KR100601004B1 - Acrylate-vinyl chloride based hard resin with high impact resistance, the preparation method thereof and the pipe produced therewith - Google Patents

Abstract

The present invention relates to an acrylic-vinyl chloride-based hard resin, a method for producing the same, and a pipe made therefrom that are excellent in impact resistance and free from other physical and chemical properties. 100 parts by weight of the (meth) acrylate monomer, ② 30 to 50 parts by weight of the hydroxy alkyl (meth) acrylate monomer, and ③ 10 to 20% by weight of the acrylic polymer obtained by polymerizing 10 to 20 parts by weight of ethylene glycol, (b) ethylene Acryl-vinyl chloride impact-resistant hard resin obtained by graft copolymerization of 5 to 10 wt% of ethylene propylene diene monomer (EPDM), followed by additional graft copolymerization of 50 to 80 wt% of vinyl chloride. And a method for producing the same and a pipe manufactured therefrom.

Acrylic-vinyl chloride type, impact resistant hard resin

Description

Acrylate-vinyl chloride based hard resin with high impact resistance, the preparation method approximately and the pipe produced therewith}

The present invention relates to an acrylic-vinyl chloride-based impact resistant hard resin having excellent impact resistance and good surface condition even for long time continuous molding, a method for producing the same, and a pipe produced therefrom.

The vinyl chloride resin composition has excellent mechanical strength, weather resistance, and chemical resistance, and thus is widely used as a building member, a pipe, a housing material, etc., but has a weakness of showing low impact resistance.

In order to improve this, a method of blending rubber-based resins such as chlorinated polyethylene (hereinafter referred to as 'CPE'), methyl methacrylate butadiene styrene copolymer (hereinafter referred to as 'MBS'), and an acrylic modifier with a vinyl chloride resin using a reinforcing agent This has been used mainly. However, when the method of blending such a reinforcing agent is used, there is a problem that blending CPE worsens low-temperature impact resistance and results in a very narrow molding temperature width at which sufficient impact resistance is obtained in the molded body, and when blending MBS, the resistance after exposure test There is a problem that the impact property is greatly lowered, or the addition during molding is increased. When blending the acrylic modifier, the particles are difficult to uniformly disperse during molding, resulting in defects such as staining of the impact resistance of the vinyl chloride resin depending on the processing conditions.

On the other hand, a method of blending a reinforcing agent was also used, but the molded article such as hard vinyl chloride tube, hard vinyl chloride tube modulus molded into the vinyl chloride-based resin composition obtained through this has a problem that the impact resistance is not sufficient.

Japanese Patent Laid-Open No. 62-36412 discloses a vinyl chloride resin composition obtained by graft polymerization of vinyl chloride on an acrylic copolymer. However, technically, the impact resistance of the obtained vinyl chloride resin composition is improved, but mechanical strength and heat resistance are deteriorated.

In order to solve the conventional problems as described above, the present invention has been made to improve the impact resistance and at the same time to produce an acrylic-vinyl chloride-based hard resin that does not degrade other physical and chemical properties including mechanical properties It came to invention. Accordingly, an object of the present invention is to provide an acrylic-vinyl chloride-based hard resin having good surface resistance even in a long time continuous molding, which is excellent in impact resistance and does not degrade other physical and chemical properties.

Other objects, specific aspects of the present invention, and the like are described below.

According to one aspect of the invention,

(a) 100 parts by weight of an alkyl (meth) acrylate monomer, ② 30 to 50 parts by weight of a hydroxy alkyl (meth) acrylate monomer, and ③ 10 to 20% by weight of an acrylic polymer obtained by polymerizing 10 to 20 parts by weight of ethylene glycol. ,

(b) graft copolymerization of 5 to 10% by weight of ethylene propylene diene monomer,

(c) 50-80% by weight of vinyl chloride is further graft copolymerized acrylic-vinyl chloride-based impact resistant hard resin.

As a specific embodiment of the above aspect, 100 parts by weight of the graft copolymer (A) prepared as described above may be further blended with 10 to 15 parts by weight of (B) styrene-butadiene rubber, to improve impact resistance and other It is preferable to prevent the deterioration of physicochemical properties.

Here, when the vinyl chloride exceeds 80% by weight, the impact resistance of the molded body is lowered, and if it is less than 50% by weight, the mechanical strength of the molded body is lowered.

In view of the mechanical strength of such a molded article, it is more preferable to graft copolymerize (a) 13-17% by weight of the acrylic polymer, (b) 5-9% by weight of ethylene propylene diene monomer, and (c) vinyl chloride 75-79 It is preferable to obtain an acrylic-vinyl chloride impact resistant hard resin prepared by additional graft copolymerization by weight, most preferably (a) 15% by weight of acrylic polymer, and (b) 7% by weight of ethylene propylene diene monomer. After copolymerization, (c) 77% by weight of vinyl chloride is additionally graft copolymerized to obtain an acrylic-vinyl chloride-based hard resin.

In this case, the hydroxy alkyl (meth) acrylate monomer and ethylene glycol crosslink the polymer of the shell portion to reduce the adhesiveness of the copolymer and at the same time smooth the graft copolymerization of vinyl chloride to enhance the impact resistance For each of them, the use of less than the lower limit of the above range may destroy the particle shape of the acrylic copolymer to reduce the impact resistance, and when used in an amount exceeding the upper limit, the crosslinking density of the copolymer is increased to reduce the impact resistance. Problems may arise.

In addition, when the ethylene propylene diene monomer is used in a content outside the above range, there may be a problem that does not obtain sufficient flexibility for high-speed deformation during molding processing.

It is preferable that the graft rate of vinyl chloride be 0.5 to 2 weight% here, and the graft rate of vinyl chloride as used herein means the weight fraction of the vinyl chloride molecule copolymerized with the acrylic copolymer and chemically bonded.

When the graft ratio of the vinyl chloride is less than 0.5% by weight, the surface of the acrylic copolymer cannot be sufficiently covered with vinyl chloride molecules, and it is adhered to the mold surface of the molding machine at the time of molding, so that a molded article having a good surface state cannot be obtained, and 2 weight Exceeding the% may cause a problem of deterioration of mechanical properties due to excessive graft.

According to another aspect of the present invention, it relates to a molded article produced using the hard resin of the present invention described above.

In the case of the molded article manufactured as described above, it is preferable that the shelly impact value is 200 kgf · cm / cm ² or more and the tensile strength is 600 kgf / cm ² or more, and the form may be a tube or a mold extrusion molded product.

If the shelly impact value is less than 200 kgf · cm / cm 2, it cannot be sufficiently tolerated for use in cold regions, and if the tensile strength is less than 600 kgf / cm 2, the pulsation resistance is insufficient when used for water supply purposes.

Since the resin molded article according to the present invention has the above characteristics, it is required not only to provide high impact resistance and tensile strength, such as a plastic chassis, but also to have good appearance and formability in applications requiring extremely high impact resistance and tensile strength. It is also applicable to the intended use.

According to another aspect of the invention,

(a) 100 parts by weight of an alkyl (meth) acrylate monomer, ② 30 to 50 parts by weight of a hydroxy alkyl (meth) acrylate monomer, ③ 10 to 20 parts by weight of ethylene glycol to obtain an acrylic polymer,

(b) graft copolymerizing 5 to 10 wt% of ethylene propylene diene monomer to 10 to 20 wt% of the acrylic polymer to obtain a graft copolymer, and

(c) 50 to 80% by weight of the graft copolymer further relates to a method of producing an acrylic-vinyl chloride-based impact resistant hard resin comprising the step of graft copolymerization.

In the above-described manufacturing method of the present invention, more preferably, 100 parts by weight of the graft copolymer obtained in the step (c) is blended with 10 to 15 parts by weight of styrenebutadiene rubber, thereby acryl-vinyl chloride-based It is preferable to prepare the impact hard resin in order to improve the impact resistance and to prevent the deterioration of other physical properties.

In the present invention, examples of the monomer that can be used as the "alkyl (meth) acrylate monomer" include ethyl acrylate, n-propyl acrylate, isobutyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2- Ethyl hexyl acrylate, lauryl methacrylate or mixtures thereof may be included, but is not limited thereto. More preferably ethyl acrylate, n-propyl acrylate, isobutyl acrylate or mixtures thereof may be used, in particular using ethyl acrylate is most preferred for enhancing impact resistance and other physicochemical properties, in particular It is preferable at the point that sufficient flexibility with respect to the high speed deformation at the time of forming processing can be obtained.

Also in the present invention, examples of the monomer that can be used as "hydroxy alkyl (meth) acrylate monomer" may include, but are not limited to, 2-hydroxy ethyl methacrylate, 2-hydroxy propyl methacrylate, or mixtures thereof In particular, the use of 2-hydroxy ethyl methacrylate is preferred for strengthening impact resistance and lowering of other physicochemical properties, and particularly in that sufficient flexibility can be obtained for high-speed deformation during molding.

In the present invention, the polymerization method is not particularly limited, and for example, emulsion polymerization, suspension polymerization, and the like may be used, but in terms of impact resistance expression and suspension polymerization in terms of particle size control of the acrylic copolymer. It is preferable to carry out.

The emulsion polymerization method can be broadly divided into three types such as a batch polymerization method, a monomer dropping method, and an emulsion dropping method according to the difference in the method of adding a monomer. In the present invention, any method may be used. It is preferable to carry out by the dropping method or the emulsion dropping method.

Specifically, each polymerization method is a batch polymerization method, for example, pure water, an emulsion dispersant, a polymerization initiator, and a monomer are collectively added to a polymerization reactor with a jacket to depressurize the inside of the polymerization reactor to remove oxygen. Under a nitrogen atmosphere filled with air, nitrogen is sufficiently emulsified by stirring to adjust the inside of the polymerization reaction tank to a predetermined temperature with a jacket, and then a polymerization initiator is added to polymerize.

In the monomer dropping method, for example, pure water, an emulsion dispersant, and a polymerization initiator are placed in a polymerization reactor with a jacket, and the inside of the polymerization reactor is jacketed under a nitrogen atmosphere filled with nitrogen after removing the oxygen by depressurizing the inside of the polymerization reactor. It is a method of making it superpose | polymerize gradually by making a predetermined temperature and then dropping a monomer by fixed quantity.

In the emulsion dropping method, for example, the monomer, emulsion dispersant, and pure water are sufficiently emulsified by stirring to prepare an emulsion monomer, and then, pure water and a polymerization initiator are put in a polymerization reactor with a jacket to depressurize the inside of the polymerization layer reactor. In the nitrogen atmosphere filled with nitrogen after removing oxygen, it is the method of superposing | polymerizing by first adjusting the inside of a polymerization reaction tank to predetermined temperature with a jacket, and then dropping the said emulsifying monomer by a fixed amount. In this method, when a part of the said emulsified monomer (hereinafter referred to as "seed monomer") is added at the initial stage of polymerization and the method of dropping the remaining emulsified monomer is then used, the polymer is easily generated by changing the amount of seed monomer. It is possible to control the particle diameter.

An acryl-type copolymer can be obtained as follows, for example. First, alkyl (meth) acrylate, hydroxy alkyl (meth) acrylate, and ethylene glycol are polymerized by emulsion polymerization in the presence of an emulsifying dispersant and a polymerization initiator to form a copolymer as a core part. Next, EPDM is added in the presence of the copolymer, the emulsion dispersant and the polymerization initiator, and graft polymerization is carried out by emulsion polymerization to form a shell, thereby obtaining an acrylic copolymer according to the present invention, which is an acrylic copolymer.

The shell portion may be formed by a series of polymerization processes from the synthesis of the core portion, or the core portion may be polymerized by adding EPDM again after synthesizing and recovering the core portion.

The said emulsifier dispersant is added in order to improve the dispersion stability in the emulsion of the said monomer, and to superpose | polymerize efficiently. There is no restriction | limiting in particular as said emulsion dispersant, For example, anionic surfactant nonionic dispersing agents, such as polyoxyethylene alkylphenyl ether pate, gelatin, etc. are mentioned. Among them, anionic surfactants are preferred.

There is no restriction | limiting in particular as said polymerization initiator, For example, water-soluble polymerization initiators, such as potassium peroxide, ammonium peroxide, hydrogen peroxide, etc. Organic peroxides, such as benzoyl peroxide and lauroyl peroxide, such as azobis isobutyl nitrile, etc. Azo initiator redox initiator etc. are mentioned.

In the said reaction, pH adjuvant, antioxidant, etc. may be added as needed. Moreover, in order to improve the mechanical stability of the emulsion of the said acrylic copolymer (a), the protective colloid agent may be added as needed at the time of completion | finish of a polymerization reaction.

As described above, the obtained acrylic copolymer is a two-layered particle composed of a core part and a shell part. The particle | grains of the said acryl-type copolymer are 60-250 nm in average particle diameter. If the thickness is less than 60 nm, it contains a large number of fine particles of 10 nm or less, which increases the adhesiveness, and the overall adhesiveness is increased, thereby adhering to the mold surface of the molding machine, which causes a poor appearance of the molded body, and when it exceeds 25 nm, the impact resistance and the tensile strength of the molded body are lowered together. Limited to scope. 100 ~ 200nm is good.

The acrylic copolymer of the present invention preferably has a gel fraction of 50 to 100% by weight. If the content is less than 50% by weight, the degree of crosslinking is low, and thus acrylic molecules of crosslinking at the end of the molding process bleed out to the surface of the molded body, thereby damaging the appearance of the molded body. More preferably, it is 75-100 weight%.

In addition, it is preferable that the acrylic copolymer has a resin solid content of 10 to 60% by weight. If the acrylic copolymer is less than 10% by weight, the productivity of the acrylic copolymer is not sufficient. If the acrylic copolymer exceeds 60% by weight, the polymerization is performed with a vinyl unit containing vinyl chloride as a main component. The reaction stability is bad.

In addition, the method of graft copolymerizing vinyl chloride on the acrylic copolymer prepared as described above is not particularly limited. For example, emulsion polymerization, solution polymerization, bulk polymerization, and preferably, suspension polymerization may be used. Impact-resistant acrylic-vinyl chloride-based hard resin according to the invention can be prepared.

The hard resin of this invention can be obtained, for example by the following method. A pure water, an acrylic copolymer, a dispersing agent, a water-soluble polymerization initiator, a water-soluble thickener, and a polymerization degree regulator are added to a reaction vessel equipped with a stirrer and a jacket, and then the air in the reaction vessel is discharged with a vacuum pump, and under stirring conditions. After adding vinyl chloride, the reaction vessel is heated with a jacket to graft copolymerize vinyl chloride. Since the graft copolymerization is a semi-thermal reaction, by changing the jacket temperature, it is possible to control the temperature in the reaction vessel, that is, the polymerization temperature. After the completion of the reaction, the unreacted vinyl chloride is removed to form a slurry, and dehydration and drying to obtain the hard resin according to the present invention.

The above dispersant is used to improve the dispersion stability of the above acrylic copolymer and to efficiently graft polymerization of vinyl chloride. The above dispersants are not particularly limited and include, for example, poly (meth) acrylate, (meth) acrylate-alkylacrylate copolymer, methyl cellulose, ethyl cellulose, hydroxy propyl methyl cellulose, polyethylene glycol, polyvinyl acetate and The partially hardened gelatin, polyvinyl pyrrolidone, starch, maleic anhydride styrene copolymer, etc. are mentioned. These may be used independently and may use 2 or more types together.

The above oil-soluble polymerization initiator is not particularly limited but is advantageous in graft copolymerization, and therefore, a radical polymerization initiator is preferable. The radical polymerization initiator is not particularly limited, and for example, lauroyl peroxide, t-butyl peroxy fiberrate, diisopropyl peroxy carbonate, dioctyl peroxy dicarbonate, t-butyl peroxy neodicanoate and azo compounds such as organic peroxides 2, 2-azobis isobutylonitrile, 2,2-azobis 2, 4-dimethyl pareronitrile, such as a-millyl peroxy neodecanoate, and the like. .

Examples of the water-soluble thickener include, without limitation, poly (meth) acrylic acid, alkyl (meth) acrylate (meth) acrylic acid copolymers, casein, and these metal salts.

The above degree of polymerization degree is not particularly limited, and examples thereof include a chain transfer agent such as melcapto methanol, melcapto ethanol, and mercapto propanol, and a crosslinking agent such as divinylbenzene and ethylene glycol dimethacrylate.

For the above polymerization reaction, in order to reduce the amount of adhesion of the above acrylic copolymer (a) to the reaction vessel during the reaction, a flocculant may be added to the above acrylic copolymer (a) in advance.

In the above polymerization reaction, a pH adjuster, an antioxidant, or the like may be added as necessary.

It is preferable that the impact resistant hard resin of this invention is 300-2000 degree of polymerization of polyvinyl chloride. Even if it is less than 300, even if it exceeds 2000, sufficient moldability will become difficult to obtain. More preferably, it is 400-1600.

In addition, as a specific embodiment of the above aspect of the present invention, it is preferable to obtain an impact-resistant acrylic-vinyl chloride-based hard resin according to the present invention by blending SBR in the acrylic copolymer thus prepared, the method of blending is Any method can be used without particular limitation, as long as it is commonly performed in the art.

The hard resin of the present invention is formed and processed after the addition of heat stabilizers, stabilizing aids, lubricants, processing aids, antioxidants, light stabilizers, fillers, pigments and the like as necessary.

The above heat stabilizer is not particularly limited, and for example, dimethyl tin mercapto, dibutyl tin mercapto, dioctyl tin mercapto, dibutyl tin malate, dibutyl tin malate polymer, dioctyl tin malate, Organic tin stabilizers such as dioctyl tin malate polymer, dibutyl tin laurate, dibutyl tin laurate polymer, lead-based stabilizers such as stearic acid lead, dibasic phosphite, tribasic lactate lead, calcium-zinc stabilizer, barium-zinc stabilizer And a barium cadmium stabilizer.

The stabilizing aid is not particularly limited, and examples thereof include epoxidized soybean oil, epoxidized amanidu oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphate ester.

The above lubricant is not particularly limited, and examples thereof include montanic acid wax, paraffin wax, polyethylene wax, stearic acid, stearyl alcohol, butyl stearate, and the like.

The above processing aid is not particularly limited, and examples thereof include acrylic processing aids such as alkyl acrylate / alkyl methacrylate copolymers having a weight average molecular weight of 100,000 to 2,000,000. The above acrylic processing aids are not particularly limited, and examples thereof include n-butyl acrylate / methyl methacrylate copolymer, 2-ethylhexyl acrylate / methyl methacrylate / butyl methacrylate copolymer, and the like. Can be.

The above antioxidant is not particularly limited, and examples thereof include phenolic antioxidants. The above light stabilizer is not particularly limited, and examples thereof include ultraviolet stabilizers such as salicylic acid esters, benzophenones, benzotriazoles, and cyano acrylates.

The above filler is not particularly limited, and examples thereof include calcium carbonate, talc, and the like. There is no particular limitation to the above pigments. For example, inorganic pigments such as azo-based, phthalocyanine-based, styrene-based and dye-lake-based organic pigment oxides, chromium molybdenum-based, sulfide-selenide-based and persianized Etc. can be mentioned.

The method of mixing the above various additives with the above acrylic-vinyl chloride-based hard resin is not particularly limited, and may be, for example, a hot blend method or a cold blend method.

The molding method of the above vinyl chloride-based resin is not particularly limited, and examples thereof include an extrusion molding method, an injection molding method, a calender molding method, and a press molding method.

In the acrylic-vinyl chloride-based resin of the present invention, since the core portion of the acrylic copolymer is formed of a polymer rich in flexibility, it is possible to maintain very excellent impact resistance.

In addition, since the shell portion of the acrylic copolymer is highly crosslinked, the acrylic-vinyl chloride resin of the present invention has a high hardness and elasticity on the particle surface as well as a multi-pipe that serves as a crosslinking agent, as compared with conventional vinyl chloride resins. By using a large amount of a functional unit, the graft ratio of vinyl chloride can improve and the adhesiveness of an acryl-type copolymer (a) can be reduced. Therefore, it is possible to prevent the hair particles from adhering to and depositing on the mold surface of the molding machine during molding, and defects such as scratches, cracks, stains, and cracks do not occur on the surface of the molded body even after continuous molding for a long time.

The acrylic-vinyl chloride-based resin molded article according to the present invention, such as a pipe, may be, for example, a heat stabilizer, a stabilizing aid, a lubricant, a processing aid, an antioxidant, or a light stabilizer as necessary for the acrylic-vinyl chloride-based resin of the present invention. It can obtain by adding and forming additives, such as a filler and a pigment.

There is no restriction | limiting in particular as the method of the said shaping | molding, For example, an extrusion molding method, an injection molding method, a calendar molding method, a press molding method, etc. are mentioned. In addition, the shape of the acrylic-vinyl chloride-based hard resin molded article is not particularly limited and is appropriately selected from tubes, plates and other shapes depending on the use.

Example

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

Examples and Comparative Examples

(1) Preparation of Acrylic Copolymer

According to the compounding composition shown in Table 1, each acryl- vinyl chloride type resin was obtained by the following operation procedures. First, the predetermined amount of ion-exchange water used for superposition | polymerization, an emulsion dispersing agent (polyoxyethylene nonyl phenyl ether ammonium sulfate), the core unit, and ethylene glycol were mixed and stirred, and the core emulsion unit was prepared. In addition, a predetermined amount of ion-exchanged water, an emulsion dispersant (polyoxyethylene nonylphenyl ether ammonium sulfate), a shell unit, and ethylene glycol were mixed and stirred to prepare a shell emulsion unit. On the other hand, a predetermined amount of ion-exchange water was put into the polymerization reactor, and stirring was started. After depressurizing the polymerization vessel and deoxygenating the inside of the vessel, it was replaced by a platen ring with nitrogen, and the polymerization tank was heated to 70 ° C. In the polymerization tank in which the temperature was completed, all the emulsified units were collectively added to the seed unit in the ammonium peroxide (APS) and the above-mentioned emulsified unit for the core to initiate polymerization. Subsequently, the remainder of the emulsion unit for core was added dropwise. And the shell unit was dripped, and dripping of all the emulsification unit was complete | finished in 3 hours. Thereafter, the polymerization was terminated with a maturation period of 1 hour to obtain an acrylic polymer having a solid content concentration of about 30% by weight.

(2) Preparation of acrylic-vinyl chloride hard resin

Subsequently, in a reaction vessel equipped with a stirrer and a jacket, pure water, acryl-based polymer latex, 3% aqueous solution of partially developed polyvinyl acetate, t-butyl peroxy neodecanoate, and --millyl peroxy neodecanoate were collectively After the addition, the air in the polymerization reactor was discharged by a vacuum pump, and after the EPDM was introduced under stirring conditions, polymerization was started at the polymerization temperature of 57 ° C by jacket temperature control. After completion | finish of reaction by confirming that the pressure in a reactor fell to 6.0 kg / cm <2>, after cooling and stopping, unreacted EPDM was removed and dehydrated. Vinyl chloride was graft copolymerized in the same manner to obtain an acrylic-vinyl chloride resin having a vinyl chloride polymerization degree of about 1,000 in the acrylic-vinyl chloride resin.

Experimental Example

(1) Evaluation of Graft Rate

About 10 g (preferably W3g) of vinyl chloride-type resin was crushed, and it stirred and mixed in 100 ml of THF for 50 hours. The THF insoluble portion was separated from the THF solution portion with a 200 mesh wire mesh and dried overnight at 70 ° C. The content of the obtained dried product was weighed (called W4g) and the chlorine content was quantified (called C%). The graft rate was evaluated according to the following formula.

Graft Rate (%) = ((C X W4 / 56. 8) X l00) / (W3-W4 X (1-C / 56.8))

(2) production of molded articles

To 100 parts by weight of the hard resin obtained in the above Examples and Comparative Examples, 0.8 parts by weight of organic tin stabilizer, 0.5 parts by weight of polyethylene-based lubrication, 0.2 parts by weight of stearic acid and 0.5 parts by weight of calcium stearate, a supermixer (100L, manufactured by Kawata) The mixture was stirred with to obtain a vinyl chloride resin composition. The obtained vinyl chloride resin composition was supplied to a biaxial twin screw extruder (BT-50, manufactured by Plastic Engineering Research Institute) having a screw diameter of 50 mm, and a vinyl chloride resin tube having a diameter of 20 mm was continuously molded for 24 hours. Appearance evaluation, impact resistance, and tensile strength were measured about the obtained hard vinyl chloride tube.

(3) tube appearance evaluation

The inner and outer surfaces of the obtained hard vinyl chloride tube were visually observed, and the time from the start of molding to the appearance defects such as scratches, gold, and stains was measured. The surface condition of the tube was marked with O, Δ, and X for 24 hours depending on the degree of goodness. The results are shown in Table 1.

(4) impact resistance laterality

In accordance with JIS K 7111, the Charpy impact test was conducted. The sample was cut out from the sample for 30 minutes of molding time in the molded article, and used. The measurement temperature was 23 ° C. The results are shown in Table 1 and Table 2.

(5) Tensile strength measurement

Tensile strength tests were carried out in accordance with JIS K 7I13. The sample was cut out from the sample for 30 minutes of molding time and used for the molded article. The measurement temperature was 23 ° C. The results are shown in Table 1.

As described above, it was confirmed that the acrylic-vinyl chloride-based impact resistant hard resin and the molded article according to the present invention were excellent in impact resistance and not deteriorated in other physical and chemical properties.

Claims (8)

(a) 100 parts by weight of an alkyl (meth) acrylate monomer, ② 30 to 50 parts by weight of a hydroxy alkyl (meth) acrylate monomer, and ③ 10 to 20% by weight of an acrylic polymer obtained by polymerizing 10 to 20 parts by weight of ethylene glycol. , (b) graft copolymerization of 5 to 10% by weight of ethylene propylene diene monomer, (c) 50-80% by weight of vinyl chloride additionally prepared by graft copolymerization of acrylic-vinyl chloride impact resistant hard resin. An acrylic-vinyl chloride impact resistant hard resin prepared by blending 100 parts by weight of the graft copolymer (A) and 10 to 15 parts by weight of (B) styrenebutadiene rubber prepared according to claim 1. The acryl-methacrylate of claim 1 or 2, wherein the alkyl (meth) acrylate monomer is ethyl acrylate and the hydroxy alkyl (meth) acrylate monomer is 2-hydroxy ethyl methacrylate. Vinyl chloride-based impact resistant hard resin. The acryl-vinyl chloride impact resistant hard resin according to claim 3, wherein the graft ratio of the vinyl chloride is 0.5 to 2% by weight. In the manufacturing method of the acrylic-vinyl chloride-based impact resistant hard resin, (a) 100 parts by weight of an alkyl (meth) acrylate monomer, ② 30 to 50 parts by weight of a hydroxy alkyl (meth) acrylate monomer, ③ 10 to 20 parts by weight of ethylene glycol to obtain an acrylic polymer, (b) graft copolymerizing 5 to 10 wt% of ethylene propylene diene monomer to 10 to 20 wt% of the acrylic polymer to obtain a graft copolymer, and (C) a method of producing an acrylic-vinyl chloride-based impact resistant hard resin comprising the step of additional graft copolymerization of 50 to 80% by weight of vinyl chloride to the graft copolymer. The method of claim 5, wherein (d) 100 parts by weight of the graft copolymer obtained in the step (c) of 10 to 15 parts by weight of the styrene-butadiene rubber to prepare an acrylic-vinyl chloride impact-resistant hard resin Way. Pipe manufactured using the hard resin of claim 4. The pipe according to claim 7, wherein the shelly impact value is 200 kgf · cm / cm ² or more, and the tensile strength is 600 kgf / cm ² or more.