JP2002003689A - Vinyl chloride-based resin composition for reproductive tube and reproductive tube made of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide vinyl chloride-based resin composition suitable for obtaining reproductive tube having excellent mechanical strength, impact strength and workability, and provide a reproductive tube using the same. SOLUTION: This vinyl chloride-based resin composition is the one the to 100 weight parts of composite vinyl chloride resin of means polymerization degree of 400 to 2500 that to an acrylic copolymer of 10 to 40 wt.% obtained from copolymerization of 100 pts.wt. of acrylic monomer component composed of more than 50 wt.% alkyl (meth)acrylate monomer that glass tansition temperature is -140 deg.C to -20 deg.C and less than 50 wt.% other acrylic monomer and 0.01 to 30 pts.wt. of polyfunctional monomer component and 90 to 60 wt.% vinyl chloride monomer or vinyl chloride monomer and other copolymerizable monomer are grafted, 3 to 30 pts.wt. of a thermoplastic eleatomer compartible with the composite vinyl chloride resin is added reproductive vinyl chloride-based resin tube is made of the above resin composition.

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 for a rehabilitation pipe and a vinyl chloride resin rehabilitation pipe using the vinyl chloride resin composition.

[0002]

2. Description of the Related Art In recent years, the number of aging pipes has been increasing. One of the methods for repairing such aging pipes is a vinyl chloride resin having excellent mechanical strength and chemical resistance. There is a method using a tube.

[0003] For example, Japanese Patent Publication No. Hei 6-508647 discloses a method of repairing a resin pipe by adding a thermoplastic elastomer that can be mixed with a vinyl chloride resin.
However, in the case of this method, it is necessary to add a large amount of a thermoplastic elastomer, an impact modifier, etc. in order to develop impact resistance sufficient to prevent breakage of the resin tube during transportation or construction. There is a problem that the mechanical strength of the obtained resin tube is insufficient.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to combine excellent mechanical strength and impact resistance,
An object of the present invention is to provide a vinyl chloride resin composition for a rehabilitation pipe suitable for obtaining a rehabilitation pipe excellent in workability, and a vinyl chloride resin rehabilitation pipe using the vinyl chloride resin composition.

[0005]

Means for Solving the Problems A vinyl chloride resin composition for a rehabilitation pipe according to the invention of claim 1 (hereinafter referred to as "the present invention 1") (hereinafter simply referred to as "vinyl chloride resin composition"). ) Is the glass transition temperature (T
g) 100 parts by weight of an acrylic monomer component containing 50% by weight or more of an alkyl (meth) acrylate monomer having a temperature of -140 to -20 ° C and 50% by weight or less of another acrylic monomer, and a polyfunctional monomer component 0 .
Acrylic copolymer 10 copolymerized from 01 to 30 parts by weight
Composite vinyl chloride resin having an average degree of polymerization of 400 to 2500 obtained by graft copolymerizing a vinyl chloride monomer or a vinyl chloride monomer and other copolymerizable monomers in an amount of more than 60% by weight to less than 90% by weight to more than 40% by weight. 100
It is characterized in that 3 to 30 parts by weight of a thermoplastic elastomer compatible with the composite vinyl chloride resin is added to the parts by weight. In addition, (meth) acrylate here means acrylate or methacrylate.

The vinyl chloride resin composition according to the second aspect of the present invention (hereinafter referred to as "the present invention 2") is the vinyl chloride resin composition according to the first aspect of the present invention, wherein the thermoplastic elastomer comprises acrylonitrile- It is a thermoplastic elastomer containing one or more selected from the group consisting of butadiene copolymer, ethylene-vinyl acetate copolymer and ethylene-vinyl acetate-carbon monoxide copolymer. .

Further, a vinyl chloride resin rehabilitation pipe (hereinafter, referred to as “the present invention 3”) according to the invention of claim 3 (hereinafter, referred to as “the present invention 3”).
The abbreviated simply as “rehabilitating pipe”) is made of the vinyl chloride resin composition of the present invention 1 or 2 and is inserted into the existing pipe and heated to adhere to the inner surface of the existing pipe. It is characterized by doing.

The Tg of the homopolymer contained in the acrylic monomer component used in the present invention 1 and the present invention 2 is-
As the alkyl (meth) acrylate monomer having a temperature of 140 to -20 ° C, for example, ethyl acrylate (-2
4 ° C), 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. These alkyl (meth) acrylate monomers may be used alone or in combination of two or more.
The parentheses indicate the Tg of the homopolymer.

If the homopolymer of the above alkyl (meth) acrylate monomer has a Tg of less than -140 ° C., the mechanical strength of the obtained vinyl chloride resin composition and the rehabilitation pipe becomes insufficient, and conversely, the alkyl (meth) acrylate ) When the Tg of the homopolymer of the acrylate monomer exceeds -20 ° C, the impact resistance of the obtained vinyl chloride resin composition and the rehabilitated pipe becomes insufficient.

Other acrylic monomers that may be contained in the acrylic monomer component used in the present invention 1 and 2 include, for example, phenyl acrylate, 2-chloroethyl acrylate, phenylmethyl methacrylate, hydroxy Ethyl acrylate and the like can be mentioned. These other acrylic monomers may be used alone or in combination of two or more.

The Tg of the homopolymer in the acrylic monomer component used in the present invention 1 and the present invention 2 is-
When the content of the alkyl (meth) acrylate monomer at 140 to -20 ° C is less than 50% by weight or the content of the other acrylic monomer exceeds 50% by weight, the obtained vinyl chloride resin composition is obtained. In addition, the impact resistance of the rehabilitation pipe becomes insufficient, or the adhesion of the rehabilitation pipe to the existing pipe becomes insufficient.

The polyfunctional monomer component used in the present invention 1 and the present invention 2 may be any as long as it can be copolymerized with the above-mentioned acrylic monomer component. For example, ethylene glycol di (meth) acrylate, diethylene glycol di ( Polyfunctional (meth) acrylates such as meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane tri (meth) acrylate; diallyl phthalate, diallyl maleate, Polyfunctional allyl compounds such as triallyl isocyanurate; and unsaturated compounds such as butadiene. These polyfunctional monomer components may be used alone or in combination of two or more.

The acrylic copolymer used in the present inventions 1 and 2 is obtained by copolymerizing 100 parts by weight of the acrylic monomer component and 0.01 to 30 parts by weight of the polyfunctional monomer component. Acrylic copolymer.
If the copolymerization amount of the polyfunctional monomer component is less than 0.01 parts by weight or more than 30 parts by weight with respect to 100 parts by weight of the acrylic monomer component, the acrylic copolymer sufficiently exerts an elastomeric function. Otherwise, the impact resistance of the obtained vinyl chloride resin composition and the rehabilitated pipe becomes insufficient.

The acrylic copolymer can be obtained, for example, by an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method or the like. A polymerization method is preferably employed. The method of the emulsion polymerization may be a conventionally known method and, if necessary, within a range not hindering the achievement of the object of the present invention, for example, an emulsifying dispersant,
Emulsion polymerization may be performed by adding one or more of various additives such as a polymerization initiator, a pH adjuster, and an antioxidant.

[0015] Examples of the emulsifying dispersant include anionic surfactants, nonionic surfactants, partially saponified polyvinyl alcohol, cellulose dispersants, and gelatin. Among them, anionic surfactants are preferred. Used. Examples of commercially available anionic surfactants include, for example, polyoxyethylene nonyl phenyl ether sulfate (trade name “HITENOL N-08”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). These emulsifying and dispersing agents may be used alone or in combination of two or more.

Examples of the polymerization initiator include water-soluble initiators such as ammonium persulfate, potassium persulfate and hydrogen peroxide; benzoyl peroxide, lauroyl peroxide, t-butylperoxydecanoate, α-cumylperoxyneo. Organic peroxides such as decanate; azo initiators such as azobisisobutyronitrile; These polymerization initiators may be used alone or in combination of two or more.

Specific examples of the emulsion polymerization method include a batch polymerization method, a monomer dropping method, and an emulsion dropping method. In the batch polymerization method, pure water, an emulsifying dispersant, a polymerization initiator, and an acrylic mixed monomer (the acrylic monomer component + a polyfunctional monomer component) are charged all at once into a jacketed polymerization reactor, and the mixture is placed in a nitrogen stream. In this method, the mixture is sufficiently emulsified by stirring under pressure, and then the temperature inside the polymerization reactor is raised by a jacket to start the polymerization reaction. or,
The monomer dropping method uses pure water in a jacketed polymerization reactor,
This is a method in which an emulsifying dispersant and a polymerization initiator are charged, the temperature inside the polymerization reactor is raised under a nitrogen stream, and then the above-mentioned acrylic mixed monomer is dropped in a fixed amount to start a polymerization reaction. Further, in the emulsion dropping method, the above-mentioned mixed monomer, emulsifying dispersant, and pure water are stirred to prepare an emulsifying monomer liquid in advance,
Next, pure water and a polymerization initiator are charged into a polymerization reactor with a jacket, and after the temperature in the polymerization reactor is increased under a nitrogen stream, the polymerization reaction is started by dropping the emulsified monomer liquid by a predetermined amount. is there.

The structure and form of the acrylic copolymer (acrylic resin) thus obtained are not particularly limited, but the stability of the resin particles can be improved, and the mechanical properties of the vinyl chloride resin composition and the rehabilitation pipe can be improved. For example, those having a so-called core-shell structure in which the monomer composition and the cross-linked structure are different between the surface layer portion and the inside of the resin particle are preferable because the mechanical strength can be improved.

The above-mentioned core-shell structure can be formed, for example, by adding a polymerization initiator to an emulsified monomer liquid previously prepared from the above-mentioned acrylic mixed monomer, emulsifying dispersant, and pure water, which constitutes the core portion, and conducting a polymerization reaction First, the resin particles of the core portion are formed. Then, a method of adding the above-mentioned acrylic mixed monomer, an emulsifying dispersant, and an emulsifying monomer liquid prepared in advance from pure water, which constitutes the shell portion, and graft-copolymerizing the above-mentioned core portion may be used.

In the above method, the graft copolymerization of the shell with respect to the core may be carried out continuously in the same polymerization step as the polymerization of the core. The ratio of core and shell is
It can be freely adjusted by adjusting the ratio of the acrylic mixed monomer forming the core portion and the acrylic mixed monomer forming the shell portion. Further, in order to form a three-dimensional cross-linked structure in the shell portion, the polyfunctional monomer component may be used only in the shell portion, or may be used by being biased in the shell portion. Also in this case, the amount of the polyfunctional monomer component used is 0.01 to 30 parts by weight of the polyfunctional monomer component with respect to 100 parts by weight of the acrylic monomer component for the entire acrylic copolymer.

In the acrylic copolymer particles obtained by such a method, the shell part three-dimensionally covers the surface of the core part, and the resin constituting the shell part and the resin constituting the core part are partially covered. They are covalently bonded and the shell forms a three-dimensional crosslinked structure.

The composite vinyl chloride resin used in the present invention 1 and the present invention 2 contains 10% by weight of the acrylic copolymer.
Obtained by graft copolymerization of less than 90% by weight or more than 60% by weight or less of vinyl chloride monomer or vinyl chloride monomer and other copolymerizable monomers with respect to more than 40% by weight or less.
It is a resin having an average degree of polymerization of 400 to 2500.

The other copolymerizable monomer that may be used in combination with the vinyl chloride monomer may be any monomer that can be copolymerized with the vinyl chloride monomer. Examples thereof include α-olefins such as ethylene, propylene, and butylene; and propionic acid. Vinyl esters such as vinyl; vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, and hydroxyethyl (meth) acrylate; styrene, α-methylstyrene, and the like Aromatic vinyls; vinyl fluoride, vinylidene fluoride,
Vinyl halides such as vinylidene chloride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. These other copolymerizable monomers may be used alone or in combination of two or more.

When the vinyl chloride monomer is used in combination with the above-mentioned other copolymerizable monomer, the amount of the other copolymerizable monomer to be used is appropriately determined according to the performance and purpose to be imparted to the vinyl chloride resin composition and the rehabilitating tube. The setting is not particularly limited, but is preferably 20% by weight or less in a vinyl chloride-based mixed monomer composed of a vinyl chloride monomer and another copolymerizable monomer. If the amount of the other copolymerizable monomer exceeds 20% by weight of the vinyl chloride-based mixed monomer, the intrinsic properties of the vinyl chloride-based resin may not be obtained.

In the composite vinyl chloride resin used in the present invention 1 and the present invention 2, the content of the acrylic copolymer is 10% by weight or less, or the use of a vinyl chloride monomer or the above vinyl chloride mixed monomer. 90% by weight
If it is above, the impact resistance of the obtained vinyl chloride resin composition and the rehabilitation pipe becomes insufficient, and conversely, the content of the acrylic copolymer exceeds 40% by weight, or the vinyl chloride monomer or vinyl chloride 60% by weight of mixed monomer
If it is less than 1, the inherent characteristics of the vinyl chloride resin cannot be obtained.

When the average degree of polymerization of the composite vinyl chloride resin is less than 400, the mechanical strength of the obtained vinyl chloride resin composition and the rehabilitation pipe becomes insufficient, and conversely, the composite vinyl chloride resin has When the average degree of polymerization exceeds 2500,
The moldability of the obtained vinyl chloride resin composition is impaired. The above average degree of polymerization refers to a resin obtained by dissolving a composite vinyl chloride resin in tetrahydrofuran (THF), removing insoluble components by filtration, and then drying and removing THF in the filtrate as a sample. -6721 means the average degree of polymerization measured in accordance with "Test Method for Vinyl Chloride Resin".

The graft copolymerization method between the acrylic copolymer and the vinyl chloride monomer or the vinyl chloride-based mixed monomer may be a conventionally known method, such as a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method. In general, a method in which an acrylic copolymer in an emulsified state (emulsion state) is suspension-polymerized with a vinyl chloride monomer or a vinyl chloride-based mixed monomer is used. In the suspension polymerization method, the emulsifying dispersant, the polymerization initiator, and the like are used.

As a specific method of the suspension polymerization method, for example, pure water, an emulsifying dispersant, a polymerization initiator, and an acrylic copolymer emulsion are charged into a polymerization reactor equipped with a stirrer and a temperature controller. After the air in the polymerization reactor is eliminated by a vacuum pump, a vinyl chloride monomer or a vinyl chloride-based mixed monomer is introduced into the polymerization reactor. Next, the temperature of the polymerization reactor is raised to start the polymerization reaction at a desired polymerization temperature. After completion of the polymerization reaction, the remaining monomer is discharged out of the polymerization reactor to obtain a slurry of the composite vinyl chloride-based resin, and then subjected to steps such as dehydration by a dehydrator and drying by a dryer, thereby obtaining a desired composite vinyl chloride. A system resin can be obtained.

The vinyl chloride resin composition of the present invention 1 is obtained by adding 3 to 30 parts by weight of a thermoplastic elastomer compatible with the composite vinyl chloride resin to 100 parts by weight of the composite vinyl chloride resin. Become.

The thermoplastic elastomer may be any thermoplastic elastomer compatible with the above-mentioned composite vinyl chloride resin, such as acrylonitrile-butadiene copolymer (NBR) and ethylene-vinyl acetate copolymer (EVA). ), Vinyl chloride-based thermoplastic elastomers such as ethylene-vinyl acetate-carbon monoxide copolymer (EVACO), vinyl chloride-vinyl acetate copolymer and vinyl chloride-vinylidene chloride copolymer, styrene-based thermoplastic elastomers, olefins Thermoplastic elastomer, urethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, and the like. These thermoplastic elastomers may be used alone or in combination of two or more.

If the amount of the thermoplastic elastomer is less than 3 parts by weight based on 100 parts by weight of the composite vinyl chloride resin, a rehabilitation pipe made of the obtained vinyl chloride resin composition is inserted into an existing pipe and heated. Workability when closely contacting the existing pipe is impaired, and conversely, the composite vinyl chloride resin 100
When the addition amount of the thermoplastic elastomer to the weight part exceeds 30 parts by weight, the mechanical strength of the obtained vinyl chloride resin composition and the rehabilitation pipe becomes insufficient.

Among the above thermoplastic elastomers, N
BR, EVA, EVACO and the like are particularly preferably used. In the vinyl chloride resin composition according to the second aspect of the present invention, NBR, EVA, EVACO is used as the thermoplastic elastomer.
A thermoplastic elastomer containing one or more selected from the group consisting of

NBR, EV as thermoplastic elastomer
A, a thermoplastic elastomer containing one or more selected from the group consisting of EVACO, and adding 3 to 30 parts by weight of the thermoplastic elastomer to 100 parts by weight of the composite vinyl chloride-based resin, thereby obtaining a chloride obtained. The balance between the mechanical strength and impact resistance of the vinyl resin composition and the rehabilitated pipe becomes better, and when the rehabilitated pipe is inserted into the existing pipe and heated to adhere to the inner surface of the existing pipe. Workability will also be better.

The vinyl chloride resin compositions of the present invention 1 and the present invention 2 may, if necessary, besides the essential components of the composite vinyl chloride resin and the thermoplastic elastomer as long as the object of the present invention is not hindered. , Fillers, pigments, lubricants, processing aids, stabilizers, stabilization aids, light stabilizers, ultraviolet absorbers,
One or more of various additives such as an antioxidant (antiaging agent), an antistatic agent and a flame retardant may be added. The method and order of addition of these additives are not particularly limited, and may be any method and any order.

Examples of the filler include inorganic fillers such as calcium carbonate, talc, clay and silica. These fillers may be used alone or 2
More than one type may be used in combination.

Examples of the pigment include organic pigments such as azo type, phthalocyanine type, sulene type and dye lake type; and inorganic pigments such as molybdenum chromate type and ferrocyanide type. These pigments may be used alone or in combination of two or more.

Examples of the lubricant include fatty acids such as stearic acid; fatty acid esters; olefin waxes. These lubricants may be used alone or in combination of two or more.

Examples of the processing aid include homopolymers or copolymers of (meth) acrylate monomers such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate; And copolymers of a vinyl monomer and a vinyl monomer such as styrene, vinyl toluene and acrylonitrile. These processing aids may be used alone or in combination of two or more.

Examples of the stabilizer include organic tin stabilizers such as dibutyltin malate and dioctyltin laurate; lead white, basic lead sulfite, dibasic lead sulfite, tribasic lead sulfate, dibasic phosphorous acid Lead stabilizers such as lead, silica gel coprecipitated lead silicate, lead stearate, lead benzoate, dibasic lead stearate, lead naphthenate; metal soap based stabilizers such as calcium stearate, barium stearate and zinc stearate Agents; inorganic stabilizers such as hydrotalcite and zeolite; These stabilizers may be used alone or in combination of two or more.

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

Examples of the light stabilizer include a hindered amine light stabilizer. These light stabilizers are
They may be used alone or in combination of two or more.

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

Next, the rehabilitating pipe according to the third aspect of the present invention is made of the above-mentioned vinyl chloride resin composition of the first or second aspect of the present invention. It is characterized in that it comes into close contact with the inner surface.

The above rehabilitated pipe is used in the present invention 1 using an extruder.
Or melt-kneading the vinyl chloride resin composition of the present invention 2,
It is manufactured by extruding and shaping into a tubular body having a desired cross-sectional shape. The cross-sectional shape of the rehabilitation pipe can be inserted into an existing pipe to be rehabilitated (repaired),
The shape is not particularly limited as long as the shape can be brought into close contact with the inner surface of the existing pipe by heating.

[0045]

The vinyl chloride resin composition of the present invention comprises a specific amount of an acrylic copolymer obtained by copolymerizing a specific amount of a specific acrylic monomer component with a specific amount of a polyfunctional monomer component. A specific amount of the system-mixed monomer is graft-copolymerized, and, for a specific amount of the composite vinyl chloride-based resin having a specific average degree of polymerization, a thermoplastic elastomer compatible with the composite vinyl chloride-based resin. Since a specific amount is added, it exhibits excellent balance between mechanical strength and impact resistance, and also has excellent workability when used as a rehabilitated pipe.

In particular, N is preferred as the thermoplastic elastomer.
By using a thermoplastic elastomer containing one or more selected from the group consisting of BR, EVA and EVACO, the balance between the above mechanical strength and impact resistance, and the workability when a rehabilitated pipe is used. Will be better.

Further, since the rehabilitating pipe of the present invention is made of the above-mentioned vinyl chloride resin composition of the present invention, it has both excellent mechanical strength and impact resistance, and also has excellent workability. Inserted into the existing pipe to be rehabilitated (repaired)
By being heated, it can easily adhere to the inner surface of the existing pipe.

[0048]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”, and “%” means “% by weight”.

(Example 1)

(1) Preparation of acrylic copolymer 95% of n-butyl acrylate (Tg of homopolymer: -54 ° C.) as an acrylic monomer component and 5% of trimethylolpropane triacrylate as a polyfunctional monomer component. Acrylic mixed monomer 2.3 contained
6 kg, trade name "HITENOL N-0" as an emulsifying dispersant
An emulsified monomer solution comprising 50 g of a 10% aqueous solution of "8" (Daiichi Kogyo Seiyaku Co., Ltd.) and 1.5 kg of pure water was prepared in advance.

4 kg of pure water and 24 g of a 10% aqueous solution of ammonium persulfate as a polymerization initiator were charged into a polymerization reactor (internal volume 10 liter) equipped with a stirrer and a temperature controller, and the inside of the polymerization vessel was replaced with nitrogen gas. Thereafter, the temperature inside the polymerization reactor was raised to 75 ° C. with stirring. Next, the above-prepared emulsified monomer liquid was dropped at a constant dropping rate into the polymerization reactor after the temperature was raised. The dropping of the entire amount of the emulsified monomer liquid was completed in 3 hours, and thereafter, stirring was continued for 1 hour. Then, the polymerization reaction was terminated, and an acrylic copolymer emulsion having a solid content of 30% was prepared.

(2) Preparation of Composite Vinyl Chloride Resin A polymerization reactor (with an internal volume of 15
Liters), 7.5 kg of pure water, 1.5 kg of the acrylic copolymer emulsion obtained above (solid content: 0.4
5 kg), partially saponified polyvinyl alcohol as an emulsifying dispersant (trade name "Kuraray Povar L-8", manufactured by Kuraray Co., Ltd.)
330 g of a 3% aqueous solution of, and 1.1 g of t-butylperoxydecanate and α-cumylperoxyneodecanate as polymerization initiators, and the air in the polymerization reactor was exhausted by a vacuum pump, and then the solution was stirred under stirring. 3.2 vinyl monomer
kg was added. Next, the temperature inside the polymerization reactor was raised to 64 ° C. to start the graft polymerization reaction. After confirming the completion of the graft polymerization reaction by lowering the pressure in the polymerization reactor, unreacted vinyl chloride monomer was discharged to produce a composite vinyl chloride resin. The graft amount of vinyl chloride in the obtained composite vinyl chloride resin was 85%, and the content of the acrylic copolymer was 15%. When the average degree of polymerization of the obtained composite vinyl chloride resin was measured in accordance with JIS K-6721, the average degree of polymerization was 800.

(3) Preparation of Vinyl Chloride Resin Composition and Rehabilitation Pipe The composite vinyl chloride resin 10 obtained above was placed in a Henschel mixer (manufactured by Kawada Kogyo Co., Ltd.) having an internal volume of 100 liters.
0 parts, EVACO (trade name "Elvaloy 742", manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.) as a thermoplastic elastomer, and 10 parts as an organic tin-based stabilizer (trade name "O
NZ-142F "(manufactured by Sankyo Co., Ltd.), 1 part, polyethylene wax-based lubricant (trade name" Hiwax220 ")
MP, manufactured by Mitsui Petrochemical Industries, Ltd.) 0.5 part, and stearic acid (trade name "S-30", manufactured by Kao Corporation) as a lubricant
0.5 part and trade name "METABLEN P50" as a processing aid
1A "(manufactured by Mitsubishi Rayon Co., Ltd.) was charged in an amount of 3 parts and uniformly stirred and mixed to prepare a vinyl chloride resin composition.

The above-obtained vinyl chloride resin composition was subjected to a 50 mm diameter biaxial counter-rotating extruder (trade name “SLM”).
-50 "(manufactured by Nagata Seisakusho) to obtain a vinyl chloride resin molded article having an outer diameter of 50 mm. The obtained molded body is 80
After standing for 20 minutes in a gear oven heated to
The cross section of the rehabilitating pipe was formed into a four-folded shape, and while maintaining this shape, the molded body was cooled down to a temperature of 20 ° C. to produce a rehabilitating pipe.

(4) Evaluation The performance (flexural modulus, impact resistance, workability) of the rehabilitated pipe obtained above was evaluated by the following method. The results were as shown in Table 1.

Flexural modulus: The flexural modulus of the rehabilitated pipe was measured in accordance with JIS K-7203 “Bending test method for hard plastics”. The measurement was performed in an atmosphere at 20 ° C.

Impact resistance: In accordance with JIS K-7111 “Method for testing Charpy impact of hard plastic”
The Charpy impact value of the rehabilitated tube was measured using a notched (notched) test piece. The measurement was performed in an atmosphere at 23 ° C.

Workability: Insert the rehabilitated pipe into a steel pipe having an inner diameter of 50 mm, and insert 90
C. hot air was blown for 10 minutes to bring the rehabilitation pipe into close contact with the inner surface of the steel pipe. Next, after cooling by blowing air at 20 ° C. for 30 minutes, the adhesion between the steel pipe and the rehabilitation pipe was visually observed, and the workability was evaluated according to the following criteria. [Judgment criteria] ○ ‥‥ The rehabilitation pipe was completely in contact with the steel pipe × ‥‥ The rehabilitation pipe was not in close contact with the steel pipe partially or completely

(Example 2) The graft amount of vinyl chloride was 8
A vinyl chloride resin composition and a rehabilitation tube were prepared in the same manner as in Example 1 except that a composite vinyl chloride resin having 0% and an acrylic copolymer content of 20% was used. did.

(Example 3) In the same manner as in Example 1 except that a composite vinyl chloride resin having an average degree of polymerization of 1200 measured according to JIS K-6721 was used.
A vinyl chloride-based resin composition and a rehabilitation pipe were prepared.

Example 4 A vinyl chloride resin composition was prepared in the same manner as in Example 1 except that the amount of EVACO “Elvaloy 742” was changed to 15 parts in the preparation of the vinyl chloride resin composition. And a rehabilitation pipe was produced.

Example 5 In the preparation of a vinyl chloride resin composition, EVACO was used as a thermoplastic elastomer.
A vinyl chloride resin composition and a vinyl chloride resin composition were prepared in the same manner as in Example 1 except that 10 parts of NBR (trade name “PN-20HA”, manufactured by JSR Corporation) was added instead of 10 parts of “Elvaloy 742”. A rehabilitation tube was prepared.

Example 6 In the preparation of a vinyl chloride resin composition, EVACO was used as the thermoplastic elastomer.
"Elvaloy 742" 10 parts and NBR "PN-20H"
A) A vinyl chloride resin composition and a rehabilitated tube were prepared in the same manner as in Example 1 except that 5 parts of "A" were added.

Comparative Example 1 A graft amount of vinyl chloride was 9
A vinyl chloride resin composition and a rehabilitating tube were prepared in the same manner as in Example 1 except that a composite vinyl chloride resin having an acrylic copolymer content of 8% was used. did.

(Comparative Example 2) A vinyl chloride resin composition and a rehabilitation pipe were prepared in the same manner as in Example 1 except that no thermoplastic elastomer was added in the preparation of the vinyl chloride resin composition. did.

Comparative Example 3 A vinyl chloride resin composition was prepared in the same manner as in Example 1 except that the amount of EVACO “Elvaloy 742” was changed to 40 parts in the preparation of the vinyl chloride resin composition. An object and a rehabilitation tube were prepared.

(Comparative Example 4) A vinyl chloride homopolymer having an average degree of polymerization of 800 measured according to JIS K-6721 was used instead of using the composite vinyl chloride-based resin. As in the case of Example 1,
A vinyl chloride-based resin composition and a rehabilitation pipe were prepared.

The performance (flexural modulus, impact resistance, workability) of the rehabilitated pipes obtained in Examples 2 to 6 and Comparative Examples 1 to 4 was determined in the same manner as in Example 1. evaluated. The results were as shown in Table 1.

[0069]

[Table 1]

As is apparent from Table 1, Examples 1 to 6 prepared using the vinyl chloride resin composition of the present invention.
The rehabilitated pipe had excellent flexural modulus (mechanical strength), impact resistance and workability.

On the other hand, when the graft amount of vinyl chloride is 9
The rehabilitated tube of Comparative Example 1 comprising a vinyl chloride resin composition prepared using a composite vinyl chloride resin having a content of 0% by weight or more (98% by weight), and the regenerated pipe without using the composite vinyl chloride resin. Comparative Example 4 consisting of a vinyl chloride resin composition produced using a vinyl chloride homopolymer instead
The rehabilitation pipe had extremely poor impact resistance.

The rehabilitating pipe of Comparative Example 2 made of a vinyl chloride resin composition in which no thermoplastic elastomer was added to the composite vinyl chloride resin had poor workability. Further, the rehabilitation pipe of Comparative Example 3 comprising the vinyl chloride resin composition in which the addition amount of the thermoplastic elastomer (EVACO) per 100 parts by weight of the composite vinyl chloride resin exceeded 30 parts by weight (40 parts by weight) was bent. The elastic modulus (mechanical strength) was low.

[0073]

As described above, the vinyl chloride resin composition of the present invention exhibits excellent mechanical strength and impact resistance and also has excellent workability when used as a rehabilitated pipe. ,
It is suitably used as a resin for producing rehabilitating tubes.

Further, since the rehabilitating pipe of the present invention is made of the above-mentioned vinyl chloride resin composition of the present invention, it has excellent mechanical strength and impact resistance at a high level and also has excellent workability. Yes, it is suitable for rehabilitating (restoring) existing pipes.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) F16L 11/06 F16L 11/06 4J026 55/16 55/16 // (C08L 51/06 (C08L 51/06) 101: 00) 101: 00) (C08L 51/06 (C08L 51/06 9:02) 9:02) (C08L 51/06 (C08L 51/06 23:04) 23:04) B29K 27:06 B29K 27 : 06 B29L 23:00 B29L 23:00 F term (reference) 3H025 EA01 EB21 EC06 ED02 3H111 AA02 BA15 BA34 CB02 DA26 DB27 4F071 AA12 AA12X AA15 AA15X AA24 AA24X AA28 AA28X AA33 AA13 AA19 AA19 AA19 AA19 AA19 AA19 AA19 AA19 AA19 AA19 AA19 AA19 AA19 AA19 AA19 AA19 AA13A BC17 4F211 AA10 AA15E AA20E AA21E AA45 AA46E AD05 AD12 AG03 AG08 AH43 SA13 SC03 SD04 SH06 SP12 SP15 SP21 4J002 AC082 BB062 BB152 BD052 BN121 BP012 CF102 CJ002 CK022 CL002 FD010 AFD40 FD050 AFD40 A40 AA45 AA46 AC09 BA10 BB01 BB03 DA02 DA03 DA04 DA07 DA12 DA13 DA14 DB02 DB03 DB04 DB08 DB12 DB13 DB14 FA02 GA08 GA09

Claims (3)

[Claims] The glass transition temperature of the homopolymer is -140.
50% by weight or more of an alkyl (meth) acrylate monomer having a temperature of -20 ° C and other acrylic monomers 50
Acrylic monomer component 10 containing at most 10% by weight
0 parts by weight and an acrylic copolymer obtained by copolymerizing 0.01 to 30 parts by weight of a polyfunctional monomer component, more than 10% by weight and 40% by weight or less of a vinyl chloride monomer or a vinyl chloride monomer and other copolymerizable monomers 90 An average degree of polymerization of less than 60% by weight and less than 60% by weight is obtained by graft copolymerization.
For 100 parts by weight of 2500 composite vinyl chloride resin,
A vinyl chloride resin composition for rehabilitating tubes, wherein 3 to 30 parts by weight of a thermoplastic elastomer compatible with the composite vinyl chloride resin is added. 2. The thermoplastic elastomer comprises one or more selected from the group consisting of acrylonitrile-butadiene copolymer, ethylene-vinyl acetate copolymer and ethylene-vinyl acetate-carbon monoxide copolymer. The vinyl chloride resin composition for a rehabilitation pipe according to claim 1, which is a thermoplastic elastomer contained therein. 3. It is made of the vinyl chloride resin composition for rehabilitating pipes according to claim 1 or 2, and is inserted into an existing pipe and heated to adhere to the inner surface of the existing pipe. Characterized vinyl chloride resin rehabilitation pipe.