JP3316042B2 - Vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition and, more particularly, to a vinyl chloride resin composition which is obtained by adding a mixed alcoholic ester of pyromellitic acid and has a good gelling property and a remarkably improved heat resistance. The present invention relates to a resin composition.

[0002]

2. Description of the Related Art Vinyl chloride resins can be used from hard applications to soft applications by using plasticizers. However, especially in a soft formulation in which a relatively large amount of a plasticizer is blended,
There is a disadvantage that the plasticizer is degraded by heat or volatilized from the resin composition to cause deterioration in physical properties.

[0003] Applications requiring such heat resistance include:
Polyester carboxylic acid ester plasticizers such as polyester plasticizer, trimellitic acid, and pyromellitic acid are used, and pyromellitic acid ester is particularly excellent in heat resistance.

For example, US Pat. No. 3,218,289 proposes to add a mixed alcohol ester of pyromellitic acid having 6 to 8 carbon atoms to a polyvinyl chloride resin, as disclosed in JP-A-61-97248. Has proposed that an isononyl or isodecyl ester compound of pyromellitic acid is effective as a plasticizer for a vinyl chloride resin. However, the effect of improving the heat resistance of these vinyl chloride resin compositions is still insufficient.

Accordingly, it is an object of the present invention to provide a vinyl chloride resin composition having good gelling properties and extremely excellent heat resistance and cold resistance.

[0006]

Means for Solving the Problems The present inventors have made intensive studies and as a result, have found that the above object can be achieved by adding a specific mixed alcohol ester of pyromellitic acid to a vinyl chloride resin. I learned.

[0007] The present invention has been made based on the above-mentioned findings, and a vinyl chloride resin is represented by the following general formula (I):
It is intended to provide a vinyl chloride resin composition to which at least one kind of pyromellitic acid ester represented by the above formula (I) is added.

[0008]

Embedded image

Hereinafter, the vinyl chloride resin composition of the present invention will be described in more detail.

The vinyl chloride resin used in the present invention includes, for example, polyvinyl chloride, post-chlorinated polyvinyl chloride, polyvinylidene chloride, vinyl chloride-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-styrene-maleic anhydride terpolymer, vinyl chloride-alkyl , Cycloalkyl or arylmaleimide copolymer, vinyl chloride
Styrene-acrylonitrile copolymer, vinyl chloride-butadiene polymer, vinyl chloride-isoprene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer,
Vinyl chloride such as vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-urethane copolymer Resin and the above-mentioned vinyl chloride resin, and an α-olefin polymer such as polyethylene, polypropylene, polybutene and poly-3-methylbutene or a polyolefin such as an ethylene-vinyl acetate copolymer and an ethylene-propylene copolymer, and a copolymer thereof. Copolymer, polystyrene, acrylic resin, copolymer of styrene with other monomers (eg, maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymer, methacrylate-butadiene-styrene copolymer , Polyure Such as a blend of down products can be mentioned.

In the compound represented by the above general formula (I) used in the present invention, an alkyl having 4 to 12 carbon atoms represented by R ₁ , R ₂ , R ₃ and R ₄ in the general formula (I) Examples of the group include groups such as butyl, isobutyl, tert-butyl, amyl, tertiary amyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl and dodecyl. Of all the alkyl groups, 90% or more, preferably 95% or more are linear alkyl groups, of which 5 to 50%, preferably 5 to 30%, hexyl groups, and 20 to 70%, preferably, octyl groups. 30-60%, decyl groups occupy 20-70%, preferably 30-60%,
Other components are 5% or less.

The compound represented by the above general formula (I) used in the present invention has a linear ratio of 90% or more with pyromellitic acid, 5 to 50% hexanol, and 20 to 20% octanol.
It can be easily obtained by esterifying 70%, decanol occupying 20 to 70%, and a specific ratio of a mixed alcohol in which another alcohol component having 4 to 12 carbon atoms is 5% or less. A usual method is used for the esterification.

The amount of the compound represented by formula (I) used in the present invention is preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Department.

In the vinyl chloride resin composition of the present invention, together with the compound represented by the above formula (I) as a plasticizer, a plasticizer commonly used in vinyl chloride resins can be optionally used. . As such a plasticizer, for example,
Phthalate-based plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; Adipate plasticizers such as glycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate octyl diphenyl phosphate Such as phosphate plasticizers; polyvalent alcohol Ethylene glycol, diethylene glycol, triethylene glycol as Le, 1,2
Propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc., and oxalic acid as a dibasic acid , Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., using monohydric alcohol and monocarboxylic acid as stoppers if necessary Polyester plasticizer used; epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized safflower oil, epoxidized methyl stearate, -butyl, -2
-Ethylhexyl, -stearyl ester, epoxidized polybutadiene, epoxidized tall oil fatty acid ester,
Epoxy plasticizers such as epoxidized linseed oil fatty acid ester; other, tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid Plasticizers and the like.

The composition of the present invention may contain commonly used metal stabilizers. Examples of such metal stabilizers include lead stabilizers, calcium stabilizers, zinc stabilizers, and magnesium stabilizers. System stabilizer, barium system stabilizer,
Organic tin-based stabilizers and double salts thereof are exemplified.

The above-mentioned lead-based stabilizer includes, for example, lead white,
Basic lead silicate, basic lead sulfate, dibasic lead sulfate, tribasic lead sulfate, basic lead sulfite, dibasic lead phosphite, silica gel coprecipitated lead silicate, dibasic lead phthalate, tribasic Lead maleate, lead salicylate, lead stearate, basic lead stearate, dibasic lead stearate, lead laurate,
Examples include lead octylate, lead 12-hydroxystearate, lead behenate, and lead naphthenate.

Examples of the above-mentioned zinc-based, calcium-based, magnesium-based and barium-based stabilizers include:
These oxides, hydroxides, carbonates, basic carbonates,
(Meth) borate, (meth) silicate, (sub) phosphate, basic phosphate, aluminate, titanate, stannate,
Organic metal salts with inorganic compounds such as rhodanates and organic carboxylic acids, phenols and organic phosphoric acids can be mentioned.

The organic carboxylic acid constituting the organic metal salt includes acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, neodecanoic acid, capric acid. Acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, Dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylamino Benzoic acid, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicyl , Monohydric carboxylic acids such as elaidic acid, oleic acid, linoleic acid, linoleic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid,
Terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid,
Divalent carboxylic acids such as thiodipropionic acid or monoesters or monoamide compounds thereof; trivalent or tetravalent carboxylic acids such as butanetricarboxylic acid, butanetetracarboxylic acid, hemi-mellitic acid, trimellitic acid, melophanic acid, and pyromellitic acid Acid di- or triester compounds may be mentioned.

Examples of the phenols constituting the organic metal salt include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, and isoamyl. Phenol, ethyl phenol, isopropyl phenol, isooctyl phenol, 2-
Examples include ethylhexyl phenol, tertiary nonyl phenol, decyl phenol, tertiary octyl phenol, isohexyl phenol, octadecyl phenol, diisobutyl phenol, methyl propyl phenol, diamyl phenol, methyl isohexyl phenol, and methyl tertiary octyl phenol.

The above-mentioned organic phosphoric acids constituting the above-mentioned organic metal salt include mono- or di-octyl, -decyl, -dodecyl, -tridecyl, -tetradecyl, -hexadecyl, -octadecyl, -phenyl, -tolyl,
-Xylyl, -octylphenyl, -nonylphenylphosphoric acid, pyrophosphoric acid, phosphorous acid and the like.

Examples of the organotin-based stabilizer include methyl stanoic acid, butyl stanoic acid, octyl stanoic acid, dimethyl tin oxide, dibutyl tin oxide, dioctyl tin oxide, dimethyl tin sulfide, and the like. Dibutyltin sulfide, dioctyltin sulfide, dicyclohexyltin sulfide, monobutyltin oxide sulfide, methyl thiostannoic acid, butyl thiostannoic acid, octyl thiostannoic acid, dibutyl tin dilaurate, dibutyl tin distearate, dioctyl tin diolate, Dibutyltin basic laurate, dibutyltin dicrotonate, dibutyltin bis (butoxydiethylene glycol malate), dibutyltin methyl octyl neopentyl glycol malate, dibutyl Isooctyl 1,4-butanediol malate, dibutyltin dimethacrylate, dibutyltin dicinnate, dioctyltin bis (oleylmalate), dibutyltin bis (stearylmalate), dibutyltin itaconate, dioctyltin malate, diamyltin bis ( Cyclohexyl malate), dimethyl tin dicrotonate, diethyl tin bis (isooctyl citronate), dipropyl tin bis (benzyl malate), diisobutyl tin bis (propyl malate), dicyclohexyl tin malate, dioctyl tin bis (butyl malate), dibutyl tin Dimethoxide, dibutyltin dilauroxide, dioctyltin ethyleneglycoxide, pentaerythritol / dibutyltin oxide condensate, dibutyltin bis (lauryl mercaptide), dimethyltin bis ( (Tearyl mercaptide), monobutyltin tris (laurylmercaptide), dibutyltin-β-mercaptopropionate, dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, monobutyltin tris (isooctylmercaptoacetate) ), Monooctyltin tris (2-ethylhexylmercaptoacetate), dibutyltinbis (isooctylmercaptoacetate), dioctyltinbis (isooctylmercaptoacetate), dioctyltinbis (2-ethylhexylmercaptoacetate), dimethyltinbis (iso) Octylmercaptoacetate), dimethyltin bis (isooctylmercaptopropionate), monobutyltin tris (isooctylmercaptopropionate), bis [monobutyldi (a Octoxycarbonylethyl methylene thio)
Tin] sulfide, bis [dibutylmono (isooctoxycarbonylmethylenethio) tin] sulfide, monobutylmonochlorotinbis (isooctylmercaptopropionate), monobutylmonochlorotinbis (isooctylmercaptoacetate), monobutylmonochlorotinbis (Laurylmercaptide), butyltin bis (ethylcellulose bromalate), bis (dioctyltin butylmalate) malate, bis (methyltin diisooctyltyl glycolate) disulfide, bis (methyl / dimethyltin mono / diiso) (Octylthioglycolate) disulfide, bis (methyltin diisooctylthioglycolate) trisulfide, bis (butyltin diisooctylthioglycolate) trisulfide, 2-butoxycarbonylethyltin trisulfide (Butyl thioglycolate).

The addition amount of these metal stabilizers is preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

In the composition of the present invention, other stabilizers and other additives usually used for chlorine-containing resins may be used in combination.

Other stabilizers that can be used in combination with the composition of the present invention include epoxy compounds, organic phosphite compounds, phenolic antioxidants, and other organic stabilizing aids. Among these, the phenolic antioxidant has an effect of further improving the heat resistance of the vinyl chloride resin composition of the present invention.

Examples of the epoxy compound include bisphenol type and novolak type epoxy resins, epoxidized natural oils such as epoxidized soybean oil and epoxidized linseed oil, and epoxidized unsaturated fatty acid alkyls such as epoxidized tall oil fatty acid octyl. Alicyclic epoxy compounds such as esters and vinylcyclohexene diepoxy;

The amount of these epoxy compounds to be added is preferably 0.0
It is 1 to 20 parts by weight, more preferably 0.05 to 10 parts by weight.

As the organic phosphite compound, triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl)
Phosphite, tris (mono and dinonylphenyl)
Phosphite, diphenyldecyl phosphite, trioctyl phosphite, phenyl dioctyl phosphite, trioctyl phosphite, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) bisphenol A diphosphite, tetra (C ₁₂ ~
C ₁₅ mixed alkyl) bisphenol A diphosphite,
Hexa (tridecyl) -1,1,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butanetriphosphite, diphenylacid phosphite, bis (nonylphenyl) acid phosphite and the like can be mentioned.

The amount of the organic phosphite compound to be added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

The phenolic antioxidants include, for example, 2,6-di-tert-butyl-p-cresol,
4'-thiobis (6-tert-butyl-m-cresol),
4,4'-butylidenebis (6-tert-butyl-m-cresol), 4,4'-isopropylidenebis (2-tert-butylphenol), 4,4'-methylenebis (2,6
-Di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2 '
-Methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-ethylidenebis (4,6-ditertbutylphenol), 2,2'-ethylidenebis (4-secbutyl-6-tert-butylphenol) Butylphenol), 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl-β- (3,5-di-tert-butyl-4-) (Hydroxyphenyl) propionate, 1,6-hexamethylenebis [β- (3,5-ditert-butyl-4-hydroxyphenyl) propionate], 3-thia-1,5-pentanebis [β- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-bis [4- {2-
(Β- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy) ethyl @ phenyl] propane, 3,7-dioxa-1,8-octanebis [β-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis [1,1-dimethyl-2- (β- (3-tert-butyl-4-hydroxy-5
-Methylphenyl) propionyloxy) ethyl-2,
4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [β- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3 , 5-ditert-butyl-4-
(Hydroxybenzyl) isocyanurate, 2-octylthio-4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, bis [2-tert-butyl-4-methyl-6- ( 2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5- Tris (3,5-di-tert-butyl-4-hydroxybenzyl)-
2,4,6-trimethylbenzene, 1,2-ethanebis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyrate] and the like.

The addition amount of these phenolic antioxidants is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Examples of the organic stabilizing aid include phenols such as bisphenol A and hydrogenated bisphenol A;
Polyhydric alcohols such as pentaerythritol, dipentaerythritol, dipentaerythritol adipate, mannitol, sorbitol and their ester compounds or partial ester compounds; β- such as dibenzoylmethane, benzoylacetone, stearyl benzoylmethane, dehydroacetic acid, etc. Diketone compounds and metal salts thereof; 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid didodecyl ester, 2
-Organic nitrogen-containing compounds such as phenylindole and melamine.

The amount of the organic stabilizing aid is preferably 0.1 to 100 parts by weight of the vinyl chloride resin.
001 to 5 parts by weight, more preferably 0.005 to 3 parts by weight.

These other stabilizers can be used in combination of two or more depending on the purpose.

If necessary, the composition of the present invention may contain, for example, an ultraviolet absorber, a light stabilizer, a cross-linking agent, a filler, a pigment, a foaming agent, an antistatic agent, a plate-out preventing agent, a surface treatment agent, and a lubricant. , A flame retardant, a fluorescent agent, a light degrading agent, a fungicide, a bactericide, a non-metal stabilizer, a processing aid, a mold release agent, and the like.

[0035]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by the following examples.

Example 1 Rolls were kneaded according to the following composition to prepare a 1 mm press sheet, and a tensile test was performed according to JIS K7113. In addition, at 160 ° C., 26
A tensile test was similarly performed on the sample left to stand for 0 hours, and the volatilization loss (%) of the sample was measured. In order to evaluate cold resistance, the embrittlement temperature was measured according to JIS K7216. Furthermore, the gelation property was evaluated using Labo Plastmill (Toyo Seiki Seisakusho).

Evaluation of the gelling property was made by measuring the time until the maximum torque (t2), the maximum torque value (M2), and the time until the steady torque was reached (t4). Where t
2, The smaller the t4 and the larger the M2, the better the gelling property.

The results are shown in Table 1 below.

[Blending] Parts by weight Vinyl chloride resin (Mw = 2500) 100 Tribasic lead sulfate 5 Dibasic lead stearate 1 Plasticizer (see Table 1 below) 50

[0040]

[Table 1]

[0041]

[Table 2]

Example 2 With the following composition, a tensile test was carried out in the same manner as in Example 1, and the volatilization loss (%) and the embrittlement temperature were measured.

The results are shown in Table 3 below.

[Blending] Parts by weight Vinyl chloride resin (Mw = 1450) 100 Lead silicate 9 n-Pb stearate 1 Plasticizer (see [Table 3] below) 50

[0045]

[Table 3]

The following can be seen from the results of the above embodiment.
When a single alcohol ester of pyromellitic acid is used for the vinyl chloride resin, it does not exhibit sufficient heat resistance and cold resistance. When simply considering the performances of heat resistance and cold resistance only, a straight-chain mixed alcohol ester having 8 to 10 carbon atoms gives sufficient performance. A mixed alcohol ester having 8 to 10 atoms has a practical problem.

On the other hand, the composition of the present invention in which a specific mixed alcohol ester of pyromellitic acid is added to a vinyl chloride resin has good gelling properties and excellent properties in terms of heat resistance and cold resistance. Show.

[0048]

The vinyl chloride resin composition of the present invention has good gelling properties and extremely excellent heat resistance and cold resistance.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Teruo Arai 5-2-13-1 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. (56) References JP-A-6-279642 (JP, A) JP-A-1-297707 (JP, A) JP-A-61-97248 (JP, A) JP-A-57-35000 (JP, A) JP-A-2-209994 (JP, A) JP-A-2-138355 (JP) , A) Special Table Heisei 3-505600 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 27/06

Claims (1)

(57) [Claims] 1. A vinyl chloride resin composition obtained by adding at least one pyromellitic acid ester represented by the following general formula (I) to a vinyl chloride resin. Embedded image