JP2000230191A - Surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyglycerin ester surfactant having surface activity different from the conventional polyglycerin carboxylic acid ester containing cyclic polyglycerins in a larger content. SOLUTION: A polyglycerin monovalent carboxylic acid partial ester obtained from a polyglycerin and a monovalent carboxylic acid or monovalent carboxylic acid derivative. The surfactant comprises a polyglycerin monovalent carboxylic acid partial ester in which the ratio of a cyclic polyglycerin having a degree of polymerization of 2-4 in the polyglycerin is 0.1-30 FID% (here, FID% expresses an area percentage in an FID detector chart in the case of gas chromatographic analysis of trimethyl silylated compounds in a polyglycerin)) based on the total polyglycerins.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surfactant comprising a specific polyglycerol monocarboxylic acid partial ester.

[0002]

2. Description of the Related Art Polyglycerin esters are excellent emulsifiers, and at the same time, have high safety to the human body and the environment. Therefore, they are used in foods, pharmaceuticals, cosmetics and the like. It is also useful as a cleaning agent, and is also used as a tableware cleaning agent because of its high safety. Furthermore, since it has antifogging property and antistatic performance, it may be added to resins used for food wraps and agricultural greenhouses. Polyglycerol esters are not only highly safe as described above, but also because the degree of polymerization of polyglycerin, acid composition, esterification rate, etc. can be appropriately selected to obtain products with various physical properties, It is said that the range and amount of use will increase.

The polyglycerin fatty acid ester is usually obtained by dehydrating polyglycerin and a fatty acid by a conventional method. Among them, polyglycerin can be obtained by a method such as dehydration condensation of glycerin, polymerization of glycidol, polymerization of epichlorohydrin and the like. Several kinds of polyglycerols produced in this way are commercially available depending on the degree of polymerization. The degree of polymerization indicated there is often a value calculated from the hydroxyl value of the product. However, in practice, polyglycerin is a mixture of variously condensed glycerins, which includes not only linear polyglycerin but also cyclically condensed polyglycerin. Generally, when polyglycerin having a high degree of polymerization is to be produced, a tendency is observed that cyclic polyglycerin increases. Therefore, it is a reality that the degree of polymerization obtained by calculating backward from the hydroxyl value of the product polyglycerin does not always represent the original degree of polymerization of the product polyglycerin. In particular, in polyglycerin having a high degree of polymerization, the molecular weight distribution hardly becomes a normal distribution due to by-products of cyclic polyglycerin and the like.

[0004]

Therefore, when a fatty acid ester is produced from polyglycerin having a high polymerization degree as a raw material, an ester of cyclic polyglycerin is produced, which is different from a chain-like polyglycerin ester. Has physical properties. Therefore, it may have physical properties different from those originally expected. Cyclic polyglycerin is said to be suspected for its safety to the human body. Accordingly, an object of the present invention is to provide a surfactant comprising a polyglycerin monovalent carboxylic acid partial ester obtained from polyglycerin containing a specific proportion of cyclic polyglycerin and having a small proportion.

[0005]

That is, the present invention relates to a polyglycerol monovalent carboxylic acid partial ester obtained from polyglycerin and a monovalent carboxylic acid or a monovalent carboxylic acid derivative, wherein the polymer contained in the polyglycerin is contained. The ratio of the cyclic polyglycerin having a degree of 2 to 4 is 0.1 to 30 FID%, preferably 1 to 20 FID, based on the total polyglycerin.
% Of polyglycerin monovalent carboxylic acid partial ester.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Polyglycerin, which is a raw material of the polyglycerol monovalent carboxylic acid partial ester of the present invention, is produced by dehydration condensation of glycerin and polymerization of glycidol, epichlorohydrin, propylene chlorohydrin and the like. Can be used. The average degree of polymerization of this polyglycerin is 2 or more, preferably 2 to 12. Ordinary polyglycerol produced by the above method includes not only those polymerized in a chain but also those polymerized in a cyclic manner. In the present invention, among these cyclic polyglycerins, the cyclic polyglycerin having a degree of polymerization of 2 to 4 must be in the range of 0.1 to 30 FID%, preferably 1 to 20 FID%, based on the total polyglycerin. Must. However, FID% is the area% in the gas chromatogram when the trimethylsilylated polyglycerin is analyzed by gas chromatography using a flame ionization detector (FID). When polyglycerin is produced by a conventionally generally used method, the amount of cyclic polymer produced increases as the degree of polymerization becomes higher, especially when glycidol and epichlorohydrin are used as reaction raw materials, and reaction conditions and the like are used. By carefully carrying out the reaction by selecting the above, polyglycerin having less cyclic polyglycerin can be obtained. A monovalent carboxylic acid partial ester of polyglycerol containing such a specific ratio of cyclic polyglycerin is
It has a different surface activity from polyglycerin monovalent carboxylic acid partial ester containing a large amount of cyclic polyglycerin or linear polyglycerin monovalent carboxylic acid partial ester.

[0007] Generally, the above polyglycerin analysis method is to hydrolyze a polyglycerol monovalent carboxylic acid partial ester with an aqueous alkali solution or the like, and then add a hydrocarbon-based solvent such as hexane to separate phases and to separate the aqueous layer. After extracting polyglycerin from the polysaccharide, the hydroxyl group of polyglycerin is trimethylsilylated by a conventional method and blocked, followed by gas chromatography. By this method, chain polyglycerin and cyclic polyglycerin having a polymerization degree of 2 to 4 can be separated and detected.

The monohydric carboxylic acid which is a raw material of the polyglycerin monovalent carboxylic acid partial ester of the present invention includes acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, Myristic acid, palmitic acid, stearic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, arachinic acid, gadrenic acid, behenic acid, erucic acid, lignoceric acid, seracoleic acid, serotinic acid, montanic acid, melicic acid, celloplastic acid , Ricinoleic acid, fatty acids such as 12-hydroxystearic acid, and aromatic monocarboxylic acids such as benzoic acid. Further, mixed fatty acids derived from natural fats and oils containing these fatty acids may be used. As natural fats and oils, for example, linseed oil, eno oil, deer oil, olive oil,
Cacao butter, kapok oil, white mustard oil, sesame oil, rice bran oil, safflower oil, shea nut oil, cinnamon oil, soybean oil, teaseed oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, Vegetable fats such as sunflower oil, cottonseed oil, coconut oil, wood wax, peanut oil, etc., animal fats such as horse fat, beef tallow, beef tallow, beef tallow, lard, goat fat, sheep fat, milk fat, fish oil, whale oil, etc. Is mentioned. Among the above-mentioned monovalent carboxylic acids, a fatty acid having 6 to 22 carbon atoms or a mixed fatty acid derived from fats and oils containing a fatty acid having 6 to 22 carbon atoms is preferable because the surface activity is easily developed.

The polyglycerin monovalent carboxylic acid partial ester of the present invention comprises the above-mentioned polyglycerin, the above-mentioned monovalent carboxylic acid or esters of these monovalent carboxylic acids such as methyl ester and glyceride, acid anhydrides, acid chlorides and the like. Can be produced by a conventional method. At this time, the esterification rate of the polyglycerol monovalent carboxylic acid partial ester (the number of esterified hydroxyl groups with respect to the total number of hydroxyl groups of the polyglycerin before esterification) can be controlled by the reaction ratio between the two. When all the hydroxyl groups of the polyglycerin are esterified, the surface activity decreases, so that the polyglycerol monovalent carboxylic acid partial ester of the present invention must have at least one hydroxyl group remaining in the molecule. The preferred esterification rate is 90% or less, more preferably 70% or less, and most preferably 50% or less. The lower limit of the esterification ratio may be any range as long as it has an interfacial performance, but is preferably 3% or more, more preferably 7% or more.

Specific uses of the surfactant of the present invention include, for example, an antifoaming agent, an emulsifier, a detergent, a rinse aid, a dispersant, a deinking agent, a release agent, a fiber treatment agent, and an additive for adhesives. Agent,
Antifogging agents, polishes, foam stabilizers such as urethane foam, paint additives, lubricating oil additives, antistatic agents, lubricants, resin internal lubricants, resin modifiers, cosmetic additives, agricultural chemicals Spreading agents and the like.

[0011]

The present invention will be described more specifically with reference to the following examples. In the following examples, parts and percentages are by weight unless otherwise specified. Table 1 shows the surfactants of the present invention (Examples 1 to 10) and comparative surfactants (Comparative Examples 1 to 10) used in the following tests.

[0012]

[Table 1]

*: Molar ratio of carboxylic acid to 1 mol of polyglycerin. With respect to the surfactants of Example 1 and Comparative Example 8 in Table 1, the results of gas chromatographic analysis of the polyglycerin are shown in FIGS. 1 and 2. Table 2 shows the FID% of the components of each degree of polymerization obtained from these figures.

<Analytical Conditions> Column: OV-1 (GL Science) Column length: 50 cm Column temperature: 80 to 330 ° C. (heating at 10 ° C./min). Then hold at 330 ° C for 15 minutes. Injection temperature: 330 ° C Carrier gas: nitrogen (pressure 3.6 kgf / cm ² )

[0015]

[Table 2]

* C in the degree of polymerization in the figures and tables represents cyclic polyglycerin. Test 1: Emulsion stability test 1 Each of polyglycerin partial esters of Examples or Comparative Examples
, 0.5 parts of acetic acid and 2.0 parts of sodium chloride were added to 66.5 parts of water, and the mixture was stirred and dissolved at 40 ° C. Then, while stirring with a homomixer at about 4,000 rpm, 30 parts of rapeseed white oil was added. Then, while cooling with water, the number of rotations was 6,000r
pm and stirred for 10 minutes to obtain an emulsion. These emulsions were examined for stability over time when allowed to stand at 40 ° C. for one week. The stability was evaluated visually by the following criteria. ：: No change ○: Slight water separation (within 5%) △: Water separation (with 5% or more) ×: Phase separation occurs

Test 2: Emulsion stability test 2 Each emulsion prepared in the same manner as in Test 1 was centrifuged at 4,000 rpm (average gravitational acceleration 1,8).
80G) for 15 minutes. The stability was evaluated by visually observing the appearance according to the same criteria as in Test 1.

Test 3: Detergency test 2 of each of the polyglycerin partial esters of Examples and Comparative Examples
0 parts, ethanol 10 parts, sodium pyrophosphate 5 parts,
A detergent composition consisting of 65 parts of water was prepared, and a dish washing test was performed. First, 180 g of beef tallow, 20 g of yolk powder, and 100 g of water were kneaded at 40 to 50 ° C. to obtain a soil substance. 1.0 g of this was collected, spread evenly on the surface of the dish with a finger, and allowed to stand overnight. Next, the concentration of each of the above detergent compositions was 0.5.
A 6% aqueous solution was prepared, and a dish with dirt was put into each cleaning solution and the surface was rubbed 10 times with a brush. The number of dishes made was recorded. This is 2
The average was obtained by performing the test twice.

Test 4: Rinsing test The dish with dirt used in Test 3 was washed with an automatic dishwasher JWD-6 manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd. using a commercially available alkaline cleaning agent and then carried out. The drying speed (seconds) of the dishes after rinsing with a 80 ° C. rinsing solution containing 0.01% of a rinsing aid consisting of 80 parts of each of the polyglycerin partial esters of Examples and Comparative Examples and 20 parts of water was determined. ,
The presence or absence of spots on the surface after drying was observed according to the following criteria. ◎: 0 to 3 ○: 3 to 9 △: 10 or more ×: defective

Test 5: Thermal stability test Each 0.5 g of each of the polyglycerin partial esters of the examples and comparative examples was uniformly applied to a stainless steel dish having a diameter of 7 cm, and dried in a dry heat tester at 250 ° C. for 8 hours. Held.
The state of the applied polyglycerin partial ester after the treatment was visually observed and evaluated according to the following criteria. ：: The fluidity was maintained and there was little discoloration. ：: Maintained fluidity, but discolored. Δ: Tar-like, large discoloration. X: Solidification and discoloration are large.

Test 6: Antifogging test Linear low density polyethylene resin (density: 0.92 g / cm)
³ , Mw = 51,200) 100 parts, calcium stearate 0.1 part, tetrakis @ 3- (3,5-di-t-)
Butyl-4-hydroxyphenyl) propionyloxymethyl methane (ADK STAB A manufactured by Asahi Denka Kogyo Co., Ltd.)
O-60), 0.1 part, tris (2,4-di-t-butylphenyl) phosphite (Adeka Stab 2112, manufactured by Asahi Denka Kogyo KK), 0.1 part, and polyglycerin of the examples or comparative examples Each 3 parts of partial ester is blended,
The pellets were extruded at 230 ° C. into pellets, and a film having a thickness of 20 μm was formed by a T-die method at a die temperature of 250 ° C. The anti-fog properties of these films were evaluated by the following method. 150m water in 300mL wide mouth bottle
L, the mouth was sealed with each of the above films, and these bottles were placed in a refrigerator at 5 ° C. for 1 hour. Then, the bottles were taken out, and the cloudiness of these films was examined according to the following evaluation criteria. 5: Completely transparent without fogging. 4: Almost transparent, but with slight water droplets. 3: Large water droplets adhere, but there is transparency. 2: Large water droplets adhere to the entire surface and are opaque. 1: The surface is opaque with fine water droplets. Table 3 shows the results of the above evaluation tests.

[0022]

[Table 3]

From these results, it can be seen that the surfactant of the present invention in which the cyclic polyglycerin is in the range of 0.1 to 30% FID% has emulsion stability, oil / fat detergency, rinsing property, heat stability, antifogging property and the like. In terms of various properties as a surfactant, the cyclic polyglycerin has properties superior to those having more than 30 FID%.

[0024]

The effect of the present invention is to provide a surfactant comprising a polyglycerol monovalent carboxylic acid partial ester obtained from polyglycerin containing a specific proportion of cyclic polyglycerin.

[Brief description of the drawings]

FIG. 1 is a gas chromatogram of tetraglycerin used in Example 1.

FIG. 2 is a gas chromatogram of decaglycerin used in Comparative Example 8.

Continued on the front page F term (reference) 4C083 AB282 AC102 AD111 AD112 BB04 4D077 AB08 AB10 AB11 AB12 AB20 AC01 BA15 CA12 DC02Y DC02Z DC07Y DC07Z DC12Y DC16Z DC19Y DC24Y DC36Y DD29Y DD36Y DE02Y DE07Y DE08Y DE09Y DE12Y EB ED 003

Claims (3)

[Claims] 1. Polyglycerin and monovalent carboxylic acid or 1
Polyglycerol monovalent carboxylic acid partial ester obtained from a polycarboxylic acid derivative, the ratio of cyclic polyglycerol having a degree of polymerization of 2 to 4 contained in the polyglycerin,
0.1% to 30% FID% of the total polyglycerin (however, FID% represents an area% in a FID detector when a trimethylsilylated product of polyglycerin is analyzed by gas chromatography). Surfactant consisting of acid partial ester. 2. The number of esterified hydroxyl groups relative to the total number of hydroxyl groups of polyglycerin before esterification is 90.
% Of the surfactant according to claim 1. 3. The surfactant according to claim 1, wherein the monovalent carboxylic acid is a fatty acid having 6 to 22 carbon atoms.