JPH05132600A - Vinyl chloride resin composition improved in weatherability, impact resistance and secondary processability - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride resin composition which is very excellent in weatherability, impact resistance and fabricalility and gives a molding that can be uniformly and highly stretched in pressure or vacuum forming. CONSTITUTION:The objective composition comprises a mixture of a vinyl chloride resin and a graft copolymer which is obtained by polymerizing a monomer component consisting mainly of methyl methacrylate in the presence of a specified acrylic crosslinked rubber polymer and which satisfies the following relations: etasp/C > A/80 (wherein A is the parts by weight of the crosslinked rubber polymer in 100 pts.wt. of the copolymer, and C is the number of grams of the methyl ethyl ketone extract of the graft copolymer dissolved in 100 cc of actone); and {(the percentage of the methyl ethyl ketone insolubles in the graft copolymer) / (the percentage of the crosslinked rubber polymer in the graft copolymer) -1}> 0.1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has a high degree of weather resistance, impact resistance and secondary workability, and evenly and highly stretches a molded product obtained by molding and forming it by pressure molding or vacuum molding. And a vinyl chloride resin composition that can be used.

[0002]

2. Description of the Related Art As is generally known, a vinyl chloride resin molded article has poor impact resistance. Many methods have been proposed to improve this impact resistance. Among them, MBS resins obtained by graft-polymerizing methyl methacrylate, styrene or acrylonitrile onto a butadiene rubber polymer are widely used at present.

However, when the MBS resin is mixed with a vinyl chloride resin, the impact resistance is improved but the weather resistance is poor, and when the manufactured molded article is used outdoors, the impact resistance is significantly lowered. There is a drawback that. Therefore, currently MBS
Limited use of resin.

It is considered that the main cause of the deterioration of the weather resistance is due to the ultraviolet deterioration of the butadiene unit contained in the MBS resin. In order to improve the weather resistance of MBS resin and to impart impact resistance, a crosslinked alkyl acrylate rubbery polymer consisting of an alkyl acrylate containing no double bonds and a cross-linking agent, methyl methacrylate, an aromatic vinyl compound, A method of graft-polymerizing an unsaturated nitrile has been proposed (Japanese Patent Publication No. 51117/1978).

When the graft copolymer produced by this method is used, the molded article produced has excellent weather resistance, and in recent years, it has been used in earnest in fields requiring long-term weather resistance such as window frames. .

When the graft copolymer produced by this method is used, the molded article produced is satisfactory in terms of weather resistance, but impact resistance and molding sheet, which is generally said to be secondary processability, are used again. Formability when heating and reworking,
It is still insufficient to satisfy workability.

The secondary workability is becoming more important for the following reasons.

For example, in the case of large signboards, large-sized televisions, display housings, etc., the same products were conventionally molded in large quantities by the injection molding method, but the same products were molded in large quantities due to the diversification of user preferences. It is becoming less common, and rather the production of small lots and varieties is increasing.

Under such circumstances, the injection molding method requires a high die cost, resulting in an increase in cost, and the cost is becoming uncomfortable.

Therefore, in recent years, for such applications,
Mold the vinyl chloride resin composition consisting of vinyl chloride resin and weather resistance enhancer by calendering method or extrusion molding method to obtain a molded plate, and then heat it again to about 150 to 200 ° C to perform pressure molding or vacuum molding. Thus, the number of processing methods for obtaining a desired molded body is increasing.

When a composition using a weather resistance enhancer made by a conventional technique is applied to such a molding method, the elongation at 150 to 200 ° C. (elongation at high temperature) is insufficient. Therefore, there arises a problem that the corners of the molded product do not become acute, or the thickness of the molded product is uneven so that a uniform molded product cannot be obtained. Therefore, the use of weathering enhancers for these applications is limited.

That is, the composition according to the technology disclosed heretofore has sufficient moldability and workability (secondary workability) when the molded plate obtained as described above is reheated and reprocessed. This is because the demand for those satisfying such characteristics is increasing.

[0013]

A graft copolymer using a crosslinked rubber polymer mainly containing an alkyl acrylate, which is obtained when the graft copolymer is used in a vinyl chloride resin composition. If the proportion of the crosslinked rubber polymer used is increased to improve the impact resistance of the product, the elongation at high temperature will be insufficient when the molded product is subjected to secondary processing such as pressure molding, and as a result, blurring and uneven thickness will result. Occurs, and so-called secondary workability becomes insufficient.

The present invention solves the problem of secondary processability that occurs as a result of increasing the use ratio of the crosslinked rubber polymer as described above, and makes the molded product of the vinyl chloride resin composition exhibit high impact resistance. It is intended to provide excellent weather resistance as well as being able to do so.

[0015]

SUMMARY OF THE INVENTION The present invention is an alkyl acrylate having an alkyl group having 2 to 8 carbon atoms 79.9 to 99.9%
(Wt%, same below), 40 to 75 parts of crosslinked rubber polymer consisting of 0.1 to 5% of polyfunctional monomer and 0 to 20% of other monomer copolymerizable with these (part by weight, same below) ) In the presence of 50 to 100% of methyl methacrylate, 0 to 50% of alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms and 0 to 30% of other monomer copolymerizable therewith. In the presence of a graft copolymer (a) obtained by polymerizing all of 60 to 25 parts of the body component (the total amount of the crosslinked rubber polymer and the monomer component is 100 parts by weight) or the crosslinked rubber polymer. A graft copolymer which is a mixture (c) of a graft copolymer (b) obtained by polymerizing a part of the monomer component and a polymer obtained by separately polymerizing the rest of the monomer component.
of the components extracted from (d) (either the graft copolymer (a) or the mixture (c)) with methyl ethyl ketone
Η _sp obtained by measuring 0.2g / 100cc acetone solution at 30 ℃
And the number of crosslinked rubber polymer parts in 100 parts of the graft copolymer (d)
(A) is the formula (1): η _sp / C> (A) / 80 (1) (In the formula, C is g of the component dissolved in 100 cc of acetone.
The ratio (%) in the graft copolymer (d) and the graft copolymer that satisfy the relationship of the number, that is, 0.2) and are separated as insolubles in the extraction of methyl ethyl ketone
The ratio (%) of the crosslinked rubber polymer in (d) is expressed by the formula (2): {(ratio (%) of insoluble matter in the graft copolymer (d)) /
(Ratio (%) of cross-linked rubber polymer in graft copolymer (d))-1}> 0.1 (2) 10 to 30 parts by weight of the graft copolymer (d) and vinyl chloride resin 100 It is a vinyl chloride resin composition excellent in weather resistance, impact resistance, and secondary workability, which is characterized by being mixed with 1 part by weight.

[0016]

EXAMPLE A crosslinked rubber polymer used in the present invention is an alkyl acrylate having an alkyl group having 2 to 8 carbon atoms.
99.9%, polyfunctional monomer 0.1-5%, preferably 0.5-
5%, more preferably 1 to 4% and 0 to 20% of another monomer copolymerizable therewith are used, for example, by a conventional emulsion polymerization method.

The alkyl acrylate having 2 to 8 carbon atoms in the alkyl group is a component used for forming a rubber component having excellent weather resistance and impact resistance, and its specific example is ethyl acrylate. , Propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like are exemplified as typical ones. These may be used alone or in combination.

The polyfunctional monomer is a component used as a crosslinking agent, and specific examples thereof include aromatic polyfunctional vinyl compounds such as divinylbenzene, monoethylene glycol dimethacrylate, and 1,3-butane. Dimethacrylic acid ester or trimethacrylic acid ester of polyhydric alcohol such as diol dimethacrylate, diacrylic acid ester or triacrylic acid ester, allyl acrylate, allyl ester of unsaturated carboxylic acid such as allyl methacrylate, diallyl phthalate, triallyl Representative examples include diallyl compounds such as isocyanurate and triallyl compounds. Among these polyfunctional crosslinking agents, those in which the reactivity of at least one of the functional groups is different from the reactivity of the other functional groups can give a crosslinked rubber polymer with a small amount of the polyfunctional monomer. Therefore, it is preferable.

The specific examples of the monomer copolymerizable with the alkyl acrylate and the polyfunctional monomer used in the production of the crosslinked rubber polymer include an alkyl group having a carbon number other than 2-8. Have alkyl acrylate,
Other acrylic ester, acrylic acid, metal salt of acrylic acid, acrylamide, alkyl methacrylate,
Methacrylic acid, metal salts of methacrylic acid, methacrylamide, aromatic vinyl compounds, derivatives thereof, acrylonitrile, methacrylonitrile, vinyl ester compounds, vinyl halides and the like can be mentioned. These may be used alone or in combination.

When the proportion of the alkyl acrylate in the production of the crosslinked rubber polymer is less than 79.9%, impact resistance or weathering discoloration becomes a problem, and when it exceeds 99.9%, the proportion of the polyfunctional monomer decreases. Too much, and the effect of using this becomes insufficient. Further, when the proportion of the polyfunctional monomer exceeds 5%, impact resistance when molding a vinyl chloride resin composition containing a graft copolymer produced from the crosslinked rubber polymer Is decreased, which is not preferable.

The average particle size of the crosslinked rubber polymer thus produced is preferably large from the viewpoint of improving impact resistance, and is practically 1500 A or more, preferably 1700 A or more. desirable. There are various methods for obtaining the average particle diameter of such a crosslinked rubber polymer, and there is no particular limitation, but it is usually easily produced.
Those having an average particle diameter of about 00A may be coagulated and enlarged by a usual method before graft polymerization. However, it is more preferable to obtain a crosslinked rubber polymer having an average particle diameter of 1500 A or more by a normal seed polymerization method, because the proportion of small particles that contribute little to impact resistance decreases.

In the present invention, in the presence of the above-mentioned crosslinked rubber polymer, methylmethacrylate 50 to 100%, preferably 70 to 100%, alkylmethacrylate having an alkyl group having 2 to 4 carbon atoms, 0 to 50%, All or part of the monomer component consisting of preferably 0 to 30% and 0 to 30% of other monomer copolymerizable therewith, preferably 0 to 20% is polymerized.

When the above-mentioned monomer component which is polymerized in the presence of the crosslinked rubber polymer is a part of the whole, the rest is separately polymerized and mixed with the graft polymer (b) to obtain the graft polymer ( d)

When the monomer component is polymerized in the presence of the crosslinked rubber polymer and separately polymerized, both compositions may be the same or different. Further, both the portion of the monomer component which is polymerized in the presence of the crosslinked rubber polymer and the portion of the monomer component which is separately polymerized are preferably 50 to 100% of methyl methacrylate (more preferably 70 to 10%).
0%), 0 to 50% (more preferably 0 to 30%) of alkyl methacrylate having 2 to 4 carbon atoms in the alkyl group, and 0 to 30% (more preferably other monomers copolymerizable with these). Is 0 to 20%).

The amount of the monomer component separately polymerized is preferably 80% by weight or less based on the total amount of the monomer components.

The above-mentioned monomer component is a component used to improve the impact resistance and the degree of improvement in secondary processability, and it is important that it is a component compatible with the vinyl chloride resin. Methyl methacrylate is well known as a typical component compatible with the vinyl chloride resin, and it is essential to use methyl methacrylate also in the present invention.

On the other hand, the alkyl methacrylate in which the alkyl group has 2 to 4 carbon atoms is a component used for improving the dispersibility of the graft copolymer without deteriorating the excellent compatibility with methyl methacrylate. Specific examples thereof include ethyl methacrylate, butyl methacrylate, propyl methacrylate and the like.

The other monomer components copolymerizable with the methyl methacrylate used as the above-mentioned monomer component are, for example, alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, and styrene. A monomer component selected from acrylonitrile is preferred because it has a high effect of developing impact resistance and secondary processability without impairing excellent compatibility with methyl methacrylate.

If the amount of methyl methacrylate in the monomer component is less than 50%, the secondary processability is deteriorated, which is not preferable.

The graft copolymer (d) according to the present invention comprises a cross-linked rubber polymer of 40 to 75 parts, preferably 45 to 65 parts, and a monomer component of 60 to 25 parts, preferably 55 to 35 parts. Amount 100
It can be obtained by polymerizing by using it as a part. When the amount of the crosslinked rubber polymer is less than 40 parts, when a vinyl chloride resin composition is prepared to produce a molded article, the impact resistance improving effect becomes poor and it becomes unpractical. If it exceeds the area, the effect of improving the secondary workability becomes insufficient.

In the graft polymerization, the whole amount of the monomer components may be added all at once for the polymerization, or the whole amount or a part thereof may be added continuously or intermittently for the polymerization. In order to increase the degree of polymerization, it is preferable to add all or part of the monomer components at once in the presence of a small amount of catalyst to proceed the polymerization. Further, all of the monomer components may be mixed and used, or may be polymerized in two or more stages.

The graft copolymer latex thus obtained is subjected to spray drying, salting out or aciding out, followed by heating, filtration, washing and drying.

An antiaging agent or an ultraviolet absorber which is usually added at the time of solidification may be added.

Further, a latex obtained by adding a part of a monomer component and polymerizing it in the presence of a latex of a crosslinked rubber polymer and a remaining monomer component in a system free of the crosslinked rubber polymer. The graft copolymer (d) according to the present invention may be obtained by mixing with a latex obtained by emulsion polymerization in a latex state, coagulating, dehydrating and drying.

Further, a powder obtained by adding a part of the monomer component in the presence of the latex of the crosslinked rubber polymer, polymerizing, and then coagulating, dehydrating and drying, and a system free from the crosslinked rubber polymer. Alternatively, the graft copolymer (d) according to the present invention may be obtained by mixing with the powder obtained by polymerizing the remaining monomer components in a powder state.

In the present invention, the graft copolymer (d)
It is possible to increase the degree of polymerization of the polymer obtained by polymerizing the monomer components in the polymer. The obtained η _sp is represented by the formula (1): η _sp / C> (A) / 80 (1) (where C is g of a component dissolved in 100 cc of acetone).
Number, ie 0.2, (A) Graft copolymer
(d) represents the number of crosslinked rubber polymer parts, that is, the number of parts of the crosslinked rubber polymer contained in 100 parts of the graft copolymer (d)), so that good secondary processability can be obtained, In addition, it is essential for improving impact resistance by increasing the proportion of the crosslinked rubber polymer used. η _sp / C is the formula
If (1) is not satisfied, the degree of polymerization of the polymer obtained by polymerizing the monomer components will be low, and sufficient secondary processability cannot be obtained.
In addition, the elongation at high temperature decreases.

Η _sp / C of the methyl ethyl ketone extract component
Is a range satisfying the formula (1), and may be a mixture of components having different molecular weight distributions.

Further, in the present invention, when the obtained graft copolymer (d) is extracted with methyl ethyl ketone, the ratio of the component (%) in the graft copolymer (d) which is separated as an insoluble component by extraction with methyl ethyl ketone. ) And the ratio (%) of the crosslinked rubber polymer in the graft copolymer (d) are expressed by the formula
(2): {(ratio (%) of insoluble matter in the graft copolymer (d)) /
(Ratio (%) of crosslinked rubber polymer in graft copolymer (d))-1}> 0.1 (2) must be satisfied, and in this case, elongation at high temperature and strength should be good. Become.

Graft copolymer (d) in the above formula (2)
The proportion (%) of insoluble matter in the composition means the graft copolymer (d) 100
Is the number of parts of the precipitate obtained by centrifuging after dissolving parts in methyl ethyl ketone. Graft copolymer
The ratio (%) of the crosslinked rubber polymer in (d) means the number of parts of the crosslinked rubber polymer used when 100 parts of the graft copolymer (d) was polymerized.

The graft copolymer (d) according to the present invention as described above is formed from a crosslinked rubber polymer mainly containing alkyl acrylate and optionally a specific monomer component mainly containing alkyl methacrylate. , The degree of polymerization of the polymer obtained by polymerizing the monomer components (the degree of polymerization of the extracted methyl ethyl ketone) and the proportion of the insoluble matter extracted by the methyl ethyl ketone were prepared so as to satisfy the relationships of the formulas (1) and (2). Is. Further, the proportion of the crosslinked rubber polymer in the graft copolymer (d) is 40 to 75%. As a result, when a vinyl chloride resin composition is used to form a molded article, the impact resistance can be kept high, and the secondary workability of the molded article can be greatly improved. Becomes

By mixing the obtained graft copolymer (d) with a vinyl chloride resin, weather resistance and impact resistance can be kept high when the molded product is formed, and at the same time, the secondary processability of the molded product can be maintained. A vinyl chloride resin composition capable of significantly improving the above is obtained.

The vinyl chloride resin referred to in the present specification includes vinyl chloride homopolymer and 70% vinyl chloride.
It is a copolymer containing the above.

Monomers copolymerizable with vinyl chloride up to 30% include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate. , Methacrylamide and other copolymerizable monoolefon-based monomers. These may be used alone or in combination of two or more.

The amount of the graft copolymer (d) mixed with the vinyl chloride resin varies depending on the use, but generally 100 parts of the vinyl chloride resin is added to the graft copolymer (d).
0 to 30 parts. If the amount is less than 10 parts, sufficient strength and secondary moldability cannot be obtained, and if it exceeds 30 parts, a decrease in tensile strength of the molded product becomes a problem.

The vinyl chloride resin composition of the present invention comprises a stabilizer, a lubricant, a plasticizer, a colorant, a filler, a matting agent, an antioxidant, in addition to the vinyl chloride resin and the graft copolymer (d). Agents, ultraviolet absorbers, foaming agents, etc. can be added and used for molding.

Next, the method of the present invention will be described based on examples.

Example 1 (A) Production of Seed Used for Production of Crosslinked Rubber Polymer A glass reactor equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet device and a monomer addition device was prepared as follows. I put things in.

Distilled water 250 parts Potassium rosinate 0.5〃 Potassium stearate 0.5〃 Sodium formaldehyde sulfoxylate (SFS) 0.1〃 Na ₃ PO ₄・ 12H ₂ O 0.45〃 EDTA ・ 2Na 0.008〃 Ferrous sulfate ・ 7hydrate 0.002 〃 Then, heat to 40 ℃ with stirring in a nitrogen stream,
Butyl acrylate 100 parts, allyl methacrylate 2.0
And 5% of a monomer mixed solution consisting of 0.1 part of cumene hydroperoxide and 0.1 part of cumene hydroperoxide. Then, the remaining 95% monomer mixed solution was added dropwise over 4 hours. After the addition is complete
Polymerization was completed after 1.5 hours to complete the polymerization.

The yield of the obtained polymer was 97%, and the average particle size of the obtained latex was 900A.

(B) Production of Crosslinked Rubber Polymer Using the latex obtained in (A) as a seed, seed polymerization was carried out.

Latex obtained with 250 parts (A) of distilled water (as solid content) 10 〃 SFS 0.1 〃 EDTA ・ 2Na 0.008 〃 ferrous sulfate heptahydrate 0.002 〃 Charge the mixture of the above composition into a glass reactor After heating to 40 ° C. at 40 ° C., a monomer mixture consisting of 90 parts of butyl acrylate, 2 parts of allyl methacrylate and 0.1 part of cumene hydroperoxide was added continuously over 4 hours. At the same time as the addition of the monomer mixture, 1 part of potassium stearate in 5% aqueous solution was continuously added for 4 hours. After the addition was completed, 0.05 part of SFS was added and the polymerization was carried out for further 5 hours to obtain a crosslinked rubber polymer latex.

The conversion of the monomer mixture was 98%,
The average particle diameter of the obtained latex was 2000A.

(C) Production of Graft Copolymer A glass reactor was charged with the raw materials so as to have the following composition, and 45
The mixture was heated and stirred under a nitrogen stream at 0 ° C. until the oxygen concentration of the aqueous dispersion became 0.5 ppm or less.

Crosslinked rubber polymer latex obtained in (B) (as solid content) 55 parts SFS 0.05 〃 EDTA ・ 2Na 0.01 〃 ferrous sulfate heptahydrate 0.005 〃 Then, the following monomer components in 3 hours Added continuously.

Methyl methacrylate 40 parts Butyl acrylate 5 〃 cumene hydroperoxide 0.04 〃 After the addition was completed, 0.01 part of cumene hydroperoxide was further added, and stirring was continued for 2 hours to complete the polymerization. The conversion rate was 99.7%.

The target graft copolymer was obtained by salting out, dehydrating and drying the obtained graft copolymer latex.

The η _sp / C and the graft ratio of the component extracted from the obtained graft copolymer with methyl ethyl ketone were determined by the methods described below. The results are shown in Table 1.

After the (η _sp / C) graft copolymer was immersed in methyl ethyl ketone at 30 ° C. for 24 hours, the soluble component was separated by centrifugation, reprecipitated with methanol, purified and dried. 0.2g / 100cc acetone solution
The viscosity is measured at 30 ° C and η _sp is calculated. C is the g number of the extracted component dissolved in 100 cc of solvent, which is 0.2 in this case.

(Graft ratio) The graft copolymer is immersed in methyl ethyl ketone at 30 ° C. for 24 hours and then centrifuged to separate insoluble and soluble components. The graft ratio is calculated according to the following formula from the ratio (%) of the insoluble matter in the graft copolymer and the ratio (%) of the crosslinked rubber polymer contained in the graft copolymer.

Graft ratio = (ratio of insoluble matter in graft copolymer (%)) / (ratio of crosslinked rubber polymer in graft copolymer (%))-1 The obtained graft copolymer was The ingredients were blended according to the following blending recipe 1, roll-kneaded at 180 ° C. for 8 minutes, compression-molded at 190 ° C. for 15 minutes, and 0 ° C. Izod impact strength and high temperature elongation were measured by the following methods. The results are shown in Table 1.
Shown in.

(Formulation 1)

[0062]

[Outer 1]

Graft copolymer 20 〃 Butyltin mercapto stabilizer 3 〃 Butyl stearate 1 〃 Polyglycol ester of fatty acid 0.5 〃 (Izod impact strength) According to ASTM D 256-56, 0
℃, thickness 3mm, V notch sample strength (kg · cm / c
m ² ) was measured.

(Elongation at high temperature) A 3 mm thick plate obtained by roll pressing was cut to produce a JIS No. 2 dumbbell. This dumbbell was pulled at 180 ° C. according to JIS K6745, and the elongation (%) at break was measured.

Examples 2 to 4 Methyl ethyl ketone was obtained by varying the number of parts of the crosslinked rubber polymer used in (C) of Example 1 and the number of parts of the initiator system (SFS, cumene hydroperoxide) used in the graft polymerization. Example 1 except that η _sp / C of the melt was changed
A graft copolymer was obtained in the same manner as in.

In the same manner as in Example 1, the graft copolymer was evaluated and the physical properties of the molded article were measured. The results are shown in Table 1.

Comparative Examples 1 to 5 Examples (C) of Example 1 except that the number of crosslinked rubber polymer and the number of initiator system used were changed to change the η _sp / C of the methyl ethyl ketone soluble component. A graft copolymer was obtained in the same manner as in 1.

In the same manner as in Example 1, the graft copolymer was evaluated and the physical properties of the molded article were measured. The results are shown in Table 1.

[0069]

[Table 1]

From the results shown in Table 1, the graft ratio exceeds 0.1, η _sp / C and the number of crosslinked rubber polymer parts (A) in the graft copolymer satisfy the relationship of the formula (1), and 40 parts or more. It can be seen that the graft copolymer containing the crosslinked rubber polymer of 1) is excellent in both Izod impact strength and elongation at high temperature (Examples 1 to 4).

On the other hand, when η _sp / C does not satisfy the relation of the formula (1), it is understood that the elongation at high temperature is remarkably reduced (Comparative Examples 1 to 3).

It is also found that the elongation at high temperature is low even when the graft ratio is 0.1 or less (Comparative Example 4).

Further, when the crosslinked rubber polymer is less than 40 parts, the Izod impact strength is remarkably lowered (Comparative Example 5).

Examples 5 to 7 The same operations as in Example 1 were carried out except that the monomer components in (C) of Example 1 were changed as shown in Table 2 to obtain graft copolymers.

In the same manner as in Example 1, the graft copolymer was evaluated and the physical properties of the molded article were measured. The results are shown in Table 2.

Further, (A) / of the obtained graft copolymer
80 was all 0.69.

In Table 2, MMA is methyl methacrylate, BMA is butyl methacrylate, BA is butyl acrylate, and AN is acrylonitrile.

Comparative Examples 6 to 8 The same operations as in Example 1 were carried out except that the monomer components in (C) of Example 1 were changed as shown in Table 2 to obtain graft copolymers.

In the same manner as in Example 1, the graft copolymer was evaluated and the physical properties of the molded article were measured. The results are shown in Table 2.

Further, (A) / of the obtained graft copolymer
All 80 were 0.69.

[0081]

[Table 2]

From the results shown in Table 2, when the composition of the monomer component is within the composition range of the present invention, the molded article exhibits excellent high temperature elongation, but the proportion of methyl methacrylate in the monomer component is high. When it is less than 50% (Comparative Examples 6 and 8) and the proportion of methyl methacrylate is 50% or more, the proportion of monomers other than methyl methacrylate and alkyl methacrylate having 2 to 4 carbon atoms is 30%. It can be seen that the elongation at high temperature decreases when the temperature exceeds the range (Comparative Example 7).

Example 8 (D) Production of Copolymer Containing Monomer Components Only 200 parts of distilled water, 2.0 parts of potassium stearate and 0.1 part of potassium persulfate were charged in a glass reactor and heated to 70 ° C.
After heating to 100 ° C., 100 parts of a monomer mixture having the same composition as the monomer component used in (C) of Example 1 (88.9 parts of methyl methacrylate, 11.1 parts of butyl acrylate) was continuously added over 5 hours. After completion of the addition, stirring was continued for 2 hours to obtain a copolymer latex (L-1) consisting of only the monomer component.

The obtained latex was coagulated and dried, and then 0.2 g / 100 cc acetone solution was prepared to obtain η _sp / C of 1.
It was 0.

(E) Production of Graft Copolymer (d) A copolymer of the graft copolymer (b) obtained in Comparative Example 1 and the monomer component obtained in (D) only. The latex (L-1) and the latex (L-1) were mixed in a latex state at a ratio of 3: 1 in the solid state, coagulated and dried to obtain the final graft copolymer (d).

The methyl ethyl ketone-soluble component η _sp / C of the obtained graft copolymer (d) was 0.95.

Graft copolymer as in Example 1
The evaluation of (d) and the measurement of the physical properties of the molded body were carried out.
The results are shown in Table 3.

Comparative Example 9 (F) Production of Copolymer from Monomer Component Only In the copolymerization of the monomer component of (D) of Example 8 alone, 0.5 part of tertiary decyl mercaptan was added to the monomer mixture. The same operation as in (D) of Example 8 was carried out except that was added to obtain a copolymer latex (L-2). The obtained latex was coagulated and dried, and then a 0.2 g / 100 cc acetone solution was prepared to obtain η _sp / C of 0.2.

(G) Preparation of Graft Copolymer Same as (E) of Example 8 except that latex (L-2) was used instead of latex (L-1) in (E) of Example 8. Was carried out to obtain the final graft copolymer.

The final graft copolymer obtained had a methyl ethyl ketone-soluble component η _sp / C of 0.3. Example 1
In the same manner as above, the graft copolymer was evaluated and the physical properties of the molded article were measured. The results are shown in Table 3.

Example 9 Instead of mixing and coagulating and drying in the latex state performed in (E) of Example 8, each latex was coagulated and dried separately and mixed in a powder state to obtain the final graft co-polymerization. A polymer (d) was obtained.

The graft copolymer (d) thus obtained had a methyl ethyl ketone-soluble component η _sp / C of 0.95. In the same manner as in Example 1, the graft copolymer (d) was evaluated and the physical properties of the molded article were measured. The results are shown in Table 3.

[0093]

[Table 3]

From the results shown in Table 3, a part of the monomer component was separately polymerized in a system without a crosslinked rubber polymer, and the remaining monomer component was polymerized in the presence of the crosslinked rubber polymer. The final graft copolymer (d) was also prepared by mixing the obtained graft copolymer (b) part in a latex state (Example 8), or by mixing in a powder state. It can be seen that even if the polymer (d) is produced (Example 9), the graft copolymer (d) having the desired properties can be obtained.

Examples 10 to 11 The same procedure as in Example 8 except that the monomer components were changed as shown in Table 4 in the production of the copolymer containing only the monomer components of (D) of Example 8. The operation was performed to obtain a graft copolymer (d).

Graft copolymer as in Example 1
The evaluation of (d) and the measurement of the physical properties of the molded body were carried out.
The results are shown in Table 4.

Further, the obtained graft copolymer (d)
(A) / 80 were all 0.70 and the graft ratios were all 0.18.

[0098]

[Table 4]

When the monomer component is divided into a component which is polymerized in the presence of the crosslinked rubber polymer and a component which is separately polymerized, it is understood that the compositions of both may be different.

Next, in order to evaluate the outdoor durability of the impact resistance improving effect of the vinyl chloride resin, Example 1,
The Izod impact strength of each sample after 300 hours and 600 hours of exposure was evaluated by conducting an artificial accelerated exposure test with a weatherometer (Toyo Rika's WESUN-HC type) of the compression molded samples obtained in 8, 10, and 11. It was For comparison, instead of the graft copolymer used in the present invention, MBS
The same formulation as in Example 1 was used except that a resin (trade name Kane Ace B-22, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) was used.
The obtained molded samples were evaluated together. The results are also shown in Table 5.

[0101]

[Table 5]

[0102]

INDUSTRIAL APPLICABILITY The vinyl chloride resin composition of the present invention gives a molded article excellent in weather resistance, impact resistance and secondary workability.

Claims (4)

[Claims] 1. An alkyl acrylate having an alkyl group having 2 to 8 carbon atoms in an amount of 79.9 to 99.9% by weight, and a polyfunctional monomer of 0.
1-5% by weight and other monomers copolymerizable with them 0
In the presence of 40 to 75 parts by weight of a crosslinked rubber polymer consisting of 20 to 20% by weight, 50 to 100% by weight of methyl methacrylate and an alkylmethacrylate having an alkyl group of 2 to 4 carbon atoms 0 to
50% by weight and other monomers copolymerizable therewith
Graft copolymer (a) obtained by polymerizing all of 60 to 25 parts by weight of a monomer component consisting of -30% by weight (the total amount of the crosslinked rubber polymer and the monomer component is 100 parts by weight). A mixture of a graft copolymer (b) obtained by polymerizing a part of the monomer component in the presence of the crosslinked rubber polymer and a polymer obtained by separately polymerizing the rest of the monomer component. Measure 0.2g / 100cc acetone solution of the component extracted with methyl ethyl ketone from graft copolymer (d) ((c) which is either graft copolymer (a) or mixture (c)) at 30 ℃ to the eta _sp obtained, the graft copolymer (d) a crosslinked rubber polymer parts in 100 parts by weight (a), but the formula _{(1): η sp / C} > (a) / 80 (1) (In the formula, C is g of the component dissolved in 100 cc of acetone.
The ratio (%) in the graft copolymer (d) and the graft copolymer satisfying the relationship of the number, that is, 0.2) and separated as insoluble matter in the extraction of methyl ethyl ketone
The ratio (%) of the crosslinked rubber polymer in (d) is expressed by the formula (2): {(ratio (%) of insoluble matter in the graft copolymer (d)) /
(Ratio (%) of cross-linked rubber polymer in graft copolymer (d))-1}> 0.1 (2) 10 to 30 parts by weight of the graft copolymer (d) and vinyl chloride resin 100 A vinyl chloride resin composition excellent in weather resistance, impact resistance and secondary workability, characterized by containing parts by weight. 2. The vinyl chloride resin composition according to claim 1, wherein all of the monomer components are added and polymerized in the presence of the latex of the crosslinked rubber polymer to obtain the graft copolymer (d). . 3. A latex obtained by adding a part of a monomer component and polymerizing it in the presence of a latex of a crosslinked rubber polymer, and a remaining monomer component in a system having no crosslinked rubber polymer. A graft copolymer (d) is obtained by mixing with a latex obtained by emulsion polymerization in a latex state.
The vinyl chloride resin composition described. 4. A powder obtained by adding a part of a monomer component and polymerizing it in the presence of a latex of a crosslinked rubber polymer, and a remaining monomer component in a system free of the crosslinked rubber polymer. The vinyl chloride resin composition according to claim 1, wherein the graft copolymer (d) is obtained by mixing the powder obtained by the polymerization with the powder.