JPH0676529B2 - Chlorine-containing resin composition with improved processability and stability - Google Patents

Description

TECHNICAL FIELD The present invention relates to a chlorine-containing resin composition having improved processability and stability. More specifically, the present invention relates to a chlorine-containing resin composition which has little initial coloring and is excellent in roll processability in sheet molding by a calendar roll process method.

[Conventional technology]

For the purpose of preventing thermal decomposition during molding of vinyl chloride resin, metallic soap and organic compounds (JP-A-51-67349).
No., Japanese Patent Publication No. 58-11897), organotin compounds and organic compounds (see Japanese Patent Publication No. 45-39176, Japanese Patent Publication No. 49-11258), and organic tin compounds and metallic soap (Japanese Patent Publication No. 52-30173, Japanese Patent Publication Sho) 53
-20062 and Japanese Examined Patent Publication No. 55-45095) are used together for stabilization.

[Problems to be solved by the invention]

However, in the sheet molding by the calendar roll processing method, both of the above methods are inferior in initial colorability and roll processing property (for example, adhesion to the roll), and there is a difficulty in transparency, and a satisfactory product cannot be obtained. .

[Means for solving problems]

As a result of various studies, the inventors of the present invention have identified a metal soap having two or more kinds of 8 carbon atoms by combining a mono-higher alkyltin compound and a di-higher alkyltin compound as an organic tin compound with a chlorine-containing resin. The present inventors have found that by adding phosphite, the above-mentioned drawbacks in the calender roll processing method can be solved and a nontoxic chlorine-containing resin composition can be obtained, and the present invention has been completed.

That is, the present invention relates to (a) monooctyltin tris (isooctylthioglycolate ester), monooctyltin tris (C ₁₀ -C ₁₆ alkylthioglycolate ester) and monolauryl tin per 100 parts by weight of a chlorine-containing resin. 0.01 to 5 parts by weight of one or more monoalkyltin thioglycolic acid ester compounds selected from tris (isooctylthioglycolic acid ester), (b) dioctyltin bis (isooctylthioglycolic acid ester), dioctyl one or tin bis (C ₁₀ -C ₁₆ alkyl thioglycolate) and dilauryl tin bis dialkyltin thioglycollic acid ester compound selected from (isooctyl thioglycolate)
0.01 to 5 parts by weight, (c) 0.01 to 2 parts by weight of zinc 2-ethylhexylate, (d) calcium 2-ethylhexylate and / or 2-
0.01 to 2 parts by weight of magnesium-ethylhexanoate and (e) 4,4'-isopropylidene - diphenol alkyl (C ₁₂ ~C ₁₅₎ workability phosphite characterized by adding together 0.01 to 5 parts by weight And a chlorine-containing resin composition having improved stability.

Examples of the chlorine-containing resin to be stabilized by the present invention include homopolymers such as vinyl chloride resin or vinylidene chloride resin, and vinyl chloride in which vinyl acetate, ethylene,
Copolymers such as those formed by polymerizing with one or more comonomers such as propylene, styrene, isobutylene, vinylidene chloride, maleic anhydride, butadiene, isoprene, methylmethacrylate, acrylonitrile, dialkylmalates and the like. Examples include coalesced and post-chlorinated vinyl chloride resin. It can also be applied to a mixture of a chlorine-containing resin and an impact resistance improving resin such as acrylonitrile / butadiene / styrene resin, methylmethacrylate / butadiene / styrene resin, vinyl acetate / ethylene copolymer resin, chlorinated polyethylene or chlorinated rubber.

In the present invention, the compound added to the chlorine-containing resin consists of components (a) to (e). Examples of the compound of the component (a) include monooctyltin tris (isooctylthioglycolic acid ester) and monooctyltin tris (C _{10 to} C ₁₆
Alkyl thioglycolic acid ester) and monolauryl tin tris (isooctyl thioglycolic acid ester). These compounds are used singly or in combination, as the C ₁₀ -C ₁₆ alkyl group, a higher alkyl group derived from a synthetic mixture of higher alcohols by the oxo process. "Isooctyl" is "2-ethylhexyl".
Is a concept that can include. As the compound of component (b),
Dioctyltin bis (isooctyl thioglycolate), dioctyltin bis (C ₁₀ -C ₁₆ alkyl thioglycolate) and dilauryl tin bis (isooctyl thioglycolate) and the like. These compounds are used singly or in combination, C ₁₀ -C ₁₆ alkyl and "isooctyl" indicates the same meaning as above. Component (c) is zinc 2-ethylhexylate and component (d)
Is calcium 2-ethylhexylate and / or magnesium 2-ethylhexylate. Ingredient (e) is 4,4 '
- Pisopuropiriden - diphenol alkyl (C ₁₂ ~
C ₁₅ ) phosphite, and as the C _{12 to} C ₁₅ alkyl group, a higher alkyl group derived from a synthetic higher alcohol synthesized by the oxo method is shown.

In the present invention, the amount of each component added to 100 parts by weight of the chlorine-containing resin is 0.01 to 5 parts by weight for components (a) to (b), 0.01 to 2 parts by weight for components (c) to (d), and In (e), it is 0.01 to 5 parts by weight. If it is used below the lower limit of this addition amount, there is no improvement in workability and stability, and if it is used above the upper limit, it is uneconomical.

The chlorine-containing resin composition having improved processability and stability according to the present invention may optionally contain a reinforcing agent, a plasticizer, an epoxy compound, another metal soap stabilizer, an ultraviolet absorber, an antioxidant, and other Organic phosphites, polyol compounds, diketone compounds, keto acid compounds, lubricants, pigments, fillers, antistatic agents, antifogging agents and the like can also be used.

[Action]

According to the present invention, firstly, by using the components (a) to (b) mono-higher alkyltin thioglycolic acid ester compounds and di-higher alkyltin thioglycolic acid ester compounds in combination, the initial coloring of the chlorine-containing resin during processing is achieved. Improve sex,
The thermal stability is remarkably improved, and the roll separation during processing is improved and the workability is improved as compared with the case of using the methyltin compound and the butyltin compound in place of the higher alkyltin compound of the present invention. it can. Secondly, component (c)-
By using (d) zinc 2-ethylhexylate in combination with calcium 2-ethylhexylate and / or magnesium 2-ethylhexylate, the initial colorability can be improved and the transparency can be improved. Here, it was revealed that the metal soap having a carbon number of 7 or less was inferior in processability, and the metal soap having a carbon number of 9 or more was inferior in initial colorability and transparency. Thirdly, 4,4′-isopropylidene of the component (e)
By adding diphenol alkyl (C ₁₂ ~C ₁₅₎ phosphite, as compared with the case of adding another organic phosphorus compound to improve the initial coloring, can improve processability and thermal stability. Fourth, since the compounds of the components (a) to (e) of the present invention are all nontoxic, the addition of which is recognized,
By adding these, non-toxic chlorine-containing resin molded products can be obtained.

〔Example〕

Next, the present invention will be described with reference to examples, but parts in the examples represent parts by weight.

Example 1 8 inches 2 in which the organotin stabilizer shown in Table 1 below was added to the following compounding ingredients in a total amount of 1.0 part and the temperature was kept at 185 ° C.
After kneading with this roll, a 0.5 mm-thick sheet piece was taken out at intervals of 2 minutes, and the thermal stability was examined by changing the color tone up to 20 minutes. Compound component part Vinyl chloride resin (Geon103Ep-8, made by Zeon Corporation) 100
Methyl methacrylate butadiene styrene resin (Kaneace B-11A, manufactured by Kanebuchi Chemical Co., Ltd.) 10 Epoxidized soybean oil 3 Zinc 2-ethylhexylate 0.15 Magnesium 2-ethylhexylate 0.3 4,4'-isopropylidene-diphenolalkyl (C ₁₂
~ C ₁₅ ) Phosphite 1 Stearic acid 1 Glycerin monostearate 0.5 The numbers in the table indicate the following evaluations. The following table of thermal stability tests is the same.

 1: Colorless 2: Light yellow 3: Light yellow 4: Yellow 5: Light brown 6: Brown 7: Red brown 8: Black brown 9: Black The results are shown in Table 1.

Example 2 Organotin stabilizers shown in Table 2 below were added to the same compounding ingredients as in Example 1 so that the total amount was 0.5 parts, and the mixture was kneaded with an 8-inch two-roll roller maintained at a temperature of 185 ° C., and was separated by 2 minutes. A 0.5 mm thick sheet piece was taken out and the thermal stability was examined by changing the color tone up to 20 minutes.

The results are shown in Table 2.

Example 3 The total amount of metal soap stabilizers shown in Table 3 below was added to the following ingredients.
5 to 0.7 parts was added and the temperature was maintained at 185 ° C. 8
After kneading with a two-inch roll for 10 minutes, a 0.5 mm thick sheet was taken out, and the transparency and the initial colorability were examined. Ingredients of the vinyl chloride resin (Geon103Ep-8) 100 methyl methacrylate-butadiene-styrene resin (Kane Ace B-11A) 3 epoxidized soybean oil 1 4,4'-isopropylidene - diphenol alkyl (C ₁₂
-C ₁₅ ) Phosphite 1 Stearic acid 0.5 Stearyl alcohol 0.5 Monooctyltin tris (isooctylthioglycolic acid ester) 0.5 Dioctyltin bis (isooctylthioglycolic acid ester) 0.5 The symbols in the table indicate the following evaluations.

 A: Very good B: Good C: Normal D: Poor

The results are shown in Table 3.

Example 4 The total amount of the metal soap stabilizers shown in Table 4 below was added to the following ingredients.
5 parts were added, and kneading was continued with an 8-inch twin roll kept at a temperature of 190 ° C., and the time until the sheet did not come off from the roll was measured to examine the workability. Ingredients of the vinyl chloride resin (Geon103Ep-8) 100 methyl methacrylate-butadiene-styrene resin (Kane Ace B-11A) 3 epoxidized linseed oil 2 4,4'-isopropylidene - diphenol alkyl (C ₁₂
~ C ₁₅ ) Phosphite 1.5 Stearic acid 0.5 WaxOP (manufactured by Hoechst) 0.2 Monooctyltin tris (isooctylthioglycolic acid ester) 0.1 Dioctyltin bis (isooctylthioglycolic acid ester) 0.4 Dilauryltin bis (2-ethylhexylthio) Glycolic acid ester) 0.5 The results are shown in Table 4.

Example 5 The organic phosphorus compounds shown in the following Table 5 were added to the following compounding ingredients in an amount of 2 parts, and the mixture was kneaded with an 8-inch two-roll roller maintained at a temperature of 190 ° C. and a thickness of 0.5 mm was set at intervals of 2 minutes. Taking out sheet pieces,
The thermal stability was examined by changing the color tone up to 20 minutes. Mixing component part Vinyl chloride resin (Geon103Ep-8D, manufactured by Zeon Corporation) 100
Methyl methacrylate / butadiene / styrene resin (Kaneace B-11A) 10 Dioctyl adipate 1 Stearic acid 0.3 Glycerin monostearate 0.5 Hiwax220Mp (Mitsui Petrochemical Co., Ltd.) 0.1 Monooctyltin tris (C _10-16 alkyl thioglycolic acid ester) 0.3 Dioctyltin bis (C _10-16 alkyl thioglycolic acid ester) 0.2 Dioctyl tin bis (isooctyl thioglycolic acid ester) 1.0 Zinc 2-ethylhexylate 0.3 Calcium 2-ethylhexylate 0.2 The results are shown in Table 5.

[Effect of the Invention] As is clear from the results of the thermal stability test of Examples 1 and 2, in the present invention, the combined use of the mono-higher alkyltin compound and the di-higher alkyltin compound significantly improves the thermal stability, The combined use of the mono-lower alkyltin compound and the di-lower alkyltin compound did not significantly improve the thermal stability. As is clear from Examples 3 to 4, when the metal soap of the present invention was used in combination, it was compared with other metal soaps. In addition, the initial colorability and transparency are excellent, and the peeling from the roll is good, so that the processability is excellent. When the phosphite compound of the present invention is used from Example 5, it is more heat stable than other organic phosphorus compounds. The property has improved. These effects are achieved by the configuration of the present invention.

Claims (1)

[Claims] 1. A monooctyltin tris (isooctyl thioglycolate ester), monooctyl tin tris (C ₁₀ -C ₁₆ alkylthioglycolate ester) and monolauryl tin tris per 100 parts by weight of a chlorine-containing resin. 0.01 to 5 parts by weight of one or more monoalkyltin thioglycolic acid ester compounds selected from (isooctylthioglycolic acid ester), (b) dioctyltin bis (isooctylthioglycolic acid ester), dioctyltin bis (C ₁₀ -C ₁₆ alkyl thioglycolate) and dilauryl tin bis one or dialkyl tin thioglycolate compound selected from (isooctyl thioglycolate)
0.01 to 5 parts by weight, (c) 0.01 to 2 parts by weight of zinc 2-ethylhexylate, (d) calcium 2-ethylhexylate and / or 2-
0.01 to 2 parts by weight of magnesium-ethylhexanoate and (e) 4,4'-isopropylidene - diphenol alkyl (C ₁₂ ~C ₁₅₎ workability phosphite characterized by adding together 0.01 to 5 parts by weight And a chlorine-containing resin composition having improved stability.