CN106133128B - Liquid detergent composition for clothes - Google Patents
Liquid detergent composition for clothes Download PDFInfo
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- CN106133128B CN106133128B CN201580015112.7A CN201580015112A CN106133128B CN 106133128 B CN106133128 B CN 106133128B CN 201580015112 A CN201580015112 A CN 201580015112A CN 106133128 B CN106133128 B CN 106133128B
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D1/835—Mixtures of non-ionic with cationic 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- 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
- C11D1/62—Quaternary ammonium 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Liquid detergent composition for clothes of the invention, it is characterized in that, contain (A) nonionic surfactant, (B) cross-linking type carboxyl vinyl polymer, (C) cationic surfactant and (D) chelating agent, and the gross mass relative to liquid detergent composition for clothes, the content of (D) ingredient are 0.03 mass % or more.
Description
Technical field
The present invention relates to liquid detergent composition for clothes.
This application claims based on April 1st, 2014 Japanese publication Patent 2014-075696 CLAIM OF PRIORITY,
This quotes its content.
Background technique
The viscosity of liquid detergent composition for clothes be related to ingredient it is dense sense or feeling of high class, it is easy to use, be not easy
The important quality of splashing.
As the thickening method of liquid detergent composition for clothes, existing makes it contain carboxylic serials macromolecule, glycol system
The method of the tackifier such as macromolecule and natural sugar system macromolecule.
However, as time goes by, viscosity is easy to reduce when using these methods, it is difficult to long-term to maintain defined viscosity.
On the other hand, the cationic surface that addition assigns degerming in liquid detergent composition for clothes and antibacterial requires
Activating agent.
In liquid detergent composition for clothes, when shown in liquid anionic property anionic property viscosify body and sun from
When sub- surfactant coexists, they form compounds and can not obtain sufficient Efficient Adhesive Promotion, thus in the presence of be difficult to viscosify to
The case where providing viscosity.
It is recorded in patent document 1: comprising nonionic surfactant, as the cross-linking type carboxyl of anionic system tackifier
In the liquid detergent composition of polyvinyl and cationic surfactant, by keeping cross-linking type carboxy vinyl poly-
Close object/cationic surfactant molar ratio within the specified scope, can make (25 DEG C) of initial viscosity for 150~
1500mPas makes rate of change in viscosity when saving 1 month at 50 DEG C be decreased below ± 20%.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2007-297510 bulletin
Summary of the invention
Problems to be solved by the invention
However, the viscosity stability in the method for patent document 1 over time is not necessarily sufficient, need better
Good viscosity stability.
It is used the purpose of the present invention is to provide a kind of containing the clothing of anionic system tackifier and cationic surfactant
Liquid detergent composition with good washing performance and antibiotic property and has good viscosity and viscosity stability.
The means solved the problems, such as
Liquid detergent composition for clothes of the invention has following form.
[1] a kind of liquid detergent composition for clothes, which is characterized in that contain following (A) ingredients, (B) ingredient, (C)
Ingredient and (D) ingredient, and the gross mass relative to liquid detergent composition for clothes, the content of (D) ingredient are 0.03 matter
Measure % or more；
(A) ingredient: nonionic surfactant；
(B) ingredient: cross-linking type carboxyl vinyl polymer；
(C) ingredient: cationic surfactant；
(D) ingredient: chelating agent.
[2] such as the liquid detergent composition for clothes of [1] record, wherein (D) ingredient is amino carboxylic acid system chelating
Agent.
[3] such as the liquid detergent composition for clothes of [1] record, wherein (D) ingredient is to select the sweet ammonia of free methyl
Sour oxalic acid, methylglycine diacetic acid salt, Pidolidone oxalic acid, Pidolidone diacetin, five second of diethylenetriamines
Acid, diethylentriamine pentacetate, ethylenediamine succinic acid, ethylenediamine succinic acid salt, 3- hydroxyl -2,2'- imino-diacetic fourth two
Acid, 3- hydroxyl -2,2'- imino disuccinates, L-Aspartic acid-N, N- oxalic acid and L-Aspartic acid-N, N- oxalic acid
At least one of the group that salt is constituted chelating agent.
[4] such as the liquid detergent composition for clothes of [1] record, wherein relative to the total of liquid detergent composition
Quality, the content of (A) ingredient are 5~40 mass %.
[5] such as the liquid detergent composition for clothes of [1] record, wherein relative to the total of liquid detergent composition
Quality, the content of (B) ingredient are 0.05~1 mass %.
[6] such as the liquid detergent composition for clothes of [1] record, wherein relative to the total of liquid detergent composition
Quality, the content of (C) ingredient are 0.01~1.5 mass %.
[7] such as the liquid detergent composition for clothes of [1] record, wherein the quality indicated with (C) ingredient/(D) ingredient
Than being 0.1~17.0.
[8] such as the liquid detergent composition for clothes of [1] record, wherein the quality indicated with (B) ingredient/(C) ingredient
Than being 0.09~8.0.
[9] such as the liquid detergent composition for clothes of [1] record, wherein the quality indicated with (B) ingredient/(D) ingredient
Than being 0.09~14.0.
Invention effect
According to the present invention, it can get the clothing containing anionic system tackifier and cationic surfactant to wash by liquid
Agent composition with good washing performance and antibiotic property and has good viscosity and viscosity stability.
Specific embodiment
" liquid detergent composition for clothes "
Liquid detergent composition for clothes of the invention is (hereinafter, in the presence of the feelings for being only called liquid detergent composition
Condition.) contain (A) nonionic surfactant (hereinafter also referred to as (A) ingredient), (B) cross-linking type carboxyl vinyl polymer
(hereinafter also referred to as (B) ingredient), (C) cationic surfactant (hereinafter also referred to as (C) ingredient) and (D) chelating agent (hereinafter,
Also referred to as (D) ingredient).
Hereinafter, being described in detail to each ingredient.
In the range of specification and claims, alkyl can be linear chain or branched chain, unless otherwise indicated.In addition, alkene
Base can be linear chain or branched chain, unless otherwise indicated.
" water solubility " in the present invention refers to that the solubility at 25 DEG C is 0.1g or more/100g water.
<(A) ingredient>
(A) ingredient is a kind of nonionic surfactant.In the present invention, (A) ingredient is the ingredient for undertaking washing function,
By the way that washing performance can be improved containing (A) ingredient.(A) ingredient also contributes to improving liquid stability.
It as (A) ingredient used in the present invention, is not particularly limited, institute in liquids in general detergent composition can be used
The nonionic surfactant used.
As nonionic surfactant, preferably poly (oxyalkylene) fundamental mode nonionic surfactant, as concrete example
Son can enumerate the following general formula (1) compound represented (hereinafter also referred to as compound (1)).
[changing 1]
R5-Y-(AO)n-R6 (1)
[in formula, R5It is the alkyl of carbon atom number 9~22 or the alkenyl of carbon atom number 9~22, R6It is hydrogen atom or carbon atom
The alkyl of number 1~3 or the alkenyl of carbon atom number 2~3 ,-Y- are-O- or-COO-, and AO indicates the oxygen alkylene of carbon atom number 2 or 3
Base, n indicate the average addition molal quantity of oxyalkylene.]
In general formula (1), when-Y- is-O-, preferably R5For the alkyl or carbon atom number 10~22 of carbon atom number 10~22
Alkenyl and R6For hydrogen atom.
That is, when-Y- is-O-, compound (1) preferably the following general formula (1') shown in saturated or unsaturated alcohol
Alcoxylates.
R5-O-(AO)n-H...(1')
[general formula (1') in, R5, AO and n meaning as above-mentioned.]
When-Y- is-O-, R5The preferably alkyl of carbon atom number 10~20 or the alkenyl of carbon atom number 10~20, it is more excellent
Select the alkyl of carbon atom number 10~16 or the alkenyl of carbon atom number 10~16.Specifically, preferably decyl, undecyl, 12
Alkyl, tridecyl, myristyl, pentadecyl, cetyl, decynyl, hendecyne base, dodecyne base, 13 carbon
Alkynyl, 14 carbyne bases, pentadecane alkynyl and hexadecine base.
In general formula (1), when-Y- is-COO-, preferably R5For the alkyl or carbon atom number 9~21 of carbon atom number 9~21
Alkenyl and R6For the alkyl of carbon atom number 1~3 or the alkenyl of carbon atom number 2~3.That is, when-Y- is-COO-, chemical combination
Object (1) is preferably saturated or undersaturated aliphatic acid ester shown in the following general formula (1 ").
R5-COO-(AO)n-R6...(1″)
[in general formula (1 "), R5、R6, AO and n meaning as above-mentioned.]
When-Y- is-COO-, R5The preferably alkyl of carbon atom number 11~21 or the alkenyl of carbon atom number 11~21.Tool
For body, preferably undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, ten
Eight alkyl, isooctadecane base, nonadecyl, eicosyl, undecyne base, dodecyne base, tridecyne base, 14 alkynyls, 15
Alkynyl, hexadecine base, 17 alkynyls, octadecyne base, different octadecyne base, 19 alkynyls and 20 alkynyls.
R6The preferably alkyl of carbon atom number 1 or 2.
In general formula (1), AO is the oxyalkylene of carbon atom number 2 or 3, i.e. oxygen ethylidene (hereinafter also referred to as EO) or oxygen is sub-
Propyl (hereinafter also referred to as PO).
It, can be only comprising any one of EO and PO or to include the two as oxyalkylene in compound (1).In addition,
When simultaneously including EO and PO, EO and PO can be by random additions or as block by addition.
When simultaneously including EO and PO, relative to the gross mass of whole oxyalkylenes, the total amount of EO be preferably 60 mass % with
Upper, 100 mass % or less.More particularly, it is preferable that 60~100 mass %, more preferable 70~100 mass %.
In general formula (1), n indicates the average addition molal quantity of oxyalkylene.Compound (1) is to be added to alkylene oxide open loop
Hydrophobic based raw material is (for example, primary alconol (R5- OH), secondary alcohol and fatty acid alkyl esters etc.) obtained by compound, n is each molecule chemical combination
The average value of the molal quantity of the alkylene oxide for being added to hydrophobic based raw material of object (1).
N is preferably 2~20, and more preferable 5~20.By making n within the above range, the raising effect of washing performance can be sufficiently obtained
Fruit.
In the manufacture of compound (1), using base catalysts such as general sodium hydroxide or potassium hydroxide by alkylene oxide addition
When to hydrophobic based raw material, n is preferably 5~20, and more preferable 6~18.By making n 20 hereinafter, mentioning for washing performance can sufficiently be obtained
High effect；By making 5 or more n, the high-temperature stability of liquid detergent composition can be improved.
In addition, being added to Al using what Japanese Patent Laid-fair 6-15038 bulletin was recorded3+、Ga3+、In3+、Tl3+、Co3 +、Sc3+、La3+And Mn2+The specific alkoxylating catalysts such as the magnesia of equal metal ions, add to hydrophobic group for alkylene oxide
When raw material, n is preferably 3~10, and more preferable 3~7.
In compound (1), the addition molal quantity distribution (distribution of alkylene oxide addition molal quantity) of alkylene oxide is according to addition epoxy
Reaction method when alkane and it is different.
For example, when alkylene oxide being added to hydrophobic based raw material using above-mentioned general base catalyst, alkylene oxide addition mole
Number distribution becomes wider.
In addition, the specific alkoxylating catalyst recorded using above-mentioned Japanese Patent Laid-fair 6-15038 bulletin is by ring
When oxygen alkane adds to hydrophobic based raw material, the distribution of alkylene oxide addition molal quantity is become narrow.
(A) ingredient used in the present invention can be distributed wide substance or alkylene oxide addition for alkylene oxide addition molal quantity and rub
The substance of your number narrowly distributing.In particular, as (A) ingredient, by the substance and alkylene oxide of alkylene oxide addition molal quantity wider distribution
Simultaneously washing performance can be improved in the substance of addition molal quantity narrow distribution if, so it is preferred that.
In the present invention, (A) ingredient can be used alone any one or be used in combination two or more.
For example, it is appointing in the alcohol alkoxylates of-O- that the-Y- in above compound (1), which can be used, as (A) ingredient
More than one or use-Y- are more than any in the aliphatic ester of-COO-, or use their mixture.
Wherein, when using alcohol alkoxylates as (A) ingredient, particularly preferred following (A ') ingredients and (A ") ingredient are simultaneously
With.By the way that they are used in combination, the low-temperature stability of washing performance and composition appearance can be improved simultaneously.
(A ') ingredient: oxidation of primary alcohols Addition on ethylene object, wherein the average addition molal quantity of n is 10~20, and relative to complete
Portion's carbochain quality, R5In branched univalent alkyl and monovalence alkenyl total proportion be 70 mass % or less (preferably
60 mass % or less).
(A ") ingredient: oxidation of primary alcohols Addition on ethylene object, wherein the average addition molal quantity of n is 5~15, and relative to complete
Portion's carbochain quality, R5In branched univalent alkyl and monovalence alkenyl total proportion be 80 mass % or more (preferably
90 mass % or more, more preferable 95 mass % or more).
In above-mentioned (A ') ingredient, relative to whole carbochain quality, R5In branched univalent alkyl and monovalence alkenyl
Amounting to proportion is preferably 0~70 mass %, more preferable 0~60 mass %.
In above-mentioned (A ") ingredient, relative to whole carbochain quality, R5In branched univalent alkyl and monovalence alkenyl
Amounting to proportion is preferably 80~100 mass %, more preferable 90~100 mass %, further preferred 95~100 mass %.
By quality ratio, the mixed proportion of (A ') ingredient and (A ") ingredient preferably (A ') ingredient/ingredient=1/5 (A ")~
In the range of 5/1.By making 1/5 times or more of ratio (A ") ingredient of (A ') ingredient, washing performance can be improved, on the other hand,
By make 5 times of ratio (A ") ingredient of (A ') ingredient hereinafter, the low-temperature stability of composition appearance can be improved.
As the suitable specific example of (A ') ingredient, can enumerate in CO-1214 (ProductName, carbon atom number 12,14:P&G public affairs
Department's manufacture) and the natural alcohols such as ECOROL (ProductName, carbon atom number 12 and 14:Ecogreen Oleochemicals company manufacture)
Substance obtained by the ethylene oxide of upper 15 molar equivalent of addition and (trade name, carbon atom number 13: Mitsubishi Chemical is public in Diadol
Department's manufacture) etc. substance etc. obtained by the ethylene oxide of 15 molar equivalent of addition on the synthol that is obtained by oxo synthesis.
Wherein, particularly preferably on the natural alcohol of carbon atom number 12 and 14 obtained by the ethylene oxide of 15 molar equivalent of addition
Substance.
As the suitable specific example of (A "), it can enumerate and the resulting C12 alkene of butylene trimerizing is being supplied in carbonyl conjunction
Substance (BASF AG's system obtained at the ethylene oxide of 7 moles of addition or 10 molar equivalents on 1 mole of C13 alcohol obtained by method
Make, ProductName: Lutensol TO7, Lutensol TO10) etc..
As other suitable specific examples other than the above of (A) ingredient, for example, the ethylene oxide addition of secondary alcohol can be enumerated
Object.
As the ethylene oxide adduct of secondary alcohol, the ethylene oxide adduct etc. of the secondary alcohol of containg branched alkyl radical can be enumerated.On
Stating the atomic number of alkyl carbon in ethylene oxide adduct is preferably 11~13, ethylene oxide be averaged addition molal quantity be preferably 6~
12。
Relative to the gross mass of liquid detergent composition, the content of (A) ingredient is preferably 5~40 mass %, more preferably
For 10~20 mass %.By making content more than 5 mass %, washing performance can be improved, on the other hand, due to content even more than
40 mass % do not observe dramatically increasing for washing performance yet, and therefore, content is economical below 40 mass %.
<(B) ingredient>
(B) ingredient is cross-linking type carboxyl vinyl polymer, is a kind of anionic system tackifier.
By making liquid detergent composition contain (B) ingredient, can obtain as liquid detergent composition for clothes
It is suitable for viscosity.Suitable viscosity as clothing means liquid detergent composition being directly applied to dirt in bottle or lid
When on dirty part, playing has thixotropic viscosity, and liquid disconnects well, and liquid does not drip.Thixotropy is property below:
Under static state, mobility is low, and by stirring or shaking, mobility is got higher, and when keeping its static, it is low to turn again to mobility
State.
(B) ingredient is that have carboxyl and the polymer with cross-linked structure, in terms of its molecular structure, it is believed that carboxyl is in water
When ionized, by the ion repulsions of intramolecular, mesh-shape is diffused into water and by the way that hydrone to be maintained in structure,
There is thixotropic viscosity to embody.
As in the present invention it is preferable to use (B) ingredient, for example, can enumerate by acrylic acid, methacrylic acid or they
Crosslinking obtained by the copolymer of one or more of monomer that ester is constituted and alkyl acrylate is crosslinked by crosslinking agent is poly-
Close object.
The preferred carbon atom number 8~40 of the alkyl chain length of alkyl acrylate, more preferable 10~30.The carbon atom number is 8
When above, polymer is easy to be swollen；When carbon atom number is 40 or less, the good solubility that is easily obtained in water.Acrylic acid alkyl
In ester, as the specific example of alkyl chain, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, ten can be enumerated
Tetraalkyl, pentadecyl, cetyl, heptadecyl, octadecyl, isooctadecane base, nonadecyl, eicosyl, 20
One alkyl, docosyl, tricosyl, tetracosyl, pentacosyl, cerul, heptacosane base, 20
Eight alkyl, nonacosyl and melissyl.
As crosslinking agent, the allyl ether of sucrose and the allyl ether of pentaerythrite etc. can be enumerated.
As specific example, acrylic alkyl ester copolymer (INCI: acrylate/C10-30 third can be enumerated
Olefin(e) acid alkyl ester cross-linked polymer) etc..
As the allyl ether crosslinking agent by the allyl ether of sucrose and pentaerythrite by acrylic acid and acrylic acid alkyl
The example of cross-linked polymer obtained by the copolymer of ester (carbon atom number 10~30 of alkyl chain) is crosslinked, can enumerate
Carbopol Ultrez21、Carbopol Ultrez20、Carbopol EZ4、Carbopol EZ5、Carbopol 1342、
Carbopol 1382、Carbopol ETD2020、PemulenTR-1、PemulenTR-2、Carbopol AquaSF-1、
Carbopol Ultrez20 and Carbopol ETD2020 (being ProductName, Lubrizol Corp.'s manufacture).
In addition, as (B) ingredient, it is possible to use main chain is polyacrylic acid and the polyacrylic acid is crosslinked by crosslinking agent
And the cross-linking type polyacrylic acid formed.As polyacrylic acid, for example, the poly- of Japan Patent examined patent publication 32-4141 record can be enumerated
Acrylic acid.As crosslinking agent, allyl sucrose and pentaerythrite etc. can be enumerated.
(B) ingredient is that a kind of anionic system for show anionic property in a liquid viscosifies body, can with as (C) ingredient
Cationic surfactant forms ion complex and is precipitated.When generating this precipitation, it is unable to fully obtain by (B) at separating
The Efficient Adhesive Promotion risen, and the case where there are liquid appearance gonorrhoeas.
Further, since existing simultaneously the chelating agent (D) of display anionic property in liquid, and by with ionic caused screening
Effect is covered, the formation of the eyed structure as caused by (B) ingredient becomes inadequate.When the formation of eyed structure is insufficient, Wu Fachong
Separately win to obtain the Efficient Adhesive Promotion as caused by (B) ingredient.
Relative to the gross mass of liquid detergent composition, the content of (B) ingredient is preferably 0.05~1 mass %, more excellent
Select 0.1~0.5%.When the content is 0.05 mass % or more, even if being also easy to obtain in the case where (C) ingredient and (D) ingredient coexist
Obtain sufficient Efficient Adhesive Promotion.When content is below 1 mass %, the viscosity of liquid is not excessively high, is easily obtained into clothes fiber
The excellent permeability in portion.
In liquid detergent composition of the invention, the water-soluble cross-linked type carboxyl second as (B) ingredient can be used directly
Alkenyl polymer.
In addition, the partially or completely neutralization salt of water-soluble cross-linked type carboxyl vinyl polymer also can be used.In this feelings
It under condition, may be used at before preparing liquid detergent composition, the polymer is partially or completely neutralized in advance and is obtained
Salt.In addition, maying be used in the process for preparing composition, the partially or completely neutralization salt of the polymer.
In use, to use in the form of the partially or completely neutralization salt by water-soluble cross-linked type carboxyl vinyl polymer
To alkali compounds.As the alkali compounds, monoethanolamine, diethanol amine, triethanolamine, 2- amino -2- first can be enumerated
The alkanolamines such as base -1- propyl alcohol, 2- amino-2-methyl -1,3- propylene glycol, isopropanolamine and diisopropanolamine (DIPA)；Sodium hydroxide and hydrogen
The alkali metal hydroxides such as potassium oxide；The basic amino acids such as arginine and lysine；And ammonia etc..In general, using monoethanolamine,
Diethanol amine, triethanolamine, isopropanolamine, diisopropanolamine (DIPA) and sodium hydroxide.
For the additive amount of these alkali compounds, anionic property polymer crosslinking type carboxylic is used as long as sufficiently neutralizing
The amount of base polyvinyl can suitably be set according to the type and usage amount of cross-linking type carboxyl vinyl polymer
It is fixed.
<other tackifier>
In detergent composition of the invention, can obtain in desired effective scope, can also and with other than (B) ingredient
Other tackifier.For example, its thickening can also be made by mixing non-crosslinked type macromolecule.However, these non-crosslinked high molecular increasings of type
Viscous inefficient, it is then desired to largely use.In this case, macromolecule or natural polymer are either synthesized, is all easy to
Cause liquid separation etc., that is to say, that appearance stability is easy to be deteriorated, and brings adverse effect to the stability of enzyme.Further, since
The degree of stringiness as one of liquid physical property increases, and liquid disconnection property is deteriorated, and can lead to the problem of usability.
Relative to the gross mass of detergent composition, the non-crosslinked high molecular usage amount of type be preferably 0.5 mass % hereinafter,
More preferable 0.3 mass % is hereinafter, most preferably zero.Specifically, preferably 0~0.5 mass %, more preferable 0~0.3 mass %.
<(C) ingredient>
It is suitable for using the well known cationic surface activity in liquid detergent composition for clothes as (C) ingredient
Agent.By making that highly viscous ageing stability can be mentioned containing (C) ingredient in liquid detergent composition.In addition, also assigning clothing
It washes the degerming of agent composition or antibiotic property by liquid, and the smelly effect of suppression of the clothes smell after inhibition is washed or after dry can be obtained
Fruit.
As (C) ingredient, preferably monovalent cation surfactant.Especially in terms of mixed stability, preferred ammonium
Salt form cationic surfactant, more preferable the following general formula (2) compound represented.
[changing 2]
[in formula, for R1~R4, R1And R2Respectively stand alone as the alkyl or carbon atom number 8~10 of carbon atom number 8~10
Alkenyl and R3And R4For methyl or R1For benzyl, R2For the alkyl and R of carbon atom number 12~143And R4For methyl or R1For
The alkyl of carbon atom number 16~18 or the alkenyl and R of carbon atom number 16~182、R3And R4For methyl.X-For halide ion or alkyl
Sulfate ion.]
In formula (2), R1~R4Meet the either condition in following (c1)~(c3).
(c1): R1And R2Respectively stand alone as the alkyl of carbon atom number 8~10 or the alkenyl and R of carbon atom number 8~103And R4
For methyl.It is preferred that dialkyl dimethyl is cationic.
(c2): R1For benzyl, R2For the alkyl and R of carbon atom number 12~143And R4For methyl.It is preferred that monoalkyl monobenzyl
Dimethyl cation.
(c3): R1For the alkyl of carbon atom number 16~18 or the alkenyl and R of carbon atom number 16~182、R3And R4For methyl.
It is preferred that monoalkyl trimethyl is cationic.
In formula (2), as X-Halide ion, for example, chloride ion, bromide ion, fluorine ion and iodide ion can be enumerated.As
X-Alkylsurfuric acid, for example, the alkylsurfuric acid ion of carbon atom number 1~3 shown in the following general formula (x1) can be enumerated.
R7-SO4 -(x1)
[in formula (x1), R7For the alkyl of carbon atom number 1~3.]
As X-, the preferred alkylsurfuric acid ion of chloride ion, bromide ion, iodide ion or carbon atom number 1~3.
The preferred specific example of satisfaction (c1) condition as (C) ingredient, the atomic number of alkyl carbon that can enumerate straight-chain are
Didecyldimethyl ammonium salt (for example, " Arquad 210 " of Shi Wang Aksu company manufacture) etc. of 10 substance as main body.
The preferred specific example of satisfaction (c2) condition as (C) ingredient can enumerate benzalkonium chloride (for example, lion king's Acker
" the Arquad CB " of Su company manufacture) etc..
The preferred specific example of satisfaction (c3) condition as (C) ingredient, can enumerate R1For the stearyl front three of stearyl
Base ammonium salt is (for example, " the Arquad T-800 " and R of the manufacture of the Aksu Shi Wang company1For the octadecyl trimethyl of octadecyl
Ammonium salt etc..
(C) ingredient can be used alone one kind or is used in combination two or more.
Relative to the gross mass of liquid detergent composition, the content of (C) ingredient is preferably 0.01~1.5 mass %, more
It is preferred that 0.1~0.8 mass %, further preferred 0.2~0.8 mass %.When the content is 0.01 mass % or more, it can obtain
The abundant Efficient Adhesive Promotion as caused by (B) ingredient, meanwhile, the ageing stability of its viscosity can be also improved well.In addition, being also easy to
Obtain the good smelly effect of suppression.When the content is 1.5 mass % or less, the formation with the compound of (A) ingredient is easy to be pressed down
System is in less level.As a result, being easy to prevent the gonorrhoea of liquid appearance, and it is easily obtained liquid viscosity appropriate.
<(D) ingredient>
(D) ingredient is chelating agent.The known chelating agent as metal ion block agent in detergent applications can be used.This
In invention, by containing (D) ingredient, the ageing stability of liquid viscosity can be improved.Although its reason is unclear, due to
(D) ingredient shows anionic property in a liquid, can form compound with (C) ingredient.So, it is believed that (B) ingredient and (C) ingredient
The formation of compound is partially hindered, and is easy to sufficiently obtain the Efficient Adhesive Promotion as caused by (B) ingredient.
In addition, passing through the weak compound for forming (B) ingredient, (C) ingredient and (D) ingredient, it is believed that the net as caused by (B) ingredient
Ocular structure becomes difficult to decompose, and becomes prone to obtain the ageing stability of viscosity.
Further, since the formation of (B) ingredient and the compound of (C) ingredient is suppressed, liquid gonorrhoea is also suppressed.
As (D) ingredient, the chelating agent with carboxylic acid group or its salt of preferably 3~4 valences.It is sub as its concrete example, it can
Enumerate citric acid, sodium citrate and amino carboxylic acid system chelating agent.Amino carboxylic acid refers in a molecule comprising carboxyl and from ammonia, primary amine
Or a hydrogen atom is removed in secondary amine and at least each 1 compound of 1 valence functional group for being formed；Amino carboxylic acid system chelating agent refers to
Chelating agent as amino carboxylic acid.
In these, in terms of viscosity stability after being saved, preferred aminocarboxylic chelants.
Amino carboxylic acid system chelating agent can be used in detergent applications as substance well known to chelating agent.As concrete example
Son can enumerate methylglycine diacetic acid (MGDA), methylglycine diacetic acid salt, Pidolidone oxalic acid (GLDA), L- paddy
Propylhomoserin diacetin, diethylene-triamine pentaacetic acid (DTPA), diethylentriamine pentacetate, ethylenediamine succinic acid
(EDDS), ethylenediamine succinic acid salt, 3- hydroxyl -2,2'- imino-diacetic succinic acid (HIDS), 3- hydroxyl -2,2'- imino-diacetic fourth
Diacid salt, L-Aspartic acid-N, N- oxalic acid and L-Aspartic acid-N, N- diacetin etc..As the type of salt, preferably (sodium
Salt).More preferable MGDA or its salt, particularly preferred methylglycine diacetic acid trisodium.
Relative to the gross mass of liquid detergent composition, the content of (D) ingredient is preferably 0.03 mass % or more, more excellent
Select 0.04 mass % or more, further preferred 0.06 mass % or more.When the content is 0.03 mass % or more, it is easy to abundant
The ageing stability improvement effect or liquid gonorrhoea for obtaining the liquid viscosity as caused by (D) ingredient prevent effect.
On the other hand, when the content of (D) ingredient is excessive, the liquid Efficient Adhesive Promotion as caused by (B) ingredient is reduced, and therefore, is
Acquisition liquid viscosity appropriate, needs to increase the additive amount of (B) ingredient, and manufacturing cost is got higher.In addition, even if (D) ingredient
Content is more than 1.0 mass %, does not also observe the increase of the ageing stability improvement effect of viscosity, thus, economically preferably
For 1.0 mass % hereinafter, more preferable 0.6 mass % is hereinafter, further preferred 0.5 mass % or less.More specifically, it is preferable to 0.03
~1.0 mass %, more preferable 0.04~0.6 mass %, further preferred 0.06~0.5 mass %.
<(E) ingredient>
(E) ingredient is water-soluble metal salt.The substance of hydrate form can also be used in water-soluble metal salt.
As (E) ingredient, for example, water soluble silver salt, water-soluble copper salt, water-soluble zinc salt, water-soluble iron salts, water can be enumerated
Dissolubility manganese salt, water-soluble aluminum salt or their hydrate etc..Wherein, preferably water soluble silver salt, water-soluble copper salt, water-soluble zinc salt
Or their hydrate, more preferable water-soluble zinc salt, water-soluble copper salt or their hydrate, particularly preferred water-soluble zinc salt or
Its hydrate.
As water soluble silver salt, specifically, can enumerate silver sulfate (meltage 0.83g: water 100g, below as note
Carry) and silver nitrate (70.7g) etc..
As water-soluble copper salt, specifically, copper nitrate (60.8g), copper sulphate (18.2g) and copper chloride can be enumerated
(75.7g) etc..Wherein, preferably sulfuric acid copper hydrate, more preferable copper sulfate pentahydrate.
As water-soluble zinc salt, specifically, zinc nitrate (56.1g), zinc sulfate (36.49g), zinc chloride can be enumerated
(77g) and zinc acetate (40.0g) etc., preferably sulfuric acid zinc and zinc chloride.
As water-soluble iron salts, specifically, ferric sulfate (29.5g) etc. can be enumerated.
As water-soluble manganese, specifically, manganese chloride (72.3g) etc. can be enumerated.
Water-soluble metal salt can be used alone one kind or to be used in combination two or more.
In the present invention, it can improve clothing containing (E) ingredient in liquid detergent composition by making and wash agent group by liquid
The degerming or antibiotic property of object are closed, and improves the smelly effect of suppression of the clothes smell after inhibition is washed and after dry.Though its reason is not
It is clear, but it is presumably due to the combination of the protein in the presence of the cellular matrix of bacterium and metal ion.
Relative to the gross mass of liquid detergent composition, the content of (E) ingredient in liquid detergent composition is preferred
For 0.05~2 mass %, more preferable 0.1~1 mass %.Content within the above range when, be easy to sufficiently obtain and press down smelly effect.
<other ingredients>
, within the scope of the effect of the invention, can be as needed in liquid detergent composition of the invention, it is mixed into
Other ingredients other than above-mentioned (A)~(E) ingredient and other tackifier.
It as other ingredients, is not particularly limited, can be mixed into liquid detergent composition for clothes and usually be used
Ingredient.
As specific example, the surfactant other than water and ethyl alcohol equal solvent, (A) ingredient or (B) ingredient can be enumerated, increased
Solvent (or viscosity reductant), preservative, washing performance auxiliary agent, quality enhancer, pH regulator, moves dye preventing agent, is dirty again antioxidant
Contaminate preventing agent, pearling agent, soil releasing agent, fragrant agent, capsule fragrance, colorant, opacifiers, fluorescer, enzyme and extract etc..
As solvent, preferably water.
Relative to the gross mass of liquid detergent composition, the content of solvent is preferably 60~94 mass %, and more preferable 75
~90 mass %.
<(C) ingredient/(D) ingredient>
" (C) ingredient/(D) ingredient mass ratio " in the present invention means relative to (D) ingredient in liquid detergent
The ratio (mass ratio) (meaning of other ingredient ratios is also identical) of (C) component content of content.
In the present invention, (C) ingredient/(D) ingredient mass ratio is preferably 0.1~17.0, and more preferable 0.2~14.0.(C) at
Point/(D) ingredient more than the lower limit value of above range when, be easy to sufficiently obtain by the smelly effect of suppression caused by (C) ingredient, and (D)
Ingredient is not excessive, it is therefore easy to obtain liquid viscosity appropriate.(C) ingredient/(D) ingredient above range upper limit value with
When lower, it is easily obtained the good ageing stability of viscosity, and since (C) ingredient is not excessive, therefore, it is difficult to generate gonorrhoea etc. no
Good liquid appearance.
<(B) ingredient/(C) ingredient>
In the present invention, (B) ingredient/(C) ingredient mass ratio is preferably 0.09~8.0, and more preferable 0.1~5.0.(B) at
Point/(C) ingredient more than the lower limit value of above range when, be easy to sufficiently obtain the Efficient Adhesive Promotion as caused by (B) ingredient, and be easy to
Obtain the good ageing stability of viscosity.In addition, since (C) ingredient is not excessive, therefore, it is difficult to generate the undesirable liquid such as gonorrhoea
It is external to see.(B) when ingredient/(C) ingredient is below the upper limit value of above range, it is easy to sufficiently obtain the suppression caused by (C) ingredient
Smelly effect, and since (B) ingredient is not excessive, thus, it is also easy to obtain liquid viscosity appropriate.
<(B) ingredient/(D) ingredient>
In the present invention, (B) ingredient/(D) ingredient mass ratio is preferably 0.09~14.0, and more preferable 0.13~9.0.(B)
When ingredient/(D) ingredient is more than the lower limit value of above range, it is easy to sufficiently obtain the Efficient Adhesive Promotion as caused by (B) ingredient.(B)
When ingredient/(D) ingredient is below the upper limit value of above range, it is easily obtained the good ageing stability of viscosity.
Liquid detergent composition for clothes of the invention contain following (A) ingredients, (B) ingredient, (C) ingredient and (D) at
Point, and the gross mass relative to liquid detergent composition for clothes, the content of (D) ingredient are preferably 0.03 mass % or more.
(A) ingredient: nonionic surfactant is above-mentioned formula (1) compound represented.
(B) ingredient: one or more of monomer being made of acrylic acid, methacrylic acid or their ester and alkyl acrylate
Cross-linked polymer obtained by the copolymer of base ester is crosslinked by crosslinking agent.
(C) ingredient: cationic surfactant is cationic surfactant shown in above-mentioned formula (2), and formula
(2) R in1~R4Meet the either condition in following (c1)~(c3).
(c1): R1And R2Respectively stand alone as the alkyl of carbon atom number 8~10 or the alkenyl and R of carbon atom number 8~103And R4
For methyl.
(c2): R1For benzyl, R2For the alkyl and R of carbon atom number 12~143And R4For methyl.
(c3): R1For the alkyl of carbon atom number 16~18 or the alkenyl and R of carbon atom number 16~182、R3And R4For methyl.
(D) ingredient: chelating agent, selected from by methylglycine diacetic acid, methylglycine diacetic acid salt, Pidolidone two
Acetic acid, Pidolidone diacetin, diethylene-triamine pentaacetic acid, diethylentriamine pentacetate, ethylenediamine succinic acid, second
Diamines succinate, 3- hydroxyl -2,2'- imino-diacetic succinic acid, 3- hydroxyl -2,2'- imino disuccinates, L- asparagus fern ammonia
At least one of the group that acid-N, N- oxalic acid and L-Aspartic acid-N, N- diacetin are constituted.
Liquid detergent composition for clothes of the invention contain following (A) ingredients, (B) ingredient, (C) ingredient and (D) at
Point, and the gross mass relative to liquid detergent composition for clothes, the content of (D) ingredient are preferably 0.03 mass % or more.
(A) ingredient: nonionic surfactant, it includes selected from the group being made of following (A ') ingredients and (A ") ingredient
At least one of surfactant.
(A ') ingredient: oxidation of primary alcohols Addition on ethylene object shown in above-mentioned formula (1 '), wherein average addition molal quantity n is 10
~20, R5In branched univalent alkyl and monovalence alkenyl total proportion be 70 mass % or less.
(A ") ingredient: oxidation of primary alcohols Addition on ethylene object shown in above-mentioned formula (1 "), wherein average addition molal quantity n is 5~
15、R5In branched univalent alkyl and monovalence alkenyl total proportion be 80 mass % or more.
(B) ingredient: cross-linked polymer is one in the monomer being made of acrylic acid, methacrylic acid or their ester
Kind or more be crosslinked with the copolymer of alkyl acrylate by crosslinking agent obtained by cross-linked polymer, and alkyl acrylate
Alkyl chain length be carbon atom number 8~40.
(C) ingredient: cationic surfactant is cationic surfactant shown in above-mentioned formula (2), and formula
(2) R in1~R4Meet the either condition in following (c1) or (c2).
(c1): R1And R2Respectively stand alone as the alkyl of carbon atom number 8~10 or the alkenyl and R of carbon atom number 8~103And R4
For methyl.
(c2): R1For benzyl, R2For the alkyl and R of carbon atom number 12~143And R4For methyl.
(D) ingredient: citric acid or methylglycine diacetic acid salt.
<manufacturing method of liquid detergent composition for clothes>
The preparation method of liquid detergent composition for clothes of the invention is not particularly limited, can be such as common liquid
Body detergent composition is conventionally prepared, for example, can be prepared by the following method: be mixed into above-mentioned essential component and according to
The above-mentioned any ingredient and suitable quantity of water needed, and they are mixed.
For example, can easily prepare liquid detergent composition for clothes by the following method: by (A) ingredient and (B) at
Divide after being respectively dissolved in water, the solution of (B) ingredient is slowly added in the solution of (A) ingredient, and in the mixed liquor
(C) ingredient and (D) ingredient is added.
<viscosity of liquid detergent composition for clothes>
The viscosity of liquid detergent composition of the invention can type and combined amount by adjusting (B) ingredient, (C) ingredient
Type and the type and combined amount of combined amount and (D) ingredient control.
Suitable viscosity in liquid detergent composition for clothes is preferably determined according to aftermentioned initial viscosity measuring method
30 DEG C at viscosity be 80~3000mPas, more preferable 100~2500mPas, further preferred 150~1500mPa
s.When the viscosity is 80mPas or more, even if direct coating detergent composition, liquid are also difficult at the dirt of clothing
Drippage, and the composition residual in coating detergent composition on clothing also becomes good.It is brought adequately to user
The dense sense of ingredient and feeling of high class.
On the other hand, when the viscosity is 3000mPas or less, permeability of the detergent composition into clothing becomes good
Good, Painting effect improves.In addition, be easy to take out and be difficult to from bottle the residual such as covering, thus, service condition is good.
According to the present invention, it can get liquid detergent composition for clothes below: being determined according to aftermentioned measuring method
(30 DEG C) of initial viscosity be 80~3000mPas, preferably 100~2500mPas, and gluing when being saved 2 months at 60 DEG C
Spending change rate is 40% or more, preferably 50% or more.
Obtainable liquid detergent composition for clothes is more preferably following composition: according to aftermentioned measuring method
(30 DEG C) of identified initial viscosity are 150~1500mPas, and rate of change in viscosity when saving 6 months at 60 DEG C is 40%
More than, preferably 50% or more.
<measuring method of initial viscosity>
After just preparing liquid detergent composition for clothes, 60g is taken to be put into bottle, it is small that 1 is stood in 30 DEG C of water-bath
Shi Hou measures viscosity with Brookfield viscometer, obtains initial viscosity.The determination condition of viscosity is as follows: 30 DEG C, 30rpm, 30 seconds, using
No.3 rotor.However, using No.2 rotor when being less than 1000mPas.
<pH of liquid detergent composition for clothes>
The pH (30 DEG C) of liquid detergent composition of the invention is preferably 7~11, and more preferable 7.5~10.5, further
It is preferred that 8~10.As needed, pH regulator can also be added to adjust pH value.As pH regulator, liquid detergent group can be used
It closes in object as compound well known to pH regulator.As specific example, can enumerate alkanolamine, sodium hydroxide, potassium hydroxide,
Hydrochloric acid and sulfuric acid etc..
(B) ingredient is easy to viscosify in alkali side, and therefore, the pH of liquid detergent composition is more than the lower limit value of above range
When, it is easily obtained liquid viscosity appropriate.When the pH of liquid detergent composition is below the upper limit value of above range, mixing is steady
It is qualitative good.
Embodiment
With embodiment, the present invention will be described in more detail below, but the invention is not limited to these embodiments.Under
It states in example, " % " expression " quality % ", unless otherwise indicated.
[example 1~15,21~25]
The liquid detergent composition for clothes formed shown in table 1,2 is prepared in accordance with the following methods.
Example 1~15 is embodiment, and example 21~25 is comparative example.
Firstly, adding (A) ingredient after diethanol amine is dissolved in water and dissolving, as solution A.In addition, in advance will
(B) ingredient is equably dissolved in the water, and as solution B.Solution B is slowly added in solution A, and as mixed liquor.
In the mixed liquor be added (C) ingredient, then, be added (D) ingredient after, adjust pH as needed, be added aequum water make it is whole
A mixture reaches 100%.Other pH regulators can be added as needed in adjustment for pH, so that the concentration of diethanol amine
It is 0.8 mass %, pH (30 DEG C) in the range of 8~10.
Thus obtained liquid detergent composition for clothes can be evaluated by the following method.As a result shown in table 1 and
2。
Also shown in table (C) ingredient/(D) ingredient mass ratio, (B) ingredient/(C) ingredient mass ratio and (B) ingredient/
(D) mass ratio of ingredient.
<explanation of ingredient shown in table 1 and 2>
[(A) ingredient]
AE EO15 (on the alcohol mixture of carbon atom number C12, C14 alcohol obtained by average 15 moles of addition of ethylene oxide
Alcoxylates): the manufacture of Ecolat 24-15/85, Ecogreen company.
AE EO7 (on the alcohol mixture of carbon atom number C12, C14 alcohol alkane obtained by average 7 moles of addition of ethylene oxide
Oxygroup compound): レ オ ッ Network ス CL-70, the manufacture of lion princes and dukes department.
[(B) ingredient]
The manufacture of Ultrez20:Lubrizol company.
The manufacture of ETD2020:Lubrizol company.
[(C) ingredient]
The manufacture of C-1:Arquad 210, Shi Wang Aksu company.Dimercaptodimethyl ammonium chloride.
The manufacture of C-2:Arquad CB50, Shi Wang Aksu company.Benzalkonium chloride.Chlorination cocoalkyl dimethyl benzyl ammonium.
[(D) ingredient]
Citric acid: methylglycine diacetic acid ester 3Na:Trilon M Liquid, BASF AG's manufacture.Shown in following formula (3)
Compound.
[changing 3]
[other ingredients]
Diethanol amine: Northeast chemical company manufacture.
Water: purified water.
<evaluation method>
[initial appearance]
After just preparing liquid detergent composition for clothes, detect by an unaided eye appearance immediately, and carries out by following benchmark
Determine.
Zero (qualification): liquid is uniform and transparent.
△ (qualification): liquid is uniform and translucent.
× (unqualified): liquid generates gonorrhoea or separation, inhomogenous.
[washing performance (evaluation method of sebum dirt washing performance)]
In this method, the measuring reflectance of cloth be by using colour difference meter (manufacture of Japanese electricity Se industrial group, ProductName:
SE-2000) and according to the following equation, reflectivity R progress is calculated by Hunter whiteness Z.
R=Z/100
Firstly, the wet type artificial contamination cloth before measurement washing is (purchased from washing scientific institution respectively.Hereinafter also referred to as pollution
Cloth) 10 pieces of reflectivity.Terg-O-Tometer (manufacture of U.S.Testing company) is used as decantation test device.Using
Cleaning solution below: liquid detergent composition for clothes is dissolved in 25 DEG C of tap water 900ml, and reaches its concentration
1000ppm。
In sink, being put into 10 pieces of pollution cloth and filling cloth (will cut out thin looped fabric sufficiently to be washed and rinsed simultaneously
Cloth obtained by drying), and it is put into cleaning solution.The amount of filling cloth is set as that bath raio is made to reach 30 times.
It washs at revolving speed 120rpm, 25 DEG C of temperature after ten minutes, is carried out 2 times 3 minutes with 25 DEG C of tap water 900ml
Rinsing.It is dry.The reflectivity R of the pollution cloth after drying (hereinafter also referred to as washing cloth), and root are measured using 460nm optical filter
Washing ratio (unit: % is calculated according to following formula (i) and (ii).Decimal point rounds up later).In formula, K indicates absorptivity, S table
Show that scattering coefficient, R indicate reflectivity.Standard calico is the calico (original cloth) without the original sample state of dirt, standard calico
Reflectivity R is calculated with 80.
Value by following formula (i) He (ii) resulting Washing ratio is bigger, indicates that washing performance is higher.The Washing ratio of 10 pieces of cloth of pollution
Average value be 65% or more when, be evaluated as zero (qualification)；The average value be 50% or more and when less than 65%, be evaluated as Δ
(qualification)；When the average value is less than 50%, it is evaluated as × (unqualified).
[number 1]
[initial viscosity]
After just preparing liquid detergent composition for clothes, take 60g be put into bottle (ProductName: SV50A, day physics and chemistry nitre
Sub- Co., Ltd.'s manufacture.Hereinafter referred to as SV50 bottles) in, after standing 1 hour in 30 DEG C of water-bath, measured with Brookfield viscometer viscous
Degree obtains initial viscosity.The determination condition of viscosity is as follows: 30 DEG C, 30rpm, 30 seconds, using No.3 rotor.However, being less than
When 1000mPas, No.2 rotor is used.
When initial viscosity is 80mPas~3000mPas, it is determined as qualified (zero).
[viscosity stability]
It is put into the liquid detergent composition for clothes 60g just prepared in SV50 bottles, saves 2 when being kept for 60 DEG C
The moon or 6 months.Viscosity after preservation, after standing 1 hour in 30 DEG C of water-bath, after being saved using Brookfield viscometer measurement.Viscosity
Determination condition as initial viscosity determination condition.
Rate of change in viscosity according to following formula, after finding out the preservation relative to initial viscosity.
Viscosity [mPas]/initial viscosity [mPas] × 100 after the change rate [%] of viscosity=preservation
For viscosity stability, if the rate of change in viscosity for saving 2 months is 50% or more, as zero (qualification)；This is viscous
Change rate is spent less than 50% and at 40% or more, as △；When the rate of change in viscosity is less than 40%, as ×.
[smell inhibition]
It will be used in daily life about 7 days, and made using 10 pieces of difference of wiping hand towel more than half a year in family
To test towel.
Under the conventional program of washing machine (ProductName: JW-Z23A type, the manufacture of company, Haier), test towel is washed
Wash processing (about 25 DEG C of water temperature, inject tap water, 30 times of bath raio).At this point, washing agent group by liquid to the clothing that washing machine is put into
Conjunction object amount is 30g/ tap water 30L (1000ppm).
In addition, the filling cloth as adjustment bath raio, uses material below: in automatic washing machine (Matsushita Electric Industrial
Company's manufacture, ProductName: NA-F70SD1) auto-programming under, the shirt (BVD company) of completely new cotton 100% is carried out 5 times
Pre-wash processing (about 25 DEG C of water temperature, inject tap water).It is pre-washed in processing at this, uses commercially available synthetic detergent TOP (ト ッ
プ) (ProductName, the manufacture of lion princes and dukes department) is used as detergent, and the detergent usage amount washed every time is 25g/ tap water 30L.
Test towel washing after, about 25 DEG C of room temperature, relative humidity 90%RH interior to the test towel
It is dried 8 hours.Then, 6 panellists wash the test after dry (indoor seasoning) to 10 pieces smelt respectively
The smell of towel carries out sensory evaluation.
The sensory evaluation is to be carried out according to following evaluation criteria (a) by giving a mark.Specifically, according to evaluation base
The odour intensity of 6 grades of quasi- (a) shows that each panellists are by sense organ to 10 pieces of test towels after indoor seasoning
Respective smell evaluated, and by they carry out comprehensive judgement, with determine a score.
Evaluation criteria (a)
5 points: overpowering odor
4 points: stronger smell
3 points: the odour intensity for the degree that can cosily perceive
2 points: know be the degree of which kind of smell odour intensity
1 point: the odour intensity for the degree that can be perceived reluctantly
0 point: odorlessness
Then, in the score of 6 experts, the average mark of 4 expert analysis modes after removing best result and minimum point is found out,
And according to following evaluation criteria (b), smell inhibitory effect is evaluated.◎ and zero in evaluation criteria (b) is as qualified.
Evaluation criteria (b)
Shuo≤1.0 point ◎ (qualification): Fen
Zero (qualification): 1.0 points < Fen Shuo≤2.0 point △ (qualification): 2.0 points < Fen Shuo≤3.0 point × (unqualified): 3.0 points <
Score
[table 1]
[table 2]
As shown in the result of table 1 and 2, the liquid detergent composition for clothes of example 1~15 have good washing performance and
Antibiotic property, and there is good viscosity and viscosity stability.
In particular, when example 1 and example 11, example 13 and example 15 are compared respectively, with use citric acid as the example of (D) ingredient
1 compares with example 15, high using the example 11 of amino carboxylic acid system chelating agent and the initial viscosity of example 13, and the viscosity change in preservation
Small, storage stability is excellent.
Example 21 is free from the comparative example of (A) ingredient, and initial appearance is poor, and washing performance is insufficient, and initial viscosity is low.In addition, gas
Taste inhibitory effect is also insufficient.Since initial viscosity is low, evaluated without viscosity stability.
Example 22 is free from the comparative example of (B) ingredient, and initial viscosity is low.Therefore, it is evaluated without viscosity stability.In addition,
Viscosity " 10 > " in table means initial viscosity less than 10.
Example 23 is free from the comparative example of (C), and smell inhibitory effect is insufficient.
Example 24 is free from the comparative example of (D) ingredient, and initial viscosity is good, but through when viscosity decline big, viscosity stability is poor.
Example 25 be include (C) ingredient but the comparative example for being free of (D) ingredient, through when viscosity decline big, viscosity stability is poor.
Example 26 and 27 includes (A)~(D) ingredient, but the content of (D) ingredient is reduced to 0.01 mass %, and therefore, viscosity is steady
It is qualitative insufficient.
Utilization possibility in industry
According to the present invention, it can get the clothing containing anionic system tackifier and cationic surfactant to wash by liquid
Agent composition, and it with good washing performance and antibiotic property and has good viscosity and viscosity stability.
Claims (8)
1. a kind of liquid detergent composition for clothes, which is characterized in that containing following (A) ingredients, (B) ingredient,
(C) ingredient and (D) ingredient, and the gross mass relative to liquid detergent composition for clothes, the content of (D) ingredient are
0.03 mass % or more, the mass ratio indicated with (C) ingredient/(D) ingredient is 0.1~17.0；
(A) ingredient: poly (oxyalkylene) fundamental mode nonionic surfactant；
(B) ingredient: one or more of monomer being made of acrylic acid, methacrylic acid or their ester and alkyl acrylate
Copolymer be crosslinked by crosslinking agent obtained by cross-linking type carboxyl vinyl polymer；
(C) ingredient: ammonium salt type cationic surfactant；
(D) ingredient: citric acid, sodium citrate, amino carboxylic acid system chelating agent.
2. the liquid detergent composition for clothes recorded such as claim 1, wherein (D) ingredient is amino carboxylic acid system chela
Mixture.
3. the liquid detergent composition for clothes recorded such as claim 1, wherein (D) ingredient is to select free methyl sweet
Propylhomoserin oxalic acid, methylglycine diacetic acid salt, Pidolidone oxalic acid, Pidolidone diacetin, diethylenetriamines five
Acetic acid, diethylentriamine pentacetate, ethylenediamine succinic acid, ethylenediamine succinic acid salt, 3- hydroxyl -2,2'- imino-diacetic fourth
Diacid, 3- hydroxyl -2,2'- imino disuccinates, L-Aspartic acid-N, N- oxalic acid and L-Aspartic acid-N, N- diethyl
At least one of the group that hydrochlorate is constituted chelating agent.
4. the liquid detergent composition for clothes recorded such as claim 1, wherein relative to the total of liquid detergent composition
Quality, the content of (A) ingredient are 5~40 mass %.
5. the liquid detergent composition for clothes recorded such as claim 1, wherein relative to the total of liquid detergent composition
Quality, the content of (B) ingredient are 0.05~1 mass %.
6. the liquid detergent composition for clothes recorded such as claim 1, wherein relative to the total of liquid detergent composition
Quality, the content of (C) ingredient are 0.01~1.5 mass %.
7. the liquid detergent composition for clothes recorded such as claim 1, wherein the matter indicated with (B) ingredient/(C) ingredient
Amount is than being 0.09~8.0.
8. the liquid detergent composition for clothes recorded such as claim 1, wherein the matter indicated with (B) ingredient/(D) ingredient
Amount is than being 0.09~14.0.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-075696 | 2014-04-01 | ||
| JP2014075696 | 2014-04-01 | ||
| PCT/JP2015/060328 WO2015152324A1 (en) | 2014-04-01 | 2015-04-01 | Liquid detergent composition for clothing |
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|---|---|
| CN106133128A CN106133128A (en) | 2016-11-16 |
| CN106133128B true CN106133128B (en) | 2019-10-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201580015112.7A Active CN106133128B (en) | 2014-04-01 | 2015-04-01 | Liquid detergent composition for clothes |
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|---|---|
| JP (1) | JP6489708B2 (en) |
| CN (1) | CN106133128B (en) |
| MY (1) | MY175681A (en) |
| SG (1) | SG11201608135XA (en) |
| WO (1) | WO2015152324A1 (en) |
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|---|---|---|---|---|
| CN106635456A (en) * | 2016-11-04 | 2017-05-10 | 广州立白企业集团有限公司 | Kitchen oil dirt cleaner and preparation method thereof |
| CN113652314A (en) * | 2021-09-10 | 2021-11-16 | 中国热带农业科学院农产品加工研究所 | Duck down detergent |
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| CN1143672A (en) * | 1995-04-10 | 1997-02-26 | 花王株式会社 | Aqueous gel cleanser composition |
| CN1176302A (en) * | 1996-09-06 | 1998-03-18 | 花王株式会社 | Liquid bleaching agent composition with enhanced viscosity |
| JP2007297510A (en) * | 2006-04-28 | 2007-11-15 | Lion Corp | Liquid detergent composition for clothes |
| EP2169040A1 (en) * | 2008-09-30 | 2010-03-31 | The Procter and Gamble Company | Liquid detergent compositions exhibiting two or multicolor effect |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3670802B2 (en) * | 1996-09-06 | 2005-07-13 | 花王株式会社 | Thickened liquid bleach composition |
-
2015
- 2015-04-01 CN CN201580015112.7A patent/CN106133128B/en active Active
- 2015-04-01 SG SG11201608135XA patent/SG11201608135XA/en unknown
- 2015-04-01 JP JP2016511978A patent/JP6489708B2/en not_active Expired - Fee Related
- 2015-04-01 MY MYPI2016703563A patent/MY175681A/en unknown
- 2015-04-01 WO PCT/JP2015/060328 patent/WO2015152324A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143672A (en) * | 1995-04-10 | 1997-02-26 | 花王株式会社 | Aqueous gel cleanser composition |
| CN1176302A (en) * | 1996-09-06 | 1998-03-18 | 花王株式会社 | Liquid bleaching agent composition with enhanced viscosity |
| JP2007297510A (en) * | 2006-04-28 | 2007-11-15 | Lion Corp | Liquid detergent composition for clothes |
| EP2169040A1 (en) * | 2008-09-30 | 2010-03-31 | The Procter and Gamble Company | Liquid detergent compositions exhibiting two or multicolor effect |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015152324A1 (en) | 2015-10-08 |
| CN106133128A (en) | 2016-11-16 |
| SG11201608135XA (en) | 2016-11-29 |
| JPWO2015152324A1 (en) | 2017-04-13 |
| MY175681A (en) | 2020-07-06 |
| JP6489708B2 (en) | 2019-03-27 |
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