JP2927294B2 - Liquid bleach composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a hydrogen peroxide-containing liquid which is suitably used for bleaching and mold removal of clothes, fibers, pulp and kitchen accessories, especially for bleaching clothes and dishes. It relates to a bleach composition.

[Conventional technology]

Conventionally, chlorine bleach, which is widely used as a liquid bleaching agent, is inexpensive and has strong bleaching power, but has the disadvantage that it cannot be used in colored pattern clothing to discolor or fade the color of colored clothing. Furthermore, in recent years, there has been a social problem that chlorine gas is generated due to erroneous mixing with an acidic cleaning agent, resulting in death.

On the other hand, the oxygen-based bleaching agent is excellent in that a wide range of clothes can be used and there is no problem of generating chlorine gas. However, most of the oxygen-based bleaches on the market are powder types using sodium percarbonate or sodium perborate as a main component, and are not easy to use.
In particular, it has a drawback that it cannot be applied to partial stains such as stains.

The use of hydrogen peroxide as a base for oxygen-based bleaching is widely used among laundry companies, mainly in laundry factories, but hydrogen peroxide used for bleaching such industrial clothing The liquid has a hydrogen peroxide concentration of 35% by weight.
And 60% by weight (hereinafter simply referred to as%). By the way, the decomposition reaction of hydrogen peroxide And pKa = 11.6 (literature; Encyclopedia of Chemical T
echnology (Vol.14)), the pH of the hydrogen peroxide solution
The lower the value, the more difficult it is to decompose. For this reason, commercially available high-concentration hydrogen peroxide is usually in a state where the pH is adjusted to neutral or acidic, but it is still impossible to completely suppress the decomposition, and the oxygen finally generated by the decomposition is not possible. In order to prevent the internal pressure from being increased due to gas and damage to the container, the container is sold in a special container in which a cap or the like is designed to escape the gas. On the other hand, in Japan, the concentration of hydrogen peroxide
Those with 36% or more are classified as "first-class dangerous goods" according to the Fire Service Law.
In addition, those exceeding 6% are designated as "non-medicinal substances" by the "Poisonous and Deleterious Substances Control Law", so for safe use in ordinary households, dilute the hydrogen peroxide concentration to at least 6% or less. There is a need to. However, high-concentration products of hydrogen peroxide are relatively stable, but when diluted, the stability rapidly deteriorates, and there is a problem that they are easily decomposed.

For this reason, it is necessary to suppress decomposition of a low concentration hydrogen peroxide solution more than a high concentration hydrogen peroxide solution. For this reason, various techniques have been proposed. For example, phosphoric acid, babitool acid are used as stabilizers for oxidol (this is a 3-3.5% hydrogen peroxide solution) in the Japanese Pharmacopoeia. , Uric acid, acetanilide, oxyquinoline, tetrasodium pyrophosphate, phenacetin and the like. Certainly, this may not be a problem for products whose distribution channels are kept relatively cool and dark, such as pharmaceuticals, but extremely harsh natural environmental threats (for example, midsummer) for distribution of daily necessities. Warehouses are exposed to temperatures in the daytime exceeding 50 ° C), so it is necessary to provide even better decomposition control.

Japanese Patent Application Laid-Open No. 63-110294 discloses a chelating agent such as aminopolyphosphonate or ethylenediaminetetraacetic acid, BHT (dibutylhydroxytoluene) or MTBHQ (mono-t-) as a stabilizer for hydrogen peroxide. (Butyl hydroquinone). Certainly, in terms of the decomposition rate of hydrogen peroxide, it is possible to reach a practically acceptable level by using these methods. However, in terms of the amount of generated gas, this level is insufficient. For example, 55
A 0 ml container was filled with 500 ml of a 6% hydrogen peroxide solution (liquid specific gravity 1.0 g / ml) at 25 ° C., and after one month of storage at 50 ° C., the hydrogen peroxide concentration was reduced to 5.8%. Then, the decomposition rate of hydrogen peroxide is only 3%, but the amount of generated oxygen gas becomes 380 ml (50 ° C.), and the pressure inside the container alone becomes about 9 atm. . In addition to this, the pressure due to the thermal expansion of the air initially sealed in the port head space and the water vapor pressure of the balance water are also added, so that a larger internal pressure is applied to the bottle. Although it depends on the thickness of the container, ordinary polyethylene containers will not withstand this internal pressure and will swell or even burst. Of course,
There is no problem if the cap is provided with a mechanism to release gas by devising the container.However, in the case of high-concentration products as described above, the container cost of low-concentration products is higher than that of the contents. Too economical.

[Problems to be solved by the invention]

Therefore, the present invention further suppresses the generation of oxygen gas generated by the decomposition of hydrogen peroxide, and the liquid oxygen containing hydrogen peroxide as a main component which does not cause swelling or breakage of the container even when filled in a plastic container or the like. It is an object to provide a system bleaching composition.

[Means for solving the problem]

According to the present invention, when a fragrance having a specific property value is added to a hydrogen peroxide solution, the generation of oxygen gas caused by the decomposition of the hydrogen peroxide is hardly affected by the decomposition rate of the hydrogen peroxide. It is based on the knowledge that can be suppressed.

That is, the present invention relates to a fragrance compound having (A) hydrogen peroxide and (B) one or less unsaturated bonds in the molecule.
Provided is a liquid bleaching composition, characterized by containing one or more species.

The hydrogen peroxide of the component (A) used in the present invention is produced by various production methods such as an electrolysis method and an autoxidation method, and has a concentration of 30%.
% To 60% of JIS standard products are commercially available, and any of these can be used without any particular problem. When used in the present invention, it is preferable to dilute to about 2 to 10%. However, as described above, hydrogen peroxide liquids exceeding 6% in Japan are classified as deleterious substances, so compositions containing more than 6% hydrogen peroxide can be sold as sundry goods. Can not.

These concentrated hydrogen peroxide, it is common being (hereinafter 0.0003% as PO ₄ in example JIS special grade standard) Normal traces of phosphates is added in small amounts as a decomposition stabilizer by the manufacturer. However, when the concentrated hydrogen peroxide solution is diluted to a desired concentration, the decomposition stabilizer added by the manufacturer alone is not sufficient, and it is preferable to add various decomposition stabilizers at the same time as the dilution. As a stabilizer used for such purpose, it is effective to use a combination of a chelating agent and an antioxidant. That is,
The chelating agent prevents the hydrogen peroxide from being abnormally decomposed by these heavy metals by capturing the mixed heavy metals,
This is because an antioxidant has an effect of preventing an organic substance mixed in the composition from being oxidized by hydrogen peroxide. Such chelating agents and antioxidants partially overlap with the compounds described in JP-A-63-110294, but aminopolyamines represented by ethylenediaminetetraacetate, diethylenetriaminepentaacetate and the like. Carboxylic acids,
Inorganic phosphorus compounds typified by tripolyphosphate and pyrophosphate, phosphonates such as 1-hydroxyethane-1,1-diphosphonic acid and 2-phosphono-1,2,4-tricarboxylic acid and the following general formula ( Examples thereof include polyaminophosphonic acids represented by the compounds represented by I) to (III) and organic phosphates represented by phytic acid. Examples of the antioxidant include DL-α-tocopherol, gallic acid derivatives, and butyl Hydroxyanisole (BHA), 2,6-di-
tert-butyl-4-methylphenol (BHT) and the like. The amount of these stabilizers depends on the concentration of hydrogen peroxide, but it is usually 0 to 5%, preferably about 0.01 to 3%.

As the fragrance compound of the component (B) used in the present invention, any compound may be used as long as the number of unsaturated bonds in the molecule is 1 or less. Surprisingly, it was found that adding a fragrance to a diluted hydrogen peroxide solution has almost no effect on the decomposition rate of hydrogen peroxide, and also has the effect of significantly reducing the amount of oxygen gas generated. . In addition, although there are various structures of fragrances, those having a large number of unsaturated bonds in the structure have a relatively remarkable initial gas generation suppressing effect, but during the long-term storage test. Oxygen gas is suddenly generated, and in the end it may be almost the same as the case without fragrance added or in some cases worse than the case without addition, while there is no unsaturated bond,
Even at about one perfume compound, an excellent gas generation suppressing effect was recognized even during a long storage period, and the present invention was completed.

The fragrance compound having 1 or less unsaturated bonds used in the present invention includes benzyl acetate, 3,7-dimethyloctanol,
2-phenylethanol, 4-t-butylcyclohexyl acetate, 2-t-butylcyclohexyl acetate, 2-methyl-3- (p-isopropylphenyl) propionaldehyde, pt-butyl-α-methylhydrocinnamic aldehyde, Octyl aldehyde, n
-Decylaldehyde, 1-nonanol, 1,3,3-trimethyl-2-norbonanol, p-methyl-iso-propylbenzene, 5-methyl-2-isopropylcyclohexanol, 1,3,4,6,7,8 −Hexahydro-4,6,6,7,8,8
-Hexamethylcyclopenta-γ-2-benzopyran,
7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene, ethylene undecane dicarboxylate, 2,6-dinitro-3,5-dimethyl-4-acetyl-t
-Butylbenzene, cedrol, 2,6-dimethyloctane-1-ol, phenylethylphenylacetate,
3- (isocamphyl-5) -cyclohexane-1-ol, α-methyl-3,4-methylene-dioxyhydrocinnamic aldehyde, benzylbenzenecarboxylate, 1,7,7-trimethylbicyclo (2,2, 1) -2-
Heptanone, 1,7,7-trimethylbicyclo-1,2,2-heptanol-2, methyl salicylate, diphenyl ether, 2-methylundecanal, methylphenylacetate, ethylbutyrate, methyl-2-aminobenzoate, undecyllactone These compounds are perfume compounds having zero unsaturated bonds in the molecule. Also, 2-isopropenyl-5-methyl-5-vinyltetrahydrofuran, hexylcinnamic aldehyde, cis-3-hexanol, methyl-
(2-Amyl-3-oxocyclopentyl) acetate, benzopyrrole, 2-methoxy-4-allylphenol, 3,7-dimethyl-6-octen-1-ol, 3,7
-Dimethyl-6-octen-1-yl acetate, 1-
Methyl-4-isopropyl-cyclohexen-8-ol, 1,2-benzopyrone, 9-decene-1-ol, cis-2- (2'-methyl-1'-propenyl) -4-methyltetrahydropyran, 1 -Bromo-2-phenylethylene, 4- (4-methyl-4-hydroxyamyl)
-3-cyclohexenecarboxaldehyde and the like;
These compounds are fragrance compounds having one unsaturated bond in the molecule. In the present invention, the above fragrance compounds can be used alone or in combination of two or more. The chemical names and common names of the fragrances described here are Steffen Arctander, Perf
ume and Flavor Chemicals, (Aroma Chemi-cals), Mon
This has been described according to the name described in tclair, NJ (1969). The compound having an unsaturated bond as referred to in the present invention means a chain unsaturated compound having a double bond (ethylene bond) or a triple bond (acetylene bond) in a bond between carbon atoms among organic compounds, Alternatively, it refers to a cyclic unsaturated compound having these bonds in a side chain. Therefore, in the present invention, unsaturated bonds do not include conjugated double bonds and bonds such as C≡O, CＮN, and N ＝ O that constitute the (4n + 2) π electron system such as aromatic compounds. .

In the present invention, the compounded fragrance can be adjusted using a fragrance compound having two or more unsaturated bonds in addition to the fragrance compound having one or less unsaturated bonds. However, in this case, it is necessary that at least 60% or more, preferably 70% or more of the prepared perfume be a perfume compound having one or less unsaturated bonds. If the number of perfume compounds having one or less unsaturated bonds is less than 60%, a sufficient gas generation suppressing effect cannot be obtained. The amount of the fragrance compound of the component (B) is 0.005 to 2%, preferably 0.01 to 2%, from the viewpoint of suppressing the generation of oxygen gas.
It is effective to set it to about 0.5%. The fragrance compound is a lower alcohol or hexylene glycol (2-methyl-
In some cases, it may be used in the form of being dissolved in a solvent represented by a polyol such as (2,4-pentanediol).

The liquid oxygen-based bleach of the present invention contains hydrogen peroxide of the component (A), the component (B) and the specific fragrance compound as essential components, and the content ratio of the components (A) and (B) is arbitrary. However, the mixing ratio of the two can be expressed as component (A) / (B) =
It is desirable to be 1,000 / 1 to 2/1 (weight ratio).

The pH of the liquid bleach of the present invention is 7 or less, preferably 6 or less, particularly preferably 5 to 1, and the lower the pH, the more stable. This is because, as described above, since the pKa of hydrogen peroxide is 11.6, self-decomposition starts rapidly when the pH becomes alkaline. When an aminocarboxylic acid-based chelating agent such as ethylenediaminetetraacetic acid is used as a stabilizer for hydrogen peroxide, if the pH is adjusted to 3 or less, the chelating agent becomes insoluble in water and precipitates. Extremely lowering the pH is not appropriate because degradation stability is poor. still,
In the case of a phosphoric acid ester type chelating agent such as phytic acid or a phosphonic acid type chelating agent, there is no particular problem even if the pH is lowered to about 1 to 2. To adjust the pH, sulfuric acid,
Phosphoric acid, inorganic acids such as hydrochloric acid or organic acids such as toluene sulfonic acid and benzene sulfonic acid, or the above-mentioned chelating agent or anionic surfactant described below is added in the form of an acid. It is preferable to use a caustic alkali such as potassium hydroxide.

Various additives can be added to the liquid bleach composition of the present invention, if necessary, in addition to the above-mentioned hydrogen peroxide stabilizer. Among these, additives that are relatively important are various surfactants incorporated for the purpose of assisting dissolution and dispersion of the component (B), and enhancing penetration power and a cleaning effect. Particularly preferred as such a surfactant is a nonionic surfactant. Examples of nonionic surfactants include higher alcohols having about 8 to 24 carbon atoms, polyhydric alcohols, fatty acids, fatty acid amides, fatty acid amines, alkylphenols and alkylenes of synthetic alcohols obtained by oxidizing n-paraffins and α-olefins. It is an oxide adduct.
As the alkylene oxide, ethylene oxide, propylene oxide, and butylene oxide are used. Specifically, POE (= 10) lauryl ether, POE (=
9) _C12-14 secondary alkyl ether, POE (= 15) hexyldecyl ether, POE (= 20) nonylphenyl ether, POE (= 11) stearyl ether, POE (
= 10) glyceryl monostearate, POE (= 10) isostearyl ether, POE (= 50) trimethylolpropane, POE (= 30) hydrogenated castor oil, POE (= 60)
Hydrogenated castor oil monolaurate, POE (= 20) sorbitan monooleate, POE (= 30) glyceryl triisostearate, POE (= 20) glyceryl monostearate, POE (= 10) monostearate, POE (= 6) ) Stearylamine, lauroyldiethanolamide, POE
(= 10) Stearylamide, POE (= 9) POP (=
5) _C12-14 secondary alkyl ether and the like. In addition, POE
Is polyoxyethylene, POP is polyoxypropylene,
p represents the average number of moles of the alkylene oxide added.

In addition to nonionic surfactants, alkyl benzene sulfonate, olefin sulfonate, polyoxyethylene (= 0.5 to 8) alkyl ether sulfate, POE (=
3-15) Anionic surfactants such as alkylphenyl sulfate sulfonate salts, alkyl (alkenyl) sulfate salts, saturated or unsaturated fatty acid salts and α-sulfo fatty acid salts or esters, and dialkyldimethylammonium chloride, alkyltrimethylammonium chloride Cationic surfactants, amphoteric surfactants such as alkylaminobetaine, semipolar surfactants such as mono- or diethanolamide having alkyldimethylamine oxide or N-acyl group, and fluorine-based surfactants. Here, the alkyl group or acyl group is a general term for a saturated, unsaturated or branched alkyl group or acyl group having an average carbon number of 8 to 20. The amount of the surfactant is usually about 0 to 20%, preferably 0.1 to 5%.
%.

It is also possible to add 0 to 30%, preferably 0.1 to 10% of a hydrotrope to obtain a hardening such as stabilization of the liquid at a low temperature and prevention of liquid separation at a high temperature. In general, alcohols represented by short-chain alkylbenzene sulfonates represented by toluenesulfonate and xylenesulfonate, alcohols represented by ethanol, ethylene glycol, propylene glycol, hexylene glycol, glycerin and the like are used. Alcohols and the like.

Tinopal CBS [Ciba Geigy (Ciba) is used as an optical brightener to increase the bleaching effect on white fiber.
-Geigy)], 0-5% of a fluorescent whitening agent such as Tinopearl SWN (Ciba-Geigy) or a color index fluorescent whitening agent 28, 40, 61, 71.

For the purpose of increasing the viscosity of the composition and improving the usability, it is possible to add a thickener in an amount of 0 to 20%, preferably 0.1 to 5%. Generally, synthetic polymers such as polyacrylates, acrylate-maleic acid copolymers, carboxymethylcellulose derivatives, methylcellulose and hydroxymethylcellulose, natural polymers such as xanthan gum, guar gum and kelzan, and water-swellable viscosity minerals such as montmorillonite and veegum And so on.

Compounds such as organic peracids can also be used to enhance the bleaching effect. Examples of such organic peracids include dodecane diperacid, monoperphthalic acid, and the like. These organic peracids are preferably adjusted to a water dispersion by a known method and added.

Further, in order to enhance the bleaching effect, a known hydrogen peroxide activator may be used. Examples of such an activator include N-acyl, O which reacts with hydrogen peroxide to generate an organic peracid.
-Acyl peracid precursors are known. In particular,
Tetraacetylglycoluril, pentaacetylglucose, tetraacetylethylenediamine, sodium nonanoyloxybenzenesulfonate and the like. Moreover, the use of types of active agents which generate singlet oxygen reacts with hydrogen peroxide ⁽¹ O _2), on a high bleaching effect is obtained, breakthrough of not discoloration color patterned clothing The effect can be obtained. Examples of such an activator include JP-A-63-270800, U.S. Patent No. US-4820437, West German Patent DE-3731506.4A, JP-A-63-10700, and JP-A-1-9298. 1-chloro-4-
N-halo hindered amines such as hydroxy-2,2,6,6-tetramethylpiperidine and N-halogens such as chloramine T
-Halosulfonamide and the like. The amount of the activator, it is desirable to add about 1 mole per activator 0.02 molar amount of H ₂ O ₂ contained in the hydrogen peroxide adduct components used (A). As a compounding method, if these compounds are directly added, the stability of hydrogen peroxide is impaired.For example, by melting and dispersing in a compound such as a solid fatty acid, or coating with a solid fatty acid to store the hydrogen peroxide during storage. It is better to add in a form that does not react with.

Further, the product of the present invention may further contain appropriate amounts (each about 0 to about 2%) of various trace additives such as coloring agents such as pigments and dyes, silicones, bactericides, and ultraviolet absorbers.

〔The invention's effect〕

According to the present invention, the amount of gas generated is small even if the hydrogen peroxide solution is stored for a long period of time, so that even if the container is filled with an inexpensive container such as a plastic that does not have a gas leakage mechanism, the container may be swelled or damaged. Because there is no, it is extremely economical.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

〔Example〕

In the examples, the gas generation amount and the swelling of the bottle were measured by the following methods.

How to measure the amount of gas generated After filling up to the top of the opening of a 500ml Erlenmeyer flask with a stoppered glass stopper (total content of about 555ml) light-shielded with aluminum foil, fill the water surface with a pipette to remove 55ml of water. Marked. The water was discarded and the liquid bleach was injected to this position. After leaving it in a thermostat at a specified temperature for 30 minutes, the glass tube with a stopper and a stopper (100 cm in length above the screw-in, 15 cm in length below the screw-in and having a uniform inside diameter) A thin piece of silicone grease was applied and inserted into the flask (be careful that the meniscus is on top of the stopper). After confirming that the grease had spread over the entire circumference of the plug, it was fixed using a spring or rubber band. After the stopper plug was covered with aluminum foil, the position of the meniscus was recorded after leaving it in a thermostat at a predetermined temperature (the level of the water surface of the thermostat was the opening of the flask) or in a thermostat for 2 hours. At the same time, a similar set was prepared with ion-exchanged water. It was left for a predetermined period, the rise of meniscus was measured, and the gas generation amount was calculated by the following equation.

Gas generation amount (ml / 500 ml) = (x−x ₀ ) π (d / 2) ² x = increase in meniscus of liquid bleach (cm) x ₀ = increase in meniscus of ion exchange water (cm) d = Measurement of internal diameter of glass tube (cm) Measurement of bolt swelling The bleach composition was placed in a polyethylene cylinder bottle (full filling amount: 725 ml, bottom wall thickness: 0.6 mm, bottom of this bottle is concave inside). After filling 600 ml, sealing the cap at 25 ° C. and storing in a thermostat at a predetermined temperature, the swelling of the bottle was visually observed at that temperature. Since the bottle is cylindrical, the state where the lower part of the bottle bulges outward when gas is generated and the internal pressure is increased was evaluated according to the following criteria.

：: No change (bottom part of the bottle remains concave) △: Bottom part of the bottle swelled slightly and became flat.

×: The lower part of the bottle was swollen, and the bottle was tilted (or fell down).

Example 1 (A) Hydrogen peroxide (Mitsubishi Gas Chemical: Special grade reagent) 5.0% (B) Fragrance compound (single fragrance compound having a different number of unsaturated bonds) 0.2% (C: optional component) 1-hydroxyethane Various bleaching compositions comprising -1,1-diphosphonic acid 0.1% (D: optional component) POE (= 9) lauryl ether 2.0% (E: optional component) ion exchange water balance It was prepared with different kinds of compounds. In addition, the whole with ion exchange water
Immediately before the balance was adjusted to 100%, the pH of the composition was adjusted to 4.5 using 0.1N sodium hydroxide solution and 0.1N sulfuric acid solution.

Table 1 shows the amounts of gas generated at 45 ° C. and the swelling of the bottles of these various bleach compositions. In addition, 45 ℃
Storage for 30 days is a storage period equivalent to one year storage at room temperature in Tokyo area.

As is apparent from Table 1, the fragrance compound in which the number of unsaturated bonds in the fragrance compound is 1 or less has a high effect of suppressing the amount of generated gas, and as a result, the swelling of the bottle is small (the present invention). . In the case of a fragrance compound having two or more unsaturated bonds, generation of gas is not particularly problematic up to about 14 days. It can be seen that gas is generated more than that. The residual ratio of hydrogen peroxide was 98% or more in any of the compositions even after 60 days at 45 ° C., and no large difference was observed.

Example 2 An example in which a compounded fragrance is used will be described. A liquid bleach composition having the same composition as in Example 1 was prepared except for the compounded fragrance shown in Table 2, and the effect of suppressing the amount of gas generation was examined. Table 2 also shows the results.

As can be seen from Table 2, when a perfume compound containing 60% or more of a perfume compound having 1 or less unsaturated bonds in the perfume compound molecule was used, good gas generation was obtained as in the case of a single perfume compound. It turns out that it has a suppressing effect. The residual ratio of hydrogen peroxide was 98% or more, and no large difference was observed.

Example 3 Bleach compositions were prepared by using the flavorings prepared in Example 2 and varying the amount and pH of the stock solution, and the storage stability was evaluated. The results are shown in Table-3. All of these compositions exhibited good storage stability.

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-4598 (JP, A) JP-A-2-34696 (JP, A)

Claims (2)

(57) [Claims] (A) 2 to 10% of hydrogen peroxide, (B) one or more kinds of fragrance compounds having 1 or less unsaturated bonds in a molecule, and (C) 0.01 to 2%. 3% aminopolycarboxylic acids, inorganic phosphorus compounds, phosphonates, polyaminophosphonic acids, organophosphates, DL-α-tocopherol, gallic acid derivatives, butylated hydroxyanisole and 2,6-di-tert-butyl- A liquid bleach composition comprising one or more stabilizers selected from the group consisting of 4-methylphenol. 2. The composition according to claim 1, wherein said composition contains at least
A liquid bleach composition according to claim 1, wherein 60% is the perfume compound of component (B).