WO1998026035A1 - Composition detergente haute densite - Google Patents

Composition detergente haute densite Download PDF

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Publication number
WO1998026035A1
WO1998026035A1 PCT/JP1997/004315 JP9704315W WO9826035A1 WO 1998026035 A1 WO1998026035 A1 WO 1998026035A1 JP 9704315 W JP9704315 W JP 9704315W WO 9826035 A1 WO9826035 A1 WO 9826035A1
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Prior art keywords
formula
weight
represented
acid
aluminosilicate
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PCT/JP1997/004315
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English (en)
Japanese (ja)
Inventor
Shuji Tagata
Yohei Kaneko
Genjiro Hagino
Hiroshi Danjo
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Kao Corporation
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to high density detergent compositions. More specifically, the present invention relates to a high-density detergent composition containing a specific organic chelating agent, easily dissolving in cold water, and having excellent detergency. Background art
  • Detergents for clothing solubilize stains, surfactants that dissolve and disperse from fibers into the washing liquid, alkaline agents that promote the decomposition and solubilization of stains, high molecular compounds that disperse stains, and surfactants It is basically composed of a sequestering agent for removing calcium, magnesium, and the like from the washing liquid, which lower the ability of the washing liquid.
  • a sequestering agent for removing calcium, magnesium, and the like those that do not exhibit cleaning performance by themselves, but are intended to improve the cleaning power by combining with a surfactant or the like, are generally called detergent builders.
  • the sequestering agent described above is a substance for more effectively exhibiting the performance of a surfactant, and is one of the very important detergent builders.
  • clothing detergents contained phosphorus compounds such as sodium tripolyphosphate as a detergent builder (sequestering agent), but phosphorus compounds are considered as one of the causes of eutrophication in lakes and swamps.
  • the detergent industry has voluntarily regulated the use of phosphate builders and has been developing detergents that do not contain phosphate builders. Dephosphorization of such detergents has been promoted since around 1980, and is now confined to a specific structure. Crystalline sodium aluminosilicate (referred to as zeolite in the industry) has no problems with phosphate-type builders and has recently become stable in price, making it a major component of sequestering agents. ing.
  • the washing conditions in Japan are special, and it is not uncommon to wash with cold water at around 5 ° C in winter.
  • the standard cleaning time in households (excluding rinsing and dehydration steps) is very short, about 10 minutes. Under such low-temperature and short-time washing conditions, it is essential to improve the solubility of the compact detergent in order to obtain good detergency. is there.
  • zeolite which is the mainstream of detergent builders today, is itself water-insoluble, and when detergent particles containing zeolite come into contact with water, a high-viscosity detergent paste such as surfactants and inorganic salts is produced. To make, the solubility decreases.
  • the mechanism of sequestering the hardness component of zeolite is based on ion exchange, but the exchange rate is kinetic-limited by the diffusion of exchanged ions in zeolite. Therefore, at low water temperatures, ion exchange takes a long time, resulting in insufficient cleaning power. In particular, there was a problem that it took a very long time to exchange Mg ions in the hydrated shell.
  • Zeolite is widely used as a phosphorus-free builder, but as described above, in some cases, the performance cannot be sufficiently exerted by washing with time, and a polymer dispersant such as a polycarboxylic acid-based polymer is generally incorporated into the detergent in order to compensate for such insufficient washing power of zeolite.
  • This polycarboxylic acid-based polymer is also a kind of ion exchanger and has a function of blocking polyvalent cations. Since this builder is water-soluble, it is effective at sequestering polyvalent cations at low water temperatures. However, the polycarboxylic acid-based polymer tends to thicken the detergent paste, and thus has a problem that the solubility of the zeolite-containing detergent may be reduced.
  • the present inventors have conducted intensive studies to solve the problems, and as a result, by blending a zeolite-containing detergent composition with a specific organic builder represented by the following general formula (I), The inventors have found that a detergent composition having excellent detergency and solubility can be obtained, and have completed the present invention.
  • the present invention relates to an aminopolycarboxylic acid compound (a) represented by the formula (1) of 1 to 30% by weight, an aluminosilicate (b) of 5 to 40% by weight, and an interface of 5 to 50% by weight.
  • a high-density detergent composition containing an activator (c) and having a bulk density of 0.5 to 1.8 g Zml.
  • A is a hydrogen or - CH 2 0H, it may be the same or different.
  • M H, Na, selected from K and ⁇ 4 may be the same or different.
  • aminopolycarboxylic acid represented by the general formula (I) 1 to 30% by weight, preferably 2 to 20% by weight of the component (a) of the aminopolycarboxylic acid represented by the general formula (I) is blended.
  • the amount is less than 1% by weight, the washing power is reduced, and when the amount is more than 30% by weight, the storage stability is reduced.
  • Preferred as the aminopolycarboxylic acid represented by the general formula (I) are compounds represented by the following general formulas (1-1), (I2) and (1-3).
  • the aminopolycarboxylic acid represented by the general formula (I) used in the present invention is an excellent hardness component sequestering agent and has a function as a normal builder.
  • Aminopolycarboxylic acids represented by the above general formulas (1-1) and (1-3) are described in JP-A-63-26751 and JP-A-2-295954. Does not mention the effect of improving the low-temperature solubility when crystalline aluminosilicate is used in combination.
  • Aluminosilicate which is the component (b) of the present invention will be described.
  • Aluminosilicates can be roughly classified into crystalline ones and amorphous ones, and any of them can be used in the present invention.
  • the crystalline aluminosilicate is generally called zeolite, and Notation (iii)
  • M is an alkali metal atom
  • a ', b', and w represent the molar ratio of each component. Generally, 0.7 ⁇ a' ⁇ l.5, 0.8 ⁇ b ' It is a positive number. :
  • zeolite crystalline aluminosilicate
  • synthetic zeolites having an average primary particle size of 0.1 to 10 xm represented by A-type, X-type and P-type zeolites are preferably used.
  • the zeolite may be blended as zeolite aggregated dry particles obtained by drying the powder and / or the zeolite slurry.
  • amorphous aluminosilicate silicon as Si0 2, 30 wt% or more, good Mashiku may those containing more than 40 wt%, and Ru der pH of 5% dispersion least 9
  • the use of the composition further improves the solubility of the detergent after storage at high humidity.
  • Examples of the amorphous aluminosilicate used in the present invention include those represented by the following general formula (i), which have high oil absorption and high cation exchange ability.
  • M is an alkali metal atom
  • a, b, and c represent the number of moles of each component. In general, 0.7 ⁇ a ⁇ 2.0, 0.8 ⁇ b ⁇ 4, and c is any positive number.
  • an amorphous aluminosilicate of 200 ml ZlOO g or more can be produced with reference to JP-A-6-179899.
  • the oil absorption ability contributes to the powder properties when a liquid or paste-like surfactant is used at room temperature, particularly when a nonionic surfactant is used.
  • Amorphous aluminosilicate is preferred because it has ion-exchange water activity and an action as an oil-absorbing carrier.
  • Amorphous aluminosilicates with oil-absorbing ability can be used when 5% by weight or more, especially 10% by weight, of a nonionic surfactant with a melting point of 40 ° C or less is used as a surfactant. And it is effective for anti-caking.
  • the amorphous aluminosilicate is preferably used in combination with the crystalline aluminosilicate.
  • Zeolite or amorphous aluminosilicate is used for the purpose of improving the hygroscopicity of the aminopolycarboxylic acid compound represented by the general formula (I), suppressing the generation of water-insoluble components, and improving the caking property when storing the detergent.
  • the combination of salt is effective.
  • the surface of the detergent particles containing the aminopolycarboxylic acid compound is preferably coated with these zeolite / amorphous aluminosilicate.
  • the detergent particles are coated with an amorphous aluminosilicate having an oil absorbing ability, a small amount of a suitable result can be obtained.
  • the aluminosilicate be incorporated in an amount of 5% by weight or more. Therefore, in order to satisfy the requirements of the solubility, the masking property and the water-insoluble content of the detergent, it is preferable that zeolite or amorphous aluminosilicate is mixed in the detergent in an amount of 5 to 40% by weight. Preferred is 5 to 30% by weight.
  • the high-density detergent composition of the present invention contains a surfactant. It is incorporated in the composition in an amount of 5 to 50% by weight, preferably 10 to 40% by weight.
  • Surfactants include anionic surfactants, Nonionic surfactants, cationic surfactants, and amphoteric surfactants can be used. Particularly, anionic surfactants and nonionic surfactants are preferable, and these are preferably used in combination.
  • anionic surfactants include alkylbenzene sulfonic acids having 8 to 16 carbon atoms, alkane sulfonic acid salts (SAS), hypoolefin sulfonic acid salts, sulfate salts of primary and secondary higher alcohols, and polyalkylene sulfonic acids.
  • SAS alkane sulfonic acid salts
  • hypoolefin sulfonic acid salts sulfate salts of primary and secondary higher alcohols
  • polyalkylene sulfonic acids One or more selected from ester salts of oxyethylene alkyl ethers and salts of ⁇ -sulfofatty acids are used.
  • nonionic surfactant examples include those obtained by adding an alkylene oxide such as ethylene oxide to propylene oxide to a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms, or a similar nonionic surfactant.
  • alkylene oxide such as ethylene oxide to propylene oxide
  • a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms or a similar nonionic surfactant.
  • polyoxyalkylene ether polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyalkylene sorbite fatty acid ester, polyoxyalkylene higher fatty acid alkanolamide, polyoxyalkylene higher fatty acid obtained by the above method.
  • examples include esters of polyhydric alcohols.
  • the high-density detergent composition of the present invention may contain the following builder in addition to the above-mentioned aminopolycarboxylate compound.
  • the high-density detergent composition of the present invention preferably contains a crystalline silicate.
  • Polyaminocarboxylic acid dissociates stepwise depending on ⁇ , and dissociates almost completely at pH 11 and above.
  • the metal ion hydrate complex becomes stable and affects the formation of chelates. Due to this effect, the chelate stability constant shows a pH dependence.
  • chelation formation by aminopolycarboxylic acid is usually more effective when used at high ⁇ ( ⁇ 11 112).
  • For clothing It is important that the pH of the cleaning solution is kept high in order to use the chelating agent effectively in the detergent. '
  • detergents contain sodium carbonate and sodium silicate as typical alkali agents. Since sodium silicate gives a higher pH than sodium carbonate, it is advantageous in emulsifying sebum soil and stabilizing dispersion of solid particle soil.
  • JIS sodium silicate in particular is amorphous, is susceptible to moisture absorption, and has a problem of producing relatively large water-insoluble components with zeolite during storage.
  • crystalline silicate is characterized in that the washing solution has a high pH equivalent to that of silicate and that the amount of water-insoluble components generated during storage is very small.
  • this compound since this compound has an ion exchange function like a crystalline aminosilicate, it is a very preferable base material because it can reduce the amount of a hardening agent to be mixed.
  • Crystalline silicate used in the present invention is a silicate (S i 0 2) an alkali metal salt rather preferable, especially up to pH of 0.1 percent dispersion 1 1 or more (25 ° C), the dispersion It is preferable that the volume of 0.1N HC1 aqueous solution required for lowering the pH of 1 liter of liquid to 10 to be 5 ml or more.
  • S i O ZMzO of alkali metal silicate, where M represents an alkali metal. ) Is preferably from 0.5 to 2.6.
  • Conventionally known crystalline silicates have a Sit ZNasO of 1.9 to 4.0, but those with a ratio of more than 2.6 are not suitable for blending high-density detergents that are the subject of the present invention. There are cases.
  • the condensable silicate used in the present invention has an ion exchange capacity of at least 100 CaCOsmg / g or more, preferably 200 to 600 CaC (hmgZg), and is one of the substances having an ion trapping ability in the present invention. is there.
  • the crystalline silicate has an alkali function and an alkali buffering effect as described above, and further has an ion exchange function
  • the aforementioned washing conditions can be suitably adjusted by appropriately adjusting the amount of the crystalline silicate.
  • the crystalline silicate preferably has an average particle size of 0.1 to 100 m, more preferably 1 to 60 mm.
  • the average particle size is the median size of the particle size distribution.
  • the crystalline silicate having such an average particle size and particle size distribution can be prepared by pulverizing using a pulverizer such as a vibration mill, a hammer mill, a ball mill, a roller mill and the like.
  • the preferred crystalline silicate used in the present invention has the following composition.
  • M represents an element belonging to group la of the periodic table
  • M is selected from the la group elements of the periodic table, and examples of the la group elements include Na, K and the like. These may constitute the Micromax 2 0 component alone or, for example by mixing and the Na 2 0 and K 2 0.
  • Me is selected from Ila group element, lib group element, Ilia group element, IVa group element or VIII group element in the periodic table, and examples thereof include Mg, Ca, Zn, Y, Ti, Zr, and Fe. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. These may be used alone or as a mixture of two or more kinds. For example, Mg0, CaO and the like may be mixed to form a MemOn component.
  • yZx is 0.5 to 2.6, preferably 1.5 to 2.6. 2.2.
  • yZx is less than 0.5, the water resistance is insufficient, and the caking property, the solubility, and the powder properties of the detergent composition are significantly adversely affected.
  • yZx exceeds 2.6, the alkalinity becomes low and becomes insufficient as an alkali agent, and the ion exchange ability also becomes low, making it insufficient as an ion exchanger.
  • zZx is 0.01 to 1.0, preferably 0.02 to 0.9, and most preferably 0.05 to 0.9.
  • ⁇ / ⁇ is less than 0.01, the water resistance is insufficient, and if ⁇ / ⁇ exceeds 1.0, the ion exchange capacity is low and the ion exchange capacity is insufficient.
  • X, y, and z are not particularly limited as long as they have the relationship shown in the above-mentioned yZx ratio and z / x ratio.
  • x (M20) is, for example, x ′ (Na 20 ) ⁇ ′ ′ (K 2 0) ⁇ as described above, X is ⁇ ′ + ⁇ ′′.
  • ⁇ indicates the number of oxygen ions coordinated to the element, and is substantially selected from values of 0.5, 1.0, 1.5, and 2.0.
  • the production method of the crystalline silicate represented by the general formula (II) can be referred to JP-A-7-89712.
  • This crystalline silicate has the general formula (III)
  • M represents an alkali metal
  • This crystalline silicate is also one of the substances having an ion-capturing ability in the present invention.
  • the production method of the crystalline silicate represented by the general formula (III) is described in JP-A-60-227895. Generally, amorphous glassy sodium silicate is treated at 200 to 1000 ° C. Burning To be crystalline.
  • the crystalline silicate represented by the general formula (III) is, for example, a powdery or granular form of Na-SKS-6 ( ⁇ -a 2 Si 20 s ) from Hoechst. Get one.
  • the crystalline silicate represented by the general formula (II) and the crystalline silicate represented by the general formula (III) can be used alone or in combination of two or more. It is desirable that the alkali agent occupy 10 to 100% by weight, preferably 30 to 100% by weight of the alkali agent to be incorporated in the composition.
  • the crystalline silicate is blended in the composition in an amount of 1 to 40% by weight, preferably 5 to 35% by weight. If the content of the crystalline silicate is less than 1% by weight, the detergency will decrease. If it exceeds 40%, the hygroscopicity will increase, and powder properties such as caking will deteriorate, making handling difficult. Become.
  • Builders have the effect of dispersing solid particulate soil from the clothing into the washing bath and the effect of preventing the particles from re-adhering (recontaminating) to the clothing.
  • a polycarboxylic acid having a molecular weight of several hundred to 100,000 such as a copolymer represented by the following formula (V) or a homopolymer represented by the following formula (vi) can be used.
  • Z is maleic acid (anhydrous) such as olefin having 1 to 8 carbon atoms, acrylic acid, methacrylic acid, itaconic acid, methallylsulfonic acid, or a monomer copolymerizable with maleic acid salt and maleic anhydride (anhydrous)
  • the acid copolymer salts m and n are such that the molecular weight of the copolymer is from several hundred to 100,000.
  • the copolymer obtained from maleic acid and a monomer copolymerizable with maleic acid is a random polymer.
  • M is Na, K, NH 4, H . )
  • P is a monomer capable of being homopolymerized, for example, acrylic acid, methacrylic acid, maleic acid, etc. 1 is a value such that the molecular weight of the homopolymer indicates several hundred to 100,000. there. homopolymers one has become Na, K, and NH 4 salt.
  • the compounding amount of the copolymer of the formula (v) or the homopolymer of the formula (vi) is 1 to 8 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the detergent composition.
  • these polycarboxylates salts of acrylic acid-maleic acid copolymer and polyacrylic acid Salt (Na, ⁇ , ⁇ 4) are particularly excellent.
  • the molecular weight is suitably from 1,000 to 80,000.
  • the following inorganic or organic builders can be used.
  • Alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sesquicarbonate, and JIS No. 1 and No. 2 amorphous sodium silicates.
  • Orthophosphate pyrophosphate, etc.
  • Phosphates such as tripolyphosphate
  • Salts of phosphonic acids such as 1,1,1-diphosphonic acid and 1,2-diphosphonic acid
  • Polymer electrolytes such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, and polyaspartic acid 3
  • Organic acid salts such as diglycolic acid and oxydisuccinic acid.
  • the following components can be blended as components other than the builder.
  • the bleaching agent include sodium percarbonate, sodium perborate (preferably monohydrate), and sodium hydrogen peroxide adduct. Particularly preferred is sodium percarbonate, which is used in combination with aluminosilicate. In the present invention, it is preferable to use sodium percarbonate coated with sodium borate.
  • bleach activator examples include tetraacetylethylenediamine, acetooxybenzenesulfonate, and organic peracids described in JP-A-59-22999, JP-A-63-258447 and JP-A-6-1316700.
  • examples include a precursor or a metal catalyst in which a transition metal is stabilized with a sequestering agent.
  • Enzymes Enzymes that inherently perform enzymatic action during the washing process.
  • hydralases oxidoreductases, lyases, transferases and isomerases, and any of them can be applied to the present invention.
  • Particularly preferred are proteases, esterases, lipases, nucleases, cellulases, amylases and vectorinases.
  • proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elasase, sptilisin, BPN, papain, promerin, carboxypeptidase A and B, and aminopeptidylase.
  • a and B are inferior A and B, and are commercially available products such as Sabinase, Alcalase (Novo Industry Co., Ltd.), API 21 (Showa Denko KK), and Maxacal (Gyst Procaides).
  • Proteases K-14 or K-16 described in JP-A-5-43892 can also be used.
  • esterases include gastric lipase, bankreatic lipase, plant lipases, phospholipases, cholinesterases and phospholipases.
  • a commercially available lipase such as ribolase (Novo Industry Co., Ltd.) can be used.
  • cellulase there is a commercially available cellulase (Novo Industry Co., Ltd.) KAC 50 (manufactured by Kao Corporation), and the cellulase described in claim 4 of JP-A-63-264699. Can be used.
  • KAC 50 manufactured by Kao Corporation
  • amylase commercially available Yuichi Mamil (Nopo Industries) can be used.
  • a reducing agent sodium sulfite, sodium bisulfite, calcium salt, magnesium salt, polyol, boron compound, etc.
  • Various bluing agents may be added as needed.
  • a blue tinting agent No. 286, JP-B-49-18005, and JP-B-53-45808.
  • caking inhibitor examples include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, magnesium oxide and the like.
  • a porous material such as finely divided silica can be used as a carrier for the nonionic surfactant.
  • Clay smectite-like clay is also effective as a softening agent.
  • Antioxidants include tertiary butylhydroxytoluene, 4,4'-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2'-butylidenebis- (6-tert-butyl-14-methylphenol), Examples include monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1′-bis (4-hydroxyphenyl) cyclohexane and the like.
  • fluorescent dyes 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative,
  • 4,4′-bis (triazole-2-yl) stilbene derivatives and bis (triazinylamino) stilbene disulfonic acid derivatives may be contained in the composition in an amount of 0 to 1% by weight. it can.
  • fluorescent dye for example, those commercially available under the names of Whitex (manufactured by Sumitomo Chemical Co., Ltd.) and Tinopearl (manufactured by Ciba-Geigy) can be used.
  • a fragrance conventionally used in detergents for example, a fragrance described in JP-A-63-101496 can be used.
  • the method for producing the powdery or bulk detergent composition of the present invention is not particularly limited, and a conventionally known method can be used.
  • the method for increasing the bulk density when obtaining a high-density detergent includes, for example, a method of spraying non-ionic surfactants onto spray-dried particles to increase the density, and a method of directly absorbing non-ions into powder components including an oil-absorbing carrier. How to increase density while JP-A-61-69897, JP-A-61-69899, JP-A-61-69900, JP-A-2-2'22498, JP-A-2-222499, The methods described in JP-A-3-33199, JP-A-5-86400, and JP-A-5-209200 can be referred to.
  • a crystalline aluminosilicate When a crystalline aluminosilicate is blended as an aluminosilicate, a small amount thereof may be added during granulation or immediately before the completion of granulation in order to use it as a surface modifier for the granulated material.
  • the crystalline silicate When a crystalline silicate is blended, the crystalline silicate is preferably added at the time of increasing the bulk density or by dry blending.
  • an alkali metal carbonate When blended, it may be added in a slurry, during granulation, or in a dry blend.
  • the powder When blended in a tablet or evening bullet detergent, the powder may be blended as it is, or may be mixed with other components in a slurry and then dried.
  • the average particle size of the cleaning composition of the present invention is desirably 200 to 1000 xm, particularly 200 to 600; m, in order to obtain preferable powder properties.
  • the detergent composition of the present invention has a bulk density of about 0.5 to 1.2 g / cm 3 , preferably about 0.6 to 1.0 g / cm 3 .
  • the bulk density is 0.8 to 1.8 g / cm 3 , preferably 1.0 to 1.6 g / cm 3 .
  • the detergent composition of the present invention can be used at a concentration suitable for each washing depending on washing methods such as washing machine washing and pickling washing, as well as the amount of clothes and water, the degree of dirt, and the use of machines. it can.
  • washing methods such as washing machine washing and pickling washing
  • a washing concentration of 0.03 to 0.3% by weight can be used.
  • the polycarboxylic acid compounds used in the following examples were obtained in the following synthesis examples 1 to 3. Synthesis example 1
  • a 1-liter four-necked flask was charged with 38 g of glycine, 63 g of glycolaldehyde and 100 g of water, and the pH was adjusted to 7 with a 40% aqueous sodium hydroxide solution.
  • 28 g of liquid hydrocyanic acid was dropped with a 40% aqueous sodium hydroxide solution over 2 hours while maintaining the pH at 7.
  • Aged at 30 ° C for 5 hours.
  • To the resulting solution containing N-carboxymethyl-iminobis (2-hydroxymethylacetonitrile) sodium salt was added 125 g of a 40% aqueous sodium hydroxide solution, and the mixture was aged at 100 ° C. for 5 hours to hydrolyze nitrile. went.
  • 401 g of an aqueous solution containing 33% of N_carboxymethyl-iminobis (2-hydroxymethylacetic acid) ⁇ 3Na salt (APC-2) represented by the general formula (1-2) was obtained.
  • Inventive product 1 of Table 1 was prepared by the following method.
  • the particles obtained by spray-drying the mixture are put into a high-speed mixer (agitated tumbling granulator, manufactured by Fukae Kogyo Co., Ltd.), and 0.5 kg of zeolite is added.
  • a high bulk density granular detergent was prepared.
  • the obtained high bulk density granular detergent composition was subjected to a detergency test and a detergent solubility test by the following methods. The results are shown in Table 1.
  • An artificially stained cloth having the following composition was attached to the cloth to prepare an artificially stained cloth.
  • the artificial contaminant was attached to the cloth by printing the artificial contaminant on the cloth using a gravure roll coater.
  • the process of making the artificially contaminated cloth by attaching the artificially contaminated liquid to the cloth was performed with a gravure roll cell volume ⁇ ⁇ ⁇ ' ⁇ 2 , a coating speed of 1.OmZmin, a drying temperature of 100 ° C, and a drying time of 1 minute.
  • the cloth used was a cotton cloth 2003 (manufactured by Tanito Shoten).
  • Oleic acid 7.75% by weight
  • Trioleic acid 1 3.06% by weight
  • the detergency is measured by measuring the reflectance at 550 nm of the original cloth before and after cleaning and the contaminated cloth before and after cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation). Average value for detergency
  • PEG polyethylene glycol with average molecular weight 7,000
  • Enzymes [Proteases (Sabinase 12.0TW (Novo Nordisk)), Lipases (Ribolases 100T (Novo Nordisk)), Cellulases (Selzym 0, (Novo Nordisk) )), Amylase (termamyl 60T (Nonopordisk)) in 2: 1: 1: 1) 1%, fluorescent dye 0.5% and sodium sulfate, the total amount of sodium sulfate is 100% was adjusted as follows.

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  • Detergent Compositions (AREA)

Abstract

Le fait d'ajouter un composé de l'acide aminopolycarboxylique, de formule générale (I), dans laquelle les A sont indépendamment hydrogène ou CH2OH et les M sont indépendamment choisis entre H, Na, K et NH4, et un aluminosilicate, en quantités spécifiées, à un détergent haute densité contenant un zéolite, peut donner une composition détergente haute densité ayant une masse volumique apparente comprise entre 0,5 et 1,8 g/ml et une solubilité et une détergence améliorées, notamment avec une eau de lavage à basse température.
PCT/JP1997/004315 1996-12-13 1997-11-26 Composition detergente haute densite WO1998026035A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP33413296A JPH10168485A (ja) 1996-12-13 1996-12-13 高密度洗剤組成物
JP8/334132 1996-12-13

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WO1998026035A1 true WO1998026035A1 (fr) 1998-06-18

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PCT/JP1997/004315 WO1998026035A1 (fr) 1996-12-13 1997-11-26 Composition detergente haute densite

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JP (1) JPH10168485A (fr)
WO (1) WO1998026035A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3352353B2 (ja) * 1997-04-07 2002-12-03 花王株式会社 洗浄剤組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63267751A (ja) * 1987-04-11 1988-11-04 ビーエーエスエフ・アクチエンゲゼルシヤフト セリン−ｎ，ｎ−ジ酢酸及びその誘導体及びその用途
JPH02295954A (ja) * 1989-05-06 1990-12-06 Basf Ag ２―メチル―又は２―ヒドロキシメチル―セリン―ｎ，ｎ―ジ酢酸及びその誘導体
JPH09287000A (ja) * 1996-01-22 1997-11-04 Kao Corp 高密度粉末洗剤組成物
JPH101660A (ja) * 1995-12-22 1998-01-06 Nitto Chem Ind Co Ltd キレート剤およびこれを用いた洗浄剤

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63267751A (ja) * 1987-04-11 1988-11-04 ビーエーエスエフ・アクチエンゲゼルシヤフト セリン−ｎ，ｎ−ジ酢酸及びその誘導体及びその用途
JPH02295954A (ja) * 1989-05-06 1990-12-06 Basf Ag ２―メチル―又は２―ヒドロキシメチル―セリン―ｎ，ｎ―ジ酢酸及びその誘導体
JPH101660A (ja) * 1995-12-22 1998-01-06 Nitto Chem Ind Co Ltd キレート剤およびこれを用いた洗浄剤
JPH09287000A (ja) * 1996-01-22 1997-11-04 Kao Corp 高密度粉末洗剤組成物

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