JPS60197753A - Stabilized halogen-containing resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which does not suffer discoloration at an initial stage and can withstand prolonged high-temperature processing, by adding a mercapto-organotin compd. and an extremely small quantity of an ortho-dihydric phenol to a halogen-contg. resin. CONSTITUTION:The titled compsn. is obtd. by adding an organotin compd. of formula I or II (wherein R1 is a 1-12C alkyl; R2 is a 1-18C alkyl, alkenyl, aralkyl, etc.; a is 1, 2; l is 1-10) such as dibutyltin bis(isooctyl thioglycolate) and 0.01-3wt% (based on the weight of the organotin compd.) ortho-dihydric phenol compd. of formula III [wherein R<3>-R<6> are each H, halogen, alkyl, aryl, amino, nitro, a group of formula IV (wherein R<7>, R<8> are each H, lower alkyl), etc., or R<3> and R<4>, R<4> and R<5> or R<5> and R<6> may be combined together to form (substd.) phenol] such as p-t-butyl-catechol to a halogen-contg. resin such as PVC.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to stabilized halogen-containing resin compositions.

...Various organotin stabilizers are used to stabilize rogen-containing resins. Compared to other organotin stabilizers (e.g. malate, laurate), mercapto-based organotin stabilizers are more effective in terms of initial coloring, especially in the very early stages.
It is widely used because it has excellent thermal stability. However, halogen-containing resins containing mercapto-based organotin stabilizers rapidly become colored when exposed to high temperatures for long periods of time.

It has a tendency to decompose, and is particularly prone to discoloration 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 the thermal stability can be improved to some extent by using phenolic compounds, especially hindered phenols, but this compound actually inhibits the initial coloring property.

The present inventors conducted research to improve the above-mentioned drawbacks, and as a result, they added a mercapto-based organic tin compound and a very small amount of ortho-dihydric phenols to the halogen-containing resin to prevent coloring in the initial stage.

They discovered scales that could withstand long-term high-temperature processing and completed the present invention.

That is, 1 the present invention provides a halogen-containing resin (a) having the general formula FL'a Sn (8(CH2)mCOOR2)
a a or (in the formula, R1 is an alkyl group having 1 to 12 carbon atoms, R2 is an alkyl group, alkenyl group, aralkyl group, or alkoxyalkyl group having 1 to 18 carbon atoms, and a is an integer of 1 or 2. (b) General formula [13. )<4. R5 and R6 are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

an aralkyl group, an alkoxy group, an amino group, a pair consisting of R3 and R4, or a pair consisting of R4 and R5; or the pair consisting of R and R may be bonded to form a substituted or unsubstituted phenyl group. It is a stabilized halogen 8-button product characterized by adding ~3% by weight.

Examples of the orthonihydric phenol compound of the above general formula to be added in the present invention include catechol p-t-phthalate, catechol, P-methylcatechol, m-ethylcatechol, P-methoxycatechol, P-propoxycatechol, and P-hexoxycatechol. Catechol, P-cyclohexylcatechol m-chlorocatechol, p-chlorocatechol P-bromocatechol, P-phenylcatechol α
, β-dihydroxynaphthylcatechol, 2,2-di(
4,5-dihydroxyphenyl)propane.

Bis(4,5-dihydroxyphenyl)methanato is mentioned.

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(inoctylthioglycolate), Monobutyltin tris(isooctylthioglycolate), dibutyltinbis(isooctylthioglycolate).

Monooctyl a) +1 sr isona power -1! −old≦ne〃
11-late), dioctyltin bis(isooctylthioglycolate), monolauryltin tris(isooctylthioglycolate), dimethyltinbis(2-ethylhexylthioglycolate)'), monobutyltintris(2-ethylhexylthioglycolate) −
ethylhexyl thioacrylate), dibutyltin bis(
2-ethylhexylthiocricolate), monooctyltin tris(2-ethylhexylthioglycolate), dioctyltinbis(2-ethylhexylthioglycolate).

Monobutyltin tris (lauryl thioglycolate).

Dibutyltin bis(laurylthioglycolate).

Monooctyltin tris (C14-16 mixed alkyl thioglycolate), dioctyltin bis (C14-16 mixed alkyl thioglycolate), dibutyltin bis (oleyl thioglycolate), dibutyltin bis (benzyl thioglycolate), dibutyltin bis (Methoxyethoxyethylthioglycolate).

Dibutyltin bis(butoxythioglycolate).

Monobutyltin tris (isooctylmercaptopropionate), dibutyltin bis (inoctylmercaptopropionate), monooctyltin tris (inoctylmercaptopropionate).

Dioctyltin bis(isooctylmercaptopropionate), dibutyltin bis(benzylmercaptopropionate), dibutyltin bis(2-ethylhexylmercaptogropionate), dimethyltin mercaptogropionate polymer, dibutyltin mercapto Examples include propionate polymers, dioctyltin mercaptopropionate polymers, and the like. These organic tin compounds can be added singly or in combination of two or more.

The amount of orthonihydric 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 coloring properties and thermal stability will deteriorate, and -! If the amount is less than 0.01% by weight, the effects of the present invention cannot be fully exhibited.

Examples of the halogen-containing resins stabilized by the present invention include vinyl halide homopolymers such as vinyl chloride resin, vinyl bromide resin, and vinylidene chloride resin, as well as vinyl halides such as vinyl acetate, ethylene, propylene, styrene, etc. , isobutylene, vinylidene chloride, maleic anhydride, butadiene, isoprene, methyl methacrylate.

Copolymers such as those formed by polymerization with one or more comonomers such as acrylonitrile, dialkylmalates, and the like.

Examples include post-chlorinated vinyl chloride resin. In addition, halogen-containing resins, acrylonitrile, butadiene,
Styrene resin, methyl methacrylate, butadiene, styrene resin, 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, polymer blend resin with impact-improved resin such as chlorinated rubber, etc. can be mentioned.

For the halogen-containing resin composition of the present invention, known stabilizers 2 such as organotin compounds (malate type) are used.

laurate series, etc.), metal organic acid salts, epoxy compounds,
Organic surface phosphate ester, polyhydric alcohol.

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 ornihydric phenol as a stabilizer to a halogen-containing resin has excellent thermal stability even during long-term continuous processing at high temperatures. Moreover, since no coloring is observed at 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, "part" means part by weight, and "2%" means % by weight.

Example 1 A total of 2 dibutyltin bis(in-octylthioglycolate) and pt-butylcatechol was added to 100 parts of hinyl chloride resin (Geon 103EP-8, manufactured by Nippon Ceon Co., Ltd.).
1 part and stearic acid 0.2 parts, and kneaded for 3 minutes at 170°C using a test roll to give a thickness of 0.5I+0+I.
A sheet was created. Each sheet 2.5 cm x 2
．． After cutting into pieces of 5 cm in size, 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.

10...White 9...Slight yellow 7...
...Pale yellow 5...Yellow 3...Brown
1... Dark brown to black Table 1 Example 2 Hinyl chloride resin (Geon 103EP-8) 100
5 parts of methyl methacrylate-butadiene-styrene resin (Kane Ace B-12, manufactured by Kaneka Co., Ltd.), a total of 2 parts of the organic tin compounds and pyrocatechol shown in Table 2 below, and 0.2 parts of stearic acid were added to the mixture. Tests were conducted in the same manner as in Example 1 to examine thermal stability and early stage coloring properties.

The results are shown in Table 2.

Example 3 Vinyl chloride resin (Geon 103EP-8) 100
to the department.

A total of 2 parts of diptyltin bis(isooctylthioglycolate), orn dihydric phenol shown in Table 3 below or comparative hindered phenols, and 0.2 part of stearic acid were mixed, and the test was carried out in the same manner as in Example 1. The thermal stability and early stage coloring properties were investigated.

The results are shown in Table 3.

Table 3

Claims (1)

[Claims] A halogen-containing resin represented by the general formula % formula % (wherein R1 represents an alkyl group having 1 to 12 carbon atoms,
R is an alkyl group, alkenyl group, aralkyl group or alkoxyalkyl group having 1 to 18 carbon atoms, and a is 1
or an integer of 2, and t represents an integer of 1 to 10, respectively)
In stabilizing with an organotin compound represented by (b)
General formula [wherein R3, H4, R5 and R6 are hydrogen atoms, halogen atoms, alkyl groups, cycloalkyl groups + AlJ-al groups,
an aralkyl group, an alkoxy group, an amide group, a nitro group, a sulfonyl group, a hydroxymethylene group, and a pair consisting of R3 and R4, or a pair consisting of R4 and R5; or a pair consisting of R5 and R6 may be combined to form a substituted or unsubstituted phenyl group. A stabilized halogen-containing resin composition characterized by adding ~3% by weight.