JPH0251931B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition for stabilizing chlorine-containing resins. More specifically, a non-metallic chlorine-containing resin that can withstand molding process and substantially does not contain metal salts as a stabilizer is made by blending a chlorine-containing resin with a polyol partial ester and/or a polyol epoxy compound and an organic phosphite ester. This invention relates to a resin composition. Conventionally, chlorine-containing resins, especially vinyl chloride resins or vinyl chloride-based copolymers, have been stabilized by adding salts of metal carboxylic acids, phenols, mercaptans, etc. for the purpose of dehydrochlorination scavenging and prevention of double bond formation. I have been planning to change. Moreover, these metal salts are considered as essential components and have been put to practical use in the field. Non-metallic stabilizers are only treated as stabilizing aids if the above-mentioned metal salts are used as the main stabilizers. From both ideas and practical knowledge, when formulating vinyl chloride, vinyl chloride-based copolymers, and blends thereof,
Usually, a metal salt is used as the center, and the material is first assembled from a combination of metal salts. There are not so many types of metals used as metal salts; the first group metals include Na, K, and Li, and the second group metals include Mg, Ca,
Ba, Sr, Zn, Cd, 3rd group Sb, Al, 4th group metal
Sn, Pb, etc., among which frequently used metals include Ca, Ba, Zn, Cd, Sn, and Pb.
Among these, Cd and Pb are
Since Sn is expensive and has become close to the price of precious metals, there is a desire for a substitute for it, and its application as a stabilizer for Ca, Ba, and Zn is inevitable, and there are some fields where it has already been put into practical use. Thermal stability cannot be said to be sufficient at present. Furthermore, each of the above metals has its own unique properties, and a system consisting only of them does not necessarily provide a satisfactory stabilized composition. required. Among these unsatisfactory performances, focusing on the yoking property, metal soaps with carboxylic acids are a major cause of the yoking phenomenon, and measures to improve this include ultraviolet absorbers, organic phosphite esters, epoxy compounds, etc. Although it is effective to use the
It has not yet reached the point where it exhibits satisfactory performance. The inventors of the present invention focused on the fact that metal soap is a major factor in the choking phenomenon, and based on the idea of removing the causative components, they conducted extensive research into assembling a non-metallic composition that excludes metal salts. As a system that does not contain ordinary metal salts, a chlorine-containing resin composition formed by mixing a partial ester of a polyol and a carboxylic acid, or this partial ester, a polyol, an epoxy compound, and an organic phosphite ester is moldable and thermally stable. The present invention was completed based on the discovery that the material has good properties such as hardness and stiffening resistance. Surprisingly, in addition to thermal stability, ultraviolet absorbers, organic phosphite esters, epoxy compounds, etc., which are effective in suppressing the yoking phenomenon of conventional metal salt-based compositions, can also be used to suppress metal salts. It has been discovered that by removing the above, the effect can be fully brought out and satisfactory performance can be achieved. Of course, in terms of processability, physical properties, and other performance, it has no inferiority to conventional metal salt-based formulations. Examples of the chlorine-containing resin in the present invention include the following. Polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber,
Vinyl chloride-vinyl acetate copolymer, vinyl chloride-
Ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer Polymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorine propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer , vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, etc. Examples include chlorine synthetic resins, blends thereof with each other or with other chlorine-free synthetic resins, block copolymers, graft copolymers, and the like. In the present invention, the partial ester of polyol and carboxylic acid (hereinafter referred to as polyol partial ester) is composed of at least one polyhydric alcohol selected from the group consisting of pentaerythritol and dehydration condensation polyols of pentaerythritol and monocarboxylic acid. and polyol partial esters having a hydroxyl group content of 10 to 0%, which are obtained by reacting polycarboxylic acids or their esters with at least one selected from the group consisting of acid halides and acid anhydrides. The dehydration condensation polyols of pentaerythritol used here refer to polypentaerythritol itself or a mixture thereof, such as dipentaerythritol and tripentaerythritol, which are by-products during the production of pentaerythritol.
It also refers to polyols or polyol mixtures obtained by heat dehydration condensation of pentaerythritol in the presence of an appropriate catalyst and/or solvent. For example, pentaerythritol itself has a melting point of 250-260°C and a hydroxyl group content of 50%, but it can be mixed with mineral acids such as phosphoric acid and sulfuric acid, organic acids such as alkylbenzenesulfonic acid, or tin chloride. The melting point and hydroxyl group content of the polyol mixture obtained by dehydration condensation at a reaction temperature of 200 to 270° C. in the presence of an acid catalyst such as a Lewis acid such as magnesium chloride or the like changes depending on the amount of dehydration. The polyol mixture thus obtained contains unreacted pentaerythritol and polypentaerythritol such as dipentaerythritol, tripentaerythritol, and tetrapentaerythritol, as well as complex pentaerythritol condensates. Specific examples of carboxylic acids, esters, acid halides, and acid anhydrides used in esterification are shown below. Monocarboxylic acids include acetic acid, lactic acid, 4-hydroxybutyric acid, fructic acid, oxypivalic acid,
Ricinoleic acid, stearic acid, octylic acid, thioglycolic acid, polycarboxylic acids include malonic acid, succinic acid, maleic acid, adipic acid, glutaric acid, itaconic acid, malic acid, tartaric acid, citric acid, phthalic acid, isophthalic acid. , terephthalic acid, trimellitic acid, pyromellitic acid, etc. Table 1 shows the polyol partial ester compounds used in the examples to explain the present invention.

[Table] Polyols in the present invention include pentaerythritol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, ethylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, mannitol, sorbitol, xylitol,
Examples include glycerin, propylene glycol, dipropylene glycol, and the like. Regarding the above polyol partial esters or polyols, for example, polyol partial esters, each polyol alone or a combination of two types of polyol partial esters, a combination of two types of polyols,
Various combinations are considered, such as a combination of a polyol partial ester and one type of polyol, a combination of two polyol partial esters and one polyol, a combination of one polyol partial ester and two polyols, and a combination of two polyol partial esters and two polyols. However, all fall within the scope of the present invention. Epoxy compounds in the present invention include epoxidized vegetable oils, epoxidized oleic acid esters,
Examples include epoxidized erucic acid, esters, epichlorohydrin-bisphenol compounds, epichlorohydrin-polycresol compounds, and epichlorohydrin-resorcin compounds. Examples of the organic phosphite in the present invention include triphenyl phosphite, diphenyl phosphite, diphenyl scutyl phosphite,
Trisnonylphenyl phosphite, bisnonylphenyl ophthyl phosphite, diphenyl (butoxyethoxy) phosphite, diphenyl (phenoxyethyl) phosphite, tristridecyl phosphite, diphenyl mono(tridecyl)
Examples include phosphite and diphenyldecyl phosphite. In the present invention, the characteristics of the present invention will not be impaired even if non-metallic stabilizers or stabilizing aids that are generally known and used in addition to the above-mentioned compounds are used in combination. Particularly effective compounds that can be used here include the following. The phenolic antioxidant is a compound selected from the group consisting of compounds having 1 to 4 phenol groups in the same molecule, in which the hydroxyl group is hindered by at least one tertiary or secondary alkyl group. Specific examples include styrenated para-cresol, 2,6-di-tert-butylhydroxytoluene, butylated asol, 4,4'-butylidenebis (6-tert-butyl 3-methylphenol), 2,2'-methylenebis (6-tert-butyl 3-methylphenol), butyl,
4-methylphenol, 1.3.5-trimethyl,
2.4.6-Tris(3.5-ditert-butyl-4-hydroxybenzyl)benzene, tetrakis[3-
(4-hydroxy-3.5-ditertiary-butylphenyl)propionyloxymethyl]methane and the like. As ultraviolet absorbers, para-tertiary butyl, phenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-ofthoxybenzophenone, 2(2'-hydroxy-
5'-methylphenyl)benzotriazole, etc. Examples of the initial color improver include compounds included in the claims of Japanese Patent Publication No. 52-47949, and more practical ones include dibenzoylmethane, benzoylstearoylmethane, distearoylmethane, and the like. If the composition of the present invention is applied to fields where transparency is required, the above-mentioned compounds will not inhibit transparency at all. However, chlorine-containing resins are limited to the following. Polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, chloride Vinyl-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer,
Chlorine-containing synthetic resins such as vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-various vinyl ether copolymers, blends of these with each other or other chlorine-free synthetic resins, block copolymers, and graft copolymers. It is a polymer. The present invention includes lubricants, processing aids, weather resistance improvers, antistatic agents,
Antifogging agents, reinforcing agents, pigments, fillers, etc. are used in combination.
However, when applying it to the field of transparency, care must be taken to ensure that it does not generally impair transparency. Applications of the present invention include rain gutters, joints for the same purpose, pipes and joints for the same purpose, extruded board materials (commonly known as deck materials) and corrugated sheets, electric wires, irregular extrusion molded products (window frames, other construction materials) frames, etc. There is. The excellent effects of the present invention will be explained using examples, but the present invention is not limited to these examples. Comparative formulation examples (metal salt formulations) used in the examples are shown in Tables 2, 3, and 9.
In the table, the formulation example of the present invention (non-metallic formulation) is also shown in the fourth table.
Shown in Tables 8 and 10.

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[Table] Manufactured by Mitsui Petrochemical Co., Ltd.

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[Table] Example 1 Table 2 Target formulation examples No. 1 and No. 2 Table 4 Compositions of the invention formulation examples No. 1 to No. 10 6 inch 2
A sheet was prepared by kneading at 170°C for 5 minutes using this roll.
Using the sheet, a heat resistance test was conducted in an oven at 200°C, and the results shown in the table below were obtained. As is clear from the table, the sustained heat resistance performance varies depending on the performance of polyol partial ester or polyol alone, and the synergistic effect of their combination.
Even if it is better than No. 1 and No. 2, it is not inferior.

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[Table] Example 2 Table 2 Target formulation example No. 2 and Table 5 Invention formulation example
The compositions No. 11 to No. 17 were kneaded using two 6-inch rolls at 170°C for 5 minutes to prepare sheets. Using the sheet, a heat resistance test was conducted in an oven at 200°C, and the results shown in the table below were obtained. As is clear from the table, target combination example No. 2
It has better heat resistance than

[Table] Example 3 Regarding the compositions of Table 2 Target formulation examples No. 3 and 4 and Table 6 Invention formulation examples No. 18 to No. 20 6 inch, 2
A sheet was prepared by kneading with this roll at 160°C for 5 minutes.
A heat resistance test was conducted using the sheet in an oven at 180°C, and the results shown in the table below were obtained. As is clear from the table, even in the case of soft formulations, the durability of heat resistance is significantly superior to that of target formulations No. 3 and 4, which are metal salt formulations.

[Table] Example 4 Table 2 Target formulation example 5 and Table 7 Invention formulation example No.
Sheets were prepared by kneading the compositions No. 21 to No. 29 with two 6-inch rolls at 170°C for 5 minutes. A heat resistance test was conducted using a portion of the sheet in an oven at 190°C. In addition, a plate was made by stacking several remaining sheets and press-bonding them, and the transparency and color tone of the plate were observed. Furthermore, the plate is facing south 45
The weather resistance was evaluated by exposing it to sunlight on a high-temperature Bakuro stand. The respective results are shown in the table below. As is clear from the table, both the durability of heat resistance and the transparency are good, but what is especially surprising is that it has excellent stiffening resistance.

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[Table] Example 5 Plates were made using a single-screw extrusion molding machine for the compositions of target formulations Nos. 6 and 7 in Table 3 and inventive formulations Nos. 30 and 31 in Table 8. Molding conditions Extruder
50m/mφ 2/D=22 CR: 1.9 Cylinder temperature C ₁ 150℃ C ₂ 170℃ C ₃ 180℃ Head H 165℃ Die D 190℃ The appearance color tone of the molded product, and the molded product on a 45-degree south facing background Weather resistance when exposed to sunlight was evaluated.
The results are shown in the table below, and it is clear that it has amazing weather resistance.

[Table] Example 6 Plates were made using a 5-ounce injection molding machine for the compositions of target formulations Nos. 8 and 9 in Table 3 and inventive formulations Nos. 32 and 33 in Table 8. Molding conditions Injection pressure 90Kg/cm ² Holding pressure 5Kg/cm ² Screw rotation 40rpm Molding temperature C ₁ 170℃ C ₂ 180℃ C ₃ 180℃ H 170℃ The appearance color tone of the molded product and the molded product were measured on a 45-degree south facing Bacro table. Weather resistance was evaluated by exposing it to sunlight. The results are shown in the table below, and the weather resistance and yoking resistance are outstanding.

[Table] Example 7 Two 6-inch pieces for the compositions of target formulations No. 10 to No. 12 in Table 9, inventive formulation No. 34 in Table 10, and inventive formulation No. 29 in Table 7 A sheet was prepared by kneading with a roll for 5 minutes at 170°C. A heat resistance test was conducted using a portion of the sheet in an oven at 190°C. In addition, a plate was made by stacking several remaining sheets and press-bonding them, and the transparency and color tone of the plate were observed. Furthermore, we evaluated the weather resistance by exposing the plate to sunlight on a 45-degree south facing platform. The results are shown in the table below.

[Table] Example 8 Table 1: Subject formulation examples No. 1 and No. 2; Table 11: Subject formulation examples No. 13 and No. 14; Table 4: Subject formulation examples No. 5 and No. 1.
Regarding the composition of No. 8, two 6-inch rolls at 170°C,
The mixture was kneaded for 5 minutes to form a sheet. A heat resistance test was conducted using a portion of the sheet in an oven at 190°C to measure initial coloration and blackening time.
A plate was made by stacking several remaining sheets and press-bonding them, and the transparency and color tone were observed. Furthermore, the plate was exposed to sunlight on a 45° south-facing Bakuro stand to evaluate its weather resistance. The results are shown in the table below.

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Claims (1)

[Scope of Claims] 1. A partial ester of a chlorine-containing resin, a polyol, and a carboxylic acid, or a partial ester thereof and a polyol, an epoxy compound, and an organic phosphite, substantially free of metal salts as stabilizers. Stabilized chlorinated resin composition.