JP2763774B2 - Halogen-containing resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a halogen-containing resin composition having improved thermal stability at high and low temperatures.

Specifically, the halogen-containing resin may be prepared by adding (a) a metal salt of an organic acid, (b) one or more acids selected from melamine and an inorganic acid or an organic acid, to an acid of 0.01 to 1 mol per melamine.
The present invention relates to a stabilized halogen-containing resin composition to which 1.5 mol of an acid addition salt is added.

Problems to be Solved by the Prior Art and the Invention In general, halogen-containing resins, such as vinyl chloride resin, vinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer resin and chlorinated polyethylene, are significantly colored by heating during molding. And decomposition occurs.

In order to prevent such defects, stabilizers such as organic acid zinc salts, organic acid alkaline earth metal salts, organic tin compounds, nitrogen-containing compounds such as β-aminocrotonate, and polyol compounds have been used.

However, although the combination of these stabilizers has a low toxicity and is very preferable, since the resin is colored by heating at the time of molding, improvement of these has been strongly demanded.

In order to improve the thermal stability during processing, in combination with an organic acid zinc salt and an organic acid alkaline earth metal salt, among nitrogen-containing compounds, compounds having a 1,3,5-triazine ring, such as melamine It has been proposed to use (JP-B-45-14794, JP-B-47-46445).

Although various studies have been made experimentally, industrially, it is only used as a so-called masking agent, a detoxifying agent for iron in asbestos at the time of producing a vinyl chloride asbestos tile.

When melamine is used as a stabilizer for a halogen-containing resin, a metal salt of an organic acid such as an organic acid zinc salt or an organic acid alkaline earth metal salt is generated by a dehalogenation reaction of the halogen-containing resin upon heating. Due to the masking effect on metal halides which are harmful to stabilization, a certain degree of anti-coloring effect and improvement effect of thermal stability are exhibited.

However, regarding the long-term thermal stability, although it is not clear why, it is known to give a unique reddish color to the halogen-containing resin.
The range of use was very limited. For that reason,
There has been a demand for a melamine-based stabilizer having a wider stable range at a high temperature during processing. In addition, not only in the high-temperature region during processing, but also the improvement in thermal stability (low-temperature aging) when the molded article is continuously exposed to a relatively low temperature of 60 to 120 ° C. during use is required. Was.

Examples of such molded articles include wire covering materials, vehicle interior materials, and the like. In these cases, discoloration and discoloration of the molded articles and mechanical strength of the molded articles over a long period of time despite the relatively low temperature. It has been known that a decrease or the like occurs.

Means for Solving the Problem The present inventors have conducted repeated studies to eliminate the disadvantages of using melamine, which can be expected to have a masking effect as described above, as a stabilizer for a halogen-containing resin, and as a result, (A) one or more selected from metal salts of organic acids; and (b) one mole or more of melamine of one or more acids selected from melamine and an inorganic acid or an organic acid, wherein the acid is 0.1 mol per mol of melamine.
By adding the acid addition salt in an amount of from 01 to 1.5 mol, the anti-coloring property was remarkably improved, and the above problems were solved at once and the present invention was completed.

The metal referred to in (a) of the present invention includes lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, cadmium, lead, and copper.

Organic acids include acetic acid, propionic acid, caprylic acid, 2-ethylhexoic acid, capric acid, lauric acid, stearic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, linoleic acid, and thioglycolic acid. Carboxylic acids such as mercaptopropionic acid, benzoic acid, pt-butylbenzoic acid, dimethylbenzoic acid, aminobenzoic acid, glycine, glutamic acid, oxalic acid, succinic acid, adipic acid, phthalic acid, maleic acid, and thiodipropionic acid Acids.

Further, phenols such as phenol, nonylphenol, t-butylphenol, octylphenol, isoamylphenol, crusol, and xylenol are exemplified.

As the melamine used in the present invention, ordinary commercial products are sufficient, but particularly preferred is fine powder melamine.

The inorganic acid referred to in (b) of the present invention includes hydrochloric acid, perchloric acid,
Hypochlorous acid, chloric acid, bromic acid, bromic acid, periodic acid,
Means hypoiodic acid, sulfuric acid, sulfurous acid, hyposulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, nitric acid, nitrous acid, hyponitrite, carbonic acid, silicic acid and boric acid.

The organic acids referred to in (b) include formic acid, acetic acid, propionic acid, acetic acid, caprylic acid, 2-ethylhexoic acid, lauric acid, stearic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, and linoleic acid Thioglycolic acid, mercaptopropionic acid, laurylmercaptopropionic acid, benzoic acid, pt-butylbenzoic acid, dimethylbenzoic acid, aminobenzoic acid, salicylic acid, aminoacetic acid, glutamic acid, oxalic acid, succinic acid, adipic acid, phthalic acid Acid, maleic acid, thiodipropionic acid, organic phosphoric acid and the like.

The acid addition salt of melamine with an inorganic acid, an organic acid or the like in the present invention is presumed to be a salt having a structure represented by the following formula, for example, in the case of hydrochloric acid or maleic acid.

The acid addition salt of melamine used in the present invention refers to an acid addition salt of 0.01 to 3 moles, preferably 0.01 to 1.5 moles of one or more acids selected from inorganic acids and organic acids per mole of melamine. Say.

Regarding the number of moles of the acid added, it is preferable for the stabilization of the halogen-containing resin in the application to the present invention that the acid-base degree of the formed acid addition salt be not more than neutral.

Therefore, the acid addition salt can be prepared by selecting the optimum number of moles added to 1 mole of melamine according to the acidity of the inorganic acid or organic acid used. When two or more kinds of acids are used, they can be similarly prepared. Examples of combinations of the use of two or more of these acids include the case of an inorganic acid and an inorganic acid, the case of an inorganic acid and an organic acid, and the case of an organic acid and an organic acid.

In the preparation of the acid addition salt used in the present invention, when a water-soluble inorganic acid or a water-soluble organic acid is used, for example, melamine is suspended and dissolved in hot water at a temperature of 90 ° C. or higher, and the acid is used. After the reaction for 2 hours or more, the reaction can be carried out by a method of removing water by drying under reduced pressure or the like. However, since the solubility of melamine in water is low, a large amount of water and a high temperature are required to make a complete aqueous solution, but this is not an economical method, so that the above reaction is usually carried out in a suspended state. It is. For this reason, melamine to be used is preferably a fine powder (usually a melamine average particle diameter of 40 μm and a fine powder melamine average particle diameter of 4 μm or less) in order to increase the solubility as much as possible. In the case of an organic acid that is not water-soluble, a method in which melamine is suspended in warm water, a small amount of a surfactant is added thereto and reacted, and the acid is melted at a temperature equal to or higher than the melting point, and melamine is added. Or by dissolving the acid in a solvent and then adding melamine to react.

Halogen-containing resins to which the present invention is applied include, for example, vinyl halides, homopolymers and copolymers obtained by polymerization of vinylidene halides and the like, such as vinyl chloride-ethylene copolymers, and further, polyolefins such as polyethylene and polypropylene. Resin obtained by halogenating the resin, for example, chlorinated polyolefin resins such as chlorinated polyethylene and chlorinated polypropylene can be mentioned. In addition, halogen-containing resins and halogen-free resins, such as ABS, MBS, EV
The present invention can be applied to polymer blends with A, butadiene resin, and the like.

The amount of the metal salt of an organic acid added to the halogen-containing resin is 0.
01 to 1.5 parts by weight. When the amount is less than 0.01 part by weight, no synergistic improvement effect with the acid addition salt of melamine is observed, and when the amount is more than 1.5 parts by weight, problems such as compatibility with the resin occur, which is not preferable.

The amount of the acid addition salt of melamine is 0.001 to 5 parts by weight based on 100 parts by weight of the resin. When the amount of the acid addition salt of melamine is 0.001 part by weight or less based on the resin, no improvement effect is observed. When the amount is 5 parts by weight or more, an improvement effect is observed, but the increase in the improvement effect is not remarkable with an increase in the added amount, and is not appropriate from an economic viewpoint.

Scope of Application of the Invention In practicing the present invention, the halogen-containing resin may be added, if necessary, to a plasticizer, a pigment, a filler, a reinforcing agent, a foaming agent, an antistatic agent, a lubricant, a flame retardant, etc. ) Can be added. Further, by adding one or more conventional additives in addition to the compounding agent to the resin at times, an excellent synergistic effect with the compositions (a) and (b) of the present invention is obtained. Can be obtained.

Examples of such additives include metal oxides, hydroxides, basic inorganic acid salts, hydrotalcite compounds, organic phosphite compounds, organic phosphoric acid metal salts, polyols, nitrogen-containing nonmetal compounds, Examples include an antioxidant, a light stabilizer, a β-diketone compound, an epoxy compound, and an organic tin compound.

Example The following is an example illustrating the gist of the present invention. In particular, several examples of the preparation of acid addition salts of melamine will be given.

Preparation Example 1 Melamine and perchloric acid In a 300 ml flask equipped with a reflux stirrer, 100 ml of water and 12.6 g (0.1 mol) of melamine are added, and the mixture is heated to 80 ° C. to suspend the melamine. To this, 16 g (0.1 mol) of 60% perchloric acid was added. Further, the reaction was continued by stirring at 90 ° C. to 98 ° C. for 3 hours.

The product was dried under reduced pressure and melamine perchloric acid addition salt 22.1 g
I got This is designated as Sample A.

Preparation Example 2 Melamine and stearic acid 100 g of water and 12.6 g of melamine using the same apparatus as in Preparation Example 1.
(0.1 mol) and heated to 80 ° C. to suspend melamine.

To this, 8.4 g (0.03 mol) of stearic acid and 0.2 g of a nonionic surfactant were added, and stirring was continued at 90 to 98 ° C. for 3 hours. The product is dried under reduced pressure and melamine stearic acid addition salt 20.5 g
I got This is designated as Sample B.

Preparation Example 3 In the case of mixed acid of melamine and lauric acid / maleic acid Melamine 126.0 g (1 mol), lauric acid 40.0 g (0.2 mol), maleic acid 92.8 g (0.8 mol), and water 15 g were put into a high-temperature rotary mixer and placed for 20 minutes. Stirred. When the product temperature reached 90 ° C., the reaction product was taken out and dried at 100 ° C. for 10 hours to obtain 255 g of the reaction product. This is designated as Sample C.

The melamine acid addition salts D, E, and F having the compositions shown in Table 1 were prepared in the same manner as described below.

Hereinafter, the results of the thermal stability will be shown by Examples.

Example 1 In order to see the effect of the halogen-containing resin composition according to the present invention, a test sheet having a thickness of 0.5 mm was prepared from the following mixture using a kneading roll. 18 using a gear aging tester
The thermal stability at 0 ° C. and the colorability were examined. The evaluation of the thermal stability was represented by the time when the test piece turned black. The coloring was evaluated by visually observing the degree of coloring at a removal time of 10 minutes and 30 minutes from the gear aging tester, and the results are shown in Table 2. Furthermore, in order to see the effect of preventing low-temperature aging when continuously exposed to a temperature atmosphere of 80 ° C, the degree of coloring after 10 days was examined using a gear aging tester set at 80 ° C, and the results were combined. The results are shown in Table 2.

Polyvinyl chloride 100 parts by weight Compounding agent DOP 50 parts by weight Additives Epoxidized soybean oil 2.0 parts by weight (a) Barium nonylphenate 0.7 parts by weight (a) Zinc stearate 0.3 parts by weight (b) Sample (Table 2) 0.5 Parts by weight Example 2 In order to see the synergistic effect of the composition of the present invention and a conventional additive for a halogen-containing resin, Example 1 was prepared using the following mixture.
Prepare a test sheet in the same manner as in
Colorability and low temperature aging were examined. Table 3 shows the results.

As conventional additives, magnesium oxide as a metal oxide, DHT-4A manufactured by Kyowa Chemical Co., Ltd. as a hydrotalcite compound, diphenyldecyl phosphite as an organic phosphite compound, and ST manufactured by Ajinomoto Co., Ltd. as polyols -210 (partial ester of dipentaerythritol with adipic acid), THEIC (tris-2-hydroxyethyl isocyanurate) as a nitrogen-containing nonmetallic substance, and dibenzoylmethane as a β-diketone compound.

Polyvinyl chloride 100 parts by weight Compounding agent DOP 50 parts by weight Additives Epoxidized soybean oil 2.0 parts by weight (a) Barium nonylphenate 0.7 parts by weight (a) Zinc stearate 0.3 parts by weight (b) Sample (Table 3) 0.5 Additives in parts by weight (Table 3) Effects of the Invention As shown in Table 2, it is clear that the results of Experiment Nos. 1 to 6 of the present invention are all better than those of Controls 7 and 8.

Further, it is clear from Table 3 that the sample of the present invention has a synergistic effect with conventional additives.

Thus, it has been proved that the organic acid metal salt and the acid addition salt of the present invention are effective at both high and low temperatures as a stabilizer for the halogen-containing resin. This is believed to be a feature not found in conventional stabilizers.

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08K 5: 3477) (56) References JP-A-53-101044 (JP, A) JP-A-60-8349 (JP, A) JP-A-55-157640 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 27/00-27/24 C08L 23/28

Claims (1)

(57) [Claims] 1. One or two or more kinds selected from metal salts of organic acids (a) are used in an amount of 0.01 to 100 parts by weight of a halogen-containing resin.
1.5 parts by weight, (b) melamine and hydrochloric acid, perchloric acid, hypochlorous acid, chloric acid, bromic acid, bromic acid, periodic acid, hypoiodic acid, sulfuric acid, sulfurous acid, hyposulfuric acid, phosphoric acid, sulfurous acid phosphoric acid,
Hypophosphoric acid, nitric acid, nitrous acid, hyponitrite, carbonic acid, silicic acid or boric acid, one to two or more acids selected from inorganic acids and organic acids, and one mole or more of melamine with respect to 1 mole of acid.
A stabilized halogen-containing resin composition comprising 0.001 to 5 parts by weight of a molar acid addition salt.