WO2004035287A1 - Procédé et dispositif de fabrication d'élément de tuyau - Google Patents

Procédé et dispositif de fabrication d'élément de tuyau Download PDF

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Publication number
WO2004035287A1
WO2004035287A1 PCT/JP2002/010752 JP0210752W WO2004035287A1 WO 2004035287 A1 WO2004035287 A1 WO 2004035287A1 JP 0210752 W JP0210752 W JP 0210752W WO 2004035287 A1 WO2004035287 A1 WO 2004035287A1
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WO
WIPO (PCT)
Prior art keywords
light
pipe member
curing
resin
layer
Prior art date
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PCT/JP2002/010752
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English (en)
Japanese (ja)
Inventor
Kazuo Otani
Masashi Takiya
Atsushi Umino
Satoshi Makihara
Tetsuya Itagaki
Kazuaki Ishikawa
Yoshiyuki Saido
Original Assignee
Showa Highpolymer Co., Ltd.
Misawa Hobas Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Highpolymer Co., Ltd., Misawa Hobas Co., Ltd. filed Critical Showa Highpolymer Co., Ltd.
Priority to PCT/JP2002/010752 priority Critical patent/WO2004035287A1/fr
Priority to AU2002335277A priority patent/AU2002335277A1/en
Publication of WO2004035287A1 publication Critical patent/WO2004035287A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • B29C41/042—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould by rotating a mould around its axis of symmetry
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/36—Feeding the material on to the mould, core or other substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/22—Making multilayered or multicoloured articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers

Definitions

  • the present invention relates to a method for manufacturing a pipe member, a pipe member obtained therefrom, and a manufacturing apparatus for the pipe member. More specifically, the present invention relates to a method for efficiently producing a multilayer pipe member comprising a plastic, an inorganic filler and a fiber reinforced material by a combination of a centrifugal molding method and light irradiation, a multilayer pipe member obtained by this method, The present invention relates to an apparatus for manufacturing the multilayer pipe member.
  • a centrifugal molding method is known as one of the molding methods of the FRPM tube.
  • a mold in which the outer diameter of the pipe is fixed is rotated at a high speed, fibers, curable resin, aggregate, etc. are charged by a feeder (feeder), and the outer surface is formed by centrifugal force and heating.
  • This is a method for forming the FRP layer, the intermediate layer, the inner FRP layer, and the like.
  • the product is of high quality, with a maximum of about 70 G of gravity applied by high-speed rotation, making it difficult for air holes to be formed.
  • the structure consists of an outer protective layer, an outer FRP layer, a middle layer, an inner FRP layer, and an inner layer. Often it is a protective layer.
  • a conventional centrifugal molding method is described in, for example, Japanese Patent Application Laid-Open No. 2-11832 / 1990.
  • unsaturated polyester resin is mainly used as the thermosetting resin, and curing is performed by radical polymerization using a peroxide catalyst system.
  • cobalt is mixed in the resin to accelerate the curing, and when the resin is put into the rotating cylindrical mold, methyl-ketyl ketone peroxyside or the like is mixed at the tip of 50 to 8 Although it is heated and cured at about 0 ° C, it takes a long time to cure, and a process of removing the mold and performing a hard cure with warm water is essential.
  • molding by heat curing has limitations on the molding time and the shortening of the molding process, and it is difficult to further improve the molding cycle.
  • it is necessary to increase the degree of hardening of the inner surface protective layer because the corrosion resistance of the inner surface protective layer is particularly problematic. It was difficult to produce efficiently by the heating molding method.
  • An object of the present invention is to provide a method for efficiently producing a pipe member by a centrifugal molding method, and an apparatus used for the method. Disclosure of the invention
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the object can be achieved by curing a molding material containing a curable resin by a combination of centrifugal molding and light irradiation. I found it.
  • the present invention has been completed based on such findings.
  • a curable resin or a molding material containing a curable resin and an inorganic filler and / or a fiber reinforced material is put into a rotating centrifugal mold for a pipe member, and light is applied under a centrifugal force.
  • the pipe member is made of a curable resin and an inorganic filler and / or a fiber reinforced material.
  • the pipe member mainly comprises an outer protective layer, an outer FRP layer, a mortar layer, an inner FRP layer, and a curable resin obtained by curing a molding material containing a curable resin and an inorganic filler and / or a fiber reinforced material.
  • the method for producing a pipe member according to the above (1) comprising an inner surface protective layer obtained by curing a molding material as a component, and forming all the layers by applying a single light irradiation while applying a centrifugal force.
  • the pipe member mainly comprises an outer protective layer, an outer FRP layer, a mortar layer, an inner FRP layer, and a curable resin obtained by curing a molding material containing a curable resin and an inorganic filler and / or a fiber reinforced material.
  • the method comprises the steps of: forming an inner protective layer formed by curing a molding material as a component; and applying the molding material to a rotating centrifugal molding die for a pipe member while irradiating light, and curing to form each layer.
  • the curable resin in the molding material is: (a) a photopolymerization initiator sensitive to at least one region of ultraviolet light, visible light, and near-infrared light; (b) a general formula (I)
  • R 1 to R 4 each independently represent a halogen atom, a hydrocarbon group, an acyl group, a silyl group, or a heterocyclic group, and Z represents a cation.
  • An apparatus for manufacturing a pipe member comprising: a mechanism for supplying each component constituting a molding material; and a light irradiation mechanism.
  • FIG. 1 is a schematic diagram of a light-curing centrifugal molding apparatus manufactured in an example.
  • FIG. 2 is a schematic diagram of the light irradiation device manufactured in the example.
  • the method for manufacturing a pipe member of the present invention is obtained by combining a conventional centrifugal molding method with a method of curing by irradiation with light.
  • a mold (form) in which the outer diameter of the pipe is fixed is rotated at high speed, fibers, curable resin, aggregates, etc. are fed by a feeder (feeder), and the centrifugal force
  • the method of forming an outer FRP layer, a mortar layer, an inner FRP layer, and the like by heating is combined with a method of curing by irradiating light to the manufacturing method of the present invention.
  • the curable resin or the curable resin A molding material containing a resin, an inorganic filler, and Z or a fiber reinforced material is poured into a rotating centrifugal molding die for a pipe member, and is cured by light irradiation with a centrifugal force applied thereto.
  • a pipe member is manufactured.
  • the method of curing by irradiation with light in the present invention means that a photocurable resin and / or a thermosetting resin is used, and the photocuring is performed by light irradiation or the heat curing is performed using heat by light irradiation. Is the way.
  • each component used in the molding material will be described.
  • a resin in a curable resin used for light curing and heat curing a radical polymerization of an unsaturated polyester resin, a butyl ester resin, a urethane (meth) acrylate resin, etc., which cures quickly. Sex resin.
  • the unsaturated polyester resin is a polymerizable monomer such as styrene, which is obtained by condensing a product (unsaturated polyester) obtained by an esterification reaction between a polyhydric alcohol and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid). It is dissolved in one and is described in "Polyester Resin Handbook” (Nikkan Kogyo Shimbun, published in 1988) or "Paint Glossary” (edited by Coloring Material Association, published in 1993). Resin.
  • the unsaturated polyester used as a raw material for the unsaturated polyester resin may be one produced by a known method. Specifically, a polybasic acid having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid or an anhydride thereof and fumaric acid, maleic acid, A polymerizable unsaturated polybasic acid such as itaconic acid or its anhydride is used as the acid component, and Glycol, propylene glycol, methylen glycol, dipropylene glycol,, '1,2-butanediol, 1,3-butanediol, 1,5-pentendiol, 1,6-hexanediol, 2-methyl-1- , 3—Pronondiol, 2,2—Dimethyl-1,3-propanediol, Cyclohexane-1,4, -Dimethanol, Ethy
  • Bull ester resin also called epoxyacrylate resin
  • a compound with a polymerizable unsaturated bond (Bullester) dissolved in a polymerizable monomer such as styrene which is called “Polyester Resin Handbook” (published by Nikkan Kogyo Shimbun, 1988) or This is a resin described in the “Paint Glossary” (edited by The Color Materials Association, published in 1993).
  • Bull ester used as a raw material of the bullet ester resin is manufactured by a known method, and an unsaturated monobasic acid such as acrylic acid or methacrylic acid is added to an epoxy resin.
  • Examples of the epoxy resin as a raw material include bisphenol diglycidyl ether and its high molecular weight homologues, and novolak type polyglycidyl ethers.
  • a dicarboxylic acid having no active unsaturated group for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, Sebacic acid and the like.
  • the unsaturated dicarboxylic acid include dicarboxylic acids having an active unsaturated group, such as fumaric acid, maleic acid, maleic anhydride, and itaconic acid.
  • Polyhydric alcohol components include, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanedole, 1,6-I-hexanediol, 2-Methyl_1,3-propanediol, 2,2-Dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, Bisphenol A ethylene oxide adduct And polyhydric alcohols such as propylene oxide adduct of bisphenol A.
  • Glycidyl methacrylate is a typical example of the ⁇ , S-unsaturated carboxylate having an epoxy group used in the production of the polyester (meta) acrylate.
  • the unsaturated polyester used for the unsaturated polyester resin and the vinyl ester used for the vinyl ester resin those having a relatively high degree of unsaturation are preferable, and the unsaturated group equivalent (e.g., per unsaturated group) Having a molecular weight of about 100 to 800. Those having an unsaturated group equivalent of less than 100 cannot be easily synthesized. On the other hand, when the unsaturated group equivalent exceeds 800, it is difficult to obtain a cured product having high hardness.
  • Urethane (meth) acrylate resin is a resin in which urethane (meta) acrylate is dissolved in a polymerizable monomer such as styrene.
  • the urethane (meth) acrylate used for the urethane (meth) acrylate resin is not particularly limited.
  • a reaction between a polyisocyanate and a polyhydroxy compound or a polyhydric alcohol is performed.
  • a radically polymerizable unsaturated group-containing oligomer which can be obtained by reacting a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing aryl ether compound after the reaction. Further, after reacting the hydroxyl group-containing (meth) acryl compound with the polyhydroxy compound or the polyhydric alcohol, the polyisocyanate may be further reacted.
  • polyisocyanate used as a raw material of the urethane (meta) acrylate include 2,4-tolylenedienyl succinate and its isomers, diphenylmethandiyl Sociate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl methane diisocyanate, naphthalene diisocyanate Refenyl Methane Lithocyanate, Banoc D-750, Chris Bon NK (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Test Module L (trade name: Sumitomo Bayer Corporation) Retan Co., Ltd.), Coronate L (trade name: Nippon Polyurethane Industry Co., Ltd.), Takenate D 102 (trade name) : Takeda Pharmaceutical Co., Ltd.), Isonate 144 L (trade name: Mitsubishi
  • polyhydroxy compound used as a raw material for the urethane (meta) acrylate examples include polyester polyol, polyether polyol, and the like.
  • glycerin-ethylene oxide Adduct glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethyleneoxy-doped propylene oxide adduct, trimethylolpropane-ethylenoxide adduct Trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylopropane L-Ethyleneoxy-d-propylene oxide adduct dipentaethritol-ethylene-oxide adduct, dipentaethritol-l-propylene oxide adduct, dipentaethritol-l-lute tetrahydrofuran adduct dip
  • polyhydric alcohols used as a raw material of the urethane (meth) acrylate include ethylene glycol, ethylene glycol, triethylene glycol, and polyethylene glycol.
  • One of these polyhydric alcohols may be used alone, or two or more of them may be used as appropriate.
  • the hydroxyl group-containing (meth) acrylic compound used as a raw material of the urethane (meta) acrylate is not particularly limited. Preference is given to lylic acid esters, specifically, for example, 2-hydroxyhydryl (meta) acrylate, 2-hydroxypropyl (meta) acrylate, 3-hydroxybutyl (meta) Acrylate, polyethylene glycol mono (meta) acrylate, polypropylene glycol mono (meta) acrylate And di (meth) acrylate of tris (hydroxyxethyl) isosianuric acid, and pentaethritol tri (meth) atalylate.
  • lylic acid esters specifically, for example, 2-hydroxyhydryl (meta) acrylate, 2-hydroxypropyl (meta) acrylate, 3-hydroxybutyl (meta) Acrylate, polyethylene glycol mono (meta) acrylate, polypropylene glycol mono (meta) acrylate And di (meth) acryl
  • Examples of the hydroxyl group-containing aryl compound that is used as necessary as a raw material of the above-mentioned ethane (meta) acrylate include, for example, ethylene glycol monoaryl ether and diethylene glycol. Coal monolinole ether, triethylen glycol monoalkyl ether, polyethylene glycol monoaryl ether, propylene glycol monoaryl ether, dipropylene glycol monoaryl ether, tripropylene glycol monoaryl ether, polypropylene glycol Lumonoaryl ester, 1,2—butylene glycol monoaryl ester, 1,3—butylene glycol monoaryl ether, hexylene glycol alcohol monoaryl ether, octylene glycol alcohol Examples thereof include, but are not particularly limited to, trimethylolpropanediyl ether, glycerindiyl cellulose, pentaethritol triaryl ether and the like.
  • Unsaturated polyester resins, butylester resins, urethane (meth) acrylate resins, and the like used in the present invention are usually the aforementioned unsaturated polyesters, vinyl esters, and urethane (meta) acrylates.
  • a styrene monomer blended with a resin or the like according to the present invention has a kneadability with a fiber reinforcing material and a filler when a composite material is produced. It is important to increase impregnation and to improve the hardness, strength, chemical resistance, water resistance, etc. of molded products.
  • Styrene-based monomers such as styrene, butyltoluene, dibutylbenzene, etc., methyl (meth) acrylate, ethyl (meth) acrylate, ethylene glycol (meta) acrylate, etc. It is also possible to use the polymerizable monomer in place of the one that does not impair the gist of the present invention.
  • the curable resin used as one component of the molding material is selected from the above-mentioned unsaturated polyester resin, vinyl ester resin, and urethane (meth) acrylate resin.
  • At least one containing at least one polymerization initiator selected from the following (a) a photopolymerization initiator, (b) a polymerization initiator, and (c) an organic peroxide catalyst Can be mentioned favorably.
  • light in the range from ultraviolet light to near-infrared light can be used, and it is particularly preferable to use light in the wavelength range of visible light and near-infrared light.
  • Ultraviolet light refers to light in the wavelength range from 280 to 380 nm
  • visible light refers to light in the wavelength range from 380 to 780 nm
  • near-infrared light refers to light in the wavelength range from 780 to 1200 nm.
  • a compound having photosensitivity in at least one region selected from an ultraviolet region, a visible region, and a near-infrared region can be used.
  • Examples of the ultraviolet polymerization initiator having photosensitivity in the ultraviolet region include benzoins, acetophenones, anthraquinones, thioxanthones, and benzophenones.
  • benzoin Derivatives such as benzoin, benzoin methyl ether, benzoin isopropyl ether, etc .; Derivatives such as 2,2-dimethoxy-2-phenylphenyltophenone, and derivatives of anthraquinones, such as 2-methylanthraquinone, 2-chloroanthraquinone, 2-ethylanthraquinone, and 2-tert-butylanthraquinone; Derivatives such as thioxanthone and 2,54-dimethylthioxanthone; benzophenones; benzophenone, 4-benzylyl 4'-methyldiphenylsulfide; and 4,4 'dichloromouth benzophenone , N
  • Curing using ultraviolet light is advantageous for drying the surface, but because of its low light transmittance, it is desirable to use a resin that has a relatively long wavelength, and preferably has a photosensitivity in a wavelength range of 300 nm or more.
  • a (bis) acyl phosphoxide photopolymerization initiator having photosensitivity even in the visible light region.
  • Specific examples of the (bis) isacylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine chloride, and 2,6-diphenylbenzoyl-diphenylphosphide. Phenylxide, 2,6—Dimethoxybenzoyl diphenyl phosphine, 2,3,5,6—Tetramethyl benzoyl diphenyl phosphine
  • 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 117, Chivas Special 5 manufactured by TI Chemicals Co., Ltd.) and bis (2,6-dimension) Toloxybenzoyl) 1,2,4,4-Trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) mixed at a ratio of 75% / 25% 0 (Ciba Specialty—Chemicals Co., Ltd.), 1-Hydroxy-cyclohexylfluoroe
  • TP ⁇ BASF Corporation
  • 2-hydroxy-1-2-methyl-1-phenylpropane-1-one trade name: Darocurll 73, Ciba Specialty Chemicals Co., Ltd.
  • 2, 4 , 6 Trimethylbenzoyldiphenylphosphinoxide (trade name: Lu5cirin TP0, manufactured by BASF Corporation) mixed at a ratio of 50% / 50%: D arocur 4 2 6 5 and the like.
  • Examples of visible light polymerization initiators having photosensitivity in the visible light region include “Surface”, Vol. 27 (7), pp. 548 (1989), Campaquinone, Benzyl, Trimethylbenzoyldiphenylphosphine Oxide, Methylthioxanthone, and Bispentazione described in the 3rd Annual Meeting of the Polymer Material Forum, 1 BP 18 (1994). Alone such as phenyltitanium di (pentafluorophenyl)
  • organic peroxides / dyes In addition to the visible light polymerization initiator, organic peroxides / dyes, difuninyl donium salts / dyes, bimidazole / keto compounds, hexylbiimidazole compounds / hydrogen donating compounds Mercaptobenzothiazole / thiopyridium salt system, metal arene / cyanine dye system, and hexaryl ruby 10 imidazole / radical generator system described in Japanese Patent Publication No. 45-377377. And other known complex initiators and (bis) acylphosphinoxide compounds.
  • Examples of the near-infrared light polymerization initiator having photosensitivity in the near-infrared light region include a cationic dye having an absorption in the near-infrared light region represented by the general formula (1II),
  • D + is at least a kind of methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane or pyridium dye cation having sensitivity to visible light or near infrared light, A— represents various anions.
  • R 1 to R 4 each independently represent a halogen atom, a hydrocarbon group 25, an acyl group, a silyl group or a heterocyclic group, and Z represents a cation.
  • a hydrocarbon group 25 an acyl group, a silyl group or a heterocyclic group
  • Z represents a cation.
  • the hydrocarbon group among R 1 to R 4 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and the like.
  • the group, silyl group and heterocyclic group may have a suitable substituent.
  • the amount of the photopolymerization initiator (a) to be added is generally 0.1 to 7 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the resin. If the amount of the photopolymerization initiator is less than the above lower limit, curing may not proceed sufficiently. If the amount exceeds the above upper limit, it is economically disadvantageous and causes deterioration of the physical properties of the cured product. .
  • Examples of the photo-curable resin used in the present invention include, as unsaturated polyester resins, Rigoluck LC-1 110 and Rigoluck LC-1 manufactured by Showa Polymer Co., Ltd. There are LC series such as 550, vinyl ester resin manufactured by Showa Kagaku Co., Ltd., trade name: Lipoxy LC-720, Lipoxy LC-740, Lipoxy LC-760.
  • an organic peroxide catalyst or another redox catalyst can be used for a resin that is thermally cured by using heat of light irradiation in the present invention.
  • Organic peroxide catalysts may be used, but from the viewpoint of mild curing and safety, it is preferable to use redox catalysts other than organic peroxides.
  • An example thereof is a polymerization initiator comprising a combination of an organic boron compound as the component (b), an acidic compound, and an optionally used hexarylubimidazole compound. By contacting the organic boron compound with the acidic compound, the organic boron compound is decomposed and radicals are generated.
  • organic boron compound a compound represented by the general formula (I) can be used.
  • Examples of the cation “Z” in the general formula (I) include a quaternary ammonium cation, a quaternary pyridinium cation, and a quinoline cation that are insensitive to visible light and near-infrared light.
  • Diazonium Metal cations such as cations, tetrazonium cations, phosphonium cations, (oxo) sulfonium cations, sodium, potassium, lithium, magnesium, calcium, etc., flabbium, villanium (Organic) compounds having a cation charge on oxygen atoms such as salts, carbon cations such as trovinyl and cyclopropyl, halogen cations such as iodonium, arsenic, cobalt, palladium, chromium, titanium and tin And cations of metal compounds such as antimony.
  • Diazonium Metal cations such as cations, tetrazonium cations, phosphonium cations, (oxo) sulfonium cations, sodium, potassium, lithium, magnesium, calcium, etc., flabbium, villanium (Organic) compounds having a cation charge on oxygen atoms such as salts, carbon cations such
  • the acidic compound used in the present invention is, for example, an inorganic acid generally known as Brenstead acid, such as hydrochloric acid, sulfuric acid, nitric acid, or an organic acid such as acetic acid, propionic acid, maleic acid, or the like.
  • examples include carboxylic acids such as adipic acid, (meth) acrylic acid, benzoic acid, and phthalic acids, and sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethansulfonic acid.
  • compounds having a hydroxyl group such as phenols and alcohols, compounds having a mercapto group such as various thiols, and substances capable of forming a covalent bond by receiving an electron pair known as a Lewis acid, for example, aluminum chloride , Stannic chloride, boron trichloride, boron tribromide and the like can be used.
  • Lewis acid for example, aluminum chloride , Stannic chloride, boron trichloride, boron tribromide and the like.
  • a substance having an acidic active site on a solid surface such as an acidic ion exchange resin, carbon black, and alumina, or an acidic gas compound such as hydrogen chloride or sulfurous acid gas can also be used.
  • acidic compounds having a polymerizable unsaturated group such as (anhydride) maleic acid, fumaric acid, or their polyesters, (meth) acrylic acid, itaconic acid, etc. Oligomers or polymers having such functional groups are suitable.
  • the substance itself is not an acidic substance, but is decomposed or reacted by the action of heating, moisture in the air, oxygen, etc. to generate acidic compounds.
  • the compound also corresponds to the latent acidic compound of the present invention.
  • a substance which is decomposed by light irradiation to generate an acidic compound is also known.
  • a compound called a photo-induced polymerization initiator also corresponds to the photolatent acidic compound of the present invention.
  • Various compounds such as diazonium compounds, sulfonium compounds, oxide compounds, and metal complex compounds are known as the light-powered thione initiator.
  • compounds that generate an acid by light or heat are considered in consideration of availability, economy, stability in a composition, operability, and the like. Desirable. More preferred are thermal acid-generating compounds, and in particular, organic sulfonium compounds that decompose by heating to generate an acid.
  • Organic sulfonium compounds are generally composed of an ion pair of a sulfonium cation moiety having three substituents (such as an alkyl group and an aryl group) and an anion as a counter ion.
  • at least one of the substituents of the sulfonium salt is an aryl group such as a (substituted) phenyl group or a (substituted) naphthyl group. It is desirable that For example, sulfonium compounds having a cation moiety, such as trisulfonium and diphenylmethylsulfonium, may be mentioned.
  • the organic boron compound and the acidic compound come into contact with each other at the time of compounding the initiator. It is desirable to use a compound that generates an acidic compound when stimulated by heat or light.
  • the composition ratio of the organic boron compound and the (latent) acidic compound in the polymerization initiator is usually 0.1 / 5 to 5 / 0.1, preferably 0.5 / 5 to 5 / 0.5 by weight. It is.
  • Organic boron compounds and / or (latent) acids If the amount of the acidic compound is less than this ratio, curing may not proceed sufficiently, and if the amount of the organic boron compound and / or the (latent) acid compound is greater than this ratio, the economy may increase. This is disadvantageous in terms of physical properties and causes the deterioration of the physical properties of the hardened material.
  • the (anhydrous) maleic acid, fumaric acid, or their polyester or (meta) aryl contained in the unsaturated polyester resin or vinyl ester resin may be used.
  • the acid value of the unsaturated polyester resin or the butyl ester resin is preferably 0.1 to 100 mgKOH / g, more preferably 5 to 5 Omg KOH / g.
  • the amount of the heavy is initiator which is a combination of an organic boron compound and a (latent) acidic compound, is usually 0.1 to 7 parts by weight, preferably 0.5 to 100 parts by weight, based on 100 parts by weight of the resin. 5 parts by weight. If the amount of the polymerization initiator is too small, curing may not proceed sufficiently, and if the amount of the polymerization initiator is too large, it is economically disadvantageous and the cured product This may cause deterioration of the physical properties of the material.
  • the above-mentioned organic boron compound and the acidic compound may be further added to the general formula (II)
  • hexarylbimidazole examples include bis (2,4,5—triphenyl) imidazole and bis (2-0—chloromethylphenyl4,5—diphenyl) imidazo. And bis (2--0, p-dichlorophenyl 4,5-diphenyl) imidazole, and bis (2-0-bromophenyl-4,5-diphenyl) imidazole.
  • hexarylbimidazole include bis (2,4,5—triphenyl) imidazole and bis (2-0—chloromethylphenyl4,5—diphenyl) imidazo.
  • a detailed description of hexarylbimidazole is found in Japanese Patent Publication No. 41-35545.
  • the amount of the hexarybiimidazole compound to be added is usually 0.05 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 1.0 parts by weight of the total amount of the organic boron compound and the (latent) acidic compound. 1 to 3 parts by weight. If the added amount is too large, it is economically disadvantageous and may cause poor dissolution.
  • organic peroxide catalyst of the component (c) examples include, for example, Benzoylpa 1-year-old cysteine, dicumylperoxide, di-sopropylperoxide, g-t-butyl peroxide, and t-butyl-peroxy benzoate.
  • the well-known combination of ketonpoxide and a reducing agent, the combination of hydroperoxide and a reducing agent, and the combination of diasilver oxide and a reducing agent 5 can also be used.
  • the reducing agent include cobalt salts such as cobalt naphthenate and cobalt octylate, vanadium compounds such as vanadium pentoxide and the like, and amines such as dimethylaniline and the like.
  • the inorganic filler 10 used as one component of the molding material includes, for example, aluminum hydroxide, calcium carbonate, talc, clay, glass powder, silica, barium sulfate, titanium oxide, Known materials such as sand and cement are exemplified. These inorganic fillers can be used in combination of two or more kinds.
  • It is usually from 100 to 500 parts by weight, preferably from 50 to Is300 parts by weight, based on 100 parts by weight.
  • an organic filler may be added.
  • This organic filler is known and has an effect as a low-shrinking agent.
  • pigments can be used in the present invention. There is no particular restriction on the type, and organic pigments and inorganic pigments can be used.
  • the fiber reinforcing material used as one component of the molding material is an inorganic and / or organic fiber, for example, glass fiber, carbon fiber
  • the light source used in the manufacturing method of the present invention may be a light source that emits light in a wavelength range of 280 nm to 1200 nm, but it is particularly necessary to transmit light deep into the FRP layer.
  • the light source preferably emits light in the wavelength range of 380 to 1200 nm.
  • Examples of light sources include high-pressure mercury lamps, ultra-high-pressure mercury lamps, mercury lamps, metal halide lamps, xenon lamps, near-infrared light lamps, sodium lamps, laser lamps, incandescent lamps, and sunlight lamps. it can. Also, various lamps can be used in combination.
  • a lamp in which light in the low-wavelength region having a high energy order is enhanced is effective, and a metal halide lamp and a halogen lamp are particularly preferable.
  • a lamp with enhanced light in the high wavelength region is effective.
  • the shape of the light source is not particularly limited as long as it can enter the mold and irradiate the rotating surface, and there is no particular limitation, but a rod-shaped type or an evening that can be fixed to a feeder is effective.
  • a method for forming the pipe member there are the following three modes for forming a pipe member. That is, a molding material containing an outer protective layer, an outer FRP layer, a mortar layer, an inner FRP layer, and a curable resin as main components obtained by curing a molding material containing a curable resin and an inorganic filler and / or a fiber reinforcing material.
  • a method of forming each layer by hardening it by light irradiation while applying centrifugal force to form a multilayer pipe member consisting of a protective layer.
  • a mold (form) in which the outer diameter of the pipe is fixed is rotated at high speed, and the fiber strength is increased by a feeder.
  • a hardening resin, an inorganic filler, etc., and the outer protective layer, outer FRP layer, mortar layer, inner FRP layer, and inner protective layer are formed by centrifugal force. It is cured to form each layer.
  • the layers may be completely cured, or each layer may be cured so that it does not mix when the next layer is introduced from the feeder. It may be completely cured.
  • the thick layer may be cured in several steps, or two layers may be cured together.
  • the feature is that the resin in each layer can be prevented from being mixed by alternately repeating the feeding of the material from the feeder and the curing by light irradiation.
  • the curable resin to be used has a part that does not reach the light, so it is desirable to use a combination of light curing and heat curing.
  • only the inner surface protective layer need only be photocured.
  • a mold (mold) having a fixed outer diameter of the pipe is rotated at a high speed, and a fiber reinforcing material, a curable resin, an inorganic filler, and the like are charged by a feeder and centrifuged.
  • All the layers of the outer protective layer, the outer FRP layer, the mortar layer, the inner FRP layer, and the inner protective layer are molded with light, and all the layers are collectively cured to form each layer.
  • the reaction of the inner protective layer can proceed by photo-curing, and the inside proceeds mainly by thermo-curing.
  • the corrosion resistance can be improved.
  • the curable resin to be used only the inner surface protective layer may be photocured only, but the other layers are preferably thermoset or a combination of photocuring and thermosetting.
  • the outer layer does not require the use of photocuring in combination.
  • a mold (form) in which the outer diameter of the pipe is fixed is rotated at a high speed, and while irradiating light, a fiber reinforcing material, a curable resin, an inorganic filler, and the like are removed by a feeder. Throw in and out The surface protective layer, outer FRP layer, mortar layer, inner FRP layer and inner protective layer are continuously cured to form each layer.
  • This method (3) is the method that can be molded in the shortest time in the method of continuous molding. In this case, it is desirable to balance the light intensity and the material supply speed from the feeder so that curing proceeds after sufficient gravity is applied.
  • the curable resin used can be cured in a short time if it is photocurable, but it is desirable to use a combination of photocuring and thermal curing in order to expect post-curing. However, only the inner surface protective layer need only be photocured.
  • the intensity of the irradiated light is higher is desirable, for example if 4 0 0-1 0 0 0 illuminance in the wavelength range of nm is 5 0 m W / cm 2 or more, more preferably 1 0 0 m W / cm 2 or more is desirable. Since the light irradiation time varies depending on the pipe diameter and the construction method, it cannot be specified unconditionally, but it is sufficient if the total time is at least 30 minutes.
  • an apparatus used in the method for manufacturing a pipe member of the present invention is a centrifugal molding apparatus having a mechanism for supplying each component constituting the molding material and a light irradiation mechanism. Irradiation devices may be combined. Specifically, it is a device for supplying curable resin, organoboron compound, inorganic filler, and fiber reinforcement, and a centrifugal molding device for tube members equipped with a light irradiation device.
  • a peroxide or organoboron compound is mixed at the tip of the feeder with a resin to which a photoinitiator and a cobalt salt are added in advance or a resin to which a photoinitiator and an acidic compound are added. And supply it.
  • the light irradiation device may be of the type (A) that is inserted in place of the feeder, or may be of the type (B) attached to the feeder.
  • the type (A) has a shape in which a plurality of lamps with a reflector with a reflector are arranged on the circumference of a cylinder so that light can be irradiated on the entire inner surface of the mold. To irradiate light at once and harden further. Can be used for the method of
  • type (B) has a lamp attached to the tip of the feeder and its surroundings, or to the tip and all parts. It can be used for a continuous molding method.
  • Example 1 (light-curing centrifugal molding device)
  • a light-curing centrifugal molding apparatus shown in the schematic diagram of FIG. 1 was produced.
  • the photo-curing centrifugal molding machine has a function to mix an organoboron compound or a peroxide catalyst at the tip with a mold (form) 1 having an inner diameter of 60 Omm or 100 mm that can rotate at high speed.
  • Resin feeder 3, aggregate (sand) feeder 5, glass fiber feeder 7, and short-arc type 2kW meter is a feeder equipped with four lamps 8 .
  • Reference numeral 2 denotes a resin composition
  • 4 denotes an aggregate (sand)
  • 6 denotes a glass fiber.
  • the light irradiation device has a structure in which four bar-shaped 3 kW gallium lamps 10 are mounted on the circumference of a round bar 9 having a diameter of 300 mm 20 or 700 mm. .
  • Example 1 manufactured of composite tube
  • Unsaturated polyester resin 100, parts by weight, 2,2'-bis (0-chlorophenyl) 1,4,5,4 ', 5'-tetraphenyl 5-1,2' Bisimidazole [manufactured by Wako Pure Chemical Industries, Ltd.] 3.0 parts by weight and 1.5 parts by weight of 2-mercaptobenzothiazole and carbonic acid rusidium [manufactured by Bihoku Powder Chemical Industry Co., Ltd. Name: Softener 1200] 190 parts by weight was mixed to obtain a resin composition 1-2.
  • Vinyl ester resin [manufactured by Showa Polymer Co., Ltd., acid value 8 mg KOH / 10 g] 2,100'-bis (0-chlorophenyl) -1.4,5,4 ', 5' in 100 parts by weight Tetrafluo 1,2'-bisimidazole [manufactured by Wako Pure Chemical Industries, Ltd.] 3.0 parts by weight and 1.5 parts by weight of 2-mercaptobenzothiazole were added to the resin composition.
  • Tetrafluo 1,2'-bisimidazole manufactured by Wako Pure Chemical Industries, Ltd.
  • an organoboron compound for mixing at the tip, an organoboron compound; tetra-n-butylammonium.triphenyl-n-butylborate (manufactured by Showa Denko KK, hereinafter abbreviated as P3B) is N-methylpyrrolid. was dissolved in pyrrolidone were prepared initiator one 1 4 0 weight 0/0 solution.
  • the initiator 11 was charged with the resin 20 composition 11, the resin composition 11 and the resin composition 13, and simultaneously with the resin composition. An amount of 1.0% by weight was fed from the front end of the feeder.
  • the glass fiber was cut into 1-inch lengths using a glass opening (made by Nitto Boseki Co., Ltd., trade name: 425026 TX /).
  • a glass opening made by Nitto Boseki Co., Ltd., trade name: 425026 TX /.
  • For the sand we prepared JIS No. 4 mirror sand.
  • the centrifugal molding device prepared in Example 1 (Fig. 1) was used as the outer protective layer.
  • Short arc main Taruharai Doranpu a) is used without lighting, in which rotates the mold 2 5 0 rpm, the resin composition one 1 and sand the sand content 8 0 wt 0/0, the thickness was set to 1 mm.
  • the light irradiation device shown in Fig. 2 was inserted in place of the feeder, and light was irradiated for 3 minutes to cure.
  • the resin composition 12 and short glass fibers were placed on the outer protective layer, which is rotating the mold at 250 rpm as the outer FRP layer, with a glass content of 10% by weight and a thickness of 10% by weight. It was thrown so that it might be 5 mm.
  • the light irradiation device shown in Fig. 2 was inserted in place of the feeder, and light irradiation was performed for 10 minutes to cure.
  • the resin composition 12 and sand were mixed with a sand content of 70% by weight and a thickness of 4.5 mm. It was put so that.
  • the light irradiation device shown in Fig. 2 was inserted in place of the feeder, and light irradiation was performed for 10 minutes to cure.
  • a resin composition one 2 and short glass fibers, glass content 2 0 weight 0/0, the thickness was set to 4 mm.
  • the light irradiation device shown in FIG. 2 was inserted in place of the feeder, and light irradiation was performed for 10 minutes to cure.
  • the resin composition 13 was poured onto the inner surface FRP layer rotating the mold at 250 rpm so as to have a thickness of 1 mm.
  • the light irradiation device shown in Fig. 2 was inserted in place of the feeder, and light irradiation was performed for 5 minutes to cure.
  • the centrifugal molding device prepared in Example 1 (Fig. 1) was used as the outer protective layer. ) was used without turning on the short-arc metal halide lamp, and while the mold was rotating at 250 rpm, the resin composition 11 and the sand had a sand content of 80% by weight and a thickness of 80% by weight. Was set to 1 mm. After insertion, the light irradiation device shown in Fig. 2 was inserted in place of the feeder, and light was irradiated for 3 minutes to cure.
  • the outer surface protective layer which rotates the mold and the outer surface FRP layer 2 5 0 rpm, one 2 and glass wool resin composition, glass content 2 0 weight 0/0, the thickness was introduced so as to be 8 mm.
  • the light irradiation device shown in FIG. 2 was inserted in place of the feeder, and light irradiation was performed for 13 minutes to cure. .
  • the resin composition 11 and sand were mixed on the outer FRP layer, which is rotating the mold to 250 rm as a mortar layer, with a sand content of 70% by weight and a thickness of 7 mm. I put it in.
  • the light irradiator shown in Fig. 2 was inserted in place of the feeder, and light was irradiated for 13 minutes to cure.
  • the resin composition 12 and the short glass fiber are mixed with a glass content of 20% by weight and a thickness of 8%. mm.
  • the light irradiation device shown in FIG. 2 was inserted in place of the feeder, and light irradiation was performed for 13 minutes to cure.
  • the resin composition-3 was poured onto the inner surface FRP layer rotating the mold at 250 rpm so as to have a thickness of 1 mm.
  • the light irradiator shown in Fig. 2 was inserted in place of the feeder, and light was irradiated for 5 minutes to cure.
  • Example 2 Using the same equipment and materials as in Example 2, the outer protective layer, outer FRP layer, mortar layer, inner FRP layer, and inner protective layer were first rotated at 250 rpm with the same configuration as in Example 2. In a mold. Next, the light irradiation device of FIG. 2 was inserted in place of the feeder, and light irradiation was performed for 40 minutes to cure all the layers at once, and a composite tube similar to that of Example 2 (4) was formed.
  • Example 4 (Production of composite pipe)
  • each layer has the same configuration as in Example 2, the outer protective layer is 3 minutes, and the outer FRP layer is Each material was charged for 7 minutes, the mortar layer for 5 minutes, the inner FRP layer for 7 minutes, and the inner protective layer for 3 minutes, and cured continuously, and finally cured by irradiating light for another 5 minutes.
  • a composite tube similar to (4) was formed.
  • Example 2 The same material as in Example 2 was used, and each layer was processed while the short-arc metal halide lamp on the feeder of the centrifugal molding machine was turned on.
  • the outer protective layer is 3 minutes
  • the outer FRP layer is 10 minutes
  • the mole layer layer is 8 minutes
  • the inner FRP layer is 10 minutes
  • the inner protective layer is 3 minutes.

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Abstract

L'invention concerne un procédé et un dispositif de fabrication d'élément de tuyau multicouche au moyen d'un procédé de moulage centrifuge permettant de durcir les couches en une courte durée, d'augmenter le degré de dureté d'une couche protectrice de surface intérieure et d'éliminer le recours à un post-durcissement après libération du moule. Ledit procédé consiste à introduire un matériau de moulage contenant une résine durcissante, ou une résine durcissante et une charge organique, et/ou un matériau renforcé par des fibres dans une matrice de moulage centrifuge rotative d'élément de tuyau, et à irradier une lumière pour durcir ledit matériau à l'aide d'une force centrifuge appliquée sur celui-ci. L'invention concerne également un dispositif de fabrication d'élément de tuyau, c'est-à-dire, un dispositif de moulage centrifuge utilisé par ledit procédé comprenant un mécanisme de fourniture de composants au matériau moulé et un mécanisme d'irradiation de lumière.
PCT/JP2002/010752 2002-10-16 2002-10-16 Procédé et dispositif de fabrication d'élément de tuyau WO2004035287A1 (fr)

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AU2002335277A AU2002335277A1 (en) 2002-10-16 2002-10-16 Method and device for manufacturing pipe member

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5259677A (en) * 1976-11-24 1977-05-17 Kubota Ltd Method of manufacture of conjugate pipe reinforced with glass fiber
WO1986005436A1 (fr) * 1985-03-23 1986-09-25 Dow Chemical Gmbh Tuyau en plastique renforce par des fibres et son procede de fabrication par coulee centrifuge
JPS63312810A (ja) * 1987-06-17 1988-12-21 Nippon Concrete Ind Co Ltd Ｆｒｐ補強コンクリ−ト又はモルタル管の製造方法
EP0533482A1 (fr) * 1991-09-17 1993-03-24 Xerox Corporation Procédé pour la préparation de membres pour la formation d'images
US5202076A (en) * 1988-09-23 1993-04-13 Hobas Engineering & Durotec Ag Method for producing multi-layer pipe conduit components of plastic material, inorganic filler material and glass fibers
US5300391A (en) * 1991-09-17 1994-04-05 Xerox Corporation Field assisted processes for preparing imaging members
JP2000095928A (ja) * 1998-07-22 2000-04-04 Dainippon Ink & Chem Inc レジンコンクリ―ト組成物及びその成形品
JP2000117850A (ja) * 1998-10-19 2000-04-25 Shin Etsu Polymer Co Ltd シームレスベルトの製造方法
JP2002105310A (ja) * 2000-09-27 2002-04-10 Shin Etsu Polymer Co Ltd アクリル樹脂製半導電性ベルト

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5259677A (en) * 1976-11-24 1977-05-17 Kubota Ltd Method of manufacture of conjugate pipe reinforced with glass fiber
WO1986005436A1 (fr) * 1985-03-23 1986-09-25 Dow Chemical Gmbh Tuyau en plastique renforce par des fibres et son procede de fabrication par coulee centrifuge
JPS63312810A (ja) * 1987-06-17 1988-12-21 Nippon Concrete Ind Co Ltd Ｆｒｐ補強コンクリ−ト又はモルタル管の製造方法
US5202076A (en) * 1988-09-23 1993-04-13 Hobas Engineering & Durotec Ag Method for producing multi-layer pipe conduit components of plastic material, inorganic filler material and glass fibers
EP0533482A1 (fr) * 1991-09-17 1993-03-24 Xerox Corporation Procédé pour la préparation de membres pour la formation d'images
US5300391A (en) * 1991-09-17 1994-04-05 Xerox Corporation Field assisted processes for preparing imaging members
JP2000095928A (ja) * 1998-07-22 2000-04-04 Dainippon Ink & Chem Inc レジンコンクリ―ト組成物及びその成形品
JP2000117850A (ja) * 1998-10-19 2000-04-25 Shin Etsu Polymer Co Ltd シームレスベルトの製造方法
JP2002105310A (ja) * 2000-09-27 2002-04-10 Shin Etsu Polymer Co Ltd アクリル樹脂製半導電性ベルト

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