JP2019108723A - Pipe material and pipeline system - Google Patents

Abstract

To provide a pipe material and pipeline system that have sufficient strength while having high thermal expandability.SOLUTION: A pipe material contains polyvinyl chloride resin, 10-20 pts.mass particulate thermally expansible graphite relative to 100 pts.mass of the polyvinyl chloride resin, and particulate aluminum hydroxide. A ratio (B/A) of the average particle diameter (B) of the particulate aluminum hydroxide to the average particle diameter (A) of the particulate thermally expansible graphite is 0.0015 to 0.0065.SELECTED DRAWING: None

Description

  The present invention relates to a pipe and piping system.

  In a building, in the case of a fire or other emergency, one of the causes of the fire spreading from the area where the ignition source is from to another area is the presence of piping such as drainage pipes installed in the building.

  Conventionally, fireproof piping materials have been proposed in order to minimize the spread of fire through piping. Furthermore, in recent years, by constructing piping with a material as described in Patent Document 1, there is a proposal to expand the piping material by heat of the fire to close the piping itself and to prevent the spread of fire through the piping. It is done. As such piping or piping material, Patent Document 2 describes a piping material containing thermally expandable graphite.

  It is preferable to use a more thermally expandable piping material in order to more reliably prevent the burning of the fire through the piping. Therefore, it is considered that the piping material disclosed in Patent Document 2 contains a large amount of thermally expandable graphite to make the piping material having a higher thermal expansion property. However, when the content of the thermally expandable graphite in the piping material is excessive, there is a concern that the strength of the piping may be insufficient.

  Thus, the relationship between thermal expansion and strength is in a trade-off relationship as it is, and it is difficult to obtain a piping material provided with both properties at high levels.

Japanese Patent Application Laid-Open No. 03-41161 JP, 2009-74689, A

  In view of the above-mentioned circumstances, an object of the present invention is to provide a pipe member and a piping system having sufficient strength while having high thermal expansion.

  As a result of intensive studies to achieve the above object, the present inventors include particulate expansive graphite and particulate aluminum hydroxide, and set the ratio of the average particle size of both to within a predetermined range. It has been found that a pipe having sufficient strength can be obtained while having high expansivity. The present inventors have conducted further studies based on such findings, and have completed the present invention.

That is, the present invention provides the following pipe material.
Item 1.
A polyvinyl chloride resin, 10 to 20 parts by mass of thermally expandable graphite particles in an amount of 100 to 20 parts by mass of the polyvinyl chloride resin, and aluminum hydroxide particles,
A ratio (B / A) of an average particle size (A) of the particulate thermally expandable graphite to an average particle size (B) of the particulate aluminum hydroxide is 0.0015 to 0.0065, Do the pipe.
Item 2.
The pipe material according to Item 1, containing 1 to 5 parts by mass of the particulate aluminum hydroxide with respect to 100 parts by mass of the polyvinyl chloride resin.
Item 3.
The pipe material according to Item 1 or 2, wherein an average particle size (A) of the particulate thermally expandable graphite is 110 to 1000 μm.
Item 4.
The piping system comprised by the pipe material in any one of claim | item 1-3.

  The pipe material of the present invention has sufficient strength while having high thermal expansion.

<1. Pipe material>
The pipe material of the present invention comprises a polyvinyl chloride resin, 10 to 20 parts by mass of particulate thermally expandable graphite with respect to 100 parts by mass of the polyvinyl chloride resin, and particulate aluminum hydroxide, A ratio (B / A) of the average particle size (A) of the expandable graphite to the average particle size (B) of the particulate aluminum hydroxide is characterized by being 0, 0015 to 0.0065.

Polyvinyl chloride-based resin As polyvinyl chloride-based resin, for example, polyvinyl chloride homopolymer; copolymer of vinyl chloride monomer and monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer; vinyl chloride Other (co) polymers include graft copolymers obtained by graft copolymerizing vinyl chloride and the like, and these may be used alone or two or more may be used in combination. In addition, the polyvinyl chloride resin may be chlorinated as needed.

  It does not specifically limit as a monomer which has an unsaturated bond copolymerizable with the said vinyl chloride monomer, For example, (alpha) -olefins, such as ethylene, propylene, butylene; Vinyl esters, such as vinyl acetate and vinyl propionate; Vinyl ethers such as vinyl ether and cetyl vinyl ether; (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl acrylate; aromatic vinyls such as styrene and α-methylstyrene; N-phenylmaleimide And N-substituted maleimides such as N-cyclohexyl maleimide, etc., and these may be used alone, or two or more kinds may be used in combination.

  The (co) polymer for graft copolymerization of vinyl chloride is not particularly limited as long as it grafts (co) polymerizes vinyl chloride, and, for example, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate- Carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane And chlorinated polyethylene, chlorinated polypropylene and the like, which may be used alone or in combination of two or more.

  The average degree of polymerization of the polyvinyl chloride resin is not particularly limited, but when it becomes smaller, the physical properties of the molded product decrease, and when it becomes larger, the melt viscosity becomes higher and the molding becomes difficult. Preferably, 600 to 1400 are particularly preferred. The above-mentioned average degree of polymerization is obtained by dissolving the complex vinyl chloride resin in tetrahydrofuran (THF), removing insoluble components by filtration, drying the THF in the filtrate, and using it as a sample resin. 6721 means an average degree of polymerization measured in accordance with "Vinyl chloride resin test method".

  The polymerization method of the polyvinyl chloride resin is not particularly limited, and any conventionally known polymerization method may be employed, and examples thereof include bulk polymerization method, solution polymerization method, emulsion polymerization method, suspension polymerization method and the like. Be

  The chlorination method of the polyvinyl chloride resin is not particularly limited, and a conventionally known chlorination method may be employed, and examples thereof include a thermal chlorination method and a photochlorination method.

  Any of the above-mentioned polyvinyl chloride resins may be used after being crosslinked or modified within the range not inhibiting the fire resistance performance as a resin composition. In this case, a resin which has been crosslinked or modified in advance may be used, and when the additive etc. is blended, it may be simultaneously crosslinked or modified, or it may be crosslinked or modified after the above components are blended in the resin. . There is also no particular limitation on the method of crosslinking the above-mentioned resin, and there are no particular limitations on the method of crosslinking polyvinyl chloride resin, for example, various crosslinking agents, crosslinking using peroxide, crosslinking by electron beam irradiation, water-crosslinkable material And the like.

The thermally expandable graphite contained in the particulate thermally expandable graphite tube is particulate thermally expandable graphite. As the thermally expandable graphite, known materials can be widely used, and there is no particular limitation. Specifically, monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like can be mentioned. Examples of the above-mentioned alkali metal compound and alkaline earth metal compound include hydroxides such as potassium, sodium, calcium, barium and magnesium, oxides, carbonates, sulfates, organic acid salts and the like. These may be used alone or two or more may be used in combination.

  The content of the particulate thermally expandable graphite in the tubular material is 10 parts by mass or more, preferably 10.5 parts by mass or more, with respect to 100 parts by mass of the polyvinyl chloride resin. When the content of the particulate thermally expandable graphite is less than 10 parts by mass, the thermal expansion of the pipe material is insufficient. On the other hand, the content of the particulate thermally expandable graphite in the tubular material is 20 parts by mass or less, preferably 16 parts by mass or less, with respect to 100 parts by mass of the polyvinyl chloride resin. When the content of the particulate thermally expandable graphite is more than 20 parts by mass, the strength of the tube material becomes insufficient.

  The average particle size (A) of the particulate thermally expandable graphite is preferably 110 μm or more, more preferably 120 μm or more, and still more preferably 200 μm or more. When the average particle size (A) is 110 μm or more, the thermal expansion of the obtained tube can be improved. On the other hand, the average particle size (A) of the particulate thermally expandable graphite is preferably 1000 μm or less, and more preferably 400 μm or less. When the average particle size (A) is 1000 μm or less, the fire resistance and the strength of the pipe material are improved.

In the present specification, the average particle size of the particulate thermally expandable graphite is calculated as follows.
100 g of particulate thermally expandable graphite is meshed with a test sieve according to JIS Z8801-1, and the average particle size is the size of the opening of the test sieve (μm) × weight of mesh on (g) / total Weight (g)

Particulate Aluminum Hydroxide Particulate aluminum hydroxide can be used without any particular problems as long as it is particulate aluminum hydroxide. Containing particulate sodium hydroxide in the pipe contributes to the improvement of the flame retardancy of the pipe.

  The average particle size (B) of the particulate aluminum hydroxide is preferably 0.20 μm or more, and more preferably 0.40 μm or more. By being 0.20 micrometers or more, the effect that a flame retardance improves can be acquired. On the other hand, the average particle diameter (B) of the particulate aluminum hydroxide is preferably 6.0 μm or less, and more preferably 2.4 μm or less. By being 6.0 micrometers or less, the effect that the intensity | strength of a pipe material improves can be acquired.

In the present specification, the average particle size (B) of the particulate aluminum hydroxide is defined as measured by a light scattering particle size analyzer (light scattering particle size analyzer DLS-7000: manufactured by Otsuka Electronics Co., Ltd.).

  The content of the particulate aluminum hydroxide in the pipe member is preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. By having such a configuration, it is possible to obtain a pipe having both sufficient strength and fire resistance.

  In addition, the ratio (B / A) of the average particle size (A) of the particulate expandable graphite to the average particle size (B) of the particulate aluminum hydroxide is 0.0015 or more, 0.002 It is more preferable that it is more than. When the ratio (B / A) is less than 0.0.05, the strength of the pipe material is insufficient. On the other hand, the ratio (B / A) is 0.0065 or less, more preferably 0.006 or less. If the ratio (B / A) is more than 0.0065, the thermal expansion of the pipe material is insufficient.

Flame retardants, etc. Flame retardants can be used as needed to impart additional flame retardancy to the tubing. As such a flame retardant, known flame retardants can be widely adopted. Specifically, antimony oxide such as magnesium hydroxide, hydrotalcite, antimony dioxide, antimony trioxide, antimony pentoxide, molybdenum trioxide, molybdenum disulfide, molybdenum disulfide such as ammonium molybdate, tetrabromobisphenol A, tetra Bromine compounds such as bromoethane, tetrabromoethane and tetrabromoethane, phosphorus compounds such as triphenyl phosphate and ammonium polyphosphate, calcium borate, zinc borate, calcium phosphate, zinc phosphate and the like. These may be used alone, or two or more may be used in combination.

Additives and others, to the pipe material of the present invention, inorganic fillers, lubricants, processing aids, impact modifiers, heat resistance improvers, antioxidants, light stabilizers, UV absorbers, as long as the physical properties thereof are not impaired. Additives such as pigments, plasticizers and thermoplastic elastomers may be added.

  As the inorganic filler, known ones can be widely used, and there is no particular limitation. Specifically, silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic carbonate Magnesium, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, doronite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite , Sericite, glass fiber, glass beads, silica based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate At least one selected from the group consisting of aluminum “MOS”, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel, zinc borate, various magnetic powders, slag fibers, It can be mentioned.

  As the lubricant, it is possible to widely use known ones, and there is no particular limitation. The lubricants include internal lubricants and external lubricants. The internal lubricant is used for the purpose of lowering the flow viscosity of the molten resin at the time of molding processing and preventing frictional heat generation. The internal lubricant is not particularly limited. For example, one or more selected from the group consisting of butyl stearate, lauryl alcohol, stearyl alcohol, epoxy soybean oil, glycerin monostearate, stearic acid, and bisamide may be used. it can. In addition, an 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. For example, one or more selected from the group consisting of paraffin wax, polyolefin wax, ester wax, and montanic acid wax can be used.

  As the processing aid, it is possible to widely use known ones, and there is no particular limitation. For example, acrylic processing aids such as alkyl acrylate-alkyl methacrylate copolymers having a weight average molecular weight of 100,000 to 2,000,000 can be mentioned. The acrylic processing aid is not particularly limited, and examples thereof include n-butyl acrylate-methyl methacrylate copolymer, 2-ethylhexyl acrylate-methyl methacrylate-butyl methacrylate copolymer, and the like. These may be used alone or in combination of two or more.

  As the impact modifier, known ones can be widely used, and there is no particular limitation. For example, one or more selected from the group consisting of methyl methacrylate-butadiene-styrene copolymer (MBS), chlorinated polyethylene, acrylic rubber and the like can be used.

  Also as the heat resistance improver, known ones can be widely used, and there is no particular limitation. For example, α-methylstyrene-based resin, N-phenylmaleimide-based resin and the like can be used.

  The antioxidant is not particularly limited, and known ones can be widely used. For example, a phenolic antioxidant etc. are mentioned.

  The light stabilizer is not particularly limited, and known ones can be widely used. For example, light stabilizers such as hindered amines may be mentioned.

  The UV absorber is not particularly limited, and a wide variety of known UV absorbers can be used. For example, ultraviolet absorbers such as salicylic acid ester type, benzophenone type, benzotriazole type, cyanoacrylate type and the like can be mentioned. These may be used alone or in combination of two or more.

  The pigment is not particularly limited, and known pigments can be widely used. For example, organic pigments such as azo pigments, phthalocyanine pigments, slen pigments, dye lake pigments, etc .; inorganic pigments such as oxides, molybdenum chromates, sulfides and selenides, and ferrocyanides are listed. These may be used alone or in combination of two or more.

  Further, a plasticizer may be added to the polyvinyl chloride resin. The plasticizer is not particularly limited, and known ones can be widely used. For example, one or more selected from the group consisting of dibutyl phthalate, di-2-ethylhexyl phthalate, and di-2-ethylhexyl adipate can be used.

  The thermoplastic elastomer is not particularly limited, and known ones can be widely used. For example, acrylonitrile-butadiene copolymer (NBR), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate-carbon monoxide copolymer (EVACO), vinyl chloride-vinyl acetate copolymer and vinyl chloride -Selected from the group consisting of vinyl chloride-based thermoplastic elastomers such as vinylidene chloride copolymer, styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers You can use one or more of the

  As the method of mixing the particulate thermally expandable graphite, the particulate flame retardant, and the additive described above with the polyvinyl chloride resin, it is possible to adopt widely known methods. Specifically, a method by hot blending, a method by cold blending and the like can be mentioned.

<2. Piping system>
The pipe material of the present invention, which is made into the above, has a sufficient thermal expansion property and sufficient strength, and can be suitably used for a building having a plurality of floors including an apartment. Moreover, the pipe material of the present invention can be suitably used not only as a constituent material of a pipe main body but also as a constituent material of a pipe joint, and these pipes and / or joints are used. It is possible to construct a piping system.

  Although the embodiments of the present invention have been described above, the present invention is not limited to these examples, and it is needless to say that the present invention can be practiced in various forms without departing from the scope of the present invention.

  Hereinafter, the embodiments of the present invention will be more specifically described based on examples, but the present invention is not limited to these.

(Example and Comparative Example)
Based on the composition shown in Table 1 below, roll knead with an 8-inch mixing roll (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) for 3 minutes at 190 ° C., and press molding for 4 minutes with a 200 ° C. press (manufactured by Toho Machinery Co., Ltd.) Test pieces of each Example and Comparative Example having a thickness of 3 mm were produced.

Tensile Strength Evaluation Test According to the tensile test method (JIS K7113) of plastic, the tensile yield strength of each example and comparative example was measured at 5 mm / min. The measurement atmosphere at this time was 23 ° C. The tensile yield strength f (MPa) is calculated by the following formula, assuming that the maximum load until the test piece breaks is P (N) and the cross-sectional area of the test piece is S (mm ² ), and the tensile yield strength If it was 42 (MPa) or more, it was judged that there was no problem in practical use.
Tensile yield strength: f = P / S

Expansion magnification evaluation test A test piece made into a plate shape by a roll press is cut out in a rectangular parallelepiped shape, and thickness, longitudinal and lateral three points are measured with a caliper. Then, the test piece of each Example and comparative example was put into the electric furnace heated up to 950 degreeC for 4 minutes, and was expanded. Then, it took out from the electric furnace and allowed to cool at normal temperature. Measure the thickness, length and width of the test piece after expansion after cooling with a caliper and calculate the expansion ratio R by the following equation, and if the expansion ratio R is 10 or more, it has a thermal expansion coefficient sufficient for practical use It was judged.
Expansion ratio: R = (a ₁ b ₁ c ₁ ) / (a ₀ b ₀ c ₀ )
a ₀ : Specimen thickness before expansion (mm)
b ₀ : Length of test piece before expansion (mm)
c ₀ : Specimen length before expansion (mm)
a ₁ : Specimen thickness after expansion (mm)
b ₁ : Specimen length after expansion (mm)
c ₁ : Lateral length of test specimen after expansion (mm)

  As shown in Table 1 below, it was confirmed that the test pieces of each example had excellent properties in both strength and expansivity. On the other hand, it was confirmed that the test pieces of Comparative Examples 1 and 2 are practically insufficient in any of the strength and the expansibility.

Claims (4)

A polyvinyl chloride resin, 10 to 20 parts by mass of thermally expandable graphite particles in an amount of 100 to 20 parts by mass of the polyvinyl chloride resin, and aluminum hydroxide particles,
A ratio (B / A) of an average particle size (A) of the particulate thermally expandable graphite to an average particle size (B) of the particulate aluminum hydroxide is characterized by 0.0015 to 0.0065. , Tube material.   The pipe material according to claim 1, wherein the particulate aluminum hydroxide is contained in an amount of 1 to 5 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin.   The pipe material according to claim 1 or 2, wherein an average particle diameter (A) of the particulate thermally expandable graphite is 110 to 1000 μm.   The piping system comprised by the pipe material in any one of Claims 1-3.