JPS6157339B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to stabilized chlorine-containing resin compositions. Various organotin stabilizers have been used to stabilize halogen-containing resins. Compared to other organotin stabilizers (e.g. malate and laurate), mercapto-based organotin stabilizers are widely used because they are effective in terms of initial coloring, especially in the very early stages, and have excellent thermal stability. It's being used. However, halogen-containing resins containing mercapto-based organotin stabilizers rapidly become colored when exposed to high temperatures for long periods of time.
It tends to decompose, and is particularly prone to coloring and decomposition when continuously performing long-term high-temperature processing (e.g., extrusion, injection, rolling, and press processing), and is likely to cause coloration at a relatively early stage. There are some shortcomings. Therefore, it is known that phenolic compounds, particularly hindered phenols, can be used in combination to improve thermal stability to some extent, but these compounds actually inhibit initial coloring. As a result of research to improve the above-mentioned drawbacks, the present inventors added a mercapto-based organotin compound and a very small amount of ortho-divalent phenols to the chlorine-containing resin, thereby preventing coloring in the initial stage and allowing long-term use. They discovered that it could withstand high temperature processing and completed the present invention. That is, the present invention provides a chlorine-containing resin having the general formula R ¹ _a Sn[S(CH ₂ ) _n COOR ² ] _4-a or (In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms,
alkenyl group, aralkyl group or alkoxyalkyl group, a is an integer of 1 or 2, m is 1 or 2
(b) is an integer of 1 to 10.
general formula [In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, amino groups, nitro groups, sulfonyl groups, hydroxymethylene groups, and base (where R ⁷ or R ⁸ represents a hydrogen atom or a lower alkyl group), and R ³ and
The pair consisting of R ⁴ , the pair consisting of R ⁴ and R ⁵ , or the pair consisting of R ⁵ and R ⁶ may be bonded to form a substituted or unsubstituted phenyl group] This is a stabilized chlorine-containing resin composition characterized in that the compound is added in an amount of 0.01 to 3% by weight based on the organotin compound alone or as a mixture. Ortho 2 of the above general formula added in the present invention
Examples of the valent phenol compounds include catechol, p-t-butylcatechol, p-methylcatechol, m-ethylcatechol, p-methoxycatechol, p-propoxycatechol, p-hexoxycatechol, p-cyclohexylcatechol, m-chloro Catechol, p-chlorocatechol, p-bromocatechol, p-phenylcatechol, α,β-dihydroxynaphthylcatechol, 2,2-di(4,5-dihydroxyphenyl)propane, bis(4,5-dihydroxyphenyl) enyl)methane, etc. Examples of the organic tin compounds of the above general formula to be added in the present invention include dibutyltin bis(butylthioglycolate), monomethyltin tris(isooctylthioglycolate), dimethyltinbis(isooctylthioglycolate), monobutyltinbis(isooctylthioglycolate), Tin tris (isooctylthioglycolate), dibutyltin bis(isooctylthioglycolate),
Monooctyltin tris(isooctylthioglycolate), dioctyltinbis(isooctylthioglycolate), monolauryltintris(isooctylthioglycolate), dimethyltinbis(2
-ethylhexylthioglycolate), monobutyltin tris(2-ethylhexylthioglycolate), dibutyltin bis(2-ethylhexylthioglycolate), monooctyltin tris(2-ethylhexylthioglycolate), dioctyltin bis(2-ethylhexylthioglycolate), ethylhexylthioglycolate),
Monobutyltin tris (lauryl thioglycolate), dibutyltin bis (lauryl thioglycolate), monooctyltin tris ( _C14 ~ ₁₆ mixed alkyl thioglycolate), dioctyltin bis (C14~ ₁₆ )
₁₆ mixed alkyl thioglycolate), dibutyltin bis(oleyl thioglycolate), dibutyltin bis(benzyl thioglycolate), dibutyltin bis(methoxyethoxyethyl thioglycolate), dibutyltin bis(butoxythioglycolate), monobutyl Tin tris(isooctylmercaptopropionate), dibutyltin bis(isooctylmercaptopropionate), monooctyltin tris(isooctylmercaptopropionate), dioctyltin bis(isooctylmercaptopropionate), dibutyl Tin bis(benzylmercaptopropionate), dibutyltin bis(2-ethylhexylmercaptopropionate), dimethyltin mercaptopropionate polymer, dibutyltin mercaptopropionate polymer, dioctyltin mercaptopropionate polymer, etc. I can do it. These organic tin compounds can be added singly or in combination of two or more. The amount of ortho dihydric phenol added in the present invention is 0.01 to 3% by weight based on the organic tin compound. If the amount added exceeds 3% by weight, both initial colorability and thermal stability will deteriorate, and if it is less than 0.01% by weight, the effects of the present invention cannot be fully exhibited. Examples of the chlorine-containing resins stabilized according to the present invention include chlorinated vinyl homopolymers such as vinyl chloride resin and vinylidene chloride resin, and chlorinated vinyl homopolymers such as vinyl acetate, ethylene, propylene, styrene, isobutylene, and vinylidene chloride. ,
Copolymers, post-chlorinated vinyl chloride, as formed by polymerization with one or more comonomers such as maleic anhydride, butadiene, isoprene, methyl methacrylate, acrylonitrile, dialkylmalates and the like. Examples include resin. In addition, chlorine-containing resins, acrylonitrile/butadiene/styrene resins, methyl methacrylate/butadiene/styrene resins,
Acrylonitrile/chlorinated polyethylene/styrene copolymer resin, acrylic rubber/acrylonitrile/styrene copolymer resin, acrylic rubber/methyl methacrylate/acrylonitrile copolymer resin, vinyl acetate/ethylene copolymer resin, chlorinated polyethylene, chlorinated rubber Examples include polymer blend resins with impact-improving resins such as. For the halogen-containing resin composition of the present invention, known stabilizers, such as organotin compounds (malate,
laurate series, etc.), metal organic acid salts, epoxy compounds, organic phosphite esters, polyhydric alcohols,
UV absorbers can be added. A lubricant and a processing aid can also be used if necessary. According to the present invention, a resin composition obtained by adding a sulfur-containing organotin compound and a very small amount of ortho divalent phenol as a stabilizer to a chlorine-containing resin has excellent thermal stability even during long-term continuous processing at high temperatures. Moreover, since no coloring is observed in all initial stages, it can be used as a product in a wide range of fields. Next, the present invention will be explained with reference to Examples. In addition,
In the examples, parts indicate parts by weight, and percentages indicate weight %. Example 1 A total of 2 parts of dibutyltin bis(isooctylthioglycolate) and pt-butylcatechol and 0.2 parts of stearic acid were mixed into 100 parts of vinyl chloride resin (Geon103EP-8, manufactured by Zeon Corporation) and tested. After kneading with a roll for 3 minutes at 170℃, the thickness
A 0.5mm sheet was created. Each sheet is 2.5cm x 2.5
After cutting into cm-sized pieces, they were placed in a gear aging tester at 195°C to examine thermal stability and early stage coloration. The results are shown in Table 1. Note that the numbers in Table 1 indicate the following evaluations. The same applies to the table below.

【table】

[Table] Example 2 100 parts of vinyl chloride resin (Geon103EP-8), 5 parts of methyl methacrylate-butadiene-styrene resin (Kane Ace B-12, manufactured by Kaneka Co., Ltd.), and the following 2
A total of 2 parts of the organotin compound and pyrocatechol shown in the table and 0.2 part of stearic acid were mixed, and a test was conducted in the same manner as in Example 1 to examine thermal stability and coloring property in the initial stage. The results are shown in Table 2.

【table】

[Table] Example 3 To 100 parts of vinyl chloride resin (Geon103EP-8),
A total of 2 parts of dibutyltin bis(isooctylthioglycolate), ortho divalent phenols shown in Table 3 below or comparative hindered phenols, and 0.2 parts of stearic acid were mixed, and the test was conducted in the same manner as in Example 1. , the thermal stability and early stage colorability were investigated. The results are shown in Table 3.

【table】

Claims (1)

[Claims] 1 A chlorine-containing resin having the general formula R ¹ _a Sn[S(CH ₂ ) _n COOR ² ] _4-a or (In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms,
alkenyl group, aralkyl group or alkoxyalkyl group, a is an integer of 1 or 2, m is 1 or 2
(b)
general formula [In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, amino groups, nitro groups, sulfonyl groups, hydroxymethylene groups, and base (where R ⁷ or R ⁸ represents a hydrogen atom or a lower alkyl group), and R ³ and
A pair consisting of R ⁴ , a pair consisting of R ⁴ and R ⁵ , or a pair consisting of R ⁵ and R ⁶ may be bonded to form a substituted or unsubstituted phenyl group] A stabilized chlorine-containing resin composition characterized in that a phenol compound is added in an amount of 0.01 to 3% by weight based on the organotin compound alone or as a mixture.