JP2001247845A - Aqueous gelling agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous gelling agent which can give a pseudoplastic aqueous gel composition when added to an aqueous system, can bring about a good gel state even when used in an acidic system, a salt water system, or an alcohol-containing system, and is highly safe. SOLUTION: This gelling agent comprises an ester compound prepared by the esterification of trimethylolpropane or its condensate, a glycerol condensate, a 26-30C aliphatic saturated dibasic acid, and an 8-28C fatty acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an esterification product exhibiting a gelling function in an aqueous system. More specifically, by being incorporated into an aqueous composition, it has the function of converting the system into a gel having pseudoplastic flow, and has extremely high safety, and cosmetics, pharmaceuticals, agricultural chemicals, feeds,
The present invention relates to a gelling agent comprising an esterification product that can be used for a wide range of aqueous compositions such as fertilizers and paints.

[0002]

2. Description of the Related Art Generally, a gelling agent having fluidity in an aqueous system exhibits structural viscosity such as pseudoplastic flow or thixotropic flow in an aqueous system, and exhibits physical properties as a gel when left standing. When a certain level of stress is applied, the material changes to a sol-like physical property and exhibits fluidity. Such a gelling agent having physical properties is used as a water-based preparation in the fields of cosmetics, pharmaceuticals, agricultural chemicals, feed, fertilizers, paints, and the like. Many of these gelling agents contain water-soluble polymers, which form loose networks by hydrogen bonds and ionic bonds between the polymers, and form gels by physical bridging. It shows fluidity and the structure recovers instantaneously or over time. In addition, colloidal hydrated silicate, which is an inorganic compound, forms a card house structure in water and swells and gels by hydration of metal cations in the molecule, but the dispersion liquid flows easily by shearing. It shows a so-called thixotropic property that recovers to a gel over time.

Examples of such water-soluble polymers include carboxyvinyl polymers, polyacrylic acids and neutralized salts thereof in the case of anionic ones. Although this aqueous solution shows pseudoplastic flow, it loses gelling properties and does not show high viscosity due to the coexistence of a trace amount of salt. In the nonionic system, xanthan gum, carrageenan and the like exhibit thixotropic fluidity. However, these water-soluble polymers are generally useful as a thickener and have weak gel properties and no shape retention. In the range of finite swelling, the viscosity increases with increasing concentration, but the gel properties are weak. Further, due to the strong spinnability and the nature of the polysaccharide, if other solvents are blended, the solubility is lowered and the properties are not sufficiently obtained. In addition, examples of inorganic clay minerals include bentonite and aluminum magnesium silicate.
If is not the alkaline side, hydration of metal cation does not occur,
No good gelling properties. In addition, we have previously invented and applied an esterification product as a gelling agent for alcohol (Japanese Patent Application No. 5-292567), which is suitable as a gelling agent for alcohol. With hydroalcohol containing partial water, a good gel cannot be obtained, and there is no fluidity with structural viscosity. As described above, when gelling having fluidity due to shearing, there are various problems with the conventional gelling agent, and there are inevitable restrictions on formulation, and a versatile aqueous gelation that does not have these problems The appearance of the agent has been long-awaited. It should be noted that a gelling agent such as gelatin or agar gels water, but water does not show fluidity and does not recover if the gel is broken by stress. Materials with such properties differ from the purpose of the present invention.

[0004] In view of such circumstances, the present inventors have worked on the development of a gelling agent that exhibits a gelling property having structural viscosity even in all aqueous states. That is, salt resistance,
It is an aqueous gelling agent that has pH resistance, has good gelling properties without any problem even when other components are added to water, and shows flow properties due to shear. We have found that oligoesters obtained by complexly combining fatty acids and alcohols of specific molecular species satisfy the above properties. The present invention has been completed based on such findings.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a pseudo-plastic structural viscosity having fluidity due to shearing and a gel property at the time of static place by blending in an aqueous composition. And to provide an aqueous gelling agent.

[0006]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies and have found that trimethylolpropane or its condensate, glycerin condensate, specific dibasic acid and fatty acid are esterified. It was discovered that the resulting oligoester product had a high gelling effect. That is, the present invention relates to trimethylolpropane or a condensate thereof, a glycerin condensate, a long-chain linear saturated dibasic acid having 26 to 30 carbon atoms and a linear saturated fatty acid having 8 to 28 carbon atoms, a linear unsaturated fatty acid, A gelling agent comprising an esterification product obtained by reacting one or more fatty acids selected from the group consisting of branched fatty acids and hydroxy fatty acids. Although the esterification product according to the present invention exhibits a gelling function, it has a much higher molecular weight as compared with a normal esterification product, and therefore has extremely high safety.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The gelling agent of the present invention includes trimethylolpropane or a condensate thereof, a glycerin condensate, a long-chain linear saturated dibasic acid having 26 to 30 carbon atoms, and a C8 to C8 fatty acid.
It comprises an esterification product obtained by subjecting 28 fatty acids to an esterification reaction. The proportion of such components is such that trimethylolpropane or a condensate thereof is 1 to 10% by mass, a glycerin condensate is 35 to 50% by mass, and a long-chain linear saturated dibasic acid having 26 to 30 carbon atoms is 10 to 30% by mass. And it is preferable to use the fatty acid having 8 to 28 carbon atoms in the range of 15 to 40% by mass.

[0008] Essential raw materials for producing the esterification product of the present invention include trimethylolpropane or a condensate thereof and a glycerin condensate. In the present invention, trimethylolpropane or a condensate thereof includes trimethylolpropane, ditrimethylolpropane, tritrimethylolpropane, and the like. In the present invention, ditrimethylolpropane is preferable. The appropriate degree of condensation of the glycerin condensate is 5 as an average degree of condensation calculated from the hydroxyl value.
These include those having an average degree of condensation of 6 or more, more preferably about 10 glycerin condensates, and specific examples thereof include pentaglycerin, hexaglycerin, and decaglycerin. Can be used alone or as a mixture.

Next, the dibasic acids constituting the present invention include:
It is a long-chain linear saturated dibasic acid having 26 to 30 carbon atoms. Those having 26 to 30 carbon atoms exhibit pseudoplastic flow although the structure is recovered immediately, although the thixotropic property is weak. On the other hand,
Those having 6 to 24 carbon atoms are different in physical properties in that they have thixotropic properties. Those containing unsaturation have a reduced gelling function. The use of a long-chain straight-chain saturated dibasic acid improves thermal stability. Therefore, in the present invention, dibasic acids such as hexacosadicarboxylic acid, octacosandioic acid, and triacontadicarboxylic acid may be used alone or in combination. Among these, octacosandioic acid is particularly desirable, and it is desirable to mainly use such octacosandioic acid. The term "mainly" means that the proportion of the total dibasic acid in the composition is 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more. In addition, a dibasic acid having 6 to 24 carbon atoms may be added to the components for adjusting the gel properties.

Further, the fatty acid has 8 to 28 carbon atoms.
It is essential that these are linear saturated fatty acids, linear unsaturated fatty acids, branched fatty acids, and hydroxy fatty acids. Specific fatty acids include caprylic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid,
Linear saturated fatty acids such as cerotic acid and montanic acid, linear unsaturated fatty acids such as palmitooleic acid, oleic acid, linoleic acid, and linolenic acid, isooctylic acid (2-ethylhexanoic acid), isopalmitic acid (2-hexyldecane) Acid), branched fatty acids such as isostearic acid and the like, and hydroxy fatty acids such as 12-hydroxystearic acid and ricinoleic acid. In the present invention, these may be used alone or in a mixture. Among these, preferred fatty acids have 16 to 18 carbon atoms, and specifically include stearic acid, palmitic acid, isostearic acid, oleic acid, palmitooleic acid and
-One or more selected from the group consisting of hydroxystearic acid. It should be noted that, in the present invention, if a large amount of a fatty acid having a high degree of unsaturation is used, the storage stability of the esterification product of the present invention may be reduced, so care must be taken. When the fatty acid has less than 8 carbon atoms, the esterified product is less likely to exhibit the gelling function of the present invention. The maximum gelling function is realized when fatty acids having 16 to 18 carbon atoms are used.

The mixing ratio of trimethylolpropane or a condensate thereof to a glycerin condensate or a long-chain saturated dibasic acid having 26 to 30 carbon atoms is not particularly limited. It is particularly preferable that the total number of moles of the glycerin condensate exceeds the number of moles of the dibasic acid. When the number of moles of the dibasic acid is the same or more, the solubility in water is reduced.
It is necessary to adjust according to the type and amount of the fatty acid to be blended. Further, the molar ratio of trimethylolpropane or a condensate thereof is preferably 0.7 to 0.1 mol per 1 mol of the glycerin condensate. When the molar ratio of trimethylolpropane or a condensate thereof is 0.7 mol or more, an increase in the melting point is observed, and the compatibility decreases. On the other hand, when the amount is less than 0.1 mol, the water separation from the gelled material increases, and the stability decreases. In such a case, it can be adjusted by the type and amount of the dibasic acid. Therefore, the sum of the number of moles of trimethylolpropane or a condensate thereof and the glycerin condensate is larger than the number of moles of the dibasic acid, and the molar ratio of trimethylolpropane or a condensate thereof to glycerin is 0.1 to 0.1. A composition of 7: 1 is most excellent as a gelling agent. The amount of the fatty acid added to the mother nucleus may be equal to or less than the number of reactive hydroxyl groups, but in order to have a function as a gelling agent, trimethylolpropane or a condensate thereof and a glycerin condensate are used. Of all the hydroxyl groups, it is extremely desirable to leave at least 1/2 as unreacted hydroxyl groups. This is not the case when using hydroxy fatty acids as the fatty acids.

The esterification reaction is carried out in the presence or absence of an acid, alkali or metal catalyst, preferably in an organic solvent or / and a gas inert to the reaction at 100 to 240 ° C.
For several hours to about 20 hours while removing by-produced water. The transesterification reaction is carried out at 20 to 140 ° C. for several tens of minutes to several hours using a catalyst such as a metal alcoholate or a lipase. The progress of the reaction can be evaluated by measuring the acid value in the system or the composition of the acid component in a free state, and the end point of the reaction may be determined based on this.

Although it is possible to leave a free carboxyl group in the oligoester structure without completely terminating the esterification reaction, it is desirable in the present invention to make the ester group almost completely. The esterification reaction product or transesterification reaction product may contain unreacted trimethylolpropane or a condensate thereof, a glycerin condensate, a fatty acid and / or a dibasic acid, and is a known method such as treatment with an adsorbent such as silica gel. And then subjected to decolorization and deodorization treatment for purification.

The esterified product of the present invention thus obtained is a mixture of trimethylolpropane or a condensate thereof, a glycerin condensate, a fatty acid and a dibasic acid, which are oligoesterified linearly and / or branchedly. Yes, changes from a highly viscous liquid to a wax at normal temperature. The number of residual hydroxyl groups in the esterification product is extremely preferably at least 1/2 or more of the hydroxyl groups of the raw material trimethylolpropane or its condensate and glycerin condensate. However, this does not apply to hydroxy fatty acids. In addition to the hydroxy fatty acids, when the remaining hydroxyl groups are not present in an amount equal to or more than の of the total hydroxyl groups, the gelling properties of the water-gelated composition targeted in the present invention are hardly expressed, or the solubility and dispersibility are extremely poor. ,
The gel is easily separated. The hydroxyl value of the esterification product of the present invention can be easily calculated from the blending ratio of the raw materials, that is, the reaction molar equivalent of trimethylolpropane or its condensate and glycerin condensate, and the respective reaction molar equivalents of fatty acids and dibasic acids, and adjusted. it can. It can also be adjusted by the reaction temperature, the reaction time, and the amount of water produced as the reaction proceeds.

The esterification product of the present invention may be used alone or arbitrarily and added to an aqueous solution containing a hydrophilic substance such as water and, if necessary, lower alcohols and saccharides. Produces a gel with flow. Examples of lower alcohols include, but are not limited to, glycerin, diglycerin, polyglycerin, ethylene glycol, diethylene glycol, 1,3-butylene glycol, 3-methyl-1,3-butanediol, and propylene glycol. , Dipropylene glycol,
Tripropylene glycol, polyethylene glycol,
Monohydric or polyhydric alcohols such as hexylene glycol, sorbitol, ethyl cellosolve, butyl cellosolve, ethyl carbitol and butyl carbitol, and examples of saccharides such as glucose, fructose, mannose, galactose, xylose, arabinose and ribose There are saccharides, second class such as maltose, lactose and sucrose, and sugar alcohols such as mannitol, sorbitol and malbit, among which one or a combination of two or more thereof is used by mixing in an aqueous solution.

The aqueous composition containing the gelling agent of the present invention is blended with a known water-soluble component other than those described above, or a surfactant, a pigment, an oily component, or a single or a mixture of the above-mentioned esterification products. be able to. Further, the aqueous composition in which the gelling agent of the present invention exerts its effects includes not only a composition containing only a water-soluble component but also an emulsified composition such as an oily component and a powder dispersion composition such as a pigment and a pigment. When used in the fields of cosmetics, pharmaceuticals, pesticides, feed, fertilizers, paints, etc.,
The aqueous composition in which the gelling agent of the present invention exerts its effect is a composition in which 10% or more of water is contained in an aqueous system other than an insoluble component that does not dissolve in water (powder such as an oily component, a pigment, and a pigment). It is referred to as a composition and is used as a guide of the amount of compounding in an amount of 0.5 to 20% by mass, preferably 1 to 15% by mass based on the total amount of the aqueous component.

[0017]

EXAMPLES In the following synthesis examples and examples,% is based on mass. Synthesis Example 1 Ditrimethylolpropane was placed in a four-necked flask equipped with a stirrer, thermometer, gas injection tube, and water separator.
5 g (0.07 mol), 116 g of decaglycerin (0.
15 mol, but in terms of solid content), octacosandioic acid
6 g (0.14 mol) and 59.3 g of stearic acid
(0.21 mol), p-toluenesulfonic acid was used as a catalyst in an amount of 0.1% with respect to the charged amount, and 18% in a nitrogen gas stream.
The esterification reaction was carried out at 0 to 220 ° C. for 6 hours until no decrease in the acid value was observed. After completion of the reaction, purification was carried out by a conventional method to obtain 245 g of the esterification product of the present invention (referred to as sample No. 1).

Comparative Synthesis Example 1 Ditrimethylolpropane 25.0 g (0.
10 mol), 33.5 g (0.20 mol) of diglycerin, 86.3 g (0.19 mol) of octacosandioic acid,
The same operation and treatment were carried out except that 85.34 g (0.30 mol) of stearic acid was used, and the esterification product (sample no.
11) 195 g were obtained.

Synthesis Examples 2 to 9 and Comparative Synthesis Examples 2 to 5 Synthetic examples (Sample Nos. 2 to 9) by combining various polyglycerins, fatty acids and dibasic acids by the same method as described above.
Esterification products of Comparative Synthesis Examples (Sample Nos. 12 to 15) were obtained.

Synthesis Example 10 A four-necked flask equipped with a stirrer, a thermometer, a gas injection tube and a water separator was charged with 8.8 g of trimethylolpropane.
(0.07 mol), 116 g of decaglycerin (0.15
Mol, but converted to solid content), 63.6 g of octacosandioic acid
(0.14 mol) and 59.3 g of stearic acid (0.
21 mol), and p-toluenesulfonic acid as a catalyst was charged in an amount of 0.1% based on a charge of 180 to 2 in a nitrogen gas stream.
The esterification reaction was carried out at 20 ° C. for 7 hours until no decrease in the acid value was observed. After cooling to room temperature, purification was carried out by a conventional method to obtain the esterification product of the present invention (Sample No. 1).
0) 210 g were obtained.

Tables 1 and 2 summarize the raw material composition of the esterification reaction, the properties of the esterification product, and the analytical values.
The following materials were used in the table. In addition, the numerical value in the raw material formulation indicates the number of moles. Trimethylolpropane: manufactured by Hiroei Chemical Industry Co., Ltd., trade name "trimethylolpropane" Ditrimethylolpropane: manufactured by Hiroei Chemical Industry Co., Ltd., trade name: "di-trimethylolpropane" Decaglycerin: manufactured by Sakamoto Pharmaceutical Co., Ltd. Trade name "polyglycerin # 750" hexaglycerin: manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name "polyglycerin # 500" diglycerin: manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name "diglycerin" adipic acid: Asahi Chemical Industry (Trade name) Adipic acid Stearic acid: Kao Corporation, trade name "Lunac S-9"
8 "Isostearic acid: Product name" PRISORINEI "manufactured by Uniqema
SAC 3505 "Oleic acid: Nippon Seika Co., Ltd., trade name" Pamoline # 1 "
00 "n-octanoic acid: manufactured by Shin Nippon Rika Co., Ltd., trade name" caprylic acid "12-hydroxystearic acid: manufactured by Kawaken Fine Chemical Co., Ltd., trade name:" hydroxystearin "

[0022]

【table 1】

[0023]

[Table 2]

Examples 1 to 10 and Comparative Examples 1 to 5 (Evaluation of gelation of water) The esterification products obtained in Synthetic Examples 1 to 10 and Comparative Synthetic Examples 1 to 5 were evaluated for gelling ability in an aqueous composition. Evaluation was made by the following method. That is, 5 g of any of the esterification products (Sample Nos. 1 to 10) obtained in Synthesis Examples 1 to 10 was added to 95 g of water at 80 ° C., and the mixture was stirred with a propeller stirrer to uniformly dissolve or disperse. Was heated.
After stirring for another 5 minutes after the addition was completed, the mixture was cooled to 30 ° C. while stirring was continued to prepare an aqueous composition. This was left at 25 ° C. for 24 hours. The gelling ability of the obtained aqueous composition was measured at 25 ° C. with a consistency meter (JIS K2220, the cone used was made of aluminum and weighed 32 g, and the size was 1/1). The fluidity was measured using a B-type viscometer (manufactured by Tokyo Seiki Co., Ltd., BL-type, viscosity 10,000 mPa · s).
The above is the rotor NO. 4, 6 rotations, 2000 or more, 100
Less than 00 is the rotor No. 3, 6 rotations, less than 2000 rotor No. (Measured at 2, 6 rotations)
Measured in ° C. After that, 1000r with disperser
The mixture was stirred at pm, and the viscosity was measured again to confirm the recovery of the structure (Examples 1 to 10). Table 3 shows the results. Further, the esterification products obtained in Comparative Synthesis Examples 1 to 5 (sample N
o. 11 to 15) Similarly, an aqueous composition was prepared and evaluated for gelling ability (Comparative Examples 1 to 5). Table 4 shows the results. (When the consistency is less than 300, the shape retention property is such that even if 100 g is put into a glass sample bottle and it is not tilted, it does not flow out. It flows.)

[0025]

[Table 3]

[0026]

[Table 4]

Xanthan gum (manufactured by Kelco,
A 2% aqueous dispersion of Keltrol (trade name) was prepared in the same manner. The viscosity was 17,600 mPa · s, but the consistency was 36.
The gelling ability was larger than 0 and weak.

Examples 11 to 20 and Comparative Examples 6 to 10 (Evaluation of gelling of acid and water) Gelling ability was evaluated in an acidic system in the same manner. A phthalic acid standard solution (pH 4.01) was used instead of purified water. The results are shown in Tables 5 and 6.

[0029]

[Table 5]

[0030]

[Table 6]

A 4% aqueous dispersion of aluminum magnesium silicate (Smecton SA, trade name, manufactured by Kunimine Co., Ltd.) was prepared in the same manner, but the viscosity was less than 500 mPa · s.
The consistency was greater than 360 and the gelling ability was weak.

Examples 21 to 30 and Comparative Examples 11 to 15 (Evaluation of gelling ability of salt water) Gelling ability was evaluated in a salt water system in the same manner. Instead of purified water, a 1 wt% aqueous solution of sodium chloride was used. The results are shown in Tables 7 and 8.

[0033]

[Table 7]

[0034]

[Table 8]

The carboxybivir polymer (Goo
A neutralizing solution of 2% water-dispersed sodium hydroxide was prepared in the same manner as above, but the viscosity was less than 500 mPa · s, the consistency was greater than 360, and the gelling ability was weak.

Examples 31 to 40 and Comparative Examples 16 to 20 (Evaluation of gelling ability with alcohol) Gelling ability was evaluated in an alcohol-containing system in the same manner. An ethanol 50 wt% aqueous solution was used instead of the purified water. The results are shown in Tables 9 and 10.

[0037]

[Table 9]

[0038]

[Table 10]

A 2% aqueous dispersion of xanthan gum (manufactured by Kelco, trade name: Keltrol) was prepared in the same manner. The viscosity was 17,600 mPa · s, but the consistency was 342.5.
And the gelling ability was weak. Also, a carboxybivir polymer (manufactured by Goodrich, trade name Carbopol 94)
0) A 2% water-dispersed sodium hydroxide neutralized solution was prepared in the same manner. The viscosity was 87600 mPa · s, but the consistency was 345.5 and the gelling ability was weak.

From the data shown above, it was found that the esterification products of the present invention (samples Nos. 1 to 10) had a gelling ability having pseudoplastic fluidity in an aqueous system. This corresponds to the esterification product prepared in the comparative synthesis example (sample N
o. It has a remarkable effect as compared with 11 to 15) and conventionally known gelling agents, and has a gelling ability under all various conditions, which means that the product of the present invention is useful.

[0041]

According to the present invention, trimethylolpropane or a condensate thereof, a glycerin condensate, having 26 to 3 carbon atoms
An aqueous gelling agent comprising an esterified product of 0 long-chain linear saturated dibasic acid and a fatty acid having 8 to 28 carbon atoms can be provided. By adding this gelling agent to an aqueous system, an aqueous gel composition having pseudoplasticity can be obtained. Further, the esterification product of the present invention can form a good gel state even when used in an acidic system, a saline system, or an alcohol-containing system. The esterification product of the present invention having a gelling ability in such an aqueous system is used in fields related to the body such as cosmetics and pharmaceuticals,
It can be applied to a wide range of industrial aqueous compositions (including emulsified compositions and pigment dispersion compositions) for general industrial use.
Extremely useful. It should be noted that the flow characteristics of the product of the present invention are almost immediately restored even if a shear that destroys the internal structure is added.

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Claims (6)

[Claims] 1. An esterification product obtained by subjecting trimethylolpropane or a condensate thereof, a glycerin condensate, a long-chain straight-chain saturated dibasic acid having 26 to 30 carbon atoms and a fatty acid having 8 to 28 carbon atoms to an esterification reaction. Gelling agent. 2. The method according to claim 1, wherein the fatty acid having 8 to 28 carbon atoms is one or more selected from the group consisting of linear saturated fatty acids, linear unsaturated fatty acids, branched fatty acids, and hydroxy fatty acids. Gelling agent. 3. The glycerin condensate has an average degree of polymerization of 5 to 15.
The gelling agent according to claim 1 or 2, wherein 4. The method according to claim 1, wherein the total number of moles of trimethylolpropane or a condensate thereof and a glycerin condensate is larger than the number of moles of the long-chain linear saturated dibasic acid. Gelling agent. 5. The molar number of trimethylolpropane or a condensate thereof is 0.1 to 1 mol of the glycerin condensate.
The gelling agent according to any one of claims 1 to 4, wherein the amount is from 0.7 to 0.7 mol. 6. The gelling agent according to claim 1, wherein the long-chain linear saturated dibasic acid is mainly octacosandioic acid having 28 carbon atoms.