JPS6021720B2 - Label cleaning agent - Google Patents

Description

[Detailed description of the invention] TECHNICAL FIELD This invention relates to bleach cleaning agents.

More specifically, the present invention relates to a bleaching detergent containing a percarbonate having a specific shape and structure, particularly sodium percarbonate (Ga2C03, Hoso202), and an enzyme, which has excellent cleaning and bleaching power and has good stability over time. Generally, bleaching uses an oxidation reaction, and depending on the type of bleach used, it can be broadly classified into chlorine bleach and oxygen bleach.

Of these, chlorine bleach has restrictions on the types of fibers it can be used on.
In addition, it cannot be used on colored or patterned fabrics, and it also has a unique odor, so recently oxygen-based bleaches that do not have these drawbacks have been widely used. Oxygen bleaches include sodium percarbonate, sodium perborate, sodium peroxide tripolyphosphate, sodium peroxide pyrophosphate, and sodium sulfate/sodium chloride hydrogen peroxide adducts. Among these, sodium percarbonate is widely used because of its bleaching performance and ease of handling. On the other hand, there are various types of stains that adhere to clothing.

Among them, protein and starch stains such as caked on food and blood are widely recognized as stains that can be removed and removed. Even when clothes are bleached using a bleach composition that uses sodium percarbonate as a main bleaching agent, a complete bleaching effect cannot be obtained, and some kind of countermeasure or improvement is eagerly awaited. The present inventors have conducted extensive research to improve the imperfections of percarbonate, particularly sodium percarbonate bleaching detergent compositions, and have found that percarbonate and enzymes, which were conventionally thought to have poor stability over time and cannot be used in combination. We found a way to make these coexist, and completed the present invention.

It is well known that enzymes act on specific substrates, and in the field of detergent textile processing, proteases are effective against protein stains, amylase is effective against starch stains, and lipase is effective against fat stains, increasing cleaning power. It is known.

Enzymes are extremely unstable to percarbonate, and although attempts have been made to incorporate such substances into bleaching detergents, all of these have poor stability and are not suitable for practical use. The present invention allows enzymes to coexist stably with percarbonate, particularly sodium percarbonate.Surprisingly, the specific shape structure of percarbonate is involved, and such an effect is unexpected. This was not possible before, and was only made possible by the development of hollow percarbonates obtained by a specific manufacturing method.

That is, the present invention provides a bleach cleaning agent containing hollow percarbonate and an enzyme. As the hollow percarbonate of the present invention, sodium salts are particularly preferably used.

The hollow sodium percarbonate used in the present invention is, for example,
60 to 15.0% by weight of sodium carbonate and 1.5% of hydrogen peroxide; 6. An aqueous mother liquor solution containing 6% by weight of sodium carbonate was prepared, and the composition of the aqueous mother liquor solution was adjusted to 6.5% by weight of sodium carbonate.
0 None, 15.0% by weight and hydrogen peroxide 1.5 None, 6. Particulate sodium carbonate and an aqueous hydrogen peroxide solution are added simultaneously or alternately at a weight percent of Manufactured by crystallizing sodium carbonate.

The temporal stabilization effect of the combination of sodium percarbonate and enzyme of the present invention is achieved only by using sodium percarbonate that has gone through a specific manufacturing process, and the content of sodium carbonate and hydrogen peroxide in the mother liquor is an important stabilizing factor. A more preferable mother liquor composition is 7 to 1% by weight of sodium carbonate and 2 to 5% by weight of hydrogen peroxide.

The particle size of the granular sodium carbonate added to the mother liquor is not particularly required to be limited, but in view of the size of the sodium percarbonate to be produced and from the viewpoint of ease of handling, the particle size should be 50 to 2.
000 vibration, preferably 100 to 100 mm.

The hollow sodium percarbonate thus obtained is 100 to 20
00 mountain surface is preferable.

Regarding hollow percarbonates, see Japanese Patent Application Publication No. 55-91261 (Japanese Patent Application Publication No. 57-1740y. Japanese Patent Publication No. 33164-1989) filed by the present applicant dated July 4, 1973.
Hollow granular percarbonate and method for producing the same", the substance is hollow inside the particle and the shell is composed of plate-like or needle-like crystalline percarbonate. It is.

A stabilizer commonly used in producing sodium percarbonate may also be present.

As such stabilizers, magnesium compounds, silicates, phosphates, condensed phosphates, aminopolycarboxylates, amines, etc. are used. The stabilizer can be added to the mother liquor during the production of hollow sodium percarbonate, or added during ripening or before separation of the mother liquor.

The amount of stabilizer added is 0 to 50 in the case of silicates and phosphates.
0 moISi or P/k9・Na2C03, preferably 20 to 100 moISi or P/k9・Na2
In the case of C03, magnesium compounds are preferably water-soluble ones, preferably magnesium chloride and magnesium sulfate, with a moI of 0 to 15.0.
03, preferably 10-50 moIM evening/k9・N
Used in a2C03.

In the case of aminopolycarboxylic acid salts, preferred are ethylenediaminetetraacetate, nitrilotriacetate, jethylenetriaminepentaacetate, methylimi/diacetate, hydroxyethyliminoacetate, and hydroxyethylethylenediaminetriacetate. Acetate, cyclohexanediaminetetraacetate are used, and in the case of amines, alkylamines or alkylolamines having an alkyl group having 1 to 3 carbon atoms are used, and triethanolamine is particularly preferred, and all of these have 0 to 2 carbon atoms.
50 mol/kg・Na2C03, preferably 2~
50 mol/k9・Na2C03 is added (in addition,
Unless otherwise specified, alkali metal salts and alkali metal salts are particularly preferred). The enzyme used in the present invention may be an enzyme having any action such as hydrolase, transferase, oxidoreductase, lyase, isomerase, ligase, etc. In particular, protease, lipase, amylase alone,
Or used in combination.

Furthermore, it is more advantageous to use a mixture of two or more of these protease, lipase, and amylase enzymes. Enzyme sources are produced in animals, bacteria and plants. Examples include digestive enzymes or enzymes such as pepsin, pancreatin, trypsin, papain, catalase and diastase. In particular, Bacillus subtilis (
Enzymes obtained from bacterial strains such as Bacillus subtilis) and Streptomyces griseus or from filamentous fungi are preferred, and many commercially available enzymes can be used of this type. Also, the optimum temperature is 1
Particularly good are those having a pH range of 0 to 80 qo, preferably 20 to 6 pi○, and an optimum pH range of 4 to 12, preferably 7 to 11. Commercially available enzymes can be used in the present invention.

This is usually a dry powder product in which about 2% to about 80% of the active enzyme is combined with an inert powder carrier such as sodium or calcium sulfate or sodium chloride (the remainder 98-20%). The amount to be added is calculated based on the amount of active enzyme. In the case of amylase, the following commercially available products are exemplified.

Q-amylase: Midwest Biochemical Co., Ltd. (USA) Q-amylase: Nagase Sangyo Q-amylase: Warrellstein Co., Ltd. (USA) Amylase preparation: Rohm and Haas Co., Ltd. Bacterial Q-amylase A, BAN: Novo Industries Co., Ltd. Bioclystase: Daiwa Kasei Clarase: Miles Laboratory Co., Ltd. Fungamyl: Novo Industries Co., Ltd. Maxaim FA: Gist Procades Co., Ltd. Speedase: Nagase Sangyo Term Amine: Novo Industries Co., Ltd. In the case of protease, the following commercially available products are exemplified.

Alcalase:/Pond Industry Alkaline Protease: Takeda Chemical Bioplase: Nagase Sangyo Esverase: Novo Industries Mallase: Matsutani Chemical Maxatase: Gistprocades Pronase: Kaken Kagaku Protin: Yamato Kasei These are just examples; other species products can also be used.

In the present invention, in addition to the hollow percarbonate and the enzyme, known components that are usually added and blended in cleaning compositions and bleaching compositions are incorporated as necessary.

An anionic surfactant is blended as the surfactant.

In the case of anionic surfactants, counter ions include alkali metal ions such as sodium and potassium, alkali metal ions such as calcium and magnesium, ammonium ions, and alkanol groups having 2 or 3 carbon atoms. Examples include alkanolamine salts having 1 to 3 alkanolamines (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

Examples of anionic surfactants include the following.

1 Straight chain or branched chain alkylbenzene sulfonate having an average carbon number of 10 to 16 alkyl groups 2 Average carbon number of 8
Alkyl or alkenylethoxy sulfate having ~20 linear or branched alkyl or alkenyl groups and having an average of 0.5 to 8 moles of ethylene oxide added to each molecule 3 Average carbon number 10 to 20 Alkyl or alkenyl sulfate having an alkyl or alkenyl 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 Saturated or unsaturated fatty acid salt having an average of 10 to 20 carbon atoms in one molecule 7
Alkyl or alkenylethoxycarboxylic acid salt having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and having an average of 0.5 to 8 moles of ethylene oxide added to each molecule 8 Q- represented by the following formula Sulfo fatty acid salt or ester [in the formula, Y is an alkyl group having 1 to 3 carbon atoms or a counter ion of the anionic surfactant, and Z is a counter ion of the anionic surfactant.

R represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. [9] Partially neutralized succinic acid complex conductor represented by the following formula (in the formula, R2 is a saturated or unsaturated hydrocarbon group having 8 to 18 carbon atoms, and X and Y2 are each a hydrogen atom, an alkali metal, or an ammonium Or it is an alkanolamine having 2 or 3 carbon atoms.

)・〇(In the formula, A represents or, R3 is a linear or branched saturated or unsaturated hydrocarbon group, R' is hydrogen or a methyl group, and
, represents a number from 0 to 6, n represents a number from 1 to 6, and B represents -OX2
or A, and × and ×2 represent hydrogen, an alkali metal, alkyl-substituted ammonium, or hydroxyalkyl-substituted ammonium.

) Anionic phosphate ester surfactant The nonionic surfactant is exemplified by the following.

11 Polyoxyalkylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 8 to 20 and added with 1 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms 12 A polyoxyalkylene alkyl or alkenyl ether having an average carbon number of 8 to 12 Polyoxyalkylene alkylphenyl ether 13 having an alkyl group and adducting 1 to 20 moles of alkylene oxide having 2 to 4 carbon atoms Higher fatty acid alkanolamide represented by the following formula or its alkylene oxide adduct ( In the formula, R4 represents H or CH3, and R5 has 1 carbon number.
0 to 20 alkyl or alkenyl groups.

m2 is an integer of 1 to 3, and n2 is an integer of 0 to 3. )1
4 A nonionic activator having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and adding a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide (ethylene oxide nopropylene) The ratio of oxide or butylene oxide is 9.9 to 9.9/0.1)15
Examples of the sucrose fatty acid ester amphoteric surfactant consisting of a fatty acid having an average carbon number of 10 to 20 and sucrose include the following.

16 Alkylamine oxide represented by the following formula (wherein R6 is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R7 and R8 are alkyl groups having 1 to 3 carbon atoms, and may be the same or different.

)17 (In the formula, R9 represents an alkyl group or alkenyl group having 10 to 20 carbon atoms, R, o, R,. is an alkyl group having 1 to 4 carbon atoms, P is an integer of 1 to 3, and X3 is -COO Yuka-S
03e group.

)18 (R,2 means fatty acid root R, 3 is day, Na or CQCOOM Z is COOM, CH2COOM or M is Na, H or organic base G is OH, acid salt, or anionic surfactant It is a sulfate or sulfate.

) As the builder component, inorganic and organic builders are used alone or in combination.

Examples of inorganic builders include alkali metal phosphates, polyphosphates, carbonates, bicarbonates, borates, silicates, and sulfates, and ammonium salts and substituted ammonium salts can also be used.

Examples of inorganic Pilder salts of this type include sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate or their potassium salts, sodium hexametaphosphate, sodium sesquicarbonate, mono. Examples include sodium di-orthophosphate. Crystalline and/or amorphous zeolites represented by the following formulas can also be blended.

X(M20)AI203Y(Sj.

2) Z(P2Q) (day 20) (where M represents Na or K, and X, Y, Z, and w represent the number of moles of each component within the following numerical range.

0.20SXSI. 500.20 SY Mi 6.00 0 Mi ZSO. (80w: Any positive number including 0) On the other hand, organic builders include aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate, and jethylenetriaminepentaacetate, citrate, malate, glycolate, etc. Polymer electrolytes such as oxycarponate salts, polyacrylic acid, alkali hydrolyzed salts of vinyl acetate-mureic anhydride copolymers, etc. can be blended.

Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc. are used as anti-restaining agents, and commercially available crab light dyes are used as whitening agents.
Flavoring agents, bluing agents, etc. can also be added as necessary.

In addition, water-insoluble substances such as talc, finely powdered silica, clay, and calcium silicate (for example, Johns-N
VM's Microcell, etc.) can also be blended as necessary.

In addition, known stabilizers for peroxides or hydrogen peroxide adducts, such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicate, and magnesium oxide, may be used as well as N-acylated compounds and organic acid anhydrides as necessary. , a peroxide such as ester, or an activator of a hydrogen peroxide adduct.

These components are preferably blended in the following relative proportions.

The bleaching and cleaning agent of the present invention provides effective bleaching and cleaning effects in both immersion cleaning and regular cleaning.

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

Example 1 Production example of hollow sodium percarbonate Sodium carbonate 8. Fence t%, hydrogen peroxide 4.4wt%,
After gradually adding 131.0 parts of a 50% hydrogen peroxide aqueous solution and 118.3 parts of granular anhydrous soda with a residue of 100 meshes passing through 70 meshes to 408.1 parts of the mother liquor consisting of the remainder water, the mixture was aged for 15 minutes. .

Then, the precipitate was dehydrated and dried to obtain white crystalline grains of 153.0 mm. A bleaching detergent composition with the following composition was prepared using the hollow sodium percarbonate obtained above and commercially available sodium percarbonate, and each was placed in a plastic container and stored for one month at 4000℃. was measured. The results are shown in Table 1. Bleach detergent composition Sodium percarbonate 8% by weight Alcalase (protease commercially available from Po Industries)
2 Anhydrous Sodium Carbonate 18 ・Example 2 Finally, a bleaching detergent with the following composition was produced, placed in a moisture-proof carton, stored at 40 qo and 80% relative humidity for one month, and then washed under the following conditions. The test was conducted.

Blend composition Sodium linear alkylbenzene sulfonate (average carbon number 12.5) 2% by weight Sodium tripolyphosphate 2% by weight Sodium silicate (JIS2
No.) 1% by weight magnesium sulfate
1% by weight sodium percarbonate 1% by weight enzyme (alcalase) 1% by weight water
Minutes 5wt% Wakasai
Total 10G weight % detergency test Cocoa contaminated cloth (commercially available Empa 112 contaminated cloth) was heated to an initial temperature of 40 qo,
It is soaked overnight in a 0.7% bleaching detergent aqueous solution, then washed with water and dried, and the bleaching detergency is determined by the difference in reflectance of 46 meters before and after treatment.

Washing results The increase in reflectance was measured.

Commercially available sodium percarbonate type 21% Hollow sodium percarbonate type Spot % Visual observation also showed that the bleaching and cleaning properties of the present invention had a remarkable effect.

Claims (1)

[Claims] 1. 1 to 99% by weight of hollow sodium percarbonate and 0.0% enzyme
A bleaching detergent containing 01 to 10% by weight and containing other bleaching detergent components as necessary. 2 The average particle diameter of hollow sodium percarbonate is 100 to 20
The bleaching detergent according to claim 1, which has a particle diameter of 00 μm. 3. Claim 1 or 2, wherein the enzyme is selected from the group of protease, lipase, and amylase.
Bleach cleaning agent as described in Section.