JP2000273189A - Dispersant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a dispersant for thermoplastic resins which can uniformly disperse fillers into engineering plastics or super engineering plastics which are processed at 220 deg.C or higher. SOLUTION: This dispersant contains a condensed hydroxyl fatty acid polyglycerin ester, wherein the degree of condensation of the condensed hydroxy fatty acid is larger than 7, and the content of a component selected from tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and decaglycerin in the polyglycerin composition is 35% or larger against the total amount of the polyglycerin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a dispersant for a thermoplastic resin.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins have been used in a large number of fields because of their excellent mechanical and electrical properties, and have been used in various fields, such as rigidity, impact resistance, weather resistance, dimensional stability, and flame retardancy. It has been widely practiced to blend inorganic fillers, organic fillers and the like with thermoplastic resins in order to improve various properties of coloring properties. In recent years, engineering plastics processed at 220 ° C. or higher and super-engineering plastics processed at 300 ° C. or higher have appeared, and processing temperatures of conventional thermoplastic resins have been raised for the purpose of improving productivity. Currently, metal soaps such as calcium stearate and magnesium stearate, and other fatty acid soaps are used as dispersants for thermoplastic resins, but these dispersants have low heat resistance (300 ° C. or lower).
In thermoplastic resins that require high processing temperatures, the dispersant decomposes, reducing its effectiveness as a dispersant, reducing fluidity, making molding difficult, and dispersing the filler due to poor dispersion. It was not possible to obtain a thermoplastic resin product that was stable in quality, for example, in a poor state and impairing the appearance.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dispersant for a thermoplastic resin capable of uniformly dispersing a filler in an engineering plastic or a super engineering plastic processed at 220 ° C. or higher.

[0004]

Means for Solving the Problems The present inventors have made intensive studies and found that a specific condensed hydroxy fatty acid polyglycerol ester solves the above-mentioned problems, and completed this study. That is, in the present invention, the condensation degree of the condensed hydroxy fatty acid is greater than 7, and in the polyglycerin composition, one polyglycerin content selected from the group consisting of tri, tetra, penta, hexa, hepta, octa, nona, and decaglycerin Contains 35% or more of condensed hydroxy fatty acid polyglycerol ester based on the total amount of polyglycerin.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The condensed hydroxy fatty acid of the condensed hydroxy fatty acid polyglycerol ester of the present invention is a condensate of a hydroxy fatty acid and is obtained by thermally polymerizing the hydroxy fatty acid. Hydroxy fatty acids are OH
Any fatty acid having a group and a COOH group may be used, but preferred is 12-hydrostearic acid, ricinoleic acid and the like. The degree of condensation referred to in the present invention is the following (1)
It is obtained by the formula. (Condensation degree) = (acid value of fatty acid) / (acid value of condensed fatty acid) (1)

[0006] The condensation degree of the condensed hydroxy fatty acid used in the present invention needs to be larger than 7, and the condensation degree is 7
Condensed hydroxy fatty acid polyglycerol esters esterified with polyglycerin using the following condensed hydroxy fatty acids cannot achieve the desired dispersing effect and heat resistance. The condensed hydroxy fatty acid polyglycerol ester of the present invention is, for example, thermal polymerization of glycerin, epichlorohydrin, glycidol, glycerin or epiglycolhydrin, dichlorohydrin, polyglycerol synthesized from glycidol as a raw material by molecular distillation purification method, steam carrier. Purified and separated by a vacuum distillation method used, a simulated moving bed chromatograph, etc., the content of one kind of polyglycerin selected from tri, tetra, penta, hexa, hepta, octa, nona and decaglycerin in the polyglycerin composition. 35% of the total amount of polyglycerin
As described above, a condensed hydroxy fatty acid ester obtained by using a purified polyglycerin of preferably 40% or more and esterifying the condensed hydroxy fatty acid having a degree of condensation of greater than 7 with a condensed hydroxy fatty acid by a conventional method.

[0007] The polyglycerol used in the conventional polycondensed hydroxy fatty acid polyglycerol ester has a low content of a specific polyglycerin component and a high content of 20%.
A low-purity polyglycerin mixture,
Even if these condensed hydroxy fatty acid esters are used, the object of the present invention is not achieved. The composition analysis of the polyglycerin used in the polyglycerol ester of the condensed hydroxy fatty acid in the present invention is performed by trimethylsilylation to convert polyglycerin into a derivative, and then performing separation and quantification by a GC method (gas chromatography). You can ask. The analysis by the GC method is performed, for example, by using a fused silica capillary tube chemically bonded to a low-polarity liquid phase such as methylsilicone, to 10 ° C. to 100 ° C. to 320 ° C.
If the temperature rise analysis is performed per minute, it can be easily performed. The identification of peaks on a gas chromatogram can be performed, for example, by introducing a gas chromatograph into a double-focusing mass spectrograph, ionizing it by a method such as chemical ionization, and then measuring it. Determine the molecular weight of the peak on the
Further, it can be easily carried out by obtaining the degree of polymerization of glycerin from the chemical formula.

[0008] The dispersant of the present invention has a condensation degree of the condensed hydroxy fatty acid of more than 7, and contains tri, tetra, penta, hexa, hepta, octa, nona,
The content of one kind of polyglycerin selected from the group consisting of decaglycerin is 35% with respect to the total amount of polyglycerin.
It is a dispersant containing the polyglycerol ester of the condensed hydroxy fatty acid described above. The heat resistance temperature of the condensed hydroxy fatty acid polyglycerol ester of the present invention is 320 ° C.
(Tangent method) is required.
When used as a dispersant for engineering plastics processed at a temperature of 00 ° C. or higher, thermal decomposition occurs, and the effect as a dispersant is reduced, so that the object cannot be achieved. The heat-resistant temperature in the present application means that the dispersant is decomposed by heat and the mass is reduced. The heat resistance temperature can be easily measured with a differential thermal balance device. That is, 10 ° C /
The temperature was raised in minutes, the mass loss of the sample was measured, and the measurement result was analyzed by the tangential method to obtain the heat-resistant temperature. The dispersant of the present invention has a heat resistance temperature of 320 ° C. or higher, and is processed by dispersing the filler uniformly in the thermoplastic resin when the filler is added to the thermoplastic resin processed at 220 ° C. or higher. It is intended to increase the fluidity without lowering the physical properties such as the strength of the product and to improve the processing characteristics.

The condensed hydroxy fatty acid polyglycerol ester of the present invention may be used alone as a dispersant for a thermoplastic resin. However, known metal soaps such as calcium stearate, other dispersants such as fatty acid esters, and antioxidants. It may be used in combination with other additives such as heat stabilizers, ultraviolet absorbers, foaming agents, antistatic agents and the like. The thermoplastic resin of the present invention is not particularly limited as long as it is a resin having a property of being melted by heating, solidifying again upon cooling, and reversibly repeating melting and solidification. Examples of the thermoplastic resin, polyacetal, polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, engineering plastics such as polybutyl terephthalate, polyphenylene sulfide, polyether sulfone, polyether ether ketone, polyketone, Examples include super engineering plastics such as polysulfone, polyarylate, polymethylpentene, and fluororesin. The inorganic filler and the organic filler of the present invention are calcium carbonate, diatomaceous earth, clay titanium oxide, alumina, talc, barium sulfate, calcium sulfate, magnesium hydroxide, glass fiber, iron oxide,
Examples include ceramics, carbon black, rubber powder, decabromodiphenyl ether, and wood powder.

The amount of the dispersant added is 0.05 to 5% of the filler.
0% by weight, preferably 0.5 to 15% by weight. The method of use is not particularly limited, but it may be added at any time when the thermoplastic resin targeted by the present invention is produced. Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, these examples do not limit the present invention. In the examples, “%” means “% by weight”.
Means

[0011]

EXAMPLE 1 Trial Production Example 1 Using 2 kg of the condensed 12-hydrostearic acid of Trial Production Example 3 as a raw material, low-condensed 12-hydrostearic acid was removed by removing the low-condensed 12-hydrostearic acid to obtain 1.5 kg of the condensed 12-hydrostearic acid. Its acid value is 26 and the degree of condensation is
7.2. Trial Production Example 2 Ricinoleic acid (acid value = 188.0) 3 in a 50 L reaction vessel
5 kg and 100 g of NaOH were added, and 100 g of
Water was removed under a reduced pressure of Torr, and the mixture was reacted at 200 ° C. for 30 hours to obtain 25 kg of condensed ricinoleic acid. This had an acid value of 23 and a degree of condensation of 8.2. Prototype Example 3 12-hydrostearic acid (acid value = 1) was placed in a 50 L reaction vessel.
87.0) 35 kg and 100 g of NaOH were added and reacted at 200 ° C. for 13 hours while removing generated water under a nitrogen stream to obtain 30 kg of condensed 12-hydroxystearic acid. Its acid value was 32 and its condensation degree was 5.8.

Trial Production Example 4 30 kg of glycerin and 30 g of a 50% aqueous sodium hydroxide solution were added to a 50 L reaction vessel, and 100 To
heating to 240 ° C. while removing water under reduced pressure of rr,
Hold for 25 hours and react with polyglycerin reactant 1
7.5 kg were obtained. When the obtained polyglycerin reaction product was subjected to trimethylsilylation using an ion-exchange resin to remove NaOH, and measured by gas chromatography, polyglycerol 18 having 15% glycerin and a polymerization degree of 2 (diglycerin) was obtained. % Of polyglycerin having a degree of polymerization of 3 (triglycerin), 16% of polyglycerin having a degree of polymerization of 4 (tetraglycerin), 20% of polyglycerin having a degree of polymerization of 5 or more, and 1% of cyclic polyglycerin.
1%. The hydroxyl value of this product was 970. Trial Production Example 5 The reaction polyglycerin of Trial Production Example 4 was subjected to molecular distillation to obtain a polyglycerin fraction. The obtained polyglycerin fraction was subjected to trimethylsilylation and measured by gas chromatography to find that glycerin 2
%, Degree of polymerization 2 (diglycerin) polyglycerin 6%,
38% polyglycerin with a degree of polymerization of 3 (triglycerin),
Polyglycerol with a degree of polymerization of 4 (tetraglycerin) 22%
Polyglycerol having a degree of polymerization of 5 or more was 28%, and cyclic polyglycerin was 4%. The hydroxyl value of this product was 973.

Trial Production Example 6 30 kg of glycerin and 30 g of a 50% aqueous sodium hydroxide solution were added to a 50 L reaction vessel, and 100 To
While removing water at rr pressure, heat to 240 ° C.
13. Hold for 3 hours to allow polyglycerin reactant
3 kg were obtained. When the obtained polyglycerin reaction product was subjected to demethylation using an ion exchange resin and subjected to trimethylsilylation, and measured using gas chromatography, glycerin 8%, polymerization degree 2 (diglycerin)
Polyglycerin 11%, degree of polymerization 3 (triglycerin)
13% of polyglycerin, 15% of polyglycerin having a degree of polymerization of 4 (tetraglycerin), 20% of polyglycerin having a degree of polymerization of 5 (pentaglycerin), 20% of polyglycerin having a degree of polymerization of 6 or more, and 13% of cyclic polyglycerin Met. The hydroxyl value of this product was 890. Trial Production Example 7 Using the reaction polyglycerin of Trial Production Example 6 as a raw material, simulated moving bed liquid chromatography was performed using four columns packed with an ion exchange resin having a sodium sulfonic acid group to obtain a polyglycerin fraction. Was. When the composition of the obtained polyglycerin fraction was trimethylsilylated and measured using gas chromatography,
Polyglycerin 3% of polymerization degree 2 (diglycerin), polyglycerin 5% of polymerization degree 3 (triglycerin), polyglycerin 10% of polymerization degree 4 (tetraglycerin), polyglycerin 45 of polymerization degree 5 (pentaglycerin) %, Polyglycerin having a degree of polymerization of 6 or more was 32%, and cyclic polyglycerin was 5%. The hydroxyl value of this product is 8
85.

Example 1 400 g of the condensed 12-hydrostearic acid obtained in Prototype Example 1 was added to a 1 L four-necked flask, 70 g of polyglycerin obtained in Prototype Example 5 was charged, and water produced was removed under a nitrogen stream. The reaction was carried out at 200 ° C. to obtain 410 g of condensed 12-hydroxystearic acid polyglycerol ester. Example 2 400 g of the condensed ricinoleic acid obtained in Prototype Example 2 was added to a 1-liter four-necked flask, and 70 g of polyglycerin obtained in Prototype Example 7 was charged. And 408 g of condensed ricinoleic acid polyglycerol ester was obtained.

Comparative Example 1 The condensation 1 obtained in Experimental Example 3 was placed in a 1-liter four-necked flask.
400 g of 2-hydroxystearic acid was added, 70 g of the polyglycerin obtained in Prototype Example 4 was charged, and the mixture was reacted at 200 ° C. while removing generated water under a nitrogen stream to form condensation 12-.
400 g of polyglycerol hydrostearate were obtained. Comparative Example 2 Condensation 12 obtained in Prototype Example 1 in a 1-liter four-necked flask
-Prototype Example 4 by adding 400 g of hydroxystearic acid
70 g of the polyglycerin obtained in the above was charged and reacted at 200 ° C. while removing generated water under a nitrogen stream to obtain 410 g of condensed 12-hydroxystearic acid polyglycerol ester. Comparative Example 3 400 g of the condensed ricinoleic acid obtained in Prototype Example 2 was added to a 1-liter four-necked flask, 70 g of the polyglycerin obtained in Prototype Example 6 was charged, and at 200 ° C. while removing generated water under a nitrogen stream. The reaction was carried out to obtain 410 g of condensed ricinoleic acid polyglycerol ester.

Test Example 1 Method: Using a differential thermal balance measuring device, the temperature was raised to 40 to 400 ° C. at 10 ° C./min, and the weight loss of the sample was measured. did.

[0017]

[Table 1]

Test Example 2 1% by weight of each sample was added to talc, and surface treatment was performed by high-speed stirring with a Henschel mixer. 40 parts by weight of this treated filler was added to 60 parts of polyphenylene sulphite resin and melt-kneaded by a twin-screw extruder to prepare pellets. Using the pellets, the kneading torque was measured and the sheet was evaluated. Table 2 shows the results. Measuring method 1) Kneading torque: The kneading torque was measured 3 minutes after the start of melt kneading using a Labo Plastomill. Temperature during kneading is 32
The temperature was set to 0 ° C. and the number of rotations was set to 30 rpm. The lower the kneading torque, the better the formability. 2) Appearance: The sheet was prepared by heating the roll temperature to 300 ° C. for 3 minutes by desktop small roll mixing.

[0019]

[Table 2]

Test Example 3 Samples were added to titanium oxide in the amounts shown in Table 3 and surface-treated by high-speed stirring with a Henschel mixer. 30 parts by weight of a filler of this treated product was added to 70 parts by weight of polyether sulphite resin, and the mixture was melt-kneaded by a twin-screw extruder to prepare pellets. Using the pellets, the kneading torque was measured and the sheet was evaluated in the same manner as in Test Example 2. Table 3 shows the results.

[0021]

[Table 3]

[0022]

As shown in the above Test Examples, it is clear that the dispersant of the present invention is useful for dispersing fillers of engineering plastics and super engineering plastics processed at 220 ° C. or higher.

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Claims (2)

[Claims] 1. The condensation degree of a condensed hydroxy fatty acid is more than 7, and the content of one kind selected from tri, tetra, penta, hexa, hepta, octa, nona and decaglycerin in the composition of polyglycerin is the total amount of polyglycerin. A dispersant for a thermoplastic resin, which comprises 35% or more of a condensed hydroxy fatty acid polyglycerin ester based on the total amount of the polyglycerol ester. 2. The dispersant according to claim 1, wherein the heat resistance temperature of the condensed hydroxy fatty acid polyglycerol ester is 320 ° C. or higher.