EP1838832A1 - Builder for detergent containing polyhydric alcohol-polyalkylene oxide adduct - Google Patents

Builder for detergent containing polyhydric alcohol-polyalkylene oxide adduct

Info

Publication number
EP1838832A1
EP1838832A1 EP05816519A EP05816519A EP1838832A1 EP 1838832 A1 EP1838832 A1 EP 1838832A1 EP 05816519 A EP05816519 A EP 05816519A EP 05816519 A EP05816519 A EP 05816519A EP 1838832 A1 EP1838832 A1 EP 1838832A1
Authority
EP
European Patent Office
Prior art keywords
detergent
builder
polyhydric alcohol
oxide adduct
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05816519A
Other languages
German (de)
French (fr)
Inventor
Atsuro Yoneda
Takahiro Tsumori
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Publication of EP1838832A1 publication Critical patent/EP1838832A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides

Definitions

  • the present invention relates to a builder for detergent containing a polyhydric alcohol-polyalkylene oxide adduct. More particularly, the present invention relates to a builder for detergent containing a polyhydric alcohol-polyalkylene oxide adduct, which is preferable for a builder for detergent and has a excellent color tone and a slight odor, and exhibits high detergency when used as a builder for detergent together with a surfactant.
  • Abuilder for detergent is a component composing a powder or liquid detergent, and it is known that various kinds of polymeric compounds act as a builder for detergent.
  • a builder for detergent which can not only exhibit high detergency by preventing re-contamination due to stain removed in laundry but also have properties such as a preferable color tone (transparency) and a slight odor, leaves a favorable impression on consumers using the detergent. Therefore, quality of the builder for detergent needs to be enhanced by improving such properties .
  • Such apolymer is essential as a component composinga liquiddetergent because of its property of dissolution in the liquid detergent. If the polyalkyleneimine-alkylene oxide adduct is contained in a detergent together with a surfactant, the detergent exhibits high detergency by preventing re-contamination due to stain removed by laundry.
  • the builder has aninsufficient color tone and an odor because the polyalkylene imine-alkylene oxide adduct belongs to amine compounds. Therefore, there was a room for contrivance to improve these properties.
  • raw materials for such an imine monomer are so expensive that a builder for detergent as a product is not excellent in cost performance. Therefore, there was a room for contrivance to produce an economically excellent builder for detergent by using more inexpensive raw materials.
  • the following polymers are disclosed (for example, refer to Japanese Kokai Publication 2003-128738 (page 2)) : a polycarboxylic acid copolymer produced by copolymerization of monomer components containing an unsaturated monocarboxylic acid monomer and a polyalkylene glycol unsaturated monomer having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue; andapolycarboxylicacidcopolymerproducedbycopolymerization ofmonomer components containing an unsaturated carboxylic acid monomer and a polyalkylene glycol unsaturated monomer having a terminal with a hydroxyl group and a structure, in which an oxyalkylene group is bonded to a polyhydric alcohol residue.
  • a repeating unit which is formed by the polyalkylene glycol unsaturated monomer or the polyalkylene glycol unsaturatedmonomer having a terminal with a hydroxyl group and a structure, in which an oxyalkylene group is bonded to a polyhydric alcohol residue, exhibits a function for giving excellent water-reducing property and workability to a cement composition andthe like. Therefore, andarepeating unit formed by the unsaturated carboxylic acidmonomer exhibits a function of adsorbing the polycarboxylic acid copolymer to cement particles.
  • a builder for detergent which is excellent in solubility in a liquid detergent and can exhibit high basic performance in anti-redeposition and detergency, and additionally has an excellent color tone and no odor and excellent sense of use as a builder for detergent if the builder is used as a builder for detergent.
  • the present inventors made various investigations concerning a polymeric builder for detergent.
  • a polyalkylene imine-alkyleneoxideadductas abuilderfordetergentexhibiting high detergency had a characteristic amine odor because of a slight amount of amine contained in the builder for detergent.
  • a builder for detergent containing a polyhydric alcohol-polyalkylene oxide adduct are solved in a surfactant, and also it has an excellent solubility in a liquid detergent, and therefore it is preferable for not only a powder detergent but also a liquid detergent.
  • the builder can be preferably used in various uses such as a detergent additive because it is colorless and transparency, and has no odor.
  • Thepresent invention also provides abuilder fordetergent containing a polyhydric alcohol structure, wherein the builder for detergent has a detergency of 23% or more and a color tone in APHA/Hazen of 50 or less.
  • the builder fordetergentofthepresentinvention contains a polyalkylene oxide to which a polyhydric alcohol as a core region is added. And the builder exhibits high detergency by beingadsorbedto a fiber surface to remove stain, andthebuilder hasnocolorandtransparent, andnoodor. Therefore, thebuilder can exhibit high performance and high quality as a builder for detergent.
  • the above-mentioned polyhydric alcohol-polyalkylene oxide adduct is believed to improve clay dispersancy due to hydrophilicpropertyandstericrepulsionofanoxyalkylenegroup. And it is also believed that a repeating unit formed by the polyhydric alcohol-polyalkylene oxide adduct has many oxygen atoms in one molecule and also each is a monomeric unit having a branch structure. And thereby the adduct can effectively exhibit the above-mentioned functions.
  • the above-mentioned builder for detergent is preferably a builder for liquid detergent.
  • the above-mentioned builder for detergent is excellent in solubility in a surfactant and a liquid detergent because the above-mentioned polyhydric alcohol-polyalkylene oxide adduct as an essential component has the above-mentioned structure. Therefore, the builder for detergent is preferably used for liquid detergent.
  • the liquid detergent is easily used as a detergent in daily use, the above-mentionedbuilder fordetergentis essential fortheliquid detergent having excellent detergency.
  • the liquid detergent has an advantage over a powder detergent because the liquid detergent can be directly applied to a portion from which stain needs to be removed, and needs no drying in the manufacturing steps.
  • the above-mentioned polyhydric alcohol-polyalkylene oxide adduct has an excellent sense of use of colorlessness, transparency and no odor, because the adduct has the polyhydric alcohol as a core region.
  • a color tone can be evaluated byAPHA/Hazen.
  • TheAPHA/Hazen is a color testmethodof chemical products using platinum-cobalt scale, and specifically it can be determined according to JIS K 0071-1.
  • the above-mentioned builder for detergent preferably has a color tone in APHA/Hazen of 1000 or less. If the color tone is more than 1000, a coloring is highly visible when the builder is used, which might deteriorate the sense of use.
  • the color tone is more preferably 500 or less, further more preferably 100 or less.
  • the color tone in APHA/Hazen preferably satisfy a range of 0 to 1000, more preferably 0 to 500 and further more preferably 0 to 100.
  • the above-mentioned builder for detergent has a slight odor because of its structure of the polyhydric alcohol-polyalkyleneoxide adduct, andthebuilder fordetergent preferably has an ammonia odor concentration of 3 ppm or less, more preferably 0 to 2 ppm and further more preferably 0 to 1 ppm.
  • the builder for detergent having an ammonia odor concentration of 3 ppm or less is also one of preferable embodiments of the present invention.
  • the polyhydric alcohol-polyalkylene oxide adduct of the present invention may be a compound having a terminal with a hydroxyl group and a structure, in which an oxyalkylene group is bonded to a polyhydric alcohol residue.
  • the above-mentioned polyhydric alcohol residue means a group having a structure, in which an active hydrogen is removed from a hydroxyl group contained in the polyhydric alcohol, but it is not particularly limited to a group formed by a reaction with the polyhydric alcohol.
  • the above-mentioned polyhydric alcohol is not particularly limited as long as it is a compound containing three ormore hydroxyl groups on average in onemolecule.
  • Apreferable embodiment is acompound containing apolyhydric alcohol residue composed of three elements of carbon, hydrogen and oxygen.
  • the number of the hydroxyl groups contained in the above-mentioned polyhydric alcohol is preferably 3 or more and 300 or less. If the hydroxyl groups is less than 3, the functions of the polyhydric alcohol-polyalkylene oxide adduct might be insufficiently exhibited. And if it is more than 300, the polymerizability of the polyhydric alcohol-polyalkylene oxide adduct might be lowered.
  • the number of the hydroxyl groups is more preferably 4 or more, further more preferably 5 or more and particularly preferably 6 or more, and more preferably 100 or less, further more preferably 50 or less and particularly preferably 25 or less.
  • polyhydric alcohol examples include polyglycidol, glycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1, 3, 5-pentatriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol and mannitol.
  • saccharides include saccharidesofhexoses suchas glucose, fructose, mannose, indose, sorbose, gulose, talose, tagatose, galactose, allose, psicose and altrose; saccharides of pentoses such as arabinose, ribulose, ribose, xylose, xylulose and lyxose; saccharides of tetroses such as threose, erythrulose and erythrose; other saccharides such as rhamnose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose and melezitose; and sugar alcohols and sugar acids thereof (saccharides; glucose, sugar alcohols; glucitol, sugar acids; gluconic acid) .
  • derivatives such as partially etherifiedproducts and partially esterified products of these exemplified compounds are preferable.
  • sorbitol is more preferable.
  • One ore more of them are preferably used.
  • Such compounds form the polyhydric alcohol residue of the polyhydric alcohol-polyalkylene oxide adduct.
  • alkylene oxide added to the hydroxyl group contained in the above-mentioned polyhydric alcohol include alkylene oxides with 2 to 8 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monoxide andoctyleneoxide, aliphaticepoxides suchas dipentane ethylene oxide and dihexane ethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran and octylene oxide; and aromatic epoxides suchas styreneoxide and1, 1-diphenylethylene oxide. These may be used singly or in combination of two or more of them. Among these, ethylene oxide and propylene oxide are more prefer
  • the above-mentioned polyhydric alcohol-polyalkylene oxide adduct has a group formed by one oxyalkylene group or a group formed by an addition of two or more oxyalkylene groups.
  • the group formedby an addition of two ormore oxyalkylene groups is formed by one or more kinds of oxyalkylene groups. If the group is formed by two or more kinds of oxyalkylene groups, two or more kinds of oxyalkylene groups may have any addition form of random addition, block addition, alternate addition and the like. If a plurality of the above-mentioned groups formed by an oxyalkylene group exist in one molecule, these groups may be the same or different.
  • the group formed by an addition of two or more oxyalkylene groups is also referred to as a polyalkylene glycol chain.
  • the above-mentionedgroups formedby an oxyalkylene group preferably have an oxyethylene group as a main body.
  • the term "main body” means that when two or more kinds of oxyethylene groups exist in one molecule, the oxyethylene groups occupythemostpart inthe number of the total oxyalkylene groups.
  • oxyalkylene groups when the above-mentioned "occupy the most part" is denoted by mol% of oxyethylene group in 100 mol% of the entire oxyalkylene group, 50 to 100 mol% is preferable. Less than 50 mol% of oxyethylene groups might lower hydrophilic property of the group formed by the oxyalkylene group.
  • Oxyethylene groups are more preferably 60 mol% or more, further more preferably 70 mol% or more, particularly preferably 80 mol% or more and most preferably 90 mol% or more.
  • the average molar number of addition of the oxyalkylene group is preferably 0 to 100.
  • the average molar number more than 100 might lower detergency of the builder for detergent containing the adduct.
  • the average molar number is more preferably 1 or more, further more preferably 5 or more, particularly preferably 10 or more and most preferably 30 or more, and more preferably 80 or less, further more preferably 70 orless, particularlypreferably 60 orless andmostpreferably 50 or less.
  • the above-mentionedaveragemolarnumberofadditionme ans anaverage value of molar number of the added oxyalkylene groups in lmol of groups formed by the oxyalkylene groups of the polyhydric alcohol-polyalkylene oxide adduct, or the average value ofmolar number of the addedoxyalkylene groups in 1 mol ofhydroxyl groups contained in the polyhydric alcohol for forming the polyhydric alcohol-polyalkylene oxide adduct.
  • the polyhydric alcohol-polyalkylene oxide adduct having an above-mentioned average molar number of addition of 0 has no oxyalkylene group.
  • polyhydric alcohol-polyalkylene oxide adduct it is preferable that at least one terminal of an oxyalkylene group having a structure bonded to a polyhydric alcohol residue is a hydroxyl group. More preferably, all terminals of the oxyalkylene group are hydroxyl groups.
  • a sorbitol-ethylene oxide adduct represented by the following formula (1) .
  • Theweight averagemolecularweightof the above-mentioned polyhydric alcohol-polyalkylene oxide adduct is preferably 500 ormore and 500000 or less, more preferably 1000 ormore, further more preferably 5000 ormore, still further more preferably 8000 or more and particularly preferably 10000 or more, and more preferably 300000 or less, further more preferably 200000 or less, still further more preferably 100000 or less and particularly preferably 80000 or less.
  • the present invention of the builder for detergent may suitably comprise, consist of, or consist essentially of a polyhydric alcohol-polyalkylene oxide adduct.
  • the present invention provides also a detergent composition containing the above-mentioned builder for detergent.
  • the above-mentioned detergent composition maybe a powder detergent composition or a liquid detergent composition.
  • a liquid detergent composition is more preferable because the above-mentioned builder for detergent is excellent in solubility in a liquid detergent.
  • Additives typically used for detergent can be used for the above-mentioned detergent composition in addition to the above-mentioned builder for detergent.
  • Preferable examples of the above-mentioned additives include an alkali builder, a chelate builder, an anti-redeposition agent for preventing redeposition of a contaminant such as sodium carboxymethylcellulose, a stain inhibitor such as benzotriazole and ethylenetiourea, a soil release agent, a color migration inhibitor, a softening agent, an alkaline substance for pH adjustment, a perfume, a solubilizing agent, a fluorescent agent, a coloring agent, a foaming agent, a foam stabilizer, a lustering agent, a bactericide, ableachingagent, ableachingassistant, anenzyme, adye anda solvent.
  • a contaminant such as sodium carboxymethylcellulose
  • a stain inhibitor such as benzotriazole and ethylenetiourea
  • a soil release agent such as benzotriazole and ethylenetiourea
  • a color migration inhibitor such as benzotriazole and
  • Thepowderdetergent composition preferably includes zeolite. It is preferably that the blending ratio of the above-mentioned builder for detergent is typically 0.1 to 20% by weight (% by mass or mass%) based on 100% by weight of the detergent composition, more preferably 0.2% by weight or more and 15% by weight or less, more preferably 0.3% by weight or more and 10% by weight or less, further more preferably 0.4% by weight or more and 8% by weight or less, and particularly preferably 0.5% by weight or more and 5% by weight or less. If the blending ratio of the builder for detergent less than 0.1% by weight, sufficient detergent performance might not be exhibited, and if the blending ratio is more than 20% by weight, economic efficiency might be lowered.
  • the blending form of the above-mentioned builder in the above-mentioned detergent composition may be either of liquid and solid, and can be determined in accordance with a form of detergent in selling (suchas liquidmaterial or solidmaterial) .
  • the builder may be blended in a form of aqueous solution after polymerization, blended in a form of aqueous solution in which moisture is decreasedto somedegree for condensation, orblended in a state of being dried and solidified.
  • the above-mentioned detergent composition includes a synthetic detergent of a household detergent, an industrial detergentof fiber industryandthe like, ahardsurfacedetergent, and a detergent used only for specific use, such as a bleaching detergent such that the function of one component thereof is ameliorated.
  • the above-mentioned surfactant is at least one kind selected from an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant, and these surfactants can be used in one kind, or two or more kinds. If two or more kinds of the surfactants are used, the total used amount of the anionic surfactant and the nonionic surfactant is preferably 50% by weight or more based on 100% by weight of all surfactants, more preferably 60% by weight or more, further morepreferably70%byweightormore andparticularlypreferably 80% by weight or more.
  • anionic surfactant examples include alkylbenzenesulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, ⁇ -olefin sulfonate, ⁇ -sulfofatty acid or ester salt thereof alkane sulfonate, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid surfactant, N-acylamino acid surfactant, alkyl phosphate esteror salt thereof andalkenylphosphate esteror saltthereof.
  • An alkyl group and an alkenyl group in the above anionic surfactant mayhave abranchedalkyl group such as amethyl group.
  • nonionic surfactant examples include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glucoxide, fatty acid glycerin monoester and alkylamine oxide.
  • An alkyl group and an alkenyl group in the above nonionic surfactant may have a branched alkyl group such as a methyl group.
  • cationic surfactant examples include quaternary ammonium salts.
  • amphoteric surfactant examples include a carboxyl amphoteric surfactant and a sulfobetaine amphoteric surfactant.
  • An alkyl group and an alkenyl group in the above cationic surfactant and the above amphoteric surfactant may have a branched alkyl group such as a methyl group.
  • the blending ratio of the above-mentionedsurfactant is typically 10 to 60%byweightbased on 100% by weight of the detergent composition, more preferably 15% by weight or more and 50% by weight or less, further more preferably 20% by weight or more and 45% by weight or less, and particularly preferably 25% by weight or more and 40% by weight or less. If the blending ratio of the surfactant is less than 10% by weight, sufficient detergency might not be exhibited, and if the blending ratio is more than 60% by weight, economic efficiency might be lowered.
  • a moisture amount contained in the liquid detergent composition is typically 0.1 to 75% by weight based on 100% by weight of the liquid detergent composition, more preferably 0.2% by weight or more and 70% by weight or less, further more preferably 0.5% by weight or more and 65% byweight or less, particularlypreferably 0.7% byweight or more and 60% by weight or less, more particularly preferably 1% byweight ormore and 55%byweight or less, andmost preferably 1.5% by weight or more and 50% by weight or less.
  • the above-mentioned liquid detergent composition preferably has a kaolin turbidity of 200 mg/L or less, more preferably 150 mg/L or less, further more preferably 120 mg/L or less, particularly preferably 100 mg/L or less and most preferably 50 mg/L or less .
  • the difference in kaolin turbidity betweenthecaseofaddingthebuilder fordetergentofthepresent invention to the liquid detergent composition and the case of not adding it is preferably 500 mg/L or less, more preferably 400 mg/L or less, further more preferably 300 mg/L or less, particularly preferably 200 mg/L or less and most preferably 100 mg/L or less.
  • the kaolin turbidity can be measured by a measuring method mentioned below, for example. ⁇ Measurement method of kaolin turbidity> A sample (liquid detergent) homogeneously stirred is charged in a 50 max 50 mm square cell with 10 mm thickness and bubbles are removed. Then, the sample is measured for Turbidity
  • Preferable examplesofanenzymeblendedwiththedetergent composition of the present invention include protease, lipase and cellulase. Among them, protease, alkali lipase and alkali cellulase are preferable because of these high activities in alkali washings .
  • the added amount of the above-mentioned enzyme is preferably 5% by weight or less based on 100% by weight of the detergent composition. If the added amount is more than 5% by weight, the detergencyis not improved, whichmight lower economy efficiency.
  • Preferable examples of the above-mentioned alkali builder include silicate, carbonate and sulfate.
  • Preferable examples of the above-mentioned chelate builder include diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid) , DTPA (diethylenetriaminepentaacetic acid) , triphosphate, sodium tripolyphosphate, and citric acid.
  • polyhydric alcohol-polyalkylene oxide adduct may be used as a builder for detergent singly or in combination of two or more of them.
  • a polyalkyleneimine-polyalkylene oxide adduct is preferably used together with the polyhydric alcohol-polyalkylene oxide adduct.
  • the polyhydric alcohol-polyalkylene oxide adduct is preferably used together withthewater-solublepolycarboxylic acidpolymers as abuilder for detergent.
  • the above-mentioned detergent composition can be used as a detergent with extremely high-quality performance and excellent stability, because the composition is excellent in dispersancy and additionally maintains its stability if the composition is preserved for a long period and causes no precipitation of impurities and the like if maintained at low temperatures .
  • Thepresentinvention also provides abuilderfordetergent containing a polyhydric alcohol structure, the builder for detergent has a detergency of 23% or more and a color tone in APHA/Hazen of 50 or less.
  • the above-mentioned builder for detergent preferably has the above-mentioned polyhydric alcohol-polyalkylene oxide adduct as an essential ingredient.
  • preferable embodiments of a polyhydric alcohol, a polyalkylene oxide, a manufacturingmethod and the like are the same as thosementioned above.
  • the above-mentioned detergency is preferably 23% ormore. If the detergency is 23% or more, improvement of the detergency canbe clearly recognizedwith respect to blank.
  • the detergency is more preferably 24% or more.
  • the cqlor tone is more preferably 30 or less.
  • the builder for detergent of the present invention has the above-mentioned configuration and it is a builder for detergent, which is excellent insolubilityina liquiddetergent and can exhibit high basic performance in detergency and the like, and additionally is excellent in a color tone without an odor and excellent in a sense of use as a builder for detergent and furthermore excellent in cost performance if being used as a builder for detergent.
  • the inside was set at a pressure of 0.17MPa and a temperature of 150°C, and filled with ethylene oxide. While the partial pressure of nitrogen/ethylene oxide in reaction was within a dangerous range of explosion, 1487 g of ethylene oxide was charged. After the charge, the inside was aged for 2 hours, and then cooled to a temperature of 80°C and degassed. Nitrogen was added to the inside of the vessel while degassed gas was released into water to substitute the inside with nitrogen sufficiently. And then the content was taken out to produce a compound (2) .
  • a compound (3) was produced in the same manner as in Synthetic Example 2.
  • a polyethyleneimine-polyethylene oxide adduct produced by ethoxylatingpolyethyleneimine (an average molecular weight of 600, product ofNIPPONSHOKUBAI CO., LTD.) withethylene oxide equivalent to 20molpermol ofnitrogen was usedas a comparative compound.
  • a cloth obtainedfromScientific Service Corporation, was used as an artificially soiled fabric.
  • the artificially soiled fabric was previously measured for whiteness with reflectance using a colorimetric difference meter SE2000 (manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.) . Purewaterwasaddedto1.47gofcalciumchloridedihydrate to prepare 10 kg of hard water.
  • a targotometer was set at a temperature of 27 0 C, and then 1000 mL of hard water, 5 mL of the aqueous polymer solution (a concentration of 0.28%), 4.8 mL of the aqueous solution of surfactant and the artificially soiled fabrics (STC GC C cloth: 10 sheets) were put in a pot and the mixture was stirred at 100 rpm for 10 minutes.
  • the artificially soiled fabrics were taken out of the pot, and moisture was squeezed therefrom by hand.
  • In the pot was put lOOOmLofhardwater, andthemoisture-squeezedartificially soiled fabric was put therein and the mixture was stirred at 100 rpm for 2 minutes.
  • the artificially soiled fabrics were taken out of the pot andmoisture was squeezed therefrombyhand, andthereafter the artificially soiled fabrics werepressedwith filler cloths to dry them while smoothing the wrinkles.
  • the dried artificially soiled fabrics were measured for whiteness with reflectance with a colorimetric difference meter. Detergency (%) was calculated by the value by the above manner and the following formula.
  • Detergency (%) (whiteness of artificially soiled fabric after washing - whiteness of artificially soiled fabric before washing) ⁇ (whiteness of original white cloth (EMPA221) of artificially soiled fabric - whiteness of artificially soiled fabric before washing) x 100
  • Example 1 The measurement was performed in the same manner as in Example 1 except that the compound (3) was used instead of the polyhydric alcohol-polyalkylene oxide adduct (compound (2)) .
  • Table 1 shows the results .
  • Comparative Example 1 the measurement was performed in the same manner as in Example 1 except that the comparative compoundwasusedinsteadofthepolyhydricalcohol-polyalkylene oxide adduct (compound (2) ) . And in Comparative Example 2, the measurement was performed in the same manner as in Example 1 except that no polyhydric alcohol-polyalkylene oxide adduct was added (Comparative Example 2) . Table 1 shows the results.
  • a cotton cloth and a polyester cloth were cut to 5cm x 5cm to eachprepare 7white cloths.
  • Thewhite cloths werepreviously measured for whiteness with reflectance using a colorimetric differencemeterND-1001DPtype (manufacturedbyNipponDenshoku Industries Co., Ltd.).
  • Targotometer is set at 25°C, and 1000 ml of hard water, 5.0 g of a 0.2% aqueous solution of compound, 5.0 g of the aqueous solution of surfactant, 0.2 g of zeolite and 0.25 g of carbon black were put in a pot and stirred at 100 rpm for 1 minute.
  • the white cloths are wringed by hand, and 1 liter of hard water is put in a pot and stirred at 100 rpm for 2 minutes. (7) The white cloths are pressed with a filler cloth to dry them while smoothing wrinkles. And then, the white cloths were measured for whiteness again with reflectance using the colorimetric difference meter.
  • Comparative Example 3 Ameasurementwasperformedinthesamemanneras inExample 3, except that AQUALIC TL400 was used as a comparative compound instead of the builder compound(2) or (3) for detergent. Table 2 shows the result.

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Abstract

To provide a builder for detergent, which is excellent in solubility in a liquid detergent and can exhibit high basic performance in anti-redeposition and detergency, and additionally has an excellent color tone and no odor and excellent sense of use as a builder for detergent if the builder is used as a builder for detergent. A builder for detergent containing a polyhydric alcohol-polyalkylene oxide adduct as a essential component, a detergent composition containing the builder for detergent, a builder for detergent containing a polyhydric alcohol structure, wherein the builder for detergent has a detergency of 23% or more and a color tone in APHA/Hazen of 50 or less.

Description

DESCRIPTION
BUILDER FOR DETERGENT CONTAINING POLYHYDRIC
ALCOHOL-POLYALKYLENE OXIDE ADDUCT
TECHNICAL FIELD
The present invention relates to a builder for detergent containing a polyhydric alcohol-polyalkylene oxide adduct. More particularly, the present invention relates to a builder for detergent containing a polyhydric alcohol-polyalkylene oxide adduct, which is preferable for a builder for detergent and has a excellent color tone and a slight odor, and exhibits high detergency when used as a builder for detergent together with a surfactant.
BACKGROUND ART
Abuilder for detergent is a component composing a powder or liquid detergent, and it is known that various kinds of polymeric compounds act as a builder for detergent. As such a builder for detergent, which can not only exhibit high detergency by preventing re-contamination due to stain removed in laundry but also have properties such as a preferable color tone (transparency) and a slight odor, leaves a favorable impression on consumers using the detergent. Therefore, quality of the builder for detergent needs to be enhanced by improving such properties .
A polyalkyleneimine-alkylene oxide adduct having a polyalkyleneimine as a main chain, in which an alkylene oxide such as ethylene oxide is added to a nitrogen atom in the polyalkyleneimine, is disclosed, as acompoundcapableof acting as a conventional polymeric builder (for example, refer to JapaneseKokokuPublicationHei-04-54719 (pages 1 and2) ) . Such apolymer is essential as a component composinga liquiddetergent because of its property of dissolution in the liquid detergent. If the polyalkyleneimine-alkylene oxide adduct is contained in a detergent together with a surfactant, the detergent exhibits high detergency by preventing re-contamination due to stain removed by laundry.
However, if the polyalkylene imine-alkylene oxide adduct isusedas abuilderfordetergent, thebuilderhas aninsufficient color tone and an odor because the polyalkylene imine-alkylene oxide adduct belongs to amine compounds. Therefore, there was a room for contrivance to improve these properties.
Generally, raw materials for such an imine monomer are so expensive that a builder for detergent as a product is not excellent in cost performance. Therefore, there was a room for contrivance to produce an economically excellent builder for detergent by using more inexpensive raw materials.
On the other hand, the following polymers are disclosed (for example, refer to Japanese Kokai Publication 2003-128738 (page 2)) : a polycarboxylic acid copolymer produced by copolymerization of monomer components containing an unsaturated monocarboxylic acid monomer and a polyalkylene glycol unsaturated monomer having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue; andapolycarboxylicacidcopolymerproducedbycopolymerization ofmonomer components containing an unsaturated carboxylic acid monomer and a polyalkylene glycol unsaturated monomer having a terminal with a hydroxyl group and a structure, in which an oxyalkylene group is bonded to a polyhydric alcohol residue. In this polycarboxylic acid copolymer, a repeating unit, which is formed by the polyalkylene glycol unsaturated monomer or the polyalkylene glycol unsaturatedmonomer having a terminal with a hydroxyl group and a structure, in which an oxyalkylene group is bonded to a polyhydric alcohol residue, exhibits a function for giving excellent water-reducing property and workability to a cement composition andthe like. Therefore, andarepeating unit formed by the unsaturated carboxylic acidmonomer exhibits a function of adsorbing the polycarboxylic acid copolymer to cement particles. And use of such a polycarboxylic acid copolymer as a component of a cement additive can make water-reducing property and workability of the cement composition and the like excellent and also make strength and durability of a hardened product of the cement composition excellent. However, there is neither disclosure concerninguse of the above-mentioned polymer as a polymeric builder for detergent, nor disclosure concerning actions and effects if the polymer is used for detergent. In addition, there was a room for contrivance to use the copolymer as a detergent for detergent more preferably.
SlMy-ARY OF THE INVENTION
In view of the above state of the art, it is an object of the present invention to provide a builder for detergent, which is excellent in solubility in a liquid detergent and can exhibit high basic performance in anti-redeposition and detergency, and additionally has an excellent color tone and no odor and excellent sense of use as a builder for detergent if the builder is used as a builder for detergent. The present inventors made various investigations concerning a polymeric builder for detergent. A polyalkylene imine-alkyleneoxideadductas abuilderfordetergentexhibiting high detergency had a characteristic amine odor because of a slight amount of amine contained in the builder for detergent. Therefore, they found that use of not a polyalkyleneimine but a polyhydric alcohol as a core region of a builder for detergent prevents a production of amine, and whereby no characteristic odor is generated andhigh detergency as abuilder for detergent, such as excellent clay dispersancy and excellent anti-redeposition is also maintained. They also found that the use of not a polyalkylene imine but a polyhydric alcohol allows a preferable color tone in APHA/Hazen of 1000 or less. And they also found that use of the polyhydric alcohol led to reduction of raw material costs, which enables an economically superior builder for detergent to be produced. And they have admirably solved the above-mentioned problems . They further found that a builder for detergent containing a polyhydric alcohol-polyalkylene oxide adduct are solved in a surfactant, and also it has an excellent solubility in a liquid detergent, and therefore it is preferable for not only a powder detergent but also a liquid detergent. And the builder can be preferably used in various uses such as a detergent additive because it is colorless and transparency, and has no odor. These findings have now led to completion of the present invention. That is, the present invention provides a builder for detergent containing a polyhydric alcohol-polyalkylene oxide adduct.
Thepresent inventionalsoprovides abuilder fordetergent containing a polyhydric alcohol structure, wherein the builder for detergent has a detergency of 23% or more and a color tone in APHA/Hazen of 50 or less.
DISCLOSURE OF THE INVENTION The present invention is hereinafter detailed. Thebuilder fordetergentofthepresentinventioncontains a polyalkylene oxide to which a polyhydric alcohol as a core region is added. And the builder exhibits high detergency by beingadsorbedto a fiber surface to remove stain, andthebuilder hasnocolorandtransparent, andnoodor. Therefore, thebuilder can exhibit high performance and high quality as a builder for detergent.
The above-mentioned polyhydric alcohol-polyalkylene oxide adduct is believed to improve clay dispersancy due to hydrophilicpropertyandstericrepulsionofanoxyalkylenegroup. And it is also believed that a repeating unit formed by the polyhydric alcohol-polyalkylene oxide adduct has many oxygen atoms in one molecule and also each is a monomeric unit having a branch structure. And thereby the adduct can effectively exhibit the above-mentioned functions. The above-mentioned builder for detergent is preferably a builder for liquid detergent. The above-mentioned builder for detergent is excellent in solubility in a surfactant and a liquid detergent because the above-mentioned polyhydric alcohol-polyalkylene oxide adduct as an essential component has the above-mentioned structure. Therefore, the builder for detergent is preferably used for liquid detergent. The liquid detergent is easily used as a detergent in daily use, the above-mentionedbuilder fordetergentis essential fortheliquid detergent having excellent detergency. The liquid detergent has an advantage over a powder detergent because the liquid detergent can be directly applied to a portion from which stain needs to be removed, and needs no drying in the manufacturing steps.
The above-mentioned polyhydric alcohol-polyalkylene oxide adduct has an excellent sense of use of colorlessness, transparency and no odor, because the adduct has the polyhydric alcohol as a core region. Such a color tone can be evaluated byAPHA/Hazen. TheAPHA/Hazen is a color testmethodof chemical products using platinum-cobalt scale, and specifically it can be determined according to JIS K 0071-1. The above-mentioned builder for detergent preferably has a color tone in APHA/Hazen of 1000 or less. If the color tone is more than 1000, a coloring is highly visible when the builder is used, which might deteriorate the sense of use. The color tone is more preferably 500 or less, further more preferably 100 or less. The color tone in APHA/Hazen preferably satisfy a range of 0 to 1000, more preferably 0 to 500 and further more preferably 0 to 100.
The above-mentioned builder for detergent has a slight odor because of its structure of the polyhydric alcohol-polyalkyleneoxide adduct, andthebuilder fordetergent preferably has an ammonia odor concentration of 3 ppm or less, more preferably 0 to 2 ppm and further more preferably 0 to 1 ppm. Thus, the builder for detergent having an ammonia odor concentration of 3 ppm or less is also one of preferable embodiments of the present invention.
The polyhydric alcohol-polyalkylene oxide adduct of the present invention may be a compound having a terminal with a hydroxyl group and a structure, in which an oxyalkylene group is bonded to a polyhydric alcohol residue. The above-mentioned polyhydric alcohol residue means a group having a structure, in which an active hydrogen is removed from a hydroxyl group contained in the polyhydric alcohol, but it is not particularly limited to a group formed by a reaction with the polyhydric alcohol.
The above-mentioned polyhydric alcohol is not particularly limited as long as it is a compound containing three ormore hydroxyl groups on average in onemolecule. Apreferable embodiment is acompound containing apolyhydric alcohol residue composed of three elements of carbon, hydrogen and oxygen.
The number of the hydroxyl groups contained in the above-mentioned polyhydric alcohol is preferably 3 or more and 300 or less. If the hydroxyl groups is less than 3, the functions of the polyhydric alcohol-polyalkylene oxide adduct might be insufficiently exhibited. And if it is more than 300, the polymerizability of the polyhydric alcohol-polyalkylene oxide adduct might be lowered. The number of the hydroxyl groups is more preferably 4 or more, further more preferably 5 or more and particularly preferably 6 or more, and more preferably 100 or less, further more preferably 50 or less and particularly preferably 25 or less.
Preferable examples of the above-mentioned polyhydric alcohol include polyglycidol, glycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1, 3, 5-pentatriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol and mannitol. Preferable examples of saccharides include saccharidesofhexoses suchas glucose, fructose, mannose, indose, sorbose, gulose, talose, tagatose, galactose, allose, psicose and altrose; saccharides of pentoses such as arabinose, ribulose, ribose, xylose, xylulose and lyxose; saccharides of tetroses such as threose, erythrulose and erythrose; other saccharides such as rhamnose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose and melezitose; and sugar alcohols and sugar acids thereof (saccharides; glucose, sugar alcohols; glucitol, sugar acids; gluconic acid) . In addition, derivatives such as partially etherifiedproducts and partially esterified products of these exemplified compounds are preferable. Among these, sorbitol is more preferable. One ore more of them are preferably used. Such compounds form the polyhydric alcohol residue of the polyhydric alcohol-polyalkylene oxide adduct.
Preferable examples of the alkylene oxide added to the hydroxyl group contained in the above-mentioned polyhydric alcohol include alkylene oxides with 2 to 8 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monoxide andoctyleneoxide, aliphaticepoxides suchas dipentane ethylene oxide and dihexane ethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran and octylene oxide; and aromatic epoxides suchas styreneoxide and1, 1-diphenylethylene oxide. These may be used singly or in combination of two or more of them. Among these, ethylene oxide and propylene oxide are more preferable, and ethylene oxide is further more preferable.
The above-mentioned polyhydric alcohol-polyalkylene oxide adduct has a group formed by one oxyalkylene group or a group formed by an addition of two or more oxyalkylene groups. The group formedby an addition of two ormore oxyalkylene groups is formed by one or more kinds of oxyalkylene groups. If the group is formed by two or more kinds of oxyalkylene groups, two or more kinds of oxyalkylene groups may have any addition form of random addition, block addition, alternate addition and the like. If a plurality of the above-mentioned groups formed by an oxyalkylene group exist in one molecule, these groups may be the same or different. The group formed by an addition of two or more oxyalkylene groups is also referred to as a polyalkylene glycol chain.
The above-mentionedgroups formedby an oxyalkylene group preferably have an oxyethylene group as a main body. In this case, the term "main body" means that when two or more kinds of oxyethylene groups exist in one molecule, the oxyethylene groups occupythemostpart inthe number of the total oxyalkylene groups.
In the above-mentioned oxyalkylene groups, when the above-mentioned "occupy the most part" is denoted by mol% of oxyethylene group in 100 mol% of the entire oxyalkylene group, 50 to 100 mol% is preferable. Less than 50 mol% of oxyethylene groups might lower hydrophilic property of the group formed by the oxyalkylene group. Oxyethylene groups are more preferably 60 mol% or more, further more preferably 70 mol% or more, particularly preferably 80 mol% or more and most preferably 90 mol% or more.
In the above-mentioned polyhydric alcohol-polyalkylene oxide adduct, the average molar number of addition of the oxyalkylene group is preferably 0 to 100. The average molar number more than 100 might lower detergency of the builder for detergent containing the adduct. The average molar number is more preferably 1 or more, further more preferably 5 or more, particularly preferably 10 or more and most preferably 30 or more, and more preferably 80 or less, further more preferably 70 orless, particularlypreferably 60 orless andmostpreferably 50 or less. If the average molar number of addition of the oxyalkylene group in the polyhydric alcohol-polyalkylene oxide adduct is out of such ranges, functional effects, such as excellent detergency, might be insufficiently exhibited. The above-mentionedaveragemolarnumberofadditionmeans anaverage value of molar number of the added oxyalkylene groups in lmol of groups formed by the oxyalkylene groups of the polyhydric alcohol-polyalkylene oxide adduct, or the average value ofmolar number of the addedoxyalkylene groups in 1 mol ofhydroxyl groups contained in the polyhydric alcohol for forming the polyhydric alcohol-polyalkylene oxide adduct. The polyhydric alcohol-polyalkylene oxide adduct having an above-mentioned average molar number of addition of 0 has no oxyalkylene group.
In the above-mentioned polyhydric alcohol-polyalkylene oxide adduct, it is preferable that at least one terminal of an oxyalkylene group having a structure bonded to a polyhydric alcohol residue is a hydroxyl group. More preferably, all terminals of the oxyalkylene group are hydroxyl groups. One example of preferable embodiments of the above-mentioned polyhydric alcohol-polyalkylene oxide adduct is a sorbitol-ethylene oxide adduct represented by the following formula (1) .
Theweight averagemolecularweightof the above-mentioned polyhydric alcohol-polyalkylene oxide adduct is preferably 500 ormore and 500000 or less, more preferably 1000 ormore, further more preferably 5000 ormore, still further more preferably 8000 or more and particularly preferably 10000 or more, and more preferably 300000 or less, further more preferably 200000 or less, still further more preferably 100000 or less and particularly preferably 80000 or less. The present invention of the builder for detergent may suitably comprise, consist of, or consist essentially of a polyhydric alcohol-polyalkylene oxide adduct.
The present invention provides also a detergent composition containing the above-mentioned builder for detergent.
The above-mentioned detergent compositionmaybe a powder detergent composition or a liquid detergent composition. However, a liquid detergent composition is more preferable because the above-mentioned builder for detergent is excellent in solubility in a liquid detergent. Additives typically used for detergent can be used for the above-mentioned detergent composition in addition to the above-mentioned builder for detergent. Preferable examples of the above-mentioned additives include an alkali builder, a chelate builder, an anti-redeposition agent for preventing redeposition of a contaminant such as sodium carboxymethylcellulose, a stain inhibitor such as benzotriazole and ethylenetiourea, a soil release agent, a color migration inhibitor, a softening agent, an alkaline substance for pH adjustment, a perfume, a solubilizing agent, a fluorescent agent, a coloring agent, a foaming agent, a foam stabilizer, a lustering agent, a bactericide, ableachingagent, ableachingassistant, anenzyme, adye anda solvent. Thepowderdetergent compositionpreferably includes zeolite. It is preferably that the blending ratio of the above-mentioned builder for detergent is typically 0.1 to 20% by weight (% by mass or mass%) based on 100% by weight of the detergent composition, more preferably 0.2% by weight or more and 15% by weight or less, more preferably 0.3% by weight or more and 10% by weight or less, further more preferably 0.4% by weight or more and 8% by weight or less, and particularly preferably 0.5% by weight or more and 5% by weight or less. If the blending ratio of the builder for detergent less than 0.1% by weight, sufficient detergent performance might not be exhibited, and if the blending ratio is more than 20% by weight, economic efficiency might be lowered.
The blending form of the above-mentioned builder in the above-mentioned detergent composition may be either of liquid and solid, and can be determined in accordance with a form of detergent in selling (suchas liquidmaterial or solidmaterial) . The builder may be blended in a form of aqueous solution after polymerization, blended in a form of aqueous solution in which moisture is decreasedto somedegree for condensation, orblended in a state of being dried and solidified. The above-mentioned detergent composition includes a synthetic detergent of a household detergent, an industrial detergentof fiber industryandthe like, ahardsurfacedetergent, and a detergent used only for specific use, such as a bleaching detergent such that the function of one component thereof is ameliorated.
The above-mentioned surfactant is at least one kind selected from an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant, and these surfactants can be used in one kind, or two or more kinds. If two or more kinds of the surfactants are used, the total used amount of the anionic surfactant and the nonionic surfactant is preferably 50% by weight or more based on 100% by weight of all surfactants, more preferably 60% by weight or more, further morepreferably70%byweightormore andparticularlypreferably 80% by weight or more.
Preferable examples of the above-mentioned anionic surfactant include alkylbenzenesulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfofatty acid or ester salt thereof alkane sulfonate, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid surfactant, N-acylamino acid surfactant, alkyl phosphate esteror salt thereof andalkenylphosphate esteror saltthereof.
An alkyl group and an alkenyl group in the above anionic surfactantmayhave abranchedalkyl group such as amethyl group.
Preferable examples of the above-mentioned nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glucoxide, fatty acid glycerin monoester and alkylamine oxide. An alkyl group and an alkenyl group in the above nonionic surfactant may have a branched alkyl group such as a methyl group.
Preferable examples of the above-mentioned cationic surfactant include quaternary ammonium salts.
Preferable examples of the above-mentioned amphoteric surfactant include a carboxyl amphoteric surfactant and a sulfobetaine amphoteric surfactant.
An alkyl group and an alkenyl group in the above cationic surfactant and the above amphoteric surfactant may have a branched alkyl group such as a methyl group.
It is preferable that the blending ratio of the above-mentionedsurfactant is typically 10 to 60%byweightbased on 100% by weight of the detergent composition, more preferably 15% by weight or more and 50% by weight or less, further more preferably 20% by weight or more and 45% by weight or less, and particularly preferably 25% by weight or more and 40% by weight or less. If the blending ratio of the surfactant is less than 10% by weight, sufficient detergency might not be exhibited, and if the blending ratio is more than 60% by weight, economic efficiency might be lowered.
If the above-mentioned detergent composition is a liquid detergent composition, it is preferable that a moisture amount contained in the liquid detergent composition is typically 0.1 to 75% by weight based on 100% by weight of the liquid detergent composition, more preferably 0.2% by weight or more and 70% by weight or less, further more preferably 0.5% by weight or more and 65% byweight or less, particularlypreferably 0.7% byweight or more and 60% by weight or less, more particularly preferably 1% byweight ormore and 55%byweight or less, andmost preferably 1.5% by weight or more and 50% by weight or less.
The above-mentioned liquid detergent composition preferably has a kaolin turbidity of 200 mg/L or less, more preferably 150 mg/L or less, further more preferably 120 mg/L or less, particularly preferably 100 mg/L or less and most preferably 50 mg/L or less . The difference in kaolin turbidity betweenthecaseofaddingthebuilder fordetergentofthepresent invention to the liquid detergent composition and the case of not adding it is preferably 500 mg/L or less, more preferably 400 mg/L or less, further more preferably 300 mg/L or less, particularly preferably 200 mg/L or less and most preferably 100 mg/L or less. The kaolin turbidity can be measured by a measuring method mentioned below, for example. <Measurement method of kaolin turbidity> A sample (liquid detergent) homogeneously stirred is charged in a 50 max 50 mm square cell with 10 mm thickness and bubbles are removed. Then, the sample is measured for Turbidity
(kaolin turbidity: mg/L) at 25°C using NDH 2000 (trade name, turbidimeter) manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.
Preferable examplesofanenzymeblendedwiththedetergent composition of the present invention include protease, lipase and cellulase. Among them, protease, alkali lipase and alkali cellulase are preferable because of these high activities in alkali washings .
The added amount of the above-mentioned enzyme is preferably 5% by weight or less based on 100% by weight of the detergent composition. If the added amount is more than 5% by weight, the detergencyis not improved, whichmight lower economy efficiency. Preferable examples of the above-mentioned alkali builder include silicate, carbonate and sulfate. Preferable examples of the above-mentioned chelate builder include diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid) , DTPA (diethylenetriaminepentaacetic acid) , triphosphate, sodium tripolyphosphate, and citric acid. Other water-soluble polycarboxylic acid polymers except the polyhydric alcohol-polyalkylene oxide adduct in the present invention may be used. The polyhydric alcohol-polyalkylene oxide adduct may be used as a builder for detergent singly or in combination of two or more of them. A polyalkyleneimine-polyalkylene oxide adduct is preferably used together with the polyhydric alcohol-polyalkylene oxide adduct. The polyhydric alcohol-polyalkylene oxide adduct is preferably used together withthewater-solublepolycarboxylic acidpolymers as abuilder for detergent.
The above-mentioned detergent composition can be used as a detergent with extremely high-quality performance and excellent stability, because the composition is excellent in dispersancy and additionally maintains its stability if the composition is preserved for a long period and causes no precipitation of impurities and the like if maintained at low temperatures .
Thepresentinventionalsoprovides abuilderfordetergent containing a polyhydric alcohol structure, the builder for detergent has a detergency of 23% or more and a color tone in APHA/Hazen of 50 or less.
The above-mentioned builder for detergent preferably has the above-mentioned polyhydric alcohol-polyalkylene oxide adduct as an essential ingredient. And in this case, preferable embodiments of a polyhydric alcohol, a polyalkylene oxide, a manufacturingmethod and the like are the same as thosementioned above.
The above-mentioned detergency is preferably 23% ormore. If the detergency is 23% or more, improvement of the detergency canbe clearly recognizedwith respect to blank. The detergency is more preferably 24% or more.
The above-mentionedcolortone inAPHA/Hazenispreferably
50 or less. If the color tone is 50 or less, deterioration of the color tone can not be recognized when the builder having such a color tone is blended as a liquid detergent. The cqlor tone is more preferably 30 or less.
The builder for detergent of the present invention has the above-mentioned configuration and it is a builder for detergent, which is excellent insolubilityina liquiddetergent and can exhibit high basic performance in detergency and the like, and additionally is excellent in a color tone without an odor and excellent in a sense of use as a builder for detergent and furthermore excellent in cost performance if being used as a builder for detergent.
BEST MODES FOR CARRYING OUT THE INVENTION The present invention is described in more detail hereinafter with reference to Examples, but is not limited only thereto. Unless otherwise specified, "part" andXΛ%"means "part by weight" and λλ% by weight", respectively.
[Synthetic Example 1] Synthesis of 2 mol of sorbitol-ethylene oxide adduct (compound
(D)
To a 1350 ml autoclave provided with a stirrer was added 200 g of sorbitol and 1.30 gof a 30% aqueous solutionofpotassium hydroxide, and the vessel was sealed and then the mixture was heated up to a temperature of 140°C and stirred for 30 minutes while the pressure was reduced to 0.015 hPa with a decompression pump. Thereafter, nitrogen with a pressure of 0.3 Mpa was added to the vessel, and the inside was degassed to 0.1 MPa. This operationwas repeatedthreetimes andthe insideofthe apparatus was substituted with nitrogen. After the substitution with nitrogen, the inside was set at a pressure of 0.15 MPa and a temperature of 1500C, and filled with ethylene oxide. While the partial pressure of nitrogen/ethylene oxide in reaction was within a dangerous range of explosion, 580.2 g of ethylene oxide was charged. After the charge, the inside was aged for 1 hour, and then cooled to a temperature of 80°C and degassed. Nitrogen was added to the inside of the vessel while degassed gas was released into water to substitute the inside with nitrogen sufficiently. And then the content was taken out to produce a compound (1) .
[Synthetic Example 2]
Synthesis of 10 mol of sorbitol-ethylene oxide adduct (compound (2)) To a 3750 ml autoclave provided with a stirrer was added 500 g of the compound (1) and 2.47 g of a 30% aqueous solution of potassium hydroxide, and the vessel was sealed and then the mixture was heated up to a temperature of 1100C and stirred for 30 minutes while the pressure was reduced to 0.015 hPa with a decompression pump. Thereafter, nitrogen with a pressure of 0.3 Mpa was added to the vessel, and the inside was degassed to 0.1MPa. This operationwas repeatedthree times andthe inside of the apparatus was substituted with nitrogen. After the substitution with nitrogen, the inside was set at a pressure of 0.17MPa and a temperature of 150°C, and filled with ethylene oxide. While the partial pressure of nitrogen/ethylene oxide in reaction was within a dangerous range of explosion, 1487 g of ethylene oxide was charged. After the charge, the inside was aged for 2 hours, and then cooled to a temperature of 80°C and degassed. Nitrogen was added to the inside of the vessel while degassed gas was released into water to substitute the inside with nitrogen sufficiently. And then the content was taken out to produce a compound (2) .
[Synthetic Example 3] Synthesis of 20 mol of sorbitol-ethylene oxide adduct (compound (3) )
A compound (3) was produced in the same manner as in Synthetic Example 2.
[Comparative Synthetic Example]
A polyethyleneimine-polyethylene oxide adduct produced by ethoxylatingpolyethyleneimine (an average molecular weight of 600, product ofNIPPONSHOKUBAI CO., LTD.) withethylene oxide equivalent to 20molpermol ofnitrogenwas usedas a comparative compound.
Example 1
AColor tone, odor and detergency of the builder compound (2) fordetergentwere evaluatedinaccordancewiththe following methods. Table 1 shows the results. [Color Tone]
A 50% aqueous solution of the polyhydric alcohol-polyalkylene oxide adduct (compound (2) ) was measured for a APHA/Hazen. [Odor]
A 50%aqueous solution of the polyhydric alcohol-polyalkyleneoxide adduct (compound (2)) 10 gwas sealed in a 20 ml screw cap bottle, and then ammonia odor concentration (ppm) in a gaseous phase portion after still standing at a temperature of 4O0C for 24 hours was measured with an ammonia detector tube (No. 3L) manufactured by GASTEC CORPORATION. [Detergency]
A cloth (STC GC C "clay dirt" cut into a size of 4.5 cm x 7.0 cm) obtainedfromScientific Service Corporation, was used as an artificially soiled fabric. The artificially soiled fabric was previously measured for whiteness with reflectance using a colorimetric difference meter SE2000 (manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.) . Purewaterwasaddedto1.47gofcalciumchloridedihydrate to prepare 10 kg of hard water.
Pure water was added to 4.8 g of sodium polyoxyethylene lauryl ether sulfate (AES), 0.6 gofpolyoxyethylene lauryl ether
(AE), 0.6 g of sodium borate, 0.9 g of citric acid and 2.4 g of propylene glycol to produce 80 g of the mixture. And then the mixture was adjusted to a pH of 8.2 with an aqueous solution of sodium hydroxide, and then pure water was added thereto to prepare 100 g of an aqueous solution of surfactant in total.
A targotometer was set at a temperature of 270C, and then 1000 mL of hard water, 5 mL of the aqueous polymer solution (a concentration of 0.28%), 4.8 mL of the aqueous solution of surfactant and the artificially soiled fabrics (STC GC C cloth: 10 sheets) were put in a pot and the mixture was stirred at 100 rpm for 10 minutes. The artificially soiled fabrics were taken out of the pot, and moisture was squeezed therefrom by hand. In the pot was put lOOOmLofhardwater, andthemoisture-squeezedartificially soiled fabric was put therein and the mixture was stirred at 100 rpm for 2 minutes. The artificially soiled fabrics were taken out of the pot andmoisture was squeezed therefrombyhand, andthereafter the artificially soiled fabrics werepressedwith filler cloths to dry them while smoothing the wrinkles. The dried artificially soiled fabrics were measured for whiteness with reflectance with a colorimetric difference meter. Detergency (%) was calculated by the value by the above manner and the following formula.
Detergency (%) = (whiteness of artificially soiled fabric after washing - whiteness of artificially soiled fabric before washing) ÷ (whiteness of original white cloth (EMPA221) of artificially soiled fabric - whiteness of artificially soiled fabric before washing) x 100
The higher numerical value is the more preferable detergency is. Example 2
The measurement was performed in the same manner as in Example 1 except that the compound (3) was used instead of the polyhydric alcohol-polyalkylene oxide adduct (compound (2)) . Table 1 shows the results .
Comparative Examples 1 and 2
In Comparative Example 1, the measurement was performed in the same manner as in Example 1 except that the comparative compoundwasusedinsteadofthepolyhydricalcohol-polyalkylene oxide adduct (compound (2) ) . And in Comparative Example 2, the measurement was performed in the same manner as in Example 1 except that no polyhydric alcohol-polyalkylene oxide adduct was added (Comparative Example 2) . Table 1 shows the results.
Table 1
When the builders in Examples 1 and 2 are compared with the builder in Comparative Example 1, the builders in Examples 1 and 2 are equal to the builder in Comparative Example 1 in detergency; but the builders in Examples 1 and 2 are have an overwhelming superiority to the builder in color tone and odor (ammonia odor concentration) .
Example 3
Anti-redeposition when the builder compound (2) for detergentorthebuildercompound (3) fordetergentwas evaluated in the following manner. Table 2 shows the results. <Anti-redeposition>
(1) A cotton cloth and a polyester cloth were cut to 5cm x 5cm to eachprepare 7white cloths. Thewhite clothswerepreviously measured for whiteness with reflectance using a colorimetric differencemeterND-1001DPtype (manufacturedbyNipponDenshoku Industries Co., Ltd.).
(2) Pure water is added to 1.47 g of calcium chloride dihydrate to prepare 10 kg of hard water.
(3) Thereto, 3.0 g of sodium dodecylbenzenesulfonate, 3.Og of sodium carbonate, and 0.25 g of AQUALIC TL400 (a copolymer of acrylic acid and maleic acid, product of NIPPON SHOKUBAI Co., Ltd) , which is a polycarboxylic acid polymer, were added, and then pure water is added to prepare 50 g of an aqueous solution of surfactant.
(4) Targotometer is set at 25°C, and 1000 ml of hard water, 5.0 g of a 0.2% aqueous solution of compound, 5.0 g of the aqueous solution of surfactant, 0.2 g of zeolite and 0.25 g of carbon black were put in a pot and stirred at 100 rpm for 1 minute.
(5) The white cloths were put in a pot and stirred at 100 rpm for 10 minutes.
(6) The white cloths are wringed by hand, and 1 liter of hard water is put in a pot and stirred at 100 rpm for 2 minutes. (7) The white cloths are pressed with a filler cloth to dry them while smoothing wrinkles. And then, the white cloths were measured for whiteness again with reflectance using the colorimetric difference meter.
(8) From these measurements, the anti-redeposition was determined by the following equation.
Anti-redeposition (%)=(whitenessaftercleaning) / (whitenessof original white cloth) xlOO
Comparative Example 3 Ameasurementwasperformedinthesamemanneras inExample 3, except that AQUALIC TL400 was used as a comparative compound instead of the builder compound(2) or (3) for detergent. Table 2 shows the result.
Table 2
The combined use of the polycarboxylic acid polymer and the polyhydric alcohol-polyalkylene oxide adduct as a builder for detergent improved the anti-redeposition.
The present application claims priority under 35 U.S.C.§119 to Japanese Patent Application No.2004-356609 filed December 9, 2004, entitled "BUILDER FOR DETERGENT CONTAINING POLYHYDRIC ALCOHOL-POLYALKYLENE OXIDE ADDUCT." The contents of that application are incorporatedhereinbyreference intheir entirely.

Claims

1 . A builder for detergent containing a polyhydric alcohol-polyalkylene oxide adduct .
2. The builder for detergent according to Claim 1, wherein the builder for detergent is a builder for liquid detergent.
3. The builder for detergent according to Claim 1 or 2, wherein the builder for detergent has a color tone in APHA/Hazen of 1000 or less.
4. A detergent composition containing the builder for detergent according to any one of Claims 1 to 3.
5. A builder for detergent containing a polyhydric alcohol structure, wherein the builder for detergent has a detergency of 23% or more and a color tone in APHA/Hazen of 50 or less.
6. The builder for detergent according to Claim 5, wherein the builder for detergent has an ammonia odor concentration of 3 ppm or less.
EP05816519A 2004-12-09 2005-12-08 Builder for detergent containing polyhydric alcohol-polyalkylene oxide adduct Withdrawn EP1838832A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004356609 2004-12-09
PCT/JP2005/022988 WO2006062243A1 (en) 2004-12-09 2005-12-08 Builder for detergent containing polyhydric alcohol-polyalkylene oxide adduct

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EP1838832A1 true EP1838832A1 (en) 2007-10-03

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WO (1) WO2006062243A1 (en)

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
JPS62106999A (en) * 1985-11-01 1987-05-18 花王株式会社 Liquid detergent composition
JP2582626B2 (en) * 1988-08-04 1997-02-19 花王株式会社 Detergent composition
JPH09157696A (en) * 1995-12-08 1997-06-17 Kao Corp High density granular detergent composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006062243A1 *

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JP2008523164A (en) 2008-07-03

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