JPS6166799A - Modification of granular detergent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention improves the fluidity and pressure solidification of detergent particles dried by spray drying and mixed with a liquid fragrance by using a small amount of aluminosilicate fine powder. It is related to the method of improvement by.

[Conventional technology and problems]

Powdered detergents conventionally used at home must have good productivity and provide a comfortable feeling for consumers. A comfortable range of use means that the powder does not easily clump, has good fluidity, does not generate dust, and has a fragrance. Therefore, it is common practice to mix a fragrance into a powder produced by a spray drying method.

However, since fragrances are liquids, powdered detergents mixed with them tend to have reduced fluidity and tend to solidify under pressure, and there has been a need for technology to improve this.

Japanese Patent Publication No. 50-24306 (Special Publication No. 53-13203)
discloses that metal soap fine powder is attached to the surface of detergent particles using perfume as a binder, but as is well known, metal soap does not contribute in any way to cleaning, and is rather one of the dirt components. , not recommended for use in detergents.

Japanese Patent Publication No. 53-91483 (Special Publication No. 59-21360)
discloses that fine aluminosilicate powder and detergent particles are mixed and brought into frictional contact to cause the fine aluminosilicate powder to adhere to the entire surface of the detergent particles. Mixing is carried out under conditions where the granular detergent is sufficiently dried so that its surface no longer exhibits stickiness, and the use of binders, including water, is not preferred. The adhesion of aluminosilicates is explained by electrostatic forces generated by friction.

However, ordinary powder detergents contain a few percent (generally 2 to 10%).
), and because of this, the surface electrical resistance of the particles is small, and the amount of static electricity generated by friction is small, and the potential of the static electricity that is generated drops rapidly in 0.1 seconds or less. . Therefore, when the aluminosilicate adheres to the entire surface of the detergent particles when the two are mixed, a considerable proportion of the aluminosilicate particles peel off when used by consumers, generating fine powder, which impairs the comfort of use.

[Means for solving problems]

Therefore, the present inventors have found that even if a liquid fragrance is added after spray drying, it still has good fluidity and is difficult to solidify under pressure.
As a result of extensive research into a method for producing powder detergent that does not easily generate dust, the present invention was achieved.

That is, the present invention is characterized in that it contains a small amount (of at least one surfactant and at least one inorganic or organic builder, is dried by spray drying, 1. is mixed with a liquid perfume, or is mixed with the perfume at the same time). It is characterized in that 0.5 to 5 parts by weight of aluminosilicate fine powder having an average particle size of 7 μm or less is mixed with 100 parts by weight of detergent particles, and the aluminosilicate fine powder is attached to the surface of the detergent particles. The present invention provides a method for modifying granular detergent.

The present invention applies spray-dried detergent particles to particles with an average particle size of 7.
It is characterized by mixing aluminosilicate fine powder with a particle diameter of μm or less and attaching it to the surface of the detergent particles. It is more effective to spray a liquid perfume onto the spray-dried detergent particles in a fluidized state to uniformly adhere the perfume to the particles. In order to make the particles in a fluid state, the powdered detergent can be allowed to fall freely through a hopper or belt conveyor, the detergent particles can be lifted up and dropped using a drum-type agitator equipped with an internal baffle, or the detergent particles can be made to flow through fluidized bed granulation. Any method may be used, such as fluidizing with a machine or stirring with a vertical granulator. Known equipment such as a rotary mixer or a drum type stirrer can be used to deposit the aluminosilicate fine powder.

The amount of perfume is generally added between 0.05 and 1%.

It is desirable that the average particle size of the aluminosilicate is 7 μm or less. If the size is larger than that, the adhesion of the detergent particles to the surface becomes insufficient, making it difficult to exhibit the effect of improving fluidity.

In addition, when using aluminosilicate fine powder alone, 1. Because the fluidity is poor and the apparent specific gravity is small, making it difficult to transport and store, if the granules are made into granules using a binder such as carboxymethyl cellulose, they are pre-pulverized into secondary agglomerates using a crusher. It is desirable to mix the materials after crushing them.

The amount of aluminosilicate to be mixed is suitably 0.5 to 5 parts by weight per 100 parts by weight of spray-dried detergent particles mixed with perfume. If the amount is less than 0.5 parts by weight, no improvement in fluidity and pressure solidification will be observed. Further, even if more than 5 parts by weight is mixed, dust tends to be generated and fluidity tends to deteriorate, which is not preferable.

Surfactants that can be used in the present invention include the following.

1) A straight or branched alkylbenzene sulfonate having an alkyl group with an average carbon number of 10 to 16 2) A straight or branched chain alkyl group or alkenyl group having an average of 10 to 20 carbon atoms, 1 molecule Average within 0.5-8
Mol of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide/propylene oxide = 0.1/9.9 to 9.9
Alkyl or alkenyl ether sulfate added in a ratio of 70.1 or in a ratio of ethylene oxide/butylene oxide = 0.1/9.9 to 9.910.13) Alkyl group or alkenyl having an average carbon number of 10 to 20 Alkyl or alkenyl sulfate having a group 4) Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule 5) Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule 6) An average of 10 Saturated or unsaturated fatty acid salt having ~24 carbon atoms in one molecule 7) Having an alkyl group or alkenyl group with an average of 10 to 20 carbon atoms, and an average of 0.5 to 8 moles of ethylene oxide or Propylene oxide or butylene oxide or ethylene oxide/propylene oxide = 0.1/9.9 to 9.910.1 ratio ethylene oxide/butylene oxide = 0
．． Alkyl or alkenyl ether carboxylic acid salt added in a ratio of 1/9.9 to 9.910.1 8) α-Sulfofatty acid salt or ester represented by the following formula R-C) IcO,Y SO,Z (formula Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, Z
is the counterion. R represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. ) 9) Amino acid type surfactant represented by the following general formula (where Rlo is an alkyl group or alkenyl group having 8 to 24 carbon atoms, R2' is hydrogen or an alkyl group having 1 to 2 carbon atoms, R, l represents an amino acid residue, and X represents an alkali metal or alkaline earth metal ion.) Na2R+'-CO-N(CHz), C
00X6゜ (R, ° + R2゛ and X are as described above. n is an integer from 1 to 5.) (R,' is as described above. m is an integer from 1 to 8.)
(R1"+R3" and X are as described above. R4 represents hydrogen or an alkyl or hydroxyalkyl group having 1 to 2 carbon atoms.) (R1', Ri' and -28 β-hydroxyalkyl or β-hydroxyalkenyl group) (R3', Rs and
Polyoxyethylene alkyl or alkenyl ether to which ~20 moles of ethylene oxide has been added 11) Having an alkyl group with an average carbon number of 6 to 12, 1 to 2
Polyoxyethylene alkylphenyl ether to which 0 mol of ethylene oxide has been added 12) Polyoxypropylene alkyl or alkenyl ether having an average carbon number of 10 to 20 alkyl or alkenyl groups and to which 1 to 20 mol of propylene oxide has been added 13 ) Polyoxybutylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 moles of butylene oxide is added 14) Having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and a nonionic surfactant with a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added (the ratio of ethylene oxide to propylene oxide or butylene oxide is 0.1/9.9 to 9 .910.1)1
5) Higher fatty acid alkanolamide or its alkylene oxide adduct R1 represented by the following general formula
2″ RI 2′ (in the formula, R1, ゛ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, [?, □” is H or C113, n: l is an integer of 1 to 3, l, is an integer from O to 3.

) 16) Sucrose fatty acid ester consisting of a fatty acid having an average carbon number of 10 to 20 and sucrose 17) Fatty acid glycerin heptanoester consisting of a fatty acid having an average carbon number of 10 to 20 and glycerin 18) Alkylamine oxide represented by the following general formula R54""R13"-N → 0 1?15" (in the formula, R13" is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R14', R55" is an alkyl group or alkenyl group having 1 to 3 carbon atoms.
is an alkyl group. ) 19) Hetain type amphoteric surfactant represented by the following general formula (where R111 is an alkyl or alkenyl group having 8 to 24 carbon atoms or a β-hydroxyalkyl or β-hydroxyalkenyl group, and R2□ is an alkyl or alkenyl group having 8 to 24 carbon atoms, and R2□ is an amphoteric surfactant having 1 to 4 carbon atoms) Alkyl group, R
ZI represents an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms. )■ (CzH40) n2H (Here, R□ and RZI are as described above. n2 is 1 to 20
indicates an integer. ) (Here, RZI and R2U are as described above. RI4 represents a carboxyalkyl or hydroxyalkyl group having 2 to 5 carbon atoms.) 20) Sulfonic acid type amphoteric surfactant R1+ represented by the following general formula (wherein R1+ is an alkyl or alkenyl group having 3 to 24 carbon atoms, R1□ is an alkyl group having 1 to 4 carbon atoms, RI3
represents an alkyl group having 1 to 5 carbon atoms, and RI4 represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. ) RI6 (Here, R11 and RI4 are as described above. RIS+RI
6 represents an alkyl or alkenyl group having 8 to 24 carbon atoms or L to 5 carbon atoms. ) (CZ H40') nl H (Here, R11 and R14 are as described above, and n is 1 to 2
Indicates an integer of 0. ) ゛21) Phosphate ester activator 11m1 Alkyl (or alkenyl) acidic phosphate ester (R″O) 1・-P-(011) ,・(R′ is an alkyl group having 8 to 24 carbon atoms, or alkenyl group, n'+ m
'=3. n"=1-2) 2 Alkyl (or alkenyl) phosphate ester (12"0)1...-P-(Oll) m'.(R' is as described above, n"0m'=3. n'=1 to 3) Il & L3 alkyl (or alkenyl) phosphate ester salt (R'+ n"+ Ill" is as described above, the gate is Na
, K.

Ca) 22) A cationic surfactant represented by the following general formula (wherein at least one of R1"+R2"+R3"+R4" is an alkyl or alkenyl group having 8 to 24 carbon atoms, and the others are carbon atoms represents an alkyl group of 1 to 5. Xo represents a halogen.) (Here, R1''+ R2''+ R3° and .R5" is an alkylene group having 2 to 3 carbon atoms, and n4 is 1 to 3.
Indicates an integer of 20. ) The content of surfactant is 10 to 70% by weight, preferably 2
It is 5 to 50% by weight.

Further, inorganic builders that can be used in the present invention include the following.

Alkaline salts such as soda carbonate, sodium sesquicarbonate, and sodium silicate, neutral salts such as mirabilite, phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, and phytate. Aluminum resilicate, which is sold externally, can also be included.

Crystalline aluminosilicate X' (M
2'0 or M"O) ・Ah03・y'(SiOz)
・h' (HzO) (in the formula, "gate" is an alkali metal atom, "is an alkaline earth metal atom that can be exchanged with calcium,"
Xo.

yl and 1 represent the number of moles of each component, and generally,
0.7≦x+≦1.5.

Na2O・AI, 0.・n5iO,・wH,0 (where n is 1.8 to 3.0%' W represents a number from 1 to 6) Amorphous aluminosilicate X (A2
0)・A11bi・y(SiOt)・Su(0,0) (wherein M represents a sodium and/or potassium atom,
x, y, and w represent the number of moles of each component within the following marginal value range.

0.7≦X≦1.2 1.6≦y≦2.8 W is any positive number including 0) Amorphous aluminosilicate X (Mz
O) ・AlzOz ・Y(SiOz) ・Z(PzO
s) ・ω(lIzO) (in the formula, H is Na or Ni, X
, Y, Z, and 匈 represent the number of moles of each component within the following numerical range.

0.20 ≦X ≦1.10 0.20 ≦Y ≦4.00 0.001≦z ≦0.80 (any positive number including O) Furthermore, the following additives are used in the present invention. be able to.

(1) Divalent metal ion scavenger 1) Ethane-1,1-diphosphonic acid, ethane-1,2
-Triphosphonic acid, ethane-1-hydroxy-LL -
Diphosphonic acid and its derivatives, ethanehydroxy-1,
Phosphonate salts such as 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1°2-diphosphonic acid, and methanehydroxyphosphonic acid.

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

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

4) Nitrilotriacetate, ethylenediaminetetraacetate,
Aminopolyacetates such as diethylenetriaminepentaacetate.

5) Polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid,
Maleic anhydride-diisobutylene copolymer, 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 ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isobrene copolymer, maleic anhydride Poly-β-ketocarboxylic acids derived from acids and carbon monoxide, itaconic acid, ethylene copolymers, itaconic acid-acrylic acid copolymers, itaconic acid-maleic acid copolymers, itaconic,! - Acrylic acid copolymer, malonic acid-methylene copolymer, methaconic acid-fumaric acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, 1-butene-2
, 3,4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, nonpolyester polyaldehyde carboxylic acid with quaternary ammonium groups, cis-isomer of epoxysuccinic acid, poly(N,N-bis(carboxymethyl) ) acrylamide], poly(oxycarboxylic acid), starch succinic acid or maleic acid or terephthalic acid ester, starch phosphate ester, dicarboxy starch, dicarboxymethyl starch, carboxycellulose, succinate ester, and other polymer electrolytes.

6) Polyethylene glycol, polyvinyl alcohol,
Non-dissociable polymers such as polyvinylpyrrolidone, cold water soluble urethanized polyvinyl alcohol.

7) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, cyclopencune-1,2,3,
4-tetracarboxylic acid, tetrahydrofuran-1,2,
3,4-tetracarboxylic acid, tetrahydrofuran-2,
2,5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, monosaccharide, lactose, carboxymethylated products such as raffinose, carboxymethylated pentaerythritol, carboxymethylated gluconic acid, polyhydric alcohol or ! Condensates of cheek and maleic anhydride or succinic anhydride, condensates of oxycarboxylic acid and maleic anhydride or succinic anhydride, benzene polycarboxylic acids 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,
Organic acid salts such as decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulfoitaconic acid, malic acid, oxydisuccinic acid, gluconic acid, CMO3, Builder M, and the like.

(2) Re-staining prevention agent The composition may further contain one or more of the following compounds as a re-staining prevention agent in an amount of 0.1 to 5%.

Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc.

(3) Bleach agents such as sodium percarbonate, sodium percarbonate, and sodium sulfate hydrogen peroxide adducts.

(4) Enzymes (enzymes that perform their original enzymatic action during the cleaning process) Classified based on their reactivity, they include hydrolases, hydrolases, oxidoreductases, desmolases, transferases, and isomerases. , both are applicable to the present invention. Particularly preferred are hydrolases, including proteases, esterases, carbohydrases and nucleases.

Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, bromelin,
These are carboxypeptidase A and B, aminopeptidase, and aspergylopeptidase A and B.

Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases, and phosphotases.

Carbohydrases include cellulase, maltase, saccharase, amylase, pectinase, lysozyme, α-
Included are glycosidases and β-glycosidases.

(5) Blue tinting agent Various bluing agents can also be added as necessary.

For example, the following structure is used: (In the formula, the residue represents a blue to purple monoazo, disazo, or anthraquinone dye, and X and Y are a hydroxyl group, an amino group, a hydroxyl group, a sulfonic acid group, or a carboxylic acid group. group, an aliphatic amino group which may be substituted with an alkoxy group, a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, a lower alkyl group, an aromatic amino group which may be substituted with a lower alkoxy group, or It is a cycloaliphatic amino group.

R is a hydrogen atom or a lower alkyl group. However, this excludes cases in which R represents a hydrogen atom, (i) cases in which X and Y simultaneously represent a hydroxyl group or an alkanolamino group, and (i) cases in which either one of X and Y is a hydroxyl group and the other is an alkanolamino group. <an 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 alkanol amino residues or hydroxyl groups.) (6) Anti-caking agent para-toluenesulfonic acid salts, xylene sulfonates, acetates, sulfosuccinates, talc, finely divided silica, clays, calcium-silicates (e.g. Johns Man
vil1's microcell, etc.), magnesium oxide, etc.

(7) Antioxidant tert-butylhydroxytoluene, 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, etc. antioxidant.

(8) Fluorescent dye 4.4''-bis-(2-sulfostyryl)-biphenyl salt, 4.4''-bis-(4-chloro-3-sulfostyryl)-biphenyl salt, 2-(styrylphenyl) Naphthothiazole derivative, 4,4゛-bis(triazole-2
The composition may contain O-1% by weight of one or more of a -yl)stilbene derivative and a bis(triazinylamino)stilbene disulfonic acid derivative.

(9) Photoactivated bleach One or two of sulfonated aluminum phthalocyanine and sulfonated zinc phthalocyanine are added to the composition in an amount of 0 to 0.
It can be contained in an amount of 2% by weight.

The detergent of the present invention is prepared by granulating a detergent slurry containing at least one surfactant and at least one inorganic or organic Virzo 7 among the above ingredients by spray drying, and then adding a fragrance after leaving the drying tower. Mix aluminosilicate fine powder.

At this time, or before or after, thermally unstable components such as enzymes and bleach may be mixed, colored particles prepared separately, sodium carbonate, sodium sulfate,
It is optional to mix detergent raw materials such as condensed phosphates.

〔Example〕

Examples of the present invention are shown below, but the present invention is not limited to these examples.

Example 1 A detergent having the following composition was spray dried.

AS (alkyl sulfonate) 7 Soap
2 Aluminosilicate 18 Sodium silicate No. 2 (as solid content) 8 Sodium carbonate
5 Sodium sulfate 38
．． 8. Fluorescent dye 0.2 Water 5. The average particle size of the detergent particles obtained was 450 μm, and the apparent specific gravity was 0.
．． It was 25g/+n7. While fluidizing the detergent particles using a drum-type stirrer equipped with a baffle plate inside, 0.25% by weight of fragrance was added by spraying. Next, add this to capacity 3
Aluminosilicate powder (Toyo Builder manufactured by Toyo Soda Kogyo Co., Ltd.) with an average particle size of 2.3 μm was placed in a Nauta mixer with a weight ratio of 0.3.0.5.1.0.3.0.
5.0% and 7.0% were added, respectively, and mixed with stirring.

The fluidity of powder is determined by measuring the time required for powder with an apparent density of 100 mZ to flow out from a hopper for measuring specific gravity as specified in JIS K 3362, and determining that the shorter the time, the better the fluidity. .

The pressure solidification property of the powder is 15% in a cylinder with a diameter of 40mm.
g of sample is placed in an average tube, a load of 1 kg is applied with a piston, and the sample is allowed to stand for 3 minutes to form a cylinder. The molded sample is taken out of the cylinder, and the force required to break it is measured using a rheometer (manufactured by Fudo Kogyo Co., Ltd.). This force is defined as the breaking load. The smaller the value of the breaking load, the smaller the pressure solidification property of the powder, which is desirable.

The amount of dust generated was determined by measuring the degree of dispersion using a powder tester (manufactured by Hosokawa Micron Corporation). The measurement principle is that when a sample is dropped from a certain height into a receiver placed directly below, the weight ratio of the sample that is scattered as dust and not collected into the receiver is determined. The larger the value of dispersion,
Indicates that dust is likely to be generated.

These three measured values are shown in Table 1 along with those without the addition of aluminosilicate. This result shows that the appropriate amount of aluminosilicate to be added is 0.5 to 5% by weight.

Comparative Example 1 The same aluminosilicate as in Example 1 was stirred and mixed into the spray-dried detergent particles having the composition of Example 1 without adding fragrance. The measured values of fluidity, breaking load, and dispersion of this detergent particle are shown in Table 2 together with the results of Comparative Example 2.3.

Compared to the values in Table 1, this comparative example has a large degree of dispersion;
It can be seen that it is a powder that easily generates dust.

Comparative Example 2 Spray-dried detergent particles having the composition of Example 1 were stirred and mixed with the same aluminosilicate as in Example 1 without adding fragrance.
0.2% by weight of the fragrance was sprayed and adhered to the sample while fluidizing the sample (manufactured by Sekisui Chemical Co., Ltd.). Comparing the measured values of fluidity, breaking load, and dispersion degree of this detergent particle shown in Table 2 with the values in Table 1, it is found that this comparative example has poor fluidity and is a powder that easily solidifies under pressure. It is clear that

Comparative Example 3 In Example 1, aluminosilicate powder having an average particle size of 8.6 μm was used. Comparing each measurement value of this detergent particle shown in Table 2 with the value in Table 1, this comparative example shows that the fluidity,
It can be seen that both the breaking load and the degree of dispersion are inferior to the products of the present invention.

Table 1 Table 2

Claims (1)

[Scope of Claims] 1. A detergent containing at least one surfactant and at least one inorganic or organic builder, dried by spray drying, and mixed with a liquid perfume after or at the same time. A granular form characterized in that 0.5 to 5 parts by weight of aluminosilicate fine powder having an average particle size of 7 μm or less is mixed with 100 parts by weight of the particles, and the aluminosilicate fine powder is adhered to the surface of the detergent particles. Method for modifying detergent. 2. The method for modifying a granular detergent according to claim 1, wherein a liquid fragrance is sprayed onto a spray-dried granular detergent in a fluid state. 3. A method for modifying a granular detergent according to claim 1 or 2, wherein the secondary aggregates of aluminosilicate are crushed in advance by a crusher and then mixed.