JPH0380838B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a reducing bleach composition, and more particularly to a reducing bleach composition for household use. [Prior Art] Clothes are generally washed using laundry detergents (often heavy duty detergents), and in most cases stains can be removed and finished just by washing, but stains cannot be removed. If it does, it is generally treated with an oxidizing bleach. In particular, chlorine-based liquid bleach containing sodium hypochlorite as a main ingredient is most commonly used because it has a high bleaching effect at low temperatures. However, certain compounds that contain nitrogen in their structure, such as wool, silk, polyurethane, and some resin treatments, react with chlorine bleach to produce chloramines, causing yellowing instead of bleaching. The situation was ripe. Another disadvantage is that when washing clothes with water containing a large amount of iron, the iron content is oxidized from divalent to trivalent iron, reducing its solubility and depositing on clothes, causing them to turn yellow. Therefore, reducing agents are used to restore such yellowing of clothing. This reducing agent reacts with chloramine to remove chlorine, and for iron deposited on clothing, it converts water-insoluble trivalent iron to more soluble divalent iron, making clothing original. It has the effect of restoring the whiteness of the skin, but in general, other ingredients,
For example, chelating agents such as ethylenediaminetetraacetate and sodium nitrilotriacetate, builders such as sodium citrate, sodium tripolyphosphate, and sodium pyrophosphate, and additives such as nonionic surfactants and anionic surfactants are used. Used as a reconstituted bleach composition.
These reduced bleach compositions are preferably stored in a moisture-proof container to prevent stability from being impaired by moisture absorption. It is especially easy to use and convenient if a single-use pillow package is used. [Problems to be Solved by the Invention] However, it has been found that in this pillow packaging form, the container swells when stored for a long period of time, causing problems. This phenomenon of container expansion is extremely subtle; for example, as in the case of oxidizing bleach, oxygen is generated by the self-decomposition of hydrogen peroxide and sodium hypochlorite aqueous solutions, which expands thick-walled plastic bottles. It is not something that will cause harm or destruction,
Even if it is stored in a thick plastic bottle, it does not create a feeling of pressure in the container, and this phenomenon can only be recognized if it is stored in pillow packaging. Moreover, this expansion does not lead to the destruction of the pillow packaging even if the packaged item is stored as is. However, from the viewpoint of commercial value, this expansion is a big problem. In other words, pillow packaging
When 10 to 20 bags are packaged in a paper container as one case, problems arise in that the paper container is deformed, lowering the product value, and when the pillow packaging is opened, a strange odor is emitted, causing discomfort to the user. [Means for Solving the Problems] As a result of intensive research in order to prevent the above-mentioned expansion phenomenon of the reduced bleach composition, the present inventor found that the cause of expansion was the formation of mercaptans and that the composition They discovered that expansion can be prevented by adding an olefin compound to the product, and completed the present invention. Therefore, the present invention provides the following components (A) and (B) (A) a sulfur-containing reducing agent, (B) an olefinic compound selected from the following group, (a) an olefinic hydrocarbon having 10 to 15 carbon atoms. (b) an olefinic alcohol having 10 to 15 carbon atoms or an ester thereof; and (c) an olefinic ketone having 10 to 15 carbon atoms. The sulfur-containing reducing agent, component (A) of the present invention, refers to a compound that contains sulfur and has a reducing action,
Examples include thiourea dioxide, sodium dithionite, sodium sulfite, sodium thiosulfate, sodium borohydride, and among these, thiourea dioxide and sodium dithionite are particularly preferred. This component (A) contains 1
~70% by weight (hereinafter simply referred to as "%"), preferably 10 to 50%. In addition, as the olefinic compound which is component (B), (a) olefinic hydrocarbon having 10 to 15 carbon atoms, (b)
Examples include olefinic alcohols having 10 to 15 carbon atoms and esters thereof, and (iii) olefinic ketones having 10 to 15 carbon atoms. Specific compounds include, for example, the following. (a) Olefinic hydrocarbons having 10 to 15 carbon atoms: pinene, 1-methyl-p-isopropenyl-1-cyclohexene, p-mentha-1,4(8)-diene, 7-methyl-3-methylene- 1,6-octadiene and β-caryophyllene. (b) Olefinic alcohol having 10 to 15 carbon atoms and its ester: 3,7-dimethyl-1,6-octadiene-
3-ol, 2-trans-3,7-dimethyl-2,6-octadien-1-ol, 2-cis-3,7-dimethyl-2,6-octadien-1-ol, 3,7-dimethyl- 6-octen-1-ol, 3,7-dimethyl-4,6-
Octadien-3-ol, 2-methyl-6-
Methylene-7-octen-2-ol, 2-methyl-6-methylene-7-octan-2-ol, 1-methyl-4-isopropyl-1-cyclohexen-8-ol, vetiverol, 3,
7,11-trimethyl-1,6,10-dodecatrien-3-ol and cis-3-hexenol. (c) Olefinic ketone having 10 to 15 carbon atoms: 4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one,
2,6,6-trimethyl-trans-1-crotonylcyclohexene-1, 2,6,6-trimethyl-trans-1-crotonylcyclohexene-2,3-hydroxy-2-methyl-4-
Pyrone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, l-1-methyl-4-isopropenyl-6
-cyclohexen-2-one, 2-pentyl-
3-methyl-2-cyclopenten-1-one,
4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-methyl-3-buten-2-one. Among these olefinic compounds, (c) olefinic ketone is most preferred. This (B) component is contained in the composition at 0.005 to 0.5%, especially
It is preferable to add and blend 0.01 to 0.3%.
If the amount is less than 0.005%, the effect will be small, and if it is more than 0.5%, it will be uneconomical. The reduced bleach composition of the present invention can be prepared by blending component (A) and component (B) according to a conventional method. The composition of the present invention may further contain organic or inorganic builders such as sodium sulfate, sodium bicarbonate, sodium pyrophosphate, sodium tripolyphosphate, sodium silicate, sodium citrate, sodium ethylenediaminetetraacetate, nitrilotriacetic acid, etc., if necessary. Chelating agents such as sodium, polymeric anions such as carboxymethyl cellulose and polyethylene glycol, cationic, nonionic, and amphoteric surfactants,
Other fluorescent dyes, fragrances, etc. can also be used as desired. [Operation] Since the reducing agent is generally capable of absorbing oxygen, it was not expected that the container filled with the reduced bleach composition would swell even if it dented. After discovering the expansion of the pyro packaging, the inventor analyzed the gas in the packaging and detected methyl mercaptan. This mercaptan compound is
It is presumed that this is caused by a reaction between a trace amount of organic matter contained in the sulfur-containing reducing agent, various types of organic matter blended therein, or impurities contained therein, reacting with the sulfur-containing reducing agent. Although the mechanism of the anti-swelling effect of the olefin compound of the present invention is not yet clear, it is thought that the generated mercaptan compound and the olefin compound react, or that the production of the mercaptan compound itself is suppressed. Note that the anti-swelling effect of the present invention could not be observed for aldehyde compounds having highly reactive functional groups. [Effects of the Invention] The reduced bleach composition of the present invention does not expand over time even when packaged in pillow packaging, and does not generate any strange odor when opened, so it can maintain high commercial value over a long period of time. can be maintained. [Example] Next, the present invention will be explained in more detail with reference to Examples. Example 1 To 10 g of the reduced bleach base having the composition shown below, 0.1% of the stabilizer shown in Table 1 was added in a conventional manner to obtain a reduced bleach composition. This composition was coated with aluminum foil/polyethylene heat-meltable film for 5 cm
We wrapped it in 5cm pillowcases. At the end of packaging, flatten the package by hand as much as possible, seal it,
I sealed it. This pillow package was stored at 30°C for 2 months, and the state of expansion was observed during that time. The results are also shown in Table 1. (Reduced bleaching base composition) Sodium dithionite (active content 89.5%)
30 (%) Sodium pyrophosphate 15 Sodium nitrilotriacetate 3 Sodium sulfate 52 (Results)

【table】

【table】

【table】

[Table] Example 2 A reducing bleach composition having the following composition was prepared,
This is wrapped in 10g/wrapping aluminum pillow packaging.
I made 20 packages. This package was stored at 30°C for 6 months, but no blistering was observed in the container. (Composition) Thiourea dioxide 30 (%) Sodium tripolyphosphate 30 Tetrasodium ethylenediaminetetraacetate 10 Sodium sulfate 29.8 Stabilizer ^* 0.2 *Stabilizer composition 2-Pentyl-3-methyl-2-cyclopenten-1-one 25 (%) 2,6,6-trimethyl-trans-1-crotonylcyclohexene-1 25 β-caryophylene 25 Pinene 25

Claims (1)

[Scope of Claims] 1. Components (A) and (B) (A) a sulfur-containing reducing agent, (B) an olefinic compound selected from the following group, (a) an olefinic hydrocarbon having 10 to 15 carbon atoms. (b) an olefinic alcohol having 10 to 15 carbon atoms or an ester thereof; and (c) a reducing bleach composition containing an olefinic ketone having 10 to 15 carbon atoms. 2. The reducing bleach composition according to claim 1, wherein the sulfur-containing reducing agent (A) is thiourea dioxide or sodium dithionite. 3 The olefinic hydrocarbon having 10 to 15 carbon atoms in (B) is pinene, 1-methyl-p-isopropenyl-1-
Reductive bleaching according to claim 1, which is selected from cyclohexene, p-mentha-1,4(8)-diene, 7-methyl-3-methylene-1,6-octadiene and β-caryophylene. agent composition. 4 The olefinic hydrocarbon having 10 to 15 carbon atoms in (B) is 3,7-dimethyl-1,6-octadiene-3-
ol, 2-trans-3,7-dimethyl-2,
6-octadien-1-ol, 2-cis-3,
7-dimethyl-2,6-octadien-1-ol, 3,7-dimethyl-6-octen-1-ol, 3,7-dimethyl-4,6-octadiene-
3-ol, 2-methyl-6-methylene-7-octen-2-ol, 2-methyl-6-methylene-7-octan-2-ol, 1-methyl-4-ol
Isopropyl-1-cyclohexen-8-ol, vetiverol, 3,7,11-trimethyl-
A reducing bleach composition according to claim 1, which is selected from 1,6,10-dodecatrien-3-ol and cis-3-hexenol. 5 The olefinic hydrocarbon having 10 to 15 carbon atoms in (B) is 4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, 2,
6,6-trimethyl-trans-1-crotonylcyclohexene-1,2,6,6-trimethyl-
trans-1-crotonylcyclohexene-2,
3-hydroxy-2-methyl-4-pyrone, 3-
Methyl-2-(cis-2-penten-1-yl)-
2-cyclopenten-1-one, l-1-methyl-4-isopropenyl-6-cyclohexene-2
-one, 2-pentyl-3-methyl-2-cyclopenten-1-one and 4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-
A reducing bleach composition according to claim 1, which is selected from methyl-3-buten-2-one. 6. The reducing bleach composition according to claim 1, wherein the amount of (B) blended in the composition is 0.01 to 0.3% by weight.