JPH03122149A - Vinyl chloride-based resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a stabilized rigid or semi-rigid vinyl chloride resin composition, and more particularly to an epoxy compound and a perchlorate metal salt that are solid at room temperature. This invention relates to a hard or semi-hard vinyl chloride resin composition stabilized by the addition of.

[Conventional technology and problems]

Vinyl chloride resin is inexpensive, has excellent weather resistance, moldability, and gas barrier properties, and has been widely used in films, sheets, and various molded products. During processing, it is prone to thermal decomposition mainly due to dehydrochlorination, which causes a decrease in the mechanical properties and color tone of the processed product, resulting in significant disadvantages. In order to avoid such disadvantages, it is necessary to add one or more kinds of heat stabilizers to the vinyl chloride resin to suppress deterioration during processing steps.

Conventionally, various organic acid metal salts, organic tin compounds, and the like have been used for this purpose. As a result, almost satisfactory results were obtained in terms of thermal stability.

However, in recent years, these metal salts, especially cadmium salts and lead salts, have serious toxicity problems and their use has been restricted.

For this purpose, it has been proposed to use various combinations of various metal salts other than cadmium salts or lead salts, such as Ba/Zn type, Ca/Zn type, Ba/Ca/Zn type, etc. However, the performance of these combinations is still not sufficient (the use of various stabilizing aids, such as epoxy compounds, polyhydric alcohols, organic phosphorus compounds, organic sulfur compounds, phenolic compounds, β-diketone compounds, etc.) has been proposed. However, it was still not sufficient and further improvements were desired.

In addition, although the combination of the metal salt and epoxidized soybean oil has a certain degree of thermal stabilization effect,
It has the disadvantage of lowering the softening point when a hard or semi-hard vinyl chloride resin is blended. Furthermore, aminocrotonic acid esters have poor compatibility with vinyl chloride resins and tend to form plumes. Furthermore, although dehydroacetic acid improves the initial coloration, it does not have a long-term stabilizing effect.

[Means for Solving the Problems] As a result of intensive studies to improve the thermal stability, which is a drawback of rigid or semi-rigid vinyl chloride resins, the present inventors have developed an epoxy compound that is solid at room temperature and The inventors have discovered that thermal stability can be significantly improved by using metal perchlorate in combination, and have thus arrived at the present invention.

That is, in the present invention, 0.00 parts by weight of an epoxy compound that is solid at room temperature is added to 100 parts by weight of vinyl chloride resin. The present invention provides a stabilized vinyl chloride resin composition containing 1 to 5 parts by weight of t1 to 5 parts by weight and 0.01 to 5 parts by weight of a metal perchlorate.

Hereinafter, the present invention having the above-mentioned summary will be explained in more detail.

Examples of epoxy compounds that are solid at room temperature and used as stabilizers in the present invention include tris(epoxyprobyl).
Isocyanurate (melting point 90-125°C), hydroquinone diglycidyl ether (melting point 80-120°C)
, terephthalic acid diglycidyl ester (melting point 108°C
), 4,4'-sulfobisphenol polyglycidyl ether (melting point 119-167°C), N-glycidyl phthalimide (melting point 95-99°C), melting point 90-
Glycidyl (meth)acrylate resin at 120°C,
For example, a polymer of at least one of glycidyl acrylate and glycidyl methacrylate, or a polymer of at least one of glycidyl acrylate and glycidyl methacrylate, and methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
with at least one copolymerizable monomer selected from alkyl (meth)acrylates such as butyl acrylate and butyl methacrylate, aromatic vinyl compounds such as styrene and α-methylstyrene, acrylonitrile, methacrylatrile, ethylene, vinyl acetate, etc. Examples include copolymers, and epoxy compounds having a melting point of 50°C or higher, particularly preferably 70°C or higher, are preferred.

In addition, glycidyl (meth) having a melting point of 90 to 120°C
Examples of the acrylate resin include glycidyl methacrylate (GMA) homopolymer, GMA/methyl methacrylate (MMA) copolymer (75:25), G
MA/MMA copolymer (50:50), GMA/M
MA copolymer (25 near 5), GMA/ethyl methacrylate (EMA) copolymer (75: 25), GMA
/ methyl acrylate (MA) copolymer (75: 25
), GMA/MA copolymer (80: 20), GMA/
Ethyl acrylate (EA) copolymer (75:25),
GMA/styrene (SL) copolymer (60:40), G
MA/S t/MMA copolymer (30:40:30)
, GMA/S t/MMA copolymer (15; 50:35
) GMA/St/MMA/EA copolymer (30:2
4:23:23), GMA/acrylonitrile (AN)
/S as a copolymer (10:45:45), (1,M
A/AN/S copolymer (20:40:40), glycidyl acrylate (1111; A) homopolymer, G
Examples include A/M M A copolymers (50:50), which have a number average molecular weight of about 3,000 or more.

Epoxy compounds that are liquid at room temperature, such as ordinary diglycidyl ether of isopropylidene diphenol, lower the heat distortion temperature of rigid or semi-rigid vinyl chloride resins, whereas these epoxy compounds that are solid at room temperature lower the heat distortion temperature of rigid or semi-rigid vinyl chloride resins. It has a very unique effect in that it does not lower the temperature and also significantly improves thermal stability.

The amount of these epoxy compounds that are solid at room temperature is 0.1 to 5 parts by weight per 100 parts by weight of vinyl chloride resin.
More preferably, it is 0.3 to 5 parts by weight.

In addition, examples of metal salts of perchloric acid used in combination with the epoxy compound that is solid at room temperature of the present invention include Group 1a metal salts such as sodium, potassium, and lithium;
Examples include Group Ia metal salts such as magnesium and barium, zinc salts, aluminum salts, etc., and peroxychloride obtained by treating basic inorganic double salts such as hydrotalcite and zinc-modified hydrotalcite with perchloric acid. Chloric acid treatment No. 1
Hydrotalcite and the like can also be used, and among these perchlorate metal salts, group 1 [a metal salts are particularly preferred because they have a large stabilizing effect.

The amount of these metal perchlorates added is 0.01 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

In addition, the polyvinyl chloride resin used in the present invention includes vinyl chloride homopolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene vinyl acetate copolymer, vinyl chloride-ethylene copolymer, chloride Vinyl-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, vinyl chloride-acrylic acid ester copolymer , vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer , vinyl chloride-vinylidene chloride-vinyl acetate copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-maleimide copolymer, etc. Vinyl chloride copolymer, and α- of the above resins and polyethylene, polypropylene, polybutene, poly-3-methylbutene, etc.
Olefin polymers or polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resins, polyurethanes, styrene and other monomers (e.g. maleic anhydride, butadiene, Examples include copolymers with acrylonitrile (such as acrylonitrile), acrylonitrile-styrene-butadiene copolymers, aster acrylate-styrene-butadiene copolymers, and blends with methacrylic ester-styrene-butadiene copolymers.

These vinyl chloride resins may be obtained by any conventionally known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, etc.

Furthermore, by adding metal salts of carboxylic acids, organophosphoric acids, or phenols, or organotin stabilizers to the vinyl chloride resin composition of the present invention, the thermal stabilizing effect is further enhanced. Carboxylic acids, organic phosphoric acids or phenolic metals (Li, Na, K+ C
Examples of the carboxylic acids constituting the (a, Ba, Mg, Sr, Zn, Sn) salt include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid,
myristic acid, valmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, liluic acid, oleic acid, arachidic acid, behenic acid, Erucic acid, brassic acid and similar acids and naturally occurring mixtures of the above acids such as tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid acids, monohydric carboxylic acids such as isopropylbenzoic acid, toluic acid, xylic acid, salicylic acid, 5-t-octylsalicylic acid, naphthenic acid, cyclohexanecarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, superric acid, azelaic acid, cepatic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, etc. Examples include monoesters of dicarboxylic acids.

Examples of organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di(nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, etc. .

Furthermore, examples of phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, and dodecylphenol.

Further, examples of the organotin stabilizer include mono- or dialkyltin compounds such as mono- or dimethyltin-, mono- or diptylstin-, or mono- or dioctyltin compounds, and more specifically, mono- or dialkyltin compounds. sulfides, oxides or sulfide-oxides; dialkyltin octoates, laurates, malatelaurates, stearates, isostearates,
Carboxylates such as crotonate, oleate, basic laurate; cyclic maleates or maleate polymers of dialkyltin; butylmalate, octylmalate, maleate-octylmalate, stearylmalate, oleylmalate, basic butylmalate, etc. of dialkyltin; ester malates; alkyl mercaptides such as mono- or dialkyltin octyl mercaptide, lauryl mercaptide, stearyl mercaptide; mono- or dialkyl tin isooctyl thioglycolates;
Thioglycolic acid ester salts such as 2-ethylhexylthioglycolate, tetradecylthioglycolate, isooctylthioglycolate-sulfide; mono- or dialkyltin isooctylthiopropionate, 2-
Examples include thiopropionic acid ester salts such as ethylhexylthiopropionate and tetradecylthiopropionate; mercaptoethanol ester salts such as mono- or dialkyltin 2-mercaptoethyl oleate salts;
Among these organotin stabilizers, malate, ester malate, and thiocarboxylic acid ester salt stabilizers are particularly preferred.

The amount of these carboxylic acids, organic phosphoric acids, metal salts of phenols, or organic tin stabilizers added is 0.01 to 10 parts by weight, per 100 parts by weight of vinyl chloride resin.
More preferably, it is 0.1 to 5 parts by weight.

In addition, the composition of the present invention includes inorganic metal salts such as hydrotalcite; higher fatty acids such as stearic acid, higher alcohols such as stearyl alcohol, waxes such as montan wax, paraffin wax, and polyethylene wax; stearamide; It is also possible to add lubricants such as amides such as methylene bis stearamide and ethylene bis stearamide, and if necessary, pigments, dyes, fillers, antistatic agents, flame retardants, etc. can be added. You can also do it.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 (Formulation) PVC (Geon 103EP-8)
100 parts by weight stearyl alcohol 0.
5 Polyethylene wax 0/3 engineering poxy compound (Table-1) 1. .

Barium perchlorate 0. 1 The above blend was kneaded with a roll at 190°C to produce a sheet.

This sheet was placed in a gear oven at 190°C, and the thermal stability (time until significant discoloration) was measured.

Further, this sheet was pressed at 190"C for 4 minutes to prepare a test piece, and this test piece was J [S K6740
The Vicat softening point was measured according to the method.

The results are shown in Table 1 below.

Table-1 Montanic acid wax 0, 2 Perchloric acid metal salt (Table-2) 0.1 The above blend was kneaded with a roll at 190°C to prepare a sheet.

This sheet was subjected to the same test as in Example 1, and the results are shown in Table 2 below.

Table-2 *1: NOF glycidyl methacrylate resin example-2 (composition) PVC (Geon 103-EP) 1
00 parts by weight stearyl alcohol 0.3
Example 3 In order to see the effect of using together the epoxy compound of the present invention which is solid at room temperature, metal perchlorate and organotin stabilizer, the following formulation was kneaded with a roll at 190°C. A sheet was prepared.

This sheet was subjected to the same test as in Example 1, and the results are shown in Table 3 below.

(Composition) PVC (TK-1000) 100
Part by weight Stearyl alcohol 0.3 Polyethylene wax 0.3 Blemmer C
P-50M 1.5 barium perchlorate
0.15 Organotin compounds (Table 3)
0.3 Table-3 Example-4 With the following formulation, a sheet was prepared by kneading with a roll in the same manner as in Example 1. This sheet was subjected to the same test as in Example 1, and the results are shown in Table-4. show.

(Composition) PVC (S-1008) 10
0 parts by weight M B-3 resin 10
Oxidized polyethylene wax Montanic acid wax Epoxy compound (Table 4) Barium perchlorate Table 4 Extremely effective in improving the thermal stability of rigid or semi-rigid vinyl chloride resins, and also lowers the softening point of the copolymer. It is clear that it has characteristics that prevent it from occurring.

On the other hand, epoxy compounds that are liquid at room temperature not only have a small effect on improving thermal stability but also lower the softening point of vinyl chloride resins, making them unsuitable as stabilizers for vinyl chloride resins.

Claims (1)

[Claims] A vinyl chloride resin obtained by adding 0.1 to 5 parts by weight of an epoxy compound that is solid at room temperature and 0.01 to 5 parts by weight of a metal perchlorate to 100 parts by weight of a hard or semi-hard vinyl chloride resin. Composition.