JPS60219246A - Halogen-containing resin composition - Google Patents

Abstract

PURPOSE:The titled composition having excellent long-term heat stability and photo-deterioration resistance, made by adding a perchlorate type hydrotalcite compound and specified mono- and diorganophosphates of a metal to a halogen- containing resin. CONSTITUTION:To 100pts.wt. halogen-containing resin (e.g. chlorinated PE) are added 0.001-10pts.wt. perchlorate type hydrotalcite compound of formula I (where 0<X<=0.5; m is a positive number), and 0.001-10pts.wt. monoorganophosphate of a metal of formula II (where R1 is an alkyl or an alkyl containing an ether linkage; M is Na, Ba or Zn) and diorganophosphate of a metal of formula III (where R2 and R3 are each R1).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a halogen-containing resin composition having excellent heat and light stability.

-Rogen-containing resins are inherently unstable to heat and light, and decomposition due to de-loge/reaction within the nine molecular chains due to heating during molding or ultraviolet rays in sunlight during use. cause a reaction and its result.

Coloration 9: A decrease in mechanical strength is observed. Stabilizers are added to prevent such defects.

However, conventionally used stabilizers contain heavy metals such as cadmium and lead, and have the drawback of being highly toxic. In addition, organic acid zinc salts and polyacid alkaline earth metal salts are used as stabilizers with low toxicity.

Organic tin compounds, nitrogen-containing nonmetallic compounds such as β-aminocrotonic acid esters, polyols, and the like have been used in combination. However, these stabilizers cause coloration during molding, and there has been a strong demand for improvement in long-term thermal stability.

In recent years, many attempts have been made to improve long-term thermal stability by adding a halogen-containing resin containing a hydrotalcite compound, as disclosed in Japanese Patent Publication No. 58-46146. However, while these compounds have a greater ability to capture halogens generated by p-decomposition than halogen-containing resins as a stabilizing effect, they tend to actively extract halogens from the resin. This has the disadvantage that it promotes the formation of , causing strong coloring.

The present inventors have conducted repeated studies to solve the drawbacks of using hydrotalcite compounds with excellent halogen scavenging ability as stabilizers for halogen-containing resins as described above, and have found that perchlorate ion exchange type - We have completed the present invention by discovering remarkable effects on long-term thermal stability and prevention of photodeterioration of halogen-containing resins by adding idrotalcite compounds, mono-i phosphate metal salts, and di-organo phosphate metal salts.

The present invention is based on a halogen-containing resin containing (a) a perchlorate ion-type hydride a-talcite compound obtained by ion-exchanging a hydrotalcite compound with perchlorate ions, a metal phosphate, and a metal phosphate. It is a halogen-containing resin composition characterized in that it is added at the same time. [In the above formula, R + +
R11Rm represents the same or different alkyl group or an alkyl group having an ether bond, and 9M represents sodium, barium and zinc. The hydrotalcite compound used in the present invention is a hydrous ascites compound of magnesium and aluminum represented by the following general formula 1, and may be a natural product or a synthetic product.

Mg, -xAtx (O[()s Axi, yas,
O[II[] However, in the formula, 0x≦CL5. A is co,,
m indicates a positive number.

In order to obtain a compound of the perchlorate ion type hydrotalcite compound used in the present invention, by contacting the above hydrotalcite compound with a commercially available aqueous solution of perchloric acid,... A (anion, rirco,) in the buccal compound is easily substituted with (ato4, t-), and a compound having the composition as represented by [■] below can be obtained as a main component.

Mg+-xAtX("[")j("L04)l ・-
HtOCIVI where 0<x≦(15m indicates a positive number.

This is called a perchlorate ion type idrotalcite compound used in the present invention (the same applies hereinafter).

In order to obtain the mono- and di-if +77 acid metal salts used in the present invention, phosphoric anhydride is reacted with an alcohol or ether having an alkyl group while heating, and then a predetermined metal oxide or hydroxide is reacted with phosphoric anhydride. may be added as an aqueous solution and reacted. If the reactant is a solid, it may be subjected to p-filtration and dried, and if the reactant is a liquid, the aqueous layer may be separated and then dried under reduced pressure.

Furthermore, the mono- and di-organic phosphate metal salts of the present invention include basic salts and acidic salts. To obtain a basic salt, the amount of metal oxide or hydroxide to be added may be slightly more than that for a normal salt, and to obtain an acidic salt, the amount of alcohol or ether having an alkyl group to be added may be increased. It can be adjusted by making the amount slightly smaller than in the case of normal salt.

In the present invention, the term "loge-containing resin/resin" refers to, for example, homopolymers and copolymers obtained by polymerization of vinyl rogenide, vinylidene agenide, etc., and copolymers with compounds that can be copolymerized with these. Examples include vinyl chloride-ethylene copolymer, etc., and resins obtained by rogensing polyolefin resins such as polyethylene and polypropylene.9 Examples include chlorinated polyolefin resins such as chlorinated polyethylene and chlorinated polypropylene.

Furthermore, the present invention can also be suitably used in the case of polymer blends of .. rogen-containing resins and .. rogen-free resins such as ABS, MBS, EVA, butadiene resins, etc.

The amount of the perchlorate ion type hydrotalcite compound of the present invention added to these chlorogen-containing resins is as follows:
0.001 to 10 parts by weight.

Further, the amount of the monoorganic metal phosphate and the diorganic metal phosphate added is 1001 to 10 parts by weight in total of both mono and di organic phosphates.

The combined use of the composition of the present invention with a known substance commonly used as a stabilizer component does not reduce the effects of the present invention.

These commonly used stabilizers include metal organic acid salts, organic phosphite compounds, antioxidants, ultraviolet absorbers,
Metal oxides, metal hydroxides.

Patent application No. 57-196646 related to polyols, nitrogen-containing nonmetallic compounds, epoxy compounds, and applications filed by the same applicant
The hydrotalcite compound described above is subjected to a firing treatment, and the water content in the crystal structure is 5.0 to 20% relative to the total weight before treatment.
Examples include calcined products of hydrotalcite compounds whose weight is reduced within the range of 0% by weight. Furthermore, if necessary, plasticizers, pigments, fillers, blowing agents, antistatic agents, antifogging agents, great-out inhibitors, surface treatment agents, lubricants, flame retardants, etc. may be added to the formulation.

Next, examples of synthesizing the perchlorate ion-type idrotalcite M compound, mono-M organophosphate metal salt and diorganophosphate metal salt in the present invention will be shown.

In addition, in the synthesis of 9, Alcamizer ■ (hereinafter referred to as Alcamizer 1) manufactured by Kyowa Ihigaku Kogyo Co., Ltd. was used as a hydrotalcite compound.

Alkamizer■ is the general formula [J+-xp in the play]
-z-x(oH), p-x ot-=H, Or"')X-
α535.7=oo,, 'm=0.5, and substituting these into ■] gives lag 0.667A10335(OFT), (co
, )o1645・[L5H,0. Multiplying each coefficient by 6 gives Mg+ tits (OH)u (co, )・6 days,
Represented by the chemical formula of 0, 1 mole of alkamizer-■ is 46
It becomes 92.

Synthesis Example 1 Alkalyzer-1,1 2 mol equivalent of perchloric acid aqueous solution was gradually added while stirring for 4λ and mixed thoroughly. When the generation of carbon dioxide gas was completed, stirring was stopped to obtain a wet powder composite. This was dried at 50° C. for 60 minutes under reduced pressure to obtain evaluation sample 1.

Synthesis Example 2 I mol of Alkamizer H was gradually added to an aqueous solution of perchloric acid with a concentration equivalent to 1.7 mol of perchloric acid while stirring.
The mixture was thoroughly mixed until the generation of carbon dioxide gas ceased. A small amount of nonionic surfactant was added to improve mixing. Filter the combined material.

Dry the furnace slag and use sample number 16 for evaluation. It was set as 2.

Synthesis Example 3 1.5 mol of butanol and 1.5 mol of octatool were added to 1 mol of phosphoric anhydride and reacted with heating. An aqueous solution of 1 mol of barium hydroxide was added to this and reacted at room temperature.

Further, 0.5 mol of zinc white was added and the mixture was allowed to react with heating until the white turbidity due to zinc white disappeared. After separating the aqueous layer, the mixture was dried under reduced pressure at 60°C to obtain a brown paste-like compound. This was designated as sample grave 3 for evaluation. This compound is.

1 mole each of the monoorganic J non-acid metal salt and the diorgano phosphate metal salt are produced, and the above general formula [:I], [l in the former (1, R1, R1 is an alkyl group based on butanol and an octyl group) It is distributed in the alkyl group based on the tool at a ratio of 1=1.Furthermore, M in the general formula is barium and zinc, and the ratio is 2:1, but the general formula CD, [■] It is thought that barium salt and zinc salt are mixed in both.

Synthesis Example 4 1 mole of phosphoric anhydride was reacted with 1.5 moles of decanol while heating. 1.5 mol of dipentaerythritol was added to this and mixed well. Furthermore, an aqueous solution of 1.2 mol of barium hydroxide, 0.5 mol of zinc white, and 0 sodium hydroxide.
．． Add 5 moles.

The reaction was carried out at 611° C. for 2 hours while stirring. The brown powder obtained by complete filtration and drying was designated as Sample &4 for evaluation.

Synthesis Example 5 Using the same method as Synthesis 114, synthesize with 1 mol of tridecanol, 2 mol of dipentaerythritol, 1.0.5 mol of barium hydroxide, and 1.2 mol of northern lead oxide for 1 mol of anhydrous phosphorus carbon. The basic mono, gold silinate,
) The brown powder of salt was designated as sample A5 for the 5-piece value.

Synthesis Example 6 Using the same method as in Synthesis Example 3, synthesize with 1.0 mol of beptanol, 1.5 mol of tridecanoyl, 13 mol of barium hydride, and 02 mol of zinc white per 1 mol of phosphoric anhydride. An acidic product obtained by

A brown paste-like composite of metal silicate was used as sample wash 6 for evaluation.

This will be explained in detail below using examples.

In addition, the degree of coloring in the examples was expressed using the following numerical values.

Example 1 In order to examine the effects of the - and chlorine-containing resin composition according to the present invention, the following formulation was heated at an rf of 0.5 s using a mixed wire roll.
A test sheet of m was prepared. Thermal stability at 180° C. 2 coloring properties were examined using a gear aging tester. Evaluation of thermal stability was expressed by the time taken for the test piece to turn black. The colorability was determined by the time taken out from the gear aging tester: 20 minutes and 40 minutes.

The degree of coloring at 60 minutes was expressed as a numerical value of the degree of coloring.

The results are shown in Table 1. Furthermore, deterioration due to light was measured using a sunshine sea urchin meter. The degree of deterioration is 60
The percentage of elongation remaining after 0 hours and the degree of coloring of the test piece at 600 hours were expressed as numerical values of the degree of coloration. For comparison, a similar test was conducted without a sample, and the results are also shown in Table 1.

Composition Polyvinyl chloride 100 parts by weight DOP 40
1 Barium Ste°TV-t α5i Zinc Stearate 111N Perchlorate ion-type hydrotalcite compound vIJ (Table 1) α31 mono-, diorganic phosphate metal salt (Table 1) 0.5 Example 2 When a known substance that is commonly used as a stabilizer component was used in combination with the composition of the invention, even more improved effects were obtained. The effects of combined use on stability were investigated in the same manner as in Example 1 using the formulations shown below. The results are shown in Table 2.

Compounded polyvinyl chloride 100 parts by weight AB S 30 ・' DOP 45 # Barium nonyl phenate 0.51 Perchlorate ion type hyde a-talcite compound The/Glu A2 I12 j Mono-, di-organosunate gold salt type Table 2 [141 Combination stabilizer Table 2 0.51 Book 1 5T-210 manufactured by Ajinomoto Co., Inc. Dipentaerythritol partial ester *2 TlIC manufactured by Nichiryu Chemical Co., Ltd. Tris (2-hydroxyf, v) in cyanurate

Claims (1)

[Scope of Claims] 1. In a halogen-containing resin, (a) a perchlorate ion-type hydrotalcite compound 0001 to 10, and a metal mephosphate and a metal organic phosphate, (b) + The total amount of (c) is α00
A halogen-containing resin composition characterized in that 1 to 10 parts by weight are added at the same time. [In the above formula, R, , R, and R represent the same or different alkyl groups or alkyl groups having an ether bond, and 2M represents sodium, barium, and zinc. ] 2. The number of carbon atoms in the alkyl group represented by R, , R, , R is 4 or more
15. The halogen-containing resin composition according to claim 1, wherein the alkyl group having an ether bond is a polyhydroxyalkyl group derived from dipentaerythyl IJ).