JPH07308562A - Emulsifying agent composition - Google Patents

Abstract

PURPOSE:To produce a polyglycerin fatty acid ester composition improved in stickingness and capable of dispersing an dissolving satisfactorily in both of water and oil. CONSTITUTION:This composition is composed of the polyglyerin fatty acid ester composition composed of a polyglycerin fatty acid ester, having 20-40% average degree of esterification, obtained by esterifying the polyglycerin having average degree of polymerization of 6-12 with a 16-24C linear satd. fatty acid, and an unreacted polyglycerin less than equivalent to the polyglycerin fatty acid ester above and a sucrose fatty acid ester in which >=50% structural fatty acid is composed of >=16C linear satd. fatty acid and <=5% monoester is contained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyglycerin fatty acid ester composition which is widely used as an emulsifier for foods, pharmaceuticals, cosmetics and other industrial applications. Specifically, it relates to a hydrophilic polyglycerin fatty acid ester composition having improved handleability.

[0002]

2. Description of the Related Art Polyglycerin fatty acid ester (hereinafter referred to as
It is called PoGE. The composition is widely used as a surfactant (emulsifier) in the fields of foods, pharmaceuticals, cosmetics, etc., because it has no toxicity, heat resistance, acid resistance and safety. PoGE, which is the main constituent of the PoGE composition, is important for the surfactant by selecting the degree of polymerization of polyglycerin (hereinafter referred to as PoG) as a skeleton, the type of fatty acid to be ester-bonded to the polyglycerol and the degree of esterification. HLB (an index representing the ratio of the hydrophilic part and the lipophilic part in the molecule), which is a unique property, can be changed.

The PoGE composition is obtained by polycondensing glycerin in the presence of an alkali catalyst at a high temperature of 200 ° C. or higher,
PoG having a distribution of glycerin polymerization degree of about 2 to 20 is produced by performing purification such as desalting and decolorization, and then various fatty acids or fatty acid esters are added thereto under normal pressure or reduced pressure in the presence of an alkali catalyst. Reaction temperature 200-240
It is generally produced by esterification or transesterification at about ° C. The PoGE composition thus obtained is composed of PoGE and unreacted PoG, and PoGE is also a monoester, diester,
It is a very complex composition consisting of various esters such as triesters.

The control of HLB in producing a PoGE composition is controlled by the fatty acid or fatty acid ester and Po which are used in the reaction.
This is done by changing the G preparation ratio.
In order to obtain a high HLB, generally, PoG having an average degree of polymerization of 6 or more is used, and the molar ratio of the fatty acid or the fatty acid ester charged is not more than the equimolar amount with respect to PoG.
However, since this reaction is an esterification reaction, it is unavoidable that the final product has an equilibrium composition containing various esterification degrees. Therefore, when trying to obtain a hydrophilic PoGE composition, it is inevitable that unreacted PoG remains.

Separation of unreacted PoG from the obtained reaction mixture has also been studied in the past. However, when the average degree of polymerization of PoG is 4 or more, the boiling point of PoG becomes high, so that separation by distillation or the like occurs. Have difficulty. So traditionally,
The reaction mixture of PoG and a fatty acid or a fatty acid ester was steam-distilled and purified to such an extent as to remove coloring components, odorous components and the like, and was put on the market as a PoGE composition. Therefore, the conventional high HLB PoGE composition was always a composition containing a large amount of residual PoG. The commercially available PoGE composition has a residual PoG content of 50.
Some have reached a weight percentage of over.

[0006]

[Problems to be Solved by the Invention] Conventional Po of high HLB
The GE composition is viscous and sticky at around room temperature even if the constituent fatty acid is a saturated fatty acid having a high melting point. Further, in the case of a PoGE composition in which the constituent fatty acid is an unsaturated fatty acid, compared to when the constituent fatty acid is a saturated fatty acid, PoG
The melting point of E becomes low, and the tendency becomes even more severe. Therefore, the PoGE composition is often sold and distributed as a product by adding a solvent such as water or ethanol. Such P
The product of the oGE composition has high hydrophilicity, is difficult to dissolve in the oil phase, and has a limited usage. For example, since such a product is difficult to be uniformly dispersed and dissolved in oil, it is unsuitable for producing an oil-in-water emulsion by a phase inversion emulsification method in which an aqueous phase is dropped into an oil phase in which an emulsifier is dispersed and dissolved in advance. .

[0007] On the other hand, as a solid substance in the form of removing moisture, Po
The GE composition may be distributed and sold. However, this is extremely hard and sticky, and even if it is formed into a flake shape or a block shape, it is immediately solidified and is not easy to handle. In addition to the above, so-called compounded preparations, which are formulated by combining with a fat or an emulsifier having a high melting point in order to improve the handleability of the PoGE composition, have been conventionally known. It is diluted by the properties of other emulsifiers. It has also been proposed to spray-dry a solution obtained by dissolving or dispersing a decomposed product of starch in a solution obtained by dissolving the PoGE composition in water (Japanese Patent Publication 5).
-85590), this method is useful in dissolving the emulsifier in water, but it is difficult to obtain a method capable of being dispersed and dissolved in oil.

[0008]

The present inventors have found that PoGE
It was found that the sucrose fatty acid ester having a low monoester content in the composition improves the handleability of the PoGE composition, and has completed the present invention. The present invention will be described in detail. The PoGE composition targeted by the present invention is a POG having an average degree of polymerization of 6 to 12 and P which is an ester of this PoG and a linear saturated fatty acid having 16 to 24 carbon atoms.
It consists of oGE. The average esterification rate of PoGE is 20 to 40%, and the P content of the PoGE composition is P.
The ratio of oGE is 50% or more.

The physical properties of PoG and PoGE derived therefrom differ depending on the average degree of polymerization of PoG. For example,
PoGE derived from PoG having an average degree of polymerization of less than 4
Are generally poorly hydrophilic. Those having an average degree of polymerization of more than 12 are remarkably viscous and sticky, and are limited in their use in foods in terms of safety. So in general PoGE
PoG having an average degree of polymerization of 4 to 12 is used for producing the composition. The present invention can be applied to a PoGE composition produced using such PoG as a raw material, but is preferably applied to a PoGE composition using PoG having an average degree of polymerization of 6 to 12 as a raw material. PoGE in PoGE composition
Is composed of the above-mentioned PoG and a linear saturated fatty acid having 16 to 24 carbon atoms such as palmitic acid, stearic acid and behenic acid. Of these, fatty acids having 18 to 24 carbon atoms are preferable. The fatty acids may be used alone or as a mixture of two or more kinds. In addition, fatty acids other than the above may be contained in a slight amount. Usually, fatty acids obtained from natural fats and oils or hydrogenated oils are used as they are, or desired fatty acids are concentrated from these.

Since the PoGE composition produced from a fatty acid having 14 or less carbon atoms and PoG is extremely sticky, even if sucrose fatty acid ester is blended according to the present invention,
It is difficult to sufficiently improve its handleability. Further, the PoGE composition produced from unsaturated fatty acid and PoG is generally a viscous liquid at room temperature and becomes a complete liquid when heated to about 50 ° C. Therefore, it is easy to handle even without the present invention. The average esterification rate of PoGE in the PoGE composition (= ratio of esterified ones of all PoG hydroxyl groups constituting PoGE) is 20 to 40%.
Is appropriate.

PoG having a low average esterification rate of PoGE
The composition E is highly sticky, and the addition of sucrose fatty acid ester to the composition E does not sufficiently improve the handleability. Also,
This product also has poor dispersibility in the oil phase. Conversely, Po
When the average esterification rate of GE becomes too high, the PoGE composition becomes a solid, and therefore the sucrose fatty acid ester added to the composition of the present invention has a small effect of improving its handleability. However, those having a high average esterification rate have poor dispersibility in the aqueous phase. PoGE in PoGE composition
A preferred average esterification rate of 20 to 30%, especially 25
~ 30%. PoG in the PoGE composition is suitably 50% or less. PoG is hygroscopic and viscous, so PoG
If the amount of PoG in the GE composition is too large, the sucrose fatty acid ester may be added to the composition, but the handling will not be sufficiently improved. Further, even if this compound is added to the oil phase to disperse and dissolve it, PoG becomes a gel and precipitates, so that a uniform dispersed and dissolved product cannot be obtained. The preferred content of PoG in the PoGE composition is 35% or less, especially 25% or less.

The sucrose fatty acid ester blended in the PoGE composition according to the present invention is one in which 50 (wt)% or more of the constituent fatty acids are linear saturated fatty acids having 16 or more carbon atoms and the monoester content is 5% or less. Is. As the fatty acid, palmitic acid, stearic acid, behenic acid, etc. are usually used. Among them, those having 18 to 24 carbon atoms are preferable.
Usually, fatty acids obtained from natural fats and oils or hydrogenated oils, or those obtained by concentrating desired fatty acids from them are used. In the sucrose fatty acid ester in which unsaturated fatty acids and linear saturated fatty acids having 14 or less carbon atoms account for 50% or more of the constituent fatty acids, PoGE
Even if it is added to the composition, the handling property is not sufficiently improved. Since sucrose has 8 hydroxyl groups, sucrose fatty acid ester is generally a mixture of monoesters (= substitution degree 1) to octaesters (= substitution degree 8) with various substitution degrees, and its average substitution degree is Is given by

[0013]

[Equation 1] i: Substitution degree of sucrose fatty acid ester Wi: Ratio of substitution degree i of sucrose fatty acid ester (% by weight)

In the present invention, a sucrose fatty acid ester having a monoester content of 5 (wt)% or less is used. PoG for sucrose fatty acid ester with high monoester content
When it is blended with the E composition, an insoluble matter tends to be generated when the formulation is added to the oil phase and dissolved therein, and a uniform solution cannot be obtained. In addition, even if the monoester content is 5% or less, if the average degree of substitution is small, it may be difficult to uniformly disperse and dissolve the mixture when added to the oil phase. Therefore, the sucrose fatty acid ester has a monoester content of 5 or less. % Or less and an average substitution degree of 5 or more is preferably used.

The compounding ratio of the sucrose fatty acid ester to the PoGE composition is usually 10 to 100 parts by weight with respect to 100 parts by weight of the PoGE composition. If the content of the sucrose fatty acid ester is too small, the handleability of the composition will not be sufficiently improved. On the contrary, if the blending amount is too large, PoG
The properties of the E composition are diminished. A suitable amount is P
3 parts sucrose fatty acid ester per 100 parts by weight of oGE composition
It is 0 to 100 parts by weight.

The sucrose fatty acid ester can be added to the PoGE composition by any method. Preferably both are melt mixed. That is, the mixture of the PoGE composition and the sucrose fatty acid ester may be heated to 60 to 100 ° C, preferably 70 to 80 ° C to be melted, stirred and mixed, and then cooled and solidified. According to this method, a uniform compound can be easily obtained. When blending the PoGE composition and the sucrose fatty acid ester, other emulsifiers, thickeners, emulsion stabilizers, etc. may be used in combination, if necessary.

[0017]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, PoGE
The content ratio of PoG and the average esterification ratio of PoGE in the composition can be measured as follows. PoG content: Quantified according to Japanese Patent Application No. 5-302893 “polyglycerin quantification method”. Ie PoGE
A solution prepared by dissolving the composition in a hydrophilic organic solvent is introduced into a column packed with a reverse phase adsorbent to adsorb PoGE onto the adsorbent, and then pass PoG to obtain a PoG solution containing no PoGE. The solution is then analyzed by gel permeation chromatography to quantify PoG.

As a standard method, the PoGE composition is dissolved in a tetrahydrofuran / methanol = 6/4 (v / v) solution to a concentration of 0.1 to 0.5 wt%. The solution prepared above was injected into an analyzer in which a reverse phase column and a gel permeation column were connected in series, and a differential refractometer was installed as a detector at the outlet, and then methanol / water = 3/7 (v) / V) Flow the solution at 0.7 ml / min to develop. As the column, for example, YMC is used in the reverse phase
-AM312 (made by YMC), A for gel permeation
Although sahipak GS310HQ is used, other columns may be used.

Average esterification rate: The PoGE composition was evaluated for its hydroxyl value (OHV (1)), saponification value (SV) and acid value (AV) by the standard oil and fat analysis test method (established by Japan Oil Chemistry Association). taking measurement. The hydroxyl value (OHV (2)) of the PoGE composition completely saponified into PoG is measured. The average esterification rate is obtained by subtracting the number of free PoG hydroxyl groups from the total number of hydroxyl groups in the sample containing esterified hydroxyl groups and dividing the number of esterified hydroxyl groups. To be done.

[0020]

[Equation 2] (PoG: wt% free PoG in PoGE composition)

<Preparation of PoGE Composition> The molar ratio of stearic acid charged to PoG (average degree of polymerization: 11) was 0.7.
To a mixture in which the total amount of the both was changed to 1500 g and 0.04 g of sodium hydroxide was added to a reaction vessel, and the mixture was allowed to react at 220 ° C. for 3 hours under a nitrogen stream to produce a PoGE composition. I got a thing. Average esterification rate of PoGE and residual PoG determined by the above-mentioned analysis method
The contents are shown in Table-1.

[0022]

[Table 1]

<Preparation of Emulsifier Composition> 0.1 to 1.0 parts by weight of the following sucrose fatty acid ester is added to 1 part by weight of each of the above-mentioned PoGE compositions, and the mixture is melt-mixed at 80 ° C.
The emulsifier composition shown in Table-2 was obtained.

<Added sucrose fatty acid ester> I) Lyoto-sugar ester S-070 (monoester 0%, average degree of substitution 6.7) II) Lyoto-sugar ester S-170 (monoester <1%, average substitution 5.5) III) Ryoto-sugar ester S-570 (monoester 28%, average substitution degree 2.1) IV) Ryoto-sugar ester S-1170 (monoester 58%, average substitution degree 1.5) V ) Ryoto Sugar Ester S-1570 (Monoester 71%, Average degree of substitution 1.3) (The above are all products of Mitsubishi Kasei Co., Ltd., and 70% or more of the constituent fatty acids are stearic acid. Is a registered trademark of Mitsubishi Kasei Co., Ltd.)

[0025]

[Table 2]

<Evaluation of Physical Properties> The emulsifier composition obtained above was evaluated for its properties (peeling property, stickiness, cutting property, dispersibility in oil or water).

(1) Evaluation of peelability The emulsifier composition melted at 80 ° C. was dropped on a glass or polyethylene petri dish (diameter 8 cm) placed on ice, and after 2 minutes, the solidified sample was scratched with a spatula. Collecting
The peelability was evaluated according to the following criteria. Score 1: Completely peels off just by tilting. Score 2: Completely peels when lightly scratched with a spatula. Rating 3: Completely peeled off with strong force using a spatula. Rating 4: Even if you are strong with a spatula, some remain.

(2) Evaluation of stickiness The stickiness was evaluated by touching it actually and sensory evaluation according to the following criteria. Score 1: No discomfort even after touching. Rating 2: After touching, a slight slimy feeling remains. Score 3: When touched, it feels sticky. Score 4: Sticky and sticky.

(3) Evaluation of Cuttability The cuttability was evaluated by splitting the sample solidified in (1) by hand and evaluating the degree of cracking according to the following criteria. Score 1: Crisp and clean. Rating 2: It cracks but is sticky or brittle. Rating 3: It grows and cuts.

(4) Evaluation of dispersibility in oils and fats or water The dispersibility was evaluated by adding 1% by weight of a sample to 1% saline solution having a pH of 3 and rapeseed oil and heating and stirring at 60 ° C. The presence or absence of insoluble matter was observed. The evaluation results from (1) to (4) above are shown in Table-3.

[0031]

[Table 3]

<Preparation of Oil-in-Water Emulsion> An oil-in-water emulsion was produced using the emulsifier composition B and PoGE composition 3 described above. 1 part by weight of emulsifier to 30 parts by weight of rapeseed oil
After dispersing at 0 ° C., a mixture of 61.9 parts by weight of water, 2 parts by weight of salt, 5 parts by weight of 10% acetic acid and 0.1 part by weight of xanthan gum was slowly added at 70 ° C. with stirring at 5000 rpm, The mixture was stirred for 10 minutes in total. After the emulsification, the mixture was immediately cooled to room temperature in ice water and subjected to a storage test at 30 ° C. Regarding the stability of the emulsion, the emulsified state after 1 week was evaluated by the water separation rate defined by the following formula. The results are shown in Table-4.
The smaller the water separation rate, the more stable the emulsification.

[0033]

[Equation 3]

[0034]

[Table 4]

As described above, in the oil-in-water emulsification under acidic salt, the emulsifier composition B enables good oil-in-water emulsification without impairing the original properties of the PoGE composition.

[0036]

EFFECT OF THE INVENTION The emulsifier composition of the present invention has the improved stickiness and handleability found in the conventional highly hydrophilic PoGE composition. Further, since it has excellent dispersion solubility in both oil and water, it can be used in either the oil phase or the water phase depending on the purpose at the time of emulsification, and does not impair the emulsifying function inherent in the PoGE composition, and is excellent. It is possible to produce an emulsion.

Claims (3)

[Claims] 1. A polyglycerin fatty acid ester having an average esterification rate of 20 to 40%, which is composed of a linear saturated fatty acid having 16 to 24 carbon atoms and polyglycerin having an average degree of polymerization of 6 to 12, and an equivalent amount thereof. From a polyglycerin fatty acid ester composition consisting of the following free polyglycerin and a sucrose fatty acid ester in which 50% or more of the constituent fatty acids consist of linear saturated fatty acids having 16 or more carbon atoms and the monoester content is 5% or less Emulsifier composition. 2. A polyglycerin fatty acid ester composition 1
The emulsifier composition according to claim 1, wherein 10 to 100 parts by weight of sucrose fatty acid ester is mixed with 00 parts by weight. 3. The emulsifier composition according to claim 1, which is obtained by melt-mixing a polyglycerin fatty acid ester composition and a sucrose fatty acid ester at 80 to 100 ° C.