JPH1180475A - Vinyl-chloride conduit-component material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride conduit-component material which not only has a high adhesion workability but also has a high flexibility, impact resistance and vibration resistance. SOLUTION: A vinyl chloride resin composition is obtained by blending a vinyl chloride graft copolymer which is prepared through graft copolymerizing of from 80 to 30 wt.% vinyl monomer, which contains a vinyl chloride as a main component, and a vinyl-chloride resin, which contains a vinyl chloride as main component, with from 20 to 70 wt.% acrylic copolymer which is obtained by copolymerizing 100 pts.wt. acrylic monomer, which contains 50 wt.% or more alkyl (meth)acrylate monomer having a glass transition temperature of a homopolymer of from -140 to -20 deg.C, and from 0.1 to 30 pts.wt. multifunctional monomer, so that the content of the acrylic copolymer component is from 10 to 40 wt.%. A conduit-component material comprises the vinyl chloride resin composition and has a flexural modulus of from 5,000 to 20,000 kgf/cm<2> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride pipe component.

[0002]

2. Description of the Related Art Vinyl chloride resins are excellent in mechanical strength, weather resistance, chemical resistance, etc., and therefore are used in a wide variety of fields such as plumbing equipment such as water and sewage pipes, building materials, and housing materials. . Of these vinyl chloride resin products, water and sewage pipes are used underground, so repairing or updating them involves many difficulties such as excavation of roads with heavy traffic. Therefore, it is required that not only the performance is excellent in the short term, but also the performance is excellent in the long term. In particular, it is required to be excellent in fatigue strength against earthquakes and other vibrations, or fluctuations of the laid ground accompanying the vibrations, and to be highly reliable in the long term.

[0003] However, in recent years, an accident in which the pipes used in water and sewage pipes or the like are damaged by earthquakes or other vibrations, or connection parts come off or come off, making the pipes unusable. Are becoming apparent in some places, and the demand for seismic resistance of these pipeline components is increasing.

[0004] Currently, hard vinyl chloride resins generally used as these pipe constituent members are so rigid that they cannot follow vertical and horizontal vibrations caused by seismic waves, and are damaged or lose connection. It is said that this has led to accidents that slipped or slipped off.

[0005] As one of the measures against the above-mentioned accidents, some conduit members made of polyethylene having excellent flexibility and impact resistance have been used. However, conduit members made of polyethylene are acceptable. Although it is excellent in flexibility and impact resistance, it has a drawback that it cannot perform simple adhesive bonding, which is an advantage of a conduit component made of hard vinyl chloride resin.

[0006] Therefore, fusion connection is used for connecting these polyethylene conduit members.
The electric welding device disclosed in Japanese Patent Application Laid-Open No. 8-131025 is fusion-spliced. The electric welding device itself has an electric heating element buried near the connection of the pipeline components, and both ends of the electric heating element. Is guided inside the conduit member so as to be connected to a terminal for supplying current from the outside, and
This is a complicated device to which a control element for the supplied current is added, and has a problem in handling and joining costs due to a failure such as disconnection.

Such an electric welding apparatus is disclosed in
In addition to those disclosed in Japanese Patent Application Laid-Open No. 131025, for example, Japanese Patent Publication No. 55-500479 discloses an electric welding bush made of a thermoplastic material. Like the disclosed one, it had a complicated structure and poor connection workability.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above facts, and has as its object to provide not only excellent adhesiveness but also flexibility and impact resistance. Another object of the present invention is to provide a vinyl chloride pipe component having excellent earthquake resistance.

[0009]

According to the present invention, 100 parts by weight of an acrylic monomer containing 50% by weight or more of an alkyl (meth) acrylate monomer having a glass transition temperature of a homopolymer of -140 to -20 ° C. Vinyl chloride based copolymer obtained by graft copolymerizing 80 to 30% by weight of a vinyl monomer containing vinyl chloride as a main component with 20 to 70% by weight of an acrylic copolymer obtained by copolymerizing 0.1 to 30 parts by weight of a functional monomer. From a vinyl chloride resin composition obtained by blending a graft copolymer and a vinyl chloride resin containing vinyl chloride as a main component so that the content of the acrylic copolymer component is 10 to 40% by weight. The gist of the present invention is a vinyl chloride pipe constituent member characterized by having a flexural modulus of 5,000 to 20,000 kgf / cm ² .

In the present invention, the term "conduit member" is a generic term for members constituting a conduit molded from the vinyl chloride resin composition. The conduit is not particularly limited. For example, there are water supply and drainage pipes in water supply and sewerage systems, agricultural irrigation waterways, etc., communication cables, other cable protection pipes, various pipes in chemical plants, and other plants.

The above-mentioned conduit member comprises a main pipe member, a branch pipe member, a joint member and other auxiliary members.
Pipes, various branch joints, saddles, sockets, elbows, cheeses, expansion joints, various valves, strainers, caps,
Manholes, spiral tube forming profiles, and the like.

The acrylic copolymer used in the present invention has a glass transition temperature (Tg) of a homopolymer of -140 to -140.
An acrylic copolymer obtained by copolymerizing 100 parts by weight of an acrylic monomer containing 50% by weight or more of an alkyl (meth) acrylate monomer at −20 ° C. and 0.1 to 30 parts by weight of a polyfunctional monomer; It is a partially crosslinked acrylic copolymer or a partially crosslinkable acrylic copolymer having a polyfunctional monomer component of the copolymer as a crosslinking point.

When the above Tg exceeds -20 ° C., the obtained vinyl chloride resin composition is poor in flexibility and high-speed deformability. In particular, sufficient impact resistance and earthquake resistance during cold winter months cannot be obtained, and if the temperature is lower than -140 ° C, the mechanical strength such as tensile strength and flexural modulus of these molded products cannot be sufficiently obtained. It is limited to the range of Tg.

The above alkyl (meth) acrylate is not particularly limited as long as the Tg of the homopolymer is -140 to -20 ° C. For example, ethyl acrylate (T
g = −24 ° C., hereinafter, Tg is indicated in the parentheses only by temperature), n-propyl acrylate (−37 ° C.), n-butyl acrylate (−54 ° C.), isobutyl acrylate (−24 ° C.), sec-butyl Acrylate (-21
C), n-hexyl acrylate (-57C), 2-ethylhexyl acrylate (-85C), n-octyl acrylate (-85C), n-octyl methacrylate (-25C), isooctyl methacrylate (-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 may be used alone or in combination of two or more.

The acrylic monomer may be composed of only the above-mentioned alkyl (meth) acrylate. However, at least 50% by weight of the above-mentioned alkyl (meth) acrylate and 50% by weight of a radical polymerizable monomer copolymerizable therewith. % Of an acrylic monomer mixture.

The radically polymerizable monomer copolymerizable with the above alkyl (meth) acrylate is not particularly limited. For example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, s
ec-butyl methacrylate, t-butyl (meth) acrylate, phenyl acrylate, phenyl methacrylate, 2-chloroethyl acrylate, hydroxyethyl acrylate, styrene, α-methylstyrene, p-
Examples include methylstyrene, p-chlorostyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate and the like. These may be used alone or in combination of two or more.

When the content of the alkyl (meth) acrylate having a homopolymer having a Tg of -140 to -20 ° C. in a monomer mixture such as an acrylic monomer is less than 50% by weight, the resulting vinyl chloride-based The flexibility and high-speed deformability of the resin composition are poor, and the conduit component formed by using the resin composition is not limited to the above-mentioned content because the impact resistance and the earthquake resistance are not sufficiently obtained.

The polyfunctional monomer is not particularly limited as long as it can be copolymerized with the acrylic monomer and the like. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Polyfunctional (meth) acrylates such as 6-hexanediol di (meth) acrylate and trimethylolpropane tri (meth) acrylate; polyfunctional allyl compounds such as diallyl phthalate, diallyl maleate and triallyl isocyanurate; divinyl benzene and the like Divinyl compounds; diene compounds such as butadiene;
These may be used alone or in combination of two or more.

If the content of the polyfunctional monomer is less than 0.1 part by weight with respect to 100 parts by weight of the acrylic monomer or the like, the rigidity of the obtained pipe constituting member decreases,
If the required mechanical strength is hardly obtained, and if it exceeds 30 parts by weight, the flexibility is reduced, and it becomes difficult to obtain sufficient impact resistance and earthquake resistance.

The method for producing the acrylic copolymer is not particularly limited, and examples thereof include an emulsion polymerization method, a suspension polymerization method, and a dispersion polymerization method. Among them, the emulsion polymerization method is suitably used because the control of the copolymer particle size is easy. In the emulsion polymerization method, an emulsifying dispersant, a polymerization initiator, and if necessary, a pH adjuster, an antioxidant, and the like are used. Examples of the emulsifying dispersant include an anionic surfactant, a nonionic surfactant, partially saponified polyvinyl alcohol, a cellulose dispersant, and gelatin. These may be used alone or in combination of two or more.

Examples of the polymerization initiator include water-soluble polymerization initiators such as ammonium persulfate, potassium persulfate and hydrogen peroxide; organic peroxides such as benzoyl peroxide and lauroyl peroxide; and 2,2-azobis. Isobutyronitrile, 2,2-azobis-2,4-
Examples include azo compounds such as dimethylvaleronitrile.

The emulsion polymerization method includes, for example, a batch polymerization method, a monomer dropping method, and an emulsion dropping method depending on the method of charging the polymerizable monomer composition. In the present invention, these polymerization methods are used. The method is not limited, and any method may be adopted.

The structure and form of the obtained acrylic copolymer are not particularly limited. For example, a so-called so-called copolymer having different monomer component compositions and crosslinked structures between the surface layer and the core of the copolymer particles. The acrylic copolymer having the core-shell structure improves the stability of the copolymer particles and the strength performance of a molded article molded with the vinyl chloride resin composition derived from the copolymer particles. Therefore, it is preferably used.

As a method for producing the above-mentioned acrylic copolymer having a core-shell structure, for example, first, a polymerization initiator is added to an acrylic monomer constituting the core, pure water, and an emulsifying monomer comprising an emulsifying dispersant. In addition, a polymerization reaction is carried out to form a copolymer particle of the core part, and then an acrylic monomer constituting the shell part, pure water, and an emulsifying monomer comprising an emulsifying dispersant are added, and graft copolymerization is performed on the core part. And the like. In the above method, the graft copolymerization of the shell part may be performed continuously in the same polymerization step as the copolymerization of the core part, or may be performed in another polymerization step.

The acrylic copolymer particles thus obtained have a shell three-dimensionally covering the surface of the core,
The copolymer constituting the core portion and the copolymer constituting the shell portion are partially covalently bonded to form a three-dimensional crosslinked structure. The properties of the acrylic copolymer can be appropriately controlled by the monomer constitution of the core part and the shell part, the monomer ratio of the core part and the shell part, polymerization conditions, and the like.

In the present invention, the vinyl chloride graft copolymer is used in an amount of 20 to 70% by weight of the acrylic copolymer.
80 to 30% by weight of a vinyl monomer containing vinyl chloride as a main component is graft copolymerized.

The vinyl monomer containing vinyl chloride as a main component may be composed of only vinyl chloride.
It may be a mixed monomer of vinyl monomers other than vinyl chloride copolymerizable with vinyl chloride. The vinyl monomer other than the above vinyl chloride is not particularly limited as long as it is a vinyl monomer copolymerizable with vinyl chloride, but, for example, α- such as ethylene, propylene, and butylene.
Olefins; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as isopropyl vinyl ether and cetyl vinyl ether; styrene, α-
Styrene derivatives such as methylstyrene; (meth) acrylates such as n-butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate; vinyl cyanides such as acrylonitrile and methacrylonitrile; N- such as cyclohexylmaleimide and phenylmaleimide
Substituted maleimides; maleic acid derivatives, fumaric acid derivatives and the like. These may be used alone or in combination of two or more.

The content of the vinyl monomer other than vinyl chloride in the vinyl monomer containing vinyl chloride as a main component is less than 50% by weight, preferably 30% by weight or less based on 50% by weight or more of vinyl chloride. When the content of the vinyl monomer other than vinyl chloride is 50% by weight or more, the adhesiveness and strength performance of a molded article molded with the vinyl chloride resin composition derived from the obtained graft copolymer may be reduced. There is.

The graft copolymerization of the above-mentioned vinyl chloride graft copolymer is not particularly limited, and examples thereof include a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method. In the suspension polymerization method, a dispersant, a polymerization initiator, and, if necessary, a pH adjuster, an antioxidant, a chain transfer agent, and the like are used. As the dispersant, for example, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol and partially saponified products thereof,
Examples thereof include gelatin, polyvinylpyrrolidone, starch, and maleic anhydride-styrene copolymer. These may be used alone or in combination of two or more.

Examples of the above polymerization initiator include lauroyl peroxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, dioctyl peroxydicarbonate, t-butyl peroxy neodecanoate, α-cumyl par Organic peroxides such as oxyneodecanoate; and azo compounds such as 2,2-azobisisobutyronitrile and 2,2-azobis-2,4-dimethylvaleronitrile.

An example of a method for producing the above-mentioned vinyl chloride-based graft copolymer by the suspension polymerization method is as follows. Ion-exchanged water, a dispersant, a polymerization initiator and the above-mentioned acrylic After charging the copolymer and removing air from the polymerization vessel by vacuum, a vinyl chloride monomer or a vinyl monomer containing vinyl chloride as a main component is introduced into the polymerization vessel. After dispersing the acrylic copolymer in a vinyl chloride monomer or a vinyl monomer having vinyl chloride as a main component, while stirring the reaction system in the polymerization vessel,
The temperature is raised to a predetermined temperature by a heating jacket on the side wall of the polymerization vessel to start polymerization. After completion of the reaction, residual monomers are removed from the obtained vinyl chloride graft copolymer slurry, dehydrated by a dehydrator, and then dried to obtain a vinyl chloride graft copolymer.

If the vinyl chloride-based graft copolymer has a viscosity average degree of polymerization of more than 1800, the moldability of the vinyl chloride resin composition may be deteriorated. There is a possibility that the durability of the obtained vinyl chloride pipe constituent member may be deteriorated, so that it is preferably 400 to 1800, and more preferably 500 to 1.
400.

The viscosity average degree of polymerization of the vinyl chloride polymer of the vinyl chloride graft resin is determined by dissolving the vinyl chloride polymer of the vinyl chloride graft copolymer in tetrahydrofuran (THF) to remove insoluble components. Is a value measured in accordance with JIS K 6721 for a vinyl chloride polymerized component.

The copolymerizable monomer which can be used in the vinyl chloride resin containing vinyl chloride as a main component is not particularly limited as long as it is a vinyl monomer copolymerizable with vinyl chloride. In the vinyl-based graft copolymer, vinyl monomers other than vinyl chloride exemplified as the graft copolymerization monomer are similarly used.

The vinyl monomer copolymerizable with vinyl chloride may be used, for example, to reduce the melt viscosity of the vinyl chloride-based pipe component formed from the obtained vinyl chloride-based resin composition during molding. It is used as needed. For example, by copolymerizing ethylene with 8% by weight of vinyl chloride, the melt viscosity of the vinyl chloride-based pipe component at the time of molding is 10 to 15%.
° C.

The content of the vinyl chloride copolymer monomer in the vinyl chloride resin containing vinyl chloride as a main component is preferably 20% by weight or less with respect to 80% by weight or more of vinyl chloride. When the content of the vinyl monomer other than vinyl chloride exceeds 20% by weight, the adhesiveness and strength performance of a molded article molded with the vinyl chloride resin composition derived from the obtained graft copolymer may be reduced. There is.

If the viscosity average polymerization degree of the vinyl chloride resin containing vinyl chloride as a main component exceeds 2,000, the moldability of the vinyl chloride resin composition may deteriorate,
If it is less than 400, the durability of the obtained vinyl chloride pipe component may be impaired, so it is preferably from 400 to 2,000. The viscosity-average polymerization degree of the vinyl chloride resin is measured according to JIS K6721.

The vinyl chloride resin composition according to the present invention has a vinyl chloride graft copolymer content of 10 to 40% by weight, a vinyl chloride homopolymer or a vinyl chloride resin containing vinyl chloride as a main component. The resin is blended so that the content of the resin is 90 to 60% by weight.

When the content of the acrylic copolymer component in the vinyl chloride resin composition is less than 10% by weight, the flexibility and impact resistance of the resulting vinyl chloride pipe component are reduced. If it exceeds 40% by weight, the rigidity decreases, and when laying underground the polyvinyl chloride pipe component,
Since there is a possibility of deformation due to earth pressure or the like, it is limited to the above range.

The flexural modulus of the vinyl chloride resin composition is 5,000 to 20,000 kgf / cm ² . The flexural modulus is measured according to JIS K7203. The bending elastic modulus is 5000 kgf / c
If it is less than m ² , buckling may occur due to earth pressure, etc. when laying the PVC pipe component underground, and if it exceeds 20,000 kgf / cm ² , flexibility and high-speed deformability will decrease. However, since it may not be able to withstand high-speed deformation due to an earthquake or the like, it is limited to the above range.

In molding the vinyl chloride resin composition, a heat stabilizer and, if necessary, an ultraviolet absorber, a light stabilizer, an antioxidant, a lubricant, a processing aid, a filler, a colorant and the like are compounded. Is done. The heat stabilizer is added to secure the stability of the vinyl chloride resin composition from a high temperature during molding, and includes a heat stabilizer and a heat stabilization assistant.

The heat stabilizer is not particularly restricted but includes, for example, dibutyltin mercapto, dioctyltin mercapto, dimethyltin mercapto, dibutyltin maleate, dibutyltin maleate polymer, dioctyltin maleate, dioctyltin maleate. Organic tin stabilizers such as rate polymers, dibutyltin laurate and dibutyltin laurate polymers; lead stabilizers such as lead stearate, dibasic lead phosphite, and tribasic lead sulfate; calcium-zinc stabilizers; Barium-zinc stabilizers; barium-cadmium stabilizers and the like. These heat stabilizers may be used alone or in combination of two or more.

The heat stabilizing aid is not particularly restricted but includes, for example, phosphate esters such as epoxy soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene and tricresyl phosphate. And the like. These heat stabilizing aids may be used alone or in combination of two or more.

As the above-mentioned ultraviolet absorber and light stabilizer,
Although not particularly limited, for example, salicylic acid-based ultraviolet absorbers such as pt-butylphenyl salicylate, benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2 ′-(2′-hydroxy Benzotriazole-based ultraviolet absorbers such as -5-methylphenyl) benzotriazole, cyanoacrylate-based ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, nickel bis (octylphenyl) sulfide and the like. UV stabilizers, hindered amine light stabilizers (HALS) and the like.
The antioxidant is not particularly limited, but includes, for example, a phenolic antioxidant. These ultraviolet absorbers, light stabilizers and antioxidants may be used alone or in combination of two or more.

The above-mentioned lubricant is used for accelerating the gelation of the molten resin at the time of molding, lowering the flow viscosity and preventing frictional heat generation between the resins, and the internal lubricant and the molten resin at the time of molding, such as a barrel and a mold. It is made of an external lubricant or the like added to enhance the sliding effect with the metal surface. Examples of the internal lubricant include, but are not particularly limited to, butyl stearate, lauryl alcohol, stearyl alcohol, epoxy soybean oil, monoglyceride, bisamide, and the like. These internal lubricants may be used alone or in combination of two or more.
Examples of the external lubricant include, but are not particularly limited to, waxes such as paraffin wax, polyethylene wax, ester wax and montanic acid ester wax; and higher fatty acids such as stearic acid and lauric acid. These external lubricants may be used alone or in combination of two or more.

The processing aid is not particularly restricted but includes, for example, an acrylic processing aid containing methyl methacrylate having an average molecular weight of 100,000 to 5,000,000 as a main component. These processing aids may be used alone or in combination of two or more.

The filler is not particularly restricted but includes, for example, titanium oxide, calcium carbonate, talc, mica and the like. These fillers may be used alone or in combination of two or more. Further, the colorant is not particularly limited, for example, azo-based, phthalocyanine-based,
Organic pigments such as sullen and dye lakes, metal oxides,
Inorganic pigments such as sulfide-based, selenide-based, ferrocyanide-based, and molybdenum chromate-based pigments are exemplified.

The means for adding and mixing a heat stabilizer and other additives to the vinyl chloride resin composition is not particularly limited, and may be a hot blend method.
The cold blending method may be used.

The means for producing the vinyl chloride-based conduit component of the present invention is not particularly limited.
A heat stabilizer, a mixed powder or a pre-plasticized pellet obtained by adding and mixing other additives to the vinyl chloride resin composition,
Alternatively, these mixtures are kneaded using a mixing device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a mixing roll, and the like, and an extrusion molding machine, an injection molding machine, a calender roll, a blow molding machine, and a vacuum It is molded using various molding machines such as a molding machine, and further subjected to secondary processing and the like, thereby producing a desired vinyl chloride-based conduit component.

The vinyl chloride pipe component of the present invention comprises a vinyl chloride graft copolymer having the above-mentioned monomer composition and a vinyl chloride resin containing vinyl chloride as a main component. The flexural modulus of the component is 5,000-
Since it is in the range of 20,000 kgf / cm ² , in addition to excellent adhesiveness, it is rich in flexibility and impact resistance, there is no possibility of deformation due to earth pressure when buried underground, and strong vibration and crust due to earthquake etc. It has appropriate impact resistance and flexibility even under a load such as high-speed deformation due to fluctuations, has a very low possibility of breakage, and can maintain its function.
In addition, even with pipes formed by the normal bonding method, accidents such as peeling or disconnection at the connection part, which has been a problem in the past, will not be affected by strong vibration due to earthquakes or external force load due to crustal deformation. It is extremely small and can sufficiently maintain its function.

[0051]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. (Example 1) [Preparation of acrylic copolymer] Into a reaction vessel (10 liters in internal volume) equipped with a stirrer and a reflux condenser, 4 k of pure water was added.
g, 24 g of ammonium persulfate (10
% By weight), and the inside of the reaction vessel was purged with nitrogen, and then heated to 75 ° C. with stirring. 1.5 kg of pure water, an anionic emulsifying dispersant (trade name “HITENOL N” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
-08 "), an emulsified monomer solution prepared from 50 g (10% by weight aqueous solution), 2.4 kg of n-butyl acrylate (nBA) and 10 g of trimethylolpropane triacrylate (TMPA) was dropped into the reaction vessel at a constant dropping rate. After 3 hours, the dropwise addition was completed, and the polymerization reaction was continued under stirring for 1 hour to terminate the polymerization, thereby obtaining an acrylic copolymer latex having a solid content of 30% by weight.

[Preparation of vinyl chloride graft copolymer]
4.2 kg of pure water, 4.4 kg of the above-mentioned acrylic copolymer latex, partially saponified polyvinyl alcohol (trade name "Kuraray Povar L", manufactured by Kuraray Co., Ltd.) were placed in a reaction vessel (15 liter internal volume) equipped with a stirrer and a temperature controller. 130 g of a 3% by weight aqueous solution of hydroxypropyl methylcellulose (trade name “Metroze 60SH” manufactured by Shin-Etsu Chemical Co., Ltd.)
50 "), 130 g of a 3% by weight aqueous solution, t-butylperoxydecaneate and 1.0 g of α-cumylperoxyneodecanate were charged, and the air in the reaction vessel was discharged by a vacuum pump. 2.5 kg of the monomer was introduced, the temperature of the reaction vessel was raised to 64 ° C., and polymerization was started.
After the completion of the reaction was confirmed by a decrease in the pressure in the reaction vessel, an antifoaming agent (trade name “Toray Silicone SH5510” manufactured by Toray Industries, Inc.) was added under pressure, and the unreacted vinyl chloride monomer was discharged. A graft copolymer [acrylic copolymer content (hereinafter abbreviated as rubber content) 40% by weight] was produced.

Polyvinyl chloride having a viscosity average degree of polymerization of 800 (trade name "TS-800E", manufactured by Tokuyama Sekisui Kogyo Co., Ltd., Table 1)
And in Table 2, it is abbreviated as St-PVC. 100 parts by weight), 100 parts by weight of the above vinyl chloride graft copolymer (acrylic copolymer content 40% by weight, viscosity average degree of polymerization of vinyl chloride polymer 800) 100 parts by weight, dibutyltin mercapto (manufactured by Sankyoki Co., Ltd.) , Trade name "ONZ-41F") 2 parts by weight, montanic acid ester wax (trade name "Wax-OP", trade name "Wax-OP") as an internal / external lubricant, and monoglyceride (RIKEN Vitamin Co., Ltd.) as an internal lubricant. , Trade name “S-100”) in a Henschel mixer to prepare 0.5 parts by weight of a vinyl chloride resin composition (powder).
Using a pelletizer equipped with an mφ twin screw extruder, the mixture was heated to a resin temperature of 180 ° C. and pelletized.

The pellets of the vinyl chloride resin composition were kneaded with two rolls at a heating temperature of 180 ° C. for 3 minutes, and the resulting rough sheet was preheated for 4 minutes by a hot press at a heating temperature of 200 ° C. Surface pressure 75 kgf / cm ² at temperature 4
For 5 minutes, and then cooled at the same surface pressure at a cooling temperature of 15 ° C. for 5 minutes to produce plates having thicknesses of 2 mm, 3 mm and 5 mm.

Further, the pellets of the vinyl chloride resin composition were molded using an injection molding machine (manufactured by Toshiba Machine Co., trade name “IS-1200DE”) with a mold clamping pressure of 1200 tons, according to the Japan Sewerage Association Standard (JSWAS K-7). ), The merged residential land squares at 90 degrees left (abbreviation: 90Y left, square diameter 150 mm)
φ) A vinyl chloride-based conduit component was manufactured.

(Examples 2 and 3) Vinyl chloride was prepared in the same manner as in Example 1 except that the charged amounts of the acrylic copolymer and the vinyl chloride monomer were changed to rubber contents as shown in Table 1. A graft copolymer was prepared, a vinyl chloride resin and an additive having the same composition as in Example 1 were mixed, and a vinyl chloride resin composition was prepared in the same manner as in Example 1.
Next, using the obtained vinyl chloride resin composition, in the same manner as in Example 1, 2 mm, 3 mm, and 5 mm thick plates and a vinyl chloride pipe constituent member composed of a residential land square 90Y left were produced.

(Examples 4 to 6) As shown in Table 1,
A vinyl chloride resin composition was produced in the same manner as in Example 1, except that the composition of the acrylic monomer was changed and an acrylic copolymer was produced in the same manner as in Example 1.
Next, using the obtained vinyl chloride resin composition, in the same manner as in Example 1, 2 mm, 3 mm, and 5 mm thick plates and a vinyl chloride pipe constituent member composed of a residential land square 90Y left were produced.

Example 7 A vinyl chloride resin mixed with the vinyl chloride graft copolymer of Example 1 was replaced with a vinyl chloride-ethylene copolymer (manufactured by Tokuyama Sekisui Kogyo Co., Ltd .;
00, ethylene content 8% by weight, in Table 1, abbreviated as VC-Et. ) Was prepared in the same manner as in Example 1 except that the composition was changed to (1). Next, using the obtained vinyl chloride-based resin composition, in the same manner as in Example 1, 2 mm, 3 mm, and 5 mm thick plates and residential land squares 9
A vinyl chloride pipe constituent member consisting of 0Y left was produced.

Comparative Example 1 A vinyl chloride resin composition was prepared in the same manner as in Example 1 except that the amount of the vinyl chloride graft copolymer of Example 1 was changed to 14.3 parts by weight. . Next, using the obtained vinyl chloride resin composition, in the same manner as in Example 1, 2 mm, 3 mm, and 5 mm thick plates and a vinyl chloride pipe constituent member composed of a residential land square 90Y left were produced.

Comparative Example 2 A vinyl chloride resin composition was prepared in the same manner as in Example 1, except that the amount of the vinyl chloride graft copolymer in Example 3 was changed to 225 parts by weight. Then, using the obtained vinyl chloride resin composition, in the same manner as in Example 1, the thickness was 2 mm, 3 mm and 5 mm.
A vinyl chloride-based conduit component consisting of a mm plate and a residential land square 90Y left was produced.

(Comparative Examples 3 and 4) As shown in Table 2,
A vinyl chloride resin composition was produced in the same manner as in Example 1, except that the composition of the acrylic monomer was changed and an acrylic copolymer was produced in the same manner as in Example 1.
Next, using the obtained vinyl chloride resin composition, in the same manner as in Example 1, 2 mm, 3 mm, and 5 mm thick plates and a vinyl chloride pipe constituent member composed of a residential land square 90Y left were produced.

Comparative Example 5 A vinyl chloride resin (manufactured by Tokuyama Sekisui Kogyo Co., Ltd.) was used without using a vinyl chloride graft copolymer.
Using only the trade name “TS-800E” and a degree of polymerization of 800), an additive having the same composition as in Example 1 was blended, and a vinyl chloride resin composition was produced in the same manner as in Example 1. Next, using the obtained vinyl chloride resin composition, in the same manner as in Example 1, 2 mm, 3 mm, and 5 mm thick plates and a vinyl chloride pipe constituent member composed of a residential land square 90Y left were produced.

Comparative Example 6 A high-density polyethylene (manufactured by Asahi Kasei Corporation, trade name “QB780”, abbreviated as PE in Table 2) was used in the same manner as in Example 1 to have a thickness of 2 mm and a thickness of 3 mm.
A vinyl chloride pipe component comprising a 5 mm and a 5 mm plate and a house land square 90Y left was produced.

Comparative Example 7 As shown in Table 2, the same procedure as in Example 1 was carried out except that the composition of the acrylic monomer was changed and an acrylic copolymer was produced in the same manner as in Example 1. A vinyl chloride resin composition was prepared. Then
Using the obtained vinyl chloride-based resin composition, vinyl chloride-based pipe constituent members composed of plates having a thickness of 2 mm, 3 mm, and 5 mm and a residential land square 90Y left were produced in the same manner as in Example 1.

(Comparative Examples 8 to 9) Vinyl chloride graft copolymers having different rubber charge contents as shown in Table 2 were prepared by changing the amounts of the acrylic copolymer and vinyl chloride monomer. A vinyl chloride-based resin composition was prepared in the same manner as in Example 1, except that the compounding amounts were respectively mixed with the vinyl chloride-based resin. Then, using the obtained vinyl chloride resin composition, in the same manner as in Example 1, the thickness was 2 mm, and the thickness was 3 m.
A vinyl chloride-based conduit component consisting of m and 5 mm plates and a residential land square 90Y left was produced.

In order to evaluate the performances of the vinyl chloride pipe constituent members and the polyethylene pipe constituent members obtained in Examples 1 to 7 and Comparative Examples 1 to 9, impact resistance, flexural modulus, adhesive strength, Evaluation of seismic resistance High-speed tensile fracture elongation and repeated bending test of pipe insertion were tested by the following methods. The test results are shown in Tables 1 and 2.

1. Impact resistance A 30 mm × 30 mm test piece is cut out from a 3 mm thick plate, and the half crack height (5 cm interval) is measured using a Dupont falling weight impact tester (square weight, load 3 kg) according to JIS K 7211. It measured and set it as the evaluation scale of impact resistance.

2. Flexural modulus The flexural modulus of a sheet having a thickness of 3 mm was measured according to JIS K7203.

3. Four test pieces having a width of 10 mm and a length of 50 mm were cut out from a sheet having an adhesive strength of 5 mm, and as shown in FIG.
A standard adhesive (10 mm × 10 mm, manufactured by Sekisui Chemical Co., Ltd., trade name “ESDINE # 7”)
3)) 3 is applied in an application amount used for normal bonding, and the remaining two test pieces 2 and 2 are covered with the adhesive applied surface 3 just behind the remaining two test pieces as shown in FIG. The test piece was sandwiched (adhesion area: 4 cm ² ), and a surface pressure of 1 kgf / cm ² was applied between the remaining two test pieces under a temperature environment of 23 ° C., and was held in this state for 24 hours.

After the pinching, the other ends of the test pieces 1 and 1 projecting up and down from between the remaining two test pieces 2 and 2 of the test pieces are gripped by a gripper of a tensile tester. In a temperature environment of 23 ° C., a shearing force parallel to the adhesive-coated surface is applied at a pulling speed of 10 mm / min in a direction indicated by a large black solid arrow in the drawing, and a load when the adhesive surface is peeled off. The amount was read, and the value obtained by dividing the measured value by the adhesive area (2 cm ² ) was defined as the adhesive strength.

4. Evaluation of seismic resistance High-speed tensile fracture elongation A No. 2 test piece specified in JIS K 7113 was prepared, and a high-speed tensile tester (MODEL, manufactured by Orientec Co., Ltd.)
Using UTM-5), in accordance with JIS K 7113, under a temperature environment of 23 ° C., only the tensile speed is 0.9 m / s.
ec and the high-speed tensile elongation at break was measured.

The reason why the tensile speed was changed to 0.9 m / sec is that the maximum vibration speed reported by the Kobe Marine Meteorological Observatory in the 1995 Hyogoken Nanbu Earthquake was 0.9 m / sec.
/ Sec. In addition, various measured values announced by the Kobe Marine Meteorological Observatory regarding the Hyogoken Nanbu Earthquake (maximum acceleration 818 gal, maximum speed 91 kinc, maximum displacement 21
cm), it was calculated that structures with a maximum displacement of 20 cm and a tensile elongation at break of 30% or more during high-speed deformation had a high possibility of breakage or detachment of the joint. Was. In the present invention, the criterion for judging the presence or absence of earthquake resistance is a high-speed tensile fracture elongation of 30%.
% Or more.

4. Seismic evaluation pipe insertion bending test To the left of the obtained residential land square 90Y, a hard polyvinyl chloride pipe for sewerage (plain end straight pipe UV100) was JSWAS K
Adhesive (trade name "ESDINE # 7", manufactured by Sekisui Chemical Co., Ltd.)
3)), and then cured for 24 hours in a temperature environment of 23 ° C. Next, as shown in FIG. 2, the residential land mass 4 to which the plain end straight pipe 5 is adhesively bonded is fixed to the base 7 with the fixture 6 while the residential land mass 4 is standing, similarly to the actual laying site. The free end of the straight-end straight pipe 5 (length 60 cm) is slidable on a pipe fixing device 9 connected to the tip of a hydraulic cylinder 8 of a portable fatigue tester (trade name “HTM30-200-07” manufactured by Kayaba Industry Co., Ltd.). Under the condition of amplitude ± 8 degrees and vibration cycle of 0.4 Hz,
Repeated vibration was applied in the direction of the arrow in FIG. 2 to measure the maximum number of repeated bendings in a range that does not affect the function of the pipeline such as peeling of the adhesive joint surface of the plain end straight pipe 5 and damage of the residential land mass 4. . Also, the residential land mass 4, the fixture 6, and the base 7 are in the same constant temperature bath 10 as in the measuring section in which the plain end straight pipe 5 is accommodated, and the residential land mass 4, the fixture 6, and the base 7 The wall surface of the thermostat 10 of this part was cut out in order to clearly indicate the condition.

As a result of a computer simulation using various measured values (maximum acceleration 818 gal, maximum speed 91 kinc, maximum displacement 21 cm) published by the Kobe Ocean Meteorological Observatory regarding the previous Hyogoken Nanbu Earthquake, the maximum bending angle was 8 degrees. It was calculated that there was. In the present invention,
The criterion for judging the presence or absence of earthquake resistance was set to a maximum bending angle of 8 degrees or more. In order to give the amplitude of the bending angle of 8 degrees, the length of the plain end straight pipe 5 was set to 60 cm, and the amplitude was set to ± 8.4 cm by a controller attached to the portable fatigue tester.

The maximum number of vibrations during an earthquake is generally said to be about 50, and the amplitude of the vibrations attenuates with the vibration. If it is 50 times or more, it can be said that it has sufficient earthquake resistance.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

According to the present invention, the vinyl chloride pipe constituting member is
Because it is configured as described above, in addition to excellent adhesiveness, it is rich in flexibility and impact resistance, there is no risk of deformation due to earth pressure when buried underground, and strong vibration due to earthquake etc. It has appropriate impact resistance and flexibility even under a load such as high-speed deformation due to crustal deformation, etc., has very little possibility of breakage, and can maintain its function. In addition, even with pipes formed by the normal bonding method, accidents such as peeling or disconnection at the connection part, which has been a problem in the past, will not be affected by strong vibration due to earthquakes or external force load due to crustal deformation. It is extremely small and can sufficiently maintain its function.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of test piece preparation when measuring the adhesive strength of a vinyl chloride-based conduit component of the present invention.

FIG. 2 is an explanatory diagram of a pipe insertion cyclic bending test of an evaluation test of seismic resistance of a vinyl chloride pipe constituent member of the present invention.

[Explanation of symbols]

 1, 2: Vinyl chloride pipe component test piece 3: Adhesive 4: Residential land mass 5: Plain end straight pipe 6: Fixture 7: Base 8: Hydraulic cylinder 9: Pipe fixture

Claims (1)

[Claims] The glass transition temperature of the homopolymer is -140.
Acrylic monomer 100 containing 50% by weight or more of an alkyl (meth) acrylate monomer having a temperature of -20 ° C
80 to 30% by weight of a vinyl monomer containing vinyl chloride as a main component is graft copolymerized with 20 to 70% by weight of an acrylic copolymer obtained by copolymerizing 0.1 to 30 parts by weight of a polyfunctional monomer and 0.1 to 30 parts by weight of a polyfunctional monomer. A vinyl chloride-based graft copolymer and a vinyl chloride-based resin containing vinyl chloride as a main component have a content of the acrylic copolymer component of 10 to 40% by weight.
And a flexural modulus of 5000 to 20,000 kgf.
/ Cm ² , a vinyl chloride pipe component.