WO1997033960A1

WO1997033960A1 - High-density granulated detergent composition

Info

Publication number: WO1997033960A1
Application number: PCT/JP1997/000666
Authority: WO
Inventors: Shuji Tagata; Hirokazu Uenaka; Makoto Kubo; Takaya Sakai; Masaaki Yamamura; Noboru Moriyama
Original assignee: Kao Corporation
Priority date: 1996-03-13
Filing date: 1997-03-05
Publication date: 1997-09-18
Also published as: JPH09241678A

Abstract

A high-density granulated detergent composition having excellent biodegradability and safety and an enhanced detergency, which comprises an amidoamine oxide surfactant (a) of general formula (I), an aluminosilicate salt (b) and an alkaline agent (c) at specific proportions and has a bulk density of 0.6 to 1.2 g/ml. In said formula R1 is C10-C20 alkyl or alkenyl; R2 and R3 are each H, C1-C3 alkyl or alkenyl; R4 is H, C1-C5 alkyl or alkenyl; and n is 1 to 5.

Description

Description High density granular detergent composition Background of the invention

The present invention relates to high density nonionic detergent compositions. More specifically, the present invention relates to a nonionic high-density granular detergent composition having a high detergency and comprising an amidoamine oxide-type surfactant excellent in biodegradability and safety as a main component of the surfactant.

Conventional technology

Detergents for clothing are surfactants that solubilize dirt or dissolve and disperse in laundry liquid, alkaline agents that promote the decomposition and solubilization (emulsification) of dirt, polymer compounds that disperse dirt, It is basically composed of a sequestering agent or the like for removing calcium, magnesium, or the like that lowers the ability of the surfactant from the washing liquid. Of these components, those that do not exhibit cleaning performance by themselves, but are intended to improve the detergency by combining with a surfactant, are generally called detergent builder. Among these detergent builders, the above-mentioned sequestering agent is a substance for more effectively expressing the performance of the surfactant, and is a very important builder.

Surfactants serve the primary function of removing soil from the fibers, as described above. Surfactants used in detergents are broadly classified into anionic and nonionic surfactants. Representative examples of anionic surfactants include alkylbenzene sulfonates having 8 to 16 carbon atoms, sulfates of higher alcohols having 10 to 18 carbon atoms, ct-olefin sulfonates, alkane sulfonates (SAS ), Ct monosulfofatty acid ester salts and the like, and typical nonionic surfactants include polyoxetylene alkyl ether, polyoxyethylene alkyl phenyl ether and the like.

Non-ionic activators combining amine oxides and carbonates are disclosed in JP-A-47-340.

JP-A61-283695 is an amide amine oxide type surfactant. The agent is disclosed as a shampoo or a liquid detergent, and it is disclosed that an amide amine oxide is combined with an acylated amino acid. However, it does not disclose the use of zeolite or silicate in combination. Furthermore, it does not suggest that when an amide oxide type surfactant is used as a main component of a surfactant in a high-density granular detergent composition, an excellent detergency can be obtained.

Detergent densification, compactness, and miniaturization are progressing according to market demands such as resource saving, labor saving, and reduction of transportation costs. However, the above-mentioned surfactants are still used, and there is a demand for a surfactant having a higher cleaning performance suitable for a high-density detergent. Furthermore, today, in addition to densification, it is also required that detergents have a mild effect on the environment.

Amidoamine oxide surfactants have good biodegradability, are excellent in solubility in water and are safe for the human body. Sex has not yet been fully studied. DISCLOSURE OF THE INVENTION Under such circumstances, an object of the present invention is to provide a high-density granular detergent having excellent detergency by using an amide amine oxide surfactant as a main detergent base.

As a result of various studies, the present inventors have found that the high-density granular detergent obtained by a production process including spray drying using amide amine oxide represented by the following formula (I) as a main cleaning component, The present inventors have found that they exhibit superior detergency as compared with a high-density granular detergent produced based on a surfactant, and have completed the present invention.

The present invention provides: (a) 15 to 50% by weight of an amide amine oxide type surfactant represented by the following general formula (I):

(Wherein, is an alkyl group or alkylene group having 10 to 20 carbon atoms, R ₂ and R ₃ are an alkyl group or alkylene group having 1 to 3 carbon atoms or H. RiH, an alkyl group having 1 to 5 carbon atoms Or an alkylene group, and n is 1 to 5.)

(b) 5-60% by weight of aluminosilicate

(c) Anore Li agent 5-60 weight ^_0/0

And a high-density granular detergent composition having a bulk density of 0.6 to 1.2 gZmf. Preferably, the alkaline agent (c) is a crystalline silicate of the following formula (II) and / or (III). x (M 2 O) · y (SiO · z (Me m O n) · w (H 2 0) (II)

(In the formula, M represents an element in the la group of the periodic table, and Me represents one or a combination of two or more elements selected from the group consisting of the Ila group element, the lib group element, the Hla group element, the ra group element and the νΠΙ group element. , Y / χ = 0.5 to 2.6, zZx = 0.01 to 1.0, w = 0 to 20, n / m = 0.5 to 2.0.)

M 20 · xTSiO 2) · y'H 2 0 (III)

(In the formula, M represents an alkali metal, and x ′ = 1.5 to 2.6 and y ′ = 0 to 20.) (b) is preferably a crystalline aluminosilicate.

The ayuon surfactant and / or the nonionic surfactant _(a ′) may be contained in a ratio of (a ′) Z (a) = 1/100 to 100/100 by weight with respect to the above _(a). it can.

The anionic surfactant is a higher fatty acid salt having 10 to 18 carbon atoms, a sulfate salt of a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms, or an alcohol having 8 to 20 carbon atoms. Sulfuric acid ester salts of ethoxylates of kohl, alkynolebenzenesulfonate, anorecanthnolephonate, α-olefin sulfonate and α-sulfo fatty acid salt having 8 to 16 carbon atoms in the alkyl group and α — At least one selected from sulfo fatty acid alkyl ester salts, wherein the nonionic surfactant is a polyoxyalkylene alkyl ether, a polyoxyalkylene alkyl phenol ether, a polyoxyalkylene sorbitan fatty acid ester, a polyoxyalkylene glycol ether, It is preferably at least one selected from a polyoxyalkylene sorbitan fatty acid ester, a polyoxyalkylene fatty acid ester, a polyoxyethylene polyoxypropylene block polymer, and an alkynyl-methylglucamine. New

More preferred compositions comprise 20-40% by weight of (a), 8-30% by weight of (b) and 10-40% by weight of (c).

(c) 30-80% by weight of the alkaline agent may be crystalline silicate. The composition may further comprise a polycarboxylate having an average molecular weight of 1,000 to 100,000.

Composition Asuparagin di acetate salts and Z or inhibit mud as further organic builders key Consequences amino disuccinic acid salt from 0.5 to 20 weight ^_0/0 contains or at 1.0 to 5 weight Asuparagin di acetate as an organic builder, ⁰ /. It is good to contain.

The present invention provides a high-density granular detergent having excellent biodegradability and high detergency by using the above (a) as a main component and using (b) and (c) as a builder.

Hereinafter, the nonionic high-density granular detergent composition of the present invention will be described.

(a) Amidoamine oxide surfactant

The amide amine oxide type surfactant used in the present invention is represented by the above general formula (I). Most effective when R ₂ and R ₃ are methyl. Is most effective when the carbon number is 12-14.

In the present invention, (a) component of Ami door Min O key side type surfactant is 15 to 50 weight in the composition ^_0/0, preferably 20-40% by weight blend. If the amount of component (a) is less than 15% by weight, the detergency will decrease. If it exceeds 50% by weight, the hygroscopicity will increase, the powder properties will decrease, and Ca ions and Mg present in water will be reduced. Such as ions It is more susceptible to hardness and reduces cleaning power.

(b) Aluminosilicate

Both amorphous and crystalline aluminosilicates can be used.

The amorphous aluminosilicate, silicon as Si0 _2, 30 wt% or more, preferably rather may those containing more than 40 wt%, also a pH of 9 or more der shall 5% dispersion When used, deterioration of the solubility of the detergent after storage at high humidity is further improved.

Examples of the amorphous aluminosilicate used in the present invention include those represented by the following general formula G), which have high oil absorption and high cation exchange ability. _{a (M 2 0) · A} 0 3 · b (SiO 2) · c (H 2 O) (i)

(In the formula, M is a metal atom, a, b, and c represent the number of moles of each component. Generally, 0.7 ≤ a ≤ 2.0, 0.8 ≤ b <4, and c is any positive number. It is. ]

In particular, the following general formula (ii)

Na ₂ 0203BrSiO 2) ciH 20) (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

A method for producing such an amorphous aluminosilicate will be briefly described. First, Si0 ₂ and

M 20 (M denotes an alkali metal) molar ratio of a _{_{Si0 2 // M 2 0 == 1.0~}} 4.0, the molar ratio of H ₂ 0 and M ₂ 0 is _{H 2 0 / M: 0 =} 12 silicate Al Chikarari aqueous metal salt solution is 200, the molar ratio of M ₂ 0 and ₂ 0 ₃ is _{_{_{M 2 0/2 0 3 =}}} 1.0 ~ 2.0, the molar ratio of H ₂ 0 and M ₂ 0 is H _{_{2 ΟΖΜ 2 0 = 6.0~ 15~60 °}} C lower § Rukariarumin alkali metal salt solution is 500, is preferably added under stirring strong under a temperature of 30 ~ 50 ° C. Further, an aqueous solution of an alkali metal silicate may be added to the aqueous solution of an alkali metal aluminate.

The resulting white precipitate slurry is then heated to 70-100 ° C, preferably 90-100 ° C. It can be advantageously obtained by performing a heat treatment at a temperature of 10 minutes or more and 10 hours or less, preferably 5 hours or less, followed by filtration, washing and drying. By this method, an amorphous aluminosilicate having an ion exchange capacity of 100 mg or more of CaCO and an oil absorption capacity of 200 g or more can be easily obtained.

Also, amorphous aluminosilicate 5. /. The pH of the dispersion is measured based on JIS K 6220. That is, weigh out about 5 g of a sample in a hard Erlenmeyer flask, add 100 ηι of water without carbonic acid, stopper and shake for 5 minutes. Measure the pH by the glass electrode method (JIS Z 8802 7.2.3) using the liquid after shaking as the test liquid.

By selecting an amorphous aluminosilicate having a pH of 5% dispersion of 9.0 or more, it is possible to obtain a high-density detergent composition whose solubility is not deteriorated when stored under high humidity conditions.

If the alkalinity of the detergent is very high or the storage conditions are very severe, select an amorphous aluminosilicate that satisfies the stricter condition that the amount of dissolution in a 2% aqueous NaOH solution is 0.5 g or less. Good.

That is, 10 g of amorphous aluminosilicate is dispersed in a 2% aqueous NaOH solution lOOmf, and stirred at 25 ° C for 16 hours under a constant temperature condition, and SiO ₂ in the filtrate is colorimetrically determined. 25 vol., Pl56, 1976), the amount of which is less than 0.5 g as amorphous aluminosilicate.

Also, aluminosilicate crystalline, generally all SANYO which is said to Zeorai bets, the following formula a '(M 2 0) · 2 0 3 · b' (SiO · w (H 2 O) (iii)

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

In particular, the following general formula (iv)

Na 20 ・ 20 a ・ n (SiO ₂ ) w (H ₂₀ ) (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), a synthetic zeolite having an average primary particle size of 0.1 to 10 μπ typified by A-type, X-type, and P-type zeolites is suitably used. Zeolite ^: Powder and zeolite or zeolite slurry may be blended as zeolite aggregated dry particles obtained by drying.

In the present invention, the aluminosilicate is incorporated in the composition in an amount of 5 to 60% by weight, preferably 8 to 30% by weight, particularly preferably 15 to 30% by weight. If the amount of aluminosilicate is out of this range, the detergency will decrease.

(c) Al liquor agent

Examples of the alkali agent used in the present invention include inorganic alkali metal salts and polyphosphate salts. Specifically, the following (1) and (2) can be used.

(1) Inorganic alkali metal salts

Sodium carbonate, potassium carbonate, sodium silicate _{[(Na 2 0) »(Si0} 2) n, where, m is 1 to 3, n is 1-5], sodium bicarbonate, potassium bicarbonate, sulfite acid Sodium, potassium sulfite, sodium sesquicarbonate, potassium sesquicarbonate, crystalline silicate, etc.

Crystalline silicate used in the present invention, lay preferred alkali metal salt of silicic acid (Si0 _2), among others, SiO zZ M s 0 of the alkali metal silicate (wherein, M represents an alkali metal) forces; 0.5 What is 2.6 is preferably used. Conventionally known crystalline silicates have a power of SiO ₂ ZM ₂力 of 1.9 to 4.0; those having a ratio exceeding 2.6 may not be suitable for the formulation of the high-density detergent which is the object of the present invention.

The preferred crystalline silicate used in the present invention has the following composition.

_{① x (M 2 0) ·} y (SiO · z (Me m O n) · w (H a 0) (II)

(In the formula, M represents an element of group la of the periodic table, and Me represents one or more elements selected from group Ila, nb, nia, group IVa, or group VIII of the periodic table. Y / x = 0.5 ~ 2.6, z / x = 0.0】 ~ 1.0, w = 0 ~ 20, n = 0.5 to 2.0. ]

_{_{② M 2 0'x '(Si0 2}} )' y '(H 2 0) (III)

[In the formula, M represents an alkali metal, and χ ′ = 1.5 to 2.6 and y ′ = 0 to 20. First, the crystalline silicate represented by the above general formula (II) will be described. —In the general formula (Π), M is selected from the group la elements of the periodic table, and examples of the group la elements include Na and K. These may be used alone or, for example, a mixture of Na ₂₀ and K ₂₀ to constitute the M ₂₀ component.

Me is selected from the group Ila element, group lib element, group Ilia element, group IVa element or group VIII element of the periodic table, for example, Mg, Ca, Zn, Y, Ti, Zr, Fe and the like. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. These are alone or may also be a mixture of two or more, good example MgO, even constitute Me _m 0 _n components such as CaO are mixed les.

In the general formula (Π), y / x is 0.5 to 2.6, and preferably 1.5 to 2.2. When X is less than 0.5, the water resistance is insufficient, and the masking property, solubility, and powder properties of the detergent composition are significantly adversely affected. On the other hand, when y / x exceeds 2.6, the alkalinity becomes low and the alkalinity becomes insufficient, and the ion exchange ability also becomes low, making it insufficient as an ion exchanger. In the general formula (II), z / x is from 0.01 to 1.0, preferably from 0.02 to 0.9. When z / x is less than 0.01, the water resistance is insufficient, and when z / x exceeds 1.0, the ion-exchange ability is low, and the ion-exchanger is insufficient. x, y, and z are not particularly limited as long as they are in the relationship represented by the y / x ratio and the z / x ratio described above. Incidentally, '"if the (K ₂ 0), χ is χ (Na 20) · x' + χ" x (M 2 0) as in the previous SL for example x becomes. Such relationships, z (Me _m 0.) component is the same in put that _z when composed of two or more. Further, nZm 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.

- crystalline silicate represented by the general formula (II) is M ₂ 0, Si0 _2, O Me _m ternary O n Rina'. Therefore, in order to produce the crystalline silicate represented by the general formula (II), each component is required as a raw material, but is not particularly limited in the present invention. Known compounds are appropriately used. For example, M ₂ 0 component, the Me "O _n component, alone or oxides of the composite of each of those said elements, hydroxides, salts, and the element containing organic minerals are used. Specifically, for example M as the raw material of ₂ 0 component, NaOH, KOH, Na 2 CO 3, K 2 CO 3, Na 2 SO < etc., as raw materials of Me _m O _n component, CaCO 3, MgCO 3, Ca (OH) 2 , Mg (OH) ₂ , MgO, ZrO ₂ , dolomite, etc. Examples of the SiO 2 component include kaite, kaolin, talc, fused silica, and sodium silicate.

The method for preparing the crystalline silicate represented by the general formula (Π) is to mix the above-mentioned raw material components at a predetermined ratio so that the desired crystalline silicate has x, y, and z values. 300-1500. C, preferably 500-1000. C, more preferably 600-900. A method of firing and crystallization in the range of C is exemplified. In this case, if the heating temperature is lower than 300, the crystallization is insufficient and the water resistance is poor, and if the heating temperature exceeds 1500 ° C, the particles become coarse particles and the ion exchange ability decreases. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.

Thus crystalline silicate represented by the resulting general formula (II) with, a pH of 11 or more in a 0.1 wt ^_0/0 aqueous dispersion exhibits excellent alkalizing ability. In addition, the buffering effect of aluminum carbonate is particularly strong, and it has an excellent alkali buffering effect even when compared to sodium carbonate or lithium carbonate.

The crystalline silicate represented by the general formula (Π) has an ion exchange capacity of at least 100 mg of CaCOCO 3 mg Z g, preferably 200 mg to 600 mg of CaCO ₃ mg Z g. Is one of the substances having

The crystalline silicate represented by the general formula (II) has an alkali function and an alkali buffering effect as described above, and further has an ion exchange function. The washing conditions can be suitably adjusted.

—The crystalline silicate represented by the general formula (II) preferably has an average particle size of 0.1 to Ι00 μπι, more preferably 1 to 60 μιη. If the average particle size exceeds 100 μπι, the rate of onset of ion exchange tends to decrease, leading to a decrease in detergency. On the other hand, if it is less than 0.1 μπι, the specific surface area is increased, so that the hygroscopicity and CO ₂ absorption are increased, and the quality tends to be remarkably deteriorated. The average particle size referred to here is the particle size The median diameter of the distribution.

The crystalline silicate having such an average particle size and particle size distribution can be prepared by crushing using a crusher such as a vibration mill, a hammer-mill, a ball mill, a roller-mill and the like. For example, it can be easily obtained by grinding with a HB-0 type vibration mill (manufactured by Chuo Kakoki Co., Ltd.).

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

This crystalline silicate has the general formula (III)

M ₂ 0'x '(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. ] Is represented as being in force; general formula (ΙΠ) in the x ', y' is preferably a is I. ⁷ 2. ² and y '= 0, the cation exchange capacity is 100 to 400 CaCO ₃ mgZg can be used and is one of the substances having an ion trapping ability in the present invention.

—Since the crystalline silicate represented by the general formula (III) has such an alkali function and an alkali buffering effect, and further has an ion exchange function, by appropriately adjusting the blending amount thereof, The washing conditions can be suitably adjusted.

The production method of the crystalline silicate represented by the general formula (II) is described in JP-A-60-227895 (corresponding to US Pat. No. 4,664,839 or US Pat. No. 4,820,439). It is obtained by firing the glassy sodium silicate at 200 to 1000 ° C to make it crystalline. Details of the synthesis method are described in, for example, Phys, Chem. Glasses, 7, 127-138 (1966), and Z. Kris in llogr., 129, 396-404 (1969). The crystalline silicate represented by the general formula (III) is, for example, Na-SKS-6j

Powders and granules can be obtained as (5-Na ₂ Si ₂₀ i).

In the present invention, the crystalline silicate represented by the general formula (III) has an average particle size of 0.1 to !, similarly to the crystalline silicate represented by the general formula (III). It is preferably 00 μηι, more preferably 1 to 60 μπι.

In the present invention, a crystalline silicate represented by the general formula (II); The crystalline silicate represented by (II) can be used alone or in combination of two or more.

(2) Polyphosphate

In the present invention, polyphosphates such as orthophosphate, metaphosphate, pyrophosphate, tripolyphosphate, and hexametaphosphate can be used. As salts, H, Na, and K are common.

Component (c) is used in an amount of 5 to 60% by weight of the composition. /. , Preferably 10 to 40 weight ^_0/0 compounded.

It is desirable that the crystalline silicate accounts for preferably 10 to 100% by weight, more preferably 30 to 80% by weight, and particularly preferably 50 to 80% by weight of the alkaline agent contained in the composition.

Embodiment of the Invention

In the present invention, in addition to the surfactant (a), the following anionic surfactant and no or nonion surfactant (a ') can be blended. However, the weight ratio of (a ′) Z (a) is 1/100 to 100/100, preferably 50 100 or less.

The following can be used as the anionic surfactant and the nonionic surfactant (a ').

• Anion surfactant

C10-C18 higher fatty acid salts, C10-C18 linear or branched primary or secondary alcohol sulfates, C8-C20 alcohol ethoxy sulfates , Alkyl (C _B -C, benzenesulfonate, alkanesulfonate (SAS), α-olefin sulfonate and α_sulfofatty acid alkyl ester salt) Anionic surfactants • Nonionic surfactants

Polyoxyalkylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyethylene polyoxybutene pyrene block polymer and alkenyl methyl ester One or more nonionic surfactants selected from cumin. The anionic surfactant and the nonionic surfactant may be blended alone, or a mixture of both may be blended.

In the present invention, the following organic builders can be used in addition to inorganic builders such as aluminosilicate.

1) Phosphonic acid salts such as ethane-1,1-diphosphonic acid, ethane-1,2, -triphosphonic acid

2) Polymer electrolytes such as polyethylene glycol, polybutyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, polyaspartic acid, etc.

3) Organic acid salts such as diglycolic acid and oxydisuccinic acid

4) a copolymer having a molecular weight of several hundreds to 100,000 and represented by the following formula (IV) or a polycarboxylate such as a homopolymer represented by the formula (V)

(Wherein, Z is a monomer and / or its salt copolymerizable with (anhydrous) maleic acid or maleate such as 1-8 olefins, acrylic acid, methacrylic acid, itaconic acid, methallyl sulfonic acid, etc., and m is a copolymer one molecular weight have the values shown a several hundred to 100,000. M is H, Na, Κ, a ΝΗ _3.)

Ρ (V)

m

(In the formula, Ρ is a monomer capable of being homopolymerized, and examples thereof include acrylic acid, methacrylic acid, and maleic acid. M ′ indicates that the molecular weight of the homopolymer is several hundred to 100,000. It is straightforward. Homopolymer salts include Na, ,, NH and the like. )

Among the above 1) to 4), 4) is most preferable. The amount of the copolymer (IV) or the homopolymer of the formula (V) and the homopolymer of the formula (V) in 4) 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 salts of polyacrylic acid (Na, Κ, and それぞれ, respectively, are particularly excellent. A molecular weight of 1,000 to 80,000 is suitable. Biodegradation When the following builder is blended as an organic builder having good properties, a detergent composition exhibiting excellent cleaning performance can be obtained.

(1) Aspartic acid diacetate OOC-Cft CHzCOOM represented by the following chemical formula

I /

MOOC— CH— N

\

CftCOOM (where M is selected from H, Na, K, NH4)

(2) Hydroxyiminodisuccinate represented by the following chemical formula

(In the formula, R represents a hydrogen atom or a hydroxyl group, and X represents a hydrogen atom, an alkali metal or an ammonium group.)

The builder of 1) to 2) is incorporated in the composition in an amount of 0.5 to 20% by weight, preferably 1.0 to 10% by weight. Among them, 1) shows an excellent effect. Furthermore, the system containing 1.0 to 5% by weight of 1) shows excellent cleaning performance. Further, the following components can be blended as components other than the above.

Examples of the bleaching agent include sodium percarbonate, sodium perborate (preferably monohydrate), and an adduct of sodium hydrogen peroxide, and particularly preferred is sodium percarbonate.

Examples of the bleach activator include tetraacetylethylenediamine, acetooxybenzenesulfonate, an organic peracid precursor, and 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) can be classified according to their reactivity as follows: hydrolases, hydrolases, oxidoreductases, tesmolases, transferases, and isomerases. However, any of them can be applied to the present invention. Particularly preferred are hydrolases, including proteases, esterases, lipases, carbohydrases, nucleases, cellulases and amylases.

Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promerin, carboxypeptidases A and B, aminopeptidases, aspaspyreptidase A and B, and commercially available products include Sabinaze, Alcalase (Novo Industries), API21 (Showa Denko KK), Maxacal (Gistprocades), and Protea described in JP-A-5-43892. One K-14 or K-16 force;

Specific examples of esterases include gastric lipase, buncreatic lipase, plant lipases, phospholipases, cholinesterases and phosphotase.

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

Specific examples of carbohydrases include cellulase, maltase, saccharase, amylase, pectinase, lysozyme, α-glycosidase and β-glycosidase.

In addition, as cellulase, commercially available products such as Celzym (Novo Industry Co., Ltd.) The cellulase described in claim 4 of JP-A-63-264699 can be used. As the amylase, commercially available termamyl (Novo Industry Co., Ltd.) and the like 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. For example, the following structures (a) and (b) are recommended.

Two

N

R N CMM

(Wherein, D represents a blue-purple monoazo, disazo or anthraquinone dye residue, X and and are hydroxyl groups; substituted with an amino group, a hydroxyl group, a sulfonic acid group, a carboxylic acid group or an alkoxy group. An aliphatic amino group which may be substituted; a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, a lower alkyl group or an aromatic amino group or a cycloaliphatic amino group which may be substituted with a lower alkoxy group. And R represents a hydrogen atom or a lower alkyl group, provided that R represents a hydrogen atom, and (1) X and Y> simultaneously represent a hydroxyl group or an alkanolamino group; , And Y, except when one of them is a hydroxyl group and the other is an alkano-lamino group, and n represents an integer of 2 or more.)

C -Y 2

Ν (b)

ゝ

Χ 2

(Wherein D ₂ represents a blue to purple azo or anthraquinone dye residue; Represents a hydrogen atom or a lower alkyl group, and X ₂ and Y 2 represent the same or different alkanolamino groups or hydroxyl groups. -Examples of the caking inhibitor include p-toluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, tanolek, 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 tert-butylhydroxytoluene, 4,4'-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2'-butylidenebis- (6-tert-butyl-4-methylphenol) And monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, Ι, Ι-bis (4-hydroxyphenyl) cyclohexane and the like.

As fluorescent dyes, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-1-chloro-3-sulfostyryl) -biphenylinole salt, 2- (styrylphenyl) naphthothiazole derivative One or more of 4,4'-bis (triazol-2-yl) stilbene derivatives and bis (triazinylamino) stilbene disulfonic acid derivatives are contained in the composition in an amount of 0 to 1% by weight. can do.

As the fragrance, a fragrance conventionally used in detergents, for example, a fragrance described in JP-A-63-101496 can be used.

Although the high-density detergent composition of the present invention is a powdery or granular composition, its production method is not particularly limited, and a conventionally known method can be used. To increase the bulk density, for example, a method of spraying a nonionic surfactant onto spray-dried particles to increase the density, or a method of increasing the density while directly absorbing nonions into the powder component containing the oil absorbing carrier. No. 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, it is preferable to add the crystalline silicate at the time of increasing the bulk density or to add the crystalline silicate by dry blending. In addition, when the alkali metal carbonate is blended, it may be added to the slurry, during granulation or during dry blending. The amide amine oxide as the component (a) may be added before or after the spray drying step.

The average particle size of the nonionic high-density granular detergent composition of the present invention is desirably 200 to 1000 μπι, preferably 200 to 600 μιη in order to obtain preferable powder properties. Further, the bulk density of the detergent composition of the present invention is about 0.5 to 1.2 gm, preferably about 0.6 to 1.0 gZn ^.

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 machine washing, it can be used at a washing concentration of 0.03 to 0.3% by weight.

According to the present invention, a non-ionic high-density granular detergent composition having excellent detergency is obtained by using an amide amine oxide type surfactant having excellent biodegradability and excellent safety as a main component of the surfactant. Things are obtained.

Example

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1

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

Zeolite 1.0 kg, LAS 0.5 kg, AM 0.5 kg, soda ash 0.750 g, PEG 0.1 kg, fluorescent dye (4,4'-bis- (2-sulfostyryl) mono-bifuunil salt) 0.05 kg to water content 50 weight. / ₀ slurry was prepared, and the powder obtained by spray-drying the slurry was put into a high-speed mixer (stirring-rolling granulator, Fukae Kogyo Co., Ltd.). AO-1) 3.0 kg and 2.0 kg of silicate (II) are added and granulated, and further 0.5 kg of zeolite is added and granulated, and the resulting particles are mixed with the remaining 0.5 kg of zeolite and 0.1 kg of enzyme. By dry mixing, a high-density granular detergent composition was obtained (average particle size: 420 μπ :, bulk density: 800 g / liter (0.80 g / m)).

For other products of the present invention and comparative products, high-density granular detergent compositions were prepared according to the above-mentioned schemes at respective mixing ratios. However, the surfactants blended in the present products 18, 19, 20 and 26 were added to the slurry before spray drying. The porous silicic compound of the product 12 of the present invention was added to the high-speed mixer and the amount of zeolite added to the high-speed mixer was reduced accordingly.

When the amount of zeolite was small, as in the case of the products 11, 16, 17 of the present invention and the comparative products 1, 9, they were not added before spray drying, but were appropriately divided and used in the subsequent steps.

In comparative 9 porous silica force compound in a high-speed mixer and foremost, granulated by adding the same manner as such silicate or AO- 1, further 70 granulated added AE-1 of a predetermined amount heated to ^e C Then, zeolite was further added and granulated, and the remaining zeolite was further added and granulated to obtain a high-density granular detergent composition.

The resulting high-density granular detergent composition was subjected to a detergency test by the following method. The results are shown in Tables 1-4.

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 contaminated liquid was attached to the cloth using a gravure roll coater. Process for manufacturing the artificially stained cloth artificially contaminated liquid is adhered to the fabric, the cell capacity of a gravure roll 58cm a / m ² coating fabric speed l .O m Z min, drying rate 100 ^e C, drying time 1 minute question went. The cloth used was a cotton cloth 2003 (manufactured by Tanito Shoten).

[Composition of artificial contaminated liquid]

Lauric acid 0.44% by weight

Myristic acid 3.09 weight ^_0/0

2.31 weight of pentadecanoic acid. / o

6.18 weight of palmitic acid. / ₀

Heptadecanoic acid 0.44% by weight

Stearate 1.57 weight ^_0/0

Oleic acid 7.75 weight ⁰

Trioleate 13.06 weight ^_0/0

Nonoremitic acid n-hexadecyl 2.18 weight ⁰ / o

Squalene 6.53 weight ^_0/0 Egg white lecithin liquid crystal 1.94% by weight

Kanuma red clay 8.1 1% by weight

Ribon Bon Black 0.01% by weight

Tap water balance.

(Cleaning conditions and evaluation method)

Five artificial contaminated cloths of 10 cm × 10 cm prepared as described above were put in 1 liter of an aqueous cleaning agent solution for evaluation, and washed with a tartometer at 100 ηπη. The washing conditions are as follows.

• Cleaning conditions

Washing-time 10 minutes

Detergent concentration 0.067%

Water hardness 4 ° D H

Water temperature 20 ° C

Rinse in tap water for 5 minutes

The detergency was measured by measuring the reflectance at 550 nm of the original cloth before and after cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (./.) Was calculated using the following formula. The measured average value was shown as detergency. Reflectance after cleaning-reflectance before cleaning

Washing rate (./.)—two x 100

Reflectance of original cloth-reflectance before cleaning

table

Book P

Invention a

Sample number 1 2 3 4 5 6 7 8 9

(a) AO- 1 30.0 35.0 35.0 35.0 35.0 35.0 35.0 35.0 35.0 Composition AO- 2 0 0 0 0 0 0 0 0 0 min AO- 3 0 0 0 0 0 0 0 0 0

ί Zeoryuri> Re)

u Porous silica compound n u 0 n y y n u n Π n 0

Sodium carbonate 7 ς 7 c: 75 o π, composed (c) No. 2 ダ Soda 0 0 0 0 7,5 0 0 0 4.0 Synthetic soda polyphosphate TP HP TP fraction π n \ jnn 7 ς 7 *. oc A n lily

O silicate (Π) 20.0 20.0 0 10.0 20.0 20.0 20.0 20.0 20.0

1 酸 acid salt (2) 0 0 20.0 10.0 0 0 0 0 0 fit anionic surfactant AS

ς.0 li o u o o w o li n n n n%

A Ε-1 u u u u U u U u U, etc.

Oligomers ΛΜ ΛΜ ΛΜ AM AM ΛΜ AM AM AM 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Composition of other components 0 0 0 0 0 0 0 0 0 min Common component 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Total Needle (%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Washing rate (%) 73.1 75.2 75.0 75.2 75.5 76.2 75.5 75.8 75.0

Table 2

nn

Book m PP

Sample 1

Φ No. 1 Π t 1

I I l 1 A 1 c 1 c 17

10 10 lo

(a) ΛΟ- 1 35 0 35.o 35 0 'It: n n component ΛΟ- 2 0 n n π \ π Π u Π υ min ΛΟ- 3 0 0 0 0 0 0 0 0 0

Zeolite 30.0 10.0 25.0 30.0 30.0 30.0 20.0 20.0 30.0 Porous silica compound 0 0 5.0 0 0 0 0 0 0

(c) Sodium carbonate 7.5 14.5 7.5 9.5 9.5 14.5 7.5 7.5 7.5

No. 2 acid soda o 5.o o 5 o 1 o 0 10 o 0 0

Sodium polyphosphate

Min 0 0 0 0 0 0 0 0 0 min 琏 Acid salt (Π) 20 0 20 0 20 0 10 0 0 2fY 0 or) n

酸 Acid salt (III) 0 0 0 0 0 0 0 0 0

1-of the anion metabolic activator LAS o o o no o 0 o * J-y

%, AE- 1 U u u 0 U u u 0 0 Other

HIDS ASDA 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Composition of Origo ΡΛ ΛΜ ΛΜ ΛΜ ΛΜ ΛΜ ΛΜ ΛΜ ΛΜ 成分

0 0 0 0 0 0 10.0 10.0 0 minutes

Co 2.5 2.5 10.5 2.5 5.5 5.5 5.5 2.5 2.5 2.5 Total (%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Λ 'Washing rate (%) 74.6 69.5 73.3 74.7 74.5 74.0 78.4 79.6 73.8

Table 3

Table 4

• AO—1: Lauroylamide propyldimethylamine oxide

• AO-2: myristylylamide dimethylamine oxide

• AO-3: Cetiroylamide dimethylamine oxide

. Zeorai Doo (crystalline aluminosilicate: Composition _{M 20 · 2 03 · 2SiO 2} · 2H 2 0,

(Average particle size 2 μπι, ion exchange capacity 290 CaCO a mg Z g, M is Na, K)

• Porous silica compound: Thixorex 25 (manufactured by Kofran Chemical Co.)

'Sodium polyphosphate: sodium tripolyphosphate (TP), sodium hexametaphosphate (HP)

'Silicate (II): (wherein, M: Na, K, K / Na = 0.03, M composition _{_{M 2 0 · 1.8 Si0 2 ·}} 0.02ΜΌ' = Ca, Mg, Mg / Ca = 0.01), ion exchange Capacity 290 CaCO ₃ mgZg, average particle size 30 μιη (crystalline silicate represented by general formula (II))

'Silicate (III): Composition Μ _₂ 0 · 2Si0 _2, the ion exchange capacity 224 CaCOa mgZg, average particle diameter 30μτη (- general formula (III) crystalline silicate represented by)

• Anion surfactant:

• LAS: Straight chain alkyl (Na salt of C benzenesulfonic acid)

AS: Alkyl (C sulfate sodium salt

• FA: Nonoremitic acid Na salt

• AE-1: Nonionic surfactant, polyoxyethylene dodecyl ether (HLB, 13.1)

• AM: Na salt of acrylic acid / maleic acid (7-3 molar ratio) copolymer, average molecular weight 70,000

PA Na salt of polyacrylic acid, average molecular weight 8000

H I DS Hydroxyiminodisuccinic acid derivative

AS DA Aspartic acid diacetic acid derivative

PEG Polyethylene glycol with an average molecular weight of 7,000

• Common components: PEG 1%, enzyme [API-21H (Showa Denko KK), Volatize 100T (manufactured by Novo Nordisk), Celzym 0.1T (manufactured by Novo Nordisk), Tammamil 60T (manufactured by Novo Nordisk) mixed in a 2: 1: 1: 1 ratio) 1%, fluorescence The dye was 0.5% and sodium sulfate. The total amount of sodium sulfate was adjusted to 100%.

Example 2

The product 29 of the present invention in Table 5 was prepared by the following method.

Zeolite 1.0 kg, LAS 0.5 kg, AM 0.5 kg, soda ash 0.75 kg, PEG 0.1 kg, fluorescent dye (4,4'-bis- (2-sulfostyryl) monobiphenyl salt) 0.05 kg, amidamine oxide (AO - 1 solution 3.0 as kg (AO- 1) a slurry of water content 50 wt ^_0/0 were prepared from) it a powder obtained by spray drying a High Speed Domikisa (stirring rolling granulator, Fukae Kogyo Co., Ltd.), add 1.0 kg of zeolite and 2.0 kg of silicate (II) to granulate, further add 0.5 kg of zeolite and granulate, and add 0.5 kg of remaining zeolite to the obtained particles. A high-density granular detergent composition was obtained by dry-mixing 0.1 kg of the enzyme (average particle size: 430μιη, allegory density: 780 g gl)

(0.78 g / m ^)).

For other products of the present invention and comparative products, high-density granular detergent compositions having respective mixing ratios were prepared according to the above-mentioned scheme.

However, ASD A blended in the product 33 of the present invention was added to the slurry before spray drying. In Comparative Product 13, the porous silica compound was added to a high-speed mixer in the same manner as silicate, and granulated.A predetermined amount of AE-1 heated to 70 ° C was added, and the mixture was granulated and Zeolite was added. Granulation was performed, and the remaining zeolite was further added to granulate to obtain a high-density granular detergent composition.

The resulting high-density granular detergent composition was subjected to a detergency test by the following method. Table 5 shows the results.

Detergency test>

(Preparation of artificially stained cloth)

The same artificially contaminated liquid as in Example 1 was attached to the cloth to prepare an artificially contaminated cloth. The artificial contaminated liquid was attached to the cloth using a gravure roll coater. Apply artificially contaminated liquid to cloth The process of fabricating the artificially stained cloth was carried out with a gravure roll cell capacity of 58 cm ³ Z m ² , a coating speed of 1.0 m / min, a drying speed of 100 ° C., and a drying time of 1 minute. The cloth used was a cotton gold cloth 2003 (manufactured by Tanito Shoten). Reflectance after cleaning-reflectance before cleaning

Cleaning rate (%) = X 100

Reflectance of original cloth-reflectance before cleaning

Table 5 Wood n products Comparative products

Sample number 29 30 31 32 33 10 11 12 13

r ""

( _a ) Component AO- 1 30.0 35.0 30.0 30 0 35.0 35.0 35.5 0 0

on n

(b) Theophylph JO.0 30.0 30.0 20.0 3.0 30.0 30.0 10.0

1 ι zo ν1 dani U Ό U U U u U u n U

"Ai Sodium Carbonate 7 7 7 7 7

To D.

Sword 麵 Salt (II) on n n n on Π on Π on n on Π ゥ Π Π Anion activator

CO S SO 5.0 0 5.0 0 0 0 0 35.0 0

of

Other ΑΕ- 1 0 0 0 5.0 0 0 0 0 35.0

% Formed AM 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 min

AS DA 0 0 0 0 10.0 0 0 0 0 Entrainment component 2.5 2.5 2.5 2.5 2.5 29.5 30.0 2.5 2.5 Total (%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Washing rate (./.) 74.5 76.1 75.4 75.6 80.8 53.0 56.4 62.8 62.5

The symbols in Table 5 are the same as in Tables 1-4.

Claims

The scope of the claims

(a) Amidoamine oxide type surfactant represented by the following general formula (I) 15

50% by weight

In the formula, R 1 is an alkyl group or alkylene group having 10 to 20 carbon atoms, and R ₂ and R ₃ are an alkyl group or alkylene group having 1 to 3 carbon atoms or H. R iH, an alkyl group or alkylene group having 1 to 5 carbon atoms, and n is 1 to 5.

(b) 5-60% by weight of aluminosilicate

(c) Al force Li agent 5-60 weight ^_0/0

A high-density granular detergent composition having a bulk density of 0.6 to 1.2 g / mf.

2. The composition according to claim 1, wherein the alkaline agent (c) is a crystalline silicate of the following formula (II) and / or (III). x (M 20) y (SiO 2) z (Me _m 0w (H ₂ O) (In the ID formula, M represents an element of group la of the periodic table, Me represents an element of group Da, and an element of group nb. , Ilia group element, IVa group element or VIII group element, indicates one or a combination of two or more elements, y ZX = 0.5 to 2.6, z / X = 0.0] to 1.0, w = 0 to 20, n / m = 0.5 to 2.0.

M ₂ 0x '(SiO 2) y'H 20 (III) In the formula, M represents an alkali metal, and x ′ = 1.5 to 2.6 and y ′ = 0 to 20.

3. The composition according to claim 1, wherein (b) is a crystalline aluminosilicate.

4. Containing anionic surfactant and / or nonionic surfactant (a ') in a weight ratio with the above (a), (a') Z (a) = 1Z 100-100/100 The composition of claim 1, wherein the composition is:

5. The anionic surfactant is a higher fatty acid salt having 10 to 18 carbon atoms, a sulfate salt of a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms, an ethoxylated product of an alcohol having 8 to 20 carbon atoms. At least one selected from the group consisting of sulfate salts of alkylene sulfonates, alkylbenzene sulfonates having 8 to 16 carbon atoms in the alkyl group, alkane sulfonates, α-olefin sulfonates, α-sulfofatty acid salts, and α-sulfofatty acid alkyl ester salts. 5. The composition of claim 4, which is a seed.

6. The nonionic surfactant is polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sonolebitan fatty acid ester, polyoxyalkylene glycol ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxy 5. The composition according to claim 4, wherein the composition is at least one member selected from the group consisting of ethylene polyoxybutene pyrene block polymer and alkanol dimethylmethylamine.

7. 20-40 weight ^_0/0 (a), 8-30 wt% of (b) and 1C 0 wt <composition of claim 1 comprising the ½ a (c).

8. The composition according to claim 1, wherein 30 to 80% by weight of the (c) alcohol agent is a crystalline silicate.

9. Contracts containing polycarboxylates having an average molecular weight of 1,000 to 100,000 The composition of claim 1.

10. 0.5 to 20% by weight of aspartic acid diacetate and Z or hydroxyimidinosuccinate as organic builders. 2. The composition according to claim 1, which contains / ₀ .

11. The composition according to claim 1, comprising 1.0 to 5% by weight of aspartic acid diacid salt as an organic builder.