JPS63110240A - Stabilized synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition improved in, among others, weatherability and resistance to staining by metal, by incorporating a polymer blend of chlorine-contg. resin and acrylonitrile-butadiene-styrene copolymer resin with alkyltin (di)thiopropionic acid salt(s). CONSTITUTION:The objective resin composition with high thermal stability can be obtained by incorporating (A) a polymer blend composition comprising (i) 30-70pts.wt. of a chlorine-contg. resin (e.g., vinylidene chloride resin, chlorinated rubber) and (ii) 70-30pts.wt. of an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) with (B) 0.01-5pts.wt. of at least one kind selected from dialkyltin (di)tiodipropionic acid salts and monoalkyltin (di)thiodipropionic acid salts having recurring units of respective formulae I-IV (R is alkyl), and if needed, (C) other stabilizer (e.g., metal salt of organic acid, antioxidant), pigment filler etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a stabilized synthetic resin composition with improved thermal stability, particularly weather resistance and metal stain resistance.

[Conventional technology]

It is known that excellent thermal stability can be obtained by adding a dialkyltin mercapto compound or a dialkyltin malate compound to a vinyl chloride resin.

However, processing of a polymer blend in which acrylonitrile-butadiene-styrene copolymer resin is added to vinyl chloride resin requires higher temperatures. It imparts coloring properties and is unsuitable for products with a single color tone.

In addition, there is a large amount of loss on heating, which may cause contamination of the mold.

Therefore, by using a dialkyltin mercapto compound in combination with a dialkyltin malate compound, the amount of the dialkyltin malate compound added was reduced and the thermal stability and initial colorability were improved (Japanese Patent Application Laid-open No. 52-78258
No., JP-A-53-134052, JP-A-55-192
No. 63, Special Publication No. 58-25105, Special Publication No. 59-50
700 and Japanese Patent Publication No. 60-47303).

[Problem that the invention seeks to solve]

However, all of the above dialkyltin mercapto compounds have a 5n-5 bond in the molecule.

Addition of this type of compound deteriorates the weather resistance of processed products, so it has the disadvantage that it cannot be used in products that require weather resistance.

[Means for solving problems]

As a result of various researches, the inventors of the present invention 1. It was discovered that by adding organotin thiodipropionate or organotin dithiodipropionate, blend resins can be thermally stabilized even during high-temperature processing and excellent weather resistance can be imparted to processed products.1
We have arrived at the present invention.

That is, 1 the present invention comprises 30 to 70 parts by weight of a chlorine-containing resin and 7 parts by weight of an acrylonitrile-butadiene-styrene copolymer resin.
dialkyltin thiodipropionate,
0.01 to 5 weight of one or more alkyltin thio or dithiodipropionates consisting of monoalkyltin thiodipropionate, dialkyltin dithiodipropionate, and monoalkyltin dithiodipropionate. This is a stabilized synthetic resin composition characterized in that part of the compound is added.

In the present invention, as the suldialkyltin thiodipropionate added to the polymer blend composition, for example, the general formula [
For example, a compound having a repeating unit of the structure of general formula [2] is 1 as a monoalkyltinthiodipropionate, and a compound having a repeating unit of the structure of general formula [2] is 1 as a dialkyltindithiodipropionate. For example, examples of the monoalkyltin dithiodipropionate include compounds having the structure of general formula [3] as a repeating unit, and compounds having a network structure of general formula [4] as a repeating unit.

In the formula, R represents an alkyl group such as a methyl group, a butyl group, an octyl group, or a lauryl group.

In the present invention, the amount of the alkyltinthio or dithiodipropionate added is 0.01 to 5 parts by weight based on 100 parts by weight of the polymer blend composition. If the amount added is less than the lower limit, the thermal stability will not be improved, and if the amount is more than the upper limit, it is uneconomical.

The polymer blend composition stabilized by the present invention consists of a chlorine-containing resin and an acrylonitrile-butadiene-styrene copolymer resin.

Examples of chlorine-containing resins include homopolymers such as vinyl chloride resin or vinylidene chloride resin, as well as vinyl chloride, vinyl acetate, ethylene, propylene, styrene, imbutylene, and vinylidene chloride.

Copolymers, post-chlorinated vinyl chloride resins, as formed by polymerization with one or more comonomers such as maleic anhydride, butadiene/, inoprene, methyl methacrylate, acrylonitrile, dialkylmalates and the like. , post-chlorinated vinyl chloride copolymer, chlorinated polyethylene.

Examples include chlorinated rubber. As the acrylonitrile-butadiene-styrene copolymer resin, those commonly known as ABS resins can be used.

For the stabilized synthetic resin composition of the present invention.

If necessary, known stabilizers 1 such as other organotin stabilizers,
Metal organic acid salts, epoxy compounds, antioxidants, boric acid,
Borates, anhydrous borates, borate esters, ultraviolet absorbers, and organic phosphites can be added. Pigments, fillers, lubricants, antistatic agents, flame retardants,
Processing aids can also be used.

[For production]

According to the present invention, a blend resin consisting of a chlorine-containing resin and an acrylonitrile-butadiene-styrene copolymer resin can be highly thermally stabilized, and the resin can be easily processed at high temperatures without mold contamination. The resulting product is also stabilized against light and can be used in fields where weather resistance is required. If it is desired to further improve the initial colorability, a known organic tin mercapto compound may be added.

〔Example〕

Next, the present invention will be explained with reference to examples, where the parts in the examples indicate overlapping parts.

Example 1 50 parts of vinyl chloride resin (Kanevinyl S-1007, manufactured by Kanebuchi Kagaku Co., Ltd.) and 50 parts of acrylonitrile-butadiene-styrene resin (Cycolac Ex211, manufactured by Ube Cycon Co., Ltd.) were mixed with 3 stabilizers shown in Table 1 below. .0 parts added.

Knead with a test roll at 150℃ for 3 minutes to obtain a thickness of Q, 5m.
m sheets were created. Each sheet 'l tym x
After cutting it into a size of 2cxa, it was placed in a gear aging tester at 210°C to examine its thermal stability.

The numbers in the table indicate the following evaluations. The same applies to the thermal stability test table below.

1: Milky white 2: Pale yellow 3: Yellow Color 4: Yellowish brown
5: Brown 6: Dark brown The results are shown in Table 1.

Example 2 Stabilizers listed in Table 2 below were added to 60 parts of vinyl chloride resin (Kanevinyl S-1007) and 40 parts of acrylonitrile-butadiene-styrene resin (Cycolac Ex211) for a total of 4.0 parts. , 150℃.

The mixture was kneaded with a test roll for 3 minutes to create a sheet with a thickness of 9.5 mm. After each sheet was cut into a size of 2c11 x 2clI, it was placed in a gear aging tester at 215°C to examine its thermal stability.

The results are shown in Table 2.

Example 3 Vinyl chloride resin (Kanevinyl S-1007) 40
5 parts of the stabilizer below was added to 60 parts of acrylonitrile-butadiene-styrene resin (Cycolac Ex211) and kneaded with a test roll at 150°C for 3 minutes to give a thickness of 0.
A 5 mm sheet was created. After cutting each sheet into 5 x 1 size pieces, use the Sunshine Weather-Ometer ('WE)
L-5UN-TC,,1,Ga test m@) company M)Kte50
A weather resistance test was conducted after irradiation for 0 hours. Judgment is made using a color difference meter (T
ΔE (color difference) was measured using C-PII [manufactured by Tokyo Isshokusha Co., Ltd.].

The results are shown in Table 3.

Example 4 A heating loss test was conducted for each stabilizer listed in Table 4 below. The test was conducted using a thermal analyzer (TGA-31, manufactured by Shimadzu Corporation) under primary thermogravimetric measurement conditions.

The loss [4 quantity 96) after 1 hour at 210°C was determined.

Measurement conditions Temperature: Temperature increase rate 10°C/min, held at 210°C for 1 hour Nitrogen gas flow rate: 100 Ginpaku sample: approximately 50~ The results are shown in the fourth display.

Table 4 [Effects of the Invention] As is clear from the thermal stability test results of Examples 1 and 2 above, in the present invention, one or more alkyltinthio or dithiodipropionate salts are added to the polymer blend. Addition improves thermal stability to the resin, as evident from Example 3.

By using the alkyltin thio or dithiodipropionate of the present invention which provides superior weather resistance compared to known organotin mercapto compounds and further shows less loss on heating from Example 4, It has become possible to prevent mold contamination during processing. These effects can only be achieved by the configuration of the present invention.

Claims (1)

[Claims] When stabilizing a polymer blend composition consisting of 30 to 70 parts by weight of a chlorine-containing resin and 70 to 30 parts by weight of an acrylonitrile-butadiene-styrene copolymer resin, dialkyltin thiodipropionate, monoalkyltin thiodipropionic acid salt, one or two alkyltin thio or dithiodipropionates consisting of dialkyltin dithiodipropionate and monoalkyltin dithiodipropionate;
A stabilized synthetic resin composition characterized by adding 0.01 to 5 parts by weight of at least one species.