CN108949394A - A kind of concentrated type liquid detergent composition being substantially free of solubilizer - Google Patents

Abstract

The invention discloses a kind of concentrated type liquid detergent compositions for being substantially free of solubilizer.Count by weight percentage, it is grouped as by following group:

Description

A kind of concentrated type liquid detergent composition being substantially free of solubilizer

Technical field

The invention belongs to daily chemical industry technical fields, and in particular to a kind of concentrated type liquid for being substantially free of solubilizer Detergent composition.

Background technique

Currently, since concentrated type liquid detergent composition has many advantages, such as easy to use, suitable machine washing technique, and And formula is flexible, simple process, energy conservation and environmental protection, can efficiently control and reduce storage, packaging, transportation cost, therefore more next Attention more by consumer, production firm and retailer.

It is well known that surfactant increases the change that phase can occur with concentration in aqueous solvent, it is higher viscosity to be generated And it is difficult to the liquid crystalline phase dispersed.Moreover, surfactant activity object content is higher in concentrated type liquid detergent composition, it is easy There are gelation problems, causes to be difficult to be dispersed into uniform product in production, and product memory phase is easy shakiness due to layering It is fixed, while viscosity is larger, be difficult to topple over and solution rate is slow, seriously affects the convenience used, therefore enrichment washs Agent must solve the problems, such as it is the formation for preventing tenside gel.Well known in the industry, the method for preventing gelation from being formed is i.e. Solubilizer is added in the product, by changing the form of surfactant micellar, forms it by liquid crystalline phase and is easier to flow, be easier to The spherical or rod-shaped micelle of dissolution.

General solubilizer includes organic solvent and cosolvent, wherein organic solvent such as ethyl alcohol, propylene glycol, dipropyl two Alcohol n-butyl ether, ethoxylation benzyl alcohol etc.；Cosolvent is generally short-chain alkyl benzene sulfonate, such as paratoluenesulfonic acid sodium salt, isopropylbenzene Sodium sulfonate etc..Wherein the solubilizing effect of small molecular alcohol solvent is most significant, but since its flash-point is lower, security risk is larger.Such as Chinese patent CN103275829A discloses a kind of Superconcentrated washing liquid without containing solvent, uses sodium xylene sulfonate or isopropyl Benzene sulfonic acid sodium salt is solubilizer, to obtain the concentrated type product of high stability；One disclosed in Chinese patent CN107667165A It plants in dense liquids laundry detergent composition, the alcohol that solubilizer is 5~40%；And disclosed in Chinese patent CN102549133B In a kind of detergent composition, not only with a large amount of alcoholic solvent, but also include 1~6% alkamine gel breaker.

However, above-mentioned solubilizer can not provide other function in addition to the formation for being able to suppress gel state for composition Effect point.It is well known that the direct decontamination of these solubilizer itself is smaller, while can not promote washing functions, and inhibiting Foam, Color care, fabric nursing etc. are also without obvious action, but its dosage and higher cost, dramatically increase formula at This, reduces the ratio of performance to price of product.

Therefore, in concentrated type detergent product, auxiliary agent in the urgent need to address can not only destroy and inhibit surface The formation of activating agent gel state, and the technical issues of be capable of providing other Advantageous Effects points, thus guarantee composition have compared with High storage stability, while washing function is excellent.

Summary of the invention

The purpose of the present invention is to provide a kind of concentrated type liquid detergent compositions for being substantially free of solubilizer, with effective Solve the deficiencies in the prior art place.

In order to achieve the above objectives, the present invention adopts the following technical scheme:

A kind of concentrated type liquid detergent composition being substantially free of solubilizer, count by weight percentage, by such as the following group It is grouped as:

Wherein, the number-average molecular weight of the polyetheramine is less than 3000；The range of number-average molecular weight of the aryl polymer is 1000~20000；The mass ratio of the polyetheramine and aryl polymer is 10:1~1:4.

Preferably, the mass ratio of the polyetheramine and aryl polymer is 8:1~1:1.8.

Preferably, the sum of weight percent of the polyetheramine and aryl polymer is 0.2~5%.

Preferably, the number-average molecular weight of the polyetheramine is 200~1500.

Preferably, the aryl polymer is the aryl polymer that main chain and/or side chain contain aryl；The aryl packet Include phenyl.

Preferably, the aryl polymer that the main chain contains aryl is polyester polymers, and there is following general formula: A-B- C, in which: A and C is the residue of polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymers, and the molecular weight ranges of A and C are 400~10000；B is that terephthalic acid (TPA), 5- sulfonyl-M-phthalic acid or the two are gathered with what ethylene glycol or propylene glycol were formed Ester polymer residue, the molecular weight ranges of B are 400~10000；The B is connect with A and B with C with ester group；The side chain Aryl polymer containing aryl is modified styrene polymer.

Preferably, the surfactant system includes at least one selected from following surfactant: fatty acid salt, Anionic surfactant, cationic surfactant, nonionic surfactant, zwitterionic surfactant.

Preferably, the weight percent of the surfactant system in the composition is 30~50%；The surface Activating agent by 0~10% fatty acid salt, 1~30% anionic surfactant, 1~40% non-ionic surface active Agent, 0~30% zwitterionic surfactant and 0~30% cationic surface active agent composition.

Preferably, the washing assisant and additive include at least one substance selected from the following: enzyme preparation, alkaline agent, PH adjusting agent, viscosity modifier, preservative, colorant, fluorescent whitening agent, colour stabilizer and essence.

Preferably, the range of viscosities of the composition is 100~5000cst, pH range is 7.5~10.0.

The present invention has product excellent by the compound system of increase polyetheramine and aryl polymer in product formula Storage stability, gel and lamination will not occur long-term storage, but also make with excellent decontamination synergy With.

Specific embodiment

For those skilled in the art, by reading content disclosed in this specification, technology of the invention is special Sign, beneficial effect will become obvious.

Unless otherwise specified, all percentages, score and ratio are calculated by the total weight of the present composition.It removes Non- otherwise indicated, all wt in relation to ingredients listed gives the content of active material, thus they be not included in it is commercially available The solvent or by-product that may include in the material of acquisition.This paper term " weight content " available symbols " % " indicate.

Unless otherwise specified, the environment at 25 DEG C occurs for all preparations and test herein.

Herein "include", "comprise", " contain, " containing ", " having " or other variants be intended to it is non-enclosed include, It is not distinguished between these terms.Term "comprising", which refers to, can be added not the other steps for influencing final result and ingredient.Term "comprising" further includes term " Consists of " and "consisting essentially of ...".The compositions and methods of the invention/technique may include, It is made from it and substantially by essential elements described herein and limit entry and described herein any additional or optional Ingredient, component, step or limit entry composition.

Detergent composition of the present invention is substantially free of solubilizer.Term " being substantially free of ", which refers to, is preparing the present invention Solubilizer level is not artificially added in solubilizer or a combination thereof object in the detergent composition being related to less than 1%.Institute is public in the industry Know, a certain amount of solvent or residual monomer can be contained in certain raw materials of detergent composition, such as propylene glycol, ethylene glycol, ethyl alcohol Deng, therefore in compositions formulated, the substance may be brought into.Term " being substantially free of " refers to solubilizer level in composition Less than 1%.

A kind of concentrated type liquid detergent composition being substantially free of solubilizer of the present invention is by weight percentage It calculates, is grouped as by following group:

Wherein:

1, polyetheramine (PEA)

In the present invention, it is polyether structure that polyetheramine, which is a kind of main chain, and end active functional group is amine in whole or in part The polymer of base.Polyetheramine is generally by polyethers, such as polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymers, sweet Oil/propylene glycol copolymers etc., ammonification obtains at high temperature under high pressure.Well known in the industry, straight chain type polyetheramine (such as D-230) energy Aromatic in enough stable laundry detergent compositions and provide more longlasting fragrance.And high molecular weight (being higher than 1000), branched chain type, three The polyetheramine (T-5000) of function, then foam when liquid detergent can be inhibited to use.It is commercialized the polyetheramine bought at present Including mono amino, double amino, triamido polyetheramine, a series of products of the molecular weight from 230 to 5000, such as U.S. Huntsman Company production withFor M-2070, D-230, D-400, T-403 etc. of commodity.

In concentrated type liquid detergent composition of the present invention, weight of the polyetheramine in the detergent composition Percentage composition 0.1%~10% is measured, the number-average molecular weight of the polyetheramine is less than 3000, more preferably from 200~1500.

2, aryl polymer

In the present invention, the aryl polymer, which refers to, contains aryl in the main chain and/or side chain of polymer, and its number is divided equally Son amount range is 1000~20000, wherein the preferred phenyl of aryl.Wherein the polymer in main chain containing aryl is mainly that polyester is poly- Object is closed, and the polymer in side chain containing aryl is mainly modified styrene polymer.

1) polyester polymers

Polyester polymers refer to the compound with structure shown in the following general formula: A-B-C.

Wherein: A and C is the residue of polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymers, the molecular weight of A and C Range is 400~10000；B is terephthalic acid (TPA), 5- sulfonyl-M-phthalic acid or the two and ethylene glycol or propylene glycol shape At polyester polymers residue, the molecular weight ranges of B are 400~10000；The B is connect with A and B with C with ester group.

Well known in the industry, polyester polymers, such as above-mentioned polyester polyethers block copolymer, in washing process, the polymer It is adsorbed in oiliness or graininess dirt by the polyester block of hydrophobicity, hydrophilic block then stretches in water, so that dirty Dirt has hydrophily, realizes the dirt-removing power for improving detergent, and prevents dirt from returning the effect of being stained with.It is compounded with polyester polymers Detergent composition usually has the soil release performance of excellent greasy dirt and graininess dirt, and soil release performance is significantly better than surfactant more The detergent composition of high-content.Suitable polyester polymers include the Repel-o-tex series polymeric of Rhodia company production Texcare series polymer such as SRA300, SRA100 of object such as SF-2 and/or Clariant company production.

2) modified styrene polymer

Modified styrene polymer refers to that styrene and monomer containing hydrophilic radical are copolymerized, so as to improve styrene polymer Water solubility is such as used with trade name725,747 etc. of series.Well known in the industry, acrylic acid modified benzene second Alkene polymer can also inhibit metal erosion, inhibit soap scum deposition, to provide protection tableware, prevent fabric xanthochromia and whiteness from protecting The beneficial effect held.

In concentrated type liquid detergent composition of the present invention, aryl polymer is in the detergent composition Weight percentage 0.1%~10%, and in composition the mass ratio of polyetheramine and aryl polymer 10:1~1:4 it Between, preferably 8:1~1:1.8.In addition, the sum of weight percent of the polyetheramine and aryl polymer is preferred in the present invention It is 0.2~5%.

3, surfactant system

The surfactant system includes at least one selected from following surfactant: fatty acid salt, anion table Face activating agent, cationic surfactant, nonionic surfactant, zwitterionic surfactant.The surfactant The weight percent of system in the composition is preferably 30~50%.Further, the surfactant is preferably by 0~10% Fatty acid salt, 1~30% anionic surfactant, 1~40% nonionic surfactant, 0~30% both sexes from Sub- surfactant and 0~30% cationic surface active agent composition.

1) fatty acid salt

Fatty acid refers to that the organic matter of a carboxyl and aliphatic hydrocarbon chain is contained in one end, including Salt of saturated fatty acid and Unsaturated fatty acid salt.Fatty acid salt is that fatty acid is formed after alkali saponified.Usually used alkaline agent be sodium hydroxide and Potassium hydroxide.Salt of saturated fatty acid is the fatty acid salt without containing carbon-carbon double bond.Selected from octanoic acid, capric acid, lauric acid, myristic acid, Palmitic acid, stearic acid, arachidic acid one or more mixtures.Unsaturated fatty acid salt is containing one or more carbon-carbon double bonds Fatty acid salt.According to the difference of double bond number, and the monounsaturated fatty acids containing double bond can be divided into and containing multiple The polyunsaturated fatty acid of double bond.Monounsaturated fatty acids has oleic acid, and polyunsaturated fatty acid has linoleic acid, linolenic acid, peanut Tetraenoic acid etc..

In liquid detergent composition of the present invention, weight percent of the fatty acid salt in the detergent composition Content preferably is selected from 0.1~10%, more preferably from 0.5~5.0%.

In liquid detergent composition of the present invention, it is 10 to 20 that the fatty acid salt, which is selected from carbon atom, One or more mixtures of the alkali metal salt of fatty acid.

2) anionic surfactant

In the present invention, the total weight of the mixture of anionic surfactant be liquid detergent composition total amount 1%~ 30%, it preferably is selected from 1%~10%.

The anionic surfactant is selected from sulfonate surfactant, carboxylate surfactant, sulfate One or more mixtures of type surfactant；It preferably is selected from alkylbenzene sulfonate, the alkyl sulfate of C8 to C18, C8 extremely Ethoxylated fatty alcohol sulfate, alpha-alkene sulfonate, fatty acid alkyl ester sulfonate, the ethoxylized fatty alcohol ether carboxylic of C18 One or more of mixtures of hydrochlorate.

In some embodiments, the mixture of anionic surfactant preferably comprises alkylbenzene sulfonate and its derivative Object.The alkylbenzene sulfonate meets following general formula:

Wherein R₁It is the alkyl that carbon number is 6 to 24, M⁺For cation.R₁The alkyl that can be straight chain, is also possible to branch Alkyl；The alkyl that can be saturation is also possible to the alkyl containing one or more unsaturated double-bonds.More preferable R₁It is that carbon number is 8 to 18 straight chained alkyl.

In some embodiments, the mixture of anionic surfactant contains the aliphatic alcohol sulfate of ethoxylation. Ethoxylated fatty alcohol sulfate is the derivative of ethoxylate fatty alcohol, has following general formula:

Wherein R₁It is the alkyl that carbon number is 6 to 24；X is 0.5 to 30；Wherein M⁺For cation.R₁It can be the alkane of straight chain Base is also possible to the alkyl of branch；The alkyl that can be saturation is also possible to the alkane containing one or more unsaturated double-bonds Base.It is preferred that R₁It is the straight chained alkyl that carbon number is 8 to 18.X represents average ethoxylation degree, is 0.5 to 30, preferably 0.5 to 10, More preferable 0.5 to 3.

In some embodiments, containing alpha-alkene sulfonate, there is following general formula:

Wherein a is 0 to 2, wherein M⁺For cation, R₁It is the alkyl that carbon number is 6 to 24, preferably R₁Be carbon number be 8 to 18 Alkyl.

The anionic surfactant can also include one kind and a variety of mixing of alkyl sodium disulfonate or derivatives thereof Object, optimizing alkyl diphenyl oxide disulfonate, suitable example are disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt.Fatty acid can also be contained Alkyl sulfate, preferably fatty acid methyl ester sulfate (MES), fatty acid carbon number preferably 8 to 18.It can also include sulfo group Succinate, preferably disodium alkyl polyoxyethylene sulfosuccinate, are put down by fatty alcohol carbon number preferably 8 to 18 Equal degree of ethoxylation is preferably 2.0.

In some embodiments, the mixture of anionic surfactant contains fatty acid salt.Fatty acid salt is fat What acid was formed after alkaline good fortune.Usually used alkaline agent is sodium hydroxide and/or potassium hydroxide.Liquid of the present invention is washed It washs in agent composition, the fatty acid salt is selected from the metal salt for the fatty acid that carbon atom is 10 to 20, and preferably carbon atom is 10 to 16 linear alkyl fatty acids.

Its cation of anionic surfactant described above can make alkali metal ion or alkaline-earth metal ions, preferably Sodium ion.

3) nonionic surfactant

In the present invention, the total weight of the mixture of nonionic surfactant is the 1% of liquid detergent composition total weight ~40%, it preferably is selected from 1%~20%.

The nonionic surfactant is selected from fatty alcohol alkoxy compound, alkyl polyglycoside, fatty acid alkoxylate One or more mixing of object, fatty acid ethoxylate, fatty acid alkyl alcohol amide, ethoxylated sorbitan acid alcohol ester Object.

In some embodiments, non-ionic surfactant mixture preferably comprises fatty alcohol alkoxy compound, described Fatty alcohol alkoxy compound has following general formula:

Wherein, n is 6 to 24；X is that 0.5 to 30, y is 0 to 10.

The fatty alcohol alkoxy compound is the ring-opening polymerisation under basic catalyst effect of fatty alcohol and epoxyalkane Product, therefore be mixture.Fatty alcohol includes the isomery alcohol of straight chain alcohol or branch.Alkoxy grp includes ethoxy group and the third oxygen Group.The fatty alcohol that the preferred carbon number of fatty alcohol is 8 to 18, preferred alcohol includes but is not limited to hexanol, octanol, decyl alcohol, 2- second Base alcohol, 3- propyl enanthol, laruyl alcohol, different three decyl alcohol, tridecanol, tetradecanol, hexadecanol, Palmitoleyl alcohol, stearyl alcohol, One kind and its mixture of isooctadecanol, oleyl alcohol, sub- oleyl alcohol, linolenyl alcohol.Average ethoxylation degree x preferably 2 to 12.Preference Son is SHELL company NEODOL series linear primary alcohol ethoxylate product, DOW company ECOSURFEH series ethoxylation With third oxidation 2-ethylhexanol product, the ethoxylation of BASF AG LutensolXL series and third oxidation 3- propyl enanthol product and BASF AG LutensolXP series ethoxylation 3- propyl enanthol product.

In some embodiments, non-ionic surfactant mixture preferably comprises alkyl polyglycoside, has following logical Formula:

Wherein, it is 1.1 to 3 that n, which is 6 to 24, p, and preferably n is 8 to 16.Suitable alkyl polyglycoside such as BASF AG Glucopon series alkyl glycosides product.

Non-ionic surfactant mixture can contain fatty acid alkoxylates, preferably be selected from ethoxylation C8 to C18 Aliphatic ester, average ethoxylation degree are 2 to 10.Ethoxylated sorbitan acid alcohol Arrcostab, alkyl carbon number can be contained It is 6 to 18, average ethoxyquin degree is 4 to 20；Suitable example is Corda company's T ween series of products.

Non-ionic surfactant mixture can contain fatty acid alkyl alcohol amide, and the carbon number of fatty acid is 6 to 24, can To be the fatty acid of straight chain, it is also possible to the fatty acid of branch, can be the fatty acid of saturation, be also possible to unsaturated fat Acid；Alkylol number is 0 to 2.The glycollic amide that preferred fatty acid carbon number is 8 to 18, diglycollic amide, isopropanol amide, Suitable example is coconut acid diethanolamide.

Non-ionic surfactant mixture can contain fatty acid methyl ester ethoxylate, and general formula is as follows:

Wherein, n is 6 to 24；X is 2 to 20, and preferably n is that 8 to 18, x is 0.5 to 30.It is preferred that x is 4 to 10.

Non-ionic surfactant mixture can contain polyether surfactant.Polyether surfactant is a kind of Polymer, the nonionic surfactant containing oxidation ethylene and/or oxidation trimethylene repetitive unit, suitable example such as BASF are public Take charge of Pluronic series of products.

4) zwitterionic surfactant

The zwitterionic surfactant is selected from amino acid type surfactant, amine oxide type surfactant, sweet tea Dish alkaline surfactant, one or more mixtures of Imidazoline Surfactants；Including but not limited to: alkyl betaines Alkali, fatty acid amide glycine betaine, fattyamidopropyl betaine, fatty amide propyl hydroxypropyl sulfonated betaine, including alkyl second Sour sodium form imidazoline, fatty acid type imidazoline, sulfonic acid type imidazoline；Alanine derivatives, glycine derivative；Alkyl-dimethyl Base amine oxide, fatty acyl amido dimethylamine oxide etc..

5) cationic surfactant

The cationic surfactant includes quaternary ammonium salt surface active agent, heterocyclic surfactant, polymer Type cationic surfactant.It include: single long linear quaternary ammonium salt, double long linear quaternary ammonium salts, benzyl quaternary ammonium salt, hydroxyalkyl quaternary ammonium Salt, fatty amide propyl hydroxyalkyl quaternary ammonium salt, has vinyl pyrrolidone and unsaturated amides or unsaturated quaternary ammonium salt to be copolymerized The multi-quaternary ammonium salt arrived.

4, washing assisant and additive

4.1 washing assisant

Liquid detergent composition of the present invention may include washing assisant, the washing assisant be selected from enzyme preparation and Its stabilizer, bleach system, anti redeposition agent, functional polymer, chelating agent and fluorescent whitening agent.

4.1.1 enzyme preparation and its stabilizer

Detergent composition of the present invention may include one or more of enzyme preparations, to provide clean-up performance, knit Object nursing and/or other beneficial effects.The enzyme preparation is selected from the group of following enzyme composition: protease, alpha-amylase, cellulose Enzyme, hemicellulase, phosphatidase, esterase, lipase, peroxidase/oxidizing ferment, pectase, lyases, mannase, Cutinase, reductase, zytase, amylopectase, tannase, pentosanase, maltosan, arabinase, β-Portugal are poly- Carbohydrase.Common enzyme preparation is protease, amylase, lipase, cutinase and/or cellulase.Enzyme preparation content is washing The 0.001% to 5% of agent composition, preferably 0.01% to 2%.

Detergent composition of the invention may include the enzyme stabilising system for accounting for composition weight 0.001% to 10%.Institute Stating enzyme stabilising system can be compatible with detergent composition, may include calcium ion, boric acid, borax, propylene glycol, glycerol, polyalcohol One kind and its mixture.The weight and dosage of enzyme stabilising system are in the form of according to detergent composition and form and enzyme system The type of agent is adjusted.

4.1.2 bleach system

Liquid detergent composition of the present invention may include bleach system.Bleach system is bleached comprising hypohalite Agent, peroxide bleaches.Peroxide typically comprises hydrogen peroxide source and bleach activating system.Hydrogen peroxide source include but It is not limited to perborate, persulfate and their mixture.Bleach system may include bleach-activating, and the bleaching is lived For promoting peroxide, fast decoupled generates oxygen to agent at a lower temperature, the group selected from following compound composition: four acetyl Base ethylenediamine, benzoyl caprolactam, 4- nitrobenzoylcaprolactam, 3- chlorobenzoylcaprolactam, benzoyl It is oxygroup benzene sulfonate, nonanoly acyloxy benzene sulfonate, phenol benzoate, decanoyloxybenzenesulphonate, benzoyl valerolactam, pungent Acyloxybenzenesulfonic acids salt, transition metal bleach catalyst.

Liquid detergent composition of the present invention can also include ozone stabilizer, and the ozone stabilizer is for adjusting It is had suffered the speed that peroxide breaks down generates hydrogen peroxide, so that the local concentration of hydrogen peroxide is unlikely to excessive, suitable example is The organic phosphoric acid of the polyfunctionalities such as 1-hydroxy ethylidene-1,1-diphosphonic acid, ethylenediamine tetraacetic methene phosphoric acid.In some embodiments, bleach system Content be liquid detergent composition total weight 0.01% to 30%, preferably 0.01% to 20%, more preferably 0.01% to 10%.

4.1.3 anti redeposition agent

From the viewpoint of effectively improving washing effect, it may include in liquid detergent composition of the present invention anti- Redeposited agent.The anti redeposition agent includes but is not limited to the group of following compound composition: cellulose derivative, such as carboxylic first Base cellulose, ethylhydroxyethylcellulose, methylcellulose；The homopolymer and copolymer of vinyl pyrrolidone, such as straight chain Polyvinylpyrrolidone, the copolymer of vinyl pyrrolidone and vinyl acetate, vinyl pyrrolidone and vinyl miaow The copolymer of azoles；Polycarboxylate, such as polyacrylate, polyacrylic acid poly copolymer, acrylic acid-acrylic ester-sulphur Hydrochlorate copolymer.Anti redeposition agent content in liquid detergent composition is 0.01% to 5%, preferably 0.01% to 2%.

4.1.4 functional polymer

Detergent composition of the present invention may include amphipathic alkoxylate grease cleaning polymer, have balance Hydrophilicity and hydrophobic performance so that they remove fat particles from fabric surface or hard surface.The amphipathic alkoxylate A kind of embodiment of grease cleaning polymer is comprising one or more cored structures and multiple alcoxyls for being connected to the cored structure Base group, cored structure can with but be not limited to the molecular formula such as ethylenediamine, trien, tetren as H₂N (C₂H₄NH)_nThe linear amine structure of H or star-like polyethyleneimine, Alkoxylated groups can with but be not limited to polyoxyethylene Base, polyoxypropylene base and/or their block and/or random copolymerizable group.

In liquid detergent composition of the present invention, amphipathic alkoxylate grease cleaning polymer is in the liquid Weight percentage in detergent composition is 0~10.0%, preferably 0.1~5.0%, more preferably 0.5~2.0%.

Detergent composition of the present invention may include carboxylate polymer and/or modified carboxylic acid ester polymer, to increase Scavenging activity of the strong composition to grease.Including carboxylate polymer can be polyacrylate homopolymers or maleate/ The Random copolymer RCP of acrylate and alkoxylated polycarboxylates are the polyacrylate containing polyoxyethylene base side chain. Its molecular weight is usually between about 2000 to about 50000.In liquid detergent composition of the present invention, carboxylate polymer And/or weight percentage of the modified carboxylic acid ester polymer in the liquid detergent composition is 0~10.0%, preferably 0.1~5.0%, more preferably 0.5~2.0%.

Detergent composition of the present invention may include polycarboxylate and/or modified polycarboxylic acid salt, to enhance composition Scavenging activity and inhibition calcium scale to graininess dirt are formed.Gather including one or more double bond containing aliphatic carboxylic acid monomers The water soluble salt of homopolymer and copolymer made of conjunction, double bond containing aliphatic carboxylic acid monomer used include but is not limited to acrylic acid, Methacrylic acid, maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene propylmalonic acid.Modified polycarboxylic acid Contain polyoxyethylene groups or alkyl on the side chain of salt.Its molecular weight is usually between about 2000 to about 10000.The present invention relates to Liquid detergent composition in, the weight of polycarboxylate and/or modified polycarboxylic acid salt in the liquid detergent composition Percentage composition is 0~10.0%, preferably 0.1~5.0%, more preferably 0.5~2.0%.

4.1.5 chelating agent

Liquid detergent composition of the present invention may include one or more metal ion chelation agents, including copper, iron and/ Or manganese chelating agent and their mixture.These chelating agents can reduce the dense of the metal ion to dissociate in liquid detergent Degree, to reduce deactivation of these metal ions to enzyme preparation, catalyticing decomposition action to other components etc..It can be used as chela Mixture includes aminocarboxylate, amino phosphonates etc., including but not limited to edetate (EDTA), nitrilotriacetic acid salt (NTA), diethylentriamine pentacetate (DTPA), alanine diacetin (MGDA), glutamic acid diacetic acid salt (GLDA) and/ Or ethylenediamine tetraacetic (methylene phosphate salt) (EDTMPA), ammonia three (methylene phosphate salt) (ATMP), five (methylene of diethylenetriamines Based phosphates) (DTPMP), hydroxy-ethane diphosphonate (HEDP) and ethylenediamine disuccinate (EDDS) and they are mixed Close object.In liquid detergent composition of the present invention, weight percent of the chelating agent in the liquid detergent composition Content is 0~20.0%, preferably 0.1~5.0%, more preferably 0.5~2.0%.

4.1.6 fluorescent whitening agent

The technology that application of the fluorescent whitening agent in liquid detergent composition is well-known in the art, and it is commercially available glimmering Optical brightener commodity are abundant.Fluorescent whitening agent exists in the form of its alkali metal salt (mostly sodium salt).Preferred fluorescent whitening agent Include but unlimited with distyryl biphenyl compound.Suitable example is bis- (the 2- sodium sulfonate styryl) biphenyl of 4,4'-, Such as the product of BASF AG's CBS-X trade mark.The dosage of fluorescent whitening agent is the 0.01% to 2wt% of total composition, preferably 0.01% to 0.1%.

In liquid detergent composition of the present invention, weight of the fluorescent whitening agent in the liquid detergent composition Measuring percentage composition is 0.01~2.00%, preferably 0.05~1.00%, more preferably 0.05~0.50%.

4.2 additive

Liquid detergent composition of the present invention includes following optional additive: alkaline agent, viscosity modifier, anti-corrosion Agent, colorant, colour stabilizer and essence one or more compositions mixture.

Liquid detergent composition of the present invention may include one or more alkaline agents, and alkaline agent is selected from sodium hydroxide, Potassium hydroxide, alkali carbonate, the silicate of alkali metal.Weight percent of the alkaline agent in the liquid detergent composition contains Amount is 0.01~30.0%, preferably 0.05~10.0%, more preferably 0.05~5.0%.

Liquid detergent composition of the present invention may include one or more of viscosity modifiers, suitable to provide Viscosity.Suitable viscosity modifier such as salt, polysaccharide, sizing material, short chain fatty alcohol, short chain fatty alcohol alkyl ether.Suitable example Be sodium chloride, sodium formate, sodium acetate, ethyl alcohol, propylene glycol, sodium citrate, alkyl-hydroxyalkylcelluloswith ether, carragheen, xanthan gum, Polyacrylamide derivative.Weight percentage of the viscosity modifier in the liquid detergent composition be 0.01~ 30.0%, preferably 0.05~10.0%, more preferably 0.05~5.0%.

In some embodiments, liquid detergent composition of the present invention preferably comprises preservative, suitable example Son is phenoxy group alcohol, sodium benzoate；Isothiazolinone and its derivative, as methylisothiazolinone, methylchloroisothiazandnone, Or mixtures thereof one kind of benzoisothiazolinone.Preservative dosage is 0.001% to 5%, preferably 0.01% to 2%.

The dynamic viscosity of liquid detergent composition of the present invention is 10cst~15000cst, more preferable 50cst ~5000cst, and even more preferably 200cst~5000cst.The pH of liquid detergent composition of the present invention PH7.5~pH10.0, optimal selection is from pH8.0~pH9.0.

A kind of concentrated type liquid detergent composition being substantially free of solubilizer of the present invention, using art technology Various method preparations known to personnel.The preparation of the composition can be carried out by conventional means, specifically should be according to component The stability of state and effect and component in the solution selects suitable processing temperature and process time.

Without being further described, it is believed that those skilled in the art can use this using the above to the maximum extent Invention.The following examples purpose is to be further described and show specific embodiment within the scope of the present invention.Therefore, real It applies example to be interpreted as being only used for showing the present invention in more detail, without the content limiting the invention in any way.

In following embodiments, preparation method of the invention, comprising the following steps:

1) a part of deionized water and alkali are added into batch tank；

2) stirring is started, is warming up to 60 DEG C, fatty acid heating be saponified as fatty acid salt under alkaline condition, stirs to molten Solution is complete；

3) anionic surfactant, nonionic surfactant and amphoteric surfactant are sequentially added, is stirred to molten Solution is complete；

4) stop heating, balance deionized water is added into batch tank, is cooled to 40 DEG C or less；

5) polyetheramine and/or aryl polymer is added, stirs evenly；

6) pH is adjusted；

7) additives such as preservative are added, stirring is to being completely dissolved；

8) viscosity is adjusted.

In the following embodiments, unless otherwise specified, all contents are weight percentages, related ingredients listed Content is the content of the active material by conversion.

In the described embodiment, following abbreviations will be used, and have the function of being indicated.

KOH: potassium hydroxide neutralizes fatty acid saponification and prepares fatty acid salt, alkaline agent.

NaOH: sodium hydroxide neutralizes fatty acid saponification and prepares fatty acid salt, alkaline agent.

Liquid alkaline: the sodium hydrate aqueous solution that mass percent containing sodium hydroxide is 32% neutralizes fatty acid saponification and prepares rouge Fat hydrochlorate and/or neutralization LAS, alkaline agent.

LAS: sodium n-alkylbenzenesulfonate, carbon atom number are 10~13, anionic surfactant.

AOS: alpha-alkene sulfonate, anionic surfactant.

AES: ethoxylated fatty alcohol sulfate, fatty alcohol carbon atom number are 12~14, and average ethoxyquin degree is 2, yin Ionic surface active agent.

K12: lauryl sodium sulfate, anionic surfactant.

MES: fatty acid methyl ester sulfate, fatty acid carbon atoms number are 8~18, anionic surfactant.

AEO7: ethoxylized fatty alcohol, average ethoxyquin degree are 7, nonionic surfactant.

AEO9: ethoxylized fatty alcohol, average ethoxyquin degree are 9, nonionic surfactant.

TO-7: ethoxylation isomerous tridecanol, average ethoxyquin degree are 7, nonionic surfactant.

XP-80: ethoxylation 2- propyl enanthol, average ethoxyquin degree are 8, nonionic surfactant.

XL-80: ethoxylation and propoxyl group 2- propyl enanthol, average ethoxyquin degree are 8, nonionic surfactant.

MEE: fatty acid methyl ester ethoxylate, fatty acid carbon atoms number are 6~24, average ethoxyquin degree is 0.5~ 30, nonionic surfactant.

EPEI: polyethyleneimine (MW=600), each-NH have 20 ethoxylate groups, polyester soil release polymerization Object.

PE3100: polyethylene glycol and polypropylene glycol block copolymer, wherein polyethylene glycol block molecular weight is 950, poly- second Glycol monomer molecule number is the 10% of polymer monomer molecule sum, for BASF AG's productionPE3100。

Polyetheramine: amino-terminated propylene oxide, Huntsman company of the U.S. production withFor commodity M-2070, D-230, D-400, T-403, T5000 etc., wherein M2070 is monoamine sealing end, molecular weight 2000；D230 is diamino envelope End, molecular weight 230；D400 is diamino sealing end, molecular weight 430；T403 is three ammonia sealing end, molecular weight 440；T5000 is three ammonia envelope End, molecular weight 5000.

Protease: alkali protease, Novozymes Products, the trade mark are Savinase Ultra 16XL.

Enzyme stabilizers: the borax by accounting for enzyme stabilizers weight containing 20%, 50%, which accounts for the glycerol of enzyme stabilizers weight and 30%, accounts for enzyme The citric acid of stabilizer weight collectively constitutes.

Brightening agent: 4,4'- bis- (2- sodium sulfonate styryl) biphenyl, Optical Bleaching Agent, BASF AG's product, the trade mark are CBS-X。

Preservative: methylisothiazolinone and chlormethylisothiazo,ine alcohol/ketone mixtures.

Storage stability test

High-temperature stability: after the bottled sealing of composition, 45 ± 1 DEG C of environment are placed in, after constant temperature is placed 1 month, are restored to room 25 ± 5 DEG C of temperature, composition are that high-temperature stability is qualified without layering or Precipitation.

Low-temperature stability: after the bottled sealing of composition, -0 ± 2 DEG C of environment are placed in, after constant temperature is placed 1 month, are taken out immediately Observation.Composition is that low-temperature stability is qualified without layering or Precipitation.

Frozen-thawed cycled stability: -15 DEG C~-20 DEG C environment are placed in, constant temperature takes out after placing 24 hours, then is placed in room temperature (25 ± 5) DEG C environment 24 hours are circulation primary, and continuous circulation four times observes composition state every time.Composition is without layering Or composition is Frozen-thawed cycled qualified stability under the conditions of 25 ± 5 DEG C before and after Precipitation and storage.

Ordinary temperature stability: after the bottled sealing of composition, being placed in room temperature environment, and after placing 1 month, composition is without layering or sinks Precipitation goes out, and is that ordinary temperature stability is qualified.

General four kinds of stability test results are all qualification, then stability test result is " qualification "；Any one Or it is several to be unqualified, think that stability test result is " unqualified ".

Viscosity test

Viscosity is measured using the LVDV-II+Pro type Digital Viscometer of Brookfield.Sample is placed in 250mL beaker Afterwards, it is placed in thermostat, control sample temperature reaches predetermined temperature (25 DEG C ± 0.5 DEG C), and constant temperature 30 minutes.According to instrument Operation requires, and suitable types rotor is selected to measure sample viscosity.

1 detergent composition embodiment 1-4 of table

Analysis:

The composition I of comparative example 5 first using any method inhibit gel generate, therefore the composition not only viscosity compared with High and appearance is opaque, storage stability is poor.And aryl polymer (polyester Type of Collective is added in 1~embodiment of embodiment 4 Object, SRA100) and compound a kind of polyetheramine (composition A:D230；Composition B:T403；Composition C:M2070；Composition D: D400), the pH of composition is in 8.0~8.5 ranges.The result shows that the polyetheramine in embodiment can reduce the viscous of composition Degree, and guarantee its storage stability, appearance is also clear.

And 1~comparative example of comparative example 3 is using aryl polymer and high-molecular-weight poly ether amines (T5000, composition E), polyethers (EOPO block copolymer, PE3100, composition F) or alcohol ether solvents (dipropylene glycol n-butyl ether, DPnB, composition G) compounding, and Its additive amount is high compared with polyethers ammonia in embodiment.Although the polyetheramine of comparative example, polyethers and alcohol ether solvents also can reduce group The viscosity of object is closed, but can not ensure the storage stability of composition, room temperature can be layered.And the group of comparative example 4 Closing object H also has preferable stability, and appearance transparent, viscosity are lower, but uses alcoholic solvent (propylene glycol) and benzene sulfonic acid class The method of solubilizer (paratoluenesulfonic acid sodium salt) compounding, higher cost.

2 detergent composition embodiment 5-8 of table

Analysis:

Table 2 the result shows that, do not add aryl polymer and polyetheramine composition N, only add polyetheramine (D400) group The composition P for closing object O and only adding aryl polymer cannot be guaranteed the storage stability of composition, and room temperature storage can be shown Write layering.And aryl polymer (modified styrene polymer) can be obtained after compounding with polyetheramine (D400) and stablize, be transparent Composition, and with the increase of aryl polymer and polyetheramine additive amount, viscosity gradually decreases.

Dissolubility velocity test

In 150ml sesame seed cake, it is put into B620 type magneton, then weigh 20g sample, and be slowly injected into 80g deionization, use is electronic Blender starts to stir with the speed of 300r/min, while starting timer, and record is completely dissolved (ie in solution clear) institute The time needed.

3 detergent composition embodiment 9-10 of table

Analysis:

From table 3 the result shows that, relative to the composition R of the comparative example 9 and composition T of comparative example 10, using polyethers ammonia with The solution rate of the composition S of the composition Q and embodiment 10 of the embodiment 9 of aryl polymer compounding is obviously improved, and The solution rate of composition S is suitable with the solution rate of composition U, but composition U only adds a large amount of solubilizer.

Practical spot detergency test

1) cloth is tested: polyester calico (GB/T7568.4, Shanghai Textile Industry Technology Supervision Institute purchase) is cut into 6 × The square test cloth of 6cm.

2) 250ppm slurry: requiring to prepare the slurry that hardness is 250ppm according to GB/T 13174-2008, Middle calcium ions and magnesium ions ratio is 3:2.

3) test cloth pollution: common practical spot is represented with old foster-mother's chilli oil greasy dirt and golden dragonfish ready-mixed oil greasy dirt, is made For experiment spot.0.2g greasy dirt is taken, is applied on test cloth, aged at room temperature 4 hours.

Old foster-mother's chilli oil greasy dirt: the commercially available old foster-mother's chili oil of Tao Huabi only takes upper layer greasy dirt liquid.

Golden dragonfish ready-mixed oil greasy dirt: 200g ready-mixed oil and accurate weighing 0.02g Sudan colorants are taken, 45 DEG C of water-baths are placed in In, it is dissolved completely in tonyred in ready-mixed oil, to prepare coloured stains.

4) detergency ability is tested: washing test is carried out referring to GB/T 13174-2008.First with detergent to eight built-in testing cloth It is washed, is dried at room temperature after washing.Again by the old foster-mother's chilli oil oil pollution of the four built-in testing cloth dried, four With golden dragonfish ready-mixed oil oil pollution.After pollution, soiled cotton aging 4 hours at room temperature, then examination cloth is measured with WSD-3U fluorescent whiteness Whiteness W1 before washing.The test cloth that eight were polluted is washed with detergent again.It after washing, dries at room temperature, test cloth is washed rear white Spend W2.

Cleaning strength=(test cloth washes rear whiteness (W2)-test cloth and washes preceding whiteness (W1))/test cloth number

Obviously, whiteness difference is bigger, shows that cleaning strength is higher.

Wash conditions are as follows: every cylinder 1L 250ppm slurry, 2g detergent, wash time 20 minutes, wash temperature 30 DEG C, mixing speed 60r/min.

4 detergent composition embodiment 11-13 of table

Detergency of the 5 detergent composition V~Y of table to practical spot

Upper table the result shows that, in the detergency of two kinds of practical spots, embodiment 11~13 shows more excellent cleaning strength, Show that aryl polymer there can be more significant detergency hoisting power with compounding for polyetheramine.

Dimension disclosed herein and numerical value should not be construed as the stringent limitation of the exact value.Unless otherwise stated, often A such dimension is intended to indicate that described value and the functionally equivalent range around the value.For example, being disclosed as the amount of " 40mm " Guiding principle is intended to indicate that " about 40mm ".

The All Files quoted in summary of the invention are included in herein by reference all in relevant portion.For any The reference of file is not construed as recognizing that it is the prior art for the present invention.

The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, therefore Without departing from the technical solutions of the present invention, to the above embodiments according to the technical essence of the invention any simply to repair Change, equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.

Claims (9)

1. a kind of concentrated type liquid detergent composition for being substantially free of solubilizer, which is characterized in that count by weight percentage, It is grouped as by following group:

Wherein, the number-average molecular weight of the polyetheramine is less than 3000；The range of number-average molecular weight of the aryl polymer is 1000 ~20000；The mass ratio of the polyetheramine and aryl polymer is 10:1~1:4.

2. a kind of concentrated type liquid detergent composition for being substantially free of solubilizer according to claim 1, feature exist In the mass ratio of the polyetheramine and aryl polymer is 8:1~1:1.8.

3. a kind of concentrated type liquid detergent composition for being substantially free of solubilizer according to claim 2, feature exist In the sum of weight percent of the polyetheramine and aryl polymer is 0.2~5%.

4. a kind of concentrated type liquid detergent composition for being substantially free of solubilizer according to any one of claims 1 to 3, It is characterized in that, the number-average molecular weight of the polyetheramine is 200~1500.

5. a kind of concentrated type liquid detergent composition for being substantially free of solubilizer according to any one of claims 1 to 3, It is characterized in that, the aryl polymer is the polymer that main chain and/or side chain contain aryl；The aryl includes phenyl.

6. a kind of concentrated type liquid detergent composition for being substantially free of solubilizer according to claim 1, feature exist In the surfactant system includes at least one selected from following surfactant: fatty acid salt, anion surface active Agent, cationic surfactant, nonionic surfactant, zwitterionic surfactant.

7. a kind of concentrated type liquid detergent composition for being substantially free of solubilizer according to claim 6, feature exist In,

The weight percent of the surfactant system in the composition is 30~50%；

The surfactant by 0~10% fatty acid salt, 1~30% anionic surfactant, 1~40% it is non-from Sub- surfactant, 0~30% zwitterionic surfactant and 0~30% cationic surface active agent composition.

8. a kind of concentrated type liquid detergent composition for being substantially free of solubilizer according to claim 1, feature exist In the washing assisant and additive include at least one substance selected from the following: enzyme preparation, alkaline agent, pH adjusting agent, viscosity tune Save agent, preservative, colorant, fluorescent whitening agent, colour stabilizer and essence.

9. a kind of concentrated type liquid detergent composition for being substantially free of solubilizer according to claim 1, feature exist In the range of viscosities of the composition is 100~5000cst, and pH range is 7.5~10.0.