JP2725375B2 - Vinyl chloride resin composition - Google Patents

Description

The present invention relates to a vinyl chloride resin composition having excellent transparency, heat resistance and impact resistance.

More specifically, a vinyl chloride resin (a), a copolymer (b) containing α-methylstyrene, vinyl cyanide, and methyl methacrylate as main components, and a diene rubber having a specific average particle size Transparency, heat resistance, and resistance obtained by mixing a polymer with a graft copolymer (c) obtained by graft-polymerizing a monovinyl aromatic monomer and a monomer having methyl methacrylate as a main component. The present invention relates to a vinyl chloride resin composition having excellent impact properties.

b. Conventional technology Vinyl chloride resins have many excellent properties such as physical strength, transparency, chemical resistance, weather resistance, and flame retardancy, and are used in a wide variety of applications.

However, since the heat resistance is inferior, it is unsuitable as a constituent material for heat-resistant bottles, housings of home electric appliances, exteriors of OA equipment, and internal parts of automobiles.

As means for remedying this drawback, a copolymer comprising α-methylstyrene, methyl methacrylate and acrylonitrile, and a conjugated diene rubbery polymer, styrene,
A method of blending a graft copolymer obtained by graft polymerization of methyl methacrylate and acrylonitrile with a vinyl chloride resin (Japanese Patent Publication No. 48-18101), a copolymer of α-methylstyrene, methyl methacrylate and acrylonitrile, A method of blending a vinyl chloride resin with a graft copolymer obtained by graft-polymerizing styrene, methyl methacrylate and acrylonitrile on a conjugated diene rubbery polymer of 0.1 μ to 0.3 μ (Japanese Patent Publication No. 57-42094), Is being developed.

c. Problems to be Solved by the Invention However, the above-mentioned JP-B-48-18101 and JP-B-57
The modifiers disclosed in -42094 and the like have improved heat resistance, but have disadvantages such as reduced transparency and low impact resistance, and have heat resistance, transparency and impact resistance. However, it is not a modifier that sufficiently satisfies the above three, and its improvement has been desired.

That is, it has been a long-standing problem to develop a modifier having excellent transparency and impact resistance while maintaining heat resistance, and great efforts have been made to solve the problem.

c. Means for Solving the Problems The present inventors have conducted various studies in order to solve the above-mentioned problems, and as a result, a copolymer containing α-methylstyrene, vinyl cyanide, and methyl methacrylate as main components has been obtained. In the polymerization of α-methylstyrene and vinyl cyanide and methacrylic acid methyl ester, a polymerization reaction is carried out until the polymerization conversion rate becomes 85% or more, and then a specific amount of methacrylic acid methyl ester is added. , A specific amount of a copolymer that completes the polymerization reaction, and a diene rubber-like polymer having a specific average particle diameter, a monovinyl aromatic monomer, methyl methacrylate and vinyl cyanide as main components. By blending a specific amount of a graft copolymer obtained by graft-polymerizing a monomer into a vinyl chloride-based resin, a chlorinated resin having excellent heat resistance, transparency and impact resistance is obtained. It found that sulfonyl-based resin composition is obtained, in which the present invention has been completed.

That is, the vinyl chloride resin composition of the present invention comprises: (a) 30 to 80% by weight of a vinyl chloride resin; and (b) α-methylstyrene, vinyl cyanide, methyl methacrylate, and copolymerizable with them. A copolymer comprising a vinyl monomer, comprising 30 to 60% by weight of α-methylstyrene, 4 to 18% by weight of vinyl cyanide, 30 to 60% by weight of methacrylic acid methyl ester, and vinyl copolymerizable therewith. After polymerizing 85 to 98 parts by weight of a monomer (b-1) comprising 0 to 15% by weight of a system monomer until the polymerization conversion rate becomes 85% or more, methyl methacrylate (b)
-2) 2 to 15 parts by weight (provided that (b-1) + (b-2) =
100 parts by weight) to complete the polymerization reaction.
(C) 45 to 80 parts by weight of a diene rubbery polymer (c-1) having an average particle diameter of 0.1 μ or less based on 0 to 70% by weight and 100 parts by weight of the total amount of (a) and (b). In the presence of 30 to 60% by weight of a monovinyl aromatic monomer, 35 to 65% by weight of methyl methacrylate, 0 to 15% by weight of vinyl cyanide, and 0 to 15% by weight of a vinyl monomer copolymerizable therewith. Monomer (c-2) comprising 15% by weight and 0 to 3% by weight of a polyfunctional monomer
Graft copolymer obtained by graft polymerization of 20 to 55 parts by weight (provided that (c-1) + (c-2) = 100 parts by weight)
25 parts by weight are mixed.

 Hereinafter, the present invention will be described specifically.

(1) Vinyl chloride resin (a) As the vinyl chloride resin (a), polyvinyl chloride,
A copolymer of 70% by weight or more of vinyl chloride monomer and 30% by weight or less of a copolymerizable monomer such as vinyl bromide, vinylidene chloride, vinyl acetate, acrylic acid, methacrylic acid, and ethylene, or Polyvinyl chloride can be used.

(2) Copolymer (b) The copolymer (b) used in the present invention is a copolymer comprising α-methylstyrene, vinyl cyanide, methyl methacrylate and a vinyl monomer copolymerizable therewith. It is a polymer obtained by dividing the polymerization reaction into two stages.

In the first stage of the polymerization reaction, α-methylstyrene is 30 to 60% by weight, preferably 35 to 55% by weight, and vinyl cyanide 4 to 18%.
%, Preferably 6 to 15% by weight, methacrylic acid methyl ester 30 to 60% by weight, preferably 35 to 55% by weight, and 0 to 15% by weight of a vinyl monomer copolymerizable therewith,
85 to 98 parts by weight of a monomer preferably consisting of 0 to 10% by weight,
It is preferably carried out by polymerizing 88 to 97 parts by weight until the polymerization conversion becomes 85% or more.

If the amount of α-methylstyrene is less than 30% by weight, the heat resistance of the final composition will decrease. Conversely, if it exceeds 60% by weight, not only does the polymerization conversion decrease, but also the transparency of the final composition decreases.

If the amount of vinyl cyanide is less than 4% by weight, the heat distortion temperature and the transparency of the final composition are reduced. Conversely, if it exceeds 18% by weight, the color tone of the final composition turns yellow and the transparency decreases.

Note that vinyl cyanide includes acrylonitrile, methacrylonitrile, and the like, and one or more of these are used. Particularly preferred is acrylonitrile.

If the amount of methacrylic acid methyl ester is less than 30% by weight, the heat resistance and the transparency of the final composition decrease. Conversely, if it exceeds 60% by weight, the heat resistance of the final composition will be reduced.

In the second-stage polymerization reaction, after the polymerization conversion rate has advanced by 85% or more, preferably 90% or more in the first-stage polymerization reaction, 2 to 15 parts by weight, preferably 3 to 12 parts by weight of methacrylic acid methyl ester Is added to complete the polymerization reaction.

If the addition of methyl methacrylate in the second stage polymerization reaction is carried out when the polymerization addition ratio in the former stage is less than 85%, the heat resistance and transparency of the final composition are reduced.

In the present invention, since the polymerization reaction is performed in two stages,
The copolymer formed in the latter stage has good compatibility with the vinyl chloride resin. For this reason, the transparency of the final composition is significantly improved.

However, if the amount of methacrylic acid methyl ester to be polymerized in the second step exceeds 15 parts by weight, the heat resistance and transparency of the final composition are reduced. Conversely, if the amount is less than 2 parts by weight, the transparency of the final composition is reduced.

In the emulsion polymerization of the copolymer (b), commonly used emulsifiers, electrolytes, polymerization regulators, polymerization initiators and the like can be used.

Examples of the emulsifier include an alkali metal salt of rosin acid, an alkali metal salt of a fatty acid, an alkali metal salt of an aliphatic alcohol sulfate, and an alkali metal salt of an alkyl allyl sulfonic acid.As the electrolyte, sulfuric acid, phosphoric acid, hydrochloric acid, Each alkali metal salt of carbonic acid is exemplified.

Further, as a polymerization regulator, mercaptans, terpenes, halides and the like can be added as necessary. As a polymerization initiator, a persulfate, an organic hydroperoxide, or an organic hydroperoxide and a reducing agent are used. Redox catalysts and the like by a combination of the above can be suitably used.

In the polymerization of the copolymer (b), it is essential that the polymerization reaction is carried out in two stages and that methacrylic acid methyl ester is polymerized in the second stage. However, other polymerization conditions are not limited. For example, in the first-stage polymerization, batch addition polymerization of monomers, continuous addition polymerization, multi-stage polymerization, such as continuous addition polymerization of a specific monomer which is polymerized by continuously adding only a specific amount of vinyl cyanide, etc. The emulsion polymerization method generally known widely can be applied.

Emulsion polymerization methods such as batch addition polymerization of methacrylic acid methyl ester, continuous addition polymerization, and multi-stage polymerization can be applied to the latter stage polymerization as in the former stage.

(3) About Graft Copolymer (c) The graft copolymer (c) used in the present invention is a diene rubbery polymer (c-1) having an average particle diameter of 0.1 μm or less, preferably 0.04 to 0.09 μm. ) 45-80 parts by weight, preferably
Monovinyl aromatic monomer 30 in the presence of 50 to 75 parts by weight
-60% by weight, preferably 35-55% by weight, methacrylic acid methyl ester 35-65% by weight, preferably 40-60% by weight,
0 to 15% by weight, preferably 0 to 10% by weight of vinyl cyanide, 0 to 15% by weight, preferably 0 to 10% by weight of a vinyl monomer copolymerizable therewith and 0 to 0% of a polyfunctional monomer
3% by weight, preferably 0 to 2% by weight of a monomer (c)
-2) a graft copolymer obtained by graft polymerization of 20 to 55 parts by weight, preferably 25 to 50 parts by weight, (c-1)
And the sum of (c-2) is 100 parts by weight.

i) Diene-based rubbery polymer (c-1) As the conjugated diene constituting the diene-based rubbery polymer (c-1), butadiene, isoprene, chloroprene and the like can be used. preferable.

Examples of the monomer copolymerizable with the conjugated diene include aromatic vinyl, unsaturated carboxylic acid, alkyl methacrylate, alkyl acrylate, vinyl cyanide, and polyfunctional monomers.

Among them, aromatic vinyl is preferable, and a small amount of unsaturated carboxylic acid and a small amount of polyfunctional monomer can be used as needed.

However, the conjugated diene in the copolymer (c-1) is 50
If the amount is less than 10% by weight, the impact resistance of the final composition at low temperature is inferior.

The average particle size of the diene rubbery polymer (c-1) latex greatly contributes to the transparency of the final composition. When the average particle size exceeds 0.1 μm, the transparency of the final composition decreases.

If the amount of the diene rubbery polymer (c-1) is less than 45 parts by weight, the impact resistance of the final composition will be reduced. Conversely, if it exceeds 80 parts by weight, the transparency of the final composition is reduced.

In the polymerization of the diene rubbery polymer (c-1),
Emulsifiers, polymerization initiators, polymerization regulators, electrolytes and the like used in the production of the copolymer (b) can be used, and the polymerization means are the same. For example, batch addition polymerization of monomers, continuous polymerization Commonly known emulsion polymerization methods such as additive polymerization, multi-stage polymerization, and continuous addition polymerization of a specific monomer can be applied.

ii) Monomer (c-2) Monomer (c-2) used for graft copolymerization may be a monovinyl aromatic monomer, methyl methacrylate, vinyl cyanide, or a vinyl monomer copolymerizable therewith. And a monomer comprising a multifunctional monomer.

As the monovinyl aromatic monomer, styrene,
α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p
-Tert-butylstyrene, ethylstyrene, vinylnaphthalene, etc., which are used alone or in combination of two or more.

Preferred monovinyl aromatic monomers are those containing styrene or 50% by weight or more of styrene.

The above-mentioned vinyl cyanide includes acrylonitrile, methacrylonitrile and the like, and these are used alone or in combination of two or more. A particularly preferred vinyl cyanide is acrylonitrile.

Examples of the copolymerizable vinyl monomer include alkyl methacrylate, alkyl acrylate,
Examples include esters of ethylenically unsaturated carboxylic acids and hydroxyalkyls. Specific examples thereof include ethyl methacrylate, butyl methacrylate, hexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, β -Hydroxy acrylate and the like.

Examples of the polyfunctional monomer include a non-conjugated divinyl compound represented by divinylbenzene and a polyvalent acrylate compound represented by trimethylolpropane triacrylate.

When the amount of the monovinyl aromatic vinyl monomer as the monomer (c-2) to be subjected to the graft copolymerization is less than 30% by weight, the transparency of the final composition decreases, and conversely, the amount exceeds 60% by weight. However, the transparency of the final composition is reduced. If the amount of methacrylic acid methyl ester is less than 35% by weight, the transparency of the final composition decreases, and if it exceeds 65% by weight, the transparency of the final composition decreases.

If the amount of vinyl cyanide exceeds 15% by weight, the transparency of the final composition is lowered, and the color of the composition is changed to yellow, which is not preferable.

When the amount of the copolymerizable vinyl monomer exceeds 15% by weight, the transparency, heat resistance and impact resistance of the final composition decrease.

If the amount of the polyfunctional monomer exceeds 3% by weight, the impact resistance of the final composition is reduced.

If the amount of the monomer (c-2) used for the graft copolymerization exceeds 55 parts by weight, the impact resistance of the final composition decreases, and conversely, the amount of the monomer used for the graft copolymerization is less than 20 parts by weight. If it is, the transparency of the final composition decreases.

In the polymerization of the graft copolymer (c), the emulsifier, polymerization initiator, polymerization regulator, electrolyte and the like used in producing the copolymer (b) can be used. As the graft copolymerization method, various widely known graft copolymerization methods can be applied.

For example, the method of adding the monomer (c-2) to be graft-copolymerized in the presence of the diene rubbery polymer (c-1) is as follows:
Any method such as batch addition polymerization, continuous addition polymerization, and multi-stage polymerization may be used, but is divided into a portion mainly containing methacrylic acid methyl ester and a portion mainly containing monovinyl aromatic monomer. And graft copolymerization is preferred.

Also, a method of adding a small amount of dilute acetic acid prior to the graft copolymerization to enlarge the particles of the diene-based rubber-like polymer (c-1) latex and then graft-copolymerizing the diene-based rubber-like polymer (c-1) -1) to sodium chloride,
A method of adding an electrolyte such as potassium chloride, potassium sulfate, or potassium phosphate to coagulate and enlarge latex particles during graft copolymerization may be employed. However, the preferred average particle diameter of the graft copolymer (c) latex is as follows: 0.1-0.3
μ, and more preferably the average particle size is 0.15 to 0.23 μ.

The most preferred graft copolymerization method is to add an electrolyte to the diene rubbery polymer (c-1), first add a monomer containing methyl methacrylate as a main component, and form the latex particles while graft copolymerizing. Coagulation and enlargement,
Subsequently, a monomer containing a monovinyl-based aromatic monomer as a main component is added to complete the graft copolymerization.

After the completion of the graft copolymerization, an antioxidant such as 2,6-di-tert-butyl-4-methylphenol can be added.

(4) Vinyl Chloride Resin Composition The copolymer (b) and the graft copolymer (c) thus obtained may be directly mixed with the vinyl chloride resin (a). Powder after drying.

In this case, the copolymer (b) and the graft copolymer (c)
May be separately coagulated and dried to form a powder, or the copolymer (b) and the graft copolymer () may be mixed so as to obtain desired physical properties when mixed with the vinyl chloride resin (a). c)
May be mixed in advance, and then coagulated and dried to form a powder.

Usually, the copolymer (b) and the graft copolymer (c) are separately coagulated and dried, and then powdered.

The copolymer (b) and the graft copolymer (c) thus obtained are mixed in a required amount with the vinyl chloride resin (a) so as to obtain desired heat resistance, transparency and impact resistance. I just need.

In order to effectively achieve the object of the present invention, 30 to 80% by weight, preferably 40 to 70% by weight of the vinyl chloride resin (a)
And the copolymer (b) is 20 to 70% by weight, preferably 30 to 60% by weight, and the graft copolymer (c) is 3 to 25% based on 100 parts by weight of the total amount of the components (a) and (b). Parts by weight, preferably 5 to 20 parts by weight.

If the vinyl chloride resin (a) is less than 30% by weight (the copolymer (b) exceeds 70% by weight), the processability is poor,
It does not yellow and does not provide clean molded products. Conversely, if the amount of the vinyl chloride resin (a) exceeds 80% by weight (the amount of the copolymer (b) is less than 20% by weight), the desired heat resistance cannot be obtained.

If the amount of the graft copolymer (c) is less than 3 parts by weight, the effect of addition cannot be obtained and the impact resistance is poor. On the other hand, if it exceeds 25 parts by weight, heat resistance is reduced and it is not economical.

The vinyl chloride resin (a), the copolymer (b) and the graft copolymer (c) are mixed in a powder form, for example, using a ribbon blender / Henschel type mixer. Mixing can also be performed by a machine such as a mixing roll, a Banbury mixer, an extruder, and a blow molding machine, and molding can be performed.

If necessary, conventional stabilizers, pigments, fillers, plasticizers, lubricants, acrylic processing aids, and the like may be added when mixing.

e. Examples Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist.

In the following Examples and Comparative Examples, “parts” means “parts by weight” and “%” means “% by weight”.

Example 1 (1) Production of copolymer (b) 200 parts of deionized water, 2.5 parts of potassium alkenyl succinate,
42 parts of α-methylstyrene, 10 parts of acrylonitrile, 42 parts of methyl methacrylate, 0.3 part of tert-dodecyl mercaptan, 0.3 part of diisopropylbenzene hydroperoxide, 0.005 part of ferrous sulfate, 0.2 part of disodium ethylenediaminetetrasulfate 0.2 part and formaldehyde sulfoxyl 0.4 part of sodium acid was charged into an autoclave purged with nitrogen, and polymerized at 60 ° C. with stirring. When the polymerization conversion reached 94%, 6 parts of methyl methacrylate,
Diisopropylbenzene hydroperoxide 0.1
, 0.001 part of ferrous sulfate, 0.04 part of disodium ethylenediaminetetraacetate and 0.08 part of sodium formaldehyde sulfoxylate, and the polymerization was further continued for 2 hours to complete the polymerization. The polymerization conversion after 2 hours was 98%.

Next, after coagulation with a 0.5% sulfuric acid aqueous solution, the solid was washed with warm water and dried to obtain a white powder.

(2) Production of diene rubbery polymer (c-1) 150 parts of deionized water, 4 parts of potassium stearate, 1 part of potassium sulfate, 75 parts of 1,3-butadiene, 25 parts of styrene,
Tertiary dodecyl mercaptan 0.2 part, paramentan hydroperoxide 0.06 part, ferrous sulfate 0.01 part,
0.025 part of disodium ethylenediaminetetraacetate and 0.04 part of sodium formaldehyde sulfoxylate were charged into an autoclave purged with nitrogen, and polymerized at 8 ° C. for 12 hours with stirring. The polymerization was terminated at a polymerization addition rate of 95%. Subsequently, steam was blown into the obtained diene rubber-like polymer latex to remove unreacted monomers. The average particle diameter of the obtained diene rubbery polymer latex was measured using a laser particle size analyzer manufactured by Otsuka Electronics Co., Ltd., and was found to be 0.07 μm.

(3) Production of graft copolymer (c) In a nitrogen-purged autoclave, the diene rubber-like polymer latex produced in the above (2) was converted to a solid content of 65%.
, 150 parts of deionized water (including water in the diene rubbery polymer latex) and 0.5 part of potassium sulfate, and the temperature was raised to 80 ° C. Then, methyl methacrylate 18
Part, 2 parts of n-butyl acrylate, 0.1 part of diisopropylbenzene hydroperoxide and 0.04 part of sodium formaldehyde sulfoxylate were continuously added over 4 hours. After the end of the continuous addition, the graft polymerization was continued for another hour.

Next, 15 parts of styrene, 0.1 part of diisopropylbenzene hydroperoxide and 0.04 part of sodium formaldehyde sulfoxylate were continuously added over 4 hours. After completion of the continuous addition, graft polymerization was further performed for 1 hour to complete the polymerization. The polymerization conversion was 98%, and the average particle size of the graft copolymer latex was 0.23 μm.

Next, 1 part of butylated hydroxytoluene was added, coagulated with a 0.5% aqueous sulfuric acid solution, washed with warm water, and dried to obtain a white powder.

(4) Production of a vinyl chloride resin composition and evaluation of its physical properties 60 parts of a polyvinyl chloride resin having an average degree of polymerization of 700, 40 parts of the copolymer produced in the above (1) and the graft copolymer produced in the above (3) A mixture of 12 parts of the coalesced substance, 2 parts of octyltin mercaptide stabilizer and 2 parts of butylene glycol montanate was charged into a Henschel mixer, heated to 120 ° C. with stirring, and then cooled to 50 ° C.

Next, the obtained mixture was kneaded with a roll at 165 ° C. for 6 minutes, and then press-molded with a press at 185 ° C. for 8 minutes to give a test piece for an Izod impact test having a thickness of 6.35 mm and a thickness of 1.6 mm. A transparent plate and a 6.35 mm thick test piece for measuring heat deformation temperature were prepared.

The physical properties of the obtained test piece and transparent plate were evaluated by the following methods.

Note Izod impact test: ASTM-D256, with notch, 23 ° C Total light transmittance and haze: JIS K6714 Heat distortion temperature: ASTM-D648, 4.6 kg / cm ² load The evaluation results of physical properties are shown in Table 1.

Examples 2 to 6, Comparative Examples 1 to 7 In producing the copolymer (b), as shown in Table 1, the first stage monomer composition, the first stage polymerization conversion, and the second stage Copolymer (b) was produced in the same manner as in Example 1 except that the amount of methyl methacrylate was changed. Using the obtained copolymer (b) and the graft copolymer (c) produced in Example 1, physical properties were evaluated according to (4) Production of vinyl chloride resin composition of Example 1 and evaluation of physical properties thereof. did.

 Table 1 shows the physical property evaluation results.

As is clear from the results shown in Table 1, Examples 1 to 6
In the production of the copolymer (b), the composition obtained in
The first-stage monomer composition, the first-stage polymerization conversion and the amount of the second-stage methyl methacrylate are adjusted so as to be within the scope of the present invention, and the heat resistance of the resin composition is adjusted. Excellent in transparency, transparency and impact resistance.

On the other hand, in the compositions of Comparative Examples 1 to 7, the copolymer (b), which is a component of the composition, is out of the scope of the present invention, and both the heat resistance and the transparency of the resin composition are used. Either or either is significantly inferior.

From these Examples and Comparative Examples, in the production of the copolymer (b), the polymerization was divided into two stages, and methyl methacrylate was used in the second stage, the monomer composition in the first stage,
It can be seen that the polymerization conversion in the first stage and the amount of methyl methacrylate in the second stage greatly affect the heat resistance and transparency of the resin composition.

Examples 7 to 8 and Comparative Example 8 In the production of the diene rubbery polymer, which is a component of the graft copolymer (c), the diene of Example 1 was used except that the amount of potassium sulfate shown in Table 2 was changed. A diene rubbery polymer was produced by a polymerization method for a rubbery polymer.

Table 2 shows the average particle size of the diene rubbery polymer latex.

Using the obtained diene rubbery polymer, a graft copolymer (c) was produced according to the method for polymerizing the graft copolymer of Example 1.

Using the thus obtained graft copolymer (c) and the copolymer (b) produced in Example 1, production of (4) vinyl chloride resin composition of Example 1 and evaluation of its physical properties According to the above, physical properties were evaluated.

 Table 2 shows the physical property evaluation results.

As is evident from the results shown in Table 2, the compositions obtained in Examples 7 and 8 show that the latex particle diameter of the diene rubber-like polymer which is a component of the graft copolymer (c) is the present invention. The transparency and impact resistance of the resin composition are both extremely excellent.

On the other hand, the composition of Comparative Example 8 had a latex particle size of the diene rubber-like polymer outside the range of the present invention, and was extremely inferior in both impact resistance and transparency of the resin composition.

From these Examples and Comparative Examples, it can be seen that the latex particle diameter of the diene rubber-like polymer, which is a component of the graft copolymer (c), has a large effect on the impact resistance and transparency of the resin composition. I understand.

Examples 9 to 15 and Comparative Examples 9 to 15 In the production of the graft copolymer (c), the diene-based rubbery polymer of Example 1 was used instead of the monomers shown in Table-3. The graft copolymer (c) was produced according to the method for polymerizing the graft copolymer of No. 1.

Using the obtained graft copolymer (c) and the copolymer (b) produced in Example 1, the physical properties were determined according to (4) Production of vinyl chloride resin composition of Example 1 and evaluation of the physical properties thereof. evaluated.

 Table 3 shows the physical property evaluation results.

As is clear from the results shown in Table 3, Examples 9 to 15
In the composition obtained in the above, the diene rubber-like polymer and the monomer composition of the graft copolymer (c) are within the range of the present invention, and the heat resistance, transparency and impact resistance of the resin composition The properties are all excellent.

On the other hand, in the compositions of Comparative Examples 9 to 15, the graft copolymer (c) was out of the range of the present invention, and any one of the heat resistance, transparency and impact resistance of the resin composition was not satisfied. , Markedly inferior.

From these Examples and Comparative Examples, the amount of the diene rubber-like polymer and the monomer composition of the graft polymer (c) were as follows:
It can be seen that the heat resistance, transparency and impact resistance of the resin composition are significantly affected.

Examples 16 to 19, Comparative Examples 16 to 19 In producing a vinyl chloride resin composition, the copolymer (b) produced in Example 1 and the graft copolymer (c) produced in Example 1 were used. Then, the mixing with the vinyl chloride resin (a) was changed to the mixing ratio shown in Table 4 to produce a vinyl chloride resin composition, and the physical properties of (4) the vinyl chloride resin composition of Example 1 Physical properties were evaluated according to the evaluation method.

 Table 4 shows the evaluation results of the physical properties.

As is clear from the results shown in Table 4, Examples 16 to 19
The composition obtained in is adjusted so that the blending ratio of the vinyl chloride resin (a), the copolymer (b) and the graft copolymer (c) falls within the range of the present invention, The heat resistance, transparency and impact resistance of the resin composition are all excellent.

In contrast, the compositions of Comparative Examples 16 to 19 consisted of the component (a),
The compounding ratio of (b) and (c) is out of the range of the present invention, and any one of the heat resistance, transparency and impact resistance of the vinyl chloride resin composition is remarkably inferior.

From these Examples and Comparative Examples, the compounding ratio of the vinyl chloride resin (a), the copolymer (b), and the graft polymer (c) was determined to affect the heat resistance, transparency, and impact resistance of the resin composition. It can be seen that it has a significant effect.

f. Effects of the Invention The vinyl chloride resin composition of the present invention is an impact-resistant composition having both excellent transparency and heat resistance without losing the excellent properties of the vinyl chloride resin.

Due to this feature, the composition of the present invention is a heat-resistant blow bottle,
It is suitable as a molding material for heat-resistant and transparent sheets, housings for home electric appliances, automobile parts, and the like, and its use value is extremely large, and it is expected that its usage will rapidly increase in the future.

Claims (1)

(57) [Claims] 1. A copolymer comprising: (a) 30 to 80% by weight of a vinyl chloride resin; and (b) a vinyl monomer copolymerized with (b) α-methylstyrene, vinyl cyanide, methyl methacrylate, and these. 30 to 60% by weight of α-methylstyrene, 4 to 18% by weight of vinyl cyanide, 30 to 60% by weight of methyl methacrylate, and 0 to 15% by weight of a vinyl monomer copolymerizable therewith. % Of the monomer (b-1) consisting of 85% to 98% by weight of the monomer (b-1) until the polymerization conversion becomes 85% or more.
-2) 2 to 15 parts by weight (provided that (b-1) + (b-2) =
100 parts by weight) to complete the polymerization reaction.
(C) 45 to 80 parts by weight of a diene rubbery polymer (c-1) having an average particle diameter of 0.1 μ or less based on 0 to 70% by weight and 100 parts by weight of the total amount of (a) and (b) In the presence of 30 to 60% by weight of a monovinyl aromatic monomer, 35 to 65% by weight of methyl methacrylate, 0 to 15% by weight of vinyl cyanide, and 0 to 15% of a vinyl monomer copolymerizable therewith. Monomer (c-2) 20 comprising 15% by weight and 0 to 3% by weight of a polyfunctional monomer
To 25 parts by weight (provided that (c-1) + (c-2) = 100 parts by weight) was graft-polymerized to obtain a graft copolymer 3 to 25.
A vinyl chloride resin composition, which is obtained by mixing parts by weight.