JPH08253645A - Heat-stabilized chlorine-containing resin composition. - Google Patents

Abstract

PURPOSE: To obtain the subject composition effective for rigid pipe or sizing by adding a non-toxic stabilizer to a chlorine-containing resin. CONSTITUTION: This resin composition comprises (a) 60-95wt.% of di-n-octyltin bis(isooctymercaptoacetate), (b) 39-4wt.% of a poly(thio-bis-n-butyltin sulfide), (c) <=1wt.% of sodium sulfide, where the sum total of (a)+(b)+(c) is 50-98wt.% and (d) a stabilizer containing 50-2wt.% of magnesium oxide or hydroxide. The resin composition contains 0.1-8 pts.wt. of this stabilizer per 100 pts.wt. of chlorine-containing resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-stabilized chlorine-containing resin composition, which is a heat-stabilized chlorine-containing resin obtained by combining a non-toxic alkyl tin compound, sodium sulfide and a magnesium inorganic compound as a stabilizer. It relates to a composition.

[0002]

2. Description of the Related Art A chlorine-containing resin composition typified by polyvinyl chloride causes decomposition accompanied by dehydrochlorination during thermoforming to color molded articles. Has been adopted to prevent. As the stabilizer, lead stearate, tribasic lead sulfate, dibasic lead stearate and the like have been widely used. The lead-based stabilizer of this chlorine-containing resin composition is excellent in hydrogen chloride scavenging action, has good processability, and is inexpensive,
Recently, its toxicity has become a problem. As an example, the standards for leaching lead metal have been revised and regulations have been tightened for molded products such as water supply pipes and joints made of a chlorine-containing resin composition.

For this reason, conventional lead-based stabilizers cannot be practically used in this field at present, and there is an urgent need to develop alternative stabilizers. Under these circumstances, various thermal stabilization methods using lead-free stabilizers have already been proposed.

For example, Japanese Patent Publication Nos. 58-4561 and 58.
No. 56539, No. 59-49229, and Japanese Patent Publication No. 6-4
741, 7-5805, JP-A-6-2400,
7-3071, 7-3087, 7-1813
No. 8, No. 7-26094, No. 7-33936,
Proposals have been made for compounding formulations in which alkyltin sulfide is used in combination for pipes and siding, or in combination with calcium stearate and the like.

However, when the resin is thermoformed by these compounding disposals, the trapping action of hydrogen chloride generated by thermal decomposition is still inferior to that of the lead-based stabilizer, and sufficient thermal stability cannot be obtained, Further improvement is required.

[0006]

DISCLOSURE OF THE INVENTION According to the present invention, a chlorine-containing resin is added with a stabilizer which is a combination of a non-toxic alkyl tin compound and a small amount of sodium sulfide and magnesium compound. The present invention is intended to obtain a heat-stabilized chlorine-containing resin composition that is particularly effective.

[0007]

The present invention provides (a) di-n.
-Octyltin bis (mercaptoacetic acid isooctyl ester) 60 to 95% by weight, (b) poly (thiobis-n-butyltin sulfide) 39 to 4% by weight, and (c) sodium sulfide 1% by weight or less ( a) + (b) + (c)
The total amount of the stabilizers is 50 to 98% by weight, and (d) the magnesium oxide or hydroxide is 50 to 2% by weight, and the stabilizer is 0.1 to 8 parts by weight based on 100 parts by weight of the chlorine-containing resin. Which is a heat-stabilized chlorine-containing resin composition. The present invention will be further described below.

Stabilizers used in this invention, (a) di-n
-Octyltin bis (mercaptoacetic acid isooctyl ester), (b) poly (thiobis-n-butyltin sulfide), (c) sodium sulfide and (d) magnesium oxide or hydroxide.

In the present invention, the above (a), (b),
The proportion of the three components of (c) is specified, and the total of these three components is 100%, and the di-n-octyltin bis (mercaptoacetic acid isooctyl ester) of (a) is 60 to 95% by weight, (b). Of poly (thiobis-n-butyltin sulfide) of 3 to 4% by weight and sodium sulfide of (c) to 1% by weight or less. This stabilizer is 50 to 98% by weight of the total amount of these (a), (b) and (c),
50 to 2% by weight of magnesium oxide or hydroxide
Consists of

Regarding the ratio of the above three components (a), (b) and (c), the di-n-octyltin bis (mercaptoacetic acid isooctyl ester) of (a) is added in an amount of 60 to 95.
The reason why the content is 60% by weight is that if it is less than 60% by weight, no effect is obtained, and if it exceeds 95% by weight, toxicity becomes a problem. The same applies to the case where the poly (thiobis-n-butyltin sulfide) (b) is 39 to 4% by weight. It is not preferable to add more than 1% by weight of sodium sulfide from the viewpoint of toxicity. The inventor of the present invention has (a), (b),
By using the three components of (c) together in a predetermined ratio,
It was found that a stabilizer which is non-toxic and has substantially the same heat stabilizing effect as that of the lead-based stabilizer can be obtained, and a sufficient heat stabilizing effect cannot be expected if any of these stabilizers is lacking.

The stabilizer used in the present invention is the above-mentioned (a),
50 to 98% by weight of the total amount of (b) and (c), and (d)
50 to 2% by weight of magnesium oxide or hydroxide
Consists of (A) is the sum of (a) to (c)
When + (b) + (c) is less than 50% by weight, the effect of preventing initial coloration is insufficient and the effect of heat stabilization is not obtained. On the other hand, if it exceeds 98% by weight, the blending ratio of the magnesium oxide or hydroxide, which is the other component, is small and the sustained heat resistance is not sufficient. When the compounding ratio of magnesium oxide or hydroxide exceeds 50% by weight, initial coloring occurs. The compounding ratio of magnesium oxide or hydroxide is such that the lower limit is 2% by weight and the upper limit is 50% by weight. Within this range, a synergistic effect is exerted in the initial color prevention property and the continuous heat resistance.

In the chlorine-containing resin composition of the present invention, such a stabilizer is added in an amount of 0.1 to 8 per 100 parts by weight of the chlorine-containing resin.
Contains parts by weight. More preferable content is 0.3 to 5
Parts by weight. If it is less than 0.1 parts by weight, a sufficient heat stabilizing effect cannot be obtained, and if it is added in excess of 8 parts by weight, the thermal stability is not so much improved for the added amount, and the physical properties such as softening point are rather improved. Cause a decrease in

In the present invention, in addition to the above-mentioned stabilizer components, the following stabilizer components, stabilizing aids and other additives can be used in combination. For example, metal soap compounds, alkyl tin compounds, inorganic metal salt compounds and their double salts, polyhydric alcohols and their ester compounds, nitrogen-containing stabilizing aids, β-diketone compounds, phenolic compounds and organic phosphite compounds. And antioxidants, light stabilizers such as ultraviolet absorbers, ester- or wax-based processing aids, and the like. These additives can be appropriately used as needed.

The metal soap compound is a non-toxic metal such as calcium, magnesium or zinc,
Examples of the organic acid group bonded to these metals include 2-
Carboxylic acids such as ethylhexanoic acid, isodecanoic acid, lauric acid, stearic acid, behenic acid, 12-hydroxystearic acid, oleic acid and benzoic acid, which are metal salt compounds.

The alkyl tin compound is, for example, a mixture of dimethyl tin bis (thioglycolic acid isooctyl ester) and methyl tin tris (thioglycolic acid isooctyl ester) in a mixing ratio of 76:24 or 2.
1:79, a mixture of monomethyltin bis (2-methylcaptoethyltolate) sulfide and dimethyltin (2-methylcaptoethyloleate) sulfide,
Mixing ratio 90:10, a mixture of poly (thiobis-methyltin sulfide) and dimethyltin sulfide, di-
Examples thereof include n-octyltin dilaurate, poly (di-n-octyltin maleate), and n-octyltin tris (thioglycolic acid isooctyl ester).

The inorganic metal salt compound and the double salt thereof are, for example, calcium oxide, calcium hydroxide, aluminum hydroxide, synthetic hydrotalcite, wollastonite, tobermorite and aluminosilicate as the main component A.
Examples of synthetic zeolites of type X, type Y, and the like.

Polyhydric alcohols, nitrogen-containing compounds and β
Examples of the diketone compound include pentaerythritol, dipentaerythritol, mannitol, sorbitol, dipentaerythritol adipate, dipentaerythritol pyrrolidone carboxylic acid, wood rosin pentaerythritol, maleic anhydride-modified wood rosin pentaerythritol, β-aminocrotonic acid. (1,3-
Alternatively, 1,4-) butanediol, tris (hydroxyethyl) isocyanurate, tris (mercaptoethyl) isocyanurate, and β-diketone compounds dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, benzoyltetralone, stearoyltetralone. And so on.

Phenolic antioxidants are represented by, for example, alkylated phenols, alkylated phenol ethers or esters, alkylene or alkylidene bisphenols, polyalkylated phenols, thiobisalkylated phenols and thiopropionic acid esters, such as butylated. Hydroxytoluene, 4-hydroxymethyl-2,6-di-t-butylphenol, polybutylated-4,4'-isopropylidenediphenol,
2,2'-methylenebis (4-methyl-6-t-butylphenol), tetrakis [methylene-3 (5,5'-
Di-t-butyl-4-hydroxyphenyl) propionate] methane, thiobis (methyl-butylphenol)
4,4'-thiobis (6-t-butylphenol), and dilaurylthiodipropionic acid ester, distearylthiodipropionic acid ester, 2-mercaptoethyloleate, 2-methylcaptoethyltolate, and the like. Examples of organic phosphite-based antioxidants include trisnonylphenyl phosphite, triisotridecyl phosphite, 4,4 ′ isopropylidene diphenylalkyl (C ₁₂ -C ₁₅ ) phosphite, and dilauryl pentaerythritol diphosphite. Fight, distearyl pentaerythritol diphosphite, poly (dipropylene glycol) phenyl phosphite and 2-
Examples include t-butyl-α (3-t-butyl-4-hydroxyphenyl) p-cumenylbis (p-nonylphenyl) phosphite.

Those used as light stabilizers such as ultraviolet absorbers include, for example, 2 (5-methyl-2-hydroxyphenyl) benzotriazole, 2 (3,5-di-t-butyl-2-hydroxyphenyl) 5. -A benzotriazole-based compound such as chlorobenzotriazole and 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole. Also, dimethyl succinate-1-
(2-hydroxyethyl) 4-hydroxy-2,2
6,6-Tetramethylpiperidine, poly [{6- (1,
1,3,3-Tetramethylbutyl) imino-1,3,5
-Triazine-2,4-diyl} {(2,2,6,6-
Hindered amine compounds such as tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}].

Examples of processing aids such as esters and waxes include behenic acid, paraffin wax having a melting point of 45 ° C. or higher, microcrystalline wax having a melting point of 60 ° C. or higher, paraffin-based synthetic wax having a melting point of 100 ° C. or higher,
Such as polyethylene wax and fatty acid amide.

Examples of the chlorine-containing resin which is heat-stabilized by the present invention include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride- Urethane copolymer, post-chlorinated polyvinyl chloride, chlorinated polyethylene or polypropylene, polyvinyl chloride and the following polymers such as polybutene, poly-3-methylbutene, acrylonitrile-butadiene copolymer, styrene-butadiene copolymer , A styrene-ethylene-butadiene copolymer, a methacrylic acid ester-butadiene-styrene copolymer, an acrylic acid ester-butadiene-styrene copolymer, and other blended products.

The chlorine-containing resin composition of the present invention comprises a plasticizer, an epoxy compound, a filler, a pigment,
A foaming agent or the like can be appropriately used in combination. Next, the present invention will be further described based on examples.

[0023]

【Example】

(Examples 1-2, Comparative Examples 1-5) Using chlorine-containing resin compositions in which the stabilizer components (a), (b), (c) and (d) of the present invention were added to the following basic formulation. It was a compounding recipe. This was made into a sheet and used as a test piece, and the thermal stability was examined using this test piece. Further, using this chlorine-containing resin composition, extrusion molding processing was carried out, and behaviors such as discharge amount and moldability were investigated.

The basic composition is as follows. Polyvinyl chloride (degree of polymerization: 1050) 100 parts by weight Heavy calcium carbonate 3 〃 Rutile type titanium oxide 0.6 〃 Paraffin wax (Note-1) 1.0 〃 Polyethylene wax (Note-2) 0.3 〃 Calcium stearate 0.7 〃 Stabilizer component of the present invention (1 in Table 1) Note-1 HNP-10, manufactured by Nippon Seiro Co., Ltd. Note-2 High Wax-4202E, manufactured by Mitsui Petrochemical Co., Ltd. Chlorine-containing resin composition Preparation of products (dry blending) In a Henschel mixer with a capacity of 20 liters, 3,000 g of polyvinyl chloride was charged with specified amounts of fillers, lubricants, etc., and the rotation speed was 500 r. p. m. The mixture was stirred with heating. The rotation speed is gradually increased to 1,000 r.p.m. p. m. When the temperature of the resin had risen to 60 ° C., the stabilizer was sequentially added and stirred. When the temperature rose to 120 ° C., cooling and stirring were performed while decelerating, and when the resin temperature was 50 ° C., dry blending was completed.

Preparation of Sheets and Conditions 200 parts of the above dry-blended chlorine-containing resin composition was used.
Kneading for 3 minutes with a kneading roll set to ℃, thickness 0.3
A uniform sheet of mm was prepared and used as an original sheet.

Test 1 A test piece was sampled from this original sheet and put in a gear aging tester set at 195 ° C. for a certain period of time to examine the time until coloring due to heat deterioration and decomposition of black (brown). The results are shown in Table 1-1 and Table-1-2.

Table 1-1 and Table 1-2 are displayed integrally by being joined in the lateral direction. Table 1-1 shows a list of the types of raw materials used for the formulation and the test conditions. Further, 2 in Table 1 shows compounding prescriptions of Examples 1 and 2 and Comparative Examples 1 to 5 and test results.

Test 2 Ten test pieces were taken from the original sheet. This is placed on the mold and placed in a press molding machine set at 180 ° C for 150
Pressurized to kg / cm ² and taken out after a certain period of time, thickness 3m
m press plate was obtained. The degree of coloring caused by this long-time press molding was examined. The results are shown in 1 of Table 1 and 2 of Table 1.

Test 3 The characteristics of extrusion molding were examined under the following extruder and extrusion conditions. Extruder: Lapoplast mill (manufactured by Toyo Seiki Seisakusho, Ltd.), bidirectional twin-screw extruder, 2D-25-S, screw diameter 20 m
m × 2, length 600mm, L / D = 25, rotation speed 30
r. p. m. , Die / Garvey Dai
e: ASTM-2230), set temperature, C1: 150
℃, C2: 160 ℃, C3: 170 ℃, die: 200 ℃
The extrusion process was performed under these conditions, and the behavior and characteristics such as the processability during the molding process were observed. The results are shown in 1 of Table 1 and 2 of Table 1.

[0030]

[Table 1]

[0031]

[Table 2]

As can be seen from Table 1-1 and Table 1-2, Examples 1 and 2 of the present invention had no initial coloration in the gear open test and a long black (brown) decomposition time. Also,
Even in the press test, the coloring for 60 minutes is yellow and the heat resistance is continuous. On the other hand, Comparative Examples 1, 2, and 5 cannot be used because they have initial coloring. Comparative Examples 3 and 4 have no initial coloring,
There is no persistent heat resistance. Further, it is clear that Examples 1 and 2 are excellent in workability. That is, the discharge amount is large and therefore the resin pressure is small. Furthermore, dimensional stability (identity with the die), hue, surface gloss (smoothness), etc. are all superior to the comparative examples.

Examples 3 to 4 and Comparative Examples 6 to 10 In this example, a chlorine-containing resin composition containing a methylmethacrylate-butadiene-styrene resin (MBS), which is an impact resistance enhancer of a chlorine-containing resin, was used in combination. Various behaviors and characteristics were investigated.

The method and conditions of the formulation adjustment by dry blending, sheet preparation and various tests were the same as in Example 1. The basic composition was as follows. Stabilizer formulation and test results are shown in Table 1 and Table 3
2 of the above.

Blended polyvinyl chloride (polymerization degree 1050) 100 parts by weight MBS (Note-5) 8 〃 heavy calcium carbonate 3 〃 rutile titanium oxide 0.6 〃 paraffin wax 1.0 〃 polyethylene oxide wax 0. 5 〃 Calcium stearate 1.0 〃 Stabilizer component of the present invention (1 in Table 2) Note-5 Kaneace B-12 manufactured by Kanebuchi Chemical Co., Ltd.

[0036]

[Table 3]

[0037]

[Table 4]

As can be seen from Table 2-1 and Table 2-2, Examples 3 and 4 of the present invention have no initial coloration in the gear open test and a long black (brown) decomposition time. Also,
Even in the press test, 60 minutes of coloring is yellowish brown and has continuous heat resistance. In contrast, Comparative Examples 6, 7, and 10 have initial coloring. Comparative Examples 8 and 9 have no initial coloration, but have a black (brown) decomposition time of 60 minutes in the gear open test, and have a black color of 60 minutes in the press test, and have no continuous heat resistance. Further, it is clear that Examples 3 and 4 are excellent in workability. That is, the discharge amount is large and therefore the resin pressure is small.
Furthermore, dimensional stability (identity with the die), hue, surface gloss (smoothness), etc. are all superior to the comparative examples.

(Examples 5 to 6 and Comparative Examples 11 to 15) In this example, injection compounding formulations were used. The composition was adjusted, various test methods and conditions were the same as in Example 1. The basic composition was as follows. The stabilizer formulation and test results are shown in Table 3 at 1 and Table 3 at 2.

Blending Polyvinyl chloride (Polymerization degree 800) 100 parts by weight Polymethylmethacrylate (Note-6) 2〃 Rutile titanium oxide 0.6〃 Polyhydric alcohol fatty acid ester (Note-7) 1.5〃 Glycerin mono ・Distearate 1.0 〃 Calcium stearate 0.6 〃 Stabilizer of the present invention (1 in Table 3) Note-6 PA-20, manufactured by Kanebuchi Chemical Co., Ltd. Note-7 RIQUESTER EW-200, manufactured by Riken Vitamin Co., Ltd. Note- 8 Rikemar S-200, Riken Vitamin Co.

[0041]

[Table 5]

[0042]

[Table 6]

As can be seen from Tables 1 and 2 of Tables 3, Examples 5 and 6 of the present invention have no initial coloration in the gear open test and a long black (brown) decomposition time. Also,
Even in the press test, 60 minutes of coloring is yellowish brown and has continuous heat resistance. In contrast, Comparative Examples 1, 3, and 15 have initial coloring. Comparative Examples 11, 12, and 14 have no initial coloring,
It takes a long time to decompose black (brown), and the coloring in the press test for 60 minutes is black or brown and has no persistent heat resistance. Further, in Examples 5 and 6, the discharge amount was large and therefore the resin pressure was also small. Furthermore, dimensional stability (identity with the die), hue, surface gloss (smoothness), etc. are all superior to the comparative examples.

[0044]

As described above, according to the present invention, a chlorine-containing resin composition that is non-toxic, excellent in initial coloring, and has continuous heat resistance can be obtained. A chlorine-containing resin composition suitable for extruding a molded product can be obtained.

Claims (1)

[Claims] 1. (a) 60-95% by weight of di-n-octyltin bis (mercaptoacetic acid isooctyl ester),
(B) Poly (thiobis-n-butyltin sulfide) 3
The total of (a) + (b) + (c) is 50 to 98% by weight at a compounding ratio of 9 to 4% by weight and (c) sodium sulfide of 1% by weight or less, and (d) an oxide or hydroxide of magnesium. Thing 5
A heat-stabilized chlorine-containing resin composition containing 0.1 to 8 parts by weight of a stabilizer in an amount of 0 to 2% by weight, based on 100 parts by weight of the chlorine-containing resin.