JPH064872B2 - Manufacturing method of powder detergent for clothing - Google Patents

Description

The present invention relates to a method for producing a heavy-duty powder detergent for clothing. More specifically, it is possible to improve the caking resistance of the obtained detergent by later mixing the spray-dried detergent dough with sodium carbonate whose apparent specific gravity, average particle size and particle size distribution are specified. The present invention relates to a method for producing a powdered detergent for clothes, which prevents fractionation or separation of sodium carbonate and detergent cloth.

In general, heavy-duty powder detergents for clothing include various surfactants,
Organic and inorganic builder ingredients, anti-soil redistant, fluorescent dye,
A predetermined amount of a raw material selected from a group of pigments and other heat-stable additives is weighed, once uniformly mixed with a slurry, spray-dried, and further, a fragrance, an enzyme, a bleaching agent, and a particle surface modification. It is commercialized by adding and mixing agents and others.

As an important consideration item for such a powder detergent, in addition to the performance related to washing such as detergency, the powder characteristics of the product, for example, particle size, specific gravity, caking resistance, etc. are extremely high in terms of usability for consumers. This is important, and a balanced improvement in performance between the two is desired.

However, since the powder detergent is a powder system composed of multiple components, it is not easy to obtain a product that maintains both the cleaning performance and the powder characteristics at a high level. Still not enough. In particular, the recent technology establishment for non-phosphorus and low-phosphorus detergents is extremely insufficient, and among them, improvement of caking resistance is a major technical issue.

Under such circumstances, an object of the present invention is to provide a new production technique for improving the caking resistance of a powder detergent without lowering the detergency.

The present inventors have made various studies on the cause of the caking property of the powder detergent, but sodium carbonate (soda ash) having a specific powder characteristic which has not been industrially manufactured in the past.
The present invention was found to obtain a uniform detergent composition having significantly improved caking resistance and the like of a powder detergent obtained by producing a detergent composition by after-blending with a spray-dried detergent fabric. It is a thing.

According to the production method of the present invention, caking of the obtained detergent powder, that is, after the product is produced, the phenomenon of the powder being solidified during the period before the consumer is used is prevented, and further, when the consumer uses it. Since the sodium carbonate particles and the detergent dough are unlikely to be classified, the consumer can easily take them out of the packaging container, and since the composition is always constant, it is possible to provide a detergent that guarantees stable cleaning performance.

Here, "classification" means that the distribution state of the sodium carbonate particles and the detergent dough particles, which are the constituents thereof, is not uniform in the detergent composition. Hereinafter, this term is used in the same meaning.

In the present invention, the amount of sodium carbonate contained in the spray-dried detergent fabric is 10% by weight or less.
5 to 95 parts by weight of sodium carbonate having an apparent specific gravity of 0.25 to 0.7 g / ml, an average particle diameter of 250 μm or more and 600 μm or less, and a fine powder town having a particle diameter of 125 μm or less is 20 wt% or less. The powder detergent for clothes is manufactured by mixing in the range of 40 parts by weight. The powder detergent thus obtained is excellent in caking resistance, and furthermore, the classification of sodium carbonate and detergent dough during the production process, the transportation process and the use by the consumer is significantly suppressed.

Sodium carbonate having a specific apparent specific gravity, average particle size and particle size distribution according to the present invention is, for example, a method in which light ash is granulated in a fluidized drying granulator, dried and then classified by a sieve. Alternatively, the light ash can be easily obtained by a method such as a method in which the light ash is left under moisture absorption, an appropriately solidified one is crushed, dried, and then classified with a sieve.

On the other hand, when using sodium carbonate such as heavy ash, light ash, etc. that has been industrially produced and used for detergent manufacture from the past, improvement in caking resistance can be seen, but classification of sodium carbonate and detergent dough It does not occur and cannot be put to practical use.

Further, it is effective to increase the amount of the alkaline agent added in order to improve the detergency of the detergent, and it is economically and economically preferable, but in that case, the usefulness of the present invention becomes particularly high.

The detergent composition for clothing in the present invention may contain the following detergent components, but these are not particularly limited and may be blended according to the purpose. Further, among these components, any component may be blended with the spray-dried dough, or the raw materials may be used as they are, or may be granulated or coated to be mixed with the spray-dried dough.

[1] Surfactant 1) Linear or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 2) Linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 20 And has an average of 0.5 to 8 mol of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 on a day or ethylene oxide / butylene oxide = 0.
Alkyl or alkenyl ether sulfate added at a ratio of 1 / 9.9 to 9.9 / 0.1 3) Alkyl or alkenyl sulfate having an alkyl group or an alkenyl group having an average carbon number of 10 to 20 4) An average of 10 to 20 carbon atoms is 1 Olefin sulfonate having a molecule 5) Alkane sulfonate having an average of 10 to 20 carbon atoms in a molecule 6) Saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in a molecule 7) It has an alkyl group or an alkenyl group having an average carbon number of 10 to 20, and has an average of 0.5 to 8 mol of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 per molecule. Or ethylene oxide / butylene oxide = 0.1 / 9.9 to 9.9 / 0.1
Alkyl or alkenyl ether carboxylic acid salt added in the ratio of 8) α-sulfo fatty acid salt or ester represented by the following formula Here, as the counterion of the anionic surfactant, alkali metal ions such as sodium and potassium, calcium,
Examples thereof include alkaline earth metal ions such as magnesium, ammonium ions, and alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). .

9) Amino acid type surfactant represented by the following general formula (Here, R ₁ ′ is an alkyl or alkenyl group having 8 to 24 carbon atoms, R ₂ ′ is hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₃ ′ is an amino acid residue, and X is an alkali metal or an alkali. Indicates an earth metal ion.) (R ₁ ′, R ₂ ′ and X are as described above. N is an integer of 1 to 5.) (R ₁ ′ is as described above. M is an integer of 1 to 8.) (R ₁ ′, R ₃ ′ and X are as described above. R ₄ represents hydrogen or an alkyl or hydroxyalkyl group having 1 to 2 carbon atoms.) (R ₂ ′, R ₃ ′ and X are as described above. R ₅ has 6 to 6 carbon atoms.
28 is a β-hydroxyalkyl or β-hydroxyalkenyl group. ) (R ₃ ′, R ₅ and X are as described above.) 10) Phosphate Ester Activator (R 'is an alkyl group having 8 to 24 carbon atoms or an alkenyl group, n' + m '= 3, n' = 1 to 2) (R'is n ″ + m ″ = 3, n ″ = 1 to 3 as described above) (R ', n ", m" are as described above, M'is Na, K, Ca) 11) Sulfonic acid type amphoteric surfactant represented by the following general formula (Here, R ₁₁ is an alkyl or alkenyl group having 8 to 24 carbon atoms, R ₁₂ is an alkyl group having 1 to 4 carbon atoms, R ₁₃ is an alkyl group having 1 to 5 carbon atoms, and R ₁₄ is an alkyl group having 1 to 4 carbon atoms. Indicates an alkyl or hydroxyalkyl group.) (Here, R ₁₁ and R ₁₄ are as described above, and R ₁₅ and R ₁₆ are each an alkyl or alkenyl group having 8 to 24 carbon atoms or 1 to 5 carbon atoms.) (Here, R ₁₁ and R ₁₄ are as described above. N1 is an integer of 1 to 20.) 12) Betaine-type amphoteric activator represented by the following general formula. (Here, R ₂₁ is an alkyl or alkenyl having 8 to 24 carbon atoms or a β-hydroxyalkyl or β-hydroxyalkenyl group, R ₂₂ is an alkyl group having 1 to 4 carbon atoms, and R ₂₃ is an alkyl group having 1 to 6 carbon atoms or Indicates a hydroxyalkyl group.) (Here, R ₂₁ and R ₂₃ are as described above. N2 is an integer of 1 to 20.) (Here, R ₂₁ and R ₂₃ are as described above. R ₂₄ has 2 to 2 carbon atoms.
5 represents a carboxyalkyl or hydroxyalkyl group. ) 13) Polyoxyethylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol of ethylene oxide added 14) Having an alkyl group having an average carbon number of 6 to 12 , 1-2
Polyoxyethylene alkylphenyl ether having 0 mol of ethylene oxide added 15) Polyoxypropylene alkyl or alkenyl ether having an alkyl or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol of propylene oxide added 16) Polyoxybutylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol of butylene oxide added 17) Having an alkyl group or alkenyl group having an average carbon number of 10 to 20 However, a total of 1 to 30 mol of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added nonionic activator (ratio of ethylene oxide to propylene oxide or butylene oxide is 0.1 / 9.9 to 9.9 / 0.1) 18 ) Below Higher fatty acid alkanolamides or alkylene oxide adducts thereof represented by the general formula [Wherein R ₁₁ ′ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R ₁₂ ′ is H or CH ₃ , n ₃ is an integer of 1 to 3, m ₃ is an integer of 0 to 3] Is. ] 19) Sucrose fatty acid ester consisting of fatty acid having an average carbon number of 10 to 20 and sucrose 20) Fatty acid glycerin monoester consisting of fatty acid having an average carbon number of 10 to 20 and glycerin 21) Alkylamine oxide represented by the following general formula 22) Cationic surfactant represented by the following general formula (Here, at least one of R ₁ ′, R ₂ ′, R ₃ ′ and R ₄ ′ is an alkyl or alkenyl group having 8 to 24 carbon atoms, and many are alkyl groups having 1 to 5 carbon atoms. Represents halogen.) (Here, R ₁ ′, R ₂ ′, R ₃ ′ and X ′ are as described above.) (Here, R ₁ ′, R ₂ ′ and X ′ are as described above. R ₅ ′ is an alkylene group having 2 to 3 carbon atoms, and n ₄ is an integer of 1 to 20.) 1 of the above surfactants It is preferable that the composition contains 10% by weight or more of one or more species.

[2] Divalent metal ion scavenger One of the following various alkali metal salts and alkanolamine salts
It is also possible to contain 0 to 50% by weight of one or more builder components.

1) Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytate.

2) ethane-1,1 difuponic acid, ethane-1,2 triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1, Phosphonates such as 2 dicarboxylic-1,2-diphosphonic acid and methanehydroxyphosphonic acid.

3) Phosphonocarboxylic acid salts such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid.

4) Amino acid salts such as aspartic acid and glutamic acid.

5) Aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate and diethylenetriaminepentaacetate.

6) Polyacrylic acid, polyaconic acid, polyitacoic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer Combined, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-ethylene crosslink copolymer, maleic anhydride-vinyl acetate copolymer , Maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic acid ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride, -isoprene copolymer,
Poly-β-derived from maleic anhydride and carbon monoxide
Ketocarboxylic acid, itaconic acid-ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, malonic acid-methylene copolymer, metaconic acid-fumaric acid Acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, 1-butene-2,3,4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, quaternary ammonium group Of Polyester Polyaldehyde Carboxylic Acid Having Epoxysuccinic Acid
Isomers, poly [N, N-bis (carboxymethyl) acrylamide], poly (oxycarboxylic acid), starch succinic acid or maleic acid or terephthalic acid ester, starch phosphate ester, dicarboxy starch,
Polyelectrolytes such as dicarboxymethyl starch, cellulose and succinate.

7) polyethylene glycol, polyvinyl alcohol,
Non-dissociated polymers such as polyvinylpyrrolidone and cold water soluble urethane alcohol.

8) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-2,2, Carboxymethylated products such as 5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, sucrose, lactose and raffinose, carboxymethylated pentaerythritol, carboxymethylated glyconic acid, polyhydric alcohols or sugars and maleic anhydride. Alternatively, a condensate of succinic anhydride, a condensate of oxycarboxylic acid and maleic anhydride or succinic anhydride, a benzene polycarboxylic acid represented by mellitic acid, ethane-1,1,2,2-tetracarboxylic acid, Ethene
1,1,2,2-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, propane-1,2,3-tricarboxylic acid, butane-1,4-dicarboxylic acid, oxalic acid, sulfosuccinic acid acid,
Decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulfoitaconic acid, malic acid, oxydisuccinic acid,
Organic acid salts such as gluconic acid, CMOS and Builder M.

9) Aluminosilicate No. 1 Crystalline aluminosilicate represented by the following formula X ′ (M ₂ ′ O or M ″ O) · Al ₂ O ₃ · y ′ (SiO ₂ ) · w ′ (H ₂
O) (In the formula, M ′ is an alkali metal atom, M ″ is an alkaline earth metal atom that can be exchanged with calcium, and x ′, y ′, and w ′ represent the number of moles of each component, and generally 0.7 ≦ x ′ ≦
1.5, 0.8 ≦ y ′ ≦ 6, w ′ are arbitrary integers. ) No. 2 As the detergent builder, those represented by the following general formula are particularly preferable.

Na ₂ O ・ Al ₂ O ₃・ nSiO ₂・ wH ₂ O (where n is a number from 1.8 to 3.0 and w is a number from 1 to 6) No. 3 Amorphous aluminosilicate represented by the following formula x (M ₂ O) ・ Al ₂ O ₃・ y (SiO ₂ ) ・ w (H ₂ O) (In the formula, M represents a sodium and / or potassium atom, and x, y, w are within the following fine value ranges. It represents the number of moles of each component.

0.7 ≦ x ≦ 1.2 1.6 ≦ y ≦ 2.8 w is any integer including 0) No.4 Amorphous aluminosilicate x (M ₂ O) ・ Al ₂ O ₃・ Y (SiO ₂ ) ・Z (P ₂ O ₅ ) ω (H ₂ O) (In the formula, M represents Na or K, and X, Y, Z, and ω represent the moles of the respective components within the range of the following numerical values.

0.20 ≤ X ≤ 1.10 0.20 ≤ Y ≤ 4.00 0.001 ≤ Z ≤ 0.80 ω: any positive number including 0) [3] Alkaline agent or inorganic electrolyte Further, as alkali agents or inorganic electrolytes, various alkali metal salts of One or two or more kinds can be contained in the composition in an amount of 1 to 50% by weight, preferably 5 to 30% by weight. Silicate and sulfate. Also, as an organic alkaline agent, triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine, etc.

[4] Anti-soil redeposition agent Further, as a anti-soil redeposition agent, one or more of the following compounds may be contained in the composition in an amount of 0.1 to 5%. Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc.

[5] Bleaching agent Sodium percarbonate, sodium perborate, sodium hydrogen peroxide adduct, sodium chloride hydrogen peroxide adduct, etc.

[6] Enzymes (enzymes that perform the original enzymatic action during the washing step.) Categorizing from the reactivity of enzymes, hydrolases, hydrolases, oxidoreductases, desmolases, transferases and isomerases can be mentioned. However, the slip can be applied to the present invention. Particularly preferred are the hydrolases, including proteases, esterases, carbohydrases and nucleases.

Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promerin,
Carboxypeptidases A and B, aminopeptidases, aspergillopeptidases A and B.

Specific examples of esterases include gastrit lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases and phosphotase.

Carbohydrases include cellulases, lartases, satucarases, amylases, pectinases, lysozymes, α-
Glycosidases and β-glycosidases are included.

[7] Bluing agent Various bluing agents can be added as needed. For example, the following structure is recommended: (Wherein D represents a blue to purple monoazo, disazo or anthraquinone dye residue, and X and Y may be substituted with a hydroxyl group, an amino group, a hydroxyl group, a sulfonic acid group, a carboxylic acid group or an alkoxy group. An aliphatic amino group, a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, a lower alkyl group, or an aromatic amino group which may be substituted with a lower alkoxy group or a cycloaliphatic amino group.
R is a hydrogen atom or a lower alkyl group. However, it excludes the case where R represents a hydrogen atom and X and Y simultaneously represent a hydroxyl group or an alkanolamino group, and the case where either one of X and Y is a hydroxyl group and the other is an alkanolamino group. n represents an integer of 2 or more. ) (In the formula, D represents a blue to purple azo or anthraquinone dye residue, and X and Y represent the same or different alkanolamino residues or hydroxyl groups.) [8] Anti-caking agent paratoluenesulfonate, Xylene sulfonate, acetate, sulfosuccinate, tal, fine powder silica, clay,
Calcium-silicate (eg, Johns Manvill Microcell), magnesium oxide and the like.

[9] Antioxidant tert-butyl hydroxytoluene, 4,4'-butylidene bis- (6-tert-butyl-3-methylphenol), 2,
2'-butylidene bis-(-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1'-bis- (4-hydroxyphenyl) cyclohexane Antioxidant such as.

[10] Fluorescent dye 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -bisphenyl salt, 2- (styrylphenyl) naphtho Thiazole derivative, 4,4'-bis (triazole-2
One or two or more of -yl) stilbene derivative and bis (triazinylamino) stilbene disulfonic acid derivative can be contained in the composition in an amount of 0 to 1% by weight.

[11] Photoactivated bleaching agent One or two of sulfonated aluminum phthalocyanine and sulfonated zinc phthalocyanine is added to the composition in an amount of 0 to 0.2.
It may be contained in a weight percentage.

[12] Fragrance A fragrance may be added to increase the commercial value.

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

Examples 1 to 4 and Comparative Examples 1 to 4 Detergents having various formulations shown in Table 1 were manufactured.

Here, the water content of the spray-dried dough was adjusted to 8% in Examples 1 to 3 and Comparative Examples 1 to 3 and 5% in Example 4 and Comparative Example 4. The specific gravity of the dough was in the range of 0.28 g / ml ± 0.01 g / ml, and the average particle size of the dough was in the range of 560 ± 60 μm. The post-added invention was prepared by the following method.

<Preparation method of the product of the present invention> 500 g of sodium carbonate (light ash) obtained by dry-decomposing sodium bicarbonate was put into a fluidized-bed granulator (Uniglat, Glatt, Binzen, West Germany), and air was used at room temperature. While flowing the above light ash, water was sprayed to perform granulation. Subsequently, the temperature of the flowing air was raised to 130 ° C., and the air was dried for 30 minutes. Fine powder was removed from the sodium carbonate so granulated with a sieve having a mesh size of 62 μm (250 mesh) to obtain a product of the present invention.

Table 2 shows the physical properties of the post-added product of the present invention and heavy ash and light ash of sodium carbonate. Heavy ash and light ash meet the JIS k 1201 standard. The apparent specific gravity was measured by the method of JIS K-3362.

1) Caking test The detergents of the above Examples and Comparative Examples were packed in 2.62 kg each in a carton for detergent, which was not subjected to moisture-proof treatment.
It was left standing in a room prepared at 80 ° C and 80% RH. After leaving it for a certain period of time, the carton was gently opened, and the weight ratio of the detergent solidified to 5 mm or more was determined through a sieve having an opening of 5 mm to compare the ease of caking. The results are shown in Table 3.

As can be easily seen from Table 3, it can be seen that the anti-caking properties of Examples 1 to 3 are relatively improved as compared with those of Comparative Examples 1 to 3. Also, in the comparison between Example 4 and Comparative Example 4 which are non-phosphorus detergents, it can be seen that the present invention exhibits good caking resistance.

2) Classification test 2.65 kg of each of the detergents of Examples 2 and 3 and Comparative Examples 1 to 3
In a detergent carton. The carton is tilted from the specified swing outlet at the top of the carton to take out the amount of detergent (40 g) used once, according to the actual usage conditions of the consumer. afterwards,
Erect the carton. This operation is repeated to divide all the detergent in the carton into 66 sections. Next, the sodium carbonate content of each sample was analyzed and determined, and the degree of classification was compared from the variation. The results are shown in Table 4.

As can be seen from Table 4, when the variation coefficients of the inventive products of Examples 2 and 3 and those of Comparative Examples 1 to 3 are compared, the value of the inventive product is obviously small, which shows that the variation due to classification is small. ing.

Claims (2)

[Claims] 1. A garment characterized by mixing soda carbonate having the following powder characteristics in a ratio of 40 to 5 parts by weight to the former 60 to 95 parts by weight with respect to a spray-dried powder detergent cloth. Powder detergent manufacturing method. i) Apparent specific gravity 0.25 g / ml to 0.7 g / ml ii) Average particle size 250 μm to 600 μm iii) Particle size distribution 125 μm or less is 20% by weight or less 2. The method according to claim 1, wherein the content of sodium carbonate in the powder detergent dough is 10% by weight or less.