JP2002201237A - Vinyl chloride graft copolymer and molded item - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride graft copolymer excellent in heat resistance and impact resistance (especially, low-temperature impact resistance). SOLUTION: This heat- and impact-resistant vinyl chloride graft copolymer is obtained by grafting vinyl chloride and an N-substituted maleimide onto an acrylic copolymer which has an average particle size of 0.20 μm or larger and is prepared from 100 pts.wt. monomer component comprising at least one (meth)acrylate giving a homopolymer having a glass transition point of -140 deg.C or higher but lower than 0 deg.C and another free-radically polymerizable monomer and 0.1-10 pts.wt. polyfunctional monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a vinyl chloride graft copolymer and a molded product thereof.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resin has a mechanical strength,
As a material having excellent properties such as weather resistance, self-extinguishing properties, and chemical resistance, it is used in a wide range of applications such as pipes, joints, plates, sheets, films, and containers. However, a vinyl chloride resin generally has a low softening point and is inferior in heat resistance. For example, the vinyl chloride resin softens at 70 to 80 ° C. to cause thermal deformation, and cannot be used at a higher temperature.

On the other hand, as a method for improving the heat resistance of a vinyl chloride resin, for example, Japanese Patent Publication No. 41-9551
Japanese Patent Application Laid-Open Publication No. H11-157, discloses a method for producing a heat-resistant vinyl chloride resin obtained by copolymerizing vinyl chloride with an N-substituted maleimide such as N-phenylmaleimide. However,
The heat-resistant vinyl chloride resin obtained by such a production method has a problem that the heat resistance is improved but the impact resistance is reduced.

In order to improve impact resistance, an acrylic resin, a vinyl chloride-N-substituted maleimide copolymer,
When an impact modifier such as chlorinated polyethylene or MBS resin is blended, there is a problem that heat resistance is reduced. In view of this, we have already proposed a vinyl chloride-based graft copolymer resin having heat resistance. (Japanese Unexamined Patent Publication No.
No. 1191033).

[0005] This resin is an excellent resin having heat and shock resistance. However, regarding the low-temperature impact resistance required for a molded article used in a cold region or the like, a satisfactory impact resistance may not be obtained. there were. In this case, it is possible to improve the low-temperature impact resistance by increasing the content of the acrylic copolymer, but there is a problem that the heat resistance decreases.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a vinyl chloride-based graft copolymer having excellent heat and impact resistance, and in particular, a vinyl chloride-based molded article having improved low-temperature (0 ° C.) impact resistance. It is to provide a graft copolymer.

[0007]

The vinyl chloride graft copolymer of the present invention has a homopolymer having a glass transition temperature of -1.
At least one kind of (meta) having a temperature of 40 ° C or higher and lower than 0 ° C
Acrylate and other radically polymerizable monomers 1
Acrylic copolymer having an average particle diameter of 0.20 μm or more, comprising 00 parts by weight and 0.1 to 10 parts by weight of a polyfunctional monomer, is obtained by graft copolymerizing vinyl chloride and an N-substituted maleimide. It is characterized by the following.

The above (meth) acrylate monomer forms an acrylic copolymer and is blended to improve the impact resistance of the produced vinyl chloride graft copolymer resin. Therefore, the homopolymer has a glass transition temperature of −140 ° C. or more and less than 0 ° C. In order to impart sufficient flexibility to the vinyl chloride-based graft copolymer resin, the glass transition temperature is not particularly limited as long as it is less than 0 ° C. In view of the glass transition temperature of a polymer generally used industrially, A temperature of −140 ° C. or higher is appropriate.

As the above (meth) acrylate monomer, the homopolymer has a glass transition temperature of −140 ° C. or more and 0 ° C.
It is not particularly limited as long as it is less than, for example, n-butyl acrylate (Tg = −54 ° C., hereinafter, only the temperature is indicated in parentheses), n-hexyl acrylate (−57
C), 2-ethylhexyl acrylate (-85C),
n-octyl acrylate (-85 ° C), n-nonyl acrylate, isononyl acrylate (-85 ° C), n
-Decyl acrylate (-70 ° C), lauryl acrylate, lauryl methacrylate (-65 ° C), ethyl acrylate (-24 ° C), n-propyl acrylate (-37 ° C), n-butyl acrylate (-54 ° C),
Isobutyl acrylate (−24 ° C.), sec-butyl acrylate (−21 ° C.), n-hexyl acrylate (−57 ° C.), n-octyl methacrylate (−25
C), isooctyl acrylate (-45C), n-nonyl methacrylate (-35C), n-decyl methacrylate (-45C), and the like. These can be used alone or in combination of two or more. In addition,
The homopolymer has a glass transition temperature of −140 ° C. or more and 0 ° C.
The glass transition temperature of the homopolymer of the (meth) acrylate monomer is less than that according to “Polymer Data Handbook (Basic)” edited by The Society of Polymer Science, Japan (1986, Baifukan Co., Ltd.).

The radical polymerizable monomer is not particularly limited as long as it is a monomer capable of radical polymerization, and may contain a (meth) acrylate monomer having a glass transition temperature of 0 ° C. or higher.

The homopolymer has a glass transition temperature of -14.
The amount of the (meth) acrylate monomer at 0 ° C. or higher and lower than 0 ° C. is preferably 10 to 100% by weight based on the total amount of the other radically polymerizable monomers, and if it is less than 10% by weight, the impact resistance of the molded product Decrease. More preferably, 7
0 to 100% by weight.

The above-mentioned polyfunctional monomer crosslinks the above-mentioned alkyl (meth) acrylate copolymer, makes it difficult for resin particles made of the above-mentioned alkyl (meth) acrylate copolymer to coalesce, and further obtains a vinyl chloride-based resin. It is added for the purpose of improving the impact resistance of the resin.

The above-mentioned polyfunctional monomers include, for example,
Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate.
Acrylate, 1.6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and the like. As tri (meth) acrylate,
Examples thereof include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. Other polyfunctional monomers include pentaerythritol tetra (meth) acrylate, dipentaeristol hexa (meth) acrylate, diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl succinate, triallyl isocyanurate and the like. And divinyl compounds such as divinylbenzene and butadiene, etc., and these can be used alone or in combination of two or more.

[0014] The compounding amount of the polyfunctional monomer in the acrylic copolymer is (meth) acrylate having a glass transition temperature of -140 or more and less than 0 ° C of the homopolymer, which forms the acrylic copolymer; Mixed monomer component 10 comprising a radical polymerizable monomer copolymerizable therewith
It is 0.1 to 10 parts by weight with respect to 0 parts by weight. If the amount of the polyfunctional monomer is less than 0.1 part by weight, the acrylic copolymer cannot maintain an independent particle shape in the vinyl chloride-based graft copolymer resin. The impact resistance of the resin decreases. Meanwhile, 1
If the amount exceeds 0 parts by weight, the crosslinking density of the acrylic copolymer becomes high, and effective impact resistance cannot be obtained, so that the content is limited to the above range.

The particle size of the acrylic copolymer is 0.20 in view of the impact resistance of the vinyl chloride graft copolymer.
μm or more. When the particle size is less than 0.20 μm, no effect of improving the low-temperature impact resistance is observed. The upper limit of the particle diameter is not particularly limited, but is preferably 1 μm or less in order to exhibit good low-temperature impact resistance.

In the present invention, examples of the method of copolymerizing the acrylic monomer component and the radical polymerizable monomer with the polyfunctional monomer include an emulsion polymerization method and a suspension polymerization method. Among them, the emulsion polymerization method is preferable because it has good impact resistance and easily controls the particle size of the acrylic copolymer. In addition, the said copolymerization means all copolymerizations, such as a random copolymerization, a block copolymerization, a graft copolymerization.

The above emulsion polymerization method can be carried out by a conventionally known method. For example, if necessary, an emulsifying dispersant, a polymerization initiator, a pH adjuster, an antioxidant and the like may be added.

The above-mentioned emulsifying dispersant is used to improve the dispersion stability of a mixture of an acrylic monomer component and a polyfunctional monomer (hereinafter, also referred to as a mixed monomer) in an emulsion and to efficiently carry out polymerization. It is used. The emulsifying dispersant is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, partially saponified polyvinyl acetate, cellulose dispersants, and gelatin. Among these, anionic surfactants are preferable, and specific examples of the anionic surfactant include, for example, polyoxyethylene nonyl phenyl ether sulfate (“Hitenol N-08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like. Is mentioned.

The polymerization initiator is not particularly limited.
For example, water-soluble polymerization initiators such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, organic peroxides such as benzoyl peroxide and lauroyl peroxide, and azo initiators such as azobisisobutyronitrile. No.

The type of the emulsion polymerization method is not particularly limited.
For example, a batch polymerization method, a monomer dropping method, an emulsion dropping method and the like can be mentioned.

In the batch polymerization method, pure water, an emulsifying dispersant, and a mixed monomer are added all at once to a jacketed polymerization reactor, and the mixture is stirred under a nitrogen stream pressure and sufficiently emulsified.
In this method, the inside of the reactor is heated to a predetermined temperature by a jacket, and then polymerized.

In the monomer dropping method, pure water, an emulsifying dispersant, and a polymerization initiator are charged into a polymerization reactor equipped with a jacket, oxygen is removed under a stream of nitrogen, and pressure is applied. After the temperature is raised to the above temperature, the mixed monomer is dropped at a fixed amount and polymerized.

In the emulsion dropping method, an emulsion monomer is prepared in advance by stirring a mixed monomer, an emulsifying dispersant, and pure water, and then pure water and a polymerization initiator are charged into a jacketed polymerization reactor. This is a method in which oxygen is removed under a nitrogen stream and pressurization is performed, and the inside of the reactor is heated to a predetermined temperature by a jacket, and then the above-mentioned emulsified monomer is added dropwise in a predetermined amount to carry out polymerization.

In the above-mentioned emulsion dropping method, a method of adding a part of the above-mentioned emulsifying monomer at a time (hereinafter referred to as a seed monomer) at the beginning of polymerization and then dropping the remaining emulsifying monomer is used. By changing the particle size, the particle size of the produced acrylic copolymer can be easily controlled. Further, by sequentially changing and distinguishing the types and compositions of the seed monomer and the emulsified monomer to be dropped, a multilayer structure such as a core-shell can be formed.

In the above polymerization method, the solid content ratio of the acrylic copolymer obtained after the reaction is 10 to 60% by weight from the viewpoint of the productivity of the acrylic copolymer and the stability of the polymerization reaction. preferable. In the above-mentioned polymerization method, a protective colloid or the like may be added for the purpose of improving the mechanical stability of the acrylic copolymer after the completion of the reaction.

When the proportion of the acrylic copolymer in the vinyl chloride graft copolymer is small, it is difficult to obtain sufficient impact resistance, and when it is large, the mechanical strength such as bending strength and tensile strength is low. Therefore, the content is preferably 1 to 30% by weight, more preferably 4 to 20% by weight.

The N-substituted maleimide used in the present invention is represented by the following general formula.

[0028]

Embedded image

In the formula, R represents an unsubstituted or substituted aliphatic, alicyclic or aromatic group having 3 to 20 carbon atoms. Preferred examples of R include an isopropyl group, a t-butyl group, n
-Hexyl group, cyclohexyl group, phenyl group, 2-chlorophenyl group, 2-methylphenyl group, benzyl group,
Examples include a 2-chlorobenzyl group, a 2-methylbenzyl group, and a naphthyl group.

In the vinyl chloride-based graft copolymer of the present invention, if the proportion of the N-substituted maleimide is too small, it becomes difficult to obtain sufficient heat resistance, and if the proportion is too large, the fluidity during molding decreases. 4 to 40% by weight is preferred.

The method for graft copolymerizing vinyl chloride and N-substituted maleimide with the above acrylic copolymer is not particularly limited, and examples thereof include a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and the like. Although a bulk polymerization method and the like can be mentioned, a suspension polymerization method is desirable in order to carry out the present invention advantageously. The suspension polymerization method uses a dispersant and an oil-soluble polymerization initiator.

When graft copolymerizing vinyl chloride,
A coagulant may be added to the acrylic copolymer latex for the purpose of reducing the scale adhering in the polymerization tank during the polymerization.

The dispersant used in the above suspension polymerization is added for the purpose of efficiently performing the graft polymerization of vinyl chloride. For example, poly (meth) acrylate, (meth) acrylate-alkyl acrylate copolymer , Methylcellulose,
Ethyl cellulose, hydroxypropyl methyl cellulose, polyethylene glycol, polyvinyl acetate and partially saponified products thereof, gelatin, polyvinylpyrrolidone, starch, maleic anhydride-styrene copolymer, and the like, and these can be used alone or in combination of two or more kinds it can.

Among the above oil-soluble polymerization initiators, a radical polymerization initiator is preferably used because it is advantageous for graft copolymerization. Examples thereof include lauroyl peroxide, t-butylperoxypivalate, and diisopropylperoxydioxide. Organic peroxides such as carbonate, dioctyl peroxy dicarbonate, t-butyl peroxy neodecanoate, α-cumyl peroxy neodecanoate, 2,2-azobisisobutyronitrile, 2,2-
Azo compounds such as azobis-2,4-dimethylvaleronitrile;

In the graft copolymerization, the acrylic copolymer is charged into a polymerization reactor in the form of an emulsion before the start of polymerization. The N-substituted maleimide is
Prior to the start of the polymerization, the whole amount may be charged at once, or may be dividedly added during the polymerization and continuously added or intermittently dropped.

In particular, when an N-substituted maleimide such as N-phenylmaleimide having a remarkably different copolymerizability ratio from vinyl chloride is used, it is preferable to add the N-substituted maleimide separately during the polymerization or to add it continuously. Is preferred since the heat resistance of the vinyl chloride-based graft copolymer of the present invention is improved. In this case, the N-substituted maleimide is preferably dissolved in a parent solvent such as acetone or methanol or dispersed in water for use.

In the above suspension polymerization method, a pH adjuster, an antioxidant and the like may be added as necessary. The reaction conditions in the suspension polymerization method are preferably a polymerization temperature of 30 to 90 ° C. and a polymerization time of 2 to 20 hours.

As a specific method for producing the vinyl chloride graft copolymer of the present invention, for example, a reaction vessel equipped with a stirrer and a jacket is charged with pure water, the above-mentioned acrylic copolymer latex, dispersant, oil A soluble polymerization initiator and a water-soluble thickener, and if necessary, a polymerization degree regulator, are charged, and then the air in the polymerization vessel is discharged by a vacuum pump, and further, under stirring conditions, vinyl chloride and an N-substituted maleimide, In addition, a method in which another vinyl monomer is charged as required, and then the inside of the reaction vessel is heated with a jacket to carry out graft copolymerization of vinyl chloride and the N-substituted maleimide. Since the above graft copolymerization of vinyl chloride and N-substituted maleimide is an exothermic reaction, the temperature in the reaction vessel, that is, the polymerization temperature can be controlled by changing the jacket temperature. After the completion of the reaction, unreacted vinyl chloride and the like are removed to form a slurry, which is then dehydrated and dried to produce a vinyl chloride graft copolymer.

If the degree of polymerization of polyvinyl chloride in the vinyl chloride-based graft copolymer is small, it is difficult to obtain sufficient moldability of the molded article.
000, more preferably 400 to 1600.

The vinyl chloride graft copolymer obtained by the production method of the present invention may be used, if necessary, at the time of molding, as a heat stabilizer, a stabilizing aid, a lubricant, a processing aid, an antioxidant, a light stabilizer. Agents, fillers, pigments and the like are added and used.

Examples of the heat stabilizer include dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin maleate, dibutyltin maleate polymer, dioctyltin malate, dioctyltin malate polymer, dibutyltin laurate, dibutyltin Organic tin stabilizers such as laurate polymers, lead stabilizers such as lead stearate, dibasic lead phosphite, and tribasic lead sulfate, calcium-zinc stabilizer, barium-zinc stabilizer, barium- Cadmium stabilizers and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the stabilizing aid include epoxidized soybean oil, epoxidized linseed oil epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphate ester. These may be used alone or in combination of two or more.

Examples of the above lubricant include montanic acid wax, paraffin wax, polyethylene wax,
Stearic acid, stearyl alcohol, butyl stearate and the like can be mentioned. Even if these are used alone,
Two or more kinds may be used in combination.

Examples of the processing aid include an acrylic processing aid which is an alkyl acrylate / alkyl methacrylate copolymer having a weight average molecular weight of 100,000 to 2,000,000, and specific examples thereof include n-butyl acrylate / Methyl methacrylate copolymer, 2-ethylhexyl acrylate / methyl methacrylate / butyl methacrylate copolymer and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the antioxidants include phenolic antioxidants.

Examples of the light stabilizer include salicylic acid ester, benzophenone, benzotriazole and cyanoacrylate ultraviolet absorbers, and hindered amine light stabilizers. These may be used alone or in combination of two or more.

Examples of the filler include calcium carbonate and talc. These may be used alone or in combination of two or more.

Examples of the pigments include organic pigments such as azo, phthalocyanine, sulene and dye lake.
Oxide-based, molybdenum chromate-based, sulfide / selenide-based, ferrocyanide-based inorganic pigments and the like can be mentioned.
These may be used alone or in combination of two or more.

Further, a plasticizer may be added to the vinyl chloride-based graft copolymer for the purpose of improving the processability at the time of molding, for example, dibutyl phthalate, di-2-phthalate.
Ethylhexyl phthalate, di-2-ethylhexyl adipate and the like can be mentioned. These may be used alone or in combination of two or more.

The method of mixing the above-mentioned additives with the above-mentioned vinyl chloride graft copolymer may be a method by hot blending or a method by cold blending. Examples of the molding method include extrusion molding and injection molding. Method, calender molding method, press molding method and the like.

[0051]

EXAMPLES The effects of the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Production of acrylic copolymer 1: particle size of 0.1
46 μm) Examples 1-2, Comparative Example 5 (Table 1) 100 parts by weight of n-butyl acrylate (monomer), 1 part by weight of trimethylolpropane triacrylate (crosslinking agent), polyoxyethylene nonyl phenyl ether ammonium sulfate (emulsifier) One part by weight and 60 parts by weight of pure water were mixed and stirred with a homogenizer for 5 minutes to prepare an emulsified monomer liquid.

Next, pure water was charged into a reactor equipped with a stirrer and a reflux condenser (16 parts by weight based on 100 parts by weight of the monomer).
0 parts by weight), and after replacing oxygen in the container with nitrogen, the reaction temperature was raised to 70 ° C. with stirring. After completion of the heating, 0.1 parts by weight of ammonium persulfate (initiator) was charged into the reactor, and the emulsified monomer liquid was added dropwise over 8 hours. After the dropping of all emulsified monomer liquids was completed, and after an aging period of 1 hour, the polymerization was terminated and the solid content concentration was about 30%.
By weight, acrylic copolymer particles were obtained. The average particle size of the particles of the obtained acrylic copolymer was 0.46 μm. The average particle size of the particles of the acrylic copolymer was measured by the following evaluation method.

(Production of acrylic copolymer 2: particle size of 0.1
Comparative Examples 1-4 (Table 1) 100 parts by weight of n-butyl acrylate (monomer), 1 part by weight of trimethylolpropane triacrylate (crosslinking agent), 1 part by weight of polyoxyethylene nonylphenyl ether ammonium sulfate (emulsifier), 60 parts by weight of pure water was mixed and stirred with a homogenizer for 5 minutes to prepare an emulsified monomer liquid.

Next, pure water was charged into a reactor equipped with a stirrer and a reflux condenser (16 parts by weight based on 100 parts by weight of the monomer).
0 parts by weight), and after replacing oxygen in the container with nitrogen, the reaction temperature was raised to 70 ° C. with stirring. After the completion of the heating, 0.1 part of ammonium persulfate (initiator) and 30% of the emulsified monomer solution were added all at once to the reactor to initiate polymerization. Subsequently, the rest of the emulsified monomer liquid was added dropwise over 3 hours. After the dropping of all emulsified monomer liquids was completed, and after an aging period of 1 hour, the polymerization was terminated to obtain acrylic copolymer particles having a solid content concentration of about 30% by weight. The average particle size of the particles of the obtained acrylic copolymer was 0.12 μm. The average particle size of the particles of the acrylic copolymer is measured by a light scattering particle size meter (DLS-700 light scattering particle size meter).
0: Otsuka Electronics Co., Ltd.).

[Production of vinyl chloride graft copolymer] (Example 1) Then, 150 parts by weight of pure water and 23.3 parts by weight of the acrylic copolymer latex were placed in a polymerization vessel equipped with a stirrer and a jacket. (Acrylic copolymer solid content 7
Parts by weight), 5 parts by weight of a 3% aqueous solution of saponified polyvinyl alcohol (Kuraray Co., Ltd., Kuraray Poval L-8), 2.5 parts by weight of a 3% aqueous solution of hydroxypropylmethylcellulose (Shin-Etsu Chemical Co., Ltd., Metroose 60SH50), t
0.03 parts by weight of butyl peroxypivalate and aluminum sulfate were added all at once so that the aluminum ion was 3000 ppm based on 7 parts by weight of the solid content of the acrylic copolymer, and then the air in the polymerization reactor was evacuated by a vacuum pump. After discharging, 80 parts by weight of a vinyl chloride monomer (about 80% was consumed by polymerization) were further added under stirring conditions. Thereafter, graft polymerization was started at a polymerization temperature of 57.5 ° C. by controlling the jacket temperature.

Immediately after the temperature in the reactor reached 57.5 ° C., a solution prepared by dissolving 0.75 parts by weight of N-phenylmaleimide in 1.5 parts by weight of acetone was added at intervals of 10 minutes.
Each time, the mixture was pressed into the reaction vessel to perform graft polymerization. After completion of the addition, the mixture was aged for 10 minutes and then cooled to stop the reaction. After the reaction, an antifoaming agent (Toray Silicon SH, manufactured by Toray Industries, Inc.)
5510) was added under pressure, and thereafter, unreacted vinyl chloride monomer was removed, followed by dehydration and drying to obtain a vinyl chloride-based graft copolymer.

With respect to the above-mentioned vinyl chloride graft copolymer, the following items were evaluated for performance, and the results are shown in Table 1.

[Evaluation] (Component composition) The above vinyl chloride graft copolymer was
Oxygen flask method based on IS K7229 and elemental analyzer (“CHN coder MT-
5)), the contents of the acrylic copolymer and the N-substituted maleimide in the vinyl chloride-based graft copolymer were measured.

(Polymerization degree) 5 g of the above vinyl chloride graft copolymer was dissolved in 100 g of tetrahydrofuran, the insoluble portion was separated, and methanol was added to the soluble portion to precipitate. A copolymer with the substituted maleimide was obtained. The degree of polymerization of the obtained copolymer
It was measured in accordance with IS K6721.

(Impact resistance) A resin composition obtained by mixing 2 parts by weight of an organotin stabilizer and 0.3 parts by weight of a montanic acid lubricant with respect to 100 parts by weight of a vinyl chloride graft copolymer is used. Roll kneading at 190 ° C. for 3 minutes, press forming at 195 ° C. for 6 minutes, and pressing using a 3 mm thick press plate.
In accordance with IS K7111, a sample is prepared,
A Charpy impact test was performed at a measurement temperature of 23 ° C.

(Low-Temperature Impact Resistance) The impact resistance was evaluated in the same manner as in the evaluation of impact resistance except that the measurement temperature was 0 ° C.

(Heat Resistance) A load deflection temperature test (Method A) was performed using the press plate obtained in the evaluation of impact resistance in accordance with JIS K7207, and the load deflection temperature was measured.

(Example 2, Comparative Example 5) Particle size 0.46 μm
A vinyl chloride-based graft copolymer was obtained in the same manner as in Example 1, except that the acrylic copolymer was used and the copolymer composition ratio was changed as shown in Table 1. The obtained vinyl chloride-based graft copolymer was evaluated for performance in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Examples 1 to 4) In the same manner as in Example 1 except that an acrylic copolymer having a particle size of 0.12 μm was used and the composition ratio of the copolymer was changed as shown in Table 1. A vinyl chloride graft copolymer was obtained. The obtained vinyl chloride-based graft copolymer was evaluated for performance in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 6 The same performance evaluation as in Example 1 was performed using a vinyl chloride homopolymer (“TS-1000R” manufactured by Tokuyama Sekisui Co., Ltd.). The results are shown in Table 1.

(Comparative Examples 7 and 8) The same procedure as in Example 1 was repeated except that no acrylic copolymer was added and the copolymer composition was changed as shown in Table 1. A graft copolymer was obtained. The obtained vinyl chloride-based graft copolymer was evaluated for performance in the same manner as in Example 1, and the results are shown in Table 1.

[0068]

[Table 1]

[0069]

The vinyl chloride graft copolymer of the present invention is as described above, and can be molded by adding a stabilizer, a lubricant and the like generally used for a vinyl chloride resin. The obtained molded article is excellent in heat resistance and impact resistance, and thus is suitably used for pipework equipment, building members, housing materials, and the like.

Continued on the front page F term (reference) 4F071 AA24 AA24X AA33 AA33X AA35 AA35X AA77 AF17Y AF23Y AF45Y BB03 BC01 4J026 AA18 AA40 AA45 AA46 AA61 AA68 AC15 AC16 AC34 AC36 BA10 BA38 BB02 DB03 DA03 DA03 DA03 DA03 DA03 DA03 DA03 DA03 DB38 GA01

Claims (3)

[Claims] The glass transition temperature of the homopolymer is -140.
At least one kind of (meth) acrylate having a temperature of not lower than 0 ° C. and lower than 0 ° C .;
Parts by weight, and an acrylic copolymer having an average particle diameter of 0.20 μm or more, which is composed of 0.1 to 10 parts by weight of a polyfunctional monomer, is obtained by graft copolymerizing vinyl chloride and an N-substituted maleimide. A vinyl chloride graft copolymer characterized by the following. 2. 40 to 95% by weight of vinyl chloride, 4 to 40% by weight of N-substituted maleimide, and acrylic copolymers 1 to 3.
2. The vinyl chloride-based graft copolymer according to claim 1, comprising 0% by weight as a constituent. 3. The vinyl chloride graft copolymer according to claim 1 or 2, wherein a test value of a Charpy impact test at 0 ° C. is 15 kJ / m ² or more, and a test value of a load deflection temperature test is 85. Molded product whose temperature is not less than ° C.