WO1998026035A1

WO1998026035A1 - High-density detergent composition

Info

Publication number: WO1998026035A1
Application number: PCT/JP1997/004315
Authority: WO
Inventors: Shuji Tagata; Yohei Kaneko; Genjiro Hagino; Hiroshi Danjo
Original assignee: Kao Corporation
Priority date: 1996-12-13
Filing date: 1997-11-26
Publication date: 1998-06-18
Also published as: JPH10168485A

Abstract

Adding an aminopolycarboxylic acid compound of general formula (I) and an aluminosilicate respectively in specific amounts to a high-density detergent containing zeolite can give a high-density detergent composition having a bulk density of 0.5 to 1.8 g/ml and improved in the solubility and detergency, particularly those found in using low-temperature wash water, wherein A's are each independently hydrogen or -CH2OH; and M's are each independently selected among H, Na, K and NH4.

Description

Description High-density detergent composition Technical field

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. Of these components, 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. Among these 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.

In the past, 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.

Since the late 1980s, laundry detergents have undergone a transformation, and so-called compact detergents, which have a high bulk density and a small capacity when used, have become the mainstream. However, crystalline sodium aluminosilicate (zeolite) is insoluble in water, and amorphous sodium silicate (for example, nS No. 1 to 3 sodium silicate) or sodium carbonate, which is an alkaline agent and a skeletal substance in the components, or sodium carbonate Alternatively, a crystalline water-soluble salt such as mirabilite tends to decrease solubility depending on the blending conditions and storage conditions. In particular, the detergent particles of a compact detergent having a high density are tighter than conventional detergent particles, so that the solubility becomes more problematic. In addition, the washing conditions in Japan are special, and it is not uncommon to wash with cold water at around 5 ° C in winter. In addition, 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.

As mentioned above, 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.

In addition, 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.

In view of the above, there has been a need for the development of a cleaning base that promotes low-temperature solubility of a high-density detergent containing zeolite and exhibits excellent detergency. Disclosure of the invention

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.

That is, 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.

(I)

In the formula, A is a hydrogen or - CH ₂ 0H, it may be the same or different. Further, M H, Na, selected from K and Ή _4, may be the same or different.

It contains 1 to 30% by weight of an aminopolycarboxylic acid compound represented by the following general formula (I) as the component (a) and 5 to 40% by weight of an aluminosilicate as the component (b), and has a bulk density of 0. 5 to 1.8 g Zml.

In the present invention, 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. When 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).

(1 -1)

(1 -2)

( 13)

[Wherein, M is the same as in the above formula (I). ]

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.

Next, the 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)

a '(M2O) · AI2O3 · b' (S1O2) · w (H 2 0) (iii)

[Where 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. :)

In particular, the following general formula (iv)

_{Na 2 0 · AI2O3 · n (} Si0 2) · w (H 2 0) (iv)

[Where n is 1.8 to 3.0 and w is:! Represents the number of ~ 6. ]

Is preferably represented by As the crystalline aluminosilicate (zeolite), 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.

As the 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.

_{a (M 2 0) · AI2O3} · b (Si02) · c (H 2 0) (i)

[In the formula, 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. ]

In particular, the following general formula (ii)

_{Na 2 0 · AI2O3 · b (} Si0 2) · c (H 2 0) (ii)

[Where b represents a number of 1.8 to 3.2 and c represents a number of 1 to 6. ]

Is preferably represented by

In the present invention, ion exchange capacity 100 CaCOs mg / g or more, oil absorption capacity 100 mgZ 100 g or less Above, it is particularly preferable to use an amorphous aluminosilicate of 200 ml ZlOO g or more. Such an amorphous aluminosilicate 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. In that case, 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. In particular, the surface of the detergent particles containing the aminopolycarboxylic acid compound is preferably coated with these zeolite / amorphous aluminosilicate. Particularly, when the detergent particles are coated with an amorphous aluminosilicate having an oil absorbing ability, a small amount of a suitable result can be obtained. For use in these coatings, it is preferred that 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.

Examples of 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. One or more selected from ester salts of oxyethylene alkyl ethers and salts of α-sulfofatty acids are used.

Examples of the nonionic surfactant 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. Of 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.

Crystalline silicate>

The high-density detergent composition of the present invention preferably contains a crystalline silicate. Polyaminocarboxylic acid dissociates stepwise depending on ρΗ, and dissociates almost completely at pH 11 and above. On the other hand, at high pH, 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. In the case of calcium, which is a hardness component in water, chelation formation by aminopolycarboxylic acid is usually more effective when used at high ρΗ (ρΗ11 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. '

Conventionally, 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. However, when blended in a large amount, 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. On the other hand, 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. In addition, 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. Among them, 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.

In addition, since 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. Can be. The crystalline silicate preferably has an average particle size of 0.1 to 100 m, more preferably 1 to 60 mm. Here, 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.

① x (M ₂ 0) · y (Si0 ₂ ) · z (MeraOn) · w (H ₂ 0) (II)

(In the formula, M represents an element belonging to group la of the periodic table, and Me represents one or two elements selected from the group IIa element, lib group element, Ilia group element, IVa group element or VIII element of the periodic table. It shows combinations of more than one kind, yZx = 0.5 to 2.6, z / i = 0.01 to 1.0, w = O to 20, and nZm = 0.5 to 2.0. ]

② M ₂₀ · x '(Si0 ₂ ) · y' (H2O) (III)

[In the formula, M represents an alkali metal, and x ′ = 1.5 to 2.6 and y ′ = O to 20. ]. First, the crystalline silicate represented by the above general formula (II) will be described.

In the general formula (II), 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.

In the general formula (II), yZx is 0.5 to 2.6, preferably 1.5 to 2.6. 2.2. When 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. On the other hand, when 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. In the general formula (II), zZx is 0.01 to 1.0, preferably 0.02 to 0.9, and most preferably 0.05 to 0.9. If ι / τ is less than 0.01, the water resistance is insufficient, and if τ / τ 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. When x (M20) is, for example, x ′ (Na ₂₀ ) · ′ ′ (K ₂ 0) · as described above, X is χ ′ + χ ″. Such a relationship is the same for z when the z (MemOn) component is composed of two or more components. ΗΖιη 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.

Next, the crystalline silicate represented by the above general formula (III) will be described.

This crystalline silicate has the general formula (III)

Μ ₂ 0x '(S1O2) y' (H, 0) (III)

[In the formula, M represents an alkali metal, and x ′ = 1.5 to 2.6 and y ′ = O to 20. But is represented by], in the general formula (III) x ', y' is 1.7 ^ χ'≤2.2 and y '= is preferably a 0, the cation exchange capacity is 100 to 400 CAC0 ₃ ing / g can be used. 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. Details of the synthesis method are described in, for example, Phys. Chem. Glasses. 7, 127-138 (1966), Z. Kristallogr., 129, 396-404 (1969). The crystalline silicate represented by the general formula (III) is, for example, a powdery or granular form of Na-SKS-6 (δ-a ₂ Si ₂₀ _s ) from Hoechst. Get one.

In the present invention, 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.

In the present invention, 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. For this purpose, 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.

(Wherein, 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. · Alternate polymer

• Any of block polymers may be used. M is _{Na, K, NH 4, H} . )

P

(VI)

(In the formula, 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. Among these polycarboxylates, salts of acrylic acid-maleic acid copolymer and polyacrylic acid Salt (Na, Κ, ΝΗ ₄₎ are particularly excellent. The molecular weight is suitably from 1,000 to 80,000. In addition to the above-mentioned builders, the following inorganic or organic builders can be used.

(I) Inorganic builder

1) Alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sesquicarbonate, and JIS No. 1 and No. 2 amorphous sodium silicates.2) Orthophosphate, pyrophosphate, etc. Phosphates such as tripolyphosphate

(Alkali metal salts such as sodium and potassium) 3) Neutral salts such as sodium sulfate as a filler 4) Sodium sulfite to remove chlorine from tap water

(I I) Organic builder other than the (a) component

1) Salts of phosphonic acids such as 1,1,1-diphosphonic acid and 1,2-diphosphonic acid 2) Polymer electrolytes, such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, and polyaspartic acid 3 ) Organic acid salts such as diglycolic acid and oxydisuccinic acid.

Further, the following components can be blended as components other than the builder. Examples of 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.

Examples of the bleach activator 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.) When classified based on reactivity, there are 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.

Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elasase, sptilisin, BPN, papain, promerin, carboxypeptidase A and B, and aminopeptidylase. A and B are petits 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. Specific examples of esterases include gastric lipase, bankreatic lipase, plant lipases, phospholipases, cholinesterases and phospholipases.

As a specific example of the lipase, a commercially available lipase such as ribolase (Novo Industry Co., Ltd.) can be used.

Further, as the 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. As the amylase, commercially available Yuichi Mamil (Nopo Industries) can be used.

As an enzyme stabilizer, a reducing agent (sodium sulfite, sodium bisulfite, calcium salt, magnesium salt, polyol, boron compound, etc.) can be used. Various bluing agents may be added as needed. As a blue tinting agent, No. 286, JP-B-49-18005, and JP-B-53-45808.

Examples of the caking inhibitor include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, magnesium oxide and the like. Note that 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.

As fluorescent dyes, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, One or more of 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. As the 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.

As the fragrance, 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. 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. When a crystalline silicate is blended, the crystalline silicate is preferably added at the time of increasing the bulk density or by dry blending. When an alkali metal carbonate is blended, it may be added in a slurry, during granulation, or in a dry blend. 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. In the case of granular detergent, 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 . In the case of a tablet type or evening bullet type detergent, 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. For example, in the case of washing in a washing machine, a washing concentration of 0.03 to 0.3% by weight can be used. Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. The polycarboxylic acid compounds used in the following examples were obtained in the following synthesis examples 1 to 3. Synthesis example 1

In a 2-liter four-necked flask, 134 g of nitrilotriacetonitrile and 402 g of ethanol were charged, and the temperature was raised to 75 ° C. 122 g of a 37% aqueous formaldehyde solution was added dropwise at the same temperature over 3 hours. At that time, the pH of the reaction mixture was maintained at 10 using triethylamine. After completion of the dropwise addition, the mixture was aged at the same temperature for 5 hours to obtain a solution containing hydroxymethylnitrile triacetonitrile.

Here, 600 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour. At the same time, the temperature of the reaction mixture was raised to 100 ° C., and ethanol, triethylamine, formed ammonia, and a part of water were distilled out of the reaction system. Further, the temperature was kept at 100 ° C for 5 hours to completely remove ethanol, triethylamine and ammonia. As a result, 792 g of an aqueous solution containing 29% of serine mono-, di-acetic acid′3Na salt (APC-1) represented by the general formula (1-1) was obtained.

Synthesis example 2

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. At 20 ° C, 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. As a result, 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.

Synthesis example 3

In a 2-liter four-necked flask, add 134 g of nitrilotriacetonitrile, And charged to 75 ° C. Here, 220 g of a 37% aqueous formaldehyde solution was added dropwise at the same temperature in 3 hours. At that time, the pH of the reaction mixture was maintained at 10 using triethylamine. After completion of the dropwise addition, the mixture was aged at the same temperature for 5 hours to obtain a solution containing hydroxymethylnitrile triacetonitrile.

Here, 600 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour. At the same time, the temperature of the reaction mixture was raised to 100 ° C., and ethanol, triethylamine, formed ammonia, and a part of water were distilled out of the reaction system. Further, the temperature was kept at 100 ° C for 5 hours to completely remove ethanol, triethylamine and ammonia. As a result, 2-hydroxymethyl-serine—N, N—diacetate · 3Na salt represented by the above general formula (I-3)

824 g of an aqueous solution containing 35% of (AP C-3) was obtained.

Example 1

Inventive product 1 of Table 1 was prepared by the following method.

Aminopolycarboxylic acid represented by the general formula (1-1) (APC-1) 0.3kg, LAS 2.0kg, Zeolite 1.5kg, AA-MA copolymer 0.3kg, PEG 0.1kg, FA 0.2kg and 1.0 kg of sodium carbonate, 0.5 kg of sodium silicate, 0.05 kg of fluorescent dye [4,4-bis- (2-sulfostyryl) -biphenyl salt] and an aqueous slurry of 60% by weight solid content from sodium sulfate used for balance were prepared. 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. Then, 0.5 kg of AE heated to 70 ° C. was gradually added dropwise to perform granulation. 30 seconds before the end of granulation, 0.5 kg of zeolite was further added to obtain a granulated dough. The obtained granulated dough and 0.1 kg of the enzyme were mixed in a V blender to obtain a high-density granular detergent composition (average particle size: 498 nm, bulk density: 830 g / liter).

For other products of the present invention and comparative products as well, A high bulk density granular detergent was prepared.

Performance evaluation>

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.

Cleansing power test>

(Preparation of artificially stained cloth)

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 δ δ ΐΓ 'Ζπι 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).

(Composition of artificial contaminated liquid)

Lauric acid 0.44% by weight

3.09% by weight of acid

2. 31% by weight

Palmitic acid 6.18% by weight

0.44% by weight

Stearic acid 1.57% by weight

Oleic acid 7.75% by weight

Trioleic acid 1 3.06% by weight

N-Hexadecyl palmitate 2.18% by weight

6. 53% by weight

Egg white lecithin liquid crystal 1.94% by weight

Kanuma Red Clay 8.1 1 1% by weight

2) Ribon Bon Black 0.01% by weight

Tap water balance.

(Cleaning conditions and evaluation method)

Five liters of the lOcmXIOcm artificially contaminated cloth prepared above were placed in 1 liter of the aqueous solution of the cleaning agent for evaluation, and washed at night and night with a glass. The washing conditions are as follows.

• Cleaning conditions

Washing time 10 minutes

Detergent concentration Q. G67%

Water hardness 4 ° DH

Water temperature 20 ° C

Rinse in tap water for 5 minutes

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

Reflectance after cleaning-reflectance before cleaning

Cleaning rate (%) X 100

Reflectance of original cloth-reflectance before cleaning

Adjust the particle size of the detergent particles using a sieve with openings of 710 m and lOOOO zm. Take 1 liter of tap water at 5 ° C into a 1 liter beaker and stir with a water stirrer (about 55

Ά Orpm). Detergent particles are charged and the change in electrical conductivity over time is measured. The electric conductivity meter is CM-60S manufactured by Toa Electric Industry Co., Ltd. Based on the conductivity when the detergent particles were completely dissolved, the time required to reach 90% conductivity was defined as T90, which was used as an index of detergent solubility.

(Note) The symbols in Table 1 have the following meanings.

-LAS: Linear alkyl (C12) benzenesulfonic acid sodium salt

• AS: Dodecyl alcohol sulfate sodium salt

• SFE: methyl sulfo fatty acid (coconut fatty acid composition) methyl ester

• FA: sodium palmitate

• AE: polyoxyethylene dodecyl ether (HLB = 10.2, measured by the Griffin method) * AG: dodecyl darcoside (average sugar condensation degree 1.5)

• MEGA: dodecanoyl-N-methyldalcamide

• Zeolite: Composition _{_{_{Μ 2 0 · Α1 2 0 3}}} - 2Si0 2 - 2H 2 0, an average particle diameter of 2 m, the ion exchange capacity ZgOCaCOsmgZg · silicate (II): Composition _{Μ 2 0 · 1.8S1O2 · 0.02M '} 0 ( Where: M: Na, K, K / Na = 0.03

, M '= Ca, Mg, Mg / Ca = 0.01), ion exchange capacity 290CaC0 ₃ mgZ g, average particle size 30 τη [crystalline silicate represented by the general formula (II)], silicate (III): composition Μ _₂ 0 · 2Si0 _2, the ion exchange capacity 224CaC0 ₃ mgZg, average particle size 30 ^ m, [formula crystalline silicate represented by the general formula (III)] · AAZMA copolymers: acrylic acid maleic acid (molar ratio 7 / 3) Na salt of copolymer, average molecular weight 70,000. PEG: polyethylene glycol with average molecular weight 7,000

• Common components: 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.

Claims

The scope of the claims

1, 1 to 30% by weight of the aminopolycarboxylic acid compound (a) of the formula (1), 5 to 40% by weight of an aluminosilicate (b) and 5 to 50% by weight of a surfactant (c) ) And a bulk density of 0.5 to 1.8 g Zml.

(I) wherein, A is hydrogen or - CH ₂ 0H, identical or different in addition, M is selected from H Na, K and NH _4, may be the same or different.

2. The composition according to claim 1, wherein the aminopolycarboxylic acid is represented by the formula (1-1):

(1-1) In the formula, M is the same as in the formula (I).

3. The composition _c according to claim 1, wherein the aminopolycarboxylic acid is represented by the formula (1-2).

(1-2) In the formula, M is the same as the formula (I) (

4. The composition according to claim 1, wherein the aminopolycarboxylic acid is represented by the formula (1-3) ₍

(1-3) In the formula, M is the same as the above formula (I) ₍

5. The composition according to claim 1, comprising 1 to 40% by weight of at least one selected from the crystalline silicate represented by the formula (III) and the crystalline silicate represented by the formula (III). . · x (M ₂ 0) y (Si02) z (MemOn) w (H ₂ 0) (II)

In the formula, M represents an element in group la of the periodic table, and Me represents one or two elements selected from group IIa, lib, Ilia, IVa, or VI group 11 elements in the periodic table. The above combinations are shown, where y / x = 0.5 to 2.6, ζ / χ = 0.11 to 1.0, w = Ο to 20, and n / m = 0.5 to 2.0.

_{Μ 2 0 · χ '(Si0} 2) · y'H 2 0 (III)

In the formula, M represents an alkali metal, and x '= 1.5 to 2.6 and y' = O to 20.

6. The composition according to claim 1, wherein the aluminosilicate (b) is selected from an amorphous aluminosilicate of the formula (i) and a crystalline aluminosilicate of the formula (iii). _{a (M 2 0) · AI2O3} · b (Si0 2) · c (H 2 0) (i)

In the formula, M is an alkali metal atom, a, b, and c represent the number of moles of each component, 0.7 ≤ a ≤ 2.0, 0.8 ≤ b <4, and c is any positive number. a '(M2O) · AI2O · b' (S1O2) · w (H 2 0) (iii)

In the formula, M is an alkali metal atom, a ', b', w represent a molar ratio of each component, and 0.7≤a'≤1.5, 0.8≤b '<6, and w is any positive number.

7. The composition according to claim 1, further comprising a copolymer represented by the formula (V-1) having a molecular weight of several hundred to 100,000.

In the formula, Z is a monomer copolymerizable with (anhydride) maleic acid or a maleic acid salt, and m and n are values such that the molecular weight of the copolymer indicates several hundred to 100,000. The copolymer obtained from maleic acid and a monomer copolymerizable with maleic acid may be any of a random polymer, an alternating polymer and a block polymer. M is Na, K, NH4, H.