JPS5927795B2 - 1,1,1-trichloroethane composition for dry cleaning - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a 1.1.1-
The present invention relates to trichloroethane stabilizing compositions.

Conventionally, petroleum-based solvents called perchloroethylene and mineral turpentine have been mainly used as dry cleaning solvents.

However, these materials have a high boiling point and require a relatively high temperature of 60° C. to 90° C. when drying the washed items after washing. Therefore, problems such as heat shrinkage, wrinkle formation, and stain fixation are likely to occur, especially for items with low heat resistance such as recent fashion clothing. In contrast, 1,1,1-trichloroethane has a boiling point of 74°C.
It has the great advantage of not causing any thermal troubles, since it can be sufficiently dried at a low temperature of about 40°C.

Furthermore, 1,1,1-trichloroethane has high cleaning power, has relatively little re-contamination, in which dirt that has once escaped into the solvent re-attaches to the items being washed, and is extremely toxic to the human body. It has recently come into the spotlight as a dry cleaning solvent due to its excellent properties such as low dry cleaning properties. 1,1,1-Trichloroethane has traditionally been widely used for degreasing and cleaning metals, but it is chemically unstable and easily decomposes in the presence of metals, especially aluminum or its chlorides. It has a nature.

The decomposition products are mainly hydrogen chloride and tar-like substances, and this hydrogen chloride significantly corrodes the metals present in the system, so 1,1,1-trichloroethane must be stable for industrial use. agent is essential. A large number of results of research on stabilizers have been published, starting with US Pat. No. 2,811,252 in 1957, and more than 100 types of stabilizers have been published. Among them, those that are practically superior include ethers, nitriles, nitroalkanes, ketones,
Esters, alcohols, alkylene oxides,
Amines and the like are known, and conventionally these stabilizers have been used singly or in combination of two or more, mainly to stabilize 1,1,1-trichloroethane against aluminum. Recently, methods of combining the above-mentioned types of stabilizers and adding other third components have been studied in order to improve the effectiveness as well as the economic balance, and many patents have been filed. has been proposed. However, when trying to use 1,1,1-trichloroethane for dry cleaning, the conditions for using it are different from those for degreasing metals, and are generally more severe. There is a difficulty in that stabilizer formulations for degreasing and cleaning are not sufficient.

In other words, in dry cleaning, (1) 1.1.1
- Used in systems where large amounts of water coexist, which promotes the decomposition reaction of trichloroethane; (2) Used for long periods of time with extremely frequent distillation regeneration; (3) As parts of dry cleaning machines. 1.1.1-Trichloroethane comes into contact with many kinds of metals that have poor corrosion resistance, such as aluminum, zinc, copper, and their alloys, which promote the decomposition reaction of 1,1,1-trichloroethane, both at once and over a long period of time.
(4) The concentration of stabilizer contained in 1,1,1-trichloroethane gradually decreases over the course of hundreds of repeated washing operations, and even if the loss of solvent is replenished with fresh solution, There are special and harsh conditions in which the stabilizer in the stabilizer is reduced to a low equilibrium concentration under the conditions of use. Furthermore, in dry cleaning, the operations and machinery are complicated, making it difficult to manage the solvent, and once the solvent begins to deteriorate, it can lead to damage to the cleaning machine and the loss of expensive items to be washed. There is a risk of In general stabilizer formulations, the total amount of stabilizers is kept to approximately 10% by volume or less, partly for economic reasons, but this was still sufficient for degreasing and cleaning metals.

However, if we try to obtain a composition with a high stabilizing effect that can be used for dry cleaning according to the conventionally proposed method, the concentration of the stabilizer will be very high. In the case of washing, there are major restrictions on the amount and type of stabilizer added in order to avoid adverse effects on the items to be washed. Generally, 1・1・1
- Tricrylethane stabilizer is highly polar, so if you choose the wrong type or add too much, a large amount will be adsorbed to the fibers, which will attract water-soluble stains. It may cause re-contamination, it may remain and cause yellowing of the items being washed, or it may cause so-called "weeping" which causes the dye to elute. In practice, the total amount of stabilizer that does not cause any negative effects on the items to be washed must be less than 8% by volume.

In terms of safety, it is desirable that the amount be 7.5% by volume or less. In particular, "weeping" of dyes tends to occur when a large amount of one type of stabilizer is used, but "bleeping" can be alleviated by combining small amounts of several different stabilizers. Strictly speaking, "weeping" differs depending on the type of dye and the type of stabilizer, but the safe critical concentration of each stabilizer that does not cause "weeping" is about 3% by volume. As a result of these discoveries and limitations, the present inventors investigated various stabilizing formulations that provide dry cleaning compositions that are sufficiently stable and have excellent properties.
By combining the five stabilizers of methyl-3-butyn-2-ol, 1,2-butylene oxide, and nitromethane, an extremely excellent overall effect that cannot be obtained with conventionally known stabilizing formulations can be obtained. Heading, we arrived at the present invention.

That is, the present invention provides (1) 1,4-dioxane, (2
) Isobutyl alcohol, (3) 2-methyl-3-butyn-2-ol, (4) 1,2-butylene oxide,
(5) Contains five components of nitromethane as stabilizers, and the total amount of stabilizers is within the range of 3.5 to 7.5% by volume of the total amount of 1,1,1-trichloroethane and the total amount of stabilizers, Based on the total amount of stabilizer, (1) 10 to 35% by volume of 1,4-dioxane, (2) 10 to 35% by volume of isobutyl alcohol, (3) 10 to 45% by volume of 2
- Methyl-3-butyne-2-2-ol, (4) 5 to 20% by volume of 1,2-butylene oxide, and (5) 10 to 25% by volume of nitromethane. Related.

In the present invention, five components are used simultaneously as stabilizers, and the amounts added are appropriately selected within the above-mentioned range depending on the actual conditions of use.

It is also possible to further add other stabilizers as long as the effects of the present invention are not impaired. As shown in Examples and Comparative Examples below, 61.4 dioxane, isobutyl alcohol, 2-methyl-3-butyn-2-ol, and nitromethane were used in amounts less than 10% by volume of each stabilizer, and 1.
When the amount of 2-butylene oxide is less than 5% by volume of the total amount of stabilizer, the effectiveness of the present invention is somewhat diminished.

Also, if only a few of these stabilizer components are used in extremely large amounts, not only will the dye "bleed out", but
The amount of other components added must be reduced, and the stabilizing effect of the present invention is also somewhat reduced. Also, when the total amount of stabilizers is less than 3.5% by volume, the stability against aluminum and zinc tends to decrease slightly. As described above, the composition of the present invention does not adversely affect the items to be washed, has a large amount of water coexisting with it, and is stable against various metals in a system that is repeatedly distilled and regenerated, so it can be used as a dry cleaning composition. It is extremely excellent as a product.

Of course, it is clear that the composition of the present invention can also be used for degreasing and cleaning metals, which requires less severe conditions than dry cleaning. The present invention will be described in detail below along with Examples and Comparative Examples.

Test Method The present inventors selected a test method based on a concept different from conventional methods in order to reproduce the special usage conditions of dry cleaning.

That is, in dry cleaning, as any stabilizer type is used, it gradually decreases to a certain equilibrium concentration, and it is the composition containing the stabilizer at this equilibrium concentration that actually comes into contact with various metals for a long period of time. Therefore, evaluation of the stability of a formulated sample should be done using a test method that reproduces the actual situation using a composition at this equilibrium concentration. In order to obtain an equilibrium concentration solution for each formulation sample, the inventor actually conducted 500 dry cleanings at ℃ for all stabilized formulation samples.

The dry cleaning machine is Sanyo Ichi SCL-915, and it uses 2 sheets each of cotton, wool, acrylic, and polyester white cloths.
．． The common practice is to add 5k9 at a time, add 300ml of commonly used soap each time, adjust the liquid level in the tank with new liquid every 34 times, and take out the distillation sludge every 10 times. I faithfully followed the standard work. Two sets of the same items to be washed were prepared and used repeatedly. Using the equilibrium concentration solution thus obtained, the stability of the formulated sample was evaluated by the Test 1 method shown below. (1) Method A; Aluminum scratch test side (1
) Method A-1: Take 50 d of 1.1.1-trichloroethane prescription sample into a 100 ml tall beaker and place it on a hot plate.

At the point where boiling started, the aluminum alloy specimen (JIS
、． Hl4OOOO,. Immediately after dipping the sample (A2O24P) into the liquid, scratch it with a sharp knife three times in the lengthwise direction of the sample piece and twice in the perpendicular direction. When the scratch is finished, quickly cover the dish with a Petri dish and give the following evaluation on the appearance of the scratched area after 30 seconds. 1 reaction is completely suppressed.

2 reaction products are observed at intervals.

3 reaction products are present continuously along the wound.

4 Reaction products are present in a slightly bulging state from the wound.

The reaction is so intense that the liquid 5 turns significantly black.

(4) Method A-2; 1.1.1-trichloroethane prescription sample 50TIL1 was placed in a 100ml beaker, and aluminum alloy specimens (JISlHl4OOOO,
．． Soak in A2O24P) and use a sharp knife to cut it 3 times in the length direction.
Scratch twice at right angles.

Give the following rating for the appearance of the scratch location. 1 reaction is completely suppressed.

3 The reaction is temporary and stops quickly.

5 The reaction does not stop immediately.

Dry cleaning machine parts and aluminum items to be washed normally come into contact with 1.1.1 trichloroethane only at room temperature.

In this sense, 1,1,1-trichloroethane for dry cleaning can be said to pass if it can obtain a rating of 1 in the A-2 method.

If we assume that an aluminum ornament, etc. to be washed falls off during washing and is carried into the distiller along with the flow of liquid, it would be possible to obtain a rating of 3 or higher using the A-1 method. preferable. Method B; Ribrax test 10 with attached reflux condenser and soxle extractor
Into a 0 ml flask, add 1,1,1-trichloroethane formulation sample in an amount equal to the amount of liquid stored in the Soxle extractor.

Furthermore, 5% of commonly used dry cleaning soap and 3% of water were added to this, and the flask was made of stainless steel (JIS, Hl43O5, SUS), assuming that it would be inside a distiller.
A test piece of 3O4) was placed across the gas and liquid, and stainless steel (JIS.G, 4305, S
Test pieces of zinc (JIS, .H, 4321) and gun metal (JIS, .Hl5ll, BC-6) are introduced. In addition, copper (JIS, Hl3lOO.
Hang a test piece of CllOOP). Refluxing was repeated for 55 hours in an oil bath at 150°C, and the surface condition of each test piece was observed and evaluated.

The evaluation was performed on stainless steel specimens intended for use in distillers.
Give as follows.

1 No change observed at all.

2 Slight corrosion is observed only at the bottom of the metal specimen.

3. Severe corrosion is observed only at the bottom of the metal specimen.

4 Corrosion has also spread to the top of the metal specimen.

5. Severe corrosion is observed on the upper part of the metal specimen.

The copper and gunmetal in the liquid reservoir are given as follows, assuming a distillation condenser.

1. Loss of gloss or discoloration is observed in some areas.

2 Loss of gloss or discoloration is observed overall.

3. Slight patina occurred.

4. Considerable patina occurred in some areas.

5. Significant patina occurred throughout.

This Test 1 test method attempts to faithfully reproduce the harsh conditions inside a dry cleaning machine.

(3) Method C, immersion test Take a prescription sample of 30111 in a 50ml pressure pin, add 1000ppm of water to it, seal it tightly, and keep it at 60°C to completely dissolve the water.

Once the water has dissolved, quickly remove the stopper and remove the zinc (JIS.H, 4
321) so as to span the gas and liquid and seal it again.
Let stand at 60°C for 190 hours. Observe the test piece during the test and give the following evaluation. No change was observed even after 1190 hours.

Some gloss was lost after 2190 hours.

Some gloss was lost within 3100 hours.

Some gloss was lost within 450 hours.

Some gloss was lost within 51 hours.

This test method is more suitable than Method B for reproducing the conditions of zinc-using parts of dry cleaning machines.

Since zinc is a metal that has the second highest catalytic activity in the decomposition reaction of 1,1,1-trichloroethane after aluminum, it is necessary to obtain a rating of 2 in this method for use in dry cleaning. In addition, in the table described below, the following abbreviations are used for each stabilizer type.

The compositions of the new solutions of Comparative Examples 1 to 7 and Examples 1 to 18 are shown in the table below.
Shown in 1.

(, Comparative Examples 1 to 7 and Examples 1 to 18 are evaluated.

? As is clear from the above, the composition of the present invention has a remarkable effect compared to 402q, and has a high t that can be stably used even under dry conditions.

Claims (1)

[Claims] 1 (1) 1,4-dioxane, (2) isobutyl alcohol, (3) 2-methyl-3-butyn-2-ol, (
Contains 5 components as stabilizers: 4) 1,2-butylene oxide and (5) nitromethane, and the total amount of stabilizers is 1.1
- Within the range of 3.5 to 7.5% by volume of the total amount of 1-trichloroethane and stabilizer, based on the total amount of stabilizer, (1) 10 to 35% by volume of 1,4-dioxane; (2) 10 to 35% by volume of isobutyl alcohol, (3) 10 to 45% by volume of 2-methyl-3-butyn-2-ol, (4) 5 to 20% by volume of 1.2-
A stabilized 1,1,1-trichloroethane composition for dry cleaning, characterized in that it contains butylene oxide, (5) 10 to 25% by volume of nitromethane.