JP2003073518A - Vinyl chloride based resin composition for regenerated pipe and regenerated pipe - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride based resin composition suitable for producing a regenerated pipe having an excellent impact resistance and excellent in workability and to provide a regenerated pipe using the same. SOLUTION: This composition for the regenerated pipe comprises 100 pts.wt. of a vinyl chloride based resin having 600-3,000 of average molecular weight, 3-30 pts.wt. of one or more kinds of polymers comprising methylmethacrylate- butadiene-styrene copolymer, chlorinated polyethylene or an acrylic modifier, and 3-30 pts.wt. of a compound (excluding above vinyl chloride based resin) compatible with the polyvinylchloride resin and having glass transition temperature or melting point or dropping point lower than the glass transition point of the polyvinylchloride resin, and the regenerated pipe comprising the vinyl based resin composition for the regenerated pipe.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition for rehabilitating pipes and a vinyl chloride resin rehabilitating pipe using the 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 were problems that the impact resistance was insufficient to prevent damage to the resin pipe during transportation and construction, and that uniform restoration was difficult.

[0004]

In view of the above problems, an object of the present invention is to provide a vinyl chloride resin composition for rehabilitating pipe suitable for obtaining a rehabilitating pipe excellent in impact resistance and workability, and its vinyl chloride resin. It is intended to provide a vinyl chloride resin rehabilitation tube using the composition.

[0005]

A vinyl chloride resin composition for a rehabilitation pipe according to the invention of claim 1 (hereinafter referred to as "present invention 1") (hereinafter simply referred to as "vinyl chloride resin composition"). Is a vinyl chloride resin having an average degree of polymerization of 600 to 3,000, and 100 parts by weight of methyl methacrylate.
A butadiene-styrene copolymer (MBS), a chlorinated polyethylene (CPE), or an acrylic modifier, which is compatible with 3 to 30 parts by weight of at least one polymer, and the vinyl chloride resin, and It is characterized by comprising 3 to 30 parts by weight of a compound (excluding the above polymer) having a glass transition point, melting point or dropping point lower than the glass transition point of the vinyl chloride resin.

The vinyl chloride resin composition according to the invention of claim 2 (hereinafter referred to as "present invention 2") is compatible with a vinyl chloride resin and has a glass transition point of the above vinyl chloride resin. It is characterized in that a thermoplastic elastomer is used as the compound having a lower glass transition point than that of the resin.

Further, the vinyl chloride resin composition according to the invention of claim 3 (hereinafter referred to as "present invention 3") is compatible with the vinyl chloride resin and has a melting point or dropping point of the above vinyl chloride. A plasticizer is used as a compound having a glass transition point lower than that of the resin.

The vinyl chloride resin composition according to the invention of claim 4 (hereinafter referred to as "present invention 4") is compatible with the vinyl chloride resin and has a melting point or dropping point of the above vinyl chloride. An antioxidant is used as a compound lower than the glass transition point of the resin.

The vinyl chloride resin composition according to the invention of claim 5 (hereinafter referred to as "present invention 5") is compatible with the vinyl chloride resin and has a glass transition point or melting point or dropping point. Is a compound lower than the vinyl chloride resin,
At least two kinds of thermoplastic elastomers, plasticizers, and antioxidants are used.

A vinyl chloride resin composition according to the invention of claim 6 (hereinafter referred to as "present invention 6") is compatible with a vinyl chloride resin and has a glass transition point of the above vinyl chloride resin composition. The thermoplastic elastomer lower than the resin is characterized by being ethylene-vinyl acetate-carbon monoxide copolymer (EVACO) or acrylonitrile-butadiene copolymer (NBR) or urethane elastomer.

The vinyl chloride resin composition according to the invention of claim 7 (hereinafter referred to as "present invention 7") is compatible with the vinyl chloride resin and has a melting point or dropping point of the above vinyl chloride. The plasticizer having a glass transition point lower than the glass transition point of the resin is dicyclohexyl phthalate (DCHP) or triphenyl phosphate (TPP).

The vinyl chloride resin composition according to the invention of claim 8 (hereinafter referred to as "present invention 8") is compatible with the vinyl chloride resin and has a melting point or dropping point of the above vinyl chloride. It is characterized in that the antioxidant lower than the glass transition point of the system resin is dimyrstilthiopropionate (DMTP).

The rehabilitation pipe according to the invention of claim 9 (hereinafter referred to as "the present invention 9") (hereinafter simply referred to as "rehabilitation pipe") is a vinyl chloride-based resin according to the first to eighth inventions. It is characterized in that it is made of a resin composition, and after being inserted into an existing pipe, it is brought into close contact with the inner surface of the existing pipe by heating.

The vinyl chloride resin used in the present invention 1 is a vinyl chloride homopolymer, or a copolymer of vinyl chloride and a monomer or polymer copolymerizable with vinyl chloride. The vinyl chloride resin has an average degree of polymerization of 600 to 3
It is limited to 000, preferably 800 to 2000. If the average degree of polymerization is less than 600, the resulting vinyl chloride resin composition and the rehabilitating pipe have insufficient mechanical strength. Conversely, if the average degree of polymerization exceeds 3000, the vinyl chloride resin composition obtained is Moldability is impaired. The 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 removing THF from the filtrate by drying. -6721 means an average degree of polymerization measured in accordance with "Test method for vinyl chloride resin".

Examples of the monomer copolymerizable with the vinyl chloride monomer include α-olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl propionate; vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; methyl ( (Meth) acrylates such as (meth) acrylate, butyl (meth) acrylate and hydroxyethyl (meth) acrylate; aromatic vinyls such as styrene and α-methylstyrene; halogens such as vinyl fluoride, vinylidene fluoride and vinylidene chloride Vinyl chlorides; 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 kinds.

Examples of the polymer copolymerizable with the vinyl chloride monomer include acrylic copolymers composed of alkyl (meth) acrylate monomers and the like. These other copolymerizable polymers are homopolymers. May be used, or two or more kinds may be used in combination. The (meth) acrylate referred to herein means acrylate or methacrylate.

If the amount of the vinyl chloride component in the vinyl chloride resin is less than 50% by weight, the properties of the vinyl chloride resin will be lost. It may be appropriately set according to the performance and the purpose desired to be given to the composition and the rehabilitation pipe.

As a method for polymerizing the vinyl chloride resin, a conventionally known method may be used, and examples thereof include a suspension polymerization method.

The amount of the methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene or acrylic modifier used in the present invention 1 is 3 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin. Limited. If the addition amount is less than 3 parts by weight, the effect of improving impact resistance is low, and if the addition amount exceeds 30 parts by weight, mechanical strength may be reduced and moldability may be deteriorated. These may be used alone or in combination of two or more.

The amount of the compound that is compatible with the vinyl chloride resin used in the present invention 1 and has a glass transition temperature, melting point or dropping point lower than the glass transition point of the vinyl chloride resin is 100% vinyl chloride resin. 3 to 30 parts by weight
Limited to parts by weight. If the added amount is less than 3 parts by weight,
If the workability is not sufficient and conversely exceeds 30 parts by weight, the properties originally possessed by the vinyl chloride resin may be lost. This compound may be used alone or in combination of two or more kinds.

The thermoplastic elastomer used in the present invention 2 is not particularly limited as long as it is compatible with a vinyl chloride resin and has a glass transition temperature lower than that of the vinyl chloride resin, but is not limited to ethylene-vinyl acetate-carbon monoxide copolymer. A polymer, an acrylonitrile-butadiene copolymer, or a urethane elastomer is preferably used. These may be used alone or in combination of two or more.

The plasticizer used in the present invention 3 is not particularly limited as long as it is compatible with the vinyl chloride resin and has a melting point or dropping point lower than the glass transition point of the vinyl chloride resin. (DCHP) or triphenyl phosphate (TPP) is preferably used. These may be used alone or in combination of two or more.

The antioxidant used in the present invention 4 is not particularly limited as long as it is compatible with a vinyl chloride resin and has a melting point or dropping point lower than the glass transition temperature of the above vinyl chloride resin. Stillethiopropionate (DMTP) is preferably used. These may be used alone or in combination of two or more.

In the vinyl chloride resin compositions of the present inventions 1 to 8, if necessary, fillers, pigments, lubricants, processing aids, stabilizers, stabilizers and stabilizers are added as long as the object of the present invention is not hindered. One or more kinds of various additives such as an agent, a light stabilizer, an ultraviolet absorber, an antioxidant (antiaging agent), an antistatic agent, and a flame retardant may be added. The addition method and order of addition of these additives are not particularly limited,
Any method or any 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,
Two or more types may be used in combination.

Examples of the above-mentioned pigments include azo-based, phthalocyanine-based, slene-based, dye lake-based organic pigments;
Examples thereof include 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 fatty acids such as stearic acid; fatty acid esters; olefin waxes. These lubricants may be used alone or in combination of two or more kinds.

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

Examples of the above-mentioned stabilizer include organic tin-based stabilizers such as dibutyltin malate and dioctyltin laurate; lead white, basic lead sulfite, dibasic lead sulfite, tribasic lead sulfate, dibasic sulfite. Lead phosphate, silica gel co-precipitated lead silicate,
Lead stabilizers such as lead stearate, lead benzoate, dibasic lead stearate and lead naphthenate; metal soap stabilizers such as calcium stearate, barium stearate and zinc stearate; hydrotalcite, zeolite, etc. Inorganic stabilizers and the like can be mentioned. 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, and phosphoric acid ester. These stabilizing aids may be used alone or in combination of two or more.

Examples of the above light stabilizers include hindered amine light stabilizers. These light stabilizers may be used alone or in combination of two or more kinds.

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

Next, a rehabilitation pipe according to the present invention 9 comprises the vinyl chloride resin composition according to any one of the above-mentioned present inventions 1 to 8 and is inserted into an existing pipe and heated. It is characterized in that it is in close contact with the inner surface of the existing pipe.

The rehabilitation pipe is used in the present invention 1 by using an extruder.
It is produced by melt-kneading the vinyl chloride resin composition according to any one of 1 to 8 and performing extrusion molding to form a tubular body having a desired cross-sectional shape. The cross-sectional shape of the rehabilitation pipe is not particularly limited as long as it can be inserted into an existing pipe to be rehabilitated (repaired) and can be brought into close contact with the inner surface of the existing pipe by heating.

(Function) The vinyl chloride resin composition of the present invention comprises a vinyl chloride resin containing at least one or more of a methyl methacrylate-butadiene-styrene copolymer, a chlorinated polyethylene or an acrylic modifier. Since the compound and the vinyl chloride resin are compatible with each other, and a glass transition point, a melting point or a dropping point is a specific amount of a compound lower than the glass transition point of the vinyl chloride resin, the impact resistance is excellent, Moreover, it is excellent in workability as a rehabilitation pipe.

Further, since the rehabilitation pipe of the present invention is made of the above-mentioned vinyl chloride resin composition of the present invention, it has excellent impact resistance and excellent workability, and is intended to be rehabilitated (restored). It can be easily attached to the inner surface of the existing pipe by being inserted into the existing pipe and heated.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION The following examples are given to illustrate the present invention in more detail, but the present invention is not limited to these examples. In the examples, "part" means "part by weight" and "%" means "% by weight".

Example 1 [Preparation of vinyl chloride resin composition] A vinyl chloride homopolymer (trade name "TS1000R", manufactured by Tokuyama Sekisui Industry Co., Ltd.) was placed in a Henschel mixer (produced by Kawada Kogyo Co., Ltd.) having an internal volume of 100 liters. 100 copies, MBS (trade name "BTA75
1 ", manufactured by Kureha Chemical Industry Co., Ltd.), EVACO (trade name" Elvalloy 742 ", manufactured by Mitsui DuPont Polychemical Co., Ltd.) 15 parts, and an organotin stabilizer (trade name" O "
NZ-142F ", manufactured by Sansha Machine Co., Ltd., 2 parts, and a polyethylene wax lubricant as a lubricant (trade name" Hiwax 220 ").
MP ", manufactured by Mitsui Petrochemical Industry Co., Ltd.), and stearic acid (trade name" S-30 "manufactured by Kao Corporation) as a lubricant.
5 parts and a trade name as a processing aid "metabren P501
A ”(manufactured by Mitsubishi Rayon Co., Ltd.) was charged and uniformly mixed by stirring to prepare a vinyl chloride resin composition.

[Preparation of Rehabilitation Pipe] The vinyl chloride resin composition obtained above was supplied to a biaxial different-direction rotary extruder having a diameter of 50 mm (trade name “SLM-50”, manufactured by Nagata Manufacturing Co., Ltd.) A vinyl chloride resin molded body having a diameter of 50 mm was obtained. The obtained molded body was placed in a gear oven heated to 80 ° C for 2 minutes.
After standing still for 0 minutes, the cross section of the rehabilitation pipe is made into a four-fold shape, and the temperature of the molded product is kept at 20 while maintaining this shape.
It cooled to 0 degreeC and produced the rehabilitation pipe.

Example 2 [Preparation of Acrylic Copolymer] n-butyl acrylate (Tg of homopolymer:-
54 ° C.) 95% and trimethylolpropane triacrylate 5% as a polyfunctional monomer component, 2.36 kg of an acrylic mixed monomer, trade name “Hitenol N-08” (Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifying dispersant. An emulsified monomer liquid consisting of 50 g of a 10% aqueous solution (manufactured by the company) and 1.5 kg of pure water was prepared in advance. In a polymerization reactor (internal volume 10 liters) equipped with a stirrer and a temperature controller, 4 kg of pure water and 10% of ammonium persulfate as a polymerization initiator
After 24 g of an aqueous solution was charged and the inside of the polymerization vessel was replaced with nitrogen gas, the inside of the polymerization reactor was heated to 75 ° C. with stirring. Next, the previously prepared emulsified monomer solution was dropped into the polymerization reactor after heating at a constant dropping rate. The dropping of the entire amount of the emulsified monomer liquid was completed in 3 hours, and after stirring for 1 hour, the polymerization reaction was completed to prepare an acrylic copolymer emulsion having a solid content concentration of 30%.

[Preparation of Composite Vinyl Chloride Resin] In a polymerization reactor equipped with a stirrer and a temperature controller (internal volume 15 liters), 7.5 kg of pure water and the acrylic copolymer emulsion 0 obtained above were prepared. 0.5 kg (solid content 0.15 k
g), a partially saponified polyvinyl alcohol (trade name "Kuraray Poval L-8", manufactured by Kuraray Co., Ltd.) as an emulsifying dispersant.
% Aqueous solution 330 g, 1.1 g each of t-butylperoxydecanoate and α-cumylperoxyneodecanate as polymerization initiators, and the air in the polymerization reactor was exhausted with a vacuum pump, and then vinyl chloride was stirred under stirring. Monomer 3.0
kg was added. Then, the temperature inside the polymerization reactor was raised to 50 ° 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 prepare a vinyl chloride resin (A). The amount of vinyl chloride component in the obtained vinyl chloride resin (A) was 94%, and the content of the acrylic copolymer was 6%. Moreover, when the average degree of polymerization of the obtained vinyl chloride resin was measured according to JIS K-6721, the average degree of polymerization was 1,400.

Example 1 was repeated except that 100 parts of the vinyl chloride resin (A) was used.

Example 3 50 parts of vinyl chloride homopolymer and vinyl chloride resin (A)
Example 1 was repeated except that 50 parts was used.

Example 4 Example 4 was repeated except that 10 parts of CPE (trade name "JMR135C" manufactured by Daiso Co., Ltd.) was added instead of MBS.

Example 5 The procedure of Example 1 was repeated, except that 10 parts of an acrylic modifier (trade name "Kaneace FM", manufactured by Kanegafuchi Chemical Industry Co., Ltd.) was added instead of MBS.

Example 6 Example 6 was repeated except that the amount of MBS added was 8 parts and 3 parts of CPE was added.

Example 7 NBR (trade name "PN20H" instead of EVACO
A ”, manufactured by JSR) was used, and the same procedure as in Example 1 was performed.

Example 8 Example 8 was repeated except that urethane-elastomer (trade name "T-5275N", manufactured by Dainippon Ink and Chemicals, Inc.) was used instead of EVACO.

Example 9 Example 1 was repeated except that the amount of EVACO added was 5 parts and the amount of NBR added was 10 parts.

Example 10 DCHP (trade name "DCHP", instead of EVACO,
Example 1 was repeated except that 15 parts of Osaka Organic Chemical Industry Co., Ltd.) was added.

Example 11 The same procedure as in Example 1 was carried out except that 15 parts of TPP (trade name "TPP", manufactured by Daihachi Chemical Industry Co., Ltd.) was added instead of EVACO.

Example 12 The procedure of Example 1 was repeated except that 10 parts of DCHP and 5 parts of TPP were added instead of EVACO.

Example 13 Instead of EVACO, an antioxidant (trade name "DMT
P ”, manufactured by Yoshitomi Fine Chemical Co., Ltd.) was added in the same manner as in Example 1.

Example 14 The procedure of Example 1 was repeated except that 5 parts of EVACO, 5 parts of DCHP and 5 parts of DMTP were added.

Comparative Example 1 Example 1 was repeated except that the amount of MBS added was 0 part.

Comparative Example 2 Example 1 was repeated except that the amount of MBS added was 50 parts.

Comparative Example 3 Example 1 was repeated except that the amount of EVACO added was changed to 0 part.

Comparative Example 4 The procedure of Example 1 was repeated except that the amount of EVACO added was 50 parts.

Comparative Example 5 Example 10 except that the amount of DCHP added was 50 parts.
I went the same way.

Comparative Example 6 Example 13 except that the amount of DMTP added was 50 parts.
I went the same way.

[Evaluation] The performance (impact resistance, workability) of the rehabilitation pipe obtained above was evaluated by the following method. The results were as shown in Tables 1, 2 and 3. (Impact resistance) In accordance with JIS K-7111 "Charpy impact test method for hard plastics", using a notched (notched) test piece, the Charpy impact value of the rehabilitation pipe was measured in an atmosphere of 23 ° C. . (Workability) The rehabilitation pipe was left standing in a gear oven heated to 100 ° C for 30 minutes, the restoration condition of the rehabilitation pipe was visually observed, and the workability was evaluated according to the following criteria. ◯ mark: There was no concave portion and it was restored to an almost circular shape. X mark: Recessed portion remained

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

Industrial Applicability As described above, the vinyl chloride resin composition of the present invention exhibits impact resistance and is excellent in workability when used as a rehabilitating pipe. It is preferably used as a resin.

Since the rehabilitation pipe of the present invention is made of the vinyl chloride resin composition of the present invention described above, it has excellent impact resistance and workability, and rehabilitates (repairs) an existing pipe. ) It is used suitably for.

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Claims (9)

[Claims] 1. 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 600 to 3000, methylmethacrylate-
It is compatible with 3 to 30 parts by weight of at least one polymer of a butadiene-styrene copolymer, chlorinated polyethylene or an acrylic modifier, and the vinyl chloride resin, and has a glass transition point or a melting point or A vinyl chloride resin composition for a rehabilitating pipe, comprising 3 to 30 parts by weight of a compound (excluding the above polymer) having a dropping point lower than the glass transition point of the above vinyl chloride resin. 2. A vinyl chloride resin compatible with the above, and
The vinyl chloride resin composition for rehabilitation pipes according to claim 1, wherein the compound having a glass transition point lower than the glass transition point of the vinyl chloride resin is a thermoplastic elastomer. 3. A vinyl chloride resin compatible with the above, and
The vinyl chloride resin composition for rehabilitation pipes according to claim 1, wherein a compound having a melting point or a dropping point lower than the glass transition point of the vinyl chloride resin is a plasticizer. 4. A resin which is compatible with the vinyl chloride resin, and
The vinyl chloride resin composition for rehabilitation pipes according to claim 1, wherein a compound having a melting point or dropping point lower than the glass transition point of the vinyl chloride resin is an antioxidant. 5. A resin which is compatible with the vinyl chloride resin, and
At least two or more of a thermoplastic elastomer, a plasticizer and an antioxidant are used as a compound having a glass transition point, a melting point or a dropping point lower than the glass transition point of the vinyl chloride resin. Item 1 or 2
Alternatively, the vinyl chloride resin composition for rehabilitation pipe according to 3 or 4. 6. A composition compatible with the vinyl chloride resin, and
The thermoplastic elastomer having a glass transition point lower than the glass transition point of the vinyl chloride resin is an ethylene-vinyl acetate-carbon monoxide copolymer, an acrylonitrile-butadiene copolymer or a urethane elastomer. Item 1. The vinyl chloride resin composition for rehabilitating pipes according to 1 or 2 or 5. 7. A material compatible with the vinyl chloride resin, and
The plasticizer whose melting point or dropping point is lower than the glass transition point of the vinyl chloride resin is dicyclohexyl phthalate (DCH
P) or triphenyl phosphate (TPP), The vinyl chloride resin composition for rehabilitating pipes according to claim 1, 3 or 5. 8. A composition compatible with the vinyl chloride resin, and
5. The antioxidant having a melting point or dropping point lower than the glass transition point of the vinyl chloride resin is dimyrstilthiopropionate (DMTP).
Alternatively, 5 is a vinyl chloride resin composition for rehabilitation pipes. 9. The vinyl chloride resin composition according to any one of claims 1 to 8, which is adhered to the inner surface of the existing pipe by being heated after being inserted into the existing pipe. Rehabilitation pipe.