JPS592702B2 - Chlorine-containing resin composition - Google Patents

Description

[Detailed Description of the Invention] The present invention has extremely little plate-out during molding.
The present invention relates to a chlorine-containing resin composition with good thermal stability.

As is well known, chlorine-containing resins are degraded by heat and light.

In order to prevent this resin from deteriorating, metal soap, an organic tin stabilizer, an epoxy compound, an organic phosphite, an antioxidant, etc. are added to the resin 10 during the molding process. Among these, organotin stabilizers have excellent thermal stabilizing effects and are therefore widely used when molding hard products that are subjected to especially severe heating conditions. Among organotin stabilizers, especially organotin maleate polymers and organotin alkyl maleates 15
Organotin maleate stabilizers such as Boku are widely used. However, these chlorine-containing resins containing organotin maleate stabilizers have the disadvantage of causing a partial plate-out phenomenon that contaminates the metal surface of the processing machine during molding.

When plate-out occurs, it not only contaminates the product and impairs its appearance, but also reduces work efficiency due to the additional work required to remove the deposits, further impeding the transparency of the product and making it difficult to process laminates, etc. Problems caused by plate-out are extremely large, such as deterioration of lamination properties during processing and deposition properties during processing of the vapor-deposited film. Patent No. 81893 is a method to prevent this drawback of plate-out occurrence.
No. 4 (Special Publication No. 48-38766), Japanese Patent Publication No. 132-1973
No. 058, 30 JP-A-51-7051, JP-A-51-
No. 2Q251 and the like are publicly known.

These methods involve the combined addition of an organotin maleate stabilizer and phthalic acid, phthalic anhydride, phthalic acid monoester, 3-chlorophthalic anhydride, adipic acid, azelaic acid, stearic acid, etc.35. However, even with these methods, satisfactory results have not yet been obtained. The inventors of the present invention have conducted intensive research to improve these drawbacks, and as a result, they have found that a chlorine-containing resin is treated with an organotin maleate stabilizer and the general formula (1). These are a hydrogen atom, an allyl group, an alkyl group, a hydroxyalkyl group, a phenyl group, and an aralkyl group.

n is O or 1. ) The present invention has been completed by discovering a chlorine-containing resin composition that exhibits extremely low plate-out and good thermal stability by adding at least one compound selected from the compounds represented by the following. Although there is no particular restriction on the ratio of the organotin maleate stabilizer and the sulfur-containing carboxylic acid, the preferred ratio is 2 to 50 parts by weight of the sulfur-containing carboxylic acid to the organotin maleate stabilizer.

The preferred amount of the organotin maleate stabilizer used is 0.5 to 5 parts by weight per 100 parts by weight of the chlorine-containing resin. The organotin maleate stabilizer used in the present invention is
dialkyltin maleates and their polymers, dialkyltin bis(alkyl, cycloalkyl or aralkyl maleate), and bis(dialkyltin monoalkyl, cycloalkyl or aralkyl maleate) maleate,
and its polymers, 2-bis(dialkyltin alkyl maleate) oxide, etc. Examples include monomers and polymers such as dimethyltin maleate, dibutyltin maleate, dioctyltin maleate, dilauryltin maleate, dimethyltin bis(butylmaleate) ), dimethyltin bis(lauryl maleate), dimethyltin bis(oleyl maleate), dibutyltin bis(butyl maleate)
, dibutyltin bis(benzyl maleate), dibutyltin bis(cyclohexyl maleate), dibutyltin bis(
2-ethyl-xyl maleate), dibutyltin bis(lauryl maleate), dibutyltin bis(oleyl maleate), dibutyltin bis(stearyl maleate), dibutyltin bis(3-methoxybutyl maleate), dibutyltin bis( ethylbenzyl maleate), dioctyltin bis(butyl maleate), dioctyltin bis(benzyl maleate), dioctyltin bis(2-ethylhexyl maleate), dioctyltin bis(oleyl maleate), dioctyltin bis(stearyl maleate) ate), dioctyltin bis(3-methoxybutyl maleate), dilauryltin bis(butyl maleate), and bis(dimethyltin butyl maleate) oxide, bis(dimethyltin isooctyl maleate) oxide, bis(dimethyltin lauryl maleate) maleate, bis(dimethyltin oleyl maleate) maleate, bis(dibutyltin butyl maleate) maleate, bis(dibutyltin2)
-Ethylhexyl maleate) maleate, bis(dibutyltin benzyl maleate) maleate, bis(dibutyltin cyclohexyl maleate) maleate, bis(dibutyltin lauryl maleate) maleate, bis(dibutyltin oleyl maleate) maleate, bis(dibutyltin oleyl maleate) maleate Tin 3-methoxybutyl maleate) maleate, bis(dioctyltin butyl maleate) maleate, bis(
Dioctyltin benzyl maleate) maleate, bis(
Dioctyltin 2-ethylhexyl maleate) maleate, bis(dioctyltin lauryl maleate) maleate, bis(dioctyltin oleyl maleate) maleate, bis(dilauryltin butyl maleate) maleate, polymers thereof Methyl octyltin bis(iso Examples include octyl maleate), methyl lauryltin bis(butyl maleate), dibutyltin butyl maleate and benzyl maleate. General formula (1) added in combination with these organotin maleate stabilizers. (),
To explain the sulfur-containing carboxylic acid represented by the formula, the group represented by R1 in the formula is a hydrogen atom, an allyl group, an alkyl group, a hydroxyalkyl group, a phenyl group, or an aralkyl group. The alkyl group is preferably a group having 1 to 18 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl, stearyl, and the like. Hydroxyalkyl groups include both linear and branched groups, with linear groups having 2 to 2 carbon atoms.
18 groups are preferred, and specific examples include hydroxyethyl, hydroxypropyl, hydroxyoctyl, hydroxydodecyl, hydroxystearyl and the like. The branched group preferably has a structure of -CH27HOH, and specific examples include one in which R2 has 8 to 18 carbon atoms and -CH2CH-0H.

The aralkyl group 151▲37 is preferably a group having 7 to 9 carbon atoms, and specific examples include benzyl, phenethyl,
Examples include β-phenylpropyl.

Specific examples of the sulfur-containing carboxylic acids represented by the general formulas (1) and () are shown below (1) to (to).

The chlorine-containing resin used in the present invention is mainly composed of vinyl chloride resin (hereinafter referred to as PVC), vinylidene chloride resin, chlorinated polyethylene, and vinyl chloride. Copolymers with one or more of ethyl acid, acrylonitrile, styrene, vinyl acetate, isobutylene, ethylene vinyl acetate, etc., and PVC
Blended resins of the resin and an impact-resistant reinforcing agent (for example, methyl methacrylate/butadiene/styrene copolymer resin, acrylonitrile/butadiene/styrene copolymer resin), etc. can be mentioned.

Known stabilizers other than organotin maleate stabilizers and sulfur-containing carboxylic acids used in the present invention, such as metal soaps, organotin sulfur compounds, organotin fatty acid salts, epoxidized soybean oil, epoxy resins, organophosphorous esters , antioxidants, ultraviolet absorbers, etc. can be used together.

Furthermore, if necessary, pigments, fillers, binders, antistatic agents, lubricants, flame retardants, processing aids, etc. can also be used in combination. Next, the present invention will be explained with examples, but the present invention is not limited thereto.

In the examples, parts represent parts by weight.

Example 1 Plate-out test PvCceOnlO3EP-8 manufactured by Nippon Zeon Co., Ltd.] 1
00 parts of dibutyltin maleate polymer (polymerization degree 3.5
) 2.0 pitch 0.1 part of the compound shown in [Table-1] and red pigment [Φ8040 red, manufactured by Dainichiseika Co., Ltd.] 1
．． After mixing 0 parts, the mixture was kneaded using a test roll at 175°C for 5 minutes, and the sheet was removed.

After this, the plate-out material adhering to the roll is removed using PVC.
100 parts of CGeOnlO3Ep manufactured by Nippon Zeon Co., Ltd., 25 parts of DOP (dioctyl phthalate), and titanium white [
A cleaning sheet was prepared by wiping a resin composition of 2.0 parts of TA-1001 (manufactured by Fuji Titanium Co., Ltd.), 1.0 part of dibutyltin dilaurate, and 0.3 parts of cadmium stearate while kneading. Plate out was determined based on the degree of red coloring of the cleaning sheet. In addition, the state of plate-out after kneading for 10 minutes was also observed in the same manner. These results are shown in [Table 1]. The plateout numbers in [Table 1] indicate the following conditions. No plate out (cleaning sheet is milky white) ・・・・・・1
There is a little plate out (the cleaning sheet is a light pick color)...2 plates out or a lot (the cleaning sheet is a pick color)
...3 Too many plates out (cleaning sheet is red) ...4 Thermal stability test PVCCGeOnlO3Ep-8] 2.0 parts of dibutyltin maleate polymer (degree of polymerization 3.5) in 1000 parts After mixing 0.1 part of the compound shown in Table 1, the mixture was kneaded with a test roll at 165°C for 5 minutes to a thickness of 0.5 mm.
A sheet was prepared.

After cutting this sheet into a size of 3CTfL x 6 (1771), the sheet was placed in a gear type aging tester preheated to 190°C to evaluate thermal stability.The sheet was taken out at regular intervals and the The degree of color deterioration of the sheet was observed with the naked eye, and the color of the sheet was determined to be colorless...A yellowish brown...
...C Yellow ... B Black ... Shown as D in [Table-1].

The numbers of the compounds in [Table 1] indicate the numbers in the above-mentioned specific example (1) to active.

Example 2 2.0 parts of dibutyltin maleate polymer (degree of polymerization 3.5) was added to 100 parts of PVC (GeOnlO3Ep-8).
The compounds shown in Table 2 were added in an amount of 0.01 to 0.5 parts, and plate-out and thermal stability tests were conducted in the same manner as in Example 1.

These results are shown in [Table 2]. Example 3 100 copies of PVCCGe0n103Ep-8 [Table 1 3
], 20 parts of the stabilizer shown in Example 1, 0.1 part of the compound, and, if necessary, 0.3 part of Hoechstwax 0P (manufactured by Hoechst AG, West Germany) as a lubricant, were plated out and heated in the same manner as in Example 1. A stability test was conducted.

These results are shown in [Table 3]. Stabilizers (a) to (d) in [Table 3] are as follows. (a) Dioctyltin maleate polymer (degree of polymerization 2.7) (b) dibutyltin bis(butyl maleate) (c) bis(dibutyltin benzyl maleate) oxide.

(d) Bis(dioctyltin methoxybutyl maleate)
Maleate.

Claims (1)

[Claims] 1 Organotin maleate stabilizers for chlorine-containing resins and general formulas (I), (II), ▲numerical formulas, chemical formulas, tables, etc.▼(I)R^1SCH_2COOH(II) ( In the formula, R_1 is a hydrogen atom, an allyl group, an alkyl group, a hydroxyalkyl group, a phenyl group, or an aralkyl group. n is 0 or 1. A chlorine-containing resin composition characterized by being formed by adding chlorine.