JPH10316816A - Vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin composition excellent in thermal stability and giving molded products having a high impact resistance by using a recycled raw material comprising vinyl chloride resin product wastes. SOLUTION: This vinyl chloride resin composition comprises (A) the ground product of vinyl chloride resin molded products and (B) a vinyl chloride-based graft copolymer produced by graft-copolymerizing 99-40 wt.% of vinylic chloride or a vinyl monomer mixture consisting mainly of the vinyl chloride to 1-60 wt.% of an acrylic copolymer comprising 100 pts.wt. of a (meth)acrylate monomer giving its homopolymer having a secondary transition point of -140 to -20 deg.C and 0.1-30 pts.wt. of a multifunctional monomer, wherein the content of the acrylic copolymer component in the vinyl chloride resin composition is 1-50 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition, and more particularly, to a vinyl chloride resin composition having excellent impact resistance, which makes it possible to pulverize and recycle vinyl chloride resin product waste. The present invention relates to a vinyl resin composition.

[0002]

2. Description of the Related Art Vinyl chloride resins have been used in a wide range of applications because of their excellent mechanical strength, weather resistance and chemical resistance. However, once the vinyl chloride resin is molded and used, the mechanical strength such as impact resistance is reduced due to aging and the like. Has also decreased in thermal stability.

When such vinyl chloride resin product waste is recycled and remolded, even if it is bent, the mechanical strength such as impact resistance is low. It cannot be used as a part, and the thermal stability during thermoforming has also been reduced, so it cannot be used as a product or part that requires surface color or gloss, and the moldability is poor. The possible shapes and the like are also greatly restricted, so that they can be reused only as low value-added products and parts.

[0004] As an attempt to reuse the waste of vinyl chloride resin products as described above, for example, Japanese Patent Application Laid-Open No.
Japanese Patent No. 107886 discloses that as a waste recycling raw material of vinyl chloride resin products having different heat stabilizers such as lead and tin, zinc stearate is 1 and dibenzoylmethane or stearoylbenzoylmethane is 1 to 20 ( It has been proposed to add a stabilizer for preventing coloration (weight ratio) and reuse the stabilizer.

[0005] In addition, addition of impact modifiers such as styrene-butadiene copolymer and acrylonitrile-butadiene-styrene copolymer to the waste recycled raw materials of the vinyl chloride resin products has been attempted. The raw materials for recycling vinyl resin products are generally indefinite, not very finely pulverized, and not as porous as new raw materials. However, there is a problem that the thermal stability during molding is not sufficiently improved, and the surface properties and impact resistance of the obtained recycled product are not sufficiently improved.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above facts, and an object of the present invention is to use a vinyl chloride resin product as a waste recycling material during molding. An object of the present invention is to provide a vinyl chloride resin composition which gives a molded article having excellent thermal stability and high impact resistance.

[0007]

According to the present invention, (A) a pulverized vinyl chloride resin molded product and (B) a homopolymer having a secondary transition point of -140 to -20 ° C are (meth) acrylates. 100 parts by weight of a system monomer and 0.1 to 3 of a polyfunctional monomer
1 to 60% by weight of an acrylic copolymer composed of 0 parts by weight
A vinyl chloride-based resin composition comprising: a vinyl chloride-based graft copolymer obtained by graft-copolymerizing vinyl chloride or a vinyl monomer mainly composed of vinyl chloride at 99 to 40% by weight; The gist of the present invention is a vinyl chloride resin composition characterized in that the content of the acrylic copolymer component in the composition is 1 to 50% by weight.

[0008] The (A) pulverized vinyl chloride resin molded product used in the present invention is a molded product in which a vinyl chloride resin is once thermoformed as a product or member, or discarded as a defective product during thermoforming. Has been crushed using a crusher or the like to such an extent that it can be fed to a thermoforming machine such as an ordinary extruder or injection molding machine. The size of the particles of the pulverized material is not particularly limited as long as it is pulverized to such an extent that it can be fed to the thermoforming machine. Preferably, the diameter of the granular material or the length of the rod is 30 mm or less because physical properties of the product are reduced.

The vinyl chloride resin is not particularly restricted but includes, for example, polyvinyl chloride, a copolymer of vinyl chloride and a monomer copolymerizable therewith, and a kraft copolymer of vinyl chloride. Examples include kraft copolymers and post-chlorinated chlorinated polyvinyl chloride. These vinyl chloride resins may be used alone or in combination of two or more.

The above-mentioned monomers copolymerizable with vinyl chloride include, for example, α-olefins such as ethylene, propylene and butylene, vinyl esters such as vinyl acetate and vinyl propionate, isobutyl vinyl ether, cetyl vinyl ether and phenyl vinyl ether. (Meth) acrylates such as vinyl ethers, methyl (meth) acrylate and ethyl (meth) acrylate;
Aromatic vinyls such as styrene and α-styrene, (meth)
Vinyl cyanides such as acrylonitrile; vinyl halides such as vinylidene chloride and vinyl fluoride; unsaturated dicarboxylic acids such as dimethyl maleate and dimethyl fumarate; unsaturated dicarboxylic anhydrides such as maleic anhydride;
N-substituted maleimides such as -cyclohexylmaleimide and N-phenylmaleimide.

The backbone polymer of the vinyl chloride graft copolymer obtained by graft copolymerization of vinyl chloride is not particularly limited. For example, a (meth) acrylic acid ester polymer or a copolymer of ethylene and vinyl acetate may be used. Copolymers, copolymers of ethylene and acrylate, chlorinated polyethylene, chlorsulfonated polyethylene, polyurethane and the like can be mentioned.

The secondary transition point (Tg) of the homopolymer used for the vinyl chloride graft copolymer (B) of the present invention is-
The (meth) acrylate-based monomer having a temperature of 140 to −20 ° C. is not particularly limited, but, for example, ethyl acrylate (Tg = −24 ° C., hereinafter, only the temperature is shown in parentheses), n-propyl acrylate (− 37 ° C), n-
Butyl acrylate (-54 ° C), isobutyl acrylate (-24 ° C), sec-butyl acrylate (-2
1 ° C.), n-hexyl acrylate (−57 ° C.), 2-
Ethylhexyl acrylate (-85C), n-octyl acrylate (-85C), n-octyl methacrylate (-25C), isooctyl acrylate (-45C)
C), n-nonyl acrylate (-63C), n-nonyl methacrylate (-35C), isononyl acrylate (-85C), n-decyl acrylate (-70C).
° C), n-decyl methacrylate (-45 ° C), lauryl methacrylate (-65 ° C) and the like, and one or more of these monomers are used as a mixture.

When the homopolymer of the (meth) acrylate monomer has a Tg of less than -140, the mechanical strength such as tensile strength and flexural modulus of a product molded from the obtained vinyl chloride resin composition is reduced. There is a possibility that it cannot be obtained sufficiently, and if it exceeds -20 ° C, sufficient flexibility and impact resistance cannot be obtained.

The above polyfunctional monomer is, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane. (Meth) such as tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate
Examples include acrylates, diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl succinate, allyl compounds such as triallyl isocyanurate, divinyl compounds such as divinylbenzene, and dienes such as butadiene. These polyfunctional monomers may be used alone, or two or more kinds may be used in combination.

The acrylic copolymer is composed of 100 parts by weight of a (meth) acrylate monomer having a homopolymer having a Tg of -140 to -20 ° C and 0.1 of a polyfunctional monomer.
It is obtained by copolymerization at a monomer weight ratio of ３０30 parts by weight.
When the copolymerization ratio of the polyfunctional monomer is T
If the amount is less than 0.1 part by weight, based on 100 parts by weight of the (meth) acrylate monomer having a g of -140 to -20 ° C, the impact resistance of a product molded using the obtained vinyl chloride resin composition Can not be improved enough.
On the other hand, if the amount is more than 30 parts by weight, the molded article becomes hard and brittle, the impact resistance is reduced, and the flexibility is significantly reduced.
As described above, the Tg of the homopolymer is −20 ° C. (meth)
0.1 to 100 parts by weight of the acrylate monomer
It is limited to 30 parts by weight, preferably 0.2 to 10 parts by weight.

The vinyl monomer other than vinyl chloride, which is graft-copolymerized with the above-mentioned acrylic copolymer together with vinyl chloride, is appropriately selected and used depending on the use of the obtained vinyl chloride resin composition. As is not particularly limited as long as it can be copolymerized with vinyl chloride, for example, ethylene, propylene,
Α-olefins such as butylene, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as ethyl vinyl ether and butyl vinyl ether, methyl (meth) acrylate, butyl (meth) acrylate, and hydroxyethyl (meth) acrylate. (Meth) acrylic acid esters, aromatic vinyls such as styrene and α-methylstyrene, vinyl cyanides such as (meth) acrylonitrile, vinyl halides such as vinyl fluoride, vinylidene fluoride, and vinylidene chloride; Dicarboxylic acids such as dimethyl dimethyl acid and dimethyl fumarate; unsaturated dicarboxylic anhydrides such as maleic anhydride; N
N-substituted maleimides such as -phenylmaleimide and N-cyclohexylmaleimide. These may be used alone or in combination of two or more.

The amount of the vinyl monomer other than vinyl chloride to be graft-copolymerized with the above-mentioned vinyl chloride is from 99 to 40 in total of the vinyl monomer mainly composed of vinyl chloride.
Of the parts by weight, 20 parts by weight or less is desirable. If the amount of the vinyl monomer other than vinyl chloride exceeds 20 parts by weight, preferable properties inherent in the vinyl chloride resin may be reduced or lost.

The method for obtaining the acrylic copolymer is not particularly limited, and examples thereof include an emulsion polymerization method, a suspension polymerization method, and a dispersion polymerization method. Among them, the emulsion polymerization method is a preferred polymerization method because the particle size of the obtained acrylic copolymer is easily controlled. The emulsion polymerization method is not particularly limited, and a known method such as a batch polymerization method, a monomer addition method, and an emulsion dropping method can be appropriately selected and used.

In the above polymerization, an emulsifying dispersant, a polymerization initiator, a pH adjuster, an antioxidant and the like are used as required.

Examples of the emulsifying dispersant include anionic surfactants such as polyoxyethylene nonyl phenyl ether sulfate, nonionic surfactants, partially saponified polyvinyl alcohol, cellulose dispersants, and gelatin. Examples of the polymerization initiator include water-soluble polymerization initiators such as ammonium persulfate, potassium persulfate, and hydrogen peroxide; organic peroxide-based polymerization initiators such as benzoyl peroxide and lauroyl peroxide; and azobisisobutyronitrile. And other azo compound-based polymerization initiators.

Next, the above-mentioned acrylic copolymers 1 to 60
With respect to the weight%, 99 to 40% by weight of vinyl chloride or a vinyl monomer mainly composed of vinyl chloride is graft-copolymerized. Graft copolymerization ratio of vinyl chloride (% by weight)
If the content is more than 99% by weight, the obtained vinyl chloride resin composition may not have sufficient thermal stability at the time of molding and the molded article may not have sufficient impact resistance. Yes, if it is less than 40% by weight, the moldability is reduced and the mechanical strength such as the creep strength of the molded article is decreased. Therefore, the amount of vinyl chloride or vinyl monomer mainly composed of vinyl chloride is added. Is 99 to 40% by weight, preferably 96 to 50% by weight.

The method of graft copolymerizing vinyl chloride or a vinyl monomer mainly composed of vinyl chloride with the acrylic copolymer is not particularly limited. Examples thereof include emulsion polymerization, suspension polymerization, and solution polymerization. A polymerization method and the like can be mentioned. In particular, the suspension polymerization method can be suitably used because the productivity of the vinyl chloride graft copolymer is high. In the above suspension polymerization method, a dispersant and an oil-soluble polymerization initiator are used.

The dispersant is added to enhance the dispersion stability of the acrylic copolymer and to efficiently carry out graft copolymerization of vinyl chloride or a vinyl monomer mainly composed of vinyl chloride. Ethyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, partially saponified polyvinyl acetate,
Examples thereof include gelatin, polyvinylpyrrolidone, starch, and maleic anhydride-styrene copolymer, and these can be used alone or in combination of two or more.

Among the above oil-soluble polymerization initiators, a radical polymerization initiator is preferably used because it is advantageous for graft copolymerization. Examples of the radical polymerization initiator include lauroyl peroxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, dioctyl peroxydicarbonate, t-butyl peroxy neodecanoate, α-cumyl peroxy neo Examples thereof include oil-soluble polymerization initiators such as organic peroxides such as decanoate, and azo compounds such as 2,2-azobisisobutyronitrile and 2,2-azobis-2,4-dimethylvaleronitrile. These may be used alone,
Further, two or more kinds may be used in combination.

In the above suspension polymerization method, a pH adjuster, an antioxidant and the like may be added as required.

When the above acrylic copolymer is graft-copolymerized with vinyl chloride or a vinyl monomer mainly composed of vinyl chloride by a suspension polymerization method, for example, pure water, an oil-soluble polymerization initiator is placed in a jacketed polymerization reactor. The emulsified water of the acrylic copolymer composition, a suspension stabilizer such as a dispersant, and a polymerization degree adjuster are added if necessary, and the inside of the reactor is sealed to exclude air therein. While stirring the inside, a vinyl chloride monomer and other vinyl monomers as needed are added, and the inside of the reactor is heated to a predetermined temperature to start graft copolymerization. The reaction is terminated while adjusting the inside of the reactor to a predetermined temperature by the heat medium in the jacket.

After completion of the reaction, unreacted vinyl chloride monomer and other vinyl monomers are removed to obtain a slurry-like vinyl chloride resin. This is dehydrated and dried to obtain a vinyl chloride resin product.

The degree of polymerization of the obtained vinyl chloride-based graft copolymer is not particularly limited, but if the degree of polymerization is too small, the impact resistance of the obtained molded article is reduced.
If the size is too large, the moldability decreases, and the resulting molded product becomes hard and brittle. Therefore, JIS K672
The viscosity average degree of polymerization determined in accordance with No. 1 is set in a range of preferably 300 to 2500, more preferably 400 to 2000.

In the present invention, the vinyl chloride-based graft copolymer (B) blended with the recycled material may be a so-called virgin material obtained by graft copolymerization, but the vinyl chloride-based graft copolymer may be used. The molded body may be pulverized and reused, like the recycled material.

The above-mentioned vinyl chloride resin composition may contain, if necessary, a stabilizer, a stabilizing aid, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a processing aid, a filler, a coloring agent and a plasticizer. An agent or the like is added, and these additives can be added in the same manner as a commonly used vinyl chloride resin. In the vinyl chloride resin composition, a normal vinyl chloride resin material (virgin) may be used instead of (A) a part of the recycled material composed of the pulverized vinyl chloride resin molded product.

Examples of the stabilizer include organic tin-based stabilizers such as dimethyltin mercaptan, dibutyltin mercaptan, dioctyltin mercaptan, dibutyltin maleate polymer, dioctyltin malate, dioctyltin malate polymer, and dibutyltin laurate polymer. Agents, lead stabilizers such as lead stearate, dibasic lead phosphite, and tribasic lead sulfate, calcium-zinc stabilizers, barium-zinc stabilizers, and the like.

Examples of the stabilizing aid include phosphate esters such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, and tricresyl phosphate.
Examples of the antioxidant include a phenolic antioxidant. Examples of the ultraviolet absorber and the light stabilizer include salicylic acid-based ultraviolet absorbers such as pt-butylphenyl salicylate, and benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, and 2 ′-(2 ′). -Hydroxy-5-methylphenyl)
Benzotriazole UV absorbers such as benzotriazole, cyanoacrylate UV absorbers such as 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, UV stabilizers such as nickel bis (octylphenyl) sulfide, hindered amines Light stabilizer (H
ALS).

Examples of the lubricant include montanic acid wax, paraffin wax, polyethylene wax,
Stearic acid, stearyl alcohol, butyl stearate and the like can be mentioned. As the processing aid, for example,
An acrylic processing aid composed of an alkyl acrylate-alkyl methacrylate copolymer having a weight average molecular weight of 100,000 to 2,000,000 is exemplified.

Examples of the filler include calcium carbonate and talc. As the colorant, for example, azo-based, phthalocyanine-based, sulene-based, dye lake-based organic pigments, oxides, molybdenum chromate-based,
Inorganic pigments such as sulfide / selenide and ferrocyanide are exemplified.

Examples of the plasticizer include dibutyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylhexyl adipate and the like.

The vinyl chloride resin composition of the present invention obtained as described above can be prepared by extrusion molding, injection molding, blow molding, vacuum molding, calender molding, press molding, etc.
It can be molded in the same manner as a commonly used vinyl chloride resin.

As described above, the vinyl chloride-based resin composition of the present invention can be used to prepare a pulverized vinyl chloride-based resin product by adding a (meth) acrylate monomer having a homopolymer having a Tg of -140 to -20 ° C. It consists of a graft copolymer of vinyl chloride or vinyl monomer mainly composed of vinyl chloride on an acrylic copolymer of a specific configuration with a polyfunctional monomer, and further, the acrylic copolymer has a three-dimensional crosslinked structure. The vinyl chloride-based graft copolymer is formed, and the vinyl chloride-based graft copolymer contains the acrylic copolymer component in a ratio of 1 to 50% by weight, and Since it is uniformly dispersed in the vinyl-based resin composition, the obtained molded article has excellent impact resistance and can be used as inferior to a molded article obtained from an unmolded resin.

As described above, the vinyl chloride resin composition of the present invention can promote recycling of vinyl chloride resin more widely.

[0039]

Embodiments of the present invention will be described below. [(A) Preparation of pulverized vinyl chloride resin molded article] A hard vinyl chloride pipe (outer diameter 32 mm, thickness 3.5 mm) having a nominal diameter of 25, which was exposed to the outdoors and used for 5 years, was washed and dried. These were pulverized using a pulverizer to produce pulverized pieces having a maximum diameter or a maximum length of 5 mm (hereinafter, referred to as recycled materials).

[(B) Preparation of Vinyl Chloride Graft Copolymers A, B and C] A predetermined amount of pure water is placed in a reaction vessel equipped with a stirrer and a temperature controller, and the inside of the vessel is purged with nitrogen. After the temperature of the reaction vessel was raised to 75 ° C., a polymerization initiator (ammonium persulfate, hereinafter abbreviated as APS) was charged. Separately, 1.0 part by weight of an emulsifying dispersant (polyoxyethylene nonylphenyl ether ammonium sulfate) in a predetermined amount of pure water, and n-
100 parts by weight of butyl acrylate (Tg = −54 ° C., hereinafter abbreviated as nBA), and trimethylolpropane triacrylate (hereinafter, TMP) as a polyfunctional monomer.
0.1 part by weight) was dispersed to obtain an emulsion monomer liquid.

Next, the above-mentioned emulsified monomer liquid was dropped into the reaction vessel at a constant speed while stirring, and the entire emulsified monomer liquid was dropped in 3 hours. After completion of the dropwise addition, stirring was further continued for 1 hour to terminate the polymerization reaction, thereby obtaining an acrylic copolymer having a solid content of about 30% by weight (hereinafter referred to as latex).

In a reaction vessel equipped with a stirrer and a temperature controller, a predetermined amount of pure water and a dispersant (partially saponified polyvinyl acetate) were added at the addition ratio (weight ratio) shown in Table 1. 3 wt% aqueous solution) and polymerization initiators (t-butylperoxyneodecanoate and α-cumylperoxyneodecanoate), and the air in the reaction vessel was discharged by a vacuum pump. The vinyl chloride monomer was added under stirring, and the polymerization was started by controlling the inside of the reaction vessel to 57 ° C.

The completion of the reaction was confirmed when the pressure in the reaction vessel dropped to a predetermined pressure. Unreacted vinyl chloride monomer was discharged, and the vinyl chloride graft copolymer having a vinyl chloride graft copolymerization ratio shown in Table 1 was used. Polymers (hereinafter abbreviated as graft copolymers) A, B and C were produced. The polymerization degree of the obtained vinyl chloride resin was about 1,000.

(Examples 1 to 3), (Comparative Examples 1 to 4) [Preparation of Vinyl Chloride Resin Composition] A stabilizer was added to 100 parts by weight of each of the above vinyl chloride graft copolymers A, B and C. (Trade name “ONZ-142, manufactured by Sankyoki Gosei Co., Ltd.
F ") 1.5 parts by weight, 0.5 parts by weight of a polyethylene-based lubricant (manufactured by Mitsui Petrochemical Co., Ltd., trade name" Hiwax220MP "), 0.5 of an ester-based lubricant (manufactured by Riken Vitamin Co., trade name" Richester EW100 ") 0.5 Parts by weight, processing aid (trade name “METABLEN P551A” manufactured by Mitsubishi Rayon Co., Ltd.) 1.0
Table 2 shows the vinyl chloride-based graft copolymer composition blended with parts by weight and the recycled materials (including virgin materials).
Was mixed for 5 minutes using a Henschel mixer to prepare a vinyl chloride resin composition.

The vinyl chloride resin used in Comparative Example 1 (trade name “TS-1000R”, manufactured by Tokuyama Sekisui Kogyo Co., Ltd.)
Hereinafter, referred to as unformed resin) is a general vinyl chloride-based resin for hard vinyl chloride pipes that does not contain a reinforcing agent, like the recycled material. The impact modifier used in Comparative Example 3 was Kaneace F, manufactured by Kanegafuchi Chemical Co., Ltd.
M "was used.

(Examples 4 to 5) and (Comparative Example 5) A stabilizer (manufactured by Sankyoki Gosei Co., Ltd., trade name “ONZ”) was added to 100 parts by weight of each of the vinyl chloride-based graft copolymers A, B and C. -142F ") 1.5 parts by weight, polyethylene lubricant (trade name" Hiwax220M "manufactured by Mitsui Petrochemical Co., Ltd.)
P ") 0.5 part by weight, ester-based lubricant (manufactured by Riken Vitamin Co., trade name" Richester EW100 ") 0.5 part by weight,
Processing aid (trade name “METABLEN P5 manufactured by Mitsubishi Rayon Co., Ltd.
51A ”) A mold was set in a twin-screw extruder (trade name“ BT-50 ”, manufactured by Plastics Engineering Laboratory Co., Ltd.) containing 1.0 part by weight of a vinyl chloride graft copolymer composition.
Cylinder temperature 160-190 ° C, mold temperature 190 ° C,
A hard vinyl chloride tube with a screw rotation speed of 32 rpm and an output of 35 kg / hour and a nominal diameter of 20 (outer diameter 26 mm, thickness 3
mm).

Next, the hard vinyl chloride tube was placed in a black panel temperature of 60 ° C. using a weather resistance accelerating tester (trade name “Atlas Weather O-Meter” manufactured by Toyo Seiki Seisaku-sho, Ltd.).
After 1000 hours of irradiation time, products with accelerated weathering deterioration are produced, each of which is pulverized by using a pulverizer in the same manner as the above-mentioned recycled raw material, and a pulverized piece having a maximum diameter or a maximum length of 5 mm (hereinafter referred to as pulverized graft raw material) ) Was prepared.

The above-mentioned pulverized graft material and recycled material were mixed for 5 minutes using a ribbon blender according to the composition shown in Table 2 to prepare a vinyl chloride resin composition.

[Evaluation of Performance] Examples 1 to 5 and Comparative Examples 1 to 5
In order to evaluate the impact resistance of the vinyl chloride resin composition obtained in 5, the following test was conducted. The test results are shown in Table 2.

(Preparation of Sample) The above vinyl chloride resin composition was wound on an 8-inch mixing roll at 190 ° C. at 190 ° C. and kneaded for 3 minutes to obtain a 1 mm-thick coarse sheet. The coarse sheets preheated at 200 ° C. for 3 minutes were overlapped and press-molded at a surface pressure of 70 kg / cm ² for 3 minutes to produce a 3 mm-thick vinyl chloride resin plate, which was used as a sample.

(Impact Resistance Test) A Charpy impact test was performed at a measurement temperature of 23 ° C. in accordance with JIS K 7111 to measure the impact strength.

[0052]

[Table 1]

[0053]

[Table 2]

Each of the vinyl chloride resin compositions of Examples 1 to 5 has a sufficiently high impact strength for practical use, and is the same as the vinyl chloride resin composition of Comparative Example 3 containing the ordinary impact modifier. The results show that the effect of expressing impact resistance is high.
On the other hand, all of the vinyl chloride resin compositions of Comparative Examples 1 to 3 have low impact strength, which significantly limits the use of recycled materials.

Further, in the vinyl chloride resin compositions of Comparative Examples 4 and 5, since the amount of the vinyl chloride graft copolymer component was too large, the vinyl chloride resin composition adhered to the roll surface of the kneading apparatus. Roll kneading was not possible.

[0056]

As described above, the vinyl chloride resin composition of the present invention can be used as a (meth) acrylate resin having a homopolymer having a Tg of -140 to -20 ° C. It consists of a graft copolymer of vinyl chloride or a vinyl monomer mainly composed of vinyl chloride on an acrylic copolymer of a specific configuration of a monomer and a polyfunctional monomer, and further, the acrylic copolymer is three-dimensionally crosslinked. A vinyl chloride-based graft copolymer forming a structure is blended, and the vinyl chloride-based graft copolymer contains the acrylic copolymer component in a ratio of 1 to 50% by weight, Because it is uniformly dispersed in the vinyl chloride resin composition, the resulting molded article has excellent impact resistance,
It can be used without inferior to a molded article obtained from an unmolded resin.

As described above, the vinyl chloride resin composition of the present invention makes it possible to promote recycling of vinyl chloride resin more widely.

Claims (1)

[Claims] 1. The secondary transition point of (A) a pulverized vinyl chloride resin molded product and (B) a homopolymer is -140 to -20.
1 to 60% by weight of an acrylic copolymer composed of 100 parts by weight of a (meth) acrylate monomer and 0.1 to 30 parts by weight of a polyfunctional monomer at a temperature of 100 ° C. ~ 40% by weight
Is a vinyl chloride-based graft copolymer obtained by graft-copolymerizing a vinyl chloride-based resin composition, wherein the content of the acrylic copolymer component in the vinyl chloride-based resin composition is 1 to 50. % By weight of the vinyl chloride resin composition.