JP2008248104A - Composition for dry cleaning - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for the use for dry cleaning which, being a substitute for a petroleum-based solvent generally used for dry cleaning now, has detergency equal or superior to that of the petroleum-based detergent composition containing a petroleum-based solvent and a surfactant even without containing a surfactant as the detergent. <P>SOLUTION: The composition for dry cleaning contains at least one fatty acid ester represented by formula (I): R<SP>1</SP>-O-(R<SP>3</SP>O)m-COR<SP>2</SP>(I) (wherein R<SP>1</SP>is a 1-8C alkyl group; R<SP>2</SP>a 5-21C alkyl group; R<SP>3</SP>a 2-4C alkyl group; and m a number of 0-5). In the composition (1) the content of a fatty acid ester having a carbon number of 6-12 as to R<SP>2</SP>CO is ≥50 mass% in the above fatty acid ester and (2) the content of a fatty acid ester having a carbon number of 16-22 regarding R<SP>2</SP>CO is ≤45 mass%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a dry cleaning composition. More specifically, the present invention relates to a dry cleaning composition containing a fatty acid ester derived from animal or vegetable oils and fats, which suppresses the load on the environment.

Compared with washing using water, dry cleaning that does not immerse in water and uses a chemical solvent has the advantages of removing oil (grease) stains more easily and preventing the expansion and contraction of clothing. On the other hand, water-soluble dirt such as sweat is difficult to remove, and depending on the object, the color may fade or the material itself may be damaged.
In dry cleaning, washing of natural fibers such as wool can prevent swelling of fibers compared to general wet cleaning with water, so it is possible to suppress shrinkage and loss of shape of clothing. Very useful for cleaning. However, the detergency is still not sufficient, and optimization of the solvent and the surfactant added to the solvent are continued.
Conventionally, halogen solvents such as tetrachloroethylene, 1,1,1-trichloroethane, and trichlorotrifluoroethane have been used as solvents for dry cleaning. Furthermore, in recent years, paraffin, naphthene, aromatic hydrocarbons, etc. that do not have sufficient detergency against oily and soot stains in response to environmental problems that cause halogen-based solvents to cause underground and air pollution A cleaning composition in which a cleaning agent such as a surfactant is added to a petroleum-based solvent is used (Patent Documents 1 and 2).
However, in order to further cope with environmental problems, it is desirable to convert petroleum solvents to natural solvents made from animal and vegetable oils and fats.
On the other hand, if the desired cleaning effect can be obtained without using a cleaning agent, not only can the load on the environment be reduced, but it is also economical.

Japanese Unexamined Patent Publication No. 2000-192085 (Applicant Lion) JP 2000-192094 A (Applicant Lion)

  The present invention is an alternative to petroleum-based solvents that are generally used for dry cleaning at present, and petroleum-based cleaning containing a petroleum-based solvent and a surfactant even if the surfactant is not included as a cleaning agent. It is an object of the present invention to provide a composition for use in dry cleaning, which has a cleaning power equivalent to or better than that of an agent composition.

As a result of intensive studies by the present inventors, it has been found that the above object can be achieved by adopting a fatty acid ester derived from animal and vegetable fats and oils and adjusting the carbon chain length constituting the fatty acid ester. That is, the present invention is a dry cleaning composition containing at least one fatty acid ester represented by the following formula (I):
R ¹ -O- (R ³ O) m-COR ² (I)
(Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, R ² is an alkyl group having 5 to 21 carbon atoms, R ³ is an alkyl group having 2 to 4 carbon atoms, and m is a number from 0 to 5) .)
The in the fatty acid ester (1) The content of fatty acid ester having a carbon number of 6 to 12 of the R ² CO is not less than 50 wt%, and (2) a fatty acid carbon number of R ² CO is 16 to 22 The dry cleaning composition has an ester content of 45% by mass or less.

According to the present invention, there is obtained a dry cleaning composition which has an effect as a substitute for a petroleum-based solvent and exhibits a cleaning power equivalent to or higher than that of a petroleum-based cleaning composition without containing a surfactant. be able to.
The composition of the present invention is particularly excellent in the detergency of composite soil composed of soot soil and oil soil. In particular, in the present invention, by specifying the molecular structure and adjusting the number of carbon atoms constituting the molecule to an optimal range, delicate clothing made of woolen fabric or silk, which has not been able to obtain good detergency in the past, has been obtained. The cleaning property can be improved.
When dry cleaning is performed using the composition of the present invention, the finished feeling of textiles such as clothing is good. In particular, it is possible to impart a good tactile sensation or texture without feeling slimy when worn.
The composition of the present invention is also safe because it has a low volume resistivity and is difficult to accumulate static electricity and has a high flash point. The composition of the present invention is also excellent in low temperature fluidity.

The fatty acid ester that can be used in the present invention is represented by the following formula (I), and
R ¹ -O- (R ³ O) m-COR ² (I)
(Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, R ² is an alkyl group having 5 to 21 carbon atoms, R ³ is an alkyl group having 2 to 4 carbon atoms, and m is a number from 0 to 5) .)
The in the fatty acid ester (1) The content of fatty acid ester having a carbon number of 6 to 12 of the R ² CO is not less than 50 wt%, and (2) a fatty acid carbon number of R ² CO is 16 to 22 The ester content is 45% by mass or less.

The fatty acid ester represented by the above formula (I) can be produced by a method known in the art.
The fatty acid ester in which m is 0 in the formula (I) is, for example, a method by transesterification of fats and oils with a monohydric alcohol, a method by transesterification of waste cooking oil with a monohydric alcohol, or esterification of a fatty acid with a monohydric alcohol. And a method by transesterification between a fatty acid alkyl ester and a monohydric alcohol.
The number of carbon atoms of the fatty acid residue constituting the fatty acid ester is, for example, by cutting the carbon fraction by distilling the fatty acid ester, or by blending two or more types of carbon fraction of the fatty acid ester having a desired carbon number. Can be adjusted.

  The fatty acid ester in which m is 1 to 5 in the formula (I) is, for example, a method by transesterification of fats and oils with a mono or polyalkylene glycol alkyl ether, or by transesterification of a waste edible oil with a mono or polyalkylene glycol alkyl ether A method by esterification of a fatty acid with a mono or polyalkylene glycol alkyl ether, a method by transesterification of a fatty acid alkyl ester with a mono or polyalkylene glycol alkyl ether, or a method in which an alkylene oxide is directly inserted into a fatty acid alkyl ester. be able to.

The group R ² CO in the formula (I) is a group derived from animal and vegetable fats and oils and is a fatty acid residue having 6 to 22 carbon atoms.
Fatty acids having 6 to 22 carbon atoms can be easily obtained from animal and vegetable oils, and have a carbon number within a range that can ensure the detergency necessary for dry cleaning. Vegetable oils and animal oils can be used as fats and oils that can be used to prepare fatty acid esters. Vegetable oil is preferred. Examples of vegetable oils include rapeseed oil, sunflower oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, corn oil, coconut oil, palm oil, palm kernel oil, and the like. Absent. Among these, palm kernel oil and coconut oil are preferable in that the content of fatty acids having 6 to 14 carbon atoms is large. Examples of animal oils include beef tallow, pork tallow, and fish oil, but are not particularly limited thereto.
The group R ² CO preferably has 6 to 14 carbon atoms. Detergency and texture are improved. More preferably, the group R ² CO has 8 to 12 carbon atoms. It is easy to use because it is liquid at room temperature, and it has low risk of flammability and explosiveness due to its low volume resistivity that resists static electricity. More preferably, the group R ² CO has 8 to 10 carbon atoms. Easy to use even at low temperatures, and the texture is even better.

Specific examples of fatty acids that can form the group R ² CO include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. 22 unsaturated fatty acids and unsaturated fatty acids having a total carbon number of 16 to 22 such as palmitoleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid and erucic acid. Among these, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid and the like (particularly palm kernel oil and palm oil are preferable) are preferable. Caprylic acid, capric acid, lauric acid and the like (particularly palm kernel oil and palm oil are good) are more preferable. Caprylic acid and capric acid (particularly palm kernel oil and coconut oil are preferable) are more preferable.

The group R ¹ O in the formula (I) is a group derived from a monohydric alcohol having 1 to 8 carbon atoms. Fatty acids have a high melting point. In addition, fatty acids are acidic and damage fibers. Therefore, it is necessary to set the number of carbon atoms to 1 or more (that is, an ester). When the number of carbon atoms is 8 or less, cleanability and texture are improved.
The group R ¹ O preferably has 1 to 4 carbon atoms. The reactivity at the time of synthesizing the fatty acid alkyl ester is good, and the excess during the esterification or transesterification reaction can be easily recovered and recycled. In addition, the cleanability and texture are further improved.
The number of carbon atoms of the group R ¹ O is particularly preferably 1. Detergency and texture are the best.

Examples of the monohydric alcohol that can constitute the group R ¹ O include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, and 2-ethylhexyl alcohol. It is done. Of these, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, and isobutyl alcohol are preferred. Methyl alcohol is particularly preferred.

  The dry cleaning composition of the present invention preferably contains a fatty acid ester having 6 to 12 carbon atoms in an amount of 50% by mass or more. By setting it to 50% by mass or more, detergency and texture are improved. More preferably, it is 60 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 100 mass%. The greater the amount of the fatty acid ester having 6 to 12 carbon atoms, the better the detergency.

The dry cleaning composition of the present invention is a fatty acid ester represented by the formula (I):
(1) The content of the fatty acid ester having 6 to 12 carbon atoms is 50% by mass or more, and
(2) The content of fatty acid ester having 16 to 22 carbon atoms is 45% by mass or less. By setting it within such a range, the cleaning property and texture are improved.
In the fatty acid ester represented by the formula (I),
(1) The content of fatty acid ester having 6 to 12 carbon atoms is preferably 60% by mass or more, more preferably 80% by mass or more, and (2) the content of fatty acid ester having 16 to 22 carbon atoms. Is preferably 40% by mass or less, more preferably 20% by mass or less. By setting it within such a range, the cleaning power is further improved.
In the fatty acid ester represented by the formula (I),
(1) The content of the fatty acid ester having 6 to 12 carbon atoms is 100% by mass, and (2) the content of the fatty acid ester having 16 to 22 carbon atoms is particularly preferably 0% by mass. By setting it within such a range, the cleaning rate and texture are improved.

In the formula (I), m is preferably a number from 1 to 5. If it is within this range, the cleaning property and texture are good. If m exceeds 5, the texture becomes worse. As for m, it is more preferable that it is 1-3 mol. Improved low temperature fluidity and odor. m is more preferably 1 to 2 mol. By making it within this range, the texture becomes even better.
In the formula (I), R3 is an alkyl group having 2 to 4 carbon atoms. Since the texture and the drying properties after washing become better, the carbon number of R3 is more preferably 2 to 3, and those having 3 carbon atoms are more preferable in terms of excellent washing properties, texture, and hydrolysis resistance. preferable.
Specific examples of the fatty acid ester in which m is 1 to 5 in the formula (I) include caprylic acid propylene glycol methyl ether, caprylic acid dipropylene, glycol methyl ether, caprylic acid tripropylene glycol methyl ether, capric acid propylene glycol methyl ether , Capric acid dipropylene glycol methyl ether, capric acid tripropylene glycol methyl ether, lauric acid propylene glycol methyl ether, lauric acid dipropylene glycol methyl ether, lauric acid tripropylene glycol methyl ether, caprylic acid ethylene glycol methyl ether, caprylic acid diethylene glycol Methyl ether, caprylic acid triethylene glycol methyl ether, capric acid ethylene glycol methyl Ether, capric acid diethylene glycol methyl ether, capric acid triethylene glycol methyl ether, lauric acid ethylene glycol methyl ether, lauric acid diethylene glycol methyl ether, lauric acid triethylene glycol methyl ether, caprylic acid propylene glycol ethyl ether, caprylic acid dipropylene glycol ethyl Ether, caprylic acid tripropylene glycol ethyl ether, capric acid propylene glycol ethyl ether, capric acid dipropylene glycol ethyl ether, capric acid tripropylene glycol ethyl ether, lauric acid propylene glycol ethyl ether, lauric acid dipropylene glycol ethyl ether, lauric acid Tripropylene glycol ethyl Ether, caprylic acid ethylene glycol ethyl ether, caprylic acid diethylene glycol ethyl ether, caprylic acid triethylene glycol ethyl ether, capric acid ethylene glycol ethyl ether, capric acid diethylene glycol ethyl ether, capric acid triethylene glycol ethyl ether, lauric acid ethylene glycol ethyl ether , Lauric acid diethylene glycol ethyl ether, lauric acid triethylene glycol ethyl ether, and the like. Among these, caprylic acid propylene glycol methyl ether, caprylic acid dipropylene glycol methyl ether, capric acid propylene glycol methyl ether, capric acid dipropylene glycol methyl ether, lauric acid propylene glycol methyl ether, lauric acid dipropylene glycol methyl ether, A dipropylene glycol adduct is particularly preferable from the viewpoint of detergency and texture.

  The dry cleaning composition of the present invention preferably contains 100 to 10,000 ppm of water. By including moisture in such an amount, static electricity is hardly accumulated in the composition of the present invention. If it is less than 100 ppm, static electricity tends to accumulate and there is a risk of ignition and explosion. The water content is more preferably 300 to 5000 ppm. When it is within this range, water tends to exist uniformly in the composition. More preferably, it contains 1000 to 5000 ppm.

Optional component In addition to the above fatty acid ester, the dry cleaning composition of the present invention contains additives such as surfactants (soaps), antistatic agents, pour point depressants (for example, alkyl methacrylate polymers and / or alkyls). Examples thereof include acrylate polymers. Preferably, a polyalkyl methacrylate or alkyl acrylate polymer having a weight average molecular weight of about 5,000 to 500,000 and having a linear or branched alkyl group having 1 to 20 carbon atoms can be suitably used. Specifically, the Include 100 series (132, 133, 136, 137, 138, 146, 160) manufactured by Sanyo Chemical Industries, Ltd. may be sufficient in terms of the pour point lowering action and handling properties of the esterified product. Antioxidants (2,6-di-t-butyl-p-cresol, butylated hydroxya Monophenolic antioxidants such as nisol, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), Bisphenol antioxidants such as 4,4′-butylidenebis (3-methyl-6-tert-butylphenol); tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) ) Propionate] high molecular phenols such as methane and tocopherols; dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodi Sulfur-based antioxidants such as lopionate and distearyl 3,3'-thiodipropionate; Phosphorus-based antioxidants such as triphenyl phosphite and diphenylisodecyl phosphite, etc. -Di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl ) Monophenolic antioxidants such as propionate, and tocopherols which are contained in vegetable oils and fats and have high safety to the human body are preferable, and metal corrosion inhibitors (for example, benzotriazole, benzotriazole derivatives, thiazole, etc. are used. Benzotriazole and benzotriazole derivatives that also act as fluid antistatic agents Organic chelating agents, hydrotropes, etc .; and other dry cleaning solvents such as petroleum solvents, tetrachloroethylene, ethanol, biodiesel, glycol ether (acetate), silicon, and the like.

  The fatty acid esters used to prepare the dry cleaning compositions of the examples and comparative examples are shown in Table 1 below.

[Preparation of sample Nos. 1-27]
Sample Nos. 1 to 22 were prepared using the compounds shown in Table 1. Samples Nos. 1-16 and 22 were prepared by using the compounds shown in Table 1 alone or by mixing two kinds. Samples Nos. 17 to 21 were prepared by synthesis as follows. Samples Nos. 23-27 were prepared by mixing two or three of sample Nos. 4, 8, 17-19.

<Synthesis Method of Sample Nos. 17 to 21>
≪Preparation of caprylic acid propylene glycol methyl ether (sample 17) ≫
100 parts by weight of sample 2 (methyl caprylate) and propylene glycol methyl ether ("Dawanol PM glycol ether" manufactured by Dow Chemical Japan) in a four-necked flask equipped with a nitrogen inlet tube, thermometer, stirrer, and distillation tube 120 parts by mass was added and stirred while flowing nitrogen. 1.1 parts by mass of tetraisopropyl titanate (“Orgatics TA-10” manufactured by Matsumoto Pharmaceutical Co., Ltd.) was added thereto. Then, it heated up to 100 degreeC and made it react for 5 hours, and also heated up to 180 degreeC after that, and was made to react for 5 hours. Thereafter, the mixture was cooled to 130 ° C., and the pressure was reduced at 130 ° C. (decompression degree: 3.0 kPa) to remove unreacted sample 2, propylene glycol methyl ether. Then, it cooled to 80 degreeC, 7 mass parts of ion-exchange water was added, tetraisopropyl titanate was dead activated, and it spin-dry | dehydrated at 105 degreeC and the pressure reduction degree 2.0kPa. 3 parts by mass of acid adsorbent KYOWARD 500SH (manufactured by Kyowa Chemical Industry), 0.5 parts by mass of filter aid Hyflo Supercell (manufactured by Celite), KC Flock (Nippon Paper Chemicals) at 80 ° C. Product) 0.5 parts by mass was added and stirred for 2 hours to reduce the acid value, followed by filtration to obtain caprylic acid propylene glycol methyl ether (sample 17). Caprylic acid propylene glycol methyl ether concentration (transesterification rate) was 99.9%.
The concentration of propylene glycol methyl ether of caprylic acid was determined by taking Sample 17 in a 0.1 g vial, dissolving it in 10 g of acetone, and performing gas chromatography (GC) analysis under the following conditions. Quantification was performed with a calibration curve prepared at a known concentration in advance.

GC: manufactured by Shimadzu Corporation, product name: GC6A.
Column: DEGS (diethylene glycol succinate 20% by mass).
Column temperature: 50 ° C., hold for 2 minutes → 250 ° C. (temperature rise at 10 ° C./min)
Inlet temperature: 300 ° C
Detector temperature: 300 ° C
RANGE (10n): n = 3
Carrier gas: N ₂ , 50 mL / min
Detector: FID
Injector: 1 μL

<< Preparation of propylene glycol methyl ether caprate (sample 18) >>
100 parts by weight of sample 3 (methyl caprate) and propylene glycol methyl ether ("Dawanol PM glycol ether" manufactured by Dow Chemical Japan) in a four-necked flask equipped with a nitrogen inlet tube, thermometer, stirrer, and distillation tube 100 parts by mass was added and stirred while flowing nitrogen. Thereto was added 1.0 part by mass of tetraisopropyl titanate (“Origatix TA-10” manufactured by Matsumoto Pharmaceutical Co., Ltd.). Then, it heated up to 100 degreeC and made it react for 5 hours, and also heated up to 180 degreeC after that, and was made to react for 5 hours. Thereafter, the mixture was cooled to 170 ° C., and the pressure was reduced at 170 ° C. (decompression degree: 3.0 kPa) to remove unreacted sample 3 and propylene glycol methyl ether. Then, it cooled to 80 degreeC, 7 mass parts of ion-exchange water was added, tetraisopropyl titanate was dead activated, and it spin-dry | dehydrated at 105 degreeC and the pressure reduction degree 2.0kPa. 3 parts by mass of acid adsorbent KYOWARD 500SH (manufactured by Kyowa Chemical Industry), 0.5 parts by mass of filter aid Hyflo Supercell (manufactured by Celite), KC Flock (Nippon Paper Chemicals) at 80 ° C. (Product made) 0.5 parts by mass was added and stirred for 2 hours to reduce the acid value, followed by filtration to obtain propylene glycol methyl ether caprate (sample 18). The propylene glycol methyl ether concentration of capric acid (transesterification rate) was 99.8%.

<< Preparation of lauric acid propylene glycol methyl ether (sample 19) >>
100 parts by weight of sample 4 (methyl laurate 99.5%) in a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a stirrer, and a distillation tube, propylene glycol methyl ether (Dowanol PM glycol manufactured by Dow Chemical Japan) 85 parts by mass of ether ") was added and stirred while flowing nitrogen. Thereto was added 0.9 part by mass of tetraisopropyl titanate (“Orgatics TA-10” manufactured by Matsumoto Pharmaceutical Co., Ltd.). Then, it heated up to 100 degreeC and made it react for 5 hours, and also heated up to 190 degreeC after that, and was made to react for 5 hours. Thereafter, the pressure was reduced at 190 ° C. (decompression degree: 3.0 kPa) to remove the unreacted sample 4 and propylene glycol methyl ether. Then, it cooled to 80 degreeC, 6 mass parts of ion exchange water was added, tetraisopropyl titanate was killed and activated, and it spin-dry | dehydrated at 105 degreeC and the pressure reduction degree 2.0kPa. 3 parts by mass of acid adsorbent KYOWARD 500SH (manufactured by Kyowa Chemical Industry), 0.5 parts by mass of filter aid Hyflo Supercell (manufactured by Celite), KC Flock (Nippon Paper Chemicals) at 80 ° C. (Product) 0.5 parts by mass was added and stirred for 2 hours to reduce the acid value, followed by filtration to obtain propylene glycol methyl ether of lauric acid (Sample 19). The concentration of lauric acid propylene glycol methyl ether (transesterification rate) was 99.5%.

<< Preparation of caprylic acid dipropylene glycol methyl ether (sample 20) >>
100 parts by weight of sample 2 (methyl caprylate) in a four-necked flask equipped with a nitrogen inlet tube, thermometer, stirrer, and distillation tube, dipropylene glycol methyl ether ("Dawanol DPM glycol ether" manufactured by Dow Chemical Japan) 140 parts by mass was stirred while flowing nitrogen. Thereto was added 1.2 parts by mass of tetraisopropyl titanate (“Orgathix TA-10” manufactured by Matsumoto Pharmaceutical Co., Ltd.). Then, it heated up to 140 degreeC and made it react for 5 hours, and also heated up to 220 degreeC after that, and was made to react for 5 hours. Thereafter, the mixture was cooled to 140 ° C., and the pressure was reduced at 140 ° C. (decompression degree: 3.0 kPa) to remove unreacted sample 2, dipropylene glycol methyl ether. Then, it cooled to 80 degreeC, 9 mass parts of ion-exchange water was added, tetraisopropyl titanate was dead activated, and it spin-dry | dehydrated at 105 degreeC and the pressure reduction degree 2.0kPa. To the obtained crude product at 80 ° C., 3.5 parts by mass of acid adsorbent Kyoward 500SH (manufactured by Kyowa Chemical Industry), 0.6 parts by mass of filter aid Hyflo Supercell (manufactured by Celite), KC Flock (Japan) 0.6 parts by mass (made by Paper Chemicals) was added and stirred for 2 hours to reduce the acid value, followed by filtration to obtain caprylic acid dipropylene glycol methyl ether (Sample 20). The caprylic acid dipropylene glycol methyl ether concentration (transesterification rate) was 99.9%.

<< Preparation of caprylic acid tripropylene glycol methyl ether (sample 21) >>
100 parts by mass of sample 2 (methyl caprylate) in a four-necked flask equipped with a nitrogen inlet tube, thermometer, stirrer, and distillation tube, tripropylene glycol methyl ether ("Dawanol TPM glycol ether" manufactured by Dow Chemical Japan) 200 parts by mass was stirred while flowing nitrogen. Thereto was added 1.5 parts by mass of tetraisopropyl titanate (“Origatix TA-10” manufactured by Matsumoto Pharmaceutical Co., Ltd.). Then, it heated up to 140 degreeC and made it react for 5 hours, and also heated up to 220 degreeC after that, and was made to react for 5 hours. Thereafter, the mixture was cooled to 190 ° C., and the pressure was reduced at 190 ° C. (decompression degree: 3.0 kPa) to remove unreacted sample 2, tripropylene glycol methyl ether. Then, it cooled to 80 degreeC, 10.5 mass parts of ion-exchange water was added, tetraisopropyl titanate was dead activated, and it spin-dry | dehydrated at 105 degreeC and the pressure reduction degree 2.0kPa. 4.0 parts by weight of acid adsorbent Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.), 0.8 parts by weight of filter aid Hyflo Supercell (manufactured by Celite) at 80 ° C., and KC floc (Japan) After adding 0.8 parts by mass (made by Paper Manufacturing Chemical Co., Ltd.), stirring for 2 hours, reducing the acid value, and filtering, caprylic acid tripropylene glycol methyl ether (Sample 21) was obtained. The caprylic acid tripropylene glycol methyl ether concentration (transesterification rate) was 99.6%.

[Method for measuring fatty acid composition distribution]
Collect 0.02g of each of the fatty acid esters of Sample Nos. 1 to 22 prepared above, dilute with 1g of hexane to prepare a sample for fatty acid composition distribution measurement, and perform gas chromatography (GC) analysis under the following conditions. It was. The quantification was performed with a calibration curve prepared in advance at each known fatty acid concentration. The obtained results are shown in Tables 2 to 4.
(Analysis conditions)
Model: HEWLETT PACKARD, product name: 5890A GAS CHROMATOGRAPH
Column: J & W Capillary Column DB-5HT (Product name; 0.25 mm inner diameter × 30 m length, 0.25 μm film thickness; manufactured by J & W Scientific)
Temperature: 50 → 350 ° C. (temperature increase rate 10 ° C./min)
Carrier gas: He, 30 cm / sec
Inlet: 350 ° C., Split ratio 50: 1, 1 μL
Detection port: FID, 350 ° C

The compositions of Examples and Comparative Examples were prepared using sample Nos. 1 to 27 shown in Tables 2 to 4, and the low temperature fluidity (pour point), flammability and explosiveness (flash point), and cleaning of each composition. The rate and texture (smoothness) were measured or evaluated. Evaluation was performed as follows.
<Evaluation of low temperature fluidity>
The pour point of each composition was measured by a method in accordance with JIS K2269 (pour point of petroleum and petroleum products and petroleum product cloud point test method).
<Evaluation of flammability and explosiveness>
The flash point was measured by a method according to JIS K2265 Cleveland open type.

<Evaluation of detergency of soot dirt and oily dirt combined dirt>
5 cm square artificial contamination cloth (EMPA (Switzerland), EMPA 107, carbon / olive oil / wool) and 100 mL of dry cleaning composition are placed in a 220 mL glass container and shaker (Shaker SA300 Yamato Science ( The product is shaken in the vertical direction for 10 minutes at a speed of 250 rpm at 20 ° C., and after the washing cloth is collected, per cloth at a medium temperature (hair) temperature with an iron (steam iron NI-SF30). The process of drying for 15 seconds was repeated three times. After drying, the reflectance R was measured one by one with a reflectance meter (SE2000, manufactured by Nippon Denshoku), and the value obtained by averaging the results for five sheets calculated according to the Kubelka-Munk equation below was defined as the cleaning rate.
Kubelka-Munk formula Cleaning rate (%) = (K / S of contaminated fabric−K / S of cleaned fabric) × 100 /
(K / S for contaminated fabric-K / S for standard white fabric)
K / S = (1-R / 100) / (2R / 100)

<Evaluation of texture (smoothness)>
About the texture of the to-be-washed cloth after drying, it evaluated using sensory evaluation as a slime feeling.
The sensory evaluation of the tactile sensation regarding slime feeling was performed by five specialists on the contaminated cloth after being cleaned by the method described for the evaluation of the detergency. Ratings were given according to the following criteria, and the evaluation was performed based on the following criteria from the average value of 5 people.
Score
5 points: Same as standard white cloth
4 points: slightly different from standard white cloth
3 points: Slightly slimy
2 points: Feels clearly slimy
1 point: Feels very slim Evaluation criteria ◎: 4 to 5 points (particularly preferred range)
○: 3 points or more and less than 4 points (preferable range)
△: 2 points or more and less than 3 points (problem range)
×: 1 point or more and less than 2 points (particularly problematic range)
The evaluation results are shown in Tables 5 to 8.

Reference Example According to the above evaluation method, the cleaning rate = 1% of a petroleum solvent (Exsol D-40, manufactured by Exxon Chemical) currently used as a dry cleaning cleaning agent and a detergent (Ripal DX, manufactured by Lion) 56%, slimy feeling ○.
Exol D-40 is a dry cleaning solvent with about 50% by mass of n- / iso-paraffin and about 50% by mass of naphthenic. Since it has insufficient detergency alone, a surfactant is usually added as a detergent component. Are used.

<Static suppression evaluation>
Among the samples shown above, by using the samples (test Nos. 1 to 6) shown in Table 9 below, by examining the influence of the amount of water dissolved in the sample on the volume resistivity, The hardness of each dry cleaning composition was evaluated due to static electricity.
The amount of water in the sample was adjusted as follows.
[Adjustment of water content of Test Nos. 1 to 4]
The water content of Test Nos. 1 to 4 was the saturation amount. That is, 1 kg of sample and 1 kg of distilled water were placed in a 2 L lid glass bottle and shaken up and down 100 times. Thereafter, the mixture was allowed to stand for 24 hours to separate into two layers. The sample is the upper layer and the water is the lower layer. The amount of water dissolved in the upper layer sample was measured by a method based on the JIS K0068 Karl Fischer method, and the measured value was defined as the saturation amount. The experiment was conducted in a room with a room temperature of 22 ° C. and a humidity of 60%.
[Adjustment of water content of test Nos. 5-6]
Into a glass bottle with a 2 L lid, 1.5 kg of a sample and 150 g of Molecular Sieves 4A (Pure Chemicals Reagent) were placed and shaken 100 times up and down. Then, it left still for 2 weeks and reduced the moisture content in a sample. The amount of water dissolved in the sample was measured by a method based on the JIS K0068 Karl Fischer method.
The volume resistivity of the sample whose water content was adjusted in this way was measured by a method based on the JIS C2101 electrical insulating oil test method. Table 9 shows the obtained results.

The possibility of a flammable explosion of a dry cleaning machine using petroleum solvents is that the volume resistivity of petroleum solvents is 10 ¹⁰ Ωcm or more (@ 80 ° C). Yes. Therefore, since petroleum-based solvents usually have a volume resistivity of about 10 ¹⁴ to 10 ¹⁵ Ωcm (@ 80 ° C.), the volume resistivity is made 10 ¹⁰ Ωcm or less (@ 80 ° C.) by adding a detergent. . On the other hand, according to the fatty acid ester of the present invention, the volume resistivity is 10 ¹⁰ Ωcm (@ 80 ° C.) without adding a detergent, and the volume resistivity can be lowered by increasing the water content. The risk of flammable explosion can be reduced.

Claims (3)

A dry cleaning composition containing at least one fatty acid ester represented by the following formula (I):
R ¹ -O- (R ³ O) m-COR ² (I)
(Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, R ² is an alkyl group having 5 to 21 carbon atoms, R ³ is an alkyl group having 2 to 4 carbon atoms, and m is a number from 0 to 5) .)
The in the fatty acid ester (1) The content of fatty acid ester having a carbon number of 6 to 12 of the R ² CO is not less than 50 wt%, and (2) a fatty acid carbon number of R ² CO is 16 to 22 The dry cleaning composition having an ester content of 45% by mass or less.   The composition for dry cleaning according to claim 1, wherein the fatty acid ester is a fatty acid ester in which m is 1 to 3 in the formula (I).   The dry cleaning composition according to claim 1, wherein the fatty acid ester is a fatty acid ester derived from palm kernel oil or palm oil.