JP2000178229A - Improved polyhydric alcohol fatty acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyhydric alcohol fatty acid ester having improved heat stability, workability and improved smell when added to a synthetic resin. SOLUTION: This polyhydric alcohol fatty acid ester for synthetic resin additive is an ester of a polyhydric alcohol and a 8-22C fatty acid and has <=2% free polyhydric alcohol content. One or a mixture of two or more selected form polyglycerol of dimer or polymer, sorbitan, sorbite, sorbitol, trimethylolpropane, pentaerythritol, polyethylene glycol and polypropylene glycol is preferable as the polyhydric alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyhydric alcohol fatty acid ester having improved thermal stability when added to a synthetic resin, workability in molding processing and odor.

[0002]

2. Description of the Related Art Polyhydric alcohol fatty acid esters, which are a type of nonionic surfactant, are used in chemical, fiber, pulp paper,
Widely used in various fields including food. In particular, the use for synthetic resins tends to increase year by year. Among them, anti-fog agent for polyolefin, polystyrene and acrylic synthetic resins, as antistatic agent or anti-fog agent,
It is used in large quantities as one component of antistatic agents. However, during the molding process, stain resistance of the die slip due to poor thermal stability of the polyhydric alcohol fatty acid ester and antistatic agent during molding, poor workability due to occurrence of eyes and the like, and molded products such as films and sheets. The odor is also a problem.

[0003]

Conventional polyhydric alcohol fatty acid esters include polyolefin, polystyrene,
When used as an antifogging agent and antistatic agent in synthetic resins such as acrylic resins, the antifogging and antistatic effects of molded films and sheets are good, but with regard to thermal stability, workability and odor. Are not satisfactory, and these improvements are desired. An object of the present invention is to solve these problems.

[0004]

The present inventors have made intensive studies to solve these problems, and as a result, completed the present invention. The present invention relates to a polyhydric alcohol having 8 to 22 carbon atoms.
A polyhydric alcohol fatty acid ester for addition to a synthetic resin, wherein the free polyhydric alcohol content in the ester with the fatty acid is 2% or less. Conventional polyhydric alcohol fatty acid esters contain 3 to 10% by weight of free polyhydric alcohols, whereas polyhydric alcohol fatty acid esters of the present invention have a polyhydric alcohol content of 2% or less. It is excellent in that heat stability and workability can be improved and there is almost no odor.

The polyhydric alcohol for synthesizing the polyhydric alcohol fatty acid ester of the present invention includes the following compounds. Polyglycerin of dimer or more, for example, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, etc., sorbitan, sorbide, sorbitol, trimethylolpropane, pentaerythritol, Molecular weight 200
Polyethylene glycol having a molecular weight of 0 or less, and polypropylene glycol having a molecular weight of 2000 or less. Mixtures of two or more of these may be used, for example, sorbitan (75-90%) and sorbide + sorbitol (25-10%) mixtures.

The fatty acids having 8 to 22 carbon atoms include, for example, caprylic acid, capric acid, lauric acid, myristic acid,
Saturated fatty acids such as palmitic acid and stearic acid, unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and ricinolenic acid, fatty acids having side chains such as isostearic acid, and mixtures thereof are used.

The polyhydric alcohol fatty acid ester of the present invention may remove free polyhydric alcohol from the polyhydric alcohol fatty acid ester produced by an ordinary method,
Alternatively, it may be produced by reacting a polyhydric alcohol with a fatty acid ester having 8 to 22 carbon atoms under synthesis conditions such that the amount of free polyhydric alcohol is 2% by weight or less. As a method for removing free polyhydric alcohol, for example, filtration, chromatography, centrifugation, distillation under reduced pressure, molecular distillation and the like are used. For example, diglycerin and oleic acid are subjected to an esterification reaction at a reaction temperature of 230 ° C. or higher without a catalyst, and molecular distillation is further performed at a temperature of 170 ° C. or lower under a reduced pressure of 0.05 Torr or lower to remove free diglycerin. Thereby, the polyhydric alcohol fatty acid ester of the present invention can be produced.

[0008] The content of the free polyhydric alcohol in the polyhydric alcohol fatty acid ester of the present invention is 2% by weight or less, preferably 1% by weight or less. If the content of the free polyhydric alcohol exceeds 2% by weight, satisfactory levels of thermal stability, workability and odor cannot be obtained. The polyhydric alcohol fatty acid ester of the present invention is added to the synthetic resin at a ratio of 0.2 to 4.0% by weight, preferably 0.5 to 2.0% by weight.

[0009]

EXAMPLE 1 166 parts of diglycerin and 260 parts of lauric acid were heated at 250 ° C.
Esterification reaction at a reaction temperature of 0.02 Torr
Molecular distillation at a rate of 120 l / h at a temperature of 170 ° C. under reduced pressure gave 346 parts of diglycerin laurate containing 2% of free diglycerin.
The content of free diglycerin was confirmed by gas chromatography using the internal standard method. Example 2 Diglycerol laurate 358 containing 0.5% free diglycerin was prepared in the same manner as in Example 1 except that the molecular distillation rate was 90 liters / hour, the temperature was 160 ° C. under a reduced pressure of 0.01 Torr. Parts manufactured. Example 3 374 parts of diglycerin laurate having a free diglycerin content of 0% was prepared in the same manner as in Example 1 except that the molecular distillation rate was 60 liter / hour, the temperature was 160 ° C. under a reduced pressure of 0.005 Torr. Was manufactured.

EXAMPLE 4 166 parts of diglycerin and 364 parts of oleic acid were heated at 250 ° C.
Esterification reaction at a reaction temperature of 0.05 Tor
Molecular distillation at a temperature of 170 ° C. at a rate of 120 l / h under reduced pressure produced 436 parts of diglycerin oleate containing 2% free diglycerin. Example 5 Diglycerol oleate 451 containing 0.5% free diglycerin was prepared in the same manner as in Example 2 except that the molecular distillation rate was 90 liters / hour, the pressure was reduced to 0.01 Torr, and the temperature was 165 ° C. Parts manufactured. Example 6 471 parts of diglycerin oleate having a free diglycerin content of 0% were prepared in the same manner as in Example 3, except that the molecular distillation rate was 60 liters / hour, the pressure was reduced to 0.005 Torr, the temperature was set to 160 ° C. Was manufactured.

Example 7 A diglycerin palmitic acid ester having a free diglycerin content of 0% was produced in the same manner as in Example 3 using diglycerin and palmitic acid. Example 8 A diglycerin stearate having a free diglycerin content of 0% was produced in the same manner as in Example 3 using diglycerin and stearic acid. Example 9 Triglycerin laurate having a free triglycerin content of 0% was produced in the same manner as in Example 3 using triglycerin and lauric acid.

Example 10 A sorbitan laurate ester containing 0.5% of free sorbitan was produced in the same manner as in Example 2 using sorbitan and lauric acid. Example 11 Using sorbitan and palmitic acid, a sorbitan palmitate containing 0.5% free sorbitan was produced in the same manner as in Example 2. Example 12 Using sorbitan and stearic acid, a sorbitan stearate containing 0.5% of free sorbitan was produced in the same manner as in Example 2. Example 13 Using sorbitan and oleic acid, a sorbitan oleate containing 0.5% free sorbitan was produced in the same manner as in Example 2.

Example 14 Trimethylolpropane stearate having a free trimethylolpropane content of 0% was produced in the same manner as in Example 3 using trimethylolpropane and stearic acid. Example 15 Example 3 using pentaerythritol and stearic acid
In the same manner as described above, the content of free pentaerythritol is 0%.
Pentaerythritol stearic acid ester was produced. Example 16 A polyethylene glycol oleate containing 0.5% of free polyethylene glycol was produced in the same manner as in Example 2 using polyethylene glycol (molecular weight: 600) and oleic acid. Example 17 A polypropylene glycol stearic acid ester containing 0.5% of free polypropylene glycol was produced in the same manner as in Example 2 using polypropylene glycol (molecular weight: 500) and stearic acid.

Comparative Example 1 166 parts of diglycerin and 260 parts of lauric acid were heated at 250 ° C.
The esterification reaction was carried out at a temperature of to produce diglycerin laurate. The free diglycerin content of this ester was 6%. Comparative Example 2 166 parts of diglycerin and 364 parts of oleic acid were heated at 250 ° C.
The esterification reaction was carried out at a temperature of to produce diglycerin oleate. The free diglycerin content of this ester was 6%. Comparative Example 3 164 parts of sorbitan and 260 parts of lauric acid were subjected to an esterification reaction at a temperature of 190 ° C. to produce sorbitan laurate. The free sorbitan content of the ester was 6%.

The following tests were conducted using the polyhydric alcohol fatty acid esters of Examples and Comparative Examples. (1) Thermal Stability 1 15 g of a polyhydric alcohol fatty acid ester was placed in a petri dish and placed in a hot-air dryer at 220 ° C., and the time required for discoloration (3 increase in Gardner value) was measured. Table 1 shows the results. (2) Thermal stability 2 Melt index of polyhydric alcohol fatty acid ester:
MI = 2.0 (g / 10 minutes), density = 0.912 (g
/ Cm ³ ) LLDPE (linear low density polyethylene)
2 parts by weight were added to the resin, and kneader kneading was performed at 160 ° C. for 60 minutes to determine the degree of coloring. As a result, as shown in Table 1, those to which the polyhydric alcohol fatty acid esters of Examples 1 to 17 were added were good (yellow). on the other hand,
Comparative Examples 1 and 2 were colored brown, and Comparative Example 3 was colored brown, which was poor. (3) Workability 1 part by weight of a polyhydric alcohol fatty acid ester was added to the resin used in Thermal Stability 2 and the film thickness was adjusted to 1 by the inflation method.
A 5 μm film was formed and processed, and after continuous operation for 2 days, the stain condition of the die slip was observed and evaluated. Table 1 shows the results. In the examples, there was no or almost no stain on the die slip. On the other hand, in Comparative Examples 1 and 2, there was dirt on the die slip, and in Comparative Example 3, it was slightly more.

[0016]

[Table 1]

(4) Antifogging Effect 1 Using a film having a film thickness of 15 μm by the inflation method of thermal stability 2, cucumber, tomato, and shiitake mushrooms were packed in a styrofoam tray, and the antifogging effect was observed. As a result, Examples 1 to 10, 14 and Comparative Examples 1, 2
Was good, and Examples 11 to 13, 15 to 17 and Comparative Example 3 were slightly inferior. (5) Anti-fog effect 2 A film having a film thickness of 75 μm by the inflation method of thermal stability 2 was spread on an agricultural tunnel house, and the anti-fog effect was observed. As a result, Examples 10 to 12 are good,
Other examples and comparative examples were slightly inferior.

(6) Antistatic Effect A film having a thermal stability of 2 and a film thickness of 75 μm by an inflation method was measured for its surface resistivity at 23 ° C. and 50% RH. As a result, the surface resistivity after one day of film formation was 10 ¹³ Ω in Examples 1 to 17 and Comparative Examples 1 to 3. The surface resistivity after two weeks of film formation was 10 ¹² Ω in Examples 1 to 13 and Comparative Examples 1 to 3, and 10 ¹³ Ω in Examples 14 to ^17.
Met. (7) Odor The odor of the film used for determining the antistatic effect was inspected sensitively. As a result, there was almost no odor in Examples 1 to 17, but there was a specific odor in Comparative Examples 1 to 3.

[0019]

The polyhydric alcohol fatty acid ester of the present invention is excellent in workability when used by being added to a synthetic resin and in thermal stability of the synthetic resin film. Almost no odor derived from impurities of the polyhydric alcohol fatty acid ester is perceived.

Continued on the front page (72) Inventor Mamoru Higashimoto 3-7-12 Tomobuchi-cho, Miyakojima-ku, Osaka-shi, Osaka Maru Ryoyu Kagaku Co., Ltd. F-term (reference) 4H006 AA01 AB68 BS10 4J002 BB001 BC001 BG001 CH052 EH046 EH056

Claims (2)

[Claims] A free polyhydric alcohol content in an ester of a polyhydric alcohol and a fatty acid having 8 to 22 carbon atoms is 2%.
A polyhydric alcohol fatty acid ester for addition to a synthetic resin having the following improved heat stability, workability and odor. 2. The polyhydric alcohol is a dimer or higher polyglycerin, sorbitan, sorbide, sorbitol, trimellilol propane, pentaerythritol, polyethylene glycol, polypropylene glycol, and / or a mixture of two or more thereof. The alcohol fatty acid ester according to claim 1, which is: