KR20000007217A - Polyvinyl chloride resin composition - Google Patents

Abstract

PURPOSE: A polyvinyl chloride resin composition comprising polyvinyl chloride resin, plasticizer, and internal epoxidized liquid diene polymer is provided which has a low bleed of plasticizer and has an excellent heat stability. CONSTITUTION: The composition comprises a)100 weight parts of polyvinyl chloride having epoxy equivalent of 5-1,000(preferably 100-500), b)300 weight parts of plasticizer, and c)0.5-15 weight parts of internal epoxidation polybutadiene obtained by epoxidizing polybutadiene having member average molecular weight of 1,500-15,000(preferably 2,000-5,000), above 50 mole% of 1,4-trans structure of molecular chain, and 0.1-8(preferably 0.2-5) meq/g of hydroxyl group at its end. The plasticizer is one or more compounds selected from ester phthalate, ester trimelitate, and epoxidized vegetable oil. The composition inhibits occurrence of breed of plasticizer by the use of long term and does not generate change of color and aging of molded product by heat.

Description

Polyvinyl Chloride Resin Composition

The present invention relates to a polyvinyl chloride resin composition. More specifically, it consists of a polyvinyl chloride resin, a plasticizer and an internal epoxidized polybutadiene, and does not deteriorate the physical properties of the polyvinyl chloride resin composition, and has very little bleed of the plasticizer from the composition even when used at a high temperature for a long time. The present invention relates to a polyvinyl chloride resin composition having excellent thermal stability.

Polyvinyl chloride resins are excellent in durability, processability, fouling resistance and designability, and are easy to be molded and processed, and thus are widely used in a wide range of industries, such as films or sheets, pipes, plates, floor coverings, wire coatings, toys, It is used as molding materials, such as daily necessities. In particular, the soft polyvinyl chloride resin blended with a plasticizer improves moldability and colorability, so that the designability is improved. It is widely used in apartments, mansions and detached houses. It is also used in mechanical panels or door panels of automobiles, racing boats, and interior parts associated with leather substitutes.

In recent years, in the building material which consists of said polyvinyl chloride resin, it became clear that the plasticizer and flame retardant plasticizer mix | blended with the polyvinyl chloride resin volatilize from a building material. For example, when polyvinyl chloride resin is used for the floor decoration material, the volatilized plasticizer may deteriorate the rubber of the chair wheel or dissolve the rubber to dirty the surface of the floor. When used in automobile interiors, the volatilized plasticizer has a problem of causing so-called fogging that blurs the windshield of the vehicle.

In addition, polyvinyl chloride resins undergo decomposition reactions mainly for dehydrochlorination by the action of heat, light (especially ultraviolet rays), oxygen, and the like, which are used during its production, molding, and use. It may discolor itself or age. This is a serious problem for products in which the appearance of products such as automobile interiors or building interiors is most important.

In order to solve the above problems, it is possible to consider adding various stabilizers to a composition composed of a polyvinyl chloride resin and a plasticizer, but if the environmental conditions in the state of use of these products deteriorate, avoid discoloration or aging sufficiently. There is a problem that is difficult.

For example, Japanese Patent No. 74-126752 discloses a technique for adding thermal stability by adding epoxidized polybutadiene having a high proportion of cis structure at low molecular weight to polyvinyl chloride resin. However, since the molecular weight of the epoxidized polybutadiene used is too small, the bleeding suppression of a plasticizer and the weight loss prevention at the time of heating of a polyvinyl chloride resin are not fully achieved. In addition, since a lot of sheath structure is included, there is a problem that the strength of the molded article using the same decreases.

In addition, Japanese Patent No. 77-54740 discloses a technique aimed at the same effect by adding epoxidized polyisoprene to a polyvinyl chloride resin. However, in this technique, since the polymer skeleton of the additive is polyisoprene, there is a problem that the heat resistance or weather resistance is not sufficient.

On the other hand, the method of suppressing the volatilization amount of a plasticizer is known using a high boiling point plasticizer, such as a trimellitic acid compound, without using the stabilizer as mentioned above. However, it cannot be said that volatilization of a plasticizer is necessarily fully suppressed, and it is industrially difficult to use expensive high boiling point plasticizer for all uses.

An object of the present invention is to provide a polyvinyl chloride resin composition which solves the above problems in a polyvinyl chloride resin and has a very small generation of bleed of the plasticizer and excellent thermal stability even when used for a long time.

MEANS TO SOLVE THE PROBLEM The present inventors made various examinations, and the resin composition which added the plasticizer and the specific internal epoxidation polybutadiene to the polyvinyl chloride resin can effectively prevent volatilization of a plasticizer, and also excellent thermal stability. Then, it was found that various problems caused by the bleeding of the plasticizer can be effectively suppressed, and the present invention has been completed based on this recognition.

That is, the gist of the present invention is as follows.

(1) 100 parts by weight of (A) polyvinyl chloride resin, 10 to 300 parts by weight of (B) plasticizer, and (C) number average molecular weight of 1,500 to 15,000, and the proportion of 1,4-trans structure in the molecular chain is Polyvinyl chloride resin composition which consists of 0.5-15 weight part of internal epoxidized polybutadiene obtained by epoxidizing the polybutadiene which is 50 mol% or more and has a hydroxyl group at the terminal,

(2) the polyvinyl chloride resin composition according to the above (1), wherein the amount of the terminal hydroxyl group of the polybutadiene is 0.1 to 8 milliequivalents / g,

(3) The polyvinyl chloride resin composition according to the above (1) or (2), wherein an epoxy equivalent of the internal epoxidized polybutadiene is 50 to 1,000;

(4) The polyvinyl chloride resin according to the above (1), wherein the plasticizer is composed of one or two or more compounds selected from the group consisting of phthalic acid esters, trimellitic acid esters, adipic acid esters, and epoxidized vegetable oils. Composition.

This invention relates to the polyvinyl chloride resin composition which consists of (A) polyvinyl chloride resin, (B) plasticizer, and (C) specific internal epoxidation polybutadiene.

First, as polyvinyl chloride resin which is (A) component of this invention, it can select arbitrarily from the thing currently marketed and used, and can use. The polyvinyl chloride resin may be one obtained by polymerizing vinyl chloride alone, and using vinyl chloride as a main component (specifically, 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more). And copolymerized by adding a comonomer such as acrylate ester, ethylene, propylene, vinylidene chloride, or the like. These comonomers may be used alone or in combination of two or more.

Polyvinyl chloride resin is usually produced by polymerizing a monomer such as vinyl chloride by suspension polymerization, bulk polymerization or emulsion polymerization, but the polyvinyl chloride resin of the present invention may be obtained by any of these production methods. In addition, plastisol or aqueous latex obtained by dispersing the fine particles obtained by the polymerization method in an organic medium may be used.

Moreover, the polymer-plant which mixed polyvinyl chloride resin and another resin can also be used. As other resin, polyvinylidene chloride and an ethylene vinyl acetate copolymer are mentioned, In this case, although other resin can be mixed in arbitrary ratio with respect to polyvinyl chloride resin, with respect to 100 weight part of polyvinyl chloride resins, And another resin are preferably mixed in an amount of 30 parts by weight or less, in particular 20 parts by weight or less. When more than 30 weight part of other resins are mixed, the thermal stability, mechanical strength, etc. of a polyvinyl chloride resin composition may fall.

Next, as a plasticizer which is (B) component of this invention, the plasticizer normally used for polyvinyl chloride resin can be used. Specifically, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, diisononyl phthalate, ethyl phthalate. Phthalic acid esters having an alkyl group having 1 to 12 carbon atoms, such as deylethyl glycolate, diundecyl phthalate, ditridecyl phthalate, didodecyl phthalate, diisoxyl phthalate, and dinonyl phthalate; Trimellitic acids such as trioctyl trimellitate and tri-n-octyl-n-decyl trimellitate; Adipic acid esters such as diisobutyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate and 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 gate, dibutyl sebagate, di-2-ethylhexyl sebagate, methylacetylylcynolate, and butylacetylylcynolate; Epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; Tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, triglydil phosphate, trikisilenyl phosphate, glyceryl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl di Phosphate esters such as phenyl phosphate, tris (2,3-dibropropylpropyl) phosphate and tris (2-chloroethyl) phosphate; Chlorinated paraffins; Chlorinated fatty acid esters; Epoxy butyl stearate, epoxy octyl stearate; Methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc. are mentioned. Of these, phthalic acid esters, trimellitic acid, adipic acid esters, and epoxidized vegetable oils are preferable, and di-2-ethylhexyl phthalate, diisodecyl phthalate, diisononyl phthalate, trimellitic acid-tri- 2-ethylhexyl, di-2-ethylhexyl adipate and epoxidized soybean oil are particularly preferred.

Although the compounding ratio of these plasticizers with respect to polyvinyl chloride resin has a preferable range by the use of the molded article obtained from a polyvinyl chloride resin composition, or its shaping | molding process, generally plasticizer 10-300 weight per 100 weight part of polyvinyl chloride resins. A part, Preferably it is 20-100 weight part, More preferably, it mix | blends 30-70 weight part.

Next, the internal epoxidized polybutadiene as the component (C) of the present invention refers to that part or all of the double bonds in the polymer chain except for the terminal of the polybutadiene are epoxidized polybutadiene. Specifically, it is an internal epoxidized polybutadiene obtained by epoxidizing the polybutadiene containing the hydroxyl group at the terminal whose number average molecular weight is 1,500-15,000, the ratio of a 1, 4-trans structure is 50 mol% or more.

Here, although the number average molecular weight of the polybutadiene to be epoxyized is 1,500-15,000, about 2,000-5,000 are preferable. As internal epoxidized polybutadiene which epoxidates polybutadiene of less than 1,500 in number average molecular weight, the bleeding prevention effect and the heat loss prevention effect of the said plasticizer contained in a polyvinyl chloride resin composition may not fully be acquired. On the other hand, when the number average molecular weight is larger than 15,000, the viscosity of the internal epoxidized polybutadiene itself epoxidized becomes high, which may make handling difficult or cause gelation.

Moreover, although the polybutadiene of this invention has a hydroxyl group at the terminal, about 0.1-8 meq / g (milliequivalent / g) is preferable as the hydroxyl group content, and about 0.2-5 meq / g is still more preferable. When the hydroxyl group content is less than 0.1 meq / g, the polarity of the polybutadiene becomes low, and the compatibility of the internal epoxidized polybutadiene and the plasticizer which epoxidized it may be caused. On the contrary, when it exceeds 8 meq / g, polarity may be excessive and compatibility with a plasticizer and polyvinyl chloride resin may fall.

As polybutadiene, as is generally known, double bonds of other structures such as 1,2-vinyl structure, 1,4-cis structure, 1,4-trans structure, and the like remain in the molecular chain or The ratio differs depending on the polymerization method. Although 50 mol% or more of the double bond which remain | survives in the molecular chain of the polybutadiene of this invention has a 1, 4-trans structure, it is preferable that the ratio is 60 mol% or more, and it is more preferable that it is 70 mol% or more. . The proportion of the 1,4-trans structure is smaller than 50 mol%, there are many 1,4-cis structures, the rubbery properties of the polyvinyl chloride resin composition may be strong, and the mechanical properties may decrease. In addition, the bleed in the polyvinyl chloride resin composition may not be sufficiently suppressed.

In addition, the polybutadiene of the present invention is preferably liquid at room temperature. Non-liquid polybutadiene is difficult to carry out epoxidation as described below, and also requires a large kneading machine when preparing the polyvinyl chloride resin composition.

In the present invention, the degree of epoxidation of the internal epoxidized polybutadiene can be understood as an epoxy equivalent, and the epoxy equivalent of the internal epoxidized polybutadiene is preferably about 50 to 750, and more preferably about 100 to 500. If the epoxy equivalent is less than 50, the polarity thereof becomes too high compared to the polyvinyl chloride resin, whereas if the epoxy equivalent exceeds 750, the polarity thereof is excessively lowered, and even in this case, the compatibility with the polyvinyl chloride resin may be reduced.

The internal epoxidized polybutadiene of the present invention can be prepared by radical polymerization of butadiene monomer to produce polybutadiene, followed by heating in the presence of peroxide and the like and internal epoxidation.

At this time, in the radical polymerization reaction, hydrogen peroxide and hydroxyl group-containing azo compounds such as 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] as a polymerization initiator, and cyclohexanone perox Radical polymerization is carried out using a hydroxyl group-containing peroxide such as a seed, and a hydroxyl group is contained at the terminal to obtain a liquid polybutadiene at normal temperature.

The hydroxyl-containing polybutadiene can be produced even if water, alcohol, ethylene oxide or the like is reacted with the terminal of the living polymer obtained by anionic polymerization of butadiene using naphthalenedilithium or the like as a polymerization reaction catalyst of butadiene.

In this case, the polymerization reaction of the butadiene monomer is suitably carried out in the presence of a solvent under conditions of a reaction temperature of 50 to 150 DEG C and a reaction time of 1 to 10 hours, and as a solvent, saturated hydrocarbons such as hexane or cyclohexane, n- It is preferable to use alcohols, such as butyl alcohol and isopropyl alcohol.

Subsequently, the obtained polybutene can be heated in the presence of peroxides such as hydrogen peroxide, peracetic acid and performic acid to epoxidize the double bond portion to obtain an internal epoxidized polybutadiene.

In the present invention, the internal epoxidized polybutadiene can be blended in an arbitrary ratio with respect to the polyvinyl chloride resin, and it is preferable to blend in an appropriate amount for the purpose of using the polyvinyl chloride resin composition. For example, when the polyvinyl chloride resin composition is used as a molding material, especially a thermoforming material, the internal epoxidized polybutadiene is 1 to 15 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. Preferably it is mix | blended in 2-10 weight part. If the blending ratio is less than 1 part by weight, the bleeding of the plasticizer may not be sufficiently prevented or the thermal stability of the composition may not be improved. On the other hand, when blending in excess of 15 parts by weight, the internal epoxidized polybutadiene may be thermally aged when the composition is thermoformed.

In this invention, although it is preferable to mix | blend the said plasticizer with the said polyvinyl chloride resin previously, to manufacture a plasticizer containing polyvinyl chloride resin, and to mix | blend the said internal epoxidation polybutadiene to manufacture a polyvinyl chloride resin composition, The polyvinyl chloride resin may be blended with the plasticizer and internal epoxidized polybutadiene simultaneously to produce a polyvinyl chloride resin composition. In addition, in order to mix these components and produce a homogeneous composition, it is sufficient to mix about 0.5 to 15 minutes with a mixer or a kneader at room temperature or under heating.

The obtained composition can be molded into various molded articles by methods such as extrusion molding, injection molding, calendar molding, press molding, blow molding, paste resin molding, and the like, for molding of a polyvinyl chloride resin. As molding conditions, it is good to select conditions suitable for each shaping | molding method suitably with shaping | molding temperature 150-250, Preferably l90-230 degreeC, and shaping | molding time 0.5 second-30 minutes. Basically, the same conditions as in the case of molding a conventional polyvinyl chloride resin can be adopted.

And since the polyvinyl chloride resin composition of this invention has the composition as mentioned above, the remarkable effect that the bleeding of the plasticizer which arises in long-term use peculiar to the molded article which consists of polyvinyl chloride resin containing a plasticizer effectively is suppressed effectively Can be obtained. This effect is attributable to the fact that the compatibility between the internal epoxidized polybutadiene and the plasticizer is greater than that of the polyvinyl chloride resin and the plasticizer, and that the bond between the two after the compatibility is strong.

In addition, although the polyvinyl chloride resin composition of the present invention can obtain the effect of suppressing discoloration or aging due to free chlorine, this is due to free chlorine from the polyvinyl chloride resin in the epoxy group and polybutadiene chain of the internal epoxidized polybutadiene. It originates in what can be captured by an unsaturated bond site.

The polyvinyl chloride resin composition of the present invention is composed of the above three components, but further, stabilizers, lubricants, antistatic agents, colorants, pigments, inorganic fillers, organic fillers, and the like can be appropriately selected for the type and use of the molded article, and appropriately selected. It can mix.

Examples of the stabilizer include lead salt stabilizers such as lead white, basic lead sulfite, tribasic lead sulfate, dibasic lead phosphite, dibasic lead phthalate, lead tribasic maleate, and silica gel co-precipitation lead silicate; Metal soaps such as lithium salts such as stearic acid, lauryl acid, ricinolic acid and naphthenic acid, potassium salts, calcium salts, magnesium salts, strontium salts, cadmium salts and barium salts; Metal salt stabilizers containing metal components such as cadmium, zinc, barium, calcium, tin, magnesium, sodium and potassium; Organotin stabilizers such as laurate organotin, maleate organotin, and mercktite organotin; Antimony-based organotin; Phosphite esters; Phenol derivatives; Polyhydric alcohols; Nitrogen-containing compounds; Stabilizers, such as a keto compound, are mentioned.

Since the compounding amount of these stabilizers is already sufficient for the basic composition of the present invention, it is added to further increase the amount, and a smaller amount is preferable than the compounding amount of the normal polyvinyl chloride resin. The blending amount is 0.05 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the composition.

Examples of the lubricant include hydrocarbon-based lubricants such as liquid paraffin, paraffin wax, microwax, low polymerized polyethylene, chlorinated hydrocarbon, and fluorocarbon oil; Fatty acid lubricants such as myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid; Fatty acid amide lubricants such as stearylamide, palmmethylamide, oleylamide, methylenebisstearamide, and ethylenebisstearamide; Ester lubricants such as hardened castor oil and ethylene glycol monostearate; Alcohol lubricants such as ethylene glycol, polyethylene glycol, and polyglycerol; Natural wax-based lubricants such as gabbanabana, ganderirabap, beeswax, light wax, white lead and montan wax; Metal soap-based lubricants such as lithium salts of potassium stearic acid, lauric acid, ricinolic acid and naphthenic acid, potassium salts, calcium salts, magnesium salts, strontium salts, cadmium salts and barium salts. The blending 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; Anionic activators such as sulfated oil, aliphatic alcohol sulfate ester salts and sulfates of alkyl compounds; Nonionic activators such as partial fatty acid esters of polyhydric alcohols and aliphatic alcohol adducts, amphoteric activators such as carboxylic acid derivatives and imidazoline derivatives; Inorganic compounds, such as a silica, are mentioned. The compounding quantity of this antistatic agent is 0.01-3 weight part, preferably 0.1-1 weight part per 100 weight part of compositions of this invention.

The colorants and pigments include titanium oxide, red iron oxide, sulfur lead, cadmium pigment, grouped carbon, carbon black, insoluble azo pigment, soluble azo pigment, condensed azo pigment, phthalocyanine pigment, vat dye pigment, quinacridone pigment, Metal powder pigments such as dioxadine pigments, salt lake pigments, aluminum or brass, pearl pigments, fluorescent pigments and the like. The compounding quantity of these colorants and a pigment is 0.05-50 weight part, Preferably it is 0.5-30 weight part per 100 weight part of compositions of this invention.

Moreover, as said inorganic filler, zinc, aluminum, copper, nickel, glass beads, glass flakes, glass fiber, carbon fiber, carbon black, graphite, asbestos, kaolin clay, leadstone clay, talc, fog stone, gliorite, wollastonite , Diatomaceous earth, slate rock powder, whitening powder, feldspar powder, mica, gypsum, quartz powder, fine silicate, attabalite, sericite, volcanic ash, vermiculite, silica, alumina, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide And molybdenum dioxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zeolite, potassium titanate, boron nitride, boron nitrite, molybdenum disulfide, and the like.

Examples of the organic filler include natural fibers such as rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, wood powder, cotton, hemp, wool, and silk; Synthetic fibers such as nylon, polyester, vinylon, acetate, and polyacrylonitrile; Powders or granules of synthetic resins such as polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, epoxy resin, and phenol resin Can be.

The blending ratio of these inorganic fillers and organic fillers is 500 parts by weight or less, preferably 200 parts by weight or less per 100 parts by weight of the composition of the present invention, and it is appropriate to determine the blending amount appropriately to suit the use and the required performance of the molded material.

Inorganic flame retardants such as halogen-based flame retardants, aluminum hydroxide, and antimony oxide, if necessary, in addition to the various compounding agents; Anti-aging agents such as hindered phenols, hindered amines and benzotriazoles; Organochlorine or organometallic flavoring agents: hydrocarbon solvents such as n-hexane, cyclohexane, toluene and xylene, ketone solvents such as methyl ethyl ketone and cyclohexanone, ester solvents such as butyl acetate, tetrahydrofuran and the like Viscosity-lowering agents such as ether solvents, N, N-dimethylformamide, dimethyl sulfoxide, and the like can be blended into the synthetic resin molding material in a conventional blending ratio.

Hereinafter, the present invention will be described in more detail based on Examples.

Example 1

10 g of polyvinyl chloride resin, 45 g of plasticizers, and 3 g of internal epoxidized hydroxyl group-terminated polybutadiene were respectively added to a Darlton mixer, and it knead | mixed for 5 minutes at room temperature, and the polyvinyl chloride resin composition of Example 1 was prepared.

(1) polyvinyl chloride resin

Brand name ZEST P31A (powdered polyvinyl chloride resin), average degree of polymerization; 1100

(2) plasticizer

Di-2-ethylhexylphthalate (DOP),

Boiling point; 386 ℃

(3) Internal epoxidized hydroxyl terminal polybutadiene

Trade name Epicle PB3600

Number average molecular weight; 3450

Epoxy equivalent weight; 201

Viscosity; 54 poise / 45 ℃

Hydroxyl content; 0.68 mm equivalent / g

The ratio of the 4-trans structure in the polybutadiene molecular chain; 60 mol% (the said hydroxyl content is measured based on JISK1557 (it is the same hereafter)).

The polyvinyl chloride resin composition thus obtained was put into a press molding mold for sheet molding, pressed at 230 ° C. for 3 minutes, and molded into a sheet having a thickness of 1 mm. The sheet was cut to a size of 60 mm x 90 mm to prepare a sheet-shaped test piece A for evaluation. In addition, the sheet-like test piece B was created similarly by shape | molding into the sheet | seat of thickness 4mm, cutting | disconnection to the magnitude | size of 60mm x 90mm. Using these test pieces, the physical property of the polyvinyl chloride resin composition was evaluated by the method shown below. The evaluation results are shown in Table 1.

Evaluation method of polyvinyl chloride resin composition

(a) Check for bleed

The sheet-shaped test piece A was put into a filter paper, it put into the gear type oven, and it heated at 120 degreeC for 10 days. Then, the test piece was removed from the gear type oven and cooled to room temperature. The test piece inserted in the filter paper was removed, and it was visually checked whether the plasticizer bleeds on the filter paper.

(b) heat resistance test

In the same manner as in 1), the sheet-like Test Piece A was placed in a gear oven, and the weight loss after heating at 120 ° C. for 10 days was measured.

(c) thermal stability

The sheet-like test piece A was put into a gear type oven similarly to 1), and heated at 120 degreeC for 10 days, and the change of the external appearance of the test piece was visually confirmed.

(d) tensile strength, elongation

It measured based on JISK6301 using the sheet-like test piece A.

(e) flexural strength

It measured based on JISK691L using the sheet-like test piece B.

(f) Weathering test (promoting weathering test)

Block panel temperature is 63 ± 3 ° C. using a low temperature cycle weather meter (light source: xenon lamp), and the irradiation cycle is irradiated for 112 minutes / 18 minutes under light and rain conditions. Investigate. The tensile strength and elongation of the test piece B after irradiation were measured in accordance with JIS K 6301.

Example 2

In Example 1, the polyvinyl chloride resin composition of Example 2 was prepared like Example 1 except having made the addition amount of the internal epoxidation hydroxyl terminal terminal polybutadiene into 5 g. The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table l.

Example 3

The poly of Example 3 was prepared in the same manner as in Example 1, except that diisodecylphthalate (DIOP, boiling point 420 ° C.) was used instead of di-2-ethylhexyl phthalate (DOP) as the plasticizer. A vinyl chloride resin composition was prepared. The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4

As in Example 1, except that trimellitic acid-tri-2-ethylhexyl (TOTM, boiling point 430 ° C.) was used instead of di-2-ethylhexylphthalate (DOP) as a plasticizer. The polyvinyl chloride resin composition of Example 4 was prepared. The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 1

In Example 1, the polyvinyl chloride resin composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that no internal epoxidized hydroxyl-terminated polybutadiene was used. The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 2

In Example 1, the number average molecular weight 2590, the viscosity 51 poise / 30 ° C, the hydroxyl content 0.84 milliliters / g, the ratio of the 1, 4-trans structure in the polybutadiene molecular chain instead of the internal epoxidized hydroxyl group terminal polybutadiene A polyvinyl chloride resin composition of Comparative Example 2 was prepared in the same manner as in Example 1, except that 60% by mole of non-epoxidized hydroxyl group-end polybutadiene (trade name: Polybd R-45HT, manufactured by KKK) was prepared. The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 3

In Example 1, the number average molecular weight 1800, the epoxy equivalent 220, the viscosity 3500 poise / 25 degreeC, and the ratio of the 1, 2- vinyl structure in a polybutadiene molecular chain instead of the internal epoxidation hydroxyl terminal terminal polybutadiene were 65 mol%. The polyvinyl chloride resin composition of Comparative Example 3 was prepared in the same manner as in Example 1 except that epoxidized polybutadiene (trade name E-1800-6.5, manufactured by Nippon Petrochemical Co., Ltd.) containing no hydroxyl group was used. The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 4

In Example 1, the ratio of the number average molecular weight 2900, the epoxy equivalent 1450, the viscosity 130 poise / 25 degreeC, and the 1, 4-trans structure in a polybutadiene molecular chain was 60 mol% instead of the internal epoxidation hydroxyl terminal terminal polybutadiene. The polyvinyl chloride resin composition of Comparative Example 4 was prepared in the same manner as in Example 1 except that the terminal epoxidized polybutadiene (manufactured by KK Petrochemical Co., Ltd., trade name Poly bd R-45EPT) was used. The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 5

Number average molecular weight 3000, viscosity 300 poise / 20 ° C, the ratio of 1,4-cis structure in the polybutadiene molecular chain is 80 mol%, liquid polybutadiene containing no hydroxyl group (product of Japan Xeon Co., Ltd., trade name Polyoil 130) 15 g of peracetic acid and 50 g of water were added to 100 g, and the mixture was reacted at 70 ° C. for 6 hours to epoxidize the liquid polybutadiene. After the reaction was completed, toluene was added, the mixture was stirred, and after the solution was separated into oily water, the oil layer was taken out. Toluene was distilled off from the oil layer by heating at 80 degreeC and the pressure reduction of 10 mmHg for 2 hours, and high cis internal epoxidized polybutadiene was obtained. The epoxidation equivalent of the obtained internal epoxidized polybutadiene was 250.

In Example 1, the polyvinyl chloride resin composition of Comparative Example 5 was prepared in the same manner as in Example 1 except that the high cis internal epoxidized polybutadiene obtained above was used instead of the internal epoxidized hydroxyl group terminated polybutadiene. The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 6

A liquid isoprene-based polymer containing a hydroxyl group having a number-average molecular weight of 2600, a hydroxyl content of 0.84 milliequivalents / g, a viscosity of 75 poises / 30 ° C, and a ratio of 1,4-trans structure in the polyisoprene molecular chain of 61 mol%. 15 g of peracetic acid and 50 g of water were added to 100 g of Poly ip) manufactured by Petrochemical Co., Ltd. and reacted at 70 ° C for 6 hours to epoxidize the liquid polyisoprene-based polymer. After the reaction, toluene was added and stirred, and the solution was separated with oil, and then the oil layer was taken out. Toluene was removed from the oil layer by heating under reduced pressure of 80 degreeC and 10 mmHg for 2 hours, and the high trans internal epoxidized isoprene was obtained. Obtained internal epoxidized isoprene was number average molecular weight 3560, viscosity 82 poise / 45 degreeC, epoxidation equivalence 240, and hydroxyl group content 0.6 milliliter equivalent / g.

In Example 1, the polyvinyl chloride resin composition of the comparative example 6 was prepared like Example 1 except having used the high trans internal epoxidized isoprene obtained above instead of the internal epoxidized hydroxyl terminal terminal polybutadiene. The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 7

In Example 1, the number average molecular weight l200, the hydroxyl content 1.83 milliequivalents / g, the viscosity l5 poise / 30 degreeC, the ratio of the 1, 4-trans structure in a polybutadiene molecular chain instead of the internal epoxidation hydroxyl terminal terminal polybutadiene. The poly of Comparative Example 6 was prepared in the same manner as in Example 1 except that the 60 mol% hydroxyl terminal liquid polybutadiene was epoxidized to use an internal epoxidized polybutadiene (manufactured by Elpatgem Co., Ltd., trade name Poly bd600, epoxy equivalent 460). A vinyl chloride resin composition was prepared. The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 8

Hydroxyl-terminated liquid polybutadiene having a number-average molecular weight of 2590, viscosity of 51 poise / 30 ° C, hydroxyl content of 0.84 milliequivalents / g, and 1,4-trans structure in the polybutadiene molecular chain (60 mol%) To 100 g of the brand name Poly bd R-45 HT), butanol was added as a solvent and 30 g of acetic acid and reacted at 70 ° C for 6 hours to acetylen the hydroxyl-terminated liquid polybutadiene. After completion of the reaction, toluene was added and stirred, and after the solution was separated into oily water, the oil layer was taken out. Toluene was removed from the oil layer by heating at 80 degreeC and the reduced pressure of 10 mmHg for 2 hours, and the high trans internal epoxidized polybutadiene which does not contain a hydroxyl group was obtained. Obtained internal epoxidized isoprene was number average molecular weight 3520, viscosity 59 poise / 45 degreeC, and epoxidation equivalent 255.

In Example 1, the polyvinyl chloride resin composition of the comparative example 8 was prepared like Example 1 except having used the high trans internal epoxidized polybutadiene obtained above instead of the internal epoxidized hydroxyl terminal terminal polybutadiene. . The physical properties of the obtained polyvinyl chloride resin composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Bleed Heating loss% Thermal stability Tensile Strength MPa Elongation% Flexural Strength MPa Weather resistance Tensile Strength MPa Elongation% Example 1 radish 13 Slightly black 19 310 110 17 275 Example 2 radish 13 Slightly black 18 290 106 17 270 Example 3 radish 3 Slightly black 18 280 108 16 270 Example 4 radish 0 Slightly black 18 300 112 17 280 Comparative Example 1 U 17 Turned black 20 300 113 18 310 Comparative Example 2 U 25 Turned black 16 240 103 15 225 Comparative Example 3 U 30 Slightly black 19 300 101 23 240 Comparative Example 4 U 17 Turned black 18 265 96 13 205 Comparative Example 5 U 20 Slightly black 16 320 84 13 350 Comparative Example 6 radish 16 Turned black 18 310 98 10 185 Comparative Example 7 U 29 Slightly black 17 300 102 15 280 Comparative Example 8 U 28 Turned black 19 295 100 16 270

When the polyvinyl chloride resin composition of the present invention is molded and used for a long time, very little bleed of the plasticizer can be exhibited, and a unique effect excellent in thermal stability can be exhibited.

Claims (4)

(A) 100 parts by weight of polyvinyl chloride resin, (B) 10 to 300 parts by weight of plasticizer, and (C) number average molecular weight is 1,500 to 15,000, and the proportion of 1,4-trans structure in the molecular chain is 50 mol%. The polyvinyl chloride resin composition which consists of 0.5-15 weight part of internal epoxidized polybutadiene obtained by epoxidizing the polybutadiene which has a hydroxyl group at the terminal. The method of claim 1, The polyvinyl chloride resin composition whose terminal hydroxyl group amount of polybutadiene is 0.1-8 meq / g (milliequivalent / g). The method according to claim 1 or 2, The polyvinyl chloride resin composition whose epoxy equivalent of internal epoxidized polybutadiene is 50-1,000. The method according to any one of claims 1 to 3, The polyvinyl chloride resin composition in which a plasticizer consists of 1 type, or 2 or more types of compounds chosen from the group which consists of phthalic acid ester, trimellitic acid ester, adipic acid ester, and epoxidized vegetable oil.