JPH1121402A - Polyvinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyvinyl chloride resin composition generating extremely slight bleeding of a plasticizer, etc., even in using for long period of time, also having excellent heat stability and useful for an automotive instrument panel, etc., by making the composition contain an internally epoxidized liquid diene- based polymer, etc. SOLUTION: This polyvinyl chloride resin composition is obtained by compounding 100 pts.wt. of (A) a polyvinyl chloride resin with 20-100 pts.wt. of (B) a plasticizer such as di-2-ethyl hexyl phthalate, and compounding (C) an internally epoxidized liquid diene-based polymer obtained by epoxidizing a polymer of butadiene or isoprene and containing 0.2-5 meq/g of hydroxy group at the chain end, and having 500-15,000 number-average molecular weight and 50-1,000 epoxy equivalent in an amount of 1-15 pts.wt., with totally 100 pts.wt. of the components A and B, then kneading them in a kneader, etc., at a room temperature or under heating, for about 0.5-15 min.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyvinyl chloride resin composition. More specifically, the present invention relates to a polyvinyl chloride resin composition comprising a polyvinyl chloride resin, a plasticizer, and an internally epoxidized liquid diene polymer, which has extremely low bleeding even during long-term use, and has excellent heat stability. .

[0002]

2. Description of the Related Art Polyvinyl chloride resin has excellent durability,
Because of its easy forming process, it is used as a material for forming, for example, films, sheets, pipes, plate materials, flooring materials, electric wire coatings, and daily necessities in various industrial fields. In addition, soft polyvinyl chloride resin containing a plasticizer further improves moldability and is easy to color, so it is used in automotive instrument panels, door panels, dashboards, and leather replacement products. Used for building materials such as interior parts and flooring.

As described above, the soft polyvinyl chloride resin is highly useful as a molding material, but since it contains a plasticizer, the plasticizer bleeds when used for a long period of time. There's a problem. For example, if the plasticizer bleeds from the flooring material, the rubber of the casters of the chair will deteriorate or dissolve and the floor surface will be soiled, and when bleeding from automobile interior parts, the plasticizer will volatilize and fog the windshield. There is a problem that a fogging phenomenon is caused.

[0004] In addition, polyvinyl chloride resin is
There is a problem that a decomposition reaction mainly including a dehydrochlorination reaction is caused by the action of heat, light (in particular, ultraviolet rays), oxygen, and the like during molding and use, resulting in discoloration and deterioration. In this case, it is a serious problem in products in which the appearance of a product is most important, such as an automobile interior product or a building interior product. In order to solve such problems, various stabilizers have been blended. However, when the environmental conditions in use of these products become severe, there is a problem that discoloration and deterioration cannot be sufficiently avoided. .

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in the polyvinyl chloride resin, has extremely little bleeding of the plasticizer even during long-term use, and has a high thermal stability. It is an object of the present invention to provide a polyvinyl chloride resin composition excellent in the above.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted various studies in order to achieve the above object, and have found that an internal epoxidized liquid diene-based polymer is added to a polyvinyl chloride resin and its plasticizer. It has been found that the above object can be achieved by using the blended composition, and the present invention has been completed based on such findings.

That is, the gist of the present invention is as follows. [1] A polyvinyl chloride resin composition comprising a polyvinyl chloride resin, a plasticizer, and an internally epoxidized liquid diene polymer. [2] Internal epoxidized liquid diene polymer 1 to 100 parts by weight of total amount of polyvinyl chloride resin and plasticizer
The polyvinyl chloride resin composition according to the above [1], which is blended with 15 parts by weight. [3] As the internal epoxidized liquid diene polymer,
The polyvinyl chloride resin composition according to [1] or [2], wherein a polymer of butadiene or isoprene is epoxidized and has a number average molecular weight of 500 to 15,000. [4] As the internal epoxidized liquid diene polymer,
The polyvinyl chloride resin composition according to any one of [1] to [3], wherein the epoxy equivalent is 50 to 1000. [5] As the internal epoxidized liquid diene polymer,
The polyvinyl chloride resin composition according to any one of the above [1] to [4], which uses a polymer having a hydroxyl group at a terminal of the polymer chain.

[0008]

DETAILED DESCRIPTION OF THE INVENTION As the polyvinyl chloride resin used in the present invention, a commonly used polyvinyl chloride resin is used. The polyvinyl chloride resin may be a polymer obtained by polymerizing vinyl chloride alone or a copolymer obtained by adding a comonomer such as acrylate, ethylene, propylene, and vinylidene chloride to the main component of vinyl chloride. Good.

The polyvinyl chloride resin is produced by subjecting a monomer such as vinyl chloride to a suspension polymerization method, a bulk polymerization method, or an emulsion polymerization method. The polyvinyl chloride resin used in the present invention is produced by any method. It may be a plastisol or an aqueous latex in which the fine particles are dispersed in an organic medium. Further, a polymer blend of a polyvinyl chloride resin can also be used. For example, a polymer blend comprising a polyvinyl chloride resin and polyvinylidene chloride may be used.

Next, the plasticizer used in the present invention is:
A plasticizer usually used for polyvinyl chloride resin is used. Specifically, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate,
Di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, diundecyl phthalate, ditridecyl phthalate, didodecyl phthalate, diisocumyl phthalate, dinonyl phthalate 1 to 1 carbon atoms
Phthalates having two alkyl groups; trimellitic acids such as trioctyl trimellitate and tri-n-octyl-n-decyl trimellitate; diisobutyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate , Dibutyl diglycol adipate, di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate, triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate, dimethyl seba Fatty acid esters such as kate, dibutyl sebacate, di-2-ethylhexyl sebacate, methyl acetyl ricinolate, butyl acetyl ricinolate; tri-2
-Ethylhexyl phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate,
Orthophosphates such as xylenyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate;
Chlorinated paraffins; chlorinated fatty acid esters; epoxidized soybean oil; epoxidized linseed oil; epoxy butyl stearate, epoxy octyl stearate; methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate And the like.

The mixing ratio of these plasticizers to the polyvinyl chloride resin has a suitable range depending on the use of the molded article obtained from the polyvinyl chloride resin composition and the molding method thereof. Vinyl resin 10
The plasticizer is used in an amount of 10 to 300 parts by weight, preferably 20 to 100 parts by weight per 0 parts by weight. Further, the internal epoxidized liquid diene polymer used in the present invention is obtained by polymerizing a diene monomer to produce a hydroxyl group-containing liquid diene polymer, and then heating in the presence of a peroxide or the like. Can be used.

As the diene monomer used for producing the hydroxyl group-containing liquid diene polymer, a diene hydrocarbon having 4 to 22 carbon atoms such as butadiene, isoprene, chloroprene, 1,3-pentadiene and cyclopentadiene is used. These can be used alone or in combination of two or more. Further, an addition polymerizable monomer in an amount of less than 50 mol% based on the diene-based hydrocarbon can be used as a mixture. As the addition polymerizable monomer, butene, pentene, styrene, α-methylstyrene, acrylonitrile, acrylic acid, acrylate, methacrylic acid,
Examples include methacrylate, vinyl chloride, vinyl acetate, acrylamide and the like.

In conducting the polymerization reaction of these diene monomers and the like, hydrogen peroxide or 2,2 is used as a polymerization initiator.
Hydroxyl-containing azo compounds such as 2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide;
By radical polymerization using a hydroxyl group-containing peroxide such as cyclohexanone peroxide, a diene polymer containing a hydroxyl group and liquid at room temperature can be obtained.

Further, anionic polymerization using naphthalenedilithium or the like as a catalyst for this reaction, and reaction of water, alcohol, ethylene oxide, or the like with the terminal of the obtained living polymer, can be carried out to obtain a hydroxyl group-containing liquid diene polymer. Can be obtained. When performing the polymerization reaction of this diene monomer or the like, the reaction temperature is 50 to 150 ° C., and the reaction time is 1 to 1.
The time is suitably 10 hours, and as the solvent, it is preferable to use a saturated hydrocarbon such as hexane or cyclohexane, or an alcohol such as n-butyl alcohol or isopropyl alcohol.

Then, the hydroxyl group-containing liquid diene polymer is heated in the presence of a peroxide such as hydrogen peroxide, peracetic acid, or formic acid to carry out an epoxidation reaction, whereby an internal epoxidized liquid diene polymer is obtained. A polymer can be obtained. The internally epoxidized liquid diene polymer used as one component of the polyvinyl chloride resin composition of the present invention is, among those obtained as described above, a polymer of butadiene or isoprene, and their number average molecular weight is preferable. Is 500 ~
Those having a molecular weight of 15,000, preferably 1,000 to 8,000 are suitable. If the number average molecular weight is less than 500, the bleeding preventing effect of the plasticizer may not be sufficiently obtained, and if it exceeds 15,000, the viscosity may be high and gelation may be caused. It is preferable to use those in the range of

[0016] The internal epoxidized liquid diene polymer preferably has an epoxy equivalent of 50 to 1000, preferably 100 to 300. When the epoxy equivalent is less than 50, the polarity is too high as compared with the polyvinyl chloride resin, and when it exceeds 15,000, the polarity is too low, and in any case, the compatibility with the polyvinyl chloride resin is high. May be reduced.

Further, the internal epoxidized liquid diene polymer has a hydroxyl group at the terminal of the polymer chain and has a hydroxyl group content of 0.1 to 8 meq / g, preferably 0.2 to 5 meq / g. Are preferred. When the content of the hydroxyl group is less than 0.1 meq / g, the compatibility with the plasticizer may be reduced. On the other hand, when the content is more than 8 meq / g, the polarity is too high and the plasticizer and the polyvinyl chloride resin are not used. May be reduced in compatibility.

In the present invention, the plasticizer is previously blended with the polyvinyl chloride resin to produce a polyvinyl chloride resin containing a plasticizer, and the internal epoxidized liquid diene polymer is blended therein. It is preferable to produce a polyvinyl chloride resin composition by mixing the plasticizer and the internal epoxidized liquid diene polymer into the polyvinyl chloride resin at the same time to produce the polyvinyl chloride resin composition. Good.

In this case, the mixing ratio of the polyvinyl chloride resin, the plasticizer thereof and the internal epoxidized liquid diene polymer is 10% in total of the polyvinyl chloride resin and the plasticizer.
A polyvinyl chloride resin composition comprising 1 to 15 parts by weight of an internal epoxidized liquid diene polymer per 0 parts by weight is suitable as a molding material. In order to produce a homogeneous composition by mixing these components, it is sufficient to carry out mixing for about 0.5 to 15 minutes with a mixer or kneader at room temperature or with heating.

When molding a molded article from the obtained composition, extrusion molding, injection molding, calender molding, press molding, blow molding, paste resin molding can be performed in the same manner as in the case of ordinary polyvinyl chloride resin molding. Processing and the like can be performed. As for the molding conditions, the molding temperature is 150 to 25.
0 ° C., preferably in the range of 190 to 230 ° C., and the molding time is in the range of 0.5 seconds to 30 minutes, and conditions suitable for each molding method may be selected. It is the same as in the case of molding.

Here, regarding the mixing ratio of the internally epoxidized liquid diene polymer in the polyvinyl chloride resin composition of the present invention, when this is used as a material for thermoforming, the polyvinyl chloride resin and its plasticizer are used. Total amount of 100
1 part by weight of internal epoxidized liquid diene polymer per part by weight
When the compounding ratio is less than 1 part by weight, the effect of preventing bleeding of the plasticizer and the effect of improving the thermal stability of the composition is not sufficient. This is because, when the composition is blended, there is a possibility that the internal epoxidized liquid diene polymer may be thermally deteriorated when the composition is thermoformed.

Since the polyvinyl chloride resin composition of the present invention has the above-mentioned composition, it is generated during a long-term use peculiar to a molded article made of a polyvinyl chloride resin containing a plasticizer. The remarkable effect that the bleeding of the plasticizer is effectively suppressed is obtained. Such an effect is brought about because the compatibility between the internal epoxidized liquid diene polymer and the plasticizer is greater than the compatibility between the polyvinyl chloride resin and the plasticizer, and after the compatibility. This is because the bond between the two is strong.

The polyvinyl chloride resin composition of the present invention has an effect of suppressing discoloration and deterioration caused by free chlorine. This is because free chlorine from the polyvinyl chloride resin is converted into an internal epoxidized liquid diene. This is because it can be trapped in the epoxy group of the system polymer and the unsaturated bond site in the polymer chain. The polyvinyl chloride resin composition of the present invention comprises the above three components, and further comprises a stabilizer, a lubricant, an antistatic agent, a coloring agent, a pigment, an inorganic filler, an organic filler, and the like. Can be appropriately selected and blended according to the formulation suitable for the type and use of the product.

Examples of the stabilizer include lead white, basic lead sulfite, tribasic lead sulfate, dibasic lead phosphite, dibasic lead phthalate, tribasic lead maleate and silica gel coprecipitated silicate. Lead salt stabilizers such as lead; stearic acid, lauric acid,
Metal soaps such as lithium, potassium, calcium, magnesium, strontium, cadmium, and barium salts such as ricinoleic acid and naphthenic acid; metals such as cadmium, zinc, barium, calcium, tin, magnesium, sodium, and potassium Metal salt-based stabilizers containing components: laurate-based organotin, maleate-based organotin,
Organotin stabilizers such as mercaptide organotins; antimony organotins; phosphites; phenol derivatives;
Stabilizers such as polyhydric alcohols; nitrogen-containing compounds; and keto compounds. Since the basic composition of the present invention already has sufficient thermal stability, it is added in order to further increase the amount of these stabilizers. A small amount is sufficient. The amount is from 0.05 to 100 parts by weight of the composition.
It is 10 parts by weight, preferably 0.5 to 5 parts by weight.

Examples of the lubricant include hydrocarbon lubricants such as liquid paraffin, paraffin wax, microwax, low-polymerized polyethylene, chlorinated hydrocarbon, and fluorocarboxylic oil; myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid Fatty acid-based lubricants such as stearylamide, parmethylamide, oleylamide,
Fatty acid amide-based lubricants such as methylene bis-stearamide and ethylene bis-stearamide; hardened castor oil, ester-based lubricants such as ethylene glycol monostearate;
Alcoholic lubricants such as ethylene glycol, polyethylene glycol and polyglycerol;
Natural wax lubricants such as candelilla wax, beeswax, spermaceti, ibota wax, montan wax; stearic acid, lauric acid, ricinoleic acid, lithium salt, potassium salt, calcium salt, magnesium salt, strontium salt, cadmium salt, barium salt of naphthenic acid And other metallic soap-based lubricants. The compounding amount of these lubricants is 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the composition of the present invention.

Examples of the antistatic agent include cationic activators such as primary amine salts, tertiary amines, quaternary ammonium compounds, and pyridine derivatives; sulfated oils, aliphatic alcohol sulfates, and sulfates of alkyl compounds. Anionic activators; nonionic activators such as partial fatty acid esters of polyhydric alcohols and alcohol adducts of fatty acids; amphoteric activators such as carboxylic acid derivatives and imidazoline derivatives; inorganic compounds such as silica. The amount of the antistatic agent is 0.00.0 parts by weight per 100 parts by weight of the composition of the present invention.
It is 1 to 3 parts by weight, preferably 0.1 to 1 part by weight.

The coloring agents and pigments include titanium oxide, red iron oxide, graphite, cadmium pigment, ultramarine,
Carbon black, insoluble azo pigment, soluble azo pigment, condensed azo pigment, phthalocyanine pigment, vat dye pigment,
Examples include quinacridone pigments, dioxazine pigments, dyed lake pigments, metal powder pigments such as aluminum and brass, pearl pigments, and fluorescent pigments. The amount of the colorant and pigment is 0.05 to 50 parts by weight, preferably 0.5 to 30 parts by weight, per 100 parts by weight of the composition of the present invention.

Further, as the inorganic filler, zinc,
Aluminum, copper, nickel, glass beads, glass flakes, glass fiber, carbon fiber, carbon black, graphite, asbestos, kaolin clay, limestone clay, talc, kasumilite, cryolite, wollastonite, diatomaceous earth, slate powder, Whiting, feldspar powder, mica, gypsum, quartz powder, fine silica, atavulgite,
Sericite, volcanic ash, vermiculite, silica, alumina, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, molybdenum dioxide, aluminum hydroxide,
Examples include magnesium hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zeolite, potassium titanate, boron nitride, boron nitrite, and molybdenum disulfide.

Examples of the organic filler include natural fibers such as rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, wood powder, cotton, hemp, wool, silk; nylon, polyester, vinylon, acetate, and poly. Synthetic fibers such as acrylonitrile; polyethylene, polypropylene,
Examples include powders or granules of synthetic resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, epoxy resin, and phenol resin. The mixing ratio of these inorganic fillers and organic fillers is not more than 500 parts by weight, preferably not more than 200 parts by weight, per 100 parts by weight of the composition of the present invention. The amount may be determined.

In addition to the above-mentioned various compounding agents, if necessary,
Halogen-based flame retardants, inorganic flame retardants such as aluminum hydroxide and antimony oxide; antioxidants such as hindered phenols, hindered amines, and benzotriazoles; organochlorine and organometallic fungicides; n-hexane ,
Hydrocarbon solvents such as cyclohexane, toluene, and xylene; ketone solvents such as methyl ethyl ketone and cyclohexanone; ester solvents such as butyl acetate; ether solvents such as tetrahydrofuran; and viscosity reducing agents such as N, N-dimethylformamide and dimethyl sulfoxide And the like can be blended at a blending ratio usually used for a synthetic resin molding material.

[0031]

[Example 1]

(1) Preparation of Hydroxyl-Terminal Liquid Polyisoprene In a 1-liter stainless steel pressure-resistant reaction vessel, 200 g of isoprene, 40 g of a 20% hydrogen peroxide solution and 100 g of isopropanol were charged, and the temperature was set to 120 ° C.
The polymerization reaction of isoprene was performed under the conditions of a maximum pressure of 8 kg / cm ² G and a reaction time of 2 hours.

After completion of the reaction, 600 g of water was added to the reaction product, the mixture was stirred, and allowed to stand for 3 hours to separate an organic phase and an aqueous phase.
Subsequently, the organic phase was separated and subjected to 1 mm under reduced pressure of 2 mmHg.
At 00 ° C., isopropanol, unreacted monomer and low polymer contained in the organic phase were distilled off. As a result, liquid hydroxyl-terminated polyisoprene was obtained at a yield of 69%. The resulting hydroxyl-terminated liquid polyisoprene had a number average molecular weight of 2260 and a hydroxyl content of 0.96 meq /
g, viscosity 66 poise (30 ° C.), bromine number 225 g / 10
0g, average number of hydroxyl groups per molecule 2.17, 1,4-
Trans structure content 58%, 1,4-cis structure content 33%, 1,2-vinyl structure content 6%, 3,4-
The vinyl structure content was 3%.

(2) Preparation of Liquid Polyisoprene Having Internal Epoxidized Hydroxyl Terminals The above-mentioned (1) was placed in a separable flask having an internal volume of 2 liters.
100 g of the hydroxyl-terminated liquid polyisoprene obtained in
% Hydrogen peroxide, 120 ml of secondary butyl alcohol and 0.4 g of trimethylbenzylammonium chloride.
The mixture was stirred while being cooled, and 35 ml of a 6 N aqueous sodium hydroxide solution was added dropwise at 15 ° C. over 1 hour. Then, after reacting at 25 ° C. for 3 hours, the product was put into 1 liter of water and extracted three times with diethyl ether. After washing the ether extract twice with water, 2 m
Volatile components were distilled off at 100 ° C. under a reduced pressure of mHg to obtain a target liquid polyisoprene having an internal epoxidized hydroxyl group terminal. The resulting internal epoxidized hydroxyl group-terminated liquid polyisoprene has a number average molecular weight of 329.
0, hydroxyl group content 0.75 meq / g, epoxy equivalent 1
97, the viscosity is 67 poise (45 ° C.), and the microstructure of the polyisoprene portion has a 1,4-bond structure content of 8
It was 7 mol%.

(3) Production of Polyvinyl Chloride Resin Composition The raw material polyvinyl chloride resin has an average degree of polymerization of 13
00, using a powdery resin having a bulk density of 0.5 g / milliliter (manufactured by Tosoh Corporation: TH-1300), and adding di-2 as a plasticizer to 100 parts by weight of the polyvinyl chloride resin.
-Ethylhexyl phthalate was used in a proportion of 50 parts by weight, and potassium stearate as a stabilizer was used in a proportion of 1 part by weight, and these were kneaded with a Dalton mixer to obtain a polyvinyl chloride resin containing a plasticizer. Then, 3.3 parts by weight of the internally epoxidized hydroxyl-terminated liquid polyisoprene obtained in (2) above was added to 100 parts by weight of the polyvinyl chloride resin containing the plasticizer and kneaded, whereby the polychlorinated resin was kneaded. A vinyl resin composition was obtained. The polyvinyl chloride resin composition thus obtained was put into a press molding die for sheet molding, and pressed at 230 ° C. for 3 minutes to form a 1 mm thick sheet. Separately, a columnar molded product having an outer diameter of 29 mm and a height of 13 mm was manufactured using a mold for molding.

(4) Evaluation of polyvinyl chloride resin composition The performance of the polyvinyl chloride resin composition as a molding material was evaluated by evaluating the molded article obtained in the above (3) by the following method. . Table 1 shows the evaluation results.

1) Confirmation of the presence or absence of bleed The cylindrical molded product obtained in the above (3) was placed on a filter paper, placed in a gear oven and heated to 120 ° C., and this state was maintained for 3 days. After the elapse of a predetermined heating time, the columnar molded product placed on the filter paper was taken out after cooling to room temperature, and it was visually confirmed whether or not the plasticizer had bleeded into the filter paper. 2) Heat resistance test The columnar molded product obtained in the above (3) was visually inspected for any change in appearance after the predetermined heating time in the above 2). 3) Physical property test Regarding the sheet obtained in the above (3), JIS-K-630
The tensile strength, elongation and compression set were measured according to 1.

Example 2 As an internally epoxidized liquid diene polymer, a number average molecular weight of 3450 and an epoxy equivalent of 2 were used.
01, viscosity 54 poise (45 ° C.), polybutadiene part having a microstructure of 1,4-bond structure content of 80 mol%
The same procedure as in Example 1 was carried out, except that an internal epoxidized hydroxyl group-terminated liquid polybutadiene (manufactured by Daicel Chemical Industries, Ltd .: Eporide PB3600) was used. Table 1 shows the evaluation results.

Example 3 As the internally epoxidized liquid diene polymer, the same one as used in Example 2 was used.
The procedure was the same as in Example 1 except that the mixing ratio was 6.6 parts by weight based on 100 parts by weight of the polyvinyl chloride resin containing the plasticizer. Table 1 shows the evaluation results.

Example 4 As an internally epoxidized liquid diene polymer, the number average molecular weight was 1800 and the epoxy equivalent was 4
An internal epoxidized hydroxyl group-containing liquid polybutadiene having a viscosity of 5.5 poise (25 ° C.) and a polybutadiene portion having a microstructure of 1,4-bond structure of 83 mol% [Polybd600 manufactured by Elphatochem Co.] was used. Others were the same as Example 1. Table 1 shows the evaluation results.

Example 5 As an internally epoxidized liquid diene polymer, a number average molecular weight of 2,300 and an epoxy equivalent of 2 were used.
40, a viscosity of 14.5 poise (25 ° C.), and a liquid polybutadiene having an internal epoxidized hydroxyl group (Poly bd605, manufactured by Elphatochem Co.) having a polybutadiene portion having a microstructure of 1,4-bond content of 85 mol%. Was the same as in Example 1. Table 1 shows the evaluation results.

[Comparative Example 1] A molded article was produced in the same manner as in Example 1 except that the polyvinyl chloride resin containing a plasticizer, which did not contain an internal epoxidized liquid diene polymer, was used as a molding material. Was evaluated for performance. First evaluation result
It is shown in the table.

Comparative Example 2 In place of the internal epoxidized liquid diene polymer, a non-epoxidized number average molecular weight of 2590, a hydroxyl group content of 0.84 meq / g and a viscosity of 51 were used.
The procedure was the same as in Example 1 except that a poise (30 ° C.) hydroxyl group-containing liquid polybutadiene [Poly bdR-45HT manufactured by Idemitsu Petrochemical Co., Ltd.] was used. Table 1 shows the evaluation results.

[Comparative Example 3] As the internal epoxidized liquid diene polymer, the number average molecular weight was 1210 and the epoxy equivalent was 2
10. Viscosity of 50 poise (45 ° C.), polybutadiene portion having a microstructure of 1,2-bond structure content of 90 mol%
The same procedure as in Example 1 was carried out except that the internal epoxidized nonfunctional liquid polybutadiene (manufactured by Nippon Soda Co., Ltd .: NISSOBF-1000) was used. Table 1 shows the evaluation results.

Comparative Example 4 A number average molecular weight of 380 and an epoxy equivalent of 1 were used in place of the internal epoxidized liquid diene polymer.
Example 8 was carried out in the same manner as in Example 1 except that a glycidyl ether type low molecular weight epoxy compound having a viscosity of 135 poise (25 ° C) [manufactured by Yuka Shell Epoxy: Epicoat 828] was used. Table 1 shows the evaluation results.

[0045]

[Table 1]

[0046]

According to the present invention, the polyvinyl chloride resin composition comprises:
This has the specific effect that the bleeding of the plasticizer during molding and long-term use is extremely small and the thermal stability is excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 15:00) (C08L 27/06 63:00)

Claims (5)

[Claims] 1. A polyvinyl chloride resin composition comprising a polyvinyl chloride resin, a plasticizer and an internally epoxidized liquid diene polymer. 2. The polyvinyl chloride resin according to claim 1, wherein 1 to 15 parts by weight of the internal epoxidized liquid diene polymer is blended with respect to 100 parts by weight of the total amount of the polyvinyl chloride resin and the plasticizer. Composition. 3. The polychlorinated polychloride according to claim 1, wherein the internal epoxidized liquid diene polymer is obtained by epoxidizing a butadiene or isoprene polymer and has a number average molecular weight of 500 to 15,000. Vinyl resin composition. 4. The polyvinyl chloride resin composition according to claim 1, wherein the internal epoxidized liquid diene polymer has an epoxy equivalent of 50 to 1,000. 5. The polyvinyl chloride resin composition according to claim 1, wherein the internal epoxidized liquid diene polymer has a hydroxyl group at a terminal of the polymer chain.