JPH10183184A - High bulk density granular detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high bulk density granular detergent composition having an excellent washing performance. SOLUTION: This high bulk density granular detergent composition comprises (a) 5-50wt.% of a surfactant, (b) 10-50wt.% of an alkali metal carbonate or bicarbonate, and (c) a polycarboxylic acid (salt) derived by oxidizing a polysaccharide comprising anhydrous glucose molecules constituting units, having a weight-average mol.wt. of >=2000 and requiring an alkali in an amount of >=435mg (converted into sodium hydroxide) per g of the polycarboxylic acid in order to neutralize the acid type polycarboxylic acid by a titration method, or further (d) an aluminosilicate salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a high bulk density granular detergent composition having excellent cleaning performance.

[0002]

2. Description of the Related Art In recent years, from the problem of eutrophication of environmental waters,
The amount of condensed phosphate in household heavy detergents has been greatly reduced or eliminated, and at present phosphorus-free detergents using zeolite as a builder have become mainstream. This zeolite removes calcium ions, which are hardness components in the washing solution, by ion exchange, and prevents the anionic surfactant from becoming a sparingly soluble calcium salt and preventing the washing power from decreasing. Further, as a phosphorus-free calcium ion trapping builder other than zeolite, a so-called polymer builder such as polyacrylate or a copolymer of maleic anhydride and olefin is used together with zeolite. However, further improvement in detergency is desired, and studies have been made from the viewpoint of surfactants, from the viewpoint of builders, or from the viewpoint of additives such as enzymes.

[0003] In addition, a conventional detergent for clothing contains a bulking agent (usually Glauber's salt is used separately from the cleaning performance component) in the composition.
And spray-drying it to give a bulk density of 0.3 g /
It was produced as bead-shaped hollow particles of about cc. However, such detergents have a low specific gravity and a low concentration of activator, which increases transport costs, requires considerable space for storage and display, and is difficult to place in ordinary households and difficult to measure. Was. Therefore, recently, a method for producing a high bulk density granular detergent that can be washed with a small amount of detergent has been proposed (Japanese Patent Application Laid-Open No. 60-96698) and has been put on the market.

[0004]

SUMMARY OF THE INVENTION The present invention provides a high bulk density granular detergent composition having excellent cleaning performance.

[0005]

The high bulk density granular detergent composition of the present invention comprises the following components (a), (b) and (c):
Alternatively, the composition further contains the component (d), the total amount of the component (c) and the component (d) is 10 to 70% by weight, and the component (c) and the component (d) are (c) in a weight ratio. ) /
(D) = 100/0 to 1/99, characterized in that the bulk density is 0.6 to 1.2 g / cc.

(A) Surfactant: 5 to 50% by weight. (B) Carbonate or hydrogencarbonate alkali metal salt or sodium silicate: 10 to 50% by weight. (C) A polycarboxylic acid or a salt thereof derived by oxidizing a polysaccharide having anhydrous glucose as a structural unit, wherein an alkali required for neutralizing titration of an acid-type polycarboxylic acid is calculated as sodium hydroxide. A polycarboxylic acid or a salt thereof having a weight of 435 mg or more per 1 g of the polycarboxylic acid and a molecular weight of 2000 or more. (D) Aluminosilicate.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As the surfactant of the component (a), anionic and nonionic surfactants are suitable. Specific examples of the anionic surfactant include the following. (1) linear alkylbenzene sulfonate having an alkyl group having an average of 8 to 16 carbon atoms; (2) α-olefin sulfonate having an average of 10 to 20 carbon atoms; (3) α-olefin represented by the following formula 1 Sulfo fatty acid ester salt or fatty acid sulfonate disalt,

[0008]

Embedded image (R: alkyl group or alkenyl group having 8 to 20 carbon atoms Y: alkyl group having 1 to 3 carbon atoms or counter ion Z: counter ion)

(4) Alkyl sulfate having an average of 10 to 20 carbon atoms, (5) having a linear or branched alkyl or alkenyl group having an average of 10 to 20 carbon atoms, and having an average of 0.5 to 8;
(6) a saturated or unsaturated fatty acid salt having an average of 10 to 22 carbon atoms, to which an alkyl ether sulfate or an alkenyl ether sulfate to which moles of ethylene oxide have been added; As the counter ion in the above anionic surfactant,
Usually, alkali metal salts such as sodium and potassium are suitable.

The following are examples of nonionic surfactants. (7) Alcohol ethoxylate obtained by adding ethylene oxide to alcohol (8) Nonylphenol ethoxylate (9) Adduct obtained by adding propylene oxide and ethylene oxide to alcohol (10) Fatty acid alkanolamide (11) Sucrose fatty acid ester (12) Alkylamine oxide

Among the above nonionic surfactants, in particular,
The saturated or unsaturated aliphatic primary or secondary alcohol having 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms has an average of 10 to 10
Alcohol ethoxylates obtained by adding 30 moles, preferably 12 to 20 moles of ethylene oxide are preferable, and alcohol ethoxylates obtained by adding ethylene oxide to aliphatic primary alcohols are particularly preferable. Further, as the nonionic surfactant, the following ester-type nonionic surfactant may be used.

(13) An ester type nonionic surfactant represented by the following formula:

Embedded image (R₁: Having 5 to 21 carbon atoms, preferably 9 to 17 carbon atoms
An alkyl or alkenyl group, even if it is linear
It may be a branch. R_Two: Alkylene having 2 to 4 carbon atoms, preferably 2 carbon atoms
Group R_Three: An alkyl group having 1 to 4 carbon atoms n: OR_TwoAnd the number of added moles of 5 to 30
(Preferably n = 7 to 20)

The ester type nonionic surfactant (13) is structurally an alkyl ether of an alkylene oxide adduct of a fatty acid, and is formed by adding an alkylene oxide to an alcohol by a conventional method, followed by esterification with the fatty acid. Can be obtained by the two-stage method, but trivalent aluminum ion, gallium ion, indium ion, thallium ion, cobalt ion, scandium ion,
In the presence of a catalyst comprising magnesium oxide to which one or more metal ions selected from lanthanum ions and divalent manganese ions have been added, the fatty acid alkyl ester R ₁
Those produced by a one-step method of reacting COOR ₃ with an alkylene oxide are also preferable (Japanese Patent Laid-Open No. 4-279).
552). These anionic surfactants and nonionic surfactants may be used alone or in a mixture at an appropriate ratio.

The surfactant (a) is incorporated in the detergent composition in an amount of 5 to 50% by weight, preferably 20 to 45% by weight. If the amount is less than 5% by weight, sufficient detergency cannot be obtained, while if it exceeds 50% by weight, production becomes difficult.
When the anionic surfactant and the nonionic surfactant are used in combination as the surfactant of the component (a), the anionic surfactant is used in an amount of 5 to 49.5% by weight (preferably 20 to 45% by weight), and the nonionic surfactant is used. It is desirable to add 0.5 to 35% by weight (preferably 2 to 30% by weight) of the agent.

The component (b), sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium sesquicarbonate or the like, or an alkali metal salt of carbonic acid or bicarbonate, or sodium silicate is used in the detergent composition.
50% by weight, preferably 25 to 40% by weight is blended.
If the amount is less than 10% by weight or more than 50% by weight, sufficient detergency cannot be obtained. As the alkali metal salt of carbonic acid or hydrogen carbonate as the component (b), sodium carbonate and potassium carbonate are preferable, and the two are expressed in a weight ratio of Na carbonate / K carbonate.
= 90/10 to 40/60.

The polycarboxylic acid or a salt thereof as the component (c) is a polycarboxylic acid or a salt thereof obtained by oxidizing a polysaccharide having anhydrous glucose as a structural unit, and is an acid-type polycarboxylic acid. Polycarboxylic acid or a salt thereof having an alkali required for neutralization titration of 435 mg or more in terms of sodium hydroxide per 1 g of the polycarboxylic acid and having a molecular weight of 2,000 or more in weight average is used. More preferably, the neutralization titer is 486 to 582 mg / g, and the weight average molecular weight is 250.
0 to 15000.

Here, when the alkali required for neutralizing titration of the acid-type polycarboxylic acid is less than 435 mg per 1 g of the polycarboxylic acid in terms of sodium hydroxide, or when the molecular weight is less than 2,000 in weight average, In addition, its ability to capture calcium is insufficient, and sufficient detergency cannot be obtained even when it is added to a detergent system. The polycarboxylic acid or a salt thereof has an effect as a chelate builder for capturing calcium ions, which are hardness components in the washing solution. As a counter ion, an alkali metal salt such as sodium or potassium is generally used, and the detergency can be improved most when completely neutralized. However, a partially neutralized one shows good detergency.
The component (c) of the present invention has a carboxyl group, an acid-type polycarboxylic acid in which the carboxyl group is unneutralized and in a free state, and a salt-type polycarboxylic acid salt in which all the carboxyl groups are neutralized. Any of partially neutralized polycarboxylates in which the carboxyl group is partially neutralized, partially unneutralized, and the acid type and the salt type are mixed are used. The term “alkali required for neutralization titration of acid-type polycarboxylic acid” as used in the present invention is 1 g of the polycarboxylic acid in terms of sodium hydroxide.
"435 mg or more per unit" means that the amount of alkali required when the polycarboxylate is assumed to be a complete acid form in any of the acid form, salt form and partially neutralized form is 43%.
It means that it is specified as 5 mg or more, which indicates an index of the carboxyl group content in the polycarboxylic acid.

The polysaccharide used for obtaining the polycarboxylic acid (c) or a salt thereof used in the present invention is not particularly limited as long as it is a polysaccharide having anhydrous glucose as a constitutional unit. Starch, dextrin, cellulose Or amylose or amylopectin obtained by fractionating starch or hydrolysates thereof, and these may be used in a mixture of two or more. And the origin of these polysaccharides is not particularly limited, for example, in the case of starch, corn starch, wheat starch,
In the case of rice starch, tapioca starch and the like, and cellulose, cellulose obtained from softwood, hardwood, cotton and the like is used. Among these polysaccharides, use of starch or cellulose is preferred from the viewpoint of availability and economy, and starch is particularly preferably used.

The polycarboxylic acid (c) or a salt thereof used in the present invention can be obtained by oxidizing a polysaccharide having anhydrous glucose as a constitutional unit using a combination of a transition metal catalyst and an oxidizing agent. That is, it can be produced by adding an oxidizing agent to an aqueous dispersion of a polysaccharide and a metal catalyst while maintaining the pH of the solution in a certain range.

As the transition metal catalyst, Ru, Os, R
h, Ir, Pt, Pd, etc., and a ruthenium catalyst or an osmium catalyst is preferable. These metal catalysts may be used in the form of a salt such as chloride, sulfide or oxide, or may be used as a metal. The amount of these metal catalysts used is 0.05 mol% to 10 mol%, preferably 0.1 mol% to 7 mol%, based on the anhydrous glucose units of the polysaccharide.

As the oxidizing agent, hypohalite (for example, Na salt, K salt, Ca salt, Mg salt, etc.) or powdered ash can be used, and hypohalite is preferred. The amount of these oxidizing agents varies depending on the content of carboxyl groups in the polycarboxylic acid to be finally obtained, but is usually 3.5 to 12 moles per anhydroglucose unit of the polysaccharide, Preferably 4 times mol
It is 9 times mol. The reaction is carried out by adding these oxidizing agents to an aqueous dispersion of a polysaccharide metal catalyst.
The method of adding the oxidizing agent is not particularly limited, but it is usually added continuously or dividedly. The reaction time is not particularly limited, but is usually 2 hours to 8 hours. Although the reaction temperature is not particularly limited, it is usually 10 ° C to 50 ° C.

The pH of the solution during the reaction is maintained in the range of 6 to 13, preferably 7 to 12. The pH can be adjusted using a hydroxide of an alkali metal such as sodium hydroxide, potassium hydroxide, or lithium hydroxide, or an amine such as ammonia, an alkylamine, or an alkanolamine. Sodium or potassium hydroxide is used.

Under the above-mentioned reaction conditions, cleavage of the glucosidic bond in the main chain of the polysaccharide is relatively difficult to occur, and the hydroxyl group of the polysaccharide is efficiently oxidized. Of 435 mg or more per 1 g of polycarboxylic acid and a weight average molecular weight of 2,000 or more of polycarboxylic acid or a salt thereof can be obtained.

The polycarboxylic acid used in the present invention has a complicated structure, so it is difficult to show a clear structural formula. However, when starch is used as a raw material, it can be represented by the following general formula. Represented by the general formula (I) of Chemical formula 3,
When estimated from the amount of sodium hydroxide required for the neutralization titration, it is a polycarboxylic acid having an average of 2.1 or more carboxyl groups per anhydroglucose unit.

[0025]

Embedded image

As the aluminosilicate as the component (d), a crystalline or amorphous aluminosilicate represented by the following formula 4 or a mixture thereof is preferable.

## STR4 ## x (M ₂ O or M′O) .Al ₂ O ₃ .y (S
iO ₂ ) .z (H ₂ O) (wherein M is an alkali metal atom, M ′ is an alkaline earth metal atom exchangeable with calcium, x, y and z represent the number of moles of each component, Generally, x is 0.7
-1.5, y is 1-3, and z is an arbitrary number. )

The average particle size of the aluminosilicate is desirably 5 μm or less, preferably 1 μm or less from the viewpoint of detergency. The polycarboxylic acid (salt) of the component (c) and the aluminosilicate of the component (d) act as builders for capturing calcium ions, which are hard components in the washing solution. 10) to 70% by weight, preferably 15 to 50% by weight, of the total amount of the components in the detergent composition, and the components (c) and (d) are in a weight ratio of (c) / (d). = 100/0 to 1/99, preferably (c) / (d) = 100/0 to 33/67.

If the total amount of the components (c) and (d) is less than 10% by weight, sufficient washing cannot be obtained, while if it exceeds 70% by weight, the dispersibility of the builder in the washing solution is poor. At the same time, the cost is high, which is not preferable. (C)
Part of the polycarboxylic acid (salt) as the component can be replaced with the zeolite as the component (d) within the above range, whereby the desired detergency can be obtained. The high bulk density granular detergent composition of the present invention comprises the above (a), (b),
(D) which is an essential component of (c) and a partial substitute thereof.
In addition to the components, other optional components can be contained.

[0029] These optional components include protease,
Enzymes such as lipase, cellulase, amylase and keratinase; bleaching agents such as sodium percarbonate and sodium perborate; anti-recontamination agents such as carboxymethylcellulose and polyethylene glycol; fluorescent whitening agents, fragrances, dyes, etc. it can. In addition, a chelating agent such as a polymer builder or a layered silicate other than the components (c) and (d) of the present invention can also be used.

The detergent composition of the present invention is obtained by granulating the above-mentioned components to obtain a high bulk density granular detergent composition having a bulk density of 0.6 to 1.2 g / cc. This granulation method is described in the aforementioned JP-A-60-96698 and the like.
Detergent raw materials such as surfactants are kneaded and mixed with a kneader, crushed and granulated with a crusher such as a cutter mill type, and further mixed with water-insoluble fine powder to obtain the detergent composition of the present invention. Can be Also, part or all of the detergent components are spray-dried in advance, and the spray-dried product and the remaining detergent components are kneaded,
It can also be mixed to produce high bulk density detergent particles. Alternatively, high bulk density detergent particles can be produced by stirring and granulating the spray-dried particles and other detergent components. enzyme,
Components such as builders may be powder blended with the granulated detergent. It is preferable that the polycarboxylic acid or the salt thereof as the component (c) is powder-mixed after the above-mentioned crushing and granulation.

Further, when spray-dried detergent particles are prepared and stirred and granulated while spraying a binder such as a nonionic surfactant to obtain high bulk density granular detergent particles, the polycarboxylic acid of component (c) is used. Alternatively, a salt thereof may be added. Of course, the high bulk density granular detergent particles obtained after the completion of the stirring granulation may be mixed with the polycarboxylic acid or the salt thereof as the component (c) in powder form.

[0032]

According to the present invention, (a) a surfactant,
By combining (b) an alkali metal carbonate or sodium silicate and (c) a polycarboxylic acid or a salt thereof, and (d) zeolite into a high bulk density granular detergent composition, excellent cleaning performance can be obtained. it can.

[0033]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Prior to this, the evaluation method used in the examples will be described.

(1) Detergency Evaluation Method (i) Preparation of Artificial Soil A clay mainly composed of crystalline minerals such as kaolinite and vermiculite was dried at 200 ° C. for 30 hours and used as inorganic soil. did. After dissolving 3.5 g of gelatin in about 950 cc of water at about 40 ° C., 0.25 g of carbon black was dispersed in water using a powerful emulsifying and dispersing machine, Polytron (manufactured by KINEMATICA, Switzerland). Next, 14.9 g of inorganic soil was added and emulsified with Polytron,
Further, 31.35 g of organic dirt was added and emulsified and dispersed with Polytron to prepare a stable dirt bath. 10c in this dirty bath
After immersing a predetermined cleaning cloth (cotton cloth No. 60 designated by the Japan Oil Chemistry Association) of mx 20 cm (unsoiled cloth), water was squeezed with two rubber rolls to uniform the amount of stains. After drying this soiled cloth at 105 ° C. for 30 minutes, both sides of the soiled cloth were rubbed left and right 25 times. This was cut into 5 cm × 5 cm, and the one having a reflectance in the range of 42 ± 2% was provided to a dirty cloth. The soil composition of the artificial soil cloth thus obtained is shown in Table 1.

[0035]

Table 1: Soil component composition (wt%) Organic soil: oleic acid 28.3 triolein 15.6 cholesterol oleate 12.2 liquid paraffin 2.5 squalene 2.5 cholesterol 1.6 oily soil Total dirt 62.7 Gelatin 7.0 Inorganic dirt 29.8 Carbon black (Designated by Japan Oil Chemical Association) 0.5

(Ii) Washing method S. Testing Terg-O-Tomet
er, and put 10 artificial soiling cloths and knitted cloths in them, adjust the bath ratio to 30 times, and wash at 120 rpm and 25 ° C. for 10 minutes to obtain washing cloths. Use 900ml of washing solution with 0.05% detergent concentration, 900ml for rinsing
For 3 minutes. The water used is 3 ° DH.

(Iii) Evaluation method The cleaning rate was determined by the equation (1).

(Equation 1)

Here, R is an EL manufactured by Carl Twice.
It is a reflectance (%) measured by a REPHO reflectometer. The evaluation of the detergency was carried out by the average value of 10 test artificial soil cloths.

Example 1 Nonionic surfactant, granulated sodium salt of polycarboxylic acid, part of zeolite, part of sodium carbonate, enzyme and fluorescent agent were obtained from the detergent compositions shown in Tables 3 to 10 below. A detergent slurry having a solid content of 45% was prepared using the removed components. Using this detergent slurry, using a countercurrent spray drying tower,
Dry at a hot air temperature of 380 ° C to a water content of 5%,
A spray-dried product was obtained. This spray-dried product has an average particle size of 350
μm, bulk density 0.35 g / cc, angle of repose 45 °, and good fluidity.

Next, the dried product, nonionic surfactant and water were continuously kneaded (KRC Kneader #, manufactured by Kurimoto Tekkosho).
2) to obtain a dense and uniform kneaded product. At the outlet of this kneader, a perforated plate (thickness: 10 mm) having 80 hole diameters of 5 mmφ was installed, and the kneaded material was reduced to about 5 mmφ × 10 mm
Cylindrical pellets.

The pellets were doubled (weight ratio) at 15 ° C.
Crusher (speed mill ND-10)
Type, Okada Seiko Co., Ltd.). At this time, pulverized sodium carbonate (average particle size: 30 μ
m) was added in an amount of 4 parts by weight based on 100 parts by weight of the pellets.

The crusher has a cutter having a length of 15 cm at four stages of cloth, rotates at 3000 rpm, and the screen is made of 360-degree punched metal. The crushing machine was connected in three stages in succession, and the hole diameter of each stage screen was 3.5 mmφ for the first stage, 2 mmφ for the second stage, and 1.5 for the third stage.
mmφ. After separating the particles having passed through the crusher three stages from the cooling air, zeolite having an average primary particle size of 1 μm is added to the pulverized material at 2%, coated, and the polycarboxylate granules and the enzyme are powder mixed. Then, the detergent composition of the present invention having the composition shown in Tables 3 and 4 described below and having a bulk density of 0.85 g / cc was evaluated, and the detergency was evaluated.
0 indicates the result. The composition was 2 as shown in Tables 3 and 4.
The two tables show the composition of one composition and the evaluation results. The granulated product of the polycarboxylate can be obtained by a general production method such as countercurrent spray drying or fluidized bed.

The meanings and details of the abbreviations in Tables 3 and 4 are as follows. EOp indicates the average number of moles of ethylene oxide added. (1) Component (a) α-SF-Na: α-sulfo fatty acid (C ₁₂ -C ₁₈ ) methyl ester sodium AOS-K: C ₁₄ -C ₁₈ potassium α-olefin sulfonate LAS-K: linear alkylbenzene sulfone potassium acid (alkyl _{C 10 ~C 14) LAS-Na} : sodium dodecylbenzenesulfonate (alkyl _{C 10 ~C 14) AS-Na} : C 14 ~C 16 sodium alkyl sulfate AES-Na: C ₁₂ ~C Sodium ₁₃ alkyl ether sulfate (EOp = 2-5) Soap: tallow soap AE1: C ₁₂ -C ₁₃ primary alcohol ethoxylate (E
Op = 10) AE2: C ₁₂ primary alcohol ethoxylate (EOp =
15) AE3: C ₁₂ -C ₁₄ secondary alcohol ethoxylate (E
Op = 12) AE4: C ₁₂ primary alcohol ethoxylate (EOp =
_{7) FEE1: C 11 H 23} CO (OCH 2 CH 2) 15 OCH 3 FEE2: C 11 H 23 CO (OCH 2 CH 2) 10 OCH 3

(2) Component (b) Heavy Ash: Heavy sodium carbonate, density 1.01, particle size 20
0 to 300 μm light ash: light sodium carbonate, density 0.50, particle size 10
0 to 200 μm Carbonic acid K: K ₂ CO ₃ (reagent product) Silicate: Na ₂ O · 2.2 SiO ₂

(3) Component (c) Sodium polycarboxylate 1: Component (c) of the present invention Starting from wheat starch, using a ruthenium chloride catalyst,
Sodium polycarboxylate 1 obtained by performing an oxidation reaction with NaClO was used. In this sodium polycarboxylate 1, an alkali required for neutralization titration as an acid-type polycarboxylic acid is 521 mg per polycarboxylic acid in terms of sodium hydroxide, and a weight average molecular weight is 5800.
, And the the CEC was found to be 410mg-CaCO ₃ / g. The method of measuring these numerical values will be described later in (4).

An example of a fine production method of this sodium polycarboxylate 1 is shown below. Stirrer, oxidant dropping funnel,
In a 500 ml separable flask equipped with a sodium hydroxide aqueous solution dropping port, a pH electrode, and a thermometer, 10 g of absolutely dried corn starch, 100 g of ion-exchanged water and RuCl ₃ .nH ₂ O (Ru content 38 wt. 0.49 g (3 mol% based on the anhydrous glucose units of the starch). Then, the mixture was cooled in a water bath at 20 ° C., and when the internal temperature reached about 20 ° C., 230 g of a 12% by weight aqueous solution of sodium hypochlorite (six moles relative to anhydrous glucose units of starch) was distributed over 3 hours. And added. During this time, the pH was controlled at 9. After the addition of sodium hypochlorite was completed, stirring was further continued for 2 hours, and the reaction mixture was slowly poured into about 1 liter of ethanol to precipitate a reaction product. The resulting precipitate is
It was dissolved in 50 ml of ion-exchanged water, purified by diffusion dialysis with ion-exchanged water for 5 days, and then freeze-dried to obtain 7.5 g of sodium polycarboxylate 1 powder.

Sodium polycarboxylate 2: Component (c) of the present invention Sodium polycarboxylate 2 obtained by subjecting corn starch as a raw material to an oxidation reaction with NaClO using a ruthenium chloride catalyst. In this sodium polycarboxylate 2, the alkali required for neutralization titration as an acid-type polycarboxylic acid is calculated as sodium hydroxide,
489 mg per polycarboxylic acid, weight average molecular weight 8
100 and its CEC is 402 mg-CaCO ₃ /
g.

An example of a fine production method of this sodium polycarboxylate 2 is shown below. Stirrer, oxidant dropping funnel,
In a 500 ml separable flask equipped with a sodium hydroxide aqueous solution dropping port, a pH electrode, and a thermometer, 10 g of corn starch in absolute dry weight, 50 g of ion-exchanged water, and RuCl ₃ .nH ₂ O (Ru content 38 wt. %) Of 0.16 g (1 mol% based on anhydrous glucose units of starch). Then, the mixture was cooled in a water bath at 20 ° C., and when the internal temperature reached about 20 ° C., 192 g of a 12% by weight aqueous solution of sodium hypochlorite (5 times the mol of anhydrous glucose units of starch) was supplied for 5 hours. And added. During this time, a 2N aqueous sodium hydroxide solution was added using a pH stat to control the pH in the system to 10. After the addition of sodium hypochlorite, stirring was further continued for 2 hours, and sodium polycarboxylate 2 was added in the same manner as in the above-mentioned production example of sodium polycarboxylate 7.
8 g were obtained.

Sodium polycarboxylate 3: Comparative product Sodium polycarboxylate 3 obtained by hydrolyzing sodium polycarboxylate 2 under acidic conditions was used. In this sodium polycarboxylate 3, the alkali required for neutralization titration as an acid-type polycarboxylic acid is 486 mg per polycarboxylic acid and a weight average molecular weight of 1000 in terms of sodium hydroxide, and its CEC is 250 mg-CaCO 2.
₃ / g.

Sodium polycarboxylate 4: Comparative product Sodium polycarboxylate 4 obtained by using corn starch as a raw material and performing an oxidation reaction with NaClO was used. In this sodium polycarboxylate, the alkali required for neutralization titration as an acid-type polycarboxylic acid is 310% per polycarboxylic acid in terms of sodium hydroxide.
mg, weight average molecular weight 3000, and CEC of 2
Atsuta in 30mg-CaCO ₃ / g.

The carboxyl content of the polycarboxylic acid used in the present invention (the amount of alkali per 1 g of the polycarboxylic acid in terms of sodium hydroxide required for neutralizing and titrating the acid-form polycarboxylic acid), the molecular weight and the Ca ion A method for measuring chelation ability (CEC) is described below.

[Measurement of Carboxyl Group Content] About 0.2 g (absolutely dry amount) of acid-type polycarboxylic acid was precisely weighed and measured.
Weigh out into a 0 ml conical beaker, dissolve by adding about 50 ml of ion-exchanged water, titrate with 1/10 normal sodium hydroxide standard solution using phenolphthalein as an indicator, and add 1 g of acid type polycarboxylic acid. The carboxyl group content is indicated as mg of sodium hydroxide required for neutralization.

When it is clear that a part or all of the polycarboxylic acid whose carboxyl group content is to be measured is in the form of a salt, the polycarboxylic acid is converted into an acid type polycarboxylic acid by the following method. And take it out. That is, an aqueous solution of about 1% by weight of a polycarboxylate is prepared, and the solution is allowed to flow through a column filled with a cation exchange resin (DOWEX 50W-X8, manufactured by Dow Chemical Company) to carry out cation exchange. Convert to The cation exchange resin is used in an amount of 10 ml per 1 g of a 1% by weight aqueous solution of the polycarboxylate. The eluate is freeze-dried or dried under reduced pressure (40 ° C. or lower) to obtain an acid-type polycarboxylic acid in powder form.

"Measurement of molecular weight by GPC" About 5 mg of the same polycarboxylic acid powder used in the neutralization titration was used.
Dissolve in 5 ml of 0.1 mol / L phosphate buffer (pH 7) containing 0.3 mol / L NaCl, and under the following conditions,
It is measured by GPC and expressed as a weight average molecular weight. Column used: G-4000PW + manufactured by Tosoh Corporation
G-2500PW Eluent: 0.1 containing 0.3 mol / L NaCl
Mol / L phosphate buffer (pH 7) Elution degree: 0.5 ml / min Column temperature: 40 ° C. Sample injection volume: 200 μl Calibration curve: Standard sodium polyacrylate manufactured by Polyscience (weight average molecular weight 2100, 5000, 2000)
0, 35000, 165300)

"Measurement of Ca ion chelating ability (CEC)" 0.1 mol / L CaCl manufactured by Orion Research
By diluting the standard solution 100 times, a Ca solution corresponding to 100 ppm as CaCO ₃ was prepared. On the other hand, the polycarboxylic acid to be tested was dissolved in ion-exchanged water to obtain exactly 1% by weight of polycarboxylic acid Na.
Was prepared as a test solution. Ca solution 100
Then, 2 ml of a 4 mol / liter KCl solution was added, and the pH was adjusted to 10 with 1/10 N NaOH. The initial concentration of Ca ions was measured using a Ca ion electrode while stirring the aqueous solution. Next, 2 ml of the test solution was accurately added, and the pH was adjusted to 10 again.
The Ca ion concentration was measured using the a ion electrode. Ca
The Ca ion concentration after the addition of the test solution was subtracted from the initial concentration of the ions, and this amount was used as the chelated Ca ions to determine the amount of C that 1 g of sodium polycarboxylate was chelated.
The a ion content was expressed as mg of CaCO ₃ .

(5) Component (d) Zeolite: Type A synthetic zeolite (average particle size 0.9 μm)
m) (6) Others Na percarbonate: sodium percarbonate Common component: has a common composition shown in Table 2 below.

[0057]

Table 2: Other additives Common composition Sodium sulfite 1.7 wt% Water 7.0 wt% Fluorescent agent CBS 0.2 wt% Fluorescent agent SAH 0.1 wt% Protease 0.5 wt% Lipase 0.5 wt% Fluorescent agent CBS : Fluorescent agent (trade name “Tinopearl CBS-
X ", Ciba-Geigy) Fluorescent agent SKC: Fluorescent agent (trade name" WHITEX SA ")
H ", manufactured by Sumitomo Dye Tech) Protease: Sabinase 6.0T (manufactured by Novo) Lipase: Lipolase 100T (manufactured by Novo)

[0058]

Table 3: Composition of detergent composition ( No. 1) Example composition (wt%) Sample No. 1 2 3 4 5 6 7 8 (a) Component: α-SF-Na 20 20 20 20 20 20 20 20 AOS-K--------LAS-K--------LAS-Na 10 10 10 10 10 10 10--AS-Na--------AES-Na − − − − − − − − − Soap − − − − − − 10 10 AE1 5 5 5 5 5 5 − − AE2 − − − − − − − 10 7 AE3 − − − − − − − − − AE4 − − − − − − − − FEE1 − − − − − − − − − FEE2 − − − − − − − − − (b) component: Heavy ash 25 − 25 − 25 − 20 20 Light ash − 25 − 25 − 25 − − Carbonate K 10 10 10 10 10 10 10 10 Silicate − − − − − − − − − (c) Component: Sodium polycarboxylate 1 20 20 10 10 5 5 10 10 2 − − − − − − − − 3 − − − − − − − − 4 − − − − − − − − −

[0059]

[Table 4]Table 4: Composition of detergent composition (No. 2) (continuation of Table 3) Example Composition (wt%) Sample No. 1 2 3 4 5 6 7 8 Component (d): Zeolite 0 0 10 10 15 15 10 10 Na percarbonate − − − − − − − − 3 Acrylic acid / − − − − − − − − Maleic acid copolymer Polyacrylic acid − − − − − − − − Layered silicate − − − − − − − − −Common component 10 10 10 10 10 10 10 10 Mixing ratio: (c) / (d) [wt ratio] 100/0 100/0 50/50 50/50 25/75 25/75 50/50 50/50 (c) + (d) [wt%] 20 20 20 20 20 20 20 20 Detergency (%) 88 88 83 83 79 79 84 84 

[0060]

Table 5: Composition of detergent composition (Part 3) Example composition (wt%) Sample No. 9 10 11 12 13 14 15 16 (a) component: α-SF-Na − − 10 20 20 − − − AOS-K 15 15 10 − 5 − − − LAS-K 15 15 10 − − − − − LAS-Na − − − − − − −20 − − AS-Na − − − − − 10 − − AES-Na − − − 5 − − − − − Soap − − − − − − 55 5 AE1 − − − − − − − 25 − AE2 5 − − − − − − − − AE3 − 55 55 5 5 − − AE4 − − − − − − − 25 FEE1 − − − − − − − − − FEE2 − − − − − − − − − (b) component: Heavy ash 15 15 25 25 25 25 25 25 25 Light ash − − − − − − − − Carbonate K 10 10 10 10 15 10 10 15 Silicate 10 10 − − − − − − − (c) Component: Sodium polycarboxylate 1 10 10 10 10 10 10 10 10 10 2 − − − − − − − − 3 − − − − − − − − 4 − − − − − − − − −

[0061]

[Table 6]Table 6: Composition of detergent composition (No. 4) (continuation of Table 5) Example Composition (wt%) Sample No. 9 10 11 12 13 14 15 16 (d) Ingredient: Zeolite 10 10 10 15 10 10 15 10 Na percarbonate--------Acrylic acid /--------Maleic acid copolymer Polyacrylic acid--------Layered silicate---------Common component 10 10 10 10 10 10 10 10 Mixing ratio: (c) / (d) [wt ratio] 50/50 50/50 50/50 40/60 50/50 50/50 40/60 50/50 (c) + (d) [wt%] 20 20 20 25 20 20 25 20 Detergency (%) 82 81 82 83 82 79 84 85 

[0062]

Table 7: Composition of detergent composition ( No. 5) (Continuation of Table 6) Example composition (wt%) Sample No. 17 18 19 20 21 22 (a) Component: α-SF-Na − − 20 20 20 20 AOS-K − − − − − − − LAS-K − − − − − − LAS-Na − − 10 10 10 10 AS-Na − − − − − − − AES-Na − − − − − − Soap 5 5 − − − − AE1 − − 5 5 5 5 AE2 − − − − − − − AE3 − − − − − − − AE4 − − − − − − FEE1 30 − − − − − − FEE2 − 30 − − − − ( b) Component: Heavy ash 25 25 25 25 25 22 Light ash − − − − − − − Carbonate K 10 10 10 10 10 10 10 Silicate − − − − − − (c) Component: Sodium polycarboxylate 1 10 10 0 5 5 10 2 − − 10 − − − 3 − − − − − − 4 − − − − − −

[0063]

Table 8: Composition of detergent composition ( No. 6) (continuation of Table 7) Example composition (wt%) Sample No. 17 18 19 20 21 22 (d) Component: zeolite 10 10 10 10 10 10 Na percarbonate------Acrylic acid /---5--Maleic acid copolymer Polyacrylic acid----5-Layered silicate-----3 Common components 10 10 10 10 10 10 Mixing ratio: (c) / (d) [wt ratio] 50/50 50/50 50/50 33/67 33/67 50/50 (c) + (d) [wt%] 20 20 20 15 15 20 Detergency (% ) 83 82 82 83 81 84

[0064]

Table 9: (No. 1) Comparative composition (wt%) Sample No. 12 3 4 5 6 7 (a) component: α-SF-Na 20 20 20 20 −20 20 AOS-K − − − − 15 − − LAS-K − − − − − 15 − − LAS-Na 10 10 − − − 10 10 AS-Na − − − − − − − − AES-Na − − − − − − − − Soap − − 10 10 − − − AE1 5 5 − − − 55 5 AE2 − − 10 7 5 − − AE3 − − − − − − − − AE4 − − − − − − − FEE1 − − − − − − − FEE2 − − − − − − − − (B) component: heavy ash 25 − 20 20 15 25 − light ash − 25 − − − − 25 carbonate K 10 10 10 10 10 10 10 10 silicate − − − − 10 − − (c) component: polycarboxylic acid Sodium 1 − − − − − − − 2 − − − − − − − 3 − − − − − −20 − 4 − − − − − − 20

[0065]

Table 10: (No. 2) Comparative composition (wt%) Sample No. 12 345 67 7 (d) component: zeolite 20 20 20 20 200 000 Na percarbonate---- − − Acrylic acid / − − − − − − − Maleic acid copolymer Polyacrylic acid − − − − − − − Layered silicate − − − − − − − Common component 10 10 10 10 10 10 10 10 Mixing ratio: (c) / (d) [wt ratio] 0/100 0/100 0/100 0/100 0/100 100/0 100/0 (c) + (d) [wt%] 20 20 20 20 20 20 20 Detergency (% ) 76 76 77 77 75 77 76

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 17/06 C11D 17/06

Claims (1)

[Claims] (1) a surfactant: 5 to 50% by weight; (b) an alkali metal salt of carbonic acid or hydrogen carbonate or sodium silicate: 10 to 50% by weight; and (c) anhydrous glucose. A polycarboxylic acid or a salt thereof derived by oxidizing a polysaccharide, wherein an alkali required for neutralizing and titrating the acid-type polycarboxylic acid is at least 435 mg per 1 g of the polycarboxylic acid in terms of sodium hydroxide. And a polycarboxylic acid or a salt thereof having a molecular weight of 2,000 or more by weight on average, and further contains (d) an aluminosilicate, and the total amount of the component (c) and the component (d) is 10 ~
70% by weight, and the component (c) and the component (d) are blended in a weight ratio of (c) / (d) = 100/0 to 1/99, and the bulk density is 0.6 to High bulk density granular detergent composition characterized by being 1.2 g / cc.