JPH0370757A - Heat-resistant vinyl chloride-based resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in thermal stability without impairing its excellent heat resistance by incorporating a vinyl chloride/N- substituted maleimide copolymer with an epoxy compound solid at normal temperature. CONSTITUTION:Firstly, polymerization is made in the presence of a radicalgenerating catalyst between (A) 50-99wt.% of structural unit of vinyl chloride origin and (B) 1-50wt.% of structural unit stemmed from an N- substituted maleimide of the formula [R is 1-30C (substituted) aliphatic, alicyclic or aromatic hydrocarbon group] to produce a vinyl chloride/N-substituted maleimide copolymer. Thence, 100 pts.wt. of the copolymer is incorporated with (C) 0.1-10 pts.wt. of an epoxy compound solid at normal temperature (pref. with a melting point of >=70 deg.C), (D) 0.001-5 pts.wt. of a metallic salt of perchlorate as stabilizer (pref. with said metal classified as group IIa), (E) 0.01-10 pts.wt. of an organotin-based stabilizer, and (F) other ingredient(s) such as lubricating agent, thus obtaining the objective composition.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is applicable to underground electrical conduits, pipes such as hot water supply pipes, floppy disk jackets, sheets such as cash cards, films, injection molding, irregularly extruded bottom shapes, etc. This invention relates to heat-resistant vinyl chloride resin compositions used in industrial products, electrical parts, building material parts, automobile parts, etc.

[Conventional technology]

Vinyl chloride resin is inexpensive and has excellent weather resistance, moldability, and gas barrier properties, and has been widely used in films, sheets, and various molded products, but it has poor resistance to heat deformation. Because of its poor properties, it could not be used in fields that required heat resistance.

Therefore, it has been proposed to copolymerize vinyl chloride and N-substituted maleimide to improve its heat deformation resistance.

[Problems to be Solved by the Invention] Vinyl chloride/N-substituted maleimide copolymers have improved heat deformation resistance, but compared to vinyl chloride homopolymers,
Since the thermal stability and processability are extremely poor, the resin not only becomes noticeably colored during processing, but also has the disadvantage that its most important characteristic, mechanical strength, is also significantly reduced.

For this reason, among the stabilizers for vinyl chloride resin, stabilizers based on organic tin compounds, which have a particularly large thermal stabilizing effect, have been used in the past, but their effects are still insufficient, and even more effective. There is a strong desire to find a stabilizer with a large value, and several stabilizers have been proposed so far.

For example, JP-A No. 63-21054 proposes the combined use of an organotin stabilizer or lead-based stabilizer and a zeolite stabilizer, and JP-A No. 63-309549 proposes that a zeolite-based stabilizer be used in combination with an organotin stabilizer or a lead-based stabilizer. It has been proposed to use a methyltin mercaptide stabilizer, and also in JP-A-63-145351.
The publication proposes blending an organic tin compound and a lubricant with a vinyl chloride resin copolymerized with N-cyclohexylmaleimide.

However, even when these stabilizers were used, the effects were still not satisfactory.

Furthermore, in JP-A No. 63-235353, in order to improve the antistatic properties of vinyl chloride/N-substituted male ξ-do copolymers, an alkali metal salt of perchloric acid is used as an organotin-based stabilizer. Although it has been proposed that the alkali metal salt of perchloric acid be used alone, it does not show any stabilizing effect, and when used in combination with an organotin stabilizer, it may not stabilize the organotin stabilizer. Since this method did not improve the chemical effect, it could not solve the above problems.

[Means for solving problems]

The present inventors have discovered that without reducing the excellent heat resistance (heat deformation resistance) of the vinyl chloride/N-substituted maleic copolymer,
As a result of intensive studies to improve thermal stability, which is its biggest drawback, we found that by adding an epoxy compound that is solid at room temperature, thermal stability can be significantly improved without reducing heat resistance. The authors discovered that an even more remarkable stabilizing effect can be achieved by using, if necessary, a Group 11a metal salt of perchloric acid and/or an organotin stabilizer together with an epoxy compound that is solid at room temperature. invention has been achieved.

That is, the present invention comprises 50 to 50 structural units derived from vinyl chloride.
A heat-resistant product made by adding an epoxy compound that is solid at room temperature to a copolymer containing 99% by weight and 1 to 50% by weight of structural units derived from N-substituted maleimide represented by the following general formula (I). The present invention provides a polyvinyl chloride resin composition.

(In the formula, R represents a substituted or unsubstituted aliphatic, alicyclic, or aromatic hydrocarbon group having 1 to 3 carbon atoms.) Hereinafter, the present invention having the above-mentioned summary will be explained in more detail.

The vinyl chloride/N-substituted maleic acid copolymer used in the present invention is composed of vinyl chloride and the N
It can be produced by a well-known method such as polymerizing a -substituted maleimide in the presence of a radical-generating catalyst.

Examples of the N-substituted maleimide represented by the above formula (1) include N-butylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N- -t-butylmaleimide, N-hexylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(o,m,p)-)lylmaleimide, N-(o,m,p) -Hydroxyphenylmaleimide, N(01m,p)-methoxyphenylmaleimide, N-(o,m,p)-chlorophenylmaleimide,
N-(o,m,p)-carboxyphenylmaleimide,
N-(o,m,p)-nitrophenylmaleimide, N-
Bicyclo-(2°2.1)-hebutan-1-yl-3-
Methyl maleate, N-9,10-ethano-9,10-
Examples include dihydroanthracen-2-ylmaleimide and N-triphenylmethylmaleimide, and in particular N-
N-alkylmaleimides such as isopropylmaleimide, Nt-butylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide are preferred.

The content of components derived from vinyl chloride in the vinyl chloride/N-substituted maleimide copolymer used in the present invention is 50 to 99% by weight, more preferably 70 to 95% by weight.
The content of the component derived from N-substituted maleimide is 1 to 50% by weight, more preferably 5 to 30% by weight.

If the content of the component derived from N-substituted maleimide is less than 1% by weight, the heat resistance of the copolymer will not be sufficiently improved, and if it exceeds 50% by weight, the melting temperature of the copolymer will be high. Too much, making molding difficult.

In addition, the copolymer of the present invention can also contain a small amount of other copolymerizable monomer units within a range that does not impair its heat resistance, and in that case, vinyl chloride units and N
-The substituted maleic main unit must be within the above range. Examples of such copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl caproate; olefins such as ethylene, propylene, butene, and isobutylene; vinyl ethers such as isobutyl vinyl ether and octyl vinyl ether; vinylidene chloride;
Halogenated olefins such as hookah vinyl; acrylic acid or methacrylic acid esters such as ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate; acrylonitrile, acrylic acid, methacrylic acid, crotonic acid, Examples include unsaturated nitriles or carboxylic acids such as maleic anhydride and itaconic anhydride.

Examples of epoxy compounds that are solid at room temperature and used as stabilizers in the present invention include tris(epoxyprobyl).
Isocyanurate (d point 90-125°C), hydroquinone diglycidyl ether (melting point 80-120°C)
, terephthalic acid diglycidyl ester (melting point 108°C
), 4,4'-sulfobisphenol polyglycidyl ale (melting point 119-167"C), N-glycidyl phthalimide (melting point 95-99"C), melting point 90-12
0''C glycidyl (meth)acrylate resin, 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, and ethyl methacrylate. , 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, methacrylate trile, ethylene, vinyl acetate, etc. Epoxy compounds having a melting point of 50°C or higher, especially 70'C or higher are particularly preferred.

Examples of the above-mentioned glycidyl (meth)acrylate resin having a melting point of 90 to 120'C include glycidyl methacrylate (C, MA) homopolymer, GMA/methyl methacrylate (MMA) copolymer (75:25) ,
GMA/MMA copolymer (50:50), GMA/MM
A copolymer (25:75), GMA/ethyl methacrylate (HMA) copolymer (75:25), GMA/methyl acrylate (MA) copolymer (75j 25),
GMA/MA copolymer (80: 20), GMA/ethyl acrylate (EA) copolymer (75: 25),
GMA/styrene (St) copolymer (60:40), G
MA/S-t/MMA copolymer (30: 40: 3
0), CMA/S t/MMA copolymer (15:50:
35), GMA/St/MMA/EA copolymer (30
: 24 : 23 : 23L GMA/acrylonitrile (AN)/St copolymer (10:45:45),
GMA/AN/St copolymer (20: 40: 40
), glycidyl acrylate (GA) homopolymer, GA
/M M A copolymer (50:50), etc., and these have a number average molecular weight of about 3000 or more.

Epoxy compounds that are liquid at room temperature, such as ordinary diglycidyl ether of isopropylidene diphenol, are
In contrast to lowering the heat distortion temperature of N-substituted maleimide copolymers, these epoxy compounds that are solid at room temperature are extremely specific in that they do not lower the heat distortion temperature and yet significantly improve thermal stability. This has the following effects.

The amount of these epoxy compounds that are solid at room temperature to be added is 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride/N-substituted maleimide copolymer.

In addition, along with the epoxy compound of the present invention that is solid at room temperature,
By using a metal salt of perchloric acid and/or an organotin-based stabilizer together, these act synergistically and significantly improve the thermal stability of the copolymer, which requires a high degree of thermal stability. In such cases, it is preferable to use these in combination.

Examples of metal salts of perchloric acid include Group 1a metal salts such as sodium, potassium, and lithium; Group 11a metal salts such as calcium, magnesium, and barium; zinc salts; and aluminum salts. In addition, perchloric acid-treated hydrotalcite obtained by treating basic inorganic double salts such as hydrotalcite and zinc-modified hydrotalcite with perchloric acid can also be used. Among the salts, Group 11a metal salts are particularly preferred because they have a large stabilizing effect.

The amount of these perchlorate metal salts added is vinyl chloride/N-
0.00 parts by weight of substituted male-based copolymer
The amount is 1 to 5 parts by weight, more preferably 0.01 to 3 parts by weight.

Further, examples of the organic tin 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; carboxylates such as octoates, laurates, malate-laurates, stearates, isostearates, crotonates, oleates, basic laurates of dialkyltin:
Cyclic maleates or maleate polymers of dialkyltin; ester malates such as butyl maleate, octyl maleate, maleate-octyl maleate, stearyl maleate, oleyl maleate, basic butyl maleate, etc. of dialkyl tin: mono- or dialkyl tin octyl mercaptides , lauryl mercaptide, stearyl mercaptide and other alkyl mercaptides: mono- or dialkyltin isooctylthioglycolate, 2-ethylhexylthioglycolate, tetradecylthioglycolate, isooctylthioglycolate-sulfide Thioglycolic acid ester salts such as mono- or dialkyltin isooctylthiopropionate, 2-ethylhexylthiopropionate, tetradecylthiopropionate, etc.; mono- or dialkyltin 2 Examples include mercaptoethanol ester salts such as -mercaptoethyl oleate salts, and among these organotin stabilizers, malate, ester malate, and thiocarboxylic acid ester salt stabilizers are particularly preferred.

The amount of these organotin stabilizers added is vinyl chloride/N-
0.01 per 100 parts by weight of substituted maleimide copolymer
~10 parts by weight, more preferably 0.1 to 5 parts by weight.

In addition, the composition of the present invention includes metal soaps such as calcium, magnesium barium, zinc, and lead salts of organic carboxylic acids such as octylic acid, lauric acid, stearic acid, benzoic acid, and toluic acid; hydrotalcite; Inorganic metal salts such as higher fatty acids such as stearic acid, higher alcohols such as stearyl alcohol, waxes such as montan wax, paraffin wax, polyethylene wax, stearamide, methylene bis stearate, ethylene bis stearate, etc. A lubricant such as amides such as ξ-do can also be added, and if necessary, a pigment, dye, filler, antistatic agent, flame retardant, etc. can also be added.

〔Example〕

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

The type and content (% by weight) of N-substituted maleimide in the vinyl chloride/N-substituted maleimide copolymer used in each example are shown below.

Example-1 100 parts by weight of vinyl chloride/N-substituted maleic acid copolymer, 0.5 parts by weight of stearyl alcohol, 0.3 parts by weight of polyethylene wax, and 3 parts by weight of diglycidyl terephthalate (Example 1-1 to 1-6) or 3 parts by weight of epoxidized soybean oil (Comparative Examples 1-1 to 1-6),
A sheet was prepared by kneading with a roll at 0°C.

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

In addition, a test piece was prepared by pressing this sheet at 190"C for 4 minutes, and the Vicat softening point of this test piece was determined according to JIS
Measured according to K-6740.

The results are shown in Table 1 below.

Table 1 Example 2 In order to see the effect of using the epoxy compound of the present invention, which is solid at room temperature, and an organotin stabilizer in combination, vinyl chloride/N-
100 parts by weight of substituted maleimide copolymer (Nα4), 2 parts by weight of dioctyltin bis(isooctylthioglycolate), 1 part by weight of dioctyltin maleate polymer, 0.5 parts by weight of stearyl alcohol, 0 parts by weight of polyethylene wax.
．． Add 3 parts by weight and 1 part by weight of epoxy compound,
A sheet was prepared by kneading with a roll at 0°C.

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

In addition, this sheet was pressed at 190°C for 4 minutes to prepare a test piece, and the Vicat softening point of this test piece was determined according to JIS
Measured according to K-6740.

The results are shown in Table 2 below.

Table 2 Table 3 Example 3 In order to see the effect of using the epoxy compound of the present invention, which is solid at room temperature, and metal perchlorate together, vinyl chloride/N-
100 parts by weight of substituted maleimide copolymer (Nα4), 0.05 parts by weight of metal perchlorate, and 0 parts by weight of stearyl alcohol.
．． 5 parts by weight, 0.3 parts by weight of polyethylene wax, and 2 parts by weight of tris(2,3-epoxyprobyl) isocyanurate.
Parts by weight (Examples 3-1 to 3-5) or 2 parts by weight of 4,4'-isopropylidene diphenol diglycidyl ether (Comparative Examples 3-1 to 3-3) were added, and the roll was heated at 190°C. A sheet was prepared by kneading.

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

In addition, a test piece was prepared by pressing this sheet at 190°C for 4 minutes, and the Picat softening point of this test piece was determined according to JIS
Measured according to K-6740.

The results are shown in Table 3 below.

Example 4 In order to examine the effect of using together the epoxy compound of the present invention that is solid at room temperature, a metal perchlorate, and an organotin stabilizer, a vinyl chloride/N-substituted maleimide copolymer ( N
a4) 100 parts by weight, 0.5 parts by weight of stearyl alcohol, 0.3 parts by weight of polyethylene wax, 0.05 parts by weight of barium perchlorate, 0.3 parts by weight of dibutyltin bis(butyl maleate), and 1 part by weight of an epoxy compound. was added and 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.

In addition, a test piece was prepared by pressing this sheet at 190°C for 4 minutes, and the Picat softening point of this test piece was determined according to JIS
Measured according to K-6740.

The results are shown in Table 4 below.

Table 4 [Effects of the Invention] From the results of each example, the epoxy compound of the present invention, which is solid at room temperature, has an extremely large effect on improving the thermal stability of vinyl chloride/N-substituted maleic copolymer. , it is clear that the copolymer has characteristics that do not lower the softening point of the copolymer.

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 the vinyl chloride/N-substituted maleic copolymer, thereby stabilizing the copolymer. It is not suitable as a drug.

It is also clear that the thermal stabilizing effect of the epoxy compound of the present invention, which is solid at room temperature, is further improved by using it in combination with a metal perchlorate and/or an organotin stabilizer.

Claims (5)

[Claims] (1) 50 to 99% by weight of structural units derived from vinyl chloride
and a heat-resistant chlorinated copolymer containing 1 to 50% by weight of an N-substituted maleimide represented by the following general formula (I), and an epoxy compound that is solid at room temperature. Vinyl resin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R represents a substituted or unsubstituted aliphatic, alicyclic, or aromatic hydrocarbon group having 1 to 30 carbon atoms.) (2) The composition according to claim (1), wherein a metal salt of perchloric acid is added together with an epoxy compound that is solid at room temperature. (3) The composition according to claim (2), wherein the metal salt of perchloric acid is a group IIa metal salt of perchloric acid. (4) The composition according to claim (1), wherein an organotin stabilizer is added together with an epoxy compound that is solid at room temperature. (5) Claim (1) in which a metal salt of perchloric acid and an organotin stabilizer are added together with an epoxy compound that is solid at room temperature.
).