KR101941883B1 - Heat stabilizer composition of pvc comprising hydrotalcite - Google Patents

Abstract

The present invention relates to a heat stabilizer composition of PVC, comprising: hydrotalcite surface-treated with chlorinated polyethylene and to which an interlayer insert is added; and a hydroxide mixture of calcium hydroxide and aluminum hydroxide. The present invention relates to a heat stabilizer composition which is contained in PVC to enhance not only thermal stability but also processing stability and storage stability.

Description

[0001] HEAT STABILIZER COMPOSITION OF PVC COMPRISING HYDROTALCITE [0002]

The present invention relates to a thermostabilizer composition of PVC comprising hydrotalcite, and more particularly to a hydrotalcite which has an interlayer insert added thereto and which has been surface treated with chlorinated polyethylene, and a hydroxide mixture comprising calcium hydroxide and aluminum hydroxide To a thermostabilizer composition having improved properties as a heat stabilizer for PVC.

Techniques for applying toxic substances or substances with less environmental pollution problems instead of stabilizers containing heavy metal compounds such as lead, barium and cadmium applied to PVC have been developed.

For example, in Korean Patent Publication No. 10-1426604, the thermal stability of PVC is improved by adding hydrotalcite to PVC. Such hydrotalcite is added with a reactive intercalating agent by a method similar to the method disclosed in Korean Patent Publication No. 10-0909220. Since anion exchange can be performed as a layered metal hydroxide, an environmentally friendly A heat stabilizer can be provided. The thermal stability and coloring property of PVC can be improved by inserting the reactive interlayer insert between the layers of hydrotalcite. However, the pH of the material inserted between the layers changes over time, .

Due to such a problem, Korean Patent Publication No. 10-1039285 has obtained a stabilizing effect by perchlorate by applying hydrotalcite as a carrier for capturing perchlorate. However, this method can not maximize the thermal stabilization effect of the hydrotalcite itself, and does not have a better effect in long-term storage.

Japanese Laid-Open Patent Publication No. 09-110997 discloses a composition comprising hydrotalcite and calcium hydroxide or calcium hydroxide / aluminum. Japanese Patent Application Laid-Open No. 2000-026117 discloses that lithium aluminate hydrotalcite is applied as a PVC stabilizer . In this prior art, a synergistic effect of hydrotalcite and an additional component is obtained, or a PVC stabilizing effect is obtained by optimizing the kinds of metal ions contained in hydrotalcite. However, even in this case, it is difficult to secure long-term storage property have.

Korean Registered Patent No. 10-1426604 Korean Patent Publication No. 10-0909220 Korean Patent Publication No. 10-1039285 Japanese Patent Application Laid-Open No. 09-110997 Japanese Patent Application Laid-Open No. 2000-026117

DISCLOSURE Technical Problem The present invention has been conceived in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide a thermostable polyvinylidene fluoride thermosetting resin composition which, through the composition comprising hydrotalcite surface treated with chlorinated polyethylene, It is an object of the present invention to provide a thermostabilizer composition which improves not only characteristics but also processing stability and long-term storage stability.

In order to achieve the above object, the present invention provides a thermostabilizer composition for PVC comprising a hydrotalcite surface-treated with chlorinated polyethylene to which an interlayer insert is added, and a hydroxide mixture comprising calcium hydroxide and aluminum hydroxide.

The interlayer insert may be obtained by reacting fatty acid and maleic anhydride. The fatty acid may be selected from the group consisting of butyric acid, caproic acid, caprylic acid, pelargonic acid, It is also possible to use capric acid, undecylic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, oleic acid, Oleic Acid, Ricinoleic Acid, Vaccenic Acid,? -Linolenic Acid, Arachidic Acid, Gadoleic Acid, Arachidonic Acid, Behenic acid, eruic acid, and lysine carboxylic acid.

The chlorinated polyethylene has a chlorine content of 10 to 20% by weight and a weight average molecular weight of 1,000 to 10,000.

In addition, the hydrotalcite may be a mixture of hydrotalcite containing magnesium and hydrotalcite containing zinc and magnesium.

The thermostabilizer of the present invention can be used as a heat stabilizer for a PVC, through the composition comprising hydrotalcite surface-treated with chlorinated polyethylene to which an intercalant is added, as well as the thermal stability required as a heat stabilizer for PVC, .

Fig. 1 shows the results of evaluating the thermal stabilizing effect of the thermostabilizer compositions according to Examples and Comparative Examples.
Fig. 2 shows the results of evaluating the long-term storage stability of the thermostabilizer compositions according to Examples and Comparative Examples.

Hereinafter, the present invention will be described in more detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention relates to a thermostabilizer composition for PVC, which comprises hydrotalcite to which an interlayer insert is added and surface treated with chlorinated polyethylene, and a hydroxide mixture comprising calcium hydroxide and aluminum hydroxide. That is, unlike hydrotalcite which is generally applied, the present invention improves thermal stability and coloring property by adding an interlayer insert, and at the same time, when applied to PVC by surface treatment with chlorinated polyethylene, And the long-term storage property of the hydrotalcite is improved.

The hydrotalcite is obtained by firstly adding an intercalating agent and then reacting the obtained hydrotalcite surface with chlorinated polyethylene to perform surface treatment.

The interlayer insert may be prepared by a known method in Korean Patent Publication Nos. 10-1426604 and 10-0909220. The metal salt, the basic compound and the interlayer anion supplying material for constituting the hydrotalcite are dispersed and mixed and subjected to a high- , Hydrotalcite is prepared, and then a reactive interlayer insert is added thereto and reacted at a high temperature and a high pressure to obtain hydrotalcite with an interlayer insert added thereto. Further, a treatment process for coating the surface with a fatty acid is additionally performed for the stability of the material.

In the present invention, hydrotalcite with an intercalant added is obtained, and hydrotalcite surface-treated with chlorinated polyethylene for surface treatment is obtained. Korean Patent Publication No. 10-1039285 discloses that the addition of perchloric acid can improve the stabilization of PVC, and thus the effect of the chlorine-containing polymer as a PVC stabilizer is mentioned. In the present invention, the surface treatment with chlorinated polyethylene produces PVC Not only the effect as a heat stabilizer but also the stability of a heat stabilizer can be improved to enable long-term storage.

The interlayer insert can be obtained by reacting fatty acid and maleic anhydride. Examples of such fatty acids include butyric acid, caproic acid, caprylic acid, pelargonic acid, It is also possible to use an acid such as Capric Acid, undecylic acid, Lauric Acid, Myristic Acid, Palmitic Acid, Palmitoleic acid, Oleic Acid, Ricinoleic Acid, Vaccenic Acid,? -Linolenic Acid, Arachidic Acid, Gadoleic Acid, Arachidonic Acid, Behenic Acid, Various fatty acids such as Behenic Acid, Erueic acid and Ligfnoceric Acid can be applied. Among these fatty acids, it has been found that a fatty acid having 9 to 11 carbon atoms such as pelargonic acid, capric acid and undecylic acid has a better effect.

The method of inserting the interlayer insert between the layers of hydrotalcite and the method of surface treatment with chlorinated polyethylene can be applied to conventional high-temperature and high-pressure reactions, and the surface treatment of the hydrotalcite, The hydrotalcite can be stabilized.

The chlorinated polyethylene is preferably a polymer having a relatively small molecular weight. In order to ensure compatibility with the PVC when it is dispersed evenly on the surface of hydrotalcite, the present invention uses chlorinated polyethylene having a weight average molecular weight of 1,000 to 10,000 to improve the stability of such a heat stabilizer and PVC And the like. Particularly, chlorinated polyethylene having a chlorine content of 10 to 20% by weight is applied. If the chlorine content is too low, it does not show sufficient performance as a PVC heat stabilizer. If the chlorine content is too high, chlorine compound And thus the physical properties of the heat stabilizer are lowered, and it has been found to be most preferable to apply in the above range.

The chlorinated polyethylene was found to have a melt index (5.0 kg) of 0.001 to 100, a molecular weight distribution (MWD) of 20 or less, a melting temperature of 125 to 140 캜, and a density of 0.94 g / cm 3 or more.

In addition, hydrotalcite includes divalent and trivalent metals, and when applied to a thermal stabilizer, hydrotalcite containing magnesium is often applied. However, in the present invention, hydrotalcite containing magnesium and hydrotalcite containing zinc and magnesium are prepared, respectively, and mixed in an appropriate ratio to improve thermal stability according to long-term storage. A hydrotalcite containing such magnesium _{6MgO · Al 2 O 3 · CO} 2 · 12H 2 O, 4MgO · Al 2 O 3 · CO 2 · 9H 2 O, 4MgO · Al 2 O 3 · CO 2 · 6H 2 O and the like, a hydrotalcite containing zinc is _{ZnO · 3MgO · Al 2 O 3} · CO 2 · 5H 2 O, ZnO · 3MgO · Al 2 O 3 · CO 2 · 6H 2 O, ZnO · 3MgO · Al ₂ O ₃ · CO ₂ · 8H ₂ O, ZnO · 3MgO · Al ₂ O ₃ · CO ₂ · 9H ₂ O, which is particularly advantageous in hydrotalcite depositing zinc through electrochemical reactions Effect.

The hydrotalcite is preferably mixed with hydrotalcite containing magnesium and hydrotalcite containing zinc and magnesium at a weight ratio of 1: 1 to 3: 1. If it is out of the above range and one of them is too much, the long-term storage stability of the heat stabilizer is deteriorated.

In addition, since the heat stabilizer of PVC according to the present invention is used in the form of a composition, hydrotalcite surface-treated with chlorinated polyethylene added with the interlayer insert, and a hydroxide mixture composed of calcium hydroxide and aluminum hydroxide are produced.

Japanese Patent Application Laid-Open No. 09-110997 discloses that the effect of the heat stabilizer is enhanced by the addition of the above-mentioned calcium hydroxide or aluminum hydroxide. However, in the present invention, a hydroxide mixture containing calcium hydroxide and aluminum hydroxide is applied to improve not only thermal stability but also long-term storage stability. As a result of various experiments, the calcium hydroxide and aluminum hydroxide are mixed in a weight ratio of 1: 2 to 1:10, It was found that the best effect was obtained when mixing at a weight ratio of 1: 4 to 1: 6. If the amount of calcium hydroxide exceeded the above range, the thermal stability of PVC was not different from that of hydrotalcite alone, and if the amount of calcium hydroxide was too large, the storage stability of long term was poor.

It has also been found that the hydrotalcite and the hydroxide mixture are preferably mixed in a weight ratio of 1: 1 to 5: 1 throughout the composition. If the amount of hydrotalcite is too small or too large, the long-term storage stability or thermal stabilization effect is insufficient.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are only illustrative of the present invention, and the scope of the present invention is not limited to the examples.

≪ Preparation of interlayer insert >

Pelapentin and maleic anhydride were mixed at a molar ratio of 1: 1, and then maintained at a temperature of 80 to 110 ° C in a nitrogen atmosphere. To the total weight of the reactants, 2 wt% of ion exchange resin was added and reacted for 8 hours, .

≪ Preparation of chlorinated polyethylene &

5,000 parts by weight of water and 500 parts by weight of high density polyethylene (CE6040X, LG Chem), sodium polymethacrylate, oxypropylene and oxyethylene copolyether, and benzoyl peroxide were fed into the reactor, and chlorine gas And chlorinated.

The chlorinated reactant was neutralized for 4 hours by adding sodium hydroxide, washed again with flowing water for 4 hours, and finally dried at 120 DEG C to prepare powdered chlorinated polyethylene.

≪ Preparation of magnesium-containing hydrotalcite (Mg-H) >

700 parts by weight of an aqueous magnesium chloride solution prepared by mixing water and magnesium chloride in a weight ratio of 1: 1 were charged into a 3 L stainless steel high-pressure reactor, 330 parts by weight of an aqueous solution of sodium hydrogencarbonate (10% by weight of sodium hydrogencarbonate) And 130 parts by weight of sodium hydroxide in 300 parts by weight of water was charged into the high pressure reactor and reacted for 1 hour to obtain a first reaction product. 5 parts by weight of the interlayer insert was added to the obtained first reaction product, stirred for 30 minutes, and reacted at 170 캜 and 10 kgf / cm 2 for 7 hours to obtain a product. After filtering and washing the product, hydrotalcite and chlorinated polyethylene were mixed at a weight ratio of 1: 1 and reacted at 170 ° C and 10 kgf / cm 2 for 1 hour to form an interlayer insert, which was surface-treated with chlorinated polyethylene Hydrotalcite was prepared.

≪ Preparation of hydrotalcite (MgZn-H) containing zinc and magnesium >

700 parts by weight of an aqueous magnesium chloride solution prepared by mixing water and magnesium chloride in a weight ratio of 1: 1 were charged into a 3 L stainless steel high-pressure reactor, 330 parts by weight of an aqueous solution of sodium hydrogencarbonate (10% by weight of sodium hydrogencarbonate) And 130 parts by weight of sodium hydroxide in 300 parts by weight of water was charged into the high pressure reactor and reacted for 1 hour to obtain a first reaction product.

10 parts by weight of the first reactant was dispersed in 300 parts by weight of water, and a zinc plate was connected to the positive electrode and the negative electrode at intervals of 5 mm. The zinc ions were deposited on the hydrotalcite by applying a current for 0.5-3 hours at 30 V with stirring at a speed of 500 rpm. The resulting hydrotalcite was filtered and washed with water, and 5 parts by weight of interlayer insert was added. After stirring for 30 minutes, the product was reacted at 170 캜 and 10 kgf / cm 2 for 7 hours to obtain a product. After filtering and washing the product, hydrotalcite and chlorinated polyethylene were mixed at a weight ratio of 1: 1 and reacted at 170 ° C and 10 kgf / cm 2 for 1 hour to form an interlayer insert, which was surface-treated with chlorinated polyethylene Hydrotalcite was prepared.

≪ Preparation of thermostabilizer composition >

The heat stabilizer composition was prepared as in Table 1. In Table 1, the unit is parts by weight.

Mg-H MgZn-H Ca (OH) ₂ Al (OH) ₃ Example 1 20 10 3 12 Example 2 30 10 7 30 Comparative Example 1 30 10 20 - Comparative Example 2 40 - 5 25 Comparative Example 3 40 - 20 -

≪ Evaluation of thermal stability effect &

In order to evaluate the PVC thermostabilizing effect of each composition, 35 parts by weight of DOP, 3 parts by weight of TiO ₂ , 1 part by weight of a stabilizer and 2.5 parts by weight of a heat stabilizer composition of Examples 1 to 3 To prepare a specimen. The specimens were prepared by kneading at 170 ℃ for 5 minutes and then thickness of 1 mm. For comparison, PVC specimens not including the heat stabilizer composition were blanked and compared. The results are shown in FIG.

1, it can be seen that Examples 1 to 3 exhibit a good thermal stabilization effect as compared to a blank. It can be seen that Examples 1 and 2 exhibit slightly better thermal stabilization effects than Comparative Examples 1 to 3, but there is no significant difference in performance as a heat stabilizer.

<Evaluation of long-term storage>

To evaluate the long-term storage stability of each composition, the thermostabilizer compositions of Examples 1 to 3 were placed in a sealed vial and kept in an oven at 40 ° C for 30 days before use. Specimens and evaluation were prepared in the same manner as in the evaluation of the thermal stabilization effect. For comparison, PVC specimens not containing a heat stabilizer composition were blanked and compared. The results are shown in FIG.

The results of FIG. 2 show that Examples 1 and 2 exhibit remarkable effects in long-term storage stability because the thermal stability is maintained even after storage for a long period of time. On the other hand, in Comparative Examples 1 to 3, the performance as a thermal stabilizer after long-term storage was remarkably reduced, and after 80 minutes, there was no difference in the color change of the blank, indicating that it was unsuitable as a thermal stabilizer. In particular, the PVC specimens of Comparative Examples 1 to 3 at 40 to 50 minutes after lapse of time showed a drastic change in color, and the thermal stability was drastically reduced.

For the detailed evaluation of thermal stability and long-term storage, the yellow index was measured for each specimen according to ASTM D1925-70, and the change in yellow index (ΔYI) before and after the test was calculated. The results are shown in Table 2.

Yellow index (DELTA YI) Thermal Stability Evaluation Specimen Long-term storage evaluation specimen Example 1 29.2 30.1 Example 2 27.4 27.8 Comparative Example 1 39.6 56.8 Comparative Example 2 42.5 72.3 Comparative Example 3 53.4 61.5

The results of the measurement of Table 2 show that the specimens of Examples 1 and 2 maintain the effect as a heat stabilizer according to long-term storage. Therefore, the thermostabilizer composition according to the present invention can provide not only a thermostabilizing effect of PVC, but also a very stable thermostabilizer without deterioration or deterioration in performance due to long-term storage of the thermostabilizer composition itself.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments and that various changes and modifications may be made therein without departing from the spirit and scope of the invention. Change is possible. Such variations and modifications are to be considered as falling within the scope of the invention and the appended claims.

Claims (5)

A hydrotalcite surface treated with chlorinated polyethylene to which an interlayer insert is added, and a hydroxide mixture of calcium hydroxide and aluminum hydroxide,
The chlorinated polyethylene has a chlorine content of 10 to 20% by weight, a weight average molecular weight of 1,000 to 10,000,
The hydrotalcite is mixed with hydrotalcite containing magnesium and hydrotalcite containing zinc and magnesium at a weight ratio of 1: 1 to 3: 1, and the calcium hydroxide and aluminum hydroxide are mixed at a ratio of 1: 2 to 1: 10. &Lt; / RTI &gt;
The method according to claim 1,
Wherein the interlayer insert is obtained by reacting fatty acid and maleic anhydride.
The method of claim 2,
The fatty acids may be selected from the group consisting of butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, Lauric Acid, Myristic Acid, Palmitic Acid, Palmitoleic Acid, Oleic Acid, Ricinoleic Acid, Vaccenic Acid, linolenic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, eruic acid, lignoceric acid, Wherein the thermosetting resin composition is one of a thermosetting resin and a thermoplastic resin.
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