JP2005307000A - Pipe material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new pipe material composed of a polycarbonate resin composition. <P>SOLUTION: The pipe material is composed of a polycarbonate-based resin composition comprising (A-1) a polycarbonate resin or an alloy of (A-1) a polycarbonate resin and (A-2) an thermoplastic resin containing an aromatic ring in the main chain except the polycarbonate resin. The thermoplastic resin (A-2) comprises one or more kinds of resins selected from the group consisting of a polymer composed of (a) an aromatic vinyl monomer component as a constituent component of the polymer, a copolymer composed of (a) an aromatic vinyl monomer and (b) a vinyl cyanide monomer component as constituent components of the copolymer and a copolymer composed of (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component and (c) a rubber-like polymer as constituent components of the copolymer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel pipe material made of a polycarbonate resin composition.

Conventionally, a vinyl chloride pipe has been used as a communication pipe, a normal type for electric power, and a heat-resistant pipe for electric power.
On the other hand, the vinyl chloride tube is a relatively light material and has a feature that it is easy to process. Moreover, strength, heat resistance, etc. were insufficient. For this reason, impact modifiers, processing aids, heat stabilizers are added, processing methods are improved, and the like, and they are now widely used as various pipes.

  Since such polyvinyl chloride contains chlorine, it may generate harmful chlorinated compounds depending on the incineration method when it is discarded. Although heavy metal stabilizers and vinyl chloride monomers contained in vinyl may elute and may contaminate the soil, they have environmental problems and may be difficult to recycle. The appearance was desired.

The present invention has been made to solve the problems associated with the prior art, and an object of the present invention is to provide a pipe material having characteristics equivalent to those of a polyvinyl chloride pipe.
(1) The pipe material according to the present invention is
(A-1) Polycarbonate resin, or
It comprises a polycarbonate resin composition containing an alloy of (A-1) a polycarbonate resin and (A-2) a thermoplastic resin having an aromatic ring in the main chain other than the polycarbonate resin.
(2) The thermoplastic resin (A-2) is
(a) a polymer containing an aromatic vinyl monomer component as a constituent of the polymer;
a copolymer comprising (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component as a constituent of the copolymer;
a copolymer comprising (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer as a constituent of the copolymer;
It is comprised from the composition containing 1 or more types of resin selected from the group which consists of.
(3) The thermoplastic resin (A-2) is at least one resin selected from the group consisting of ABS resin, AES resin, ACS resin, AAS resin and polystyrene resin.
(4) The composition further contains a phosphate ester.
(5) The composition further contains an anti-drip agent.
(6) When the total composition is 100% by weight, (A-1) 30 to 100% by weight of the polycarbonate resin, and (A-2) a thermoplastic resin having an aromatic ring in the main chain other than the polycarbonate resin. 0
70% by weight, 0 to 5% by weight of anti-drip agent and 0 to 30% by weight of phosphate ester.
(7) The composition further comprises a rubbery substance, fibrous filler, non-fibrous filler, olefin polymer, alicyclic saturated hydrocarbon resin, higher fatty acid ester, terpene, wax, petroleum hydrocarbon, aromatic And at least one additive selected from the group consisting of group hydrocarbon petroleum resins, polyoxyalkylenes, antistatic agents, antioxidants, ultraviolet absorbers and pigments.

  In the present invention, conventionally, polycarbonate-based materials have not been used for pipe applications, but according to the present invention, it has been found that they can be suitably used as pipe materials. The polycarbonate-based materials used are extremely heat-stable and do not contain heavy metal stabilizers or vinyl chloride monomers, so they do not cause environmental problems and are extremely flame-retardant. And no harmful gas is generated during combustion.

Hereinafter, the pipe material according to the present invention is a molded article made of the polycarbonate resin composition shown below.
Polycarbonate resin composition The polycarbonate resin composition according to the present invention comprises (A-1) a polycarbonate resin, or
It contains an alloy of (A-1) polycarbonate resin and (A-2) thermoplastic resin having an aromatic ring in the main chain other than polycarbonate resin.

[Polycarbonate resin (A-1)]
The polycarbonate resin (A-1) used in the present invention is an aromatic homopolycarbonate or an aromatic copolycarbonate obtained by reacting an aromatic dihydroxy compound and a carbonate precursor.

  The carbonate-based resin generally has a repeating structural unit represented by the following formula (1).

(In the above formula, A is a divalent residue derived from an aromatic dihydroxy compound)
Examples of the aromatic dihydroxy compound include mononuclear or polynuclear aromatic compounds containing two functional hydroxyl groups, each of which is directly bonded to the carbon atom of the aromatic nucleus.

  Specific examples of the aromatic dihydroxy compound include bisphenol compounds represented by the following formula (2).

Specific examples of the aromatic dihydroxy compound represented by the formula (2) include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis ( Four-
Hydroxyphenyl) propane (so-called bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2- Bis (4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2 -Bis (hydroxyaryl) alkanes such as (4-hydroxy-3,5-dibromophenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1- (4-hydroxyphenyl) cyclohexane, etc. Bis (hydroxyaryl) cycloalkanes; Dihydroxyaryl ethers such as 4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxy-3,3′-dimethylphenyl ether; 4,4′-dihydro Dihydroxydiaryl sulfides such as sidiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide; 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone and the like, and the like, but are not limited thereto It is not a thing.

Of these aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferably used.
Moreover, the aromatic dihydroxy compound represented by following formula (3) can also be used as aromatic dihydroxy compounds other than said Formula (2).

(Wherein R ^f is independently a hydrocarbon group having 1 to 10 carbon atoms, 1 of the hydrocarbon group
The above is a halogenated hydrocarbon group substituted with a halogen atom, or a halogen atom, and p is an integer of 0 to 4)
Examples of such compounds include resorcin; and 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-t-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin, 2 Substituted resorcins such as 1,3,4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin; catechol; hydroquinone and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butyl Hydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3 , 5,6-tetrafluorohydroquinone, substituted hydroquinones such as 2,3,5,6-tetrabromohydroquinone, and the like.

  Moreover, as aromatic dihydroxy compounds other than said Formula (2), following Formula

2,2,2 ', 2'-Tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobi- [1H-
Indene] -7,7'-diol can also be used.
These aromatic dihydroxy compounds may be used alone or in combination of two or more.

Further, the polycarbonate may be linear or branched. There may also be a blend of linear polycarbonate and branched polycarbonate.
Such a branched polycarbonate is obtained by reacting a polyfunctional aromatic compound with an aromatic dihydroxy compound and a carbonate precursor. Representative examples of such polyfunctional aromatic compounds are described in U.S. Pat.Nos. 3,028,385, 3,334,154, 4,001,124 and 4,131,576, specifically 1,1,1- Tris (4-hydroxyphenyl) ethane, 2,2 ', 2 "-tris (4-hydroxyphenyl) diisopropylbenzene, α-methyl-α, α', α'-tris (4-hydroxyphenyl) -1,4 -Diethylbenzene, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) ) -Heptane-2,1,3,5-tri (4-hydroxyphenyl)
Examples include benzene, 2,2-bis- [4,4- (4,4′-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid and the like. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like are preferably used.

Intrinsic viscosity of this polycarbonate resin measured at 25 ° C. in methylene chloride is not particularly limited and is appropriately selected in view of the intended use and moldability, but is usually 0.26 dl / g or more. , Preferably 0.30 dl / g to 0.98 dl / g, more preferably 0.34 dl / g to 0.64 dl / g. When converted to a viscosity average molecular weight, it is usually 10,000 or more, preferably 12000. It is desirable to be in the range of ˜50000, more preferably 14,000 to 30,000. A plurality of polycarbonate resins having different intrinsic viscosities can be mixed and used. The viscosity average molecular weight (Mv) was determined by measuring the intrinsic viscosity (intrinsic viscosity [η]) at 20 ° C. in methylene chloride, and the Mark-Houwink viscosity formula:
[Η] = K × (Mv) ^a (K = 1.23 × 10 ⁻⁴ , a = 0.83)
Was obtained by calculation.

The polycarbonate resin used in the present invention is produced by a known production method. For example,
(i) A method of synthesizing polycarbonate by transesterification of an aromatic dihydroxy compound and a carbonate precursor (for example, carbonic acid diester) in a molten state (melting method),
(ii) A method (interface method) of reacting an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) in a solution can be mentioned.

About these production methods, for example, JP-A-2-175723, JP-A-2-124934, U.S. Pat.Nos. 4,001,184, 4,238,569, 4,238,597, and 4,474,999. It is described in the description.

In the present invention, a thermoplastic resin (A-2) other than polycarbonate may be used together with such a polycarbonate-based resin (A-1).
[Thermoplastic resins other than polycarbonate resins (A-2)]
In the present invention, a thermoplastic resin other than the polycarbonate resin (simply referred to as a thermoplastic resin) may be included together with the polycarbonate. As the thermoplastic resin (A-2), any resin other than polycarbonate and containing an aromatic ring in the main chain can be used without particular limitation.

Preferably,
(i) (a) a polymer comprising an aromatic vinyl monomer component as a constituent of the polymer;
(ii) a copolymer comprising (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component as constituents of the copolymer;
(iii) a copolymer comprising (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer as a constituent component of the copolymer;
At least one resin selected from the group consisting of:

Any of the resins shown above can be purchased as a commercial product, and the production method is not particularly limited.
(Co) polymer (i)
First, (a) the polymer (i) containing an aromatic vinyl monomer component will be described.

(a) As the aromatic vinyl monomer component, for example, styrene, α-methylstyrene, o-, m-
Or p-methylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene,
Examples thereof include ethyl styrene and vinyl naphthalene. The polymer used in the present invention may be a homopolymer of these or a copolymer of two or more monomers. Among these monomers, styrene or α-methylstyrene is preferable. Preferable examples of the polymer include styrene resin.

  There is no restriction | limiting in particular about the manufacturing method of this (co) polymer, The usual well-known methods, such as block polymerization, solution polymerization, block suspension polymerization, suspension polymerization, and emulsion polymerization, are used. It can also be obtained by blending separately polymerized resins.

Copolymer (ii)
Next, the copolymer (ii) containing (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component will be described.

Examples of the aromatic vinyl monomer component (a) are the same as those described above.
Examples of the (b) vinyl cyanide monomer component include acrylonitrile, methacrylonitrile and the like, and these components may be contained in one or more kinds in the copolymer.

The composition ratio (a) / (b) is not particularly limited and is selected according to the application. (a) / (b) is preferably such that (a) is 95 to 50% by weight and (b) is 5 to 50% by weight, more preferably (a) is 92% by weight.
(B) is 8 to 35% by weight with respect to -65% by weight.

Preferable examples of the polymer include a SAN resin (styrene-acrylonitrile copolymer). There are no particular restrictions on the method for producing this copolymer, and any conventional known method such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, or emulsion polymerization may be used. It can also be obtained by blending separately copolymerized resins.

Copolymer (iii)
Next, a copolymer containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer will be described. Examples of the (a) aromatic vinyl monomer component and the (b) vinyl cyanide monomer component include the same examples as described above.

(c) Examples of rubbery polymers include polybutadiene, polyisoprene, random copolymers and block copolymers of styrene-butadiene, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, and butadiene-isoprenes. Diene rubber such as copolymer, random copolymer and block copolymer of ethylene-propylene, copolymer of ethylene and α-olefin, ethylene-unsaturation such as ethylene-methacrylate, ethylene-butyl acrylate Copolymer with carboxylic acid ester, acrylic ester-butadiene copolymer, acrylic elastic polymer such as butyl acrylate-butadiene copolymer,
Copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene non-conjugated diene terpolymers such as ethylene-propylene-hexadiene copolymer, butylene-isobrene copolymers, chlorinated polyethylene, etc. These are used alone or in combination of two or more. Preferred rubbery polymers are ethylene-propylene non-conjugated diene terpolymers, diene rubbers and acrylic elastic polymers, particularly preferably polybutadiene and styrene-butadiene copolymers, in which the styrene content is It is preferable that it is 50 weight% or less.

Such a copolymer (iii) is preferably a graft copolymer obtained by graft copolymerization of other components in the presence of (c) a rubbery polymer. In particular, ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer), AAS resin (acrylonitrile- Acrylic elastic body-styrene copolymer) and a resin selected from these are preferred.

The weight average molecular weight (Mw) of the (co) polymer (i), the copolymers (ii) and (iii) is preferably 30,000 to 200,000, more preferably 30,000 to 150,000, particularly preferably 30,000 to 110,000. Is desirable.

In addition to the above components (a), (b), and (c), the (co) polymer (i), the copolymers (ii), and (iii) include monomers that are copolymerizable with these components. The monomer may be copolymerized as long as the object of the present invention is not impaired. Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β-unsaturated carboxylic acid esters such as (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; And imide compounds of α, β-unsaturated dicarboxylic acid such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, No-chlorophenylmaleimide, etc. Used in seeds or two or more.

There is no restriction | limiting about the manufacturing method of this copolymer, It manufactures by block polymerization, block suspension polymerization, and solution polymerization.
The thermoplastic resin (A-2) used in the present invention is preferably a copolymer (i) or (iii),
Furthermore, HIPS (high impact polystyrene), ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer) ), A resin selected from AAS resins (acrylonitrile-acrylic elastomer-styrene copolymer) is preferable, and ABS resins and HIPS are particularly preferable.

The resin composition used in the present invention is very excellent in thermal stability, and even if it is a regenerated product recovered from a molded product once molded, its mechanical properties hardly change, and the initial value Hold. Further, since the resin viscosity simply changes proportionally with the rise or fall of the resin temperature, it is easy to produce a good molded article even in different molding methods such as injection molding and extrusion molding.
[Phosphate ester]
As phosphate ester, the phosphate ester compound represented, for example by the following general formula (c-1) can be used conveniently.

(Here, Q ₁ , Q ₂ , Q ₃ , and Q ₄ independently represent an alkyl group having 1 to 6 carbon atoms. M ₁ , m ₂
, M ₃ and m _{4 each} independently represents an integer of 0 to 3. n2 represents an integer of 0 to 3. Z represents a group containing an aromatic ring. )
Among the phosphoric acid ester compounds, those in which n2 is an integer of 1 to 3 and Z in the general formula (c-1) is represented by the following general formulas (c-2) to (c-4) are preferable.

(In the formula, R ₃ represents a methyl group, n ₃ represents an integer of 0 to 2. R ₄ and R ₅ represent a methyl group, R ₆ ,
R ₇ independently represents a methyl group or hydrogen. n ₄ and n ₅ independently represent an integer of 0 to 2. R ₈ and R ₉ represent a methyl group. )
(C) In the phosphate compound (c-1), n2 is 0, the total number of carbon atoms of the substituents represented by Q ₁ , Q ₂ , and Q ₄ is 12 to 27, m ₁ , M ₂ and m ₄ are independently 1 to 3
A phosphoric acid ester compound which is an integer of is also preferred. Specific examples of the phosphoric ester compound include triphenyl phosphate, trisnonyl phenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis [di (2,6-dimethylphenyl) phosphate], 2,2- Examples include, but are not limited to, bis {4- [bis (phenoxy) phosphoryloxy] phenyl} propane, 2,2-bis {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane, and the like.

Although the above phosphoric acid ester functions as a flame retardant, it may further contain other flame retardants.
In addition to the above, as the phosphorus-based flame retardant, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, etc. Phosphate ester flame retardant, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphonate, diphenyl-4-hydroxy- 3,5-dibromobenzyl phosphonate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2 3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, and bis (chloropropyl) monooctyl phosphate hydroquinonyl diphenyl phosphate, phenylnonylphenylhydroquinonyl phosphate, phenyldi Use halogen-containing phosphoric acid (or phosphonic acid) ester flame retardants such as nonylphenyl phosphate, tetraphenylresorcinol diphosphate, tetracresyl bisphenol A diphosphate, tris (nonylphenyl) phosphate; polyphosphate; red phosphorus, etc. You can also.

You may use these in mixture of 2 or more types.
[Anti-drip agent]
The composition according to the present invention may contain an anti-drip agent. The anti-drip agent is an additive having a function of suppressing drip (dripping) during combustion, and a known one can be used.

A resin composition containing such an anti-drip agent is particularly excellent in flame retardancy.
Among such polytetrafluoroethylenes (PTFE), those having excellent dispersibility, such as those obtained by emulsifying and dispersing PTFE in a solution such as water, and resins typified by polyphenylene ether and styrene-acrylonitrile copolymers. What encapsulated PTFE is preferable because it gives a good surface appearance to a molded article made of a polyphenylene ether composition.

  In the case where PTFE is emulsified and dispersed in a solution such as water, there is no particular limitation. However, PTFE having an average particle size of 1 micron or less is preferable, and 0.5 micron or less is particularly preferable.

Specific examples of such commercially available PTFE include Teflon (registered trademark) 30J (trademark, Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-2C (trademark, Daikin Chemical Industries, Ltd.), Aflon AD1 (Trademark, Asahi Glass Co., Ltd.).

  Such polytetrafluoroethylene can also be produced by a known method (see US Pat. No. 2,393,967). Specifically, using a free radical catalyst such as sodium peroxydisulfate, potassium or ammonium, in an aqueous solvent under a pressure of 100 to 1000 psi, a temperature condition of 0 to 200 ° C., preferably 20 to 100 ° C. Then, polytetrafluoroethylene can be obtained as a white solid by polymerizing tetrafluoroethylene.

Such polytetrafluoroethylene has a molecular weight of 100,000 or more, preferably about 200,000 to 3,000,000.
For this reason, the drip at the time of combustion is suppressed in the resin composition containing polytetrafluoroethylene. Furthermore, when polytetrafluoroethylene and a silicone resin are used in combination, drip can be further suppressed and combustion time can be shortened as compared with the case where only polytetrafluoroethylene is added.

The composition used in the pipe material of the present invention has (A-1) 30 to 100% by weight of the polycarbonate resin and (A-2) a main chain other than the polycarbonate resin when the total is 100% by weight. It is desirable to contain a thermoplastic resin having a group ring in an amount of 0 to 70% by weight, an anti-drip agent in an amount of 0 to 5% by weight, and a phosphate ester in an amount of 0 to 30% by weight. (A-1) 50-100% by weight of the polycarbonate resin, (A-2) 0-50% by weight of the thermoplastic resin having an aromatic ring in the main chain other than the polycarbonate resin, It is desirable to contain 3% by weight and 0 to 20% by weight of phosphate ester.

[Other ingredients]
If necessary, rubbery substances, fibrous fillers, non-fibrous fillers, olefin polymers, alicyclic saturated hydrocarbon resins, higher fatty acid esters, terpenes, waxes, petroleum hydrocarbons, aromatic hydrocarbons It may contain at least one additive selected from the group consisting of petroleum petroleum resins, polyoxyalkylenes, antistatic agents, antioxidants, ultraviolet absorbers, and pigments.

  As the rubber-like substance, a polymer having a glass transition temperature of −100 ° C. or more and 50 ° C. or less, or a copolymer obtained by copolymerizing the polymer is used. Specific examples include isoprene, butadiene, olefin, polyester elastomer, and acrylic. These may use homopolymers, but can also be used as copolymers if necessary.

Of these, butadiene-based and olefin-based ones are used for general purposes. As the butadiene-based copolymer, a styrene-butadiene block copolymer, which is a copolymer with styrene, or a hydrogenated product thereof is used.

Furthermore, ternary copolymers with acid components are also useful. Specifically, acrylic acid-butadiene-styrene copolymers, carboxylic acid / carboxylic acid anhydride-containing acid compounds-butadiene-styrene copolymers, etc. Is mentioned.

As the olefin rubber-like substance, an ethylene-based or propylene-based material is generally used, but an ethylene-propylene copolymer in which both are combined can also be used.
Further, similarly to the butadiene rubber-like substance, an olefin rubber component modified with an acid component is also useful, and an epoxy group-containing olefin rubber component may also be used.

  A fibrous filler having a so-called aspect ratio of 2 to 100 is preferable although it depends on the degree of the purpose of reinforcement of the molded article used according to the present invention. Specific examples include glass fiber, hollow glass fiber, carbon fiber, hollow carbon fiber, titanium oxide whisker, and fibrous wollastonite. Non-fibrous fillers are widely used additives because they can improve strength and dimensional stability at the same time. There are various shapes such as plate, granular, and amorphous. Specific examples include talc, mica, clay, silica, glass flakes, glass beads, and a hollow filler.

The filler may be used alone or in combination of two or more.
Olefin polymers are useful in improving chemical resistance and mold release during molding. Homopolymers such as polyethylene, polypropylene and polybutene may be used alone or in combination depending on the purpose. Also, there are high-density type, low-density type, chain type, and branched type in the production method, and any of them can be usefully used. It can also be used as a copolymer with other compounds. For example, a carboxylic acid group-containing compound such as maleic acid or citric acid or its acid anhydride, a copolymer with an acid compound containing an acrylic acid group such as an acrylic ester, and the like can also be used.

This is a hydrogenated product of aromatic hydrocarbon resin, and generally used as aromatic hydrocarbon resin is C9 hydrocarbon resin, C5 / C9 hydrocarbon resin, indene-coumarone resin, vinyl aromatic resin, terpene
A vinyl aromatic resin etc. are mentioned. A higher hydrogenation rate is better, but at least 30% or more is desirable. When there are many aromatic components, since other physical properties are impaired, it is not preferable.

As the terpenes, terpenes made from α-pinene, β-pinene and dipentenes are used. Those modified with aromatic hydrocarbons (phenol, bisphenol A, etc.) or hydrogenated terpenes can also be used effectively. As the waxes, olefin wax, montan wax and the like are generally used, and among them, low molecular weight polyethylene is generally used. Liquid petroleum fractions are preferably used as petroleum hydrocarbons. As the aromatic hydrocarbon petroleum resin, an aromatic hydrocarbon fraction polymer represented by C9 carbons is used.
As the polyoxyalkylene, polyalkylene glycol such as polyethylene glycol and polypropylene glycol is generally used.

  The antistatic agent generally has the effect of exerting its effect by imparting hygroscopicity to the surface of the molded body. There are a case of using it as an additive in the resin and a method of applying it as a secondary process such as coating. As additives, those that promote the adsorption of water molecules such as the above-mentioned polyalkylene glycols and sulfonic acid group-containing compounds are used.

  Examples of ultraviolet absorbers include hindered amines, benzotriazoles, benzophenones, and epoxies. Only one type may be used, but further effects can be expected when used in combination.

  The addition amount of these other additives is not particularly limited, but is 0.01 to 70 parts by weight, preferably 0.1 to 50 parts by weight in total with respect to 100 parts by weight of the composition. It is desirable.

[Antioxidant]
Specific examples include trialkyl phosphites, alkylaryl phosphites, and triaryl phosphites.

[Flame retardants]
Phosphorus, silicone, or metal salt flame retardants may be mentioned.
As the silicone-based flame retardant, a polymer obtained by polymerizing at least one of the following four siloxane units (M unit, D unit, T unit, Q unit) is used.

R is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group, an alkenyl group such as a vinyl group, a propenyl group or a butenyl group, an aryl group such as a phenyl group, a biphenyl group or naphthalene, or a cyclohexyl group. , A cycloalkyl group such as a cyclooctyl group, or a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom, a cyano group, an amino group, or the like, such as a chloromethyl group, 3,3,3-trifluoropropyl Group,
Examples include cyanomethyl group, γ-aminopropyl group, N- (β-aminoethyl) -γ-aminopropyl group, etc., from the viewpoint of synthesis, availability and safety, methyl group, ethyl group, phenyl group Is preferred.

In particular, when an aryl group (phenyl group) is contained as R, the flame retardant effect can be improved.
R may contain an alkoxy group, and specifically, a methoxy group, an ethoxy group, or a propoxy group is preferably used.

The weight average molecular weight of such a silicone flame retardant is 300 to 6000, preferably 3
It is desirable to be in the range of 00 to 4000. More preferably, it exists in the range of 300-2500. If the molecular weight is too low, after mixing with the resin composition, the organosiloxane tends to bleed on the surface of the molded article, and the flame retarding effect may be reduced. If the molecular weight is too high, the dispersibility of the organosiloxane in the resin becomes poor and it becomes difficult to move, so that the flame retardant effect may be reduced.

It is desirable that the alkoxy group-containing organosiloxane used in the present invention does not substantially contain silanol groups (SiOH).
As the metal salt flame retardant, an alkali (earth) metal salt of perfluoroalkanesulfonic acid represented by the following formula is used.

_{(C n F 2n + 1 -SO} 3) m -M
(Wherein n represents an integer of 1 to 10, M represents an alkali metal or alkaline earth metal, and m represents the same integer as the valence of M).

The alkali (earth) metal salt of perfluoroalkanesulfonic acid may be used alone or in combination of two or more.
Specific examples of such perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid. Perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid and the like, and those having 1 to 8 carbon atoms [number of n in the formula] are particularly preferable.

  Specific examples of the alkali metal or alkaline earth gold represented by M in the above formula include lithium, sodium, potassium, cesium and the like (more alkali metals), magnesium, calcium, strontium, barium and the like (more alkaline earths). Metal), and potassium is particularly preferable.

Such flame retardants may be used in combination of two or more.
Preparation of Resin Composition There is no particular limitation on the method for producing the resin composition used in the present invention, and a normal method can be used satisfactorily, and a normal melt mixing method is preferably employed. Although a small amount of solvent can be used, it is generally not necessary. As an apparatus, an extruder, a Banbury mixer, a roller, a kneader, etc. can be mentioned as an example. These devices can be operated batchwise or continuously. Moreover, the mixing order of components is not particularly limited.

  For example, when melt-kneading with an extruder or the like, all the components may be blended and kneaded, or one extruder may be provided with a plurality of feed ports to feed one or more types of components sequentially along the cylinder. May be. The resin composition obtained by melt kneading may be used immediately for production of the molded product according to the present invention, or after cooling and solidification to form pellets, powders, etc. May be added and melted again.

[Pipe material]
The pipe material according to the present invention is formed from the above composition. There is no particular limitation on the molding method, and known ones such as injection molding, extrusion molding, vacuum / compression molding, etc. are employed. In molding, the above-described composition or its raw material may be directly introduced into the molding machine and molded while mixing, or may be molded after pelletizing at one end. In general, the melting temperature of the composition used in the present invention is in the range of 200-290 ° C.

The melting of the resin is introduced into a single screw extruder or a conical or parallel counter twin screw extruder and molded.
Specifically, for example, as a twin screw extruder, one having a configuration comprising an extruder, a cylindrical die, a sizing former (with temperature control and vacuum), a vacuum water tank, a take-up machine, and a cutting machine is used. .

  The pipe material according to the present invention includes a straight pipe and a joint (joint). When molding a straight pipe, extrusion molding is usually employed, and when molding a joint, injection molding is employed.

  The shape of the pipe material (straight pipe) according to the present invention is appropriately selected according to the standard of use, but it is usually sufficient if the thickness is about 1 to 20 mm. Moreover, although the cross-sectional shape of the pipe material is usually a cylindrical shape, it may be a rectangular tube shape, a hexagonal tube shape or the like depending on the purpose of use.

Further, the outer diameter and the pipe length of the pipe material (straight pipe) are also appropriately selected according to the use standard. The size of the joint is appropriately selected according to the thickness of the straight pipe used.
Such a pipe material may have a single layer structure or a laminated structure of two or more layers, and in the case of a laminated structure of two or more layers, as long as at least one layer is made of the composition described above. Good. The other layers are not particularly limited as long as they are made of a highly flame-retardant resin.

The corrugated portion may be formed on the outer peripheral surface and / or the inner peripheral surface of the pipe material according to the present invention, and it is preferable in terms of flexibility to form the corrugated portion.
The pipe material according to the present invention as described above is excellent in heat resistance, flame retardancy, and strength, and has the same characteristics as the conventionally used polyvinyl chloride pipe material.

For example, the Biccat softening point measured in accordance with JIS K7206 is 80 ° C. or higher, and is extremely excellent in heat resistance.
In addition, the pipe material according to the present invention has characteristics of high tensile strength and high impact strength.

  For this reason, when the pipe material according to the present invention is used, even if a high power amount is transmitted as in an urban area, the pipe material is not deformed or burned by the generated heat. Moreover, since it is excellent in impact resistance, it has sufficient resistance to pressure, vibration, and impact from the ground surface.

  And since it is formed from the above polycarbonate-type resin composition, the pipe material which concerns on this invention itself is light, and can also perform field work, such as piping, a connection, and a cutting | disconnection, easily. For this reason, when the pipe material according to the present invention is used, the working efficiency can be enhanced and the safety of the work can be enhanced.

In addition, as described above, the composition used does not contain harmful substances such as chlorine, and therefore does not pollute the environment. Furthermore, it does not corrode molding machines or dies.
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

In the examples and comparative examples, the following resin components and additives were used.
Component (A-1) Polycarbonate: Polycarbonate of bisphenol A LEXAN 141 (trade name; manufactured by Nippon GE Plastics Co., Ltd.) was used. The intrinsic viscosity of the polycarbonate measured at 20 ° C. in methylene chloride was 0.50 dl / g, and Mv = about 23,000 (calculated value).
Component (A-2): Santac AT-07 (trademark; manufactured by Nippon A & L Co., Ltd.) was used as an ABS resin.

Component (B): Resorcinol diphosphate: CR733S (trademark; manufactured by Daihachi Chemical Co., Ltd.) was used as the phosphate ester (FR in Table 1).
Component (C): Polytetrafluoroethylene (Polyflon PTFE D-2C (trademark; manufactured by Daikin Industries, Ltd.)) was used as an anti-drip agent.

Component (D): ADK STAB MK2112 (trademark; manufactured by Asahi Denka Kogyo Co., Ltd.) was used as a phosphite stabilizer.
Examples 1-4, Comparative Examples 1 and 2
Using each of the above-mentioned materials, the composition shown in Table 1 (all parts by weight) was extruded by a twin-screw extruder under extrusion conditions of a screw rotation speed of 200 rpm and a barrel set temperature of 270 to 280 ° C., and cut into pellets Manufactured.

  The pellets thus produced were introduced into a twin screw extruder, and each pellet was extruded to produce a pipe material having an outer diameter of 150 mm, an inner diameter of 130 mm, a wall thickness of 10 mm, and a total length of 5 m. The twin-screw extruder used is composed of an extruder, a cylindrical die, a sizing former (with temperature control and vacuum), a vacuum water tank, a take-up machine, and a cutting machine.

  The pellets thus produced were introduced into a twin screw extruder, and each pellet was extruded under the conditions shown in Table 2 to produce a pipe material having an outer diameter of 150 mm, an inner diameter of 130 mm, a wall thickness of 10 mm, and a total length of 5 m. The twin-screw extruder used is composed of an extruder, a cylindrical die, a sizing former (with temperature control and vacuum), a vacuum water tank, a take-up machine, and a cutting machine.

Tensile test Two specimens shown in FIG. 1 were cut out from the obtained protective piping, and the tensile strength was evaluated according to JIS K 7113.

Heat resistance (Biccad softening point temperature)
A sample of an appropriate size was cut out from the protective piping and evaluated under a load of 49 N (5 kgf) according to JIS K 7206.

From the obtained pipe material, a test piece having a width of 10 mm and a length of 50 mm is cut out, and one end thereof is attached to a stand as shown in FIG. 2, and a flame bunsen burner having a length of 15 mm is attached to the test piece. Place under the free end and let stand for 1 minute so that the flame tip reaches the bottom of the specimen. After 1 minute, the flame was removed and it was examined whether the flame of the test piece disappeared naturally. (Those that disappeared naturally were accepted, and those that did not disappear were rejected.)
The results are also shown in Table 1.

  Table 1 shows that the pipe material of the present invention has high tensile strength, excellent heat resistance, and has the same characteristics as conventional polyvinyl chloride, and is effective as a substitute for polyvinyl chloride piping. did.

The schematic of the sample for a tensile test in this invention is shown. The schematic of the flame-retardant evaluation apparatus in this invention is shown.

Claims (7)

(A-1) Polycarbonate resin, or
A pipe material comprising a polycarbonate-based resin composition containing an alloy of (A-1) a polycarbonate resin and (A-2) a thermoplastic resin having an aromatic ring in the main chain other than the polycarbonate resin. Thermoplastic resin (A-2)
(a) a polymer containing an aromatic vinyl monomer component as a constituent of the polymer;
a copolymer comprising (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component as a constituent of the copolymer;
a copolymer comprising (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer as a constituent of the copolymer;
The pipe material according to claim 1, wherein the pipe material is composed of a composition containing one or more kinds of resins selected from the group consisting of: The pipe according to claim 2, wherein the thermoplastic resin (A-2) is at least one resin selected from the group consisting of ABS resin, AES resin, ACS resin, AAS resin, and polystyrene resin. material.   The pipe material according to any one of claims 1 to 3, wherein the composition further contains a phosphate ester.   The pipe material according to claim 1, wherein the composition further contains an anti-drip agent. When the total composition is 100% by weight, (A-1) 30 to 100% by weight of the polycarbonate resin, and (A-2) 0 to 70% of the thermoplastic resin having an aromatic ring in the main chain other than the polycarbonate resin.
The pipe material according to any one of claims 1 to 5, wherein the pipe material contains 0 to 30% by weight, 0 to 30% by weight of a phosphate ester, and 0 to 5% by weight of an antidrip agent. The composition further comprises a rubbery substance, a fibrous filler, a non-fibrous filler, an olefin polymer, an alicyclic saturated hydrocarbon resin, a higher fatty acid ester, a terpene, a wax, a petroleum hydrocarbon, an aromatic hydrocarbon. 7. At least one additive selected from the group consisting of petroleum petroleum resins, polyoxyalkylenes, antistatic agents, antioxidants, ultraviolet absorbers, and pigments is included. The pipe material described.