KR900005570B1 - Solvent for drycleaning - Google Patents

Abstract

A dry-cleanign solvent contains (a) low molecular wt. of polyolefin and (b) 0-40 wt.% of petroleum, chlorine and/or fluorine solvent. The polyolefin is pref. polybutene or polypropylene, and its boiling point is pref. 100-280 deg.C. The solvent has an excellent stability and cleaning effect.

Description

Dry Cleaning Solvent

The present invention relates to a cleaning composition excellent in handling stability and cleaning effect.

) 등의 석유계 용제외에, 1,1,1-트리클로로에탄, 트리클로로에틸렌, 퍼클로로에틸렌, 1,1,2-트리클로로에탄 등의 염소계 용제, 혹은 물론 113 등의 불소계 용제를 사용하는 것이 알려져 있다. 어떤 용제를 사용할 것인가는, 현실적으로 사용 목적 또는 대상이 되는 오염천(布)의 종류나 오염의 정도에 따라서 상술한 용제중에서 적당히 결정된다.Conventionally, as a cleaning composition, for example, kerosene oil (

Chlorine solvents such as 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, 1,1,2-trichloroethane, or of course, fluorine solvents such as 113, besides petroleum solvents such as It is known. Which solvent is to be used is suitably determined in the above-mentioned solvents according to the kind and the degree of contamination of the contaminated cloth to be practically used or the object.

By the way, when the above-mentioned conventional cleaning solvents, for example, petroleum solvents or chlorine solvents are used, the worker sucks the gas or the gas is absorbed into the body from the skin, thereby causing the operator's backbone. Nerve or autonomic nervous system is invaded, dizziness, headache, weakness and so on. It is also known that hematopoiesis and inflammation of the skin occur when the degree of absorption or aspiration of the gas proceeds.

For these reasons, in performing the work using the above-mentioned solvents, regulations according to the "Organic Solvent Poisoning Prevention Regulation" or the "Working Environment Measurement Method" are applied, and sufficient ventilation in the workplace and, if necessary, The wearing of masks is mandatory for workers, and his gloves and safety glasses are also required.

In the case of using a fluorine-based solvent, since it is relatively expensive, the solvent is recovered by making the cleaning facility sealed, but the recovery facility for this is enlarged, and, of course, the recovery cost is large.

Moreover, although it is proposed to use normal paraffin and water addition kerosene as a solvent for the safety of handling, the composition for dry cleaning using these solvents had a problem that the washing | cleaning effect was inferior.

An object of the present invention is to provide a cleaning solvent that is safe in handling, excellent in cleaning effect, and low in cost.

The present invention for achieving the above object is at least one selected from the group consisting of a low molecular weight polyolefin having a side chain and a petroleum solvent, a chlorine solvent, a fluorine solvent as a blending ratio of 0 to 40% by weight based on the low molecular weight polyolefin It is a solvent for dry cleaning characterized by containing any one kind.

The low molecular weight polyolefin having a side chain can be obtained, for example, by homopolymerization or copolymerization in the presence of an aluminum trichloride catalyst, for example, an olefin, but the type of the catalyst and the polymerization method are not particularly limited.

As said olefin, C2-C12 alkenes, Preferably C2-C8 alkenes are mentioned.

Among these, alpha-olefins such as ethylene, propylene, butene, hexene, 4-methyl-1-pentene, octene and vinylcyclohexene or mixed olefins thereof are suitable, and propylene and butene are particularly suitable.

The low-molecular-weight polyolefin having a side chain obtained in this manner has a liquid boiling point range of about 100 ° C to about 280 ° C of IBP by the distillation method specified in JIS K 2254, among which in the present invention As used, a low molecular weight polyolefin having a side chain containing 150 to 210 ° C by the distillation method can achieve the most preferable result for cleaning.

When the boiling point of the low-polymerization polyolefin used as the cleaning solvent is in a region lower than about 150 ° C, since the flash point is lower than room temperature, fire management when handling the solvent is complicated, and on the contrary, the boiling point is about 210 ° C. When exceeded, the speed | rate of volatilization falls remarkably, and it takes a long time for the drying process of a cleaning object, and shows an undesired tendency.

Moreover, although the low molecular weight polyolefin obtained as mentioned above can also be used as it is, the low molecular weight polyolefin obtained by carrying out hydrogenation treatment separately is preferable. This is because the low molecular weight polyolefin subjected to the hydrogenation treatment has no odor and is excellent in storage stability.

In the present invention, a dry cleaning solvent suitable for the low-polymerization polyolefin containing only the side chain can be used, but at a compounding ratio not exceeding 40% by weight with respect to the low molecular weight polyolefin having a side chain and the low molecular weight polyolefin, Preferably, the solvent for dry cleaning is formed by at least one selected from the group consisting of petroleum solvents, chlorine solvents, and fluorine solvents in a blending ratio not exceeding 25% by weight.

This further increases the compatibility between the dry cleaning solvent and the dry soap by further blending the petroleum solvent, and by blending the chlorine solvent, the solubility of the fat and oil is improved, thereby improving the cleaning power for the fat and oil, and blending the fluorine solvent. This is because the touch after washing of the object to be cleaned improves. When the chlorine-based solvent and / or the fluorine-based solvent are added, the drying step after washing can be shortened. When the blending amount of at least one solvent selected from the group consisting of the petroleum solvent, the chlorine solvent and the fluorine solvent exceeds 40% by weight, the effects of toxicity to the worker cannot be ignored. In addition, the petroleum, fluorine or chlorine-based solvents have substantially small solubility and swelling property in rubber and plastics, and therefore have the advantage of significantly alleviating the restrictions on their use.

As a petroleum solvent, kerosene fraction or a C9 or 10 aromatic compound is mentioned, for example.

Examples of the chlorine-based solvents include 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, 1,1,2-trichloroethane and the like. Examples of the fluorine-based solvents include Polon 113 and Polon 112.

These solvents may be used individually by 1 type, and may use 2 or more types together.

Moreover, you may add 0-100 ppm (total weight) antioxidants, such as BHT.

The solvent for dry cleaning of this invention is mix | blended with dry soap, and the composition for dry cleaning is formed.

Examples of the dry soaps include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. These surfactants may be used alone or in combination of two or more thereof. Above all, when using two or more types together, it is not preferable to use a cationic surfactant and an anionic surfactant together, and a combination of a cationic surfactant and a nonionic surfactant [cationic nonionic composite surfactant] Combination of anionic surfactants and nonionic surfactants (anionic nonionic composite surfactants) is recommended.

According to the difference of the polar group in surfactant, the effect at the time of washing | cleaning of the composition for cleaning of this invention differs, for example, the cleaning composition which contains anionic surfactant as a dry soap has good washing power, but it washes Although the flexibility of the subsequent to-be-cleaned object was lacking, the composition for dry cleaning which uses a cationic surfactant or a cationic surfactant and a nonionic surfactant together is excellent in the flexibility of the to-be-cleaned object after washing | cleaning, but the cleaning power is not exhibited very much. It wasn't. Combining matters concerning the cleaning of the composition for dry cleaning, a combination of an anionic surfactant and a nonionic surfactant is preferable, and as such dry soap, a brand name "Raidol soft" [Japanese Gyoisha Yushi, Japan] Product] It is easy as "Send Rex dry max crystal" [Alves Co., Ltd.], "Genf Clean" [Genf Co., Ltd.], "Sansil coat" [product of Nippon-Yuyoshi, Japan] Commercially available.

Here, as anionic surfactant, a carboxylate, a sulfonate, a sulfate ester salt, a phosphate ester salt, etc. are mentioned, for example.

As said carboxylate, For example, fatty acid soap which is a sodium salt or potassium salt of a C12-C18 fatty acid, such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid, alkyl ether carboxylate, etc. Can be mentioned.

As said sulfonate, an alkylbenzene sulfonate, an alkanesulfonate, a dialkyl sulfosuccinic acid ester salt, (alpha)-olefin sulfonic acid, etc. are mentioned, for example.

As said sulfate ester salt, sulfated oil, a higher alcohol sulfate ester salt, an alkyl ether sulfate, etc. are mentioned, for example.

As said phosphate ester salt, an alkyl ether phosphate ester salt, an alkyl phosphate ester salt, etc. are mentioned.

Among these various anionic surfactants, fatty acid soap, alkylbenzene sulfonate, alkalsulfonate, α-olefin sulfonate and the like are preferable.

As said cationic active agent, an aliphatic amine salt, an aliphatic quaternary ammonium salt, etc. are mentioned, for example.

As an amphoteric surfactant, a carboxybetaine type is mentioned, for example. As a nonionic surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxy propylene block polymer, polyoxyethylene sorbitan fatty acid ester, polyoxy ethylene sorbitol fatty acid ester, polyethylene glycol Fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

The dry cleaning composition of the present invention has a dry soap content in the range of 3 to 0.5% by weight, preferably 2.8 to 0.8%, based on the total amount of the low molecular weight polyolefin having a side chain and the dry soap. For low molecular weight polyolefins, it is important to be in the range of 97 to 99.5% by weight, preferably 97.2 to 99.3% by weight).

If the content of the dry soap exceeds 3% by weight, the object to be cleaned becomes sticky after washing, and the meaning of washing is lost. If the dry soap content is less than 0.5% by weight, the cleaning power may be recontaminated during cleaning, staining the object to be cleaned, generating static electricity, or losing the flexibility of the object to be cleaned. Discomfort arises.

Since the solvent for dry cleaning of the present invention contains a low molecular weight polyolefin having a side chain as described above, the stability to the human body can be improved and the working environment can be improved.

Moreover, in the dry cleaning solvent which mix | blended the side chain containing low molecular weight polyolefin and at least 1 sort (s) chosen from the group which consists of the said petroleum solvent, a chlorine solvent, and a fluorine solvent, it improves washing power by mixing with dry soap, The composition for dry cleaning which shows the outstanding effect, such as the improvement of the touch of the to-be-cleaned object after washing | cleaning and a shortening of a drying process, can be formed.

EXAMPLE

Hereinafter, several examples and comparative examples will be shown, and the structure and effect of this invention are demonstrated further more concretely.

Example 1

Isoparaffin solvent [IBP 170 ° C., EP 192 ° C.] and anionic nonionic complex soap [mixture of anionic surfactant and nonionic surfactant made of hydrogenated low molecular weight polybutene, trade name Lydosol Soft, The to-be-cleaned object shown in the 1st table | surface was wash | cleaned using the composition for dry cleaning which consists of a mixture with Japan Kyo-Eisha Yushi Co., Ltd. product 2.5% [concentration with respect to the said solvent]. The washing temperature was room temperature and the washing time was 13 minutes. After washing, the object to be cleaned was dried over 35 minutes while being heated to 38 ° C. with a dryer (manufactured by Shin-Nippon Co., Ltd.).

The following evaluation was performed about the to-be-cleaned object after washing | cleaning. The results are shown in the first table.

{Clean rate}

It measured based on the test method prescribed | regulated to JIS LO 860. The cleaning rate is expressed as (W ₀ -W ₂ ) / (W ₁ -W ₂ ) x 100 when the whiteness of the raw material, the contaminated cloth, and the washed cloth is W ₁ , W ₂ , W ₀ . It was. In addition, the cleaning rate indicates that the larger the number, the greater the cleaning effect.

{Reverse contaminants}

The contaminated cloth was washed like 15 kg of the object to be washed as a test cloth, and after drying, the reflectance of the test cloth was measured by a reflectometer and evaluated.

In addition, reverse contamination indicates that the smaller the number, the smaller the reverse pollution.

[Comparative Examples 1,2]

Instead of the isoparaffinic solvent formed by hydrogenating a low molecular weight polybutene, in Comparative Example 1, a normal paraffinic solvent [IBP 170 ° C, EP 174 ° C, trade name Nigo-N-10, product of Nippon Nigoo Corporation] In Comparative Example 2, a hydrogenated kerosene-based solvent [IBP 159 ° C, EP 193 ° C, trade name Egusol D-40, Eguson Furniture Co., Ltd.] was used in the same manner as in Example 1 above. .

The results are shown in the first table.

[Table 1]

[Examples 2 to 4 and Comparative Examples 3 and 4]

The same procedure as in Example 1 was conducted except that the concentration of the dry soap in the Example was changed to the amount indicated in the second table, and evaluation was performed in the same manner as in Example 1.

The result is shown in a 2nd table with the result of Example 1. FIG.

[Table 2]

[Examples 6-9]

Except for changing the type of dry soap to the third table, it was carried out in the same manner as in Example 1, and the cleaning rate and the reverse contamination rate were evaluated in the same manner as in Example 1, and the flexibility was evaluated as follows. It was.

The flexibility of the to-be-cleaned object after washing | cleaning in the said Example 1 was also evaluated.

The results are shown in the third table as in the results of Example 1.

[Table 3]

Examples 10 to 15 and Comparative Examples 5 to 7

A dry cleaning composition composed of a cleaning solvent and a dry sole composed of the composition shown in Table 4 is prepared, and irritant to the skin, residual odor, and the dry cleaning solvent and the dry cleaning agent are used for the purpose of cleaning, drying and safety. Measurements (and determinations) were made for compatibility with soaps and the displayed results were obtained.

In addition, the used low molecular weight polyolefin has a boiling point of 160 to 200 ° C and a specific gravity of 0.715, and a fluorine-based solvent having a boiling point of 160 to 200 ° C obtained by distilling and cutting one part of kerosene fraction or a fluorine-based solvent, or having 9 or 10 carbon atoms. 1,1,1-trichloroethane was used as the aromatic compound and chlorine solvent.

In addition, the performance test was performed according to the following method.

{Clean rate}

As described above. As dry soap, M-88 manufactured by Nippon Yushi Co., Ltd., Japan, was used.

{Compatibility}

The commercially available dry soap (M-88, Nippon Yushi Co., Ltd. M-88) commercially available after dissolving 5 wt% in each solvent at room temperature (Test 1), and the solution of Test 1 in a humidity of 70 to 80% Was placed in an atmosphere of 1 day and night, and the solution of test 2 and the solution of test 2 were totally judged to be good (◎) and good (○) after 1 day and night standing at -20 ° C. .

{Dryness}

The wool was used as a test cloth, which was dried for 25 minutes at 50 ° C. after one day and night immersion in a dry cleaning solvent, and then dryness was determined by the touch of the wool.

Meaning of the symbols in the table

1: high moisture. 2: The humidity is moderate. 3: The humidity is small. 4: It is almost dry. 5: It is completely dry.

{Irritation to skin}

One group of ten glues are attached to the inside of the upper arm of the panel, and a patch test is carried out. 0 ~ 2 (weak stimulus), erythema to scab… 3 to 5 (medium stimulation), scab to edema formation… It determined by classifying into 6-(strong stimulus).

{Residual odor}

Artificial leather suede was used as a sample cloth, and then it was immersed in a solvent for one day and night, followed by natural drying or heat drying (60 ° C., 30 minutes), depending on the strength of the odor after the next day and one week. ◎: Very good, ○: Good, △ : It was judged according to the evaluation of: a little bad and x: bad.

{Rubber insoluble}

To 1 g of NR-based rubber vulcanizate, 100 ml of the test solvent indicated was added, and the degree of swelling of the rubber was examined, and the degree of swelling after 24 hours was divided and evaluated in the following five steps.

1: No swelling, 2: Swelling slightly, 3: Swelling to some extent, 4: Swelling remarkably, 5: Dissolution

{Plastic solubility}

Instead of the NR rubber vulcanizate, 1 g of hard vinyl chloride sheet was used, and the solubility of the plastic was examined in the same manner as in the rubber solubility test, and evaluated according to the same criteria.

[Table 4]

(A): low molecular weight polybutene (B): low molecular weight polypropylene (C): water added low molecular weight polypropylene

Petroleum solvent 1: kerosene fraction, boiling point 160 ~ 200 ℃

Petroleum solvent 2: Aromatic compound with 9 degrees of carbon atoms of 10.

As shown in Table 4, it is clear that the composition for dry cleaning of the present invention can be suitably used as a composition for dry cleaning which is very fast in drying and has high stability as a result of the residual odor test. In addition, the composition for dry cleaning of the side chain-containing low molecular weight polyolefin and dry soap with at least one selected from the group consisting of the petroleum solvent, the chlorine solvent, and the fluorine solvent has almost no deterioration in cleaning performance. In addition, the drying speed is high, and the stability is high.

Moreover, the composition for dry cleaning of this invention knows that there is no solubility (swelling property) with respect to rubber | gum and plastics universally used as a general container, a pipe, etc., and it can expect that the management restrictions can remarkably ease the use restrictions. Can be.

Claims (4)

A low molecular weight polyolefin having a side chain and at least one selected from the group consisting of a petroleum solvent, a chlorine solvent and a fluorine solvent at a compounding ratio of 0 to 40% by weight with respect to the low molecular weight olefin. Solvent for dry cleaning. The solvent for dry cleaning according to claim 1, wherein the low molecular weight polyolefin having side chains is a low molecular weight polybutene or a low molecular weight polypropylene. The solvent for dry cleaning according to claim 1, wherein the low molecular weight polyolefin having the side chain has an IBP of about 100 ° C to EP of about 280 ° C. The dry cleaning solvent according to claim 1, wherein the low molecular weight polyolefin having the side chain is hydrogenated.