JPS604879B2 - cleaning composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to cleaning compositions.

Conventionally used cleaning compositions contain an aniososurfactant as a main component, and are composed of mixed surfactants, organic or inorganic builders, photochromic dyes, etc. as necessary.

Clothes washed with such detergent compositions have a rough finish and feel, which is not desirable. Furthermore, clothing that has been washed repeatedly has a particularly noticeable stiff feel. Therefore, in order to improve the texture of clothing, there are two steps in which after removing dirt from clothing with a detergent composition, finishing treatment is performed using a texture/improving treatment agent such as softening and antistatic treatment. The process has been carried out. In order to eliminate the double effort of cleaning and finishing, cleaning compositions have recently been developed and marketed that allow cleaning and finishing to be performed simultaneously in one process.

However, since these commercially available products use cationic surfactants to impart effects such as softening and antistatic treatment, interactions with anionic surfactants, which are the main components of cleaning compositions, occur, resulting in mere Since the desired effect cannot be fully achieved by mixing both components, various other efforts have been made. For example, a combination of a cationic surfactant containing alkylene oxide, an anionic surfactant, and a nonionic surfactant (Tokukan Sho 54-1088
No. 14), a combination of a quaternary ammonium salt type cationic surfactant and an alkali metal salt, etc.
15710), those using a quaternary ammonium salt type cationic surfactant having two long mirrors (Japanese Unexamined Patent Publication No. 10629/1983), and those using a softener reaction product in a cleaning composition. Specified particle size (JP-A-55-62)
No. 998), etc. are disclosed. However, none of these prior art techniques takes into account the behavior of cationic surfactants in the washing process, and their effects are still not perfect, and improvement is desired.

The present inventors have been conducting extensive research into incorporating cationic surfactants into cleaning compositions containing anionic surfactants as main components in a manner that does not reduce their effectiveness. When pre-treated with inorganic materials and pre-treated with a specific method and used as an after-blend with detergent fabric, the content of cationic surfactant is low and it is extremely superior to conventional detergents containing cationic surfactants on the market. The present invention was completed after discovering that a cleaning composition that provides a finishing effect and good cleaning power can be obtained.

That is, the present invention provides a cleaning composition characterized in that it contains a cationic surfactant mixed and melted with an inorganic substance and then powdered by a fog cooling method.

The spray cooling method in the present invention refers to a powder manufacturing method in which a cationic surfactant and an inorganic substance are heated and melted, and then sprayed into a cold space through a pongee hole at a constant discharge pressure or higher to solidify into powder.

The cationic surfactant and the inorganic substance are preheated and heated before being sprayed into a cold space and powdered. The heating temperature is a temperature at which the cationic surfactant has sufficient fluidity, e.g.
It may be heated to about 150°C. The cold space is preferably a fog tower type in which cold air is introduced into a floor fog tower, for example, 5 to 20
It is preferable to use a cooling method in which air of q0 is introduced countercurrently or cocurrently with the thionic surfactant. The pressure discharged from the pores into the sleeve space is preferably 20K9/N or more, and more preferably 30~4
It is best to mist in the discharge pressure range of 5k9/ground. The mixture of cationic surfactant and inorganic substance obtained by this method has a rod-like crystal structure, unlike that obtained by other methods.

Although the softening effect of the present invention does not depend on the particle size of the pretreated powder, it is preferable to classify and use particles with 50 to 350 particles. The cationic surfactant used in the present invention is not particularly limited, but the following may be exemplified.

[A long chain alkyl quaternary ammonium salt where R2
, R3 is an alkyl group having 10 to 26 carbon atoms, preferably 14 to 20 carbon atoms, and R4 and R5 are preferably 1 to 5 carbon atoms.
or 2 alkyl group, X represents a halogen atom, methyl sulfate or ethyl sulfate (the same applies hereinafter). 'o' mono long chain alkyl quaternary ammonium salt
di-long-chain alkyl polyoxyethylene quaternary ammonium salt where n represents 1 to 2 or 1 to 10 (
Same below).

Here, m is 1 to 2, and m is 1 to 10 (
Same below).

W Mono-long chain alkyl borooxyethylene quaternary ammonium salt ■ Bis(hydroxyalkyl) quaternary ammonium salt H Quaternary ammonium salt having an amide or ester bond, where p represents 1 to 5, preferably 2 or 3 (hereinafter same aircraft).

reaction product with (g) Diquaternary salt Here, q represents 2 to 8 (hereinafter the same applies) Mr).

Here B is or one CH=CH- remainder represents a group.

Among these cationic surfactants, preferred are the quaternary ammonium salts shown in [A], [O], [I], and [0] above.

More specific examples include di-tallow alkyl dimethyl ammonium chloride, mono-tallow alkyl trimethyl ammonium chloride, di-tallow alkyl dipolyoxyethylene ammonium chloride, and mono-tallow alkyl monomethyl dipolyoxyethylene ammonium chloride. The inorganic substance that is an essential second component of the present invention is selected from the group consisting of calcium carbonate, sodium carbonate, sodium sulfate, sodium silicate, and aluminosilicate. 2} A crystalline or amorphous aluminosilicate represented by the formula is used.

x (M20 or M″○)・AI203・y (Si02)
・w(payment 0)'1} (in the formula, M' is an alkali metal atom,
M″ is an alkali metal atom exchangeable with calcium,
x, y, and w represent the number of moles of each component, and are generally 0.
7 mix x SI. 5, 0.8≦y≦6, w is any positive number.

)X(M20), mountain 203・Y(Sj.

2), Z (P205), (ratio.

) ■ (In the formula, M represents Na or K, and ×, Y, and Z represent the number of moles of each component within the following numerical range. 0.20
MiXSI. 10, 0.20≦Y≦4.00, 0.01mi ZSO. (80■: Any positive number including 0) As the sodium silicate, for example, sodium silicate No. 1 to No. 3 specified in JIS is used.

The mixing weight ratio of cationic surfactant and inorganic substance is 2/1~
1/10 (preferably 1/1 to 1/5) is suitable.

In the present invention, it is preferable that the pretreated powder is blended in an amount of 0.5 to 2% by weight (preferably 1 to 1% by weight) to the remaining component fabric of the cleaning composition powdered by a known method. .

In the present invention, in addition to these essential components, components of known detergent compositions can be optionally blended depending on the purpose.

A surfactant can be added as a cleaning base.

Examples of anionic surfactants include the following.

{1'A chain or branched chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 '2} Having a straight or branched chain alkyl group or alkenyl group having an average carbon number of 10 to 20, Alkyl or alkenyl ethoxy sulfate with an average of 0.5 to 8 moles of ethylene oxide added in one molecule '3' Alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms {4 } Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule '51 Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule {6
1 Saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule {7) An alkyl group or alkenyl group having an average of 10 to 20 carbon atoms, and an average of 0.
5 to 8 moles of ethylene oxide or propyne oxide or butyreth oxide or ethylene oxide nopropylene oxide = 0.1/9.9 to 9
．． Alkyl or alkenyl carboxylate shelf added in a ratio of 9/0.1 or in a ratio of ethylene oxide/butylene oxide = 0.1/9.9 to 9.9/0.1, represented by the following formula: Q-sulfo fatty acid salt or ester R7CHC02Y &Z (wherein Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, Z
is the counterion.

R7 represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. ) Counter ions for these anionic surfactants include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium,
Examples include ammonium ions and alkalamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (eg, monoethanolamine, jetanolamine, triethanolamine, triisopropanolamine, etc.).

The nonionic surfactant is not particularly limited as long as it is used in ordinary detergent compositions, and examples thereof include the following. Wind has an alkyl group or alkenyl group with an average carbon number of 10 to 20, and 1
Polyoxyethylene alkyl or alkenyl ether to which ~20 moles of ethylene oxide have been added (B-Polyoxyethylene alkyl phenyl ether having an alkyl group with an average carbon number of 6 to 12 and to which 1 to 20 ethylene oxides have been added) } Polyoxypropylene alkyl or alkenyl ether plate having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 moles of propylene oxide is added An alkyl group or alkenyl group having an average carbon number of 10 to 20 Polyoxybutylene alkyl or alkenyl ether {E} having 1 to 20 moles of butylene oxide added thereto {E} having an alkyl group or alkenyl group having an average carbon number of 10 to 20, and a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide (the ratio of ethylene oxide and propylene oxide or butylene oxide is 0.1/9.9)
~9.9/0.1)'F} Higher fatty acid alkanolamide or its alkylene oxide adduct represented by the following general formula (wherein R, . is an alkyl group or alkenyl group having 10 to 20 carbon atoms) and R,2 is H or CH3
, n' is an integer of 1 to 3, and m' is an integer of 0 to 3.

) Sucrose fatty acid ester dish consisting of a fatty acid with an average carbon number of 10 to 20 and sucrose Fatty acid glycerin monoester consisting of a fatty acid with an average carbon number of 10 to 20 and glycerin (1) Alkylamine represented by the following general formula Oxide (wherein R, 3 is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R, 5 is an alkyl group having 1 to 3 carbon atoms.

) Examples of amphoteric surfactants include those represented by the following formula.

(In the formula, R, 6 represents an alkyl group or alkenyl group having 10 to 20 carbon atoms, R, 7, R, 8 represent an alkyl group having 1 to 4 carbon atoms, p' is an integer of 1 to 3, and X' represents one COOe or -S03e group.

) The following are exemplified as the builder primary auxiliary component.

[1] Divalent metal ion scavenger The divalent metal ion scavenger may contain 0 to 50% of one or more builder components of the following various alkali metal salts and alkanolamine salts.

m Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate etc.2) Ethane-1,1-diphosphonic acid, ethane-1,2-triphosphonic acid, ethane-1-hydroxy- Phosphonate '3' 2-phosphonic acid such as 1,1-diphosphonic acid and its derivatives, ethane-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, etc. Butane-1,2-dicarboxylic acid, 1-phosphonobutane-2
・Phosphonocarboxylic acid salts such as 3,4-tricarboxylic acid and Q-methylphosphonosuccinic acid {4} Aspartic acid,
Amino acid salts such as glutamic acid '5) Aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate {6} Polyacrylic acid,
Polyaconitic acid, polytaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, polyQ-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutyl 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 Coalescence, maleic anhydride-acrylic ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-
isoprene copolymer, poly6-ketocarboxylic acid derived from maleic anhydride and carbon monoxide, itaconic acid-ethylene copolymer, itaconic acid-aconitic acid copolymer,
Itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, malonic acid-methylene copolymer, methaconic acid-fumaric acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer Polymer, 1-butyl-2,3,4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, polyester having quaternary ammonium group, polyaldehyde carboxylic acid,
cis-isomer of epoxysuccinic acid, poly[N・N-pis(carboxymethyl)acrylamide], poly(oxycarboxylic acid), starch succinic acid or maleic acid or terephthalester*, starch phosphate ester, dicarboxystarch, Polymer electrolytes such as dicarpoxymethyl starch and cellulose succinate (7' non-dissociable polymer substances such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and cold water-soluble urethanized polyvinyl alcohol {8' diglycolic acid, oxydisuccinic acid, Carboxymethyloxysuccinic acid, cyclobentane-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-1,2,.3,4-tetracarboxylic acid, tetrahydrofuran-2,2,5,5
-Carboxymethylated products of tetracarboxylic acid, citric acid, lactic acid, tartaric acid, sucrose, lactose, lafi/-ose, etc., carboxymethylated products of bentaerythritol, carboxymethylated products of gluconic acid, polyhydric alcohols or sugars, and maleic anhydride. Condensates of acid 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, Ethane-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, decane-1,1
0-dicarboxylic acid, sulfotricarballylic acid, sulfitaconic acid, malic acid, oxydisuccinic acid, gluconic acid,
Organic acid salts such as CMOS and Builder M {9} Aluminosilicate Crystalline aluminosilicate x'(M'20 or M'○)・AI203・y'(Si
02)・w'(日20)(In the formula, M' is an alkali metal atom, M'' is an alkali metal atom exchangeable with calcium, x', y', and w' represent the number of moles of each component. , generally 0.7 mm x'≦1.f 0.8≦y'≦6, w' is any positive number.

) As the detergent builder, those represented by the following general formula are particularly preferred. x(M20)・N203・y(Si0
2)・w (Sun 20) Na20・AI203・nSi02
・wH20 (where n' is 1.8 to 3.0, w is 1 to
Represents the number 6.

) Amorphous aluminosilicate represented by the following formula (where M represents a sodium and/or potassium atom, and x, y, and w represent the number of moles of each component within the following range of values) .

0.7SxSI. 2 1.6≦y≦2.8 w is any positive number including 0) Amorphous aluminosilicate X(M20)・N203・Y(Si02)・Z(P20
5)・w (ratio ○) (in the formula, M is Na or K, X, Y,
Z represents the number of moles of each component within the following numerical range.

0.20SXSI. IQ O. 20SYS4.00,0
．． 01SZSO. [2] Alkaline agent or inorganic electrolyte In addition, as an alkaline agent or inorganic electrolyte, one or more of the following various alkali metal salts are added to the composition in amounts 1 to 5. It can be contained in an amount of 5 to 30% by weight, preferably 5 to 30% by weight.

Silicates, carbonates, sulfates. Moreover, alkanolamines represented by triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine, etc. can also be contained as an organic alkali agent. [3] Anti-restaining agent Furthermore, one or more of the following compounds can be contained in the composition in an amount of 0.1 to 5% as an anti-restaining agent.

Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc.
Among these, carboxymethyl cellulose and/or polyethylene glycol are preferred, and furthermore, when used in combination with cellulase, it has a synergistic effect in removing mud stains.
[4] Bleach agents such as sodium percarbonate, sodium perborate, sodium sulfate hydrogen peroxide adduct, sodium chloride hydrogen peroxide adduct, and/or photosensitive sulfonated phthalocyanine zinc salts or ammonium salts. Bleaching dyes, etc.

Furthermore, the combination with cellulases generally improves the cleaning effect. [5] Enzymes Classified based on their reactivity, enzymes include hydrolases, hydrases, oxidoreductases, desmolases, transferases, and isomerases, all of which are applicable to the present invention.

Particularly preferred are hydrolases, including proteases, esterases, carbohydrases and nucleases. Specific examples of proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promelin, carboxybeptidase A and B, aminobeptidase, aspargylobeptidase A and B.

Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases and phosphotases. Carbohydrases include cellulase, maltase, satucarase, amylase, vectinase, and lysozyme.

-glycosidase and 8-glycosidase. [6] Blue-tinging agents and fluorescent dyes Various blue-tinging agents and fluorescent dyes can be added as necessary.

For example, the following structure is recommended: [7] Anti-caking agent In the case of a powder detergent, the following anti-caking agent may also be blended.

paratoluene sulfonate, xylene sulfonate, acetate, sulfosuccinate, talc, finely powdered silica, mucilage, calcium-silicate (e.g. Johns-Man
v; microcells from 11 companies, etc.), calcium carbonate,
Magnesium oxide etc. [8] Power thione polymer (i) Epichlorohydrin is added to a condensate with an acid value of 10 or less obtained by reacting 1 mole of jettylene triamine or dipropylene triamine with about 2 moles of a fatty acid having 12 to 24 carbon atoms. A cation obtained by adding about 1 to 2 moles, then ring-opening polymerization in the presence of an alkaline agent, and neutralizing with 0.3 to 1.5 moles of monobasic acid per mole of the above amine. polyamide compound (ii) average molecular weight loo
o to 500,000 poly(N.N-dimethyl-3.5-methylene piberidinium chloride) where y represents the cumulative number of bases.

0ii) A product obtained by quaternizing a copolymer of pinylpyrrolidone and dimethylaminoethyl methacrylic acid with dimethyl sulfuric acid has a molecular weight of 1,000 to 500,000, where s and t represent the cumulative number of groups.

GW A product obtained by adding trimethylamine to the epichlorohydrin adduct of hydroxyethyl cellulose to quaternize it, with a molecular weight of 20 to 1,000,000 M. Aminoethyl acrylate phosphate/*acrylate copolymer, with a molecular weight of 1,000 to 500,000 v. A product obtained by adding trimethylamine to a chlorohydrin adduct and quaternizing it.Of the inorganic components that are the essential second component of the present invention, silicates, aluminosilicates, etc. are well-known as detergent builders. It is a component and does not preclude it from being separately incorporated into a cleaning composition for the purpose of use.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. The production of a pretreated product of a cationic surfactant and an inorganic substance by the fog cooling method is shown as a reference example. Reference Examples 110 to 12000 were mixed and homogenized with heated and melted di-tallow alkyldimethylammonium chloride sodium sulfate in equal amounts, and then atomized in cold air at 10°C with a discharge pressure of 40k9'c to form a powder. .

Example 1 Detergent fabric (spray heat dried detergent fabric) Straight chain alkyl (CI2) Na benzenesulfonate 1% by weight Oxo alkyl (CI4) Na sulfate
3 Beef tallow alkyl fatty acid Na IST
PP (sodium tripolyphosphate) 17 Synthetic zeolite 2 JIS No. 2 Sodium silicate 13 Sodium carbonate 5 Ruboxymethyl cellulose 1 Enzyme
0.5 fluorescent dye
flavoring
〃Moisture 5 Bitter Salt Balance 10 parts by weight of the above sprayed hot air dried detergent fabric was mixed with 3 parts by weight of a pre-treated product of cationic surfactant and inorganic substance, washed under the following washing treatment conditions, and softening effect judged by a female expert panel. Sensory flexibility was evaluated by 20 people.

The results are shown in Table 1. Washing treatment conditions Using a commercially available electric washing machine, add 0.0% detergent to 20o0 tap water.
13%, Yuhi 1.0k9/30 Cotton knitted underwear was washed under these conditions, washed with Japanese cedar, dehydrated, and air-dried to be used as a sample for softness evaluation.

Table 1. Flexibility shows the main effect values of Scbeffe's modified paired comparison method.

Example 2 Water o Cleaning composition Weight % of linear alkyl (CI2) benzenesulfonic acid Na oxo alkyl (CI2.5) sulfate Na
20% Ruboxymethyl Cellulose 1% Beef Tallow Alkyldimethylammonium Salt Chloride (Component A) 1% Sodium Carbonate (
B component) 2 moisture
5. Rameshite
Detergent compositions having the above-mentioned fine balance and in which both components A and B were blended in various ways were prepared, and their flexibility was relatively compared using the same method as in Example 1.

Claims (1)

[Claims] 1. A cationic surfactant is mixed with an inorganic substance selected from the group consisting of calcium carbonate, sodium carbonate, sodium sulfate, sodium silicate, and aluminosilicate from 2/1 to 1/2.
Powder cleaning made by blending pretreated powder of a cationic surfactant obtained by mixing and melting at a mixing weight ratio of 10 and then powdering by spray cooling method into a detergent fabric containing an anionic surfactant as the main component. agent composition.