has a thixotropic property due to the structural liquid and has a viscosity characteristic such that the viscosity is high when no shear force is applied and low when the shear force is applied. That is, the liquid cleaning agent of the present invention has a high viscosity in a state where no shearing force is applied, that is, in a state close to a stationary state. Easy to stay on top. Therefore, if it is the liquid cleaning agent of this invention, the outstanding coating cleaning power can be exhibited.
  • the liquid detergent of the present invention has a low viscosity in a state where shearing force is applied, that is, in a state where the container in which the liquid detergent is stored is tilted, the liquid detergent is stirred, or pressure is applied to the liquid detergent. It is. Therefore, with the liquid cleaning agent of the present invention, it is easy to pour the liquid cleaning agent in the container into the cap, the discharge property from the cap to the inlet of the washing machine and the discharge property from the inlet are good, and the usability Excellent.
  • the compound (A4) exhibits a high cleaning effect even with a small use amount (low concentration).
  • other nonionic surfactants general-purpose alcohol ethoxylates, etc.
  • it has a characteristic that it is difficult to adsorb on the object to be washed.
  • the combination of the compound (A4) and the component (B) makes it difficult for the compound (A4) to be adsorbed on the article to be washed, so that the component (B) is preferentially adsorbed.
  • the adsorption of the component (B) makes it easier to reduce the moisture content after washing and dewatering, and also expresses a unique effect of imparting quick-drying properties that make it easier to dry.
  • Such an effect is particularly remarkable for an object to be cleaned containing chemical fibers such as acrylic fibers and polyester fibers.
  • the liquid detergent of the present invention contains a surfactant at a high concentration, it is easy to maintain a structural liquid, and is excellent in detergency in normal washing as well as detergency in application washing. In addition, since the liquid detergent of the present invention has good foam breakage during rinsing, the number of times of rinsing can be reduced.
  • a product having a higher added value than conventional is required for the cleaning agent.
  • detergents and the like containing water-soluble particles such as beads and water-insoluble particles have been developed. If it is a powder detergent, water-soluble particles and water-insoluble particles can be uniformly and stably dispersed. It was difficult to make.
  • the liquid detergent of the present invention forms a structural liquid, water-soluble particles and water-insoluble particles can be uniformly and stably dispersed.
  • compositions of the invention include: Contains the following component (A), the following component (B), the following component (C), water, and optionally an acceptable component as a liquid detergent,
  • a nonionic surfactant comprising at least one compound selected from:
  • component anionic surfactant;
  • R 1 is a hydrocarbon group having 9 to 13 carbon atoms
  • R 2 is an alkylene group having 2 to 4 carbon atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms.
  • m is a number from 5 to 25 indicating the average number of repetitions of OR 2.
  • R 4 represents a hydrocarbon group having 10 to 20 carbon atoms
  • EO represents an oxyethylene group
  • PO represents an oxypropylene group
  • s represents an average number of repetitions of EO.
  • T is a number from 1 to 4 indicating the average number of repetitions of PO; [-(EO) s- (PO) t- ] is EO and PO is the formula-(EO) (Indicates that they may be mixed and arranged regardless of the order of s ⁇ (PO) t ⁇ ).
  • R 1 is a hydrocarbon group having 10 to 20 carbon atoms;
  • a 1 O and A 2 O are each independently an oxyalkylene group having 2 to 4 carbon atoms; 1 represents the average number of repetitions of O, q represents the average number of repetitions of A 2 O, p> 0, q> 0, and p + q is a number of 10 or more and less than 60.
  • compositions of the invention include: Contains the following component (A), the following component (B), the following component (C), water, and optionally an acceptable component as a liquid detergent,
  • a nonionic surfactant comprising at least one compound and a compound represented by the following general formula (a-3);
  • component at least one compound selected from the group consisting of the compound represented by the formula (b-1) and an alcohol having 6 to 18 carbon atoms;
  • component an anionic surfactant ;
  • R 5 is a hydrocarbon group having 10 to 22 carbon atoms
  • EO is an oxyethylene group
  • n is a number of 5 to 20 indicating the average number of repetitions of EO.
  • compositions of the invention include: Contains the following component (A), the following component (B), the following component (C), water, and optionally an acceptable component as a liquid detergent,
  • a nonionic surfactant comprising at least one compound Component (B): Compound (B1-1) represented by the following general formula (b1-1), Compound (B1-2) represented by the following general formula (b1-2), and 6 or more carbon atoms, 18 At least one compound selected from the group consisting of the following alcohols; and (C) component: an anionic surfactant;
  • compositions of the invention include: Contains the following (A) component, the following (B) component, the following (C) component, water and optionally an acceptable component as a liquid detergent,
  • a nonionic surfactant comprising at least one compound
  • (B) component at least one compound selected from the group consisting of the compound represented by the formula (b-1) and an alcohol having 6 to 18 carbon atoms
  • compositions of the invention include: The following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent,
  • Component (A) selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4)
  • a nonionic surfactant comprising at least one compound and a compound represented by the formula (a-3);
  • compositions include: The following (A) component, the following (B) component, the following (C) component, water, and optionally a liquid detergent containing a component that is acceptable as a liquid detergent,
  • the total mass of the liquid detergent The total content of all the surfactants is 45% by mass or more and 80% by mass or less,
  • the component (A) is 1 to 70% by mass
  • the component (B) is 0.1 to 10% by mass
  • the component (C) is 1 to 20% by mass
  • Liquid detergent wherein the water is 5 to 35% by mass and the total amount of each component does not exceed 100% by mass:
  • a nonionic surfactant comprising at least one compound
  • (B) component at least one compound selected from the group consisting of the compound represented by the formula (b-1) and an alcohol having 6 to 18 carbon atoms
  • the total mass of the liquid detergent The total content of all the surfactants is 45% by mass or more and 80% by mass or less,
  • the component (A) is 1 to 70% by mass,
  • the component (B) is 0.1 to 10% by mass,
  • the component (C) is 1 to 20% by mass, the water is 5 to 35% by mass, and the total amount of each component does not exceed 100% by mass;
  • (C) component / (A) component, which is a mass ratio of the (C) component and the (A) component, is 0.02 to 0.7;
  • the (A) component / (B) component, which is a mass ratio of the (A) component and the (B) component is 15 to 150.
  • Liquid detergent Component (A): selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) A nonionic surfactant comprising at least one compound; (B) component: at least one compound selected from the group consisting of the compound represented by formula (b-1) and an alcohol having 6 to 18 carbon atoms; and (C) component: an anionic surfactant ; Is mentioned.
  • the total mass of the liquid detergent The total content of all the surfactants is 45% by mass or more and 80% by mass or less,
  • the component (A) is 1 to 70% by mass,
  • the component (B) is 0.1 to 10% by mass,
  • the component (C) is 1 to 20% by mass, the water is 5 to 35% by mass, and the total amount of each component does not exceed 100% by mass;
  • (C) component / (A) component which is a mass ratio of the (C) component and the (A) component, is 0.02 to 0.7;
  • the total of the following compound (A1) and the following compound (A2) and the following compound (A3) and the total ratio of the compound (A1) and the compound (A2) / the compound (A3) is 0.02 to 4.5.
  • Liquid detergent that is: Component (A): Compound (A1) represented by Formula (a-1), Compound (A2) represented by Formula (a-2), and Compound (A-4) ( A nonionic surfactant comprising at least one compound selected from the group consisting of A4) and the compound (A3) represented by the formula (a-3); (B) component: at least one compound selected from the group consisting of the compound represented by formula (b-1) and an alcohol having 6 to 18 carbon atoms; and (C) component: an anionic surfactant ; Is mentioned.
  • the total mass of the liquid detergent The total content of all the surfactants is 45% by mass or more and 80% by mass or less,
  • the component (A) is 1 to 70% by mass,
  • the component (B) is 0.1 to 10% by mass,
  • the component (C) is 1 to 20% by mass, the water is 5 to 35% by mass, and the total amount of each component does not exceed 100% by mass;
  • the (C) component / (A) component which is a mass ratio of the (C) component and the (A) component, is 0.02 to 0.7.
  • Liquid detergent Component (A): Compound (A1) represented by Formula (a-1), Compound (A2) represented by Formula (a-2), and Compound (A-4) ( A nonionic surfactant comprising at least one compound selected from the group consisting of A4) and the compound (A3) represented by the formula (a-3);
  • At least one compound selected from the group consisting of alcohols; and component (C): linear alkylbenzene sulfonic acid or a salt thereof; alkane sulfonate; polyoxyethylene alkyl ether sulfate ester; alkylene oxide having 2 to 4 carbon atoms Or carbon obtained by adding an average of 0.5 to 10 mol of ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO 0.1 / 9.9 to 9.9 / 0.1) Al
  • R 1 in the general formula (a-1) is an alkyl group having 12 or 14 carbon atoms
  • R 2 is an ethylene group
  • R 3 is a methyl group
  • m 15
  • the synthesis was performed as follows. Synthesis was performed according to the synthesis method described in JP-A-2000-144179 (corresponding to sample D).
  • alumina hydroxide / magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., “KYOWARD 330”) having a chemical composition of 2.5 MgO.Al 2 O 3 .nH 2 O was calcined at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • 4 L of calcined alumina / magnesium hydroxide (unmodified) catalyst obtained in this manner, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester
  • the autoclave was charged and the catalyst was reformed in the autoclave.
  • the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure of 3 ⁇ 10 5 Pa, 1052 g of ethylene oxide was introduced and reacted while stirring. Further, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added, and then the catalyst was filtered off to obtain MEE.
  • A2-1 EOPO (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).
  • R 4 is an alkyl group having 12 or 14 carbon atoms, s is 18 and t is 2.
  • A3-1 LMAO-1 (nonionic surfactant added with an average of 15 moles of ethylene oxide relative to natural alcohol CO-1214 (manufactured by P & G)).
  • the synthesis was performed as follows. 861.2 g of natural alcohol CO-1214 and 2.0 g of 30% NaOH aqueous solution were charged into 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 in the container was raised to 160 ° C. to obtain a reaction solution. Next, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution while stirring the reaction solution.
  • ethylene oxide was added through the blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
  • 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 was about 7, thereby obtaining LMAO-1. It was.
  • LMAO-2 nonionic surfactant added with an average of 8 moles of ethylene oxide relative to natural alcohol CO-1214 (manufactured by P & G)).
  • the synthesis was performed as follows. LMAO-2 was obtained in the same manner as the LMAO-1 synthesis method except that the amount of ethylene oxide introduced was changed to 507.4 g.
  • A4-1 was synthesized as follows. Fatty acid amine (Tokyo Chemical Industry Co., Ltd., n-hexadecylamine) was charged into an autoclave (Pressure-resistant Glass Industry Co., Ltd.) and the system was replaced with nitrogen. A tertiary amine having an average addition mole number of ethylene oxide (EO) of 2 mol was synthesized (first stage).
  • EO ethylene oxide
  • the obtained tertiary amine and an alkali catalyst NaOH; 0.8 parts by mass with respect to 100 parts by mass of the tertiary amine and 40% by mass NaOH aqueous solution
  • NaOH sodium 0.8 parts by mass with respect to 100 parts by mass of the tertiary amine and 40% by mass NaOH aqueous solution
  • the mixture was heated to 150 ° C., and ethylene oxide was added little by little until reaching a predetermined amount to obtain A4-1 having an average added mole number of EO of 20 mol ( Second stage).
  • the product was neutralized with acetic acid. Moreover, it was 1121 when the molecular weight was computed by amine value measurement.
  • A4-2 was synthesized as follows.
  • a fatty acid amine (Lion Akzo Co., Ltd., Armin 18D) is charged into an autoclave (made by pressure-resistant glass industry), the inside of the system is replaced with nitrogen, heated to 150 ° C., and propylene oxide is added little by little until a predetermined amount is reached.
  • a tertiary amine having an average addition mole number of propylene oxide (PO) of 2 mol was synthesized (first stage).
  • the obtained tertiary amine and an alkali catalyst (0.8% by mass using a 40% by mass NaOH aqueous solution) are charged into an autoclave, the inside of the system is replaced with nitrogen, and dehydration is performed by heating under reduced pressure.
  • the mixture is heated to 150 ° C., and ethylene oxide is added little by little until a predetermined amount is reached to obtain a polyoxyalkylene stearylamine having an average addition mole number of PO of 2 moles and an average addition mole number of EO of 13 moles). (Second stage). After the reaction, the product was neutralized with acetic acid. Moreover, it was 939 when molecular weight was computed by amine value measurement.
  • B1-1 castor hydrogenated oil (manufactured by NOF Corporation, “Caster Wax A Flakes”).
  • B1-2 Hardened palm oil (manufactured by Nippon Nippon Chemical Co., Ltd., “Palm Extremely Hardened Oil A”).
  • C As the component (C), the following compounds were used.
  • C-1 LAS-H (linear alkyl (carbon number 10 to 14) benzenesulfonic acid (manufactured by Lion Corporation, “Lypon LH-200”, pure content 96% by mass)).
  • C-2 Palm fatty acid (manufactured by NOF Corporation).
  • C-3 Polyoxyalkylene alkyl ether sulfate monoethanolamine salt (linear alkyl having 10 to 14 carbon atoms, PO average addition mole number 1, EO average addition mole number 3)
  • Common component a as shown in Table 1 below.
  • Common component b as shown in Table 2 below.
  • Common component c as shown in Table 3 below.
  • Common component d as shown in Table 4 below.
  • Common component e shown in Table 5 below.
  • Common component f as shown in Table 6 below.
  • Each compound included in the common components a to f is as follows.
  • Amidoamine dimethylaminopropylamide stearate (manufactured by Toho Chemical Co., Ltd.), cationic surfactant.
  • PTS-H paratoluenesulfonic acid (manufactured by Teika Co., Ltd., “Taikatox 300”).
  • -Benzoic acid Na Sodium benzoate (made by Toagosei Co., Ltd.).
  • -Citric acid Citric acid (manufactured by Yushi Kogyo Co., Ltd.).
  • PEG polyethylene glycol.
  • Coronase Coronase 48L (manufactured by Novozymes).
  • Silicone Silicone emulsion (manufactured by Shin-Etsu Chemical Co., Ltd., “KM-98”).
  • Fragrance A-1 Fragrance composition a-1-1 described in Examples of JP-A-2008-7872.
  • Fragrance A-2 Fragrance composition A described in Tables 11 to 18 of JP-A-2002-146399.
  • Fragrance B-1 BLUEFLOWERPOP “FFMHN2814” (manufactured by Firmenich).
  • Fragrance B-2 COSMICCAPS (manufactured by Givaudan)
  • Fragrance B-3 UNICAP503 (manufactured by IFF).
  • ⁇ Urea : Reagent, Junsei Chemical Co., Ltd.
  • Cluster dextrin Glico Nutrition Foods Co., Ltd.
  • Examples 1 to 26, Comparative Examples 1 to 6 A composition containing each component was prepared with the content (mass%) shown in Tables 7 to 9 by the production method shown below. Note that water (purified water) was used as a solvent, and the components other than water listed in Tables 7 to 9 and water were combined so as to be 100% by mass. The water content was “balance”.
  • ⁇ Manufacturing method> The component (A) and ethanol were placed in a 500 mL beaker, and the mixture was sufficiently stirred with a magnetic stirrer (manufactured by MITAMURA KOGYO INC.). Add optional components (excluding water and ethanol) and component (C) to this, add water so that the total amount of this solution is 90% by mass with respect to the total mass of the liquid detergent, and further stir Then, the mixture was heated to the melting point of the component (B). To this, the component (B) heated to the melting point was added and stirred until the whole became uniform (that is, each component was uniformly dispersed).
  • the filtrate was transferred to a vat (29 ⁇ 22 ⁇ 4 cm), and 10 pieces of cotton cloth (# 100 26 ⁇ 21 cm) were added and immersed for 3 minutes while turning over.
  • the cotton cloth was taken out of the vat and left overnight with the cloth upside down every 20-30 minutes. Thereafter, it was rinsed with a washing machine (manufactured by Mitsubishi Electric Corporation, “CW-C30A1-H”) for 2 minutes, dehydrated for 30 seconds, air-dried and stored in a dark place to obtain a spinach soil cloth (contaminated cloth).
  • 0.1 g of the liquid detergent after being stored at 15 ° C. for 24 hours was applied to each of 10 contaminated cloths (0.1 g of liquid detergent / one contaminated cloth) and left for 5 minutes.
  • the contaminated fabric and a commercially available T-shirt (100% cotton, manufactured by BVD) were put into a cleaning tester (Terg-O-Tometer, manufactured by UNITED STATES TESTING).
  • the input amount of the T-shirt was adjusted so that the total fabric mass was about 45 g.
  • a cleaning operation was performed in which washing was performed for 10 minutes, rinsed twice, and dehydrated for 3 minutes sequentially.
  • the contaminated cloth after the washing operation was left in a constant temperature and humidity chamber at 25 ° C. and a humidity of 65% RH for 24 hours to dry the contaminated cloth.
  • Evaluation of the coating detergency against spinach stains was determined by using the coating detergency (%) calculated by the above formula, that the detergency was good if C, B, and A in the following evaluation criteria. In addition, the average score of 10 contaminated cloths was used for the coating cleaning power (%).
  • D The cleaning rate is less than 80%.
  • Judgment criteria 1 point: Ease of pouring is very poor compared to Comparative Example 2. 2 points: Ease of pouring is slightly worse than Comparative Example 2. 3 points: equivalent to Comparative Example 2 or Comparative Example 2. 4 points: Easier to pour than in Comparative Example 2. 5 points: Ease of pouring is very good compared to Comparative Example 2.
  • Evaluation criteria A: The average score is 4.5 or more.
  • a 100 mL glass bottle (Hiroguchi standard bottle: PS-No. 6) was filled with 30 g of a liquid detergent, and 0.5 g of beads (“PFL-RED 7155T Lot. . After storing in a thermostatic bath at 25 ° C. for 1 day, the glass bottle was taken out from the thermostatic bath, the dispersion state of the beads in the liquid detergent was visually confirmed, and evaluated according to the following evaluation criteria.
  • B The beads are floating or settling.
  • Moisture content (%) (weight after drying over time (g) ⁇ initial weight (g)) / weight after drying over time (g) ⁇ 100
  • the quick drying performance was evaluated using the moisture content (%) calculated by the above formula, and when the moisture content of Comparative Example 3 after 1 hour after drying was 1, the relative moisture content in each example was obtained. Evaluation was performed according to the following criteria, and it was determined that B and A had good quick-drying performance.
  • B Relative moisture content is 0.4 or more and 0.6 or less with respect to Comparative Example 3 7 or more and 0.9 or less
  • D The relative water content is 1.0 or more with respect to Comparative Example 3.
  • the liquid detergent obtained in each example was excellent in coating cleaning power and excellent in usability. Moreover, the liquid cleaning agent obtained in each Example was able to uniformly disperse the beads. From this result, it is considered that the liquid cleaning agent obtained in each example forms a structural liquid.
  • the liquid detergent of Comparative Example 1 containing no component (A) and having a total surfactant content of 9% by mass is inferior in coating detergency and usability. It was.
  • the liquid detergent of Comparative Example 2 containing no component (A) was inferior in usability.
  • the liquid detergent of Comparative Example 3 containing no component (B) was inferior in coating cleaning power and usability.
  • the liquid cleaning agent of Comparative Example 4 having a total surfactant content of 39% by mass was inferior in coating cleaning power and usability.
  • the liquid detergent of Comparative Example 5 containing no component (C) was inferior in usability.
  • the beads could not be uniformly dispersed. Therefore, it is considered that the liquid detergents of Comparative Examples 2 to 5 do not form a structural liquid and form spherical micelles.
  • the present invention can provide a liquid detergent having excellent coating cleaning power and excellent usability, it is extremely effective industrially.

Abstract

L'invention a trait à un détergent liquide contenant des composants (A), (B) et (C) et ayant une teneur totale en tensioactifs de 45 % à 80 % en masse, par rapport à la masse totale de détergent liquide. Composant (A) : tensioactif non ionique comportant au moins un composé choisi dans un groupe constitué d'un composé de formule générale (a-1) (dans laquelle R1 représente un groupe hydrocarboné en C9 à C13, R2 représente un groupe alkylène en C2 à C4, R3 représente un groupe alkyle en C1 à C4 et m est un nombre compris entre 5 et 25) ; un composé de formule générale (a-2) (dans laquelle R4 représente un groupe hydrocarboné en C10 à C20, EO représente un groupe oxyéthylène, PO représente un groupe oxypropylène, s est un nombre compris entre 5 et 20 et t est un nombre compris entre 1 et 4) ; et un composé de formule générale (a-4) (dans laquelle R1 représente un groupe hydrocarboné en C10 à C20, A1O et A2O représentent chacun indépendamment un groupe oxyalkylène en C2 à C4, p > 0, q > 0 et p + q vaut au moins 10 mais est inférieur à 60). Composant (B) : au moins un composé choisi dans un groupe constitué par un composé de formule générale (b-1) (dans laquelle les groupes Z1 à Z3 représentent chacun indépendamment un atome d'hydrogène, un groupe hydroxyle, ou un groupe carboxyle ; a + b vaut de 7 à 19 ; c + d vaut de 7 à 19 ; et e + f = vaut de 7 à 19) et un alcool en C6 à C18. Composant (C) : tensioactif anionique.
PCT/JP2014/060809 2013-04-16 2014-04-16 Détergent liquide WO2014171476A1 (fr)

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JP2015101674A (ja) * 2013-11-26 2015-06-04 ライオン株式会社 液体洗浄剤
JP2015196813A (ja) * 2014-04-03 2015-11-09 ライオン株式会社 繊維製品用の液体洗浄剤
JP2016029130A (ja) * 2014-07-25 2016-03-03 ライオン株式会社 繊維製品用の液体洗浄剤
JP2016204508A (ja) * 2015-04-22 2016-12-08 花王株式会社 衣料用液体洗浄剤組成物
JP2018109125A (ja) * 2017-01-05 2018-07-12 第一石鹸株式会社 衣料用液体洗浄剤組成物
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