JPH04255743A - Chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having heat resistance and weather (light)resistance better several times than those of a known composition blended with a known heavy metal-containing stabilizer such as cadmium/barium/ phosphorus ester or barium/zinc/phosphorus ester. CONSTITUTION:A chlorine-containing resin composition comprises A: 0.01-2 pts.wt. of a zinc compound, B: 0.1-3 pts.wt. of a phosphorus ester, C: 0.05-5 pts.wt. of a perchlorate-containing hydrotalcite, and (D) 0.005-2 pts.wt. of a piperidine compound.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to chlorine-containing resin compositions stabilized against degradation by heat and light. More specifically, the present invention relates to a chlorine-containing resin composition that is stable against thermal deterioration during processing, and also stable against thermal deterioration (including low-temperature deterioration) and photodeterioration during use of molded products.

0002

BACKGROUND OF THE INVENTION Generally, chlorine-containing resins undergo discoloration and deterioration due to heat during processing. Furthermore, when used outdoors or in a place exposed to heat, discoloration and photodeterioration due to heat (50° C. to 120° C.) occur during use. Furthermore, when used in combination with a polyurethane foam, low-temperature heat resistance and weather (light) resistance are particularly poor. In order to prevent these deteriorations, so-called stabilizers such as cadmium/barium/phosphite, barium/zinc/phosphite, calcium/zinc/phosphite, epoxy compounds, polyol compounds, and β-diketones are used. Stabilizing aids such as, ultraviolet absorbers, and light stabilizers such as hindered amines are used. However, in recent years, due to global needs such as environmental issues and the disposal of waste plastics, there has been an increasing demand for additives that are free of heavy metals.

[0003] For these reasons, it is necessary to develop a lead-free, cadmium-free, barium-free stabilizer that has performance superior to that of cadmium/barium/phosphite and barium/zinc/phosphite stabilizers. It's being requested.

However, existing calcium/zinc/phosphite ester and magnesium/calcium/zinc/phosphite-based stabilizers without heavy metals do not contain cadmium/barium/phosphite or barium/zinc/nitrous ester. Performance comparable to phosphate ester stabilizers, especially thermal degradation (
No product has been developed that has the ability to prevent low-temperature thermal deterioration (including low-temperature thermal deterioration) or photo-degradation.

[0005]

[Problem to be solved by the invention] A stabilizer formulation without heavy metals has better thermal stability (including low-temperature heat resistance) than a cadmium/barium/phosphite or barium/zinc/phosphite stabilizer formulation. An object of the present invention is to provide a chlorine-containing resin composition having weather (light) resistance.

Another object of the present invention is to provide a chlorine-containing resin composition that has greatly improved low-temperature heat resistance and weather (light) resistance when used in combination with a polyurethane foam.

[0007]

[Means for Solving the Problems] An object of the present invention is to provide a novel chlorine-containing resin composition that is free of heavy metals and has excellent heat resistance (including low-temperature heat resistance) and weather (light) resistance. . For this purpose, A. 0.01 to 2 parts by weight of a zinc compound and B. 0.1 to 3 parts by weight of phosphite and C.I. 0.05 to 5 parts by weight of perchloric acid-containing hydrotalcite; The objective is achieved by adding 0.005 to 2 parts by weight of the piperidine compound.

A. used in the present invention. Typical examples of zinc compounds include zinc oxide, zinc carbonate, zinc aliphatic and/or aromatic carboxylates of C1 to C22, or zinc compounds of the general formula

[Chemical formula 1] and/or

It is a zinc compound represented by the following formula. These zinc compounds may be used alone or in combination of two or more.

[0009] Furthermore, the B. Typical examples of phosphite esters include triphenyl phosphite,
diphenyldecyl phosphite, trisnonylphenyl phosphite, tridecyl phosphite, 2-ethylhexyl diphenyl phosphite, di-phenyl phosphite, di-decylphenyl phosphite, di-stearyl pentaerythritol diphosphite, tetra-tridecyl-1 ,1,3-tris(2'-methyl-5'-t
ert-butyl-4'-oxyphenyl)butane di-phosphite, 2-tert-butyl-2(3-tert-
butyl-4-hydroxyphenyl)P-cumenylbis(
p-nonylphenyl) phosphite, 4,4,-isopropylidene-diphenolalkyl (C12-C15)
Phosphite, tris(4-oxy-2,-5-dite)
rt-butylphenyl) phosphite, tris-benzyl phosphite, di-benzyl phosphite, and the like.

[0010] Furthermore, the C.I. An example of perchloric acid-containing hydrotalcite is the general formula

A typical example of the compound represented by [Chemical 5] is Kyowa Kagaku Kogyo (
These include Alcamizer 5 and Alcamizer 5-20 manufactured by Co., Ltd.

[0011] Furthermore, the D. The piperidine compound has a group of

A compound having [Group 1], a typical example of which is HALS-1
Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate HALS-2 Dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine-succinate HALS-2 Condensate HALS-3 Poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2
,4-diyl}{2,2,6,6-tetramethyl-4-
piperidyl)imino}hexamethylene {(2,2,6,
6-tetramethyl-4-piperidyl)imino}]HAL
S-4 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2
,2,6,6-pentamethyl-4-piperidyl) HALS-5 2-[(2,2,6,6-tetramethyl-4-piperidyl)imino]2-butyryl[(2,2
,6,6-tetramethyl-4-piperidyl)imino]H
ALS-6 Poly[6-morpholino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[
(2,2,6,6-tetramethyl-4-piperidyl)imino] HALS-7 Tetra(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxy Rate mixture product HALS-8 m. p. 262℃ white powder

[
Chemical formula 8] HALS-9 m. p. 222℃ white powder

[
Chemical formula 9 HALS-10 Pale yellow glassy solid

[Chemical formula 10] HALS-11 Pale yellow glassy solid

[Chemical formula 11] HALS-12 m. p. 255℃ White powder

[Chemical formula 12] HALS-13 Pale yellow glassy solid

[Chemical formula 13] HALS-14 Pale yellow glassy solid

[Chemical formula 14] HALS-15 Pale yellow glassy solid

[Chemical formula 15] HALS-16 pale yellow glassy solid

[Chemical formula 16] HALS-17 Pale yellow glassy solid

[Chemical formula 17] HALS-18 Pale yellow glassy solid

[Image Omitted] Alternatively, it is a mixture product of these piperidyl group-containing compounds and at least one type of phosphoric acid, organic phosphoric acid ester, phosphorous acid, organic phosphorous acid ester, etc.

[0012] In addition, the composition of the present invention may further contain stabilizers such as calcium-based and magnesium-based stabilizers, polyhydric alcohol-based stabilizing agents, coloring inhibitors, plasticizers, lubricants,
Pigments, fillers, antioxidants, ultraviolet absorbers, antistatic agents, processing aids, etc. can be added. The present invention will be explained in more detail with reference to Examples below.

[0013]

[Example] Examples 1 to 4 and Comparative Examples 1 to 4

[Table 1-1] A film of 0.2 m/m was prepared using a kneading roll. This film was tested at 190℃ using the Congolese test method.
HCL removal time and W. O. In M, the sunspot generation time and the coloring state at 10 minutes, 30 minutes, and 50 minutes in the gear aging test at 190°C (◎colorless, ○slight yellow, △yellowish brown, ×
brown), time to blackening, and low temperature heat resistance at 110℃ (
100 hours of coloring and time to blackening) Table 1-
It was as follows.

[Table 1-2]

Examples 6 to 10, Comparative Examples 6 to 10

[Table 2-
1] was prepared into a sheet with a thickness of 0.3 m/m using a kneading roll. This sheet is laminated with foamed polyurethane.F. O.
The results of the light resistance test with M are shown in Table 2-2.

[Table 2-2]

Examples 11 to 15 and Comparative Examples 11 to 14

[
Table 3-1] was prepared into a sheet having a thickness of 0.3 m/m using a kneading roll. This sheet is Sunshine W. 0. Weather resistant (light) in M
Table 3-2 shows the results of examining the characteristics (time until sunspot appearance).

[Table 3-2]

[0016]

[Effects of the invention] Contains stabilizers without heavy metals, making it possible to replace existing cadmium/barium/phosphite esters and barium/zinc/
Performance superior to phosphite ester formulation, especially HCL removal suppression,
We have developed a chlorine-containing resin composition that is heat resistant at low temperatures and has excellent weather (light) resistance. Molded products such as films and sheets using this composition can have low-temperature heat resistance and weather (light) resistance several times higher than existing molded products.

Claims (8)

[Claims] Claim 1: Per 100 parts by weight of chlorine-containing resin, A.
0.01 to 2 parts by weight of a zinc compound and B. 0.1 to 3 parts by weight of phosphite and C.I. 0.05 to 5 parts by weight of perchloric acid-containing hydrotalcite; A chlorine-containing resin composition characterized in that 0.005 to 2 parts by weight of a piperidine compound is added. [Claim 2] A. Item 1 above, wherein the zinc compound is zinc oxide, zinc carbonate, zinc aliphatic and/or aromatic carboxylate, or one or more zinc compounds represented by the general formula [Formula 1] and/or [Formula 2] The chlorine-containing resin composition described in . [Claim 3] B. The chlorine-containing resin composition according to item 1 above, wherein the phosphite ester is represented by the general formula [Chemical Formula 3] or [Chemical Formula 4]. [Claim 4] C. The chlorine-containing resin composition according to item 1 above, wherein the perchloric acid-containing hydrotalcite is represented by the general formula: [Claim 5]D. 1 above, wherein the piperidine compound is a compound having 1 to 6 piperidyl groups in one molecule.
The chlorine-containing resin composition described in . [Claim 6]D. The chlorine-containing resin composition according to item 1 above, wherein the piperidine compound is represented by the general formula: [Claim 7]D. The piperidine compound has the general formula [
The chlorine-containing resin composition according to item 1 above, which is represented by: [Claim 8] D. The piperidine compound is a mixture product of (1) a compound having at least one piperidyl group and (2) at least one of phosphoric acid, organic phosphate, phosphorous acid, and organic phosphite. The chlorine-containing resin composition described above.