JPH06248300A - High bulk density granular detergent composition - Google Patents

Abstract

PURPOSE:To provide a high bulk density grannular detargent composition containing a specified ratio of a specified anionic surfactant, a specific hydroxyiminodisuccinic acid salt and a specified nonionic surfactant, excellent in detergency and useful for clothing, etc. CONSTITUTION:The composition is composed of (A) an anionic surfactant selected from an alpha-sulfofatty acid alkyl ester (salt), an alpha-olefinsulfonic acid (salt), an alkyl ether sulfuric acid (salt), an alkylsulfuric acid (salt) and a straight-chain alkylbenzenesulfonic acid (salt), (B) a nonionic surfactant and (C) a hydroxyiminodisuccinic acid salt represented by the formula (X is a counter ion). The weight ratio of the component (A)/the component (B) is within a range of 95/5 to 20/80 and the total amount of the components (A) and (B) is 10 to 50wt.%. The amount of the component (C) is 1 to 50wt.%.

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):
In the weight ratio (A) / (B) = 95/5 to 20/80, the total amount of the components (A) and (B) is 10 to 50% by weight, and the amount of the component (C) is 1 to 50% by weight. It is characterized by including. (A) Anionic surfactant selected from α-sulfofatty acid alkyl ester and its salt, α-olefin sulfonic acid and its salt, alkyl ether sulfuric acid and its sulfuric acid salt, alkyl sulfuric acid and its salt, linear alkylbenzene sulfonic acid and its salt Agent (B) Nonionic surfactant (C) Hydroxyiminodisuccinate represented by Formula 2 (general formula I)

[0006]

[Chemical 2]

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The anionic surfactant as the component (A) is specifically shown as the following (A-1) to (A-5), and these may be used alone or in combination of two or more kinds. Be compounded. (A-1) α-sulfofatty acid alkyl ester represented by the following chemical formula 3 (general formula II) or a salt thereof

[0008]

[Chemical 3] (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)

(A-2) α-olefin sulfonic acid having an alkyl group or alkenyl group having an average carbon number of 10 to 20, preferably 12 to 18 or a salt thereof (A-3) a straight chain having an average carbon number of 10 to 20 Or it has a branched chain alkyl group or alkenyl group and has an average of 0.5
To 8 mol of ethylene oxide-added alkyl ether sulfuric acid or salt thereof (A-4) average carbon number 10 to 20, preferably 12 to
Alkyl sulfuric acid having 18 alkyl groups or a salt thereof (A-5) Linear alkylbenzenesulfonic acid having an alkyl group having an average carbon number of 8 to 16 or a salt thereof As a counter ion in the above anionic surfactant, sodium or Alkali metal salts such as potassium are suitable.

Examples of the nonionic surfactant as the component (B) include the following. (B-1) Fatty acid ester type nonionic surfactant represented by Chemical formula 4 (general formula III)

[0011]

[Chemical 4] (R ₁ CO: C 6-22, preferably C 10
18 saturated or unsaturated fatty acid residues, which may be linear or branched R ₂ : C 2-4, ethylene oxide alone or in combination with ethylene oxide and propylene oxide Preferably added to form OR ₂ R ₃ : an alkyl group having 1 to 4 carbon atoms, preferably 1 carbon atom
~ 2 alkyl group n: represents the average number of moles of addition of OR ₂ , and is a number of 5 to 30, preferably 5 to 20).

This fatty acid ester type nonionic surfactant is structurally an alkyl ether of an alkylene oxide adduct of a fatty acid, and is obtained by a two-step method in which an alkylene oxide is added to a fatty acid by a conventional method and then an alkyl ether is formed. However, trivalent aluminum (A
l) ions, gallium (Ga) ions, indium (I
n) ion, thallium (Tl) ion, cobalt (C
o) ion, scandium (Sc) ion, lanthanum
The fatty acid alkyl ester R ₁ COOR ₃ and the alkylene oxide are reacted in the presence of a catalyst composed of magnesium oxide to which one or more metal ions selected from (La) ions and divalent manganese (Mn) ions are added. 1
Those manufactured by the step method are also preferable (Japanese Patent Application No. 3-6).
3904).

(B-2) An alcohol ethoxylate obtained by adding 5 to 20 mol of ethylene oxide on average to an alcohol having an average of 10 to 20 carbon atoms. (B-3) Propylene oxide and ethylene oxide are added in an average of 5 to 5 in an alcohol having an average of 10 to 20 carbon atoms.
Alcohol ethoxylate added with 20 mol. (B-4) Nonylphenol ethoxylate obtained by adding ethylene oxide to nonylphenol in an average of 5 to 20 moles (B-5) Fatty acid alkanolamide (B-6) Alkylamine oxide (B-7) embedded image (Formula IV) The sugar fatty acid ester-based surfactant represented by

[0014]

[Chemical 5] (R ₁ : a straight-chain or branched alkyl or alkenyl group having 5 to 17 carbon atoms R ₂ : a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

(B-8) Alkyl glycoside represented by the following formula 6 (general formula V)

Embedded image RO (R′O) y (Z) x (V) (Z: a residue derived from a reducing sugar having 5 to 6 carbon atoms R: an alkyl group, an alkenyl group, an alkylphenyl group,
A hydroxyalkyl group, a hydroxyalkylphenyl group or a mixture thereof, wherein the alkyl group or the alkenyl group has 8 to 20 carbon atoms R ': an alkylene group having 2 to 4 carbon atoms y: 0-30 x: 1.0 ~ 1.42)

Examples of the sugar residue Z include monosaccharides such as glucose, galactose, xylose, mannose, lyxose and arabinose, and polysaccharides such as maltose, xylopyose, lactose and sucrose. The weight ratio of the component (A) and the component (B) is (A) / (B) = 95/5.
The detergency can be improved by blending in the range of 20/80, preferably 90/10 to 50/50. Also,
The component (A) and the component (B) can be added to the detergent composition in a total amount of 10 to 50% by weight, preferably 15 to 35% by weight. If the content is less than 10% by weight, satisfactory cleaning performance cannot be obtained, and if it is more than 50% by weight, the rinsability becomes poor.

The hydroxyiminodisuccinate represented by the chemical formula 7 of the component (C) has an effect as a chelate builder that traps calcium ions, which is a hardness component in the washing liquid. As counter ions, alkali metal salts such as sodium and potassium are generally used. Hydroxyiminodisuccinate can improve the detergency most in the case of the completely neutralized tetra-alkali metal salt, but even the partially neutralized one shows good detergency.

[0018]

[Chemical 7]

The component (C), hydroxyiminodisuccinate, is contained in the detergent composition in an amount of 1 to 50% by weight, preferably 5 to 2%.
0 wt% can be blended. The detergent composition of the present invention comprises, in addition to the above essential components (A), (B) and (C), if necessary, other surfactants such as amphoteric surfactants and cationic surfactants, and alkalis. A builder, a builder such as a calcium ion-trapping builder, an enzyme, a bleaching agent, or other additives may be added.

The detergent composition of the present invention can be obtained by granulating each of the above 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 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. It can also be produced by adding an unneutralized product of a surfactant to a polymer such as an alkali builder or zeolite for neutralization, or by directly granulating a salt of the surfactant. Components such as enzymes may be powder blended with a granular detergent.

It is preferable that the hydroxyiminodisuccinate is powdered and then powder-mixed after the above-mentioned crushing and granulation, but it is mixed as a liquid as a part of the detergent component in the slurry before spray drying. May be. Moreover, 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 hydroxyiminodisuccinate as the component (c) is used. May be added. Of course, the high bulk density granular detergent particles obtained after the completion of the stirring granulation include 3-hydroxy- of the component (c).
The 2,2′-aminosuccinate may be powder-mixed.

[0022]

According to the present invention, (A) α-sulfofatty acid alkyl ester and its salt, α-olefin sulfonic acid and its salt, alkyl ether sulfuric acid and its salt, alkyl sulfuric acid and its salt, straight chain alkylbenzene sulfonic acid High bulk density granules by blending a surfactant component prepared by mixing anionic surfactant (B) nonionic surfactant selected from the following and a salt thereof in a specific ratio and (C) builder component of hydroxyiminodisuccinate. By using the detergent composition, excellent cleaning performance can be obtained.

[0023]

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 for evaluating detergency (i) Preparation of artificial dirt Clay containing crystalline minerals such as kaolinite and vermiculite dried at 200 ° C for 30 hours was used as inorganic dirt. 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.

[0024]

[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.

[0027]

[Equation 1] Here, R is the reflectance (%) measured by an ELREPHO reflectometer manufactured by KARL TWICE. Also,
The detergency was evaluated with an average value of 10 pieces of artificial soil cloths tested.

Example 1 Each of the detergent compositions shown in Tables 4 and 5 below, except for the nonionic surfactant, a part of zeolite, a part of sodium carbonate, an enzyme and a fragrance, was used to obtain a solid content of 60%. A detergent slurry was prepared and adjusted to an appropriate viscosity with tap water. This detergent slurry was dried at a hot air temperature of 270 ° C. to a water content of 5% using a countercurrent spray drying tower to obtain a spray dried product. This spray-dried product had a good average particle size of 385 μm, a bulk density of 0.35 g / cc, and an angle of repose of 45 degrees, and was also good in fluidity. Then, the dried product, nonionic surfactant and water were continuously kneaded (KRC Kneader # 2 manufactured by Kurimoto Iron Works Co., Ltd.).
It was introduced into a mold and a dense and uniform kneaded product was obtained. 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 made into a cylindrical pellet of about 5 mmφ × 10 mm. The pellets were introduced into a crusher (speed mill ND-10 type, Okada Seiko Co., Ltd.) together with double the amount (weight ratio) of cooling air at 15 ° C. The crusher has a cutter with a length of 15 cm in 4 cross stages,
Rotating at 3000 rpm, the screen is made of punching metal of 360 degrees, and has a hole diameter of 20 mmφ and an aperture ratio of 20%. The particles that passed through the screen were mixed with 6.5% by weight of finely divided sodium carbonate and 2% by weight of A-type zeolite powder, and an enzyme and a fragrance were added thereto, and the results are shown in Tables 4 and 5 below. It has a different composition and a bulk density of 0.95 g
Detergency was evaluated using the detergent composition of the present invention of / cc, and the results are shown in Tables 4 and 5.

The meanings and details of the abbreviations in Tables 4 and 5 are as follows. In addition, EOp shows the average addition mole number of ethylene oxide, and POp shows the average addition mole number of propylene oxide.

(1) Anionic surfactant α-SF: α-sulfofatty acid (C ₁₄ -C ₁₆ ) methyl ester sodium AOS: C ₁₄ -C ₁₈ sodium α-olefinsulfonate AES: alkyl (C ₁₂ / C ₁₈ = 1/1) ether (E
Op = 3) Sodium sulfate AS: alkyl (C ₁₂ ~C ₁₄₎ Sodium sulfate LAS: linear alkyl (C ₁₀ ~C ₁₄₎ sodium benzenesulfonate

(2) Nonionic surfactant FEE: C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) ₁₅ OCH
₃ AE: C ₁₂ alcohol ethoxylate (EOp = 15) NFE: nonylphenol ethoxylate (EOp = 1)
5)

(3) HIDS: tetrasodium hydroxyiminodisuccinate (added as a 38% aqueous solution)

(4) Other additives Zeolite: A-type zeolite (average particle size: 1.2 μm) PEG: Polyethylene glycol (molecular weight: 500 to 20)
00) Na sulfite: Sodium sulfite Common component: 2% by weight potassium carbonate 22% by weight sodium carbonate Enzyme * ¹ 1% by weight Perfume A * ² 0.2% by weight Sodium sulfate balance * 1) Enzyme: Protease (trade name "Sabinase 6.
0T ") / lipase (trade name Lipolase 100T) = 1
/ 1 mixture * 2) Fragrance A: Compounded fragrance having a composition containing the components shown in Tables 2 and 3 Fluorescent agent: 4,4-bis (sulfostyryl) biphenyl 2
Sodium / 4,4-bis [(4-toluidino-6-morpholino-1,3,5-triazin-2yl) amino]
Stilbene-2,2-disulfonic acid disodium = 1 /
Mixture of 1 (Chino Pearl CBS / Whitex SKC
= 1/1 mixture, both are trade names)

[0034]

[Table 2]Table 2: Fragrance composition Compounding amount Component (Part by weight) 3,7-Dimethyl-1,6-octadien-3-ol 80 3,7-Dimethyl-1,6-octadien-3-yl-acetate 60 3,7-Dimethyl-6-octen-1-ol 40 β- Phenylethyl alcohol 50 p-tert-butyl-α-methylhydrocinnamic aldehyde 70 α-methyl-p-isopropylphenylpropionaldehyde 60 α-n-amylcinnamic aldehyde 20 α-n-hexylcinnamic aldehyde 60 7-acetyl -1,1,3,4,4,6-hexamethyl 80 tetrahydronaphthalene 3- (5,5,6-trimethyl-norbornan-2-yl) 20 cyclohexan-1-ol bertfix 30 2-ethyl-4- ( 2,2,3-Trimethyl-3-cyclopentene 10-1-yl) -2-butan-1-ol 10% α, α-di Methyl-p-ethylhydrocinnamic aldehyde 40 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde 10 cis-3-hexenol 10 2-trans-3,7-dimethyl-2,6-octadien-1-ol 30 n-decyl aldehyde 5

[0035]

[Table 3]Table 3: Fragrance composition (continued from Table 2) Compounding amount Component (Part by weight) 10-Undecen-1-al 5 Methylnonylacetaldehyde 5 4- (4-Hydroxy-4-methylpentyl) -3-cyclohexene 30-1-Carboxaldehyde Naphthalene-2-acetyl-1,2,3,4,6,6 7,8 30-Octahydro-2,3,8,8-tetramethyl 5- (2-methylene-6,6-dimethyl-cyclohexyl) 50-4-penten-3-one 2-methoxy-4-propenylphenol 20 Allylcyclohexanepropionate 10 6,7-Dihydro-1,1,2,3,3-pentamethyl 5-4 (5H) -indanone p-propenylphenylmethyl ether 5 Methyl-2-aminobenzoate 5 Lemon oil 30 Orange oil 20 Lavandin oil 20 Patchouli oil 10 3,7-Dimethyl-2,6-octadienal 30Methyl dihydrojasmonate 50

[0036]

[Table 4] Example Sample No. 1 2 3 4 5 6 7 8 9 10 11 12 Composition (wt%) (A) Anion: α-SF 20 − − − − 20 20 20 15 25 20 20 AOS − 20 − − − − − − − − 2 − AES − − 20 − − − − − − − 3 − AS − − − 20 − − − − − − − 3 LAS − − − − 20 − − − − − − 2 (B) Nonion : FEE 55 5 5 5 − − 5 15 5 5 5 AE − − − − − 5 − − − − − − NFE − − − − − − 5 − − − − − (C) HIDS 10 10 10 10 10 10 10 20 10 10 10 10 Other additives: Zeolite 15 15 15 15 15 15 15 10 15 15 15 15 Polyacrylate 1-2 − 1 − − − − − − − PEG − − 1 − − 2 − − − − − 2-− Sulfurous acid Na − − 0.5 − 0.5 − − − − − − − Common component balance compounding ratio: (A) / (B) [wt ratio] 80/80/80/80/80/80/80 / 80/50/83/83/83/20 20 20 20 20 20 20 20 50 17 17 17 (A) + (B) [ wt%] 25 25 25 25 25 25 25 25 30 30 30 30 Detergency (%) 88 87 87 86 85 89 87 90 86 87 88 87

[0037]

[Table 5]

Claims (1)

[Claims] 1. The following components (A), (B) and (C) in a weight ratio of (A) / (B) = 95/5 to 20/80 in the range of (A) and (B) components. 10 to 50 in total
A high bulk density granular detergent composition comprising 1% to 50% by weight of component (C). (A) Anionic surfactant selected from α-sulfofatty acid alkyl ester and its salt, α-olefin sulfonic acid and its salt, alkyl ether sulfuric acid and its salt, alkyl sulfuric acid and its salt, linear alkylbenzene sulfonic acid and its salt (B) Nonionic surfactant (C) Hydroxyiminodisuccinate represented by Formula 1 (general formula I):