CN1290293A - Builder for detergents and detergent - Google Patents
Builder for detergents and detergent Download PDFInfo
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- CN1290293A CN1290293A CN99802821A CN99802821A CN1290293A CN 1290293 A CN1290293 A CN 1290293A CN 99802821 A CN99802821 A CN 99802821A CN 99802821 A CN99802821 A CN 99802821A CN 1290293 A CN1290293 A CN 1290293A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/40—Monoamines or polyamines; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
- C11D1/8355—Mixtures of non-ionic with cationic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
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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
- C11D3/30—Amines; Substituted amines ; Quaternized 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
- 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
Abstract
The invention discloses a detergent comprising a builder (A) consisting of an organic amine or quaternary ammonium salt of a carboxyl polymer and a nonionic surfactant (B) represented by the general formula (1): RO-(A<1>O)p-H wherein R is C8-C18 aliphatic hydrocarbyl; p is an integer of 1 to 30; and A<1> is C2-C4 alkylene. The builder is excellent in compatibility with the surfactant and the detergent is useful in washing clothes and particularly excellent in the detergency against mud soil.
Description
Technical field
The present invention relates to detergent builder and washing composition.More particularly, the present invention relates to the mud dirt is had the detergent builder and the washing composition of good detersive power.
Background technology
Till now, as detergent builder, an alkali metal salt of the known multipolymer that polyacrylic acid, poly-methylene-succinic acid, vinylformic acid and toxilic acid are arranged etc.In general, the washing composition that is used for clothes at home mainly contains tensio-active agent, for example the higher alcohols of an alkali metal salt of alkyl benzene sulphonate (ABS), alkyl-sulphate, fatty acid amide, mineral acid, polyoxyalkylated and alkylphenol.
Yet, though an alkali metal salt of poly carboxylic acid can improve detersive power,, there is the problem with the surfactant compatibility difference in they.
For obtaining good consistency being arranged and mud dirt etc. is had the washing composition of good detersive power with tensio-active agent, the inventor has carried out research in depth.As a result, they have been found that detergent builder of the present invention and washing composition are effective in these areas, and have realized the present invention.
Disclosure of the Invention
That is, the present invention is detergent builder, and these detergent builder comprise the organic amine salt or the quaternary ammonium salt (A) of carbonyl bearing polymer; The washing composition that comprises auxiliary agent and nonionic surface active agent (B); The washing composition that contains nonionic surface active agent (B), 1. nonionic surface active agent (B) by joining alkylene oxide (b1) in the fatty alcohol (a1) and satisfying following and 2. preparation; Washing composition further contains the 1. ratio of weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the organic amine salt of cationic surfactant (C) and/or lower molecular weight poly carboxylic acid or quaternary ammonium salt (D), Mw/Mn satisfy following relational expression (3) or (4): Mw/Mn≤0.030Ln (v)+1.010 (v＜10) (3) Mw/Mn≤-(v)+1.139 (v 〉=10) (4) { wherein, v is to the average addition mole number that joins the alkylene oxide (b1) in one mole of fatty alcohol (a1) } is 2.0 or littler from the distrubited constant c that following formula (5) calculates 2. to 0.026Ln: c=(v+n
0/ n
00-1)/[Ln (n
00/ n
0)+n
0/ n
00-1] (5) definition identical in the implication of v and formula (3) or (4) wherein, n
00Be the mole number of the fatty alcohol (a1) that in reaction, uses, n
0It is the mole number of unreacted fatty alcohol.
That invents is open in detail
As carbonyl bearing polymer of the present invention, can exemplify with α, beta-unsaturated carboxylic acid is as the unitary polymkeric substance of basic comprising.
α, the example of beta-unsaturated carboxylic acid comprises: monocarboxylic acid (for example, (methyl) vinylformic acid), dicarboxylic acid (for example, toxilic acid, fumaric acid, methylene-succinic acid and citraconic acid), dicarboxylic anhydride (for example, maleic anhydride, itaconic anhydride and citraconic anhydride) and dicarboxylic acid half ester { dicarboxylic acid and the half ester with alkanol, Trivalin SF class or cellosolve class of 2-16 carbon atom, for example toxilic acid half ester (butyl maleate, toxilic acid list ethyl carbitol ester etc.) and fumaric acid half ester (fumaric acid mono, fumaric acid list ethyl carbitol ester etc.) }, and composition thereof.Preferred vinylformic acid.
Can use the formation unit of other polymerizable monomer as polymkeric substance.
These monomeric limiting examples of replenishing are as follows:
(a) aromatics ethylenically unsaturated monomers: styrenic, for example vinylbenzene, alpha-methyl styrene, Vinyl toluene and hydroxy styrenes, halogen substituted styrenic, for example dichlorostyrene and vinyl naphthalene class;
(b) has the aliphatic ethylenically unsaturated monomers of 2-20 carbon atom: olefines, for example ethene, propylene, butylene, iso-butylene, amylene, heptene, diisobutylene, octene, dodecylene and vaccenic acid; Dienes, for example divinyl and isoprene;
(c) has the alicyclic ethylenically unsaturated monomers of 5-15 carbon atom: cyclopentadiene, firpene, limonene, indenes, Dicyclopentadiene (DCPD), ethylidene norbornene etc.;
(d) has (methyl) alkyl-acrylates of the alkyl that contains 1-50 carbon atom: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid eicosyl ester etc.;
(e) has ethylenically unsaturated monomers (the aforementioned α of hydroxyl or (gathering) oxyalkylene group (molecular weight is 44-2000), beta-unsaturated carboxylic acid) ester class: (methyl) acrylic acid hydroxy alkyl (carbon number is 2-6) ester class, for example (methyl) Hydroxyethyl acrylate and (methyl) Propylene glycol monoacrylate, (molecular weight is 44-2000 to have (gathering) oxyalkylene group, the carbon number of alkylidene group is 2-4) (methyl) acrylate, single (methyl) acrylate of polyoxyethylene glycol (molecular weight is 300) for example, single (methyl) acrylate of polypropylene glycol (molecular weight is 500), (methyl) acrylate of (methyl) acrylate of 10 moles of ethylene oxide and methyl alcohol adducts and 30 moles of ethylene oxide and lauryl alcohol adducts and except that (methyl) acrylate, corresponding to the aforementioned α of (methyl) acrylate that exemplifies above, the ester class of beta-unsaturated carboxylic acid;
(f) ethylenically unsaturated monomers of amide containing: (methyl) acrylamide, N-methylol (methyl) acrylamide etc.;
(g) contain the basic monomer of sulfuryl or vitriol (or ester): the monomer that contains sulfuryl, vinyl sulfonic acid for example, (methyl) allyl sulphonic acid, 2-hydroxyl-3-(methyl) allyloxy propane sulfonic acid, styrene sulfonic acid, alpha-methyl styrene sulfonic acid, (methyl) vinylformic acid sulphur propyl ester, 2-hydroxyl-3-(methyl) propenyloxy group propane sulfonic acid (2-hydroxy-3-(meth) acryloxy propanesulfonic acid), 2-(methyl) acrylamido-2,2-dimethyl ethane sulfonic acid and 2-(methyl) acryloxy ethane sulfonic acid, (oxyalkylene is the oxyalkylene with 2-4 carbon atom to polyoxyalkylene list (methyl) acrylate, or two or more have the mixture of the oxyalkylene of 2-4 carbon atom, when being such mixture of two or more oxyalkylenes, they can be random form or block form, and the addition mole number is generally 1-30) vitriol etc.
In polymkeric substance, as constituting unitary α, the content of beta-unsaturated carboxylic acid is generally 50-100 mole %, preferred 70-100 mole %.Other monomeric content is generally 0-50 mole %, preferred 0-30 mole %.
Polymkeric substance can wherein, can use radical polymerization initiator by above-mentioned monomeric radical polymerization preparation.
As such radical polymerization initiator, can use following material: azo-compound, for example 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2,2,24,4-trimethylpentane), '-azo two (2 Methylpropionic acid dimethyl ester), 2,2 '-azo two [2-(methylol) propionitrile] and 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane); Organo-peroxide, for example diphenyl peroxide (first) acyl, dicumyl peroxide, two (4-tert-butylcyclohexyl) peroxy dicarbonate salt (or ester), benzoyl peroxide, lauroyl peroxide and mistake succsinic acid; Inorganic peroxide, for example persulphate (or ester), superphosphate (or ester) and hydrogen peroxide etc.And, can use by these radical polymerization initiators and mix the redox initiator of forming with reductive agent.
The example that is used for the reductive agent of redox initiator comprises: xitix (salt), Rongalit, phospho acid (salt), sulfurous acid (salt), sulfurous acid hydracid (salt) (bisulfurousacid (salt)) and ferrous salt.These radical polymerization initiators can two or more mix use.
The consumption of radical polymerization initiator, with α, beta-unsaturated carboxylic acid and/or other monomeric gross weight meter are generally 0.01-20 weight %, are preferably 0.05-10 weight %, more preferably 0.1-2 weight %.
In the radical polymerization of aforementioned monomer, can use chain-transfer agent.As such chain-transfer agent, for example, can use lauryl mercaptan, Thiovanic acid, mercaptoethanol, triglycol two mercaptan (triethylene glycol dimercaptan) etc.
The consumption of chain-transfer agent, with α, beta-unsaturated carboxylic acid and/or other monomeric total mole number meter are generally 0.01-10 mole %, are preferably 0.05-3 mole %.
And radical polymerization can mass polymerization, any method in letex polymerization, suspension polymerization and the solution polymerization is carried out.The preferred solution polymerization.
In addition, polymerization temperature is 50-300 ℃, preferred 60-250 ℃.Polymerization temperature in solution polymerization can be more than the polymer solvent boiling point or following any temperature.Preferably be not less than the temperature of polymer solvent boiling point.Used herein " boiling point " is meant the boiling point under the normal atmosphere.
The number-average molecular weight Mn of the polymkeric substance of measuring by gel permeation chromatography (hereinafter referred GPC) is generally 1,000-100, and 000, preferred 3,000-30,000.The weight-average molecular weight of measuring by GPC is generally 1,100-110, and 000, preferred 3,300-33,000.
The acid number of polymkeric substance is generally 200-1, and 400, preferred 300-1,000.
The example of the organic amine that the organic amine salt of preparation polymkeric substance is used comprises: aliphatic amine, cycloaliphatic amines, heterocyclic amine or alkanolamine, or their alkylene oxide adduct.
The example of aliphatic amine comprises: have one of the alkyl that contains 1-18 carbon atom-, two-and trialkylamine, for example hexylamine, octylame, methyl hexyl amine, Methyl Octyl amine, dimethyl hexyl amine, dimethyl octyl group amine, dimethyl lauryl amine and dimethyl hexadecylamine.
Cycloaliphatic amines can be the cycloalkyl amine that for example has the cycloalkyl that contains 4-12 carbon atom, for example, and ring butylamine, hexahydroaniline, cyclopentamine, cyclooctylamine, N-methylcyclohexylamine and N-ethyl cyclohexylamine, and their alkyl (carbon number: the 1-6) product of Qu Daiing.
The example of heterocyclic amine comprises: have the heterocyclic amine of 4-10 carbon atom, for example morpholine.Alkanolamine can be for example have one of the hydroxyalkyl that contains 2-8 carbon atom-, two-and trihydroxyl alkylamine, for example monoethanolamine, diethanolamine and trolamine.
The example of alkylene oxide that is used to form the alkylene oxide adduct of these amines comprises: oxyethane, propylene oxide and butylene oxide ring.Optimization ethylene oxide.
The addition mole number of alkylene oxide is generally every active hydrogen 1-5 mole, is preferably the 1-2 mole.The example of alkylene oxide adduct comprises: dihydroxy ethyl hexyl amine and hydroxyethyl methyl hexyl amine.
Quaternary ammonium salt as for polymkeric substance, the example of quaternary ammonium cation comprises: have the tetra-allkylammonium of the alkyl that contains 1-18 carbon atom, for example trimethylammonium ethyl ammonium, triethyl ammonium methyl, trimethylammonium hexyl ammonium, trimethylammonium octyl group ammonium, tributyl octyl group ammonium, trimethylammonium decyl ammonium, trimethylammonium four decyl ammoniums, trimethylammonium cetyltrimethyl ammonium and monomethyl trioctylammonium; Have the cycloalkyl that contains 4-12 carbon atom and contain the cycloalkyl dialkyl ammonium of the alkyl of 1-6 carbon atom, N for example, N-Dimethylcyclohexyl ammonium and N, N-diethyl cyclohexyl ammonium; And have the hydroxyalkyl that contains 2-8 carbon atom and contain three hydroxyalkyl alkylammoniums of 1-6 carbon atom alkyl, trihydroxyethyl hexyl ammonium for example.
In these salt (A), preferably be derived from the salt of aliphatic series or cycloaliphatic amines or their alkylene oxide adduct, more preferably their quaternary ammonium salt.The salt that further more preferably has the quaternary ammonium cation of the alkyl that contains 2-12 carbon atom.Preferred especially triethyl methyl ammonium salt, triethyl octyl group ammonium salt, trimethylammonium decyl ammonium salt, trimethylammonium hexyl ammonium salt and trimethylammonium octyl group ammonium salt.
By with in the organic amine and polymkeric substance can synthetic polymer organic amine salt.Neutralization can be carried out in solution with solvent.The example of solvent comprises: water, alcohols (methyl alcohol, ethanol, Virahol etc.), ketone (acetone, methyl iso-butyl ketone (MIBK) etc.), ethers (Anaesthetie Ether, tetrahydrofuran (THF) etc.), aliphatic hydrocrbon (hexane, heptane etc.), aromatic hydrocarbon (toluene, dimethylbenzene etc.) and their mixture.When using nonionic surface active agent (B), can mix nonionic surface active agent (B) with in the organic amine and behind the polymkeric substance.In addition, nonionic surface active agent (B) also can with mixed with polymers, neutralize with organic amine then.Degree of neutralization is generally 30-100%, preferred 60-100%.
The quaternary ammonium salt of polymkeric substance can prepare by traditional method, for example, in one approach, tertiary amine and alkyl halide or aryl halide are (for example, halogenide with 1-10 carbon atom, for example, methyl chloride, monobromoethane and bromobenzene) reaction, form quaternary ammonium halide, the halogenide that obtains subsequently with alkali hydroxide (for example, sodium hydroxide and potassium hydroxide) reaction, hyamine hydroxide is provided, use in the oxyhydroxide that obtains at last and polymkeric substance; In one approach, and tertiary amine and dialkyl carbonate (carbon number: 1-6) ester (for example, methylcarbonate and diethyl carbonate) reaction, generate the carbonic acid quaternary ammonium salt, then, polymkeric substance and carbonic acid quaternary ammonium salt and anionresin.Neutralization or anionresin can use with organic amine in and carry out in the solution of solvent like the solvent based of usefulness.And when using nonionic surface active agent, nonionic surface active agent can mix before or after neutralization or anionresin.
The specific examples of method of anionresin that is used for polymkeric substance and carbonic acid quaternary ammonium salt is as follows.For example, under the situation of polyacrylate and trimethylammonium octyl group ammonium,, be reflected at about 120 ℃ and about 5kg/cm with 1 mole of dimethyl octyl group amine, 1 mole or more methylcarbonate and methyl alcohol threading pressurized vessel
2High pressure under carry out, make the methanol solution of carbonic acid trimethylammonium octyl group ammonium.Subsequently, at 80-90 ℃, the methanol solution of carbonic acid trimethylammonium octyl group ammonium is slowly joined in the polyacrylic acid aqueous solution.Carbonic acid gas and methyl alcohol that evaporation produces obtain polyacrylic trimethylammonium octyl group ammonium salt aqueous solution.
Neutralization or anionresin degree are generally 30-100%, preferred 60-100%.
Consider their solubleness to washing composition, the solubility parameter of the organic amine salt of polymkeric substance or quaternary ammonium salt (A) (hereinafter being called the SP value) is generally 8.0-12.0, preferred 8.5-11.5.When it changed in the 8.0-12.0 scope, detersive power was stronger, and the steady dissolution of salt in washing composition is also better.The SP value can be used general formula (6) expression:
General formula δ=(Δ H/V)
1/2(6) wherein, in formula (6), δ is the SP value, and Δ H is mole vaporization heat (card), and V is molecular volume (cm
3).
The SP value can be from mole vaporization heat (the Δ e of atomic group
1) summation (Δ H) and molecular volume (the Δ V of atomic group
1) summation (V) calculate, referring to " POLYMER ENGINEERING ANDFEBRUARY, 1974, Vol.14, No.2, ROBERT F.FEDORS, (pp.151-153) ".
Washing composition of the present invention comprises detergent builder and nonionic surface active agent (B), and these detergent builder comprise the organic salt or the quaternary ammonium salt (A) of polymkeric substance.
Nonionic surface active agent (B) for example can be, the nonionic surface active agent (b-1) of alkylene oxide addition type and polyvalent alcohol type nonionic surface active agent (b-2).
(b-1) example comprises: the alkylene oxide of higher alcohols (carbon number 8-18) (carbon number: 2-4) adducts (the addition mole number of every active hydrogen: 1-30), alkyl (carbon number: (the addition mole number of every active hydrogen: 1-30) of ethylene oxide adduct 1-12), lipid acid (carbon number: (the addition mole number of every active hydrogen: 1-30) of phenols ethylene oxide adduct 8-18), polypropylene glycol (molecular weight: (the addition mole number of every active hydrogen: 1-50) of ethylene oxide adduct 200-4000), with the lipid acid of polynary (two-octavalence or more) alcohol (carbon number: 8-24) ethylene oxide adduct of ester (the addition mole number of every active hydrogen: 1-30), polyoxyethylene (the addition mole number of every active hydrogen: 1-30) alkyl (carbon number: 1-20) allyl ethers for example, the ethylene oxide adduct of Span 20 (addition mole number: 1-30) and ethylene oxide adduct (the addition mole number: 1-30) of dehydrating sorbitol monooleate.
(b-2) example comprises: the lipid acid (carbon number: 8-24) ester of polynary (two-octavalence or more) alcohol (carbon number 2-30), for example glycerol monostearate, glycerol monoleate, Span 20 and dehydrating sorbitol monooleate, and Marlamid, for example single methyl alcohol acid amides of lauric acid and lauric acid diethyl amide.
In these, preferred (b-1), the more preferably compound of representing with following general formula (1), the especially preferably compound of representing with following general formula (2).RO-(A
1O)
p-H??(1)RO-[(C
2H
4O)
n·(A
2O)
m]-(C
2H
4O)
q-(A
2O)
r-H???(2)
In general formula (1) or (2), R is the aliphatic hydrocarbyl with 8-18 carbon atom, preferably has the aliphatic hydrocarbyl of 10-18 carbon atom.When carbonatoms changes, can obtain better detersive power in the 8-18 scope.Specifically, can be used as the example of radical of saturated aliphatic alkyl, for example: octyl group, 2-ethylhexyl, decyl, dodecyl, tetradecyl, palmityl, octadecyl and 1,1-dimethyl octyl group; Unsaturated aliphatic alkyl (alkenyl, alkadienyl, alkatriene base and alkapolyenyl), for example octenyl, decene base, dodecenyl succinic, tridecylene base, 15 carbene bases, oil base and inferior oil base; Cyclic aliphatic alkyl, for example ethyl cyclohexyl, propyl group cyclohexyl, octyl group cyclohexyl and nonyl cyclohexyl.These aliphatic hydrocarbyls can be straight chains, also can be side chains.
In general formula (1), A
1Expression has the alkylidene group of 2-4 carbon atom.What specifically, can exemplify has: ethylidene, propylidene and butylidene.Two or more (A are being arranged
1O) under the unitary situation, they can exist with any way in equal, random and the block fashion.In addition, p is 1-30, the integer of preferred 6-20.When changing in the scope of p at 1-30, can obtain better detersive power.
In general formula (2), A
2Be the alkylidene group with 3 or 4 carbon atoms, n is 0 or the integer of 1-12, preferred 1-10.And q is 1-16, the integer of preferred 2-12.When n is 0 or changes in the 1-8 scope and when q changes, can obtain better detersive power in the 1-16 scope.
And m is 0 or the integer of 1-6, and preferred 1-4, r are 0 or the integer of 1-15, preferred 1-8.When m be 0 or in the 1-6 scope, change and when r be 0 or when in the 1-15 scope, changing, the better flowability of washing composition can be provided.
And, (m+n+q) be the integer of 1-30, preferred 6-20.When (m+n+q) changes, can provide better detersive power in the 1-30 scope.
And, (n+q)/(m+n+q+r) be 0.5-1.0, preferred 0.7-0.9.When it during in the 0.5-1.0 range, can obtain better detersive power.
In the compound of general formula (2) expression, especially preferably by alkylene oxide (b1) being joined the compound of preparation in the fatty alcohol (a1), has (Mw/Mn) ratio that calculates by weight-average molecular weight (Mw) that satisfies following relational expression (3) or (4) and number-average molecular weight (Mn), have simultaneously from following general formula (5) calculate be 2.0 or littler distrubited constant c:Mw/Mn≤0.030Ln (v)+1.010 (v＜10) (3) Mw/Mn≤-(v)+1.139 (v 〉=10) (4) wherein for 0.026Ln, in formula (3) and (4), v is the average addition mole number that joins the alkylene oxide (b1) in 1 mole of fatty alcohol (a1).Ln (v) is the natural logarithm of v.
As fatty alcohol (a1), can use alcohols with the aliphatic hydrocarbyl that contains 8-18 carbon atom.The alcohol that preferably has the aliphatic hydrocarbyl that contains 10-18 carbon atom as a1.The alcohol of the aliphatic hydrocarbyl that exemplifies in the time of specifically, can listing the R that has in explaining general formula (1) or (2).As alkylene oxide (b1), can use oxyethane, propylene oxide and butylene oxide ring.Their addition mode can be in equal, random and block fashion and the mixing thereof any.c=(v+n
0／n
00-1)／[Ln(n
00／n
0)+n
0／n
00-1]????(5)
In formula (5), v has and formula (3) or the identical meaning of (4) middle definition, n
00Be the mole number of fatty alcohol (a1) used in reaction, n
0It is the mole number of unreacted fatty alcohol (a1).More preferably c is 1.0 or littler.When c is 2.0 or more hour, the content of unreacted fatty alcohol becomes minimum, therefore, can obtain better surfactivity.
Utilize traditional alkylene oxide addition reaction, can prepare the nonionic surface active agent (b-1) of above-mentioned alkylene oxide addition type.That is to say, under concrete addition mode, in the presence of catalysts,, can prepare by oxyethane, propylene oxide and butylene oxide ring are joined in the alcohol at 70-200 ℃.
For example, by alkaline catalysts (for example KOH) or acid catalyst (BF for example
3) join in the higher alcohols that contains 8-18 carbon atom, under nitrogen atmosphere, make the mixture of oxyethane and propylene oxide carry out random-addition subsequently, then carry out the block-addition of oxyethane, carry out the block-addition of propylene oxide subsequently.
As aliphatic hydrocrbon alcohol, can use saturated or undersaturated primary, the second month in a season or the tertiary alcohol with 8-18 carbon atom.In these alcohol, preferred radical of saturated aliphatic primary alconol.Preferred carbonatoms is 10-18.Aliphatic hydrocrbon alcohol can use separately, also can two or more mix use.
The specific examples of radical of saturated aliphatic primary alconol comprises: decyl alcohol, lauryl alcohol, stearyl alcohol, utilize Ziegler catalyst [for example, ALFOL 1214 (trade(brand)name), produce by CONDEA etc.] the pure and mild alcohol by the oxo synthesis preparation of synthetic is [for example, Dobanol 23,25 and 45 (trade(brand)names), by Mitsubishi Petrochemical Co., Ltd., produce, Tridecanol is (by Kyowa Hakko Kogyo Co., Ltd. produce, Oxocol 1213,1215 and 1415 (by Nissan Chemical Co., Ltd. makes) and Diadol 115-L, 115H and 135 (making) by Mitsubishi Chemical Corp..
The example of radical of saturated aliphatic secondary alcohol comprises: utilize n-paraffin to make raw material, and by the radical of saturated aliphatic secondary alcohol of method for oxidation preparation, the radical of saturated aliphatic secondary alcohol of in " oiling " (Oilchemistry, Vol.21, No.5, pp.233-242 (1972)), describing etc.
The example of unsaturated aliphatic alcohol comprises: oleyl alcohol, [for example, (trade(brand)name is by Kyowa Oil ﹠amp for Hicol 40 and 60 for the alcohol by method of reducing preparation; Fat Co., Ltd. produces), Angecol50A (by Shin-Nippon Rika Co., the Ltd. preparation).
Satisfying above-mentioned formula (3) or (4) and have the value of being calculated by above-mentioned formula (5) as production is 2.0 or the method for the compound of littler distrubited constant c, can be listed below: 1. in one approach, alkylene oxide is joined in the fatty alcohol, utilization can realize than traditional catalyst (for example basic metal such as lithium, sodium, the oxyhydroxide of potassium and caesium or carbonate, or basic catalyst such as amine compound) the more narrow molecular weight distributions that can provide catalyzer 2. in one approach, the alkylene oxide of 1-3 mole is added fatty alcohol, utilize traditional catalyst, remove unreacted alcohol by for example distillation subsequently, after this, add alkylene oxide, utilize traditional catalyst.Preferred method 1..
The catalyzer that molecular weight distribution is narrowed down can be the catalyzer that is selected from following material: burntly contain magnesian compound (JP-A1-164437), burnt hydrotalcite (JP-A2-71841), (USP 4 for perchlorate (or ester), 112,231), perhalogeno acid (perhalogenicacids) (salt), sulfuric acid (salt), nitric acid (salt) and two-or trivalent metal alkanoate (alkolates) etc.
Cationic surfactant (C) can be quaternary ammonium salt type or amine salt type cationic surfactant etc.
As quaternary ammonium salt type cationic surfactant, can use the compound that makes by tertiary amine and quaternizing agent (alkyl halide is methyl chloride, methyl bromide, chloric ethane and benzene methyl chloride, methyl-sulfate, methylcarbonate, oxyethane etc. for example) reaction.The example comprises: lauryl three chloro methanation ammoniums, didecyl dichloro-methanation ammonium, dioctyl dimethyl brometo de amonio, stearyl trimethylammonium bromide, lauryl dimethyl benzyl ammonium chloride (Zephiran chloride), cetylpyridinium chloride, polyoxyethylene three chloro methanation ammoniums, stearylamide ethyl diethylmethyl sulfuric acid dimethylammonium (stearamidethyldiethyl-methylammonium methosulfate).
Cationic surfactant as the amine salt type, for example, by compound with mineral acid (spirit of salt, nitric acid, sulfuric acid, hydroiodic acid HI etc.) or organic acid (acetate, formic acid, oxalic acid, lactic acid, glyconic acid, hexanodioic acid, alkylphosphonic acid carboxylic acid etc.) neutralization primary, the second month in a season or tertiary amine preparation.The example of primary amine salt type comprises: the inorganic acid salt or the organic acid salt of aliphatic higher amines (higher amines is lauryl amine, stearylamine, hexadecylamine, hardened tallow amine and rosin Amine D for example); The higher fatty acid of low-grade amine (stearic acid, oleic acid etc.) salt etc.
The example of secondary amine salt type comprises: the inorganic acid salt of the ethylene oxide adduct of aliphatic amine or organic acid salt.
The example of tertiary ammonium salt type comprises: aliphatic amine (triethylamine, ethyl dimethyl amine, N, N, N ', N '-Tetramethyl Ethylene Diamine etc.), cycloaliphatic amines (N-crassitude, N-methyl piperidine, N-methyl hexamethylene imine, N-methylmorpholine, 1,8-diazabicyclo (5,4,0)-7-undecylene etc.) and the inorganic acid salt or the organic acid salt of nitrogen heterocyclic ring aromatic amine (4-Dimethylamino pyridine, N-Methylimidazole, 4,4 '-dipyridyl etc.); The inorganic acid salt of tertiary amine or organic acid salt, for example, triethanolamine monostearate, stearylamide ethyl diethylmethyl thanomin etc.
As cationic surfactant (C), can use one or both or more kinds of mixtures in these compounds.Be preferably selected from one or more compounds of the compound of formula (6)-(9) expression.
In formula (6)-(9), R
1, R
2And R
3Expression hydrogen atom or have alkyl, alkenyl or the β-hydroxyalkyl of 1-24 carbon atom preferably has the alkyl or the alkenyl of 1-18 carbon atom.
Specifically, the example of alkyl comprises: methyl, ethyl, propyl group, hexyl, octyl group, 2-ethylhexyl, nonyl, different nonyl, decyl, isodecyl, undecyl, different undecyl, dodecyl, Permethyl 99A. base, tridecyl, isotridecyl, tetradecyl, different tetradecyl, pentadecyl, different pentadecyl, hexadecyl, isocetyl, octadecyl and isooctadecane base.Non-limiting examples of alkenyls comprises: octenyl, decene base, dodecenyl succinic, tetradecene base, cetene base and vaccenic acid base.The example of β-hydroxyalkyl comprises: 2-hydroxyethyl, 2-hydroxypropyl and 2-hydroxyl butyl.
R
4And R
5Can be to have the alkyl of 1-24 carbon atom or hydroxyalkyl, benzyl or by formula-(A
1O)
nGroup { the A that-Z represents
1Be the alkylidene group (for example ethylidene, propylidene and butylidene) with 2-4 carbon atom, Z is hydrogen atom or acyl group, and n is the integer of 1-50, the integer of preferred 5-30 }, preferably have the alkyl or the benzyl of 1-4 carbon atom.Specifically, can enumerate: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-and sec-butyl.
R
6Be alkyl, alkenyl or the β-hydroxyalkyl that 1-36 carbon atom arranged, preferably have the alkyl or the alkenyl of 8-24 carbon atom.Specifically, except R
1, R
2And R
3Outside the group of listing, can enumerate eicosyl, Isoeicosane base and eicosylene base.
Y is alkyl, alkenyl or the β-hydroxyalkyl that 1-36 carbon atom arranged, by formula R
4CO
2CH
2-(R
4Identical with the front) group of expression, or by formula R
4OCH
2-(R
4Identical with the front) group of expression preferably has the alkyl or the alkenyl of 1-18 carbon atom.Specifically, Y can be and R
1, R
2And R
3Identical group.
X
-Being corresponding negatively charged ion, can be to be selected from one or more following negatively charged ion: halogen ion (F
-, Cl
-, Br
-And I
-), hydroxyl ion, carbonic ether ion that the alkyl that contains 1-24 carbon atom is arranged or sulfuric ester ion, the alkyl that contains 1-4 carbon atom or the carboxylicesters (or salt) and sulphonate (or salt) ion of alkenyl are arranged.
1. the compound of formula (6) expression can be obtained by method, wherein, with haloid acid spirit of salt for example, Hydrogen bromide and hydroiodic acid HI or carboxylic acid with 1-24 carbon atom be formic acid for example, acetate, propionic acid, neutralization such as lauric acid and stearic acid has the alkyl of 1-24 carbon atom, the primary amine of alkenyl or β-hydroxyalkyl is lauryl amine and stearylamine for example, alkyl with 1-24 carbon atom, the secondary amine of alkenyl or β-hydroxyalkyl is dilaurylamine and distearyl amine for example, or has the alkyl of 1-24 carbon atom, the tertiary amine of alkenyl or β-hydroxyalkyl is Trimethylamine 99 for example, lauryl dimethyl amine and dimethyl stearylamine.
2. they also can obtain by method, wherein, tertiary amine for example Trimethylamine 99, lauryl dimethyl amine and dimethyl stearylamine with alkyl, alkenyl or β-hydroxyalkyl of 1-24 carbon atom, for example methyl chloride, benzyl chloride, methylcarbonate, diethyl carbonate and methyl-sulfate are depressed heating and reaction adding with alkylating reagent.
3. they also can obtain by method, wherein, by in the presence of alkali, oxyethane is added the primary amine tertiary amine that for example obtains in dilaurylamine and the distearyl amine of lauryl amine and stearylamine or secondary amine with alkyl, alkenyl or β-hydroxyalkyl of containing 1-24 carbon atom for example with alkyl, alkenyl or β-hydroxyalkyl of containing 1-24 carbon atom, with for example for example formic acid, acetate, propionic acid, lauric acid and neutralizations such as ester acid firmly of spirit of salt, Hydrogen bromide and hydroiodic acid HI or carboxylic acid with 1-24 carbon atom of haloid acid.
For example, by following method, can obtain the compound of formula (7) expression, wherein, pyridine and alkylating reagent that 1-24 carbon atom arranged for example methyl chloride, chloro-octane, stearyl chloride, oil base bromine and hydroxyethyl bromine are depressed heating and are reacted adding.
For example, by following method, can obtain the compound of formula (8) expression, in one approach, lipid acid with 1-36 carbon atom for example lauric acid and stearic acid and trolamine heating and condensation produces ester type tertiary amine, this amine that generates is used the acid neutralization such as spirit of salt and acetate subsequently, and in one approach, above-mentioned ester type tertiary amine and methyl chloride, methylcarbonate and methyl-sulfate are depressed heating and reacted adding.
For example, by following method, can obtain the compound of formula (9) expression, wherein, the lipid acid that will have a 1-36 carbon atom is lauric acid and stearic acid and N for example, and the acid amide type tertiary amine that heating of N-diethyl ethylenediamine and condensation obtain is used the acid neutralization such as spirit of salt and acetate, in one approach, above-mentioned acid amide type tertiary amine and methyl chloride, methylcarbonate and methyl-sulfate add depress the heating and the reaction.
With the corresponding ion X in hydroxyl ion displaced type (6)-(9)
-, can be by preparation Halogen ion as X
-Compound and carrying out to wherein adding this compound of silver hydroxide post-heating.
Constituting the organic amine salt of lower molecular weight poly carboxylic acid or the lower molecular weight poly carboxylic acid of quaternary ammonium salt (D) can be aliphatic poly carboxylic acid or aromatics poly carboxylic acid, and its molecular weight is generally 700 or littler, and preferred molecular weight is 500 or littler, and usually in molecule, 2-8 carboxyl is arranged.Carboxylic acid can have hydroxyl or amino except that carboxyl.The example of carboxylic acid comprises: oxalic acid, propanedioic acid, succsinic acid, butane tricarboxylic acid, hexanodioic acid, toxilic acid, fumaric acid, methylene-succinic acid, aconitic acid, phthalic acid, trimellitic acid, citric acid, oxysuccinic acid, ethylenediamine tetraacetic acid (EDTA) (EDTA), nitrilotriacetic acid(NTA) (NTA) and aspartic acid.The example of organic amine that is used to prepare the organic amine salt of lower molecular weight poly carboxylic acid comprises: above-mentioned aliphatic amine, cycloaliphatic amines, heterocyclic amine or alkanolamine, or their alkylene oxide adduct.About the quaternary ammonium salt (D) of lower molecular weight poly carboxylic acid, quaternary ammonium cation is for example above-mentioned quaternary ammonium cation.
In the present invention, the content of (A) in the washing composition in the gross weight of washing composition, is generally 0 or 1-30 weight %, is preferably 0 or 2-20 weight %, and more preferably 0 or 3-15 weight %.
In the gross weight of washing composition, content (B) is generally 10-95 weight %, is preferably 20-80 weight %, more preferably 30-60 weight %.With regard to the content of (B), in the content of (B), the content of the compound of general formula (1) or (2) expression is preferably 85 weight % or more.More preferably in the content of (B), the content of the compound of general formula (2) expression is 85 weight % or more.Especially preferably in the total content of (B), satisfy relational expression (3) or (4) and have the value of calculating by general formula (5) be 2.0 or the content of the compound of general formula (2) expression of littler distrubited constant c be 85 weight % or more.
In the gross weight of washing composition, content (C) is generally 0 or 0.01-10 weight %, is preferably 0 or 0.05-5 weight %.
In the gross weight of washing composition, content (D) is generally 0 or 0.1-20 weight %, is preferably 0 or 1-15 weight %.
In the gross weight of washing composition, the content of water is generally 2-80 weight %, is preferably 10-60 weight %.And, if desired,, can contain other composition except that (A), (B) with (C), in the gross weight of washing composition, its content is 0-50 weight %.
As such supplementary component, aniorfic surfactant { alkyl (carbon number the is 1-20) ether sulfate (or ester) that can contain 0-15 weight %, the sulfation of the ethylene oxide adduct (the addition mole number is 1-30) of aliphatic series (carbon number is 1-20) alcohol or carboxymethylation product etc. }, (base agent is sodium hydroxide for example for other auxiliary agent of 0-5 weight %, SODA ASH LIGHT 99.2, ammonia, trolamine and tripoly phosphate sodium STPP), fluorescence (brightening) agent of 0-5 weight %, SYNTHETIC OPTICAL WHITNER, softening agent, enzyme, sterilant, spices, tinting material etc., hydrophilic solvent (the methyl alcohol of 0-20 weight %, ethanol, Virahol, ethylene glycol, propylene glycol etc.), the defoamer of 0-5 weight % (silica-based defoamer, Pluronic type or polyoxyalkylenes defoamer, mineral oil based defoamer etc.).
Washing composition of the present invention hands over sticking weaving (cross-knitted-woven) fiber particularly useful to washing natural fiber, chemistry or synthon and their blending.The example of natural fiber comprises: cotton, hemp and hair.The example of chemistry or synthon comprises: regenerated cellulose fibre is rayon fiber and cellulose acetate for example, and synthon are trevira, tynex, acrylic fibers peacekeeping spandex fiber for example.Blending hands over the example of sticking textile fibres to comprise: by cotton or hemp and other fiber (hair, trevira, tynex, acrylic fibres etc.) sticking textile fibres is handed in the blending that constitutes, by hair and other fiber (trevira, tynex, acrylic fibres etc.) sticking textile fibres is handed in the blending that constitutes, by trevira and other fiber (rayon fiber, cellulose acetate, tynex, acrylic fibre, spandex fibers etc.) sticking textile fibres is handed in the blending that constitutes, by tynex and other fiber (rayon fiber, cellulose acetate, acrylic fibre, spandex fibers etc.) sticking textile fibres is handed in the blending that constitutes.
Washing composition of the present invention uses with the concentration of 0.001g/L-5g/L usually.
Bath raio has no particular limits, and still, is generally 1: 4-1: 40, be preferably 1: 6-1: 30.Wash temperature can be selected arbitrarily according to the kind of using fiber, still, is generally 5-80 ℃, preferred 20-50 ℃.
Washing composition of the present invention not only can be used as the washing composition of clothes, and, also can be used as industrial detergent, for example the scrubbing agent of fiber and soaping agent.
With detergent washing of the present invention the time, mode of washing is not particularly limited.When family used, washing can be washed by hand or machine-wash with washing.When industrial use, can utilize jet dyeing machine to be applied to batch processing, utilize continuous scouring machine to be applied to processing continuously etc.Be specially adapted to having for example washing of the washing machine of centrifugal force washing system etc. laundry damage system still less.The centrifugal force washing system is a kind of new washing system, and wherein, current cause by " centrifugal force " that the rotation by tub for washing machine produces, and the strength of the water by clothing is washed dirt off.For example, can adopt Co., the NA-800P centrifugal washer that Ltd. makes by Matsushita Electric Industrial.
Implement best mode of the present invention
The following examples have at length been explained the present invention, and still, the present invention is not limited.Umber and % are meant parts by weight and weight % respectively.
The condition of molecular weight of measuring carbonyl bearing polymer with GPC is as follows:＜GPC condition determination〉equipment: Waters 510, (being made by Japanese Waters Limited) post: tsk gel G5000pwXL tsk gel G3000pwXL, (making by Tosoh company) column temperature: 40 ℃ of detectors: RI solvent: sodium acetate aqueous solution water/methyl alcohol of 0.5%, (volume ratio: 70: 30) flow velocity: 1.0 ml/min sample concentrations: 0.25% volume injected: 200 μ l standards: polyethylene glycol, (made by Tosoh company; TSK STANDARD POLYETHYLENE OXIDE) data handler:SC-8010 (making) by Tosoh company
Use the gpc measurement nonionic surface active agent, the condition of molecular weight (B) is as follows:＜GPC condition determination＞equipment: HLC-8120, (being made by Tosoh company) post: tsk gel SuperH4000 tsk gel SuperH3000 tsk gel SuperH2000, (all being made by Tosoh company) column temperature: 40 ℃ of detectors: RI solvent: oxolane flow velocity: 0.6 ml/min sample concentration: 0.25% volume injected: 10 μ l standards: polyethylene glycol, (made by Tosoh company; TSK STANDARD POLYETHYLENE OXIDE) data handler:SC-8020 (making) by Tosoh company
The vapor-phase chromatography that is used for measuring the unreacted fatty alcohol concentration of nonionic surface active agent (hereinafter, be abbreviated as GC) measuring condition as follows:＜GC condition determination〉equipment: gas chromatograph GC-14B (making) detector: FID post: glass column (about 3 millimeters of internal diameter by Shimadzu company, about 2 meters of length) column material: silicon GE SE-30 5% column temperature: be raised to 280 ℃ from 90 ℃, temperature rise rate is 4 ℃ of/minute carrier gas: the nitrogen sample: 50% acetone soln volume injected: 1 μ l measures: use the fatty alcohol that lack 2 or 3 carbon atoms than used fatty alcohol to mark in doing and measure.
Embodiment 1
420 parts of Virahols and 120 parts of water are added in the pressure reacting container.Atmosphere in the container with nitrogen replacement after, with container sealing and be warmed up to 100 ℃.Under agitation, splash into following substances respectively: splashed into 77 parts of vinylformic acid through 3 hours, splashed into the uniform mixture of 228 parts of vinylformic acid, 4 parts of chain-transfer agents (triglycol two mercaptan (triethyleneglycol dimercaptan)), 2 parts of phospho acid sodium dihydrates and 0.7 part of iron protochloride tetrahydrate through 2 hours, splashed into 50 part 6% through 3.5 hours and cross (two) aqueous sodium persulfate solution.(begin simultaneously to drip.) after being added dropwise to complete, add 3 part of 35% aqueous hydrogen peroxide solution.Mixture stirred 1 hour at 100 ℃, obtained rate of polymerization and be 99.9% polymkeric substance (a), and by gpc measurement, its weight-average molecular weight is 10000, and number-average molecular weight is 7800.
195 parts of methyl alcohol and 586 parts of methylcarbonates are added in another pressurized vessel.After with the atmosphere in this container of nitrogen replacement, with container sealing and be warming up to 120 ℃.Under agitation, splash into 219 parts of triethylamines.Mixture stirred 2 hours at 120 ℃, formed the methanol solution of triethyl methyl volatile salt (b).After 60% 707 parts and the 400 parts polymkeric substance of methanol solution (a) (100% neutralization) of (b) that will obtain mix, at 100 ℃, under atmospheric pressure, Virahol, methyl alcohol and methylcarbonate are removed in evaporation, add 580 parts of water, obtain 45% aqueous solution of polyacrylic triethyl methyl ammonium salt.
The nonionic surface active agent (B), trolamine Citrate trianion, propylene glycol, alcalase 2.5L and the water that provide with this solution and table 2 together, the washing composition of the composition that provides in the table 4 is provided in preparation.
Embodiment 2,3 and 9-24
Except that nonionic surface active agent (B) is changed into shown in the table 2, with embodiment 1 same way as, the washing composition of the composition that provides among the table 4-6 is provided with the polyacrylic triethyl methyl ammonium salt preparation of preparation among the embodiment 1.
Embodiment 4,5,6 and 7
Except that neutralized salt and degree of neutralization are changed into shown in the table 1 and with nonionic surface active agent (B) change into shown in the table 2, the washing composition of the composition that provides in the table 4 is provided with polymkeric substance (a) preparation that obtains with embodiment 1 with embodiment 1 same way as.
Embodiment 8
With the polymkeric substance (a) that obtains in the dimethyl hexyl amine and among the embodiment 1.With the nonionic surface active agent that provides in the table 2 (B), triethyl ammonium methyl Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 4 is provided in preparation with the mixture that obtains.
Embodiment 25
370 parts of Virahols and 170 parts of water are added in the pressure reacting container.After with the atmosphere in the nitrogen replacement container, with container sealing and be warmed up to 100 ℃.Under agitation, splashed into mistake (two) aqueous sodium persulfate solution (beginning simultaneously to splash into) of 264.9 parts of vinylformic acid, 40.1 parts of 2-acrylamide-2-methyl propane sulfonic acid and 80 part 4% respectively respectively from container independently through 3 hours.After being added dropwise to complete, add 3 part 35% aqueous hydrogen peroxide solution.Mixture stirred 1 hour at 100 ℃, obtained rate of polymerization and be 99.9% multipolymer (c), and by gpc measurement, its weight-average molecular weight is 8000, and number-average molecular weight is 5600.
With 707 parts of 60% methanol solutions of the triethyl methyl volatile salt (b) that obtains among the embodiment 1 with after 174 parts of multipolymers (c) (100% neutralization) mix, at 100 ℃, under atmospheric pressure, Virahol, methyl alcohol and methylcarbonate are removed in evaporation, obtain polyacrylic triethyl ammonium methyl salt brine solution.
With the nonionic surface active agent that provides in the table 2 (B), triethyl ammonium methyl Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 6 is provided in preparation with this solution.
Embodiment 26
In using embodiment 5 the polyacrylic triethyl methyl ammonium salt of preparation and with nonionic surface active agent (B) change into shown in the table 2, prepare washing composition in the mode identical with the composition that provides in the table 6 with embodiment 25.
Embodiment 27
In using embodiment 6 the polyacrylic trimethylammonium octyl group ammonium salt of preparation and with nonionic surface active agent (B) change into shown in the table 2, prepare washing composition in the mode identical with the composition that provides in the table 6 with embodiment 25.
Embodiment 28-30
With the nonionic surface active agent (B), trimethylammonium octyl group ammonium Citrate trianion, propylene glycol, alcalase2.5L and the water that provide in polyacrylic trimethylammonium decyl ammonium salt for preparing among the embodiment 7 and the table 2, the washing composition of the composition that provides in the table 6 is provided in preparation.
Embodiment 31
By the reaction of methyl chloride and stearylamine, prepared cationic surfactant (c1, in formula (6), R
1=R
2=R
3=H, R
4=C
18H
37, X
-=Cl
-).
With the nonionic surface active agent that provides in the table 2 (B), trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation with the polyacrylic triethyl methyl ammonium salt for preparing among cationic surfactant (c1) and the embodiment 1.
Embodiment 32
By the reaction of methylcarbonate and dimethyl stearylamine, prepared cationic surfactant (c2, in formula (6), R
1=C
18H
37, R
2=R
3=R
4=CH
3, X
-=CH
3CO
- 3).
With the nonionic surface active agent that provides in the table 2 (B), trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation with the polyacrylic triethyl methyl ammonium salt for preparing among cationic surfactant (c2), the embodiment 1.
Embodiment 33
By chloro-octane and pyridine reaction, and the preparation cationic surfactant (c3, in formula (7), Y=C
8H
17, X
-=Cl
-).
With the nonionic surface active agent that provides in the table 2 (B), trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation with the polyacrylic triethyl methyl ammonium salt for preparing among cationic surfactant (c3) and the embodiment 1.
Embodiment 34
By sad and reaction trolamine, and the preparation cationic surfactant (c4, in formula (8), R
5=CH
3, R
6=C
7H
15, X
-=CH
3CO
- 3).
With the nonionic surface active agent that provides in the table 2 (B), trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation with the polyacrylic triethyl methyl ammonium salt for preparing among cationic surfactant (c4) and the embodiment 1.
Embodiment 35
By the reaction of methyl chloride and dilauryl methylamine, and the preparation cationic surfactant (c5, in formula (6), R
1=R
2=C
18H
37, R
3=R
4=CH
3, X
-=Cl
-).
With the nonionic surface active agent that provides in the table 2 (B), trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation with cationic surfactant (c5).
Embodiment 36
By the reaction of ethyl sulfate and triethylamine, and the preparation cationic surfactant (c6, in formula (6), R
1=R
2=R
3=R
4=C
2H
5, X
-=C
2H
5SO
- 4).
With the nonionic surface active agent that provides in the table 2 (B), trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation with cationic surfactant (c6).
Embodiment 37
By the reaction of ethyl chloride and pyridine, and the preparation cationic surfactant (c7, in formula (7), Y=C
2H
5, X
-=Cl
-).
Utilize cationic surfactant (c7) with the nonionic surface active agent that provides in the table 2 (B), trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation.
Embodiment 38
With N, the reaction of N-diethyl ethylenediamine and stearylamine is reacted the product that obtains subsequently with methyl-sulfate, prepared cationic surfactant (c8, in formula (9), R
5=CH
3, R
6=C
17H
35, X
-=CH
3SO
4 -).
Utilize cationic surfactant (c8) with the nonionic surface active agent that provides in the table 2 (B), trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation.
Comparative Examples 1 and 2
Nonionic surface active agent, trolamine Citrate trianion, propylene glycol, alcalase 2.5L and the water and Sodium dodecylbenzene sulfonate or the sodium lauryl tri(oxyethyl) sulfate that utilize table 3 to provide, the washing composition of the composition that provides in the table 7 is provided in preparation.
Comparative Examples 3
With the polymkeric substance (a) that obtains with embodiment 1 in the ammoniacal liquor.With the nonionic surface active agent that provides in the table 3, trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation with it.
Comparative Examples 4 and 5
With the polymkeric substance (a) that obtains in the sodium hydroxide and among the embodiment 1.With the nonionic surface active agent that provides in the table 3, trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation with it.
Comparative Examples 6
With the polymkeric substance (a) that obtains in the sodium hydroxide and among the embodiment 1.With the nonionic surface active agent that provides in the table 3, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation with it.
Comparative Examples 7
With the polymkeric substance (a) that obtains in the sodium hydroxide and among the embodiment 1.With the nonionic surface active agent that provides in the table 3, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation with it.
Comparative Examples 8
With polyvinyl alcohol { trade(brand)name: PVA-105 (Kuraray Co., Ltd. make), the weight-average molecular weight of gpc measurement for 22000} with the nonionic surface active agent that provides in the table 3, trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation.
Comparative Examples 9
{ trade(brand)name: Chemistat SA-9 is (by Sanyo ChemicalIndustries with sodium polystyrene sulfonate, Ltd. make), the weight-average molecular weight that GPC measures for 40000} with the nonionic surface active agent that provides in the table 3, trolamine Citrate trianion, propylene glycol, alcalase 2.5L and water, the washing composition of the composition that provides in the table 7 is provided in preparation.
Table 1
The structure of the nonionic surface active agent that uses in embodiment and the Comparative Examples is shown in table 2 and 3.
EO and PO represent oxyethylene group and oxypropylene group respectively.EO/PO and EO-PO represent random addition and block addition respectively.Mw/Mn (experiment) is the value by gpc measurement.Mw/Mn (calculating) is the value that calculates from relational expression (3) or (4).Distrubited constant c is the value that calculates from relational expression (5) with the unreacted alcohol amount of measuring.
Table 2
Table 3
| Comparative Examples | Nonionic surface active agent |
| 1-4 | Identical with embodiment 26 |
| 5-7 | Identical with embodiment 15 |
| 8 | Identical with embodiment 29 |
| 9 | Identical with embodiment 30 |
To the washing composition for preparing among embodiment 1-38 and the Comparative Examples 1-9, detersive power, foaming power and washing composition stability have been tested.The results are shown in table 4-8.Testing method is described hereinafter.
Table 4
* Alcalase 2.5L: proteolytic enzyme (enzyme that Novo-Nordisk A/S makes)
Table 5
* Alcalase 2.5L: proteolytic enzyme (enzyme that Novo-Nordisk A/S makes)
Table 6
* Alcalase 2.5L: proteolytic enzyme (enzyme that Novo-Nordisk A/S makes)
Table 7
* Alcalase 2.5L: proteolytic enzyme (enzyme that Novo-Nordisk A/S makes)
Table 8
* Alcalase 2.5L: proteolytic enzyme (enzyme that Novo-Nordisk A/S makes)＜detergency test 〉
With artificially soiled cloth (looped fabric) Matsushita Electric Industrial Co., the centrifugal washer NA-F800P that Ltd makes washed 10 minutes under the following conditions, be 50 liters of volume of water, bath raio 30,25 ℃ of washing composition consumption 25 grams and water temperatures, with post rinsing 3 minutes, twice of rinsing.Calculate and estimate detersive power from following formula.
Detersive power (%)={ (R
w-R
s)/(R
I-R
s) * 100
R
IBe the reflectance of uncontaminated cloth, R
wBe the reflectance of the cloth washed, R
sIt is the reflectance of soiled cotton.With the multiple light courcess spectrophotometric colorimeter that Suga Test Instruments makes, measure reflectance at the 540nm place.
The artificially soiled cloth that uses is that dirt is formed the wet artificially soiled cloth that is shown in table 9, can obtain from TheSociety of Laundry Science, and its reflectance at the 540nm place is 40 ± 5%.
Table 9
Judgement criteria is as follows: ◎ represent detersive power be 40% or bigger zero expression detersive power be 32% or bigger, but represent that less than 40% △ detersive power is 20% or bigger, but less than 32% * the expression detersive power is less than 20%＜foaming power test
With the water-detergent solution of 1.5L 0.1%, spray the foaming power of foaming power trier (making) under estimating 25 ℃ by Ttujii Dyeing Machine Industry by the high-pressure injection type.
Judgement criteria is as follows: zero expression foaming height is that 20 millimeters or littler △ represent that foaming height is that 20-50 millimeter * expression foaming height is 50 millimeters or bigger＜washing composition is formed stable 〉
Washing composition was placed its outward appearance of visual observations 24 hours at 25 ℃.Stability according to following standard evaluation washing composition.
Judgement criteria is as follows: zero expression is not observed washing composition separation * expression and is observed the washing composition separation
Industrial applicability
Detergent builders of the present invention produce following effect: have good compatibility with surfactant, good detergency arranged when washing clothes, and particularly to the mud dirt, low bubble. And washing agent of the present invention has demonstrated good effect as laundry being damaged particularly centrifugal scrubber washing agent of littler rinsing maching.
Claims
Modification according to the 19th of treaty
1. a washing composition comprises as the quaternary ammonium salt (A) of the carbonyl bearing polymer of auxiliary agent and the water of 10-80 weight %.
2. according to the washing composition of claim 1, wherein the solubility parameter of (A) is 8.0-12.0.
3. according to the washing composition of claim 1 or 2, carbonyl bearing polymer wherein is a polyacrylic acid.
4. according to each washing composition among the claim 1-4, this washing composition also comprises nonionic surface active agent (B).
5. according to the washing composition of claim 4, wherein (B) is the compound of following general formula (1) expression: general formula R O-(A
1O)
p(wherein, R is the aliphatic hydrocarbyl with 8-18 carbon atom to-H (1), and p is the integer of 1-30, A
1Be alkylidene group) with 2-4 carbon atom.
6. according to the washing composition of claim 5, wherein (B) is the compound of following general formula (2) expression: general formula R O-[(C
2H
4O)
n(A
2O)
m]-(C
2H
4O)
q-(A
2O)
r{ wherein R is the aliphatic hydrocarbyl with 8-18 carbon atom to-H (2), A
2Be the alkylidene group with 3 or 4 carbon atoms, n is 0 or the integer of 1-12, and m is 0 or the integer of 1-6, and q is the integer of 1-16, and r is the integer of O or 1-15, (m+n+q) is the integer of 1-30, (n+q)/(m+n+q+r) is 0.5-1.0, [(C
2H
4O)
n(A
2O)
m] random addition of expression or block addition.
7. according to the washing composition of claim 6 or 7, wherein (B) is by alkylene oxide (b1) being added to the compound of preparation in the fatty alcohol (a1), below satisfying 1. and 2.: the 2. ratio of weight-average molecular weight (Mw) and number-average molecular weight (Mn), Mw/Mn, relational expression (3) or (4): Mw/Mn≤0.030Ln below satisfying (v)+1.010 (v＜10) (3) Mw/Mn≤-(v)+1.139 (v 〉=10) (4) { wherein for 0.026Ln, v is the average addition mole number that joins the alkylene oxide (b1) in one mole of fatty alcohol (a1), } the distrubited constant c that 2. calculates from following formula (5) is 2.0 or littler: c=(v+n
0/ n
00-1)/[Ln (n
00/ n
0)+n
0/ n
00-1] (5) { same meaning of definition in v and formula (3) or (4) wherein, n
00Be the mole number of used fatty alcohol (a1) in the reaction, n
0It is the mole number of unreacted fatty alcohol (a1).}
8. comprise as the organic amine salt of the carbonyl bearing polymer of auxiliary agent or the washing composition of quaternary ammonium salt (A) and compound (B), described compound (B) is by being added to alkylene oxide (b1) preparation in the fatty alcohol (a1), below satisfying 1. and 2.: the 3. ratio of weight-average molecular weight (Mw) and number-average molecular weight (Mn), Mw/Mn, relational expression (3) or (4): Mw/Mn≤0.030Ln below satisfying (v)+1.010 (v＜10) (3) Mw/Mn≤-(v)+1.139 (v 〉=10) (4) { wherein for 0.026Ln, v is the average addition mole number that joins the alkylene oxide (b1) in one mole of fatty alcohol (a1), } the distrubited constant c that 2. calculates from following formula (5) is 2.0 or littler: c=(v+n
0/ n
00-1)/[Ln (n
00/ n
0)+n
0/ n
00-1] (5)
{ same meaning of definition in v and formula (3) or (4) wherein, n
00Be the mole number of used fatty alcohol (a1) in the reaction, n
0It is the mole number of unreacted fatty alcohol (a1).}。
9. according to each washing composition among the claim 1-8, this washing composition contains cationic surfactant (C).
10. the washing composition that comprises nonionic surface active agent (B) and cationic surfactant (C), nonionic surface active agent (B) is by being added to alkylene oxide (b1) preparation in the fatty alcohol (a1), below satisfying 1. and 2.: the 1. ratio of weight-average molecular weight (Mw) and number-average molecular weight (Mn), Mw/Mn, relational expression (3) or (4): Mw/Mn≤0.030Ln below satisfying (v)+1.010 (v＜10) (3) Mw/Mn≤-(v)+1.139 (v 〉=10) (4) { wherein for 0.026Ln, v is the average addition mole number that joins the alkylene oxide (b1) in one mole of fatty alcohol (a1), } the distrubited constant c that 2. calculates from following formula (5) is 2.0 or littler: c=(v+n
0/ n
00-1)/[Ln (n
00/ n
0)+n
0/ n
00-1] (5) (same meaning of definition in v and formula (3) or (4) wherein, n
00Be the mole number of used fatty alcohol (a1) in the reaction, n
0It is the mole number of unreacted fatty alcohol (a1).}
11., wherein, (C) be at least a compound that is selected from the compound of following general formula (6)-(9) expression according to the washing composition of claim 9 or 10:
Wherein, in formula (6)-(9), R
1, R
2And R
3Expression hydrogen atom or have alkyl, alkenyl or the β-hydroxyalkyl of 1-24 carbon atom, R
4And R
5Expression has the alkyl of 1-24 carbon atom or hydroxyalkyl, benzyl or by formula :-(A
1O)
n-Z (A
1Be the alkylidene group with 2-4 carbon atom, Z is hydrogen atom or acyl group, and n is the integer of 1-50) expression group, R
6Expression has alkyl, alkenyl or the β-hydroxyalkyl of 1-36 carbon atom, and Y represents to have alkyl, alkenyl or the β-hydroxyalkyl of 1-36 carbon atom, by formula: R
4CO
2CH
2-(R
4Identical with the front) group of expression or by formula: R
4OCH
2-(R
4Identical with the front) group of expression, corresponding ion X
-Be to be selected from halogen ion, hydroxyl ion, to have the carbonic ether (or salt) that contains 1-4 carbon atom alkyl or sulfuric ester (or salt) ion and the alkyl that contains 1-24 carbon atom to be arranged or carboxylicesters (or salt) and one or more negatively charged ion of sulphonate (or salt) ionic of alkenyl.
12. according to each washing composition among the claim 4-11, this washing composition contains the organic amine salt or the quaternary ammonium salt (D) of lower molecular weight poly carboxylic acid.
Claims (12)
1. detergent builder comprise the organic amine salt or the quaternary ammonium salt (A) of carbonyl bearing polymer.
2. according to the detergent builder of claim 1, wherein the solubility parameter of (A) is 8.0-12.0.
3. according to the auxiliary agent of claim 1 or 2, wherein (A) is the salt that is derived from aliphatic series or cycloaliphatic amines or its alkylene oxide adduct.
4. according to each auxiliary agent among the claim 1-3, wherein carboxylic polymkeric substance is a polyacrylic acid.
5. washing composition comprises according to each detergent builder and nonionic surface active agent (B) among the claim 1-4.
6. according to the washing composition of claim 5, wherein (B) is the compound of following general formula (1) expression: general formula R O-(A
1O)
p(wherein, R is the aliphatic hydrocarbyl with 8-18 carbon atom to-H (1), and p is the integer of 1-30, A
1Be alkylidene group) with 2-4 carbon atom.
7. according to the washing composition of claim 6, wherein (B) is the compound of following general formula (2) expression: general formula R O-[(C
2H
4O)
n(A
2O)
m]-(C
2H
4O)
q-(A
2O)
r{ wherein R is the aliphatic hydrocarbyl with 8-18 carbon atom to-H (2), A
2Be the alkylidene group with 3 or 4 carbon atoms, n is 0 or the integer of 1-12, and m is 0 or the integer of 1-6, and q is the integer of 1-16, and r is 0 or the integer of 1-15, (m+n+q) is the integer of 1-30, (n+q)/(m+n+q+r) is 0.5-1.0, [(C
2H
4O)
n(A
2O)
m] random addition of expression or block addition.
8. according to the washing composition of claim 6 or 7, wherein (B) is by alkylene oxide (b1) being added to the compound of preparation in the fatty alcohol (a1), below satisfying 1. and 2.: the 1. ratio of weight-average molecular weight (Mw) and number-average molecular weight (Mn), Mw/Mn, relational expression (3) or (4): Mw/Mn≤0.030Ln below satisfying (v)+1.010 (v＜10) (3) Mw/Mn≤-(v)+1.139 (v 〉=10) (4) { wherein for 0.026Ln, v is the average addition mole number that joins the alkylene oxide (b1) in one mole of fatty alcohol (a1), } the distrubited constant c that 2. calculates from following formula (5) is 2.0 or littler: c=(v+n
0/ n
00-1)/[Ln (n
00/ n
0)+n
0/ n
00-1] (5) { same meaning of definition in v and formula (3) or (4) wherein, n
00Be the mole number of used fatty alcohol (a1) in the reaction, n
0It is the mole number of unreacted fatty alcohol (a1).}
9. according to each washing composition among the claim 5-8, this washing composition contains cationic surfactant (C).
10. the washing composition that comprises nonionic surface active agent (B) and cationic surfactant (C), nonionic surface active agent (B) is by being added to alkylene oxide (b1) preparation in the fatty alcohol (a1), below satisfying 1. and 2.: the 1. ratio of weight-average molecular weight (Mw) and number-average molecular weight (Mn), Mw/Mn, relational expression (3) or (4): Mw/Mn≤0.030Ln below satisfying (v)+1.010 (v＜10) (3) Mw/Mn≤-(v)+1.139 (v 〉=10) (4) { wherein for 0.026Ln, v is the average addition mole number that joins the alkylene oxide (b1) in one mole of fatty alcohol (a1), } the distrubited constant c that 2. calculates from following formula (5) is 2.0 or littler: c=(v+n
0/ n
00-1)/[Ln (n
00/ n
0)+n
0/ n
00-1] (5) { same meaning of definition in v and formula (3) or (4) wherein, n
00Be the mole number of used fatty alcohol (a1) in the reaction, n
0It is the mole number of unreacted fatty alcohol (a1).}
11., wherein, (C) be at least a compound that is selected from the compound of following general formula (6)-(9) expression according to the washing composition of claim 9 or 10:
Wherein, in formula (6)-(9), R
1, R
2And R
3Expression hydrogen atom or have alkyl, alkenyl or the β-hydroxyalkyl of 1-24 carbon atom, R
4And R
5Expression has the alkyl of 1-24 carbon atom or hydroxyalkyl, benzyl or by formula :-(A
1O)
n-Z (A
1Be the alkylidene group with 2-4 carbon atom, Z is hydrogen atom or acyl group, and n is the integer of 1-50) expression group, R
6Expression has alkyl, alkenyl or the β-hydroxyalkyl of 1-36 carbon atom, and Y represents to have alkyl, alkenyl or the β-hydroxyalkyl of 1-36 carbon atom, by formula: R
4CO
2CH
2-(R
4Identical with the front) group of expression or by formula: R
4OCH
2-(R
4Identical with the front) group of expression, corresponding ion X
-Be to be selected from halogen ion, hydroxyl ion, to have the carbonic ether (or salt) that contains 1-4 carbon atom alkyl or sulfuric ester (or salt) ion and the alkyl that contains 1-24 carbon atom to be arranged or carboxylicesters (or salt) and one or more negatively charged ion of sulphonate (or salt) ionic of alkenyl.
12. according to each washing composition among the claim 5-11, this washing composition contains the organic amine salt or the quaternary ammonium salt (D) of lower molecular weight poly carboxylic acid.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37496598 | 1998-12-09 | ||
| JP374965/1998 | 1998-12-09 | ||
| JP28605299 | 1999-10-06 | ||
| JP286052/1999 | 1999-10-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1290293A true CN1290293A (en) | 2001-04-04 |
| CN1197945C CN1197945C (en) | 2005-04-20 |
Family
ID=26556140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998028215A Expired - Fee Related CN1197945C (en) | 1998-12-09 | 1999-11-26 | Builder for detergents and detergent |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR20010040783A (en) |
| CN (1) | CN1197945C (en) |
| MY (1) | MY132557A (en) |
| TW (1) | TWI230197B (en) |
| WO (1) | WO2000034428A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107821423A (en) * | 2017-10-18 | 2018-03-23 | 福建恒安集团有限公司 | A kind of anti-corrosion synergist, preparation method and applications |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101933512A (en) * | 2010-07-05 | 2011-01-05 | 高旭 | Disinfectant capable of being used with high dilution multiples, preparation method and application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4897642A (en) * | 1988-10-14 | 1990-01-30 | Secura Corporation | Vehicle status monitor and management system employing satellite communication |
| JP2738405B2 (en) * | 1995-12-14 | 1998-04-08 | 日本電気株式会社 | Mobile station for goods delivery vehicles, command center for delivery management, and goods delivery management system |
| JPH106846A (en) * | 1996-06-20 | 1998-01-13 | Jiyamutekusu:Kk | Remote monitoring method for prescribed information on cargo and vehicle |
| JPH10302197A (en) * | 1997-04-28 | 1998-11-13 | Yazaki Corp | Physical distribution carrier managing method/device |
| JPH10307984A (en) * | 1997-05-08 | 1998-11-17 | Mitsubishi Heavy Ind Ltd | On-vehicle running management device |
-
1999
- 1999-11-25 TW TW088120614A patent/TWI230197B/en not_active IP Right Cessation
- 1999-11-26 WO PCT/JP1999/006637 patent/WO2000034428A1/en not_active Application Discontinuation
- 1999-11-26 KR KR1020007008676A patent/KR20010040783A/en not_active Application Discontinuation
- 1999-11-26 CN CNB998028215A patent/CN1197945C/en not_active Expired - Fee Related
- 1999-12-08 MY MYPI99005346A patent/MY132557A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107821423A (en) * | 2017-10-18 | 2018-03-23 | 福建恒安集团有限公司 | A kind of anti-corrosion synergist, preparation method and applications |
| CN107821423B (en) * | 2017-10-18 | 2021-04-02 | 福建恒安集团有限公司 | Preservative |
Also Published As
| Publication number | Publication date |
|---|---|
| MY132557A (en) | 2007-10-31 |
| CN1197945C (en) | 2005-04-20 |
| TWI230197B (en) | 2005-04-01 |
| KR20010040783A (en) | 2001-05-15 |
| WO2000034428A1 (en) | 2000-06-15 |
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