JPH06100885A - High bulk density granular detergent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in detergency by mixing a surfactant, an alkali metal (hydrogen)carbonate, a salt of a specified high- molecular polymer, and an aluminosilicate to provide a specified bulk density. CONSTITUTION:This detergent composition contains 5-50wt.% surfactant (a) [e.g. a sodium salt of methyl ester of a-sulfo (12-18C) fatty acid], 10-50wt.% alkali metal (hydrogen)carbonate (b) (e.g. heavy sodium carbonate), and a salt (c) of a high-molecular polymer of a weight-average molecular weight of 1,000 to 250,000 having monoethylenically unsaturated mono- and dicarboxylic acid units (e.g. a sodium salt of maleic acid/acrylic acid copolymer) and, optionally, an aluminosilicate (d) (e.g. synthetic zeolite A), with the sum of components (c) and (d) being 10-70wt.% and the weight ratio of component (c) to component (d) being (100:0) to (1:99), and it has a bulk density of 0.6-1.2g/cc.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Recently, from the problem of eutrophication of environmental waters,
The amount of condensed phosphates in household heavy detergents has been significantly reduced or eliminated, and phosphorus-free detergents using zeolite as a builder are now predominant. This zeolite removes calcium ions, which are hardness components in the washing liquid, by ion exchange, and prevents the anionic surfactant from becoming a sparingly soluble calcium salt and deteriorating the washing power. 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 conducted from the viewpoint of surfactants and the viewpoint of builders and the viewpoint of additives such as enzymes.

In the conventional laundry detergent, a bulking agent having a bulk density of 0.3 g / cc is prepared by adding an extender (usually Glauber's salt is used) which hardly contributes to the cleaning performance to the composition and spray-drying the filler. It was manufactured as bead-shaped hollow particles of a certain degree. However, since such detergents have a low specific gravity and a low concentration of activator, they are costly to transport and require a large amount of space for storage and display. It was Therefore, recently, a method for producing a high bulk density granular detergent which can be washed with a small amount of detergent has been proposed (JP-A-60-9669).
No. 8), and is also 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, it further contains the component (d), the total amount of the component (c) and the component (d) is 10 to 70% by weight, and the weight ratio of the component (c) and the component (d) is (c). ) /
(D) = 100/0 to 1/99, and the bulk density is 0.6 to 1.2 g / cc.

(A) Surfactant: 5 to 50% by weight. (B) Alkali metal salt of carbonic acid or hydrogen carbonate: 10
50% by weight. (C) A high molecular weight polymer having a weight average molecular weight of 1,000 to 250,000 and containing monoethylenically unsaturated mono- and dicarboxylic acid units. (D) Aluminosilicate.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Anionic and nonionic surfactants are suitable as the component (a) surfactant. Specific examples of the anionic surfactant include the following.

(1) Linear alkylbenzene sulfonate having an alkyl group having an average carbon number of 8 to 16, (2) α-olefin sulfonate having an average carbon number of 10 to 20, (3) represented by the following chemical formula 1. Α-sulfo fatty acid ester salt or fatty acid sulfonate di salt,

[0009]

[Chemical 1] (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 carbon number of 10 to 20, (5) Having a linear or branched alkyl or alkenyl group having an average carbon number of 10 to 20, and having an average of 0.5 to 8
Alkyl ether sulphate or alkenyl ether sulphate with addition of moles of ethylene oxide, (6) Saturated or unsaturated fatty acid salt having an average carbon number of 10 to 22.

Alkali metal salts such as sodium and potassium are usually suitable as counterions in the above anionic surfactants. Examples of the nonionic surfactant include the following.

(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,
An average of 10 to 10 saturated or unsaturated aliphatic primary or secondary alcohols having 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms
Alcohol ethoxylates obtained by adding 30 mol, preferably 12 to 20 mol of ethylene oxide are suitable, and alcohol ethoxylates obtained by adding ethylene oxide to aliphatic primary alcohols are particularly preferable.

As the nonionic surfactant, the following ester type nonionic surfactants may be used. (13) Ester-type nonionic surfactant represented by Chemical formula 2

[0015]

[Chemical 2] (R₁: C6-22, preferably C10-18
An alkyl group or an alkenyl group of
It may be a branch. R₂: Alkylene having 2 to 4 carbon atoms, preferably 2 carbon atoms
Group R₃: C1-4 alkyl group n: OR₂The average number of added moles of
More preferably n = 7 to 20)

The ester type nonionic surfactant of (13) above is structurally an alkyl ether of an alkylene oxide adduct of a fatty acid, and an alkylene oxide is added to an alcohol by a conventional method, followed by esterification with a fatty acid. Although it can also be obtained by the two-step method described above, trivalent aluminum ions, gallium ions, indium ions, thallium ions, cobalt ions, scandium ions,
In the presence of a catalyst composed of magnesium oxide to which one or more metal ions selected from lanthanum ions and divalent manganese ions are added, fatty acid alkyl ester R ₁
Those produced by the one-step method of reacting COOR ₃ and alkylene oxide are also preferable (Japanese Patent Application No. 3-639).
No. 04 specification). These anionic surfactants and nonionic surfactants may be used alone, or may be mixed and used at an appropriate ratio.

The surfactant (a) is incorporated in the detergent composition in an amount of 5 to 50% by weight, preferably 15 to 40% by weight. If the blending amount is less than 5% by weight, sufficient detergency cannot be obtained, while if it exceeds 50% by weight, production becomes difficult.

When an anionic surfactant and a nonionic surfactant are used in combination as the component (a) surfactant, the amount of the anionic surfactant is 5 to 49.5% by weight (preferably 1).
3 to 35% by weight), 0.5 to 30 nonionic surfactant
It is desirable to add the weight% (preferably 2 to 25% by weight).

Component (b), an alkali metal salt of carbonic acid or hydrogen carbonate such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium sesquicarbonate, etc., in the detergent composition is 10 to 50% by weight, preferably 20%. ~
35 wt% is compounded. If the blending 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 both are in the weight ratio Na carbonate / K carbonate = 90/10 to 40/60.
It is desirable to mix and use in the ratio of.

The high molecular weight polymer salt of the component (c) includes a weight average molecular weight of 1,000 to 250,000 containing monoethylenically unsaturated mono- and dicarboxylic acid units,
It is preferably 10,000 to 100,000, and is preferably the polymer salt shown in Chemical formula 3.

[0021]

[Chemical 3] (X: counter ion, copolymerization ratio m / n: weight ratio 0/10 to 5/5)

This high molecular weight polymer salt comprises (i) maleic acid and (ii) acrylic acid on a weight basis of (i) / (ii).
From a homopolymer of acrylic acid polymerized at a copolymerization ratio of 0/10 to 5/5, preferably 2/8 to 5/5, or a salt such as sodium salt or potassium salt of maleic acid / acrylic acid copolymer. And the weight average molecular weight is 1,000 to 250,
000, preferably 10,000 to 100,000. If the copolymerization ratio and the molecular weight deviate from the above ranges, satisfactory cleaning performance cannot be obtained. The high molecular polymer as the component (c) is preferably made into granules by injection granulation or the like, and the average particle diameter is preferably 400 to 500 μm.

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

[0024]

## STR00004 ## x (M ₂ O or M'O) .Al ₂ O ₃ .y (SiO ₂ ) .z (H ₂ O) (In the formula, M is an alkali metal atom and M'is replaceable with calcium. Alkaline earth metal atoms, x, y and z represent the number of moles of each component, and generally x is 0.7.
~ 1.5, y is 1 to 3, and z is an arbitrary number. )

The average particle size of the aluminosilicate is preferably 5 μm or less, more preferably 1 μm or less from the viewpoint of detergency. The high molecular polymer as the component (c) and the aluminosilicate as the component (d) act as a builder that traps calcium ions, which are hard components in the washing liquid,
The total amount of the components (c) and (d) is 10 in the detergent composition.
To 70% by weight, preferably 15 to 50% by weight, and the weight ratio of the component (c) and the component (d) is (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 increased, which is not preferable. Also, (c)
A part of the high molecular polymer of the component can be replaced with the zeolite of the component (d) within the above range, and the desired detergency can be obtained also by this.

The high-bulk-density granular detergent composition of the present invention comprises the above-mentioned essential components (a), (b) and (c) and component (d) which is a partial substitute thereof, and other optional components. Can be included.

As these optional components, protease,
Enzymes such as lipase, cellulase, amylase and keratinase; bleaching agents such as sodium percarbonate and sodium perborate; anti-redeposition agents such as carboxymethyl cellulose and polyethylene glycol; soaps, optical brighteners, fragrances, dyes, etc. be able to.

The detergent composition of the present invention can be obtained by granulating each of the above components into 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 above-mentioned JP-A-60-96698,
A detergent composition of the present invention is obtained by kneading and mixing detergent raw materials such as a surfactant with a kneader, crushing with a crusher such as a cutter mill type, granulating, and further mixing with water-insoluble fine powder. To be Further, a 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, the spray-dried particles and other detergent ingredients can be agitated and granulated to produce high bulk density detergent particles. enzyme,
The ingredients such as the builder may be powder blended with the granulated detergent. The granulated product of the polymer salt as the component (c) is preferably powder-mixed after the above crushing and granulation.

Further, when spray-dried detergent particles are prepared and agitated and granulated while spraying a binder such as a nonionic surfactant to obtain high-bulk density granular detergent particles, the high molecular weight component (c) is used. Coalescence may be added. Needless to say, the high bulk density granular detergent particles obtained after the completion of the stirring granulation may be powder-mixed with the high molecular polymer as the component (c).

[0031]

According to the present invention, (a) a surfactant,
(B) an alkali metal carbonate and (c) a granulated product of a high molecular weight polymer of a maleic acid / acrylic acid polymer system, or (d) a zeolite is further mixed to obtain a high bulk density granular detergent composition, Excellent cleaning performance can be obtained.

[0032]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but prior to this, the evaluation methods used in the examples will be described.

(1) Method of evaluating detergency (i) Preparation of artificial dirt Clay containing crystalline minerals such as kaolinite and vermiculite as the main components, dried at 200 ° C. for 30 hours is used as inorganic dirt. did. After dissolving 3.5 g of gelatin in 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 (KINEMATICA, Switzerland). Next, add 14.9 g of inorganic dirt and emulsify 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 dirt bath
After immersing a prescribed clean cloth (cotton cloth No. 60 designated by Japan Oil Chemistry Association) of m × 20 cm, water was squeezed by two rubber rolls to make the amount of adhered dirt uniform. This dirt cloth is 105 ℃
After drying for 30 minutes, the both sides of the soiled cloth were rubbed 25 times on each side. This was cut into 5 cm × 5 cm, and the one having a reflectance within the range of 42 ± 2% was used as a soiled cloth. The soil composition of the artificial soil cloth thus obtained is shown in Table 1.

[0034]

[Table 1] Soil 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 Total oily soil 62.7 Gelatin 7.0 Inorganic soil 29.8 Carbon black (designated by Japan Oil and Chemical Society) 0.5

(Ii) Cleaning Method U. S. Testing's Terg-O-Tomet
er is used, 10 pieces of artificial dirt cloth and knitted cloth are put into this, the bath ratio is adjusted to 30 times, and washing is performed at 120 rpm and 25 ° C. for 10 minutes. As the cleaning liquid, 900 ml of a cleaning agent having a concentration of 0.083% is used, and rinsing is performed with 900 ml of water for 3 minutes. The water used is 3 ° DH.

(Iii) Evaluation Method The cleaning rate was calculated by the equation 1.

[0037]

[Equation 1]

Here, R is an EL manufactured by KARL TWICE
It is a reflectance (%) measured by a REPHO reflectometer. In addition, the evaluation of the detergency was performed by using the average value of 10 sheets of the artificial soil cloths tested.

Example 1 From the detergent compositions shown in Tables 3 and 4 below, a nonionic surfactant, a granulated product of a sodium salt of a maleic acid / acrylic acid copolymer (MA / AA-Na), and a part of zeolite A detergent slurry having a solid content of 45% was prepared by using each component except a part of sodium carbonate, an enzyme and a fluorescent agent. This detergent slurry was heated at a hot air temperature of 380 using a countercurrent spray drying tower.
It was dried at 5 ° C. so that the water content was 5% to obtain a spray-dried product. This spray-dried product had a good average particle size of 350 μm, a bulk density of 0.35 g / cc, and an angle of repose of 45 °, and was excellent in fluidity.

Then, the dried product, nonionic surfactant and water were continuously kneaded (KRC Kneader # manufactured by Kurimoto Iron Works Co., Ltd.).
2 type) to obtain a dense and uniform kneaded product. A perforated plate (thickness 10 mm) having 80 holes of 5 mmφ was installed at the outlet of this kneader, and the kneaded product was about 5 mmφ × 10 mm
Cylindrical pellets.

This pellet was mixed with a double amount (weight ratio) of 15 ° C.
Crushing machine (speed mill ND-10 with cooling air)
Type, Okada Seiko Co., Ltd. At the same time, as a grinding aid, ground sodium carbonate (average particle size 30 μm
4 parts by weight was added to 100 parts by weight of pellets.

The crusher has a cutter with a length of 15 cm in four stages of cross, rotates at 3000 rpm, and the screen is made of 360-degree punching metal. This crusher is continuously connected in three stages, and the hole diameter of each stage screen is 1st stage: 3.5 mmφ, 2nd stage: 2 mmφ, 3rd stage: 1.5
It was set to mmφ. After the particles that have passed through the crusher in three stages are separated from the cooling air, 2% of zeolite having an average primary particle size of 1 μm is added to the pulverized product and coated, and a granulated product of a salt of maleic acid / acrylic acid copolymer is further added. (MA / AA-N
a) and the enzyme were powder-mixed to obtain the detergent composition of the present invention having the composition shown in Tables 3 and 4 below and having a bulk density of 0.85 g / cc, and the detergency was evaluated to give Table 3 and The results are shown in Table 4. The meanings and details of the abbreviations in Tables 3 and 4 are as follows. In addition, EOp shows the average addition mole number of ethylene oxide.

(1) Component (a) α-SF-Na: α-sulfofatty acid (C ₁₂ -C ₁₈ ) methyl ester sodium AOS-K: C ₁₄ -C ₁₈ potassium α-olefinsulfonate LAS-K: direct Chain potassium alkylbenzene sulfonate (alkyl group C _{10 to} C ₁₄ ) LAS-Na: sodium linear alkylbenzene sulfonate (alkyl group C _{10 to} C ₁₄ ) AS-Na: C _{14 to} C ₁₅ sodium alkylsulfate AES-Na: C ₁₂ -C ₁₃ alkyl ether sulfate (EOp = 2 to 5) soap: tallow soap AE1: C _{12 ~C 13} 1 alcohol ethoxylate (E
Op = 10) AE2: C ₁₂ primary alcohol ethoxylate (EOp =
15) AE3: C _{12 to} 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 200
~ 300μm Light ash: Light sodium carbonate, density 0.50, particle size 100
~ 200 μm Carbonic acid K: K ₂ CO ₃ (reagent product) Silicate: Na ₂ O · 2.2SiO ₂

(3) Components (c) and (d) MA / AA-Na: granulated product of sodium salt of maleic acid / acrylic acid copolymer (average particle size 460 μm), copolymerization ratio 6/4 (weight ratio) ), Polymerization average molecular weight 50,000 to 7
50,000 zeolite: A type synthetic zeolite (average particle size 0.9μ
m)

(4) Others Na Percarbonate: Sodium Percarbonate Other Additives: Have the common composition shown in Table 2 below.

[0047]

[Table 2] Table 2: Other additives Common composition Sodium sulfite 2wt% Moisture 7wt% Fluorescent agent CBS 0.2wt% Fluorescent agent SKC 0.1wt% Protease 0.5wt% Lipase 0.5wt% Cellulase 0.5wt% Sodium sulfate balanced fluorescent agent CBS: Fluorescent agent (trade name "Chinopearl CBS-
X ”) Fluorescent agent SKC: Fluorescent agent (trade name“ Whitetex SK
C ”) Protease: Savinase 6.0T (manufactured by Novo) Lipase: Lipolase 100T (manufactured by Novo) Cellulase: Cellzyme 2400 (manufactured by Novo)

[0048]

[Table 3]Sample No. 1 2 3 4 5 6 7 8 9 10 11 12 Composition (wt%) Component (a): α-SF-Na 20 20 20 20 20 20 20 15 15 15 15 15 AOS-K − − − − − − − − − − − − LAS-K − − − − − − − − − − − − LAS-Na − − − − − − − − − − − − AS-Na − − − − − − − − − − − − AES-Na − − − − − − − − − − − 5 soap − − − − − − − − − − − − AE1 5 5 5 5 5 5 5 − − − − − AE2 − − − − − − − 10 7 10 7 5 AE3 − − − − − − − − − − − − AE4 − − − − − − − − − − − − FEE1 − − − − − − − − − − − −FEE2 − − − − − − − − − − − − Component (b): Heavy ash 15 − 15 − 15 − 15 15 15 15 15 15 Light ash − 15 − 15 − 15 − − − − − − Carbonic acid K 15 15 15 15 15 15 15 15 15 15 15 15Silicate − − − − − − − − − − − − Component (c), (d): (c) MA / AA-Na 0 0 5 5 15 15 30 0 0 15 15 15(d) Zeolite 30 30 25 25 15 15 0 30 30 15 15 15 Percarbonate Na − − − − − − − − 3 − 3 − Other additives Balance Blend ratio: (c) / (d) [wt ratio] 0/0/17/17/50/50/100 / 0/0/50/50/50/100 100 83 83 50 50 0 100 100 50 50 50 (c) + (d) [wt%] 30 30 30 30 30 30 30 30 30 30 30 30 Detergency (%) 77 77 79 79 85 85 90 76 76 84 84 84 Sample No. 1, 2, 8 and 9 are comparative examples, others are examples

[0049]

[Table 4]Sample No. 13 14 15 16 17 18 19 20 21 Composition (wt%) (a) Component: α-SF-Na − − 10 15 − − − − − AOS-K 15 15 10 5 − − − − − LAS-K 15 15 10 − − − − − − LAS-Na − − − − 20 − − − − AS-Na − − − − 10 − − − − AES-Na − − − − − − − − − Soap − − − − − 5 5 5 5 AE1 − − − − − − − 25 − − AE2 5 − − − − − − − − AE3 − 5 5 5 5 − − − − AE4 − − − − − − − − 25 FEE1 − − − − − 25 − − −FEE2 − − − − − − − 25 − Component (b): Heavy ash 5 5 10 15 5 15 15 15 15 Light ash − − − − − − − − − Carbonic acid K 5 5 10 15 5 15 15 15 15Silicate 10 10 − − 10 − − − − (c), (d) component: (c) MA / AA-Na 0 15 15 15 15 15 15 15 15(d) Zeolite 30 15 15 15 15 15 15 15 15 15 Percarbonate Na − − − − − − − − − Other additives Balance Blend ratio: (c) / (d) [wt ratio] 0/50/50/50/50/50/50/50 / 50/100 50 50 50 50 50 50 50 50(c) + (d) [wt%] 30 30 30 30 30 30 30 30 30 Detergency (%) 70 78 81 82 77 84 84 83 86  Sample No. 13 is a comparative example, others are examples

Claims (1)

[Claims] 1. (a) Surfactant: 5 to 50% by weight, (b) Alkali metal salt of carbonic acid or hydrogencarbonate: 10
50% by weight and (c) a high molecular weight polymer salt containing monoethylenically unsaturated mono- and dicarboxylic acid units having a weight average molecular weight of 1,000 to 250,000, and further (d).
Aluminosilicate is contained, and the total amount of the components (c) and (d) is 10 to 10.
70% by weight, the component (c) and the component (d) are mixed in a weight ratio of (c) / (d) = 100/0 to 1/99, and a bulk density of 0.6 to A high bulk density granular detergent composition, characterized in that it is 1.2 g / cc.