JP2003286380A - Chlorinated vinyl chloride resin composition and rehabilitation pipe - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chlorinated vinyl chloride resin composition having excellent heat resistance and a chlorinated vinyl chloride resin regenerated pipe using the chlorinated vinyl chloride resin composition. <P>SOLUTION: The chlorinated vinyl chloride resin composition is prepared by adding a compound (compound A), which is compatible with a chlorinated vinyl chloride resin and of which the glass transition temperature, melting point, dropping point, Vicat softening temperature or flow start temperature is lower than the glass transition temperature of the chlorinated vinyl chloride resin, to the chlorinated vinyl chloride resin with a chlorine content of 58-71 wt.%. The regenerated pipe comprising the chlorinated vinyl chloride resin composition is also disclosed. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a chlorinated vinyl chloride resin composition and a chlorinated vinyl chloride resin rehabilitation pipe using the chlorinated vinyl chloride resin composition.

[0002]

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

For example, Japanese Patent Laid-Open Publication No. 6-508647 discloses a method of repairing a vinyl chloride resin with a resin tube containing a thermoplastic elastomer that can be mixed.
However, in the case of this method, there is a problem that thermal deformation or the like occurs when it is used for an application requiring heat resistance.

[0004]

In view of the above problems, an object of the present invention is to provide a chlorinated vinyl chloride resin composition having excellent heat resistance and a chlorinated chlorination using the chlorinated vinyl chloride resin composition. It is to provide a vinyl-based resin rehabilitation pipe.

[0005]

The invention according to claim 1 (hereinafter referred to as "present invention 1") has a chlorine content of 58 to
71% by weight of chlorinated vinyl chloride resin is compatible with chlorinated vinyl chloride resin and has a glass transition temperature, melting point, dropping point, Vicat softening temperature or flow starting temperature of chlorinated vinyl chloride resin Is a chlorinated vinyl chloride resin composition obtained by adding a compound (compound A) having a glass transition temperature lower than the glass transition temperature. The term "compatibility" as used herein means that when the compound mixed with the chlorinated vinyl chloride resin is a polymer, the loss modulus of the molded body obtained by kneading the two appears as one peak in a temperature range of room temperature or higher. When the compound to be mixed is other than the polymer, it means that the compound is not significantly separated from the two kneading melts.

In the invention described in claim 2 (hereinafter referred to as "present invention 2"), the compound A is 0.5 to 30 parts by weight with respect to 100 parts by weight of the chlorinated vinyl chloride resin. It is a chlorinated vinyl chloride resin composition.

The invention according to claim 3 (hereinafter referred to as "present invention 3") is a chlorinated vinyl chloride resin composition in which compound A is a thermoplastic elastomer.

In the invention described in claim 4 (hereinafter referred to as "present invention 4"), the thermoplastic elastomer is ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-acrylic acid ester-monoxide. Carbon copolymer, acrylonitrile-butadiene copolymer, urethane thermoplastic elastomer, methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, or acrylic copolymer obtained by copolymerizing acrylic monomer component and polyfunctional monomer component. It is a chlorinated vinyl chloride resin composition which is one or more of polymers.

The invention according to claim 5 (hereinafter referred to as "present invention 5") is a chlorinated vinyl chloride resin composition in which compound A is a plasticizer.

In the invention according to claim 6 (hereinafter referred to as "present invention 6"), the plasticizer is selected from dicyclohexyl phthalate, triphenyl phosphate, epoxidized soybean oil, and epoxidized linseed oil. It is a chlorinated vinyl chloride resin composition of one kind or two or more kinds.

The invention according to claim 7 (hereinafter referred to as "present invention 7") is a chlorinated vinyl chloride resin composition in which compound A is an antioxidant.

In the invention described in claim 8 (hereinafter referred to as "present invention 8"), the antioxidant is one kind or two or more kinds of compounds represented by the formula (1). It is a chlorinated vinyl chloride resin composition. _{S (CH 2 -CH 2 -COO- (} CH 2) n -CH 3) 2 ... (1) where, n is a positive number of 11 to 17

The invention according to claim 9 (hereinafter referred to as "present invention 9") is a chlorinated chlorination in which compound A is an ester compound (excluding thermoplastic elastomer, plasticizer, and antioxidant). It is a vinyl resin composition.

In the invention described in claim 10 (hereinafter referred to as "present invention 10"), the ester compound is one or two kinds of glycerin monostearate or phthalic acid distearate. It is a vinyl chloride resin composition.

In the invention described in claim 11 (hereinafter referred to as "present invention 11"), the compound A is at least two kinds out of a thermoplastic elastomer, a plasticizer, an antioxidant and an ester compound. It is a chlorinated vinyl chloride resin composition used.

The invention according to claim 12 (hereinafter referred to as "present invention 12") is a rehabilitating pipe comprising the chlorinated vinyl chloride resin composition according to any one of claims 1 to 11. .

The invention according to claim 13 (hereinafter referred to as "the present invention 13") is characterized in that after the rehabilitation pipe is inserted into the existing pipe, it is heated or heated and internal pressure is applied to the existing pipe. The rehabilitation pipe according to claim 12, which is in close contact with the inner surface of the pipe.

The chlorine content of the chlorinated vinyl chloride resin used in the present invention is limited to 58 to 71% by weight. If the chlorine content is less than 58% by weight, the heat resistance of the obtained chlorinated vinyl chloride resin composition or rehabilitating pipe is insufficient, and if the chlorine content exceeds 71% by weight, molding becomes difficult. . The chlorine content is a value determined by titration of neutralization by oxygen flask combustion method according to JIS K 7229.

The above-mentioned chlorinated vinyl chloride resin is obtained by chlorinating a vinyl chloride resin, and as the chlorination method, conventionally known water suspension method, solution chlorination method, etc. are used. The water suspension method is preferred. As a method of adjusting the chlorine content in the above range, it may be adjusted in the chlorination reaction step, or a high chlorine content chlorinated vinyl chloride resin and a low chlorine content chlorinated vinyl chloride resin or It may be adjusted by blending with a vinyl chloride resin.

The vinyl chloride resin to be blended with the vinyl chloride resin before being chlorinated or the chlorinated vinyl chloride resin is a vinyl chloride homopolymer or an unsaturated bond copolymerizable with vinyl chloride. Examples thereof include a copolymer of a monomer and vinyl chloride, a graft copolymer obtained by graft copolymerizing vinyl chloride with the polymer, and the like. In the present invention, these polymers may be used alone or in combination of two or more kinds.

Examples of the monomer having an unsaturated bond copolymerizable with vinyl chloride include α-olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl acetate and vinyl propionate; butyl vinyl ether and cetyl. Vinyl ethers such as vinyl ethers; (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, phenyl (meth) acrylate;
Aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinylidene fluoride; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. One kind or two or more kinds are used.

The polymer for graft-copolymerizing vinyl chloride is not particularly limited as long as it is a polymer for graft-polymerizing vinyl chloride. For example, ethylene-vinyl acetate copolymer; ethylene-vinyl acetate-carbon monoxide copolymer. Polymers; ethylene-ethyl acrylate copolymers; ethylene-butyl acrylate-carbon monoxide copolymers; ethylene-methyl methacrylate copolymers; ethylene-propylene copolymers; acrylonitrile-butadiene copolymers;
Polyurethane, chlorinated polyethylene, chlorinated polypropylene, etc. may be mentioned, and these may be used alone or in combination of two or more kinds.

The method of polymerizing vinyl chloride is not particularly limited, and conventionally known bulk polymerization, solution polymerization, emulsion polymerization and the like can be used.

The above compound A is particularly preferable if it is compatible with a chlorinated vinyl chloride resin and has a glass transition temperature, a melting point, a dropping point, a Vicat softening temperature or a flow starting temperature lower than that of the chlorinated vinyl chloride resin. There is no limitation, and for example, thermoplastic elastomers, plasticizers, antioxidants, ester compounds, etc. are preferably used.

The thermoplastic elastomer is not particularly limited, and examples thereof include acrylonitrile-butadiene copolymer (NBR) and ethylene-vinyl acetate copolymer (EV).
A), ethylene-vinyl acetate-carbon monoxide copolymer (EV
ACO), ethylene-acrylic acid ester-carbon monoxide copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride vinylidene chloride copolymer, and other vinyl chloride-based thermoplastic elastomers, styrene-based thermoplastic elastomers, and olefin-based thermoplastic elastomers. A thermoplastic elastomer, a urethane thermoplastic elastomer, a polyester thermoplastic elastomer, a polyamide thermoplastic elastomer, a methyl methacrylate-butadiene-styrene copolymer, a chlorinated polyethylene, or an acrylic monomer component and a polyfunctional monomer component are copolymerized. Examples thereof include acrylic copolymers.
Among these, ethylene-vinyl acetate-carbon monoxide copolymer (EVACO), ethylene-acrylic acid ester-carbon monoxide copolymer, acrylonitrile-butadiene copolymer (NBR), urethane thermoplastic elastomer, or acrylic. An acrylic copolymer obtained by copolymerizing a system monomer component and a polyfunctional monomer component is preferably used. These thermoplastic elastomers may be used alone,
Two or more types may be used in combination.

Examples of the acrylic monomer constituting the above acrylic copolymer include ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
Iso-butyl acrylate, sec-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-octyl methacrylate, isooctyl acrylate, n-nonyl acrylate, n-nonyl methacrylate, isononyl acrylate, n- Decyl acrylate, n-decyl methacrylate, lauryl methacrylate, phenyl acrylate, 2-chloroethyl acrylate, phenylmethyl methacrylate, 2-hydroxyethyl acrylate and the like can be mentioned. These acrylic monomers are
They may be used alone or in combination of two or more.

The polyfunctional monomer component constituting the acrylic copolymer is not particularly limited as long as it is a monomer which can be copolymerized with the acrylic monomer, and examples thereof include ethylene glycol di (meth) acrylate and diethylene glycol di. Polyfunctional (meth) acrylates such as (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diallyl phthalate, diallyl malate Examples thereof include polyfunctional allyl compounds such as triallyl isocyanurate and polyfunctional unsaturated compounds such as butadiene. These polyfunctional monomer components may be used alone,
Two or more types may be used in combination.

The above plasticizer is not particularly limited, and examples thereof include phthalic acid plasticizers such as dicyclohexyl phthalate (DCHP), dibutyl phthalate, di-2-ethylhexyl phthalate; triphenyl phosphate (TPP).
Phosphoric acid plasticizers such as: Epoxidized soybean oil, epoxidized linseed oil, etc .; Trimellitic acid plasticizers such as trinormal octyl trimellitate, triisononyl trimellitate; Dioctyl adipate, diisodecyl Adipate plasticizers such as adipate; polyester plasticizers, chlorinated paraffin plasticizers and the like.
Of these, dicyclohexyl phthalate (DCH
P), triphenyl phosphate (TPP), epoxidized soybean oil, and epoxidized linseed oil are preferably used. These plasticizers may be used alone or in combination of two or more kinds.

The above-mentioned antioxidant is not particularly limited,
For example, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate and other compounds represented by the formula (1), 2,6-di-t
ert-butyl-P-cresol, 2,6-di-ter
t-Butyl-4-ethylphenol, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and the like can be mentioned. Among these, the compound represented by the formula (1) is preferably used. These antioxidants may be used alone or in combination of two or more kinds. _{S (CH 2 -CH 2 -COO- (} CH 2) n -CH 3) 2 ... (1) where, n is a positive number of 11 to 17

The ester compounds (excluding thermoplastic elastomers, plasticizers and antioxidants) are not particularly limited and include glycerin monostearate, phthalic acid distearate, pentaerythritol distearate, stearyl stearate and the like. . Of these, glycerin monostearate and phthalic acid distearate are preferably used. These ester compounds may be used alone or in combination of two or more kinds.

The amount of the compound A added is preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the chlorinated vinyl chloride resin. When the number of added parts of compound A is less than 0.5 part by weight, the rehabilitation pipe made of the obtained chlorinated vinyl chloride resin composition is inserted into an existing pipe, and heating is performed to bring it into close contact with the inner surface of the existing pipe. If the amount exceeds 30 parts by weight, the mechanical strength of the obtained chlorinated vinyl chloride resin composition and rehabilitating pipe decreases.

The chlorinated vinyl chloride resin composition of the present invention contains, if necessary, fillers, pigments, lubricants, processing aids, stabilizers, and stabilizing aids as long as the object of the present invention is not hindered. One or more kinds of various additives such as an impact modifier, a light stabilizer, an ultraviolet absorber, an antistatic agent, and a flame retardant may be added. The method and order of addition of these additives are not particularly limited, and any method or order may be used.

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 kind may be used in combination.

Examples of the pigments include azo-based, phthalocyanine-based, slene-based, dye lake-based organic pigments; molybdenum chromate-based and ferrocyanide-based inorganic pigments. These pigments may be used alone or in combination of two or more kinds.

Examples of the lubricant include an internal lubricant and an external lubricant. The internal lubricant is used for the purpose of lowering the flow viscosity of the molten resin during molding and preventing frictional heat generation. The internal lubricant is not particularly limited, for example, butyl stearate, lauryl alcohol, stearyl alcohol,
Examples thereof include glycerin monostearate, stearic acid, and bisamide. These may be used alone,
Two or more types may be used in combination. The external lubricant is used for the purpose of enhancing the sliding effect between the molten resin and the metal surface during molding. The external lubricant is not particularly limited, and examples thereof include paraffin wax, polyolefin wax, ester wax, and montanic acid wax. These may be used alone or in combination of two or more.

Examples of the processing aid include homopolymers or copolymers of (meth) acrylate-based monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate; the above (meth) acrylates. Examples thereof include copolymers of vinyl-based monomers with vinyl-based monomers such as styrene, vinyltoluene and acrylonitrile. These processing aids may be used alone or in combination of two or more kinds.

Examples of the stabilizer include organotin stabilizers such as dibutyltin malate and dioctyltin laurate; lead white, basic lead sulfite, dibasic lead sulfite, tribasic lead sulfate and dibasic phosphorous acid. Lead stabilizers such as lead, silica gel co-precipitated lead silicate, lead stearate, lead benzoate, dibasic lead stearate and lead naphthenate; metal soap stabilizers such as calcium stearate, barium stearate and zinc stearate. Agents: Hydrotalcite, inorganic stabilizers such as zeolite, and the like. These stabilizers may be used alone or in combination of two or more kinds.

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

As the impact modifier, for example, methyl methacrylate-butadiene-styrene graft copolymer (MBS), chlorinated polyethylene (CPE), acrylonitrile-butadiene-styrene copolymer (ABS),
Examples include acrylic modifiers. These impact modifiers may be used alone or in combination of two or more kinds.

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

Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based ultraviolet absorbers and the like. These ultraviolet absorbers may be used alone or in combination of two or more kinds.

The rehabilitating pipe according to the present invention 12 is produced by extruding the chlorinated vinyl chloride resin composition according to any one of the present inventions 1 to 11 described above with an extruder.

Furthermore, the rehabilitating pipe according to the thirteenth aspect of the present invention is characterized in that it is adhered to the inner surface of the existing pipe by heating or heating and applying internal pressure after inserting it into the existing pipe.

The cross-sectional shape of the rehabilitation pipe can be inserted into an existing pipe to be rehabilitated (restored), and after insertion into the existing pipe, heating or heating and applying an internal pressure,
The shape is not particularly limited as long as it can be in close contact with the inner surface of the existing pipe.

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 21 and Comparative Examples 1 and 2 [Preparation of Chlorinated Vinyl Chloride Resin Composition] Each material was stirred and mixed with a 200 L super mixer (manufactured by Kawata Co., Ltd.) according to the composition of Tables 1 and 2. A chlorinated vinyl chloride resin composition was obtained.

[Preparation of Rehabilitation Pipe] The chlorinated vinyl chloride resin composition obtained by the above method was subjected to a biaxial counter-rotating extruder (SLM-50, manufactured by Nagata Manufacturing Co., Ltd.) having a diameter of 50 mm,
A tubular molded body having an outer diameter of 50 mm was obtained. 110 this tubular body
After leaving it in the gear oven heated to ℃ for 20 minutes,
The tubular body was made to have a four-fold cross section, and while maintaining this shape, the temperature of the molded body was cooled to 20 ° C. or lower to obtain a rehabilitated pipe.

[Evaluation] The obtained rehabilitated pipe was evaluated for Vicat softening temperature (heat resistance), insertability and restorability by the methods described below, and the results are shown in Tables 1 and 2. (Vicat softening temperature) According to JIS K 7026,
The Vicat softening temperature of the obtained rehabilitation pipe was measured. A 5 kg weight was used for the measurement. (Insertability) The rehabilitated pipe was heated with hot air at 80 ° C. for 10 minutes and then inserted into a 45 ° L-shaped steel pipe having an inner diameter of 50 mm, and the insertability was evaluated according to the following criteria. ○: Insertion was possible, and no damage such as cracking or whitening was observed. ×: Damage such as inability to insert, cracking, or whitening occurred. (Restorability) After inserting a rehabilitation pipe into a steel pipe having an inner diameter of 50 mm, steam at 110 ° C. was supplied to the inside of the rehabilitation pipe from one end of the rehabilitation pipe for 10 minutes to bring the rehabilitation pipe into close contact with the inner surface of the steel pipe. . Then, after air of 20 ° C. was blown for 30 minutes to perform cooling, the close contact state between the steel pipe and the rehabilitating pipe was visually observed, and the restorability was evaluated according to the following criteria. ○… The rehabilitation pipe was in close contact with the steel pipe. × ... The rehabilitation pipe was not partially or entirely adhered to the steel pipe.

The materials used are as shown in Table 3.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

As described above, the chlorinated vinyl chloride resin composition of the present invention comprises a chlorinated vinyl chloride resin having a specific chlorine content to which a specific compound has been added, and thus has excellent heat resistance, and Since it is excellent in workability when it is made into a rehabilitating pipe, it is suitably used as a resin for producing a rehabilitating pipe. Further, since the rehabilitation pipe of the present invention is composed of the chlorinated vinyl chloride resin composition of the present invention, it has excellent heat resistance and excellent workability, and is for rehabilitation (restoration) of existing pipes. Is preferably used as.

Continued front page    F term (reference) 4J002 AC072 BB002 BB062 BB072                       BB242 BD042 BD052 BD082                       BD181 BG042 BG052 BN162                       CD163 CD173 CF002 CK022                       CL002 EH058 EH146 EH148                       EJ027 EV067 EW046 FD010                       FD016 FD020 FD023 FD050                       FD060 FD077 FD090 FD170                       FD208 GL00

Claims (13)

[Claims] 1. A chlorinated vinyl chloride resin having a chlorine content of 58 to 71% by weight, which is compatible with the chlorinated vinyl chloride resin and has a glass transition temperature, a melting point, a dropping point, a Vicat softening temperature, Alternatively, a chlorinated vinyl chloride resin composition comprising a compound (compound A) having a flow initiation temperature lower than the glass transition temperature of the chlorinated vinyl chloride resin. 2. The chlorinated vinyl chloride resin composition according to claim 1, wherein the compound A is 0.5 to 30 parts by weight with respect to 100 parts by weight of the chlorinated vinyl chloride resin. 3. The chlorinated vinyl chloride resin composition according to claim 1, wherein the compound A is a thermoplastic elastomer. 4. The thermoplastic elastomer is an ethylene-vinyl acetate-carbon monoxide copolymer, an ethylene-acrylic acid ester-carbon monoxide copolymer, an acrylonitrile-butadiene copolymer, a urethane-based thermoplastic elastomer,
One or more of a methyl methacrylate-butadiene-styrene copolymer, a chlorinated polyethylene, or an acrylic copolymer obtained by copolymerizing an acrylic monomer component and a polyfunctional monomer component. The chlorinated vinyl chloride resin composition according to claim 3. 5. The chlorinated vinyl chloride resin composition according to claim 1, wherein the compound A is a plasticizer. 6. The plasticizer is dicyclohexyl phthalate,
The chlorinated vinyl chloride resin composition according to claim 5, which is one or more of triphenyl phosphate, epoxidized soybean oil, and epoxidized linseed oil. 7. The chlorinated vinyl chloride resin composition according to claim 1, wherein the compound A is an antioxidant. 8. The chlorinated vinyl chloride resin composition according to claim 7, wherein the antioxidant is one kind or two or more kinds of compounds represented by the formula (1). _{S (CH 2 -CH 2 -COO- (} CH 2) n -CH 3) 2 ... (1) where, n is a positive number of 11 to 17 9. The chlorinated vinyl chloride resin composition according to claim 1, wherein the compound A is an ester compound (excluding a thermoplastic elastomer, a plasticizer and an antioxidant). 10. The chlorinated vinyl chloride resin composition according to claim 9, wherein the ester compound is one or two of glycerin monostearate or phthalic acid distearate. 11. The chlorinated chlorinated product according to claim 1 or 2, wherein at least two or more of a thermoplastic elastomer, a plasticizer, an antioxidant and an ester compound are used as the compound A. Vinyl resin composition. 12. A rehabilitation pipe comprising the chlorinated vinyl chloride resin composition according to any one of claims 1 to 11. 13. After the rehabilitation pipe is inserted into the existing pipe,
The rehabilitating pipe according to claim 12, wherein the rehabilitating pipe adheres to the inner surface of the existing pipe by being heated or being heated and being subjected to an internal pressure.