WO2004035287A1

WO2004035287A1 - Method and device for manufacturing pipe member

Info

Publication number: WO2004035287A1
Application number: PCT/JP2002/010752
Authority: WO
Inventors: 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: 2002-10-16
Filing date: 2002-10-16
Publication date: 2004-04-29
Also published as: AU2002335277A1; AU2002335277A8

Abstract

A method and a device for manufacturing a multi-layer pipe member by a centrifugal molding method capable of hardening layers in a short time, increasing the degree of hardness of an inner surface protective layer, and eliminating the need of after-curing after mold release, the method comprising the steps of inputting molding material containing curing resin or curing resin and inorganic filler, and/or fiber reinforced material into a rotating centrifugal molding die for pipe member and radiating light for curing with a centrifugal force applied thereto; the device for manufacturing the pipe member, i.e., a centrifugal molding device used for the method comprising a mechanism for feeding the components of molded material and a mechanism for radiating the light.

Description

Description Method for manufacturing pipe member and manufacturing apparatus for pipe member

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. Background art

The glass fiber reinforced plastic composite pipe composed of FRP and resin mortar, the so-called FRPM pipe, began production and sales in 1970, and has been offering excellent watertightness, corrosion resistance, workability, high strength, and earthquake resistance. Due to its many characteristics, such as water quality, it is widely used in sewerage, industrial drainage, seawater transportation, agricultural water, pipes in tunnels, pipes in shields, and so on.

A centrifugal molding method is known as one of the molding methods of the FRPM tube. In this centrifugal molding method, a mold (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.

In this method, unsaturated polyester resin is mainly used as the thermosetting resin, and curing is performed by radical polymerization using a peroxide catalyst system. Has been carried out. Actually, 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.

As described above, 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. In addition, in the case of piping that requires corrosion resistance, 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.

Under such circumstances, the present invention can cure each layer in a short time, increase the degree of curing of the inner surface protective layer, and eliminate the need for after-demolding multi-layers. 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.

That is, the present invention

(1) 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. A method for producing a tube member, characterized by curing by irradiation.

(2) The pipe member is made of a curable resin and an inorganic filler and / or a fiber reinforced material. An outer protective layer, an outer FRP layer, a mortar layer, an inner FRP layer, and an inner protective layer formed by curing a molding material mainly composed of a curable resin. The method for manufacturing a pipe member according to the above (1), wherein the tube member is formed by being cured by light irradiation while applying force.

(3) 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. (1) 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.

(4) 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. (1) a method for manufacturing a pipe member,

(5) 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)

(Wherein, 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.) Compounds and general formulas used in some cases (Π)

(Wherein L ', L ² and L ³ each independently represent an § re Ichiru group.) The combination or Ranaru polymerization initiator and (c) organic and Kisaari one Rubyi Mi imidazole compound to be represented by At least one resin selected from unsaturated polyester resins containing at least one polymerization initiator selected from peroxide catalysts, vinyl ester resins, and urethane (meta) acrylate resins (1) to (4), wherein

(6) The above (1) or (5), wherein the inorganic filler is sand and / or calcium carbonate, and the fiber reinforcing material is at least one selected from glass fiber, carbon fiber and aramide fiber. A method for manufacturing a pipe member,

(7) The method for producing a pipe member according to any one of (1) to (6), wherein the irradiation light has a wavelength in a visible light to near-infrared light region.

(8) The method for producing a pipe member according to the above (1) to (7), wherein the light source for light irradiation is a metal halide lamp and / or a halogen lamp.

(9) When a curable resin containing an organic boron compound represented by the general formula (I) is used, only the organic boron compound is not mixed into the resin in advance, and the tube is formed by centrifugal molding. (5) to (8), the method of manufacturing a pipe member,

(10) The method for producing a pipe member according to any one of the above (1) to (9), wherein the curing is promoted by heating simultaneously with light irradiation;

(11) A pipe member obtained by the method of (1) to (10) above, and

(12) Centrifugal molding used in the above methods (1) to (10) An apparatus for manufacturing a pipe member, comprising: a mechanism for supplying each component constituting a molding material; and a light irradiation mechanism.

Is provided. BRIEF DESCRIPTION OF THE FIGURES

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 symbols in the figure have the following meanings.

1: Mold (mold)

2: Resin composition

3: Resin composition supply device

4: Sand storage

5: Sand supply device

6: Glass fiber storage

7: Glass fiber feeder

8: Metal halide lamp

9: Round bar

10: Gallium lamp Best mode for carrying out the invention

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. With the conventional centrifugal molding method, 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.

In the method for manufacturing a pipe member 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. By forming each of the above-described layers, 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. Photocurable using a resin that is sensitive to ultraviolet, visible, or near-infrared light, or heat-curable with the addition of a redox-based catalyst other than organic peroxides and organic peroxides. Either a resin is used for heat curing using the heat of light irradiation, or both light curing and heat curing are used.

First, each component used in the molding material will be described. In the molding material, as 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, Ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, etc. It is produced by reacting a polyhydric alcohol as an alcohol component.

Bull ester resin, also called epoxyacrylate resin, is generally formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. 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. Epoxy (meth) acrylate obtained by the reaction, or saturated polyester or unsaturated polyester of terminal lipoxyl group obtained from saturated dicarboxylic acid and / or unsaturated dicarboxylic acid and polyhydric alcohol. It is a polyester (meta) acrylate of a saturated polyester or an unsaturated polyester obtained by reacting a β-unsaturated carboxylic acid ester having an epoxy group.

Examples of the epoxy resin as a raw material include bisphenol diglycidyl ether and its high molecular weight homologues, and novolak type polyglycidyl ethers. As the saturated dicarboxylic acid used for the terminal carboxyl polyester, 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. Examples of 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 α, S-unsaturated carboxylate having an epoxy group used in the production of the polyester (meta) acrylate.

As 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. For example, 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.

Specific examples of the 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 Chemical Co., Ltd.), etc., but are not particularly limited. One kind of these polyisocyanates may be used alone, or two or more kinds may be appropriately mixed.

Examples of the polyhydroxy compound used as a raw material for the urethane (meta) acrylate include polyester polyol, polyether polyol, and the like. Specifically, 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 dipenta-esl-l-ethylene oxide Examples thereof include adducts of xido-propylene oxide, but are not particularly limited. One of these polyhydroxy compounds may be used alone, or two or more of them may be used as a mixture.

Specific examples of polyhydric alcohols used as a raw material of the urethane (meth) acrylate include ethylene glycol, ethylene glycol, triethylene glycol, and polyethylene glycol. Propylene glycol, dipropylene glycol, polypyrene pyrene glycol, 2-methyl-13 pentadiol, 1,3-butanediol, bisphenol A and propylene oxide or ethylenoxy Adduct with 1,2,3-tetrahydroxoxybutane, glycerin, trimethicone, 1,2-cyclohexaneglycol, 13-cyclohexaneglycol, 1 4-Silicone Hexanglycol, 'Laxylene glycol, Bicyclohexyl-1-44, -diol, 26-Decalin glycol, 2,7- But not limited thereto. 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. One of these hydroxyl group-containing (meth) aryl compounds may be used, or two or more of them may be appropriately mixed.

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. One of these hydroxyl group-containing aryl ether compounds may be used alone, or two or more of them may be used as a mixture.

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. Unsaturated polyester, vinyl ester, urethane (methyl) acrylate 10 0 to 250 parts by weight per 0 parts by weight, Preferably 20 to 100 parts by weight are used. If the amount used is less than 10 parts by weight, molding becomes difficult due to high viscosity.If the amount exceeds 250 parts by weight, it is difficult to obtain a product with high hardness, heat resistance is insufficient, and FRP material and I don't like it.

In this case, part or all of the styrene monomer is replaced with chlorostyrene

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.

In 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.

For light curing in the present invention, 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, and near-infrared light refers to light in the wavelength range from 780 to 1200 nm. Accordingly, as the photopolymerization initiator of the component (a), 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.For example, in the case of 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, N-dimethylaminobenzophenone and the like, and 4,4,6-trimethylbenzoyldiphenylphosphinoxide and the like.

1 0 Can be used. 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.

In particular, it is preferable to use 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

20 Oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,6—trimethylbenzoyl-diphenylphosphine oxide, 2-phenyl-6-methyl Benzoyl diphenyl phosphinoxide,, 6 — dibromobenzyl phenyl phosphin oxide, 2, 8 — dimethyl naphthalene

2 5 Levonyl diphenyl phosphine oxide, 1, 3 — dimethoxy naphthyl lin 2 — carbonyl-diphenyl phosphine oxide, 2, 4, 6-trimethyl benzoyl roof Nylphosphinic acid methyl ester, 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester Examples thereof include butyl ester, methyl 2,6-dichlorobenzoylphenylphosphinate, and the like.

Specifically, 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

10 2 1 ketone (trade name: irgacure 1 184, Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethyloxybenzoyl) 1, 2, 4, 4 Methylpentyl phosphine oxide (manufactured by Ciba Specialty Chemicals, Inc.) mixed at a ratio of 75% / 25% (trade name: Irgacure-1800) (manufactured by Ciba Specialty Chemicals, Inc.) , 50% / 50%, trade name: Irgaki Yua 1850 (manufactured by Ciba Specialty Chemicals Co., Ltd.), bis (2,4,6-trimethylbenzoyl) Phenylphosphine oxide (trade name: irgakiyua 181-9, manufactured by Ciba-Besharti Chemicals Co., Ltd.), 2, 4, 6-trimethylbenzoy

20 Rubiphenylphosphine oxide (trade name: Lucicirin)

TP〇, BASF Corporation), 2-hydroxy-1-2-methyl-1-phenylpropane-1-one (trade name: Darocurll 73, Ciba Specialty Chemicals Co., Ltd.) and 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)

5 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),

is D ⁺ . A—... (III)

(In the formula, 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.) And the general formula (I):

(Wherein, 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.) There are things. A detailed description can be found in Japanese Patent Application Laid-Open No. H10-182727. Other known materials can be used. In the general formula (I), 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.

In the present invention, 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.

As the 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. 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. Also, 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. These acids are described in detail, for example, in Morrison Boyd, Organic Chemistry, 3rd edition, page 43.

In addition, 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.

Among these acidic compounds, 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.

In addition, 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. In addition, a substance which is decomposed by light irradiation to generate an acidic compound is also known. For example, 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. UV-Ε Β Β Β Β Β Β ととシーシーシーシーシーシーシー詳細シームム. Among these latent acidic compounds, 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. In view of the stability of the compound, the ability to generate acidic compounds, and the acid strength of the generated acidic compound, 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.

When the potable life of the resin composition containing the initiator is required and the like, it is not preferable that 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.

5 In the case where the resin or the like contains an acidic compound in advance, 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. An acid, itaconic acid, an oligomer having a ruboxyl group at the terminal, an oligomer having a ruboxyl group, a polymer, or a resin in which an arbitrary acidic compound is added. Good. In this case, 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.

20 As the polymerization initiator of the component (b), the above-mentioned organic boron compound and the acidic compound may be further added to the general formula (II)

L ² then ²

(Wherein L ¹ , L ^2, and L ³ each independently represent an aryl group.) Is preferred. In the general formula (U), an appropriate substituent may be introduced into the aryl groups represented by L ¹ , L ² and L ³ . Specific examples of hexarylbimidazole 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. 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.

Examples of the organic peroxide catalyst of the component (c) include, for example, Benzoylpa 1-year-old cysteine, dicumylperoxide, di-sopropylperoxide, g-t-butyl peroxide, and t-butyl-peroxy benzoate. 1,1,1-bis (t-butylperoxy) -1,3,3,5-trimethylcyclohexane, 2,5—dimethyl-2,5—bis (t-butylbutyloxy) hexyne-1,3-isopro Pyrhydride Mouth peroxide, t-butyl hydroperoxide, dicumylvaperoxide, dicumylhydrperoxide, acetylbaoxyside, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxycide , 3, 3, 5 — trimethylhexa Irupaokisa I de, Lau Rirupaokisai de, dichloroethylene Mirupaokisai de, di t one-butylperoxy O wherein de include t one Puchiruhai Doropaokisai Donado. Also, azobisisobutyronitrile, azobiscal Azo compounds such as bonamide are also effective.

Although the use of a room temperature curing system is effective in practice, 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. Specific examples of 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.

In the present invention, 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.

In the present invention, an organic filler may be added. This organic filler is known and has an effect as a low-shrinking agent. For example, polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene, polyvinylidene chloride micro balloon, polyacrylonitrile

20 Micro balloon and the like can be used.

Furthermore, 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.

In the present invention, 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

25, known fibers such as aramide fiber, polyethylene terephthalate fiber, and vinylon fiber are used. These fibers may be used in combination of two or more kinds. The amount of the fibers is usually 5 to 400 parts by weight, preferably 50 to 300 parts by weight, per 100 parts by weight of the curable resin. Department. 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.

In order to obtain a faster curing speed, 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. As a heat source, 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.

Next, a method for forming the pipe member will be described. In the present invention, 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. (1) 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 method in which the layer is cured by a single light irradiation while applying a centrifugal force, and (3) the molding material is put into a rotating centrifugal mold for a pipe member while being irradiated with the light, and cured. The method of forming each layer by using

Specifically, in the method (1), 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. In this case, 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. In order to improve the corrosion resistance of the inner protective layer, it is desirable to increase the degree of curing over time when the final layer is 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. However, only the inner surface protective layer need only be photocured.

In the method (2), 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. In this case, the reaction of the inner protective layer can proceed by photo-curing, and the inside proceeds mainly by thermo-curing. Also in this case, since strong light is applied to the inner protective layer for a long time, the corrosion resistance can be improved. As for 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. In particular, the outer layer does not require the use of photocuring in combination.

Further, in the method (3), 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.

In the present invention, 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.

Next, 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. For example, in a combination system of photocuring and thermosetting, 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

On the other hand, 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.

5 Example

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (light-curing centrifugal molding device)

10 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), and 6 denotes a glass fiber.

Next, a light irradiation device as shown in the schematic diagram of Fig. 2 was manufactured, so that it could be inserted instead of the feeder. 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 (manufacture of composite tube)

(1) Preparation of resin composition

25 Unsaturated polyester resin [manufactured by Showa Polymer Co., Ltd., trade name: Rigoluck 150, 57, acid value 25 mg K 0 H / g] 1, 2'-bis in 100 parts by weight (0—black mouth fern) 1-4,5,4 ', 5'-Tetraf2,1,1'-bisimidazole [manufactured by Wako Pure Chemical Industries, Ltd.] 3 0.0 parts by weight and 1.5 parts by weight of 2-mercaptobenzothiazole were added to obtain a resin composition 11.

Unsaturated polyester resin (supra) 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. Got.

() Preparation of organic boron compound solution

is 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.

In the following examples (Examples of manufacturing a composite tube), 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.

(3) Glass fiber, sand

The glass fiber was cut into 1-inch lengths using a glass opening (made by Nitto Boseki Co., Ltd., trade name: 425026 TX /). For the sand, we prepared JIS No. 4 mirror sand.

(4) Further hardening (nominal diameter 600 mm)

First, 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. 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.

Next, 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. After insertion, 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.

Next, on the outer surface FRP layer where the mold was rotated at 250 rpm as a mortar layer, 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. After insertion, 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. Next, on the mortar layer which rotates the mold and the inner surface FRP layer 2 5 O rpm, a resin composition one 2 and short glass fibers, glass content 2 0 weight ^_0/0, the thickness Was set to 4 mm. After the introduction, 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.

Finally, as an inner surface protection FRP layer, 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. After insertion, 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.

A composite tube with a nominal diameter of 600 mm, a length of 50 mm and a thickness of 15.5 mm was formed with a total light irradiation time of 38 minutes (total working time of 50 minutes).

(5) — Layer-by-layer curing (nominal diameter 100 mm)

First, 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.

Next, on 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. After the loading, 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. .

Next, 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. After loading, the light irradiator shown in Fig. 2 was inserted in place of the feeder, and light was irradiated for 13 minutes to cure. Next, on the mortar layer where the mold is rotated at 25 O rpm as the inner surface FRP layer, 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. After the loading, 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.

Finally, as an inner surface protection FRP layer, 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. After insertion, the light irradiator shown in Fig. 2 was inserted in place of the feeder, and light was irradiated for 5 minutes to cure.

With a total irradiation time of 47 minutes (total work time of 65 minutes), a composite tube with a nominal diameter of 100 Omm, a length of 50 mm, and a thickness of 25 mm was formed. Example 3 (manufacture of composite pipe) (1) All layers are cured at once (nominal diameter 600 mm)

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.

() All layers are cured at once (Nominal diameter: 100 mm)

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 shown in FIG. 2 was inserted in place of the feeder, and light irradiation was performed for 60 minutes to cure all the layers at once, and a composite tube similar to that of Example 2 (5) was formed. Example 4 (Production of composite pipe)

(1) Light curing while supplying the material (nominal diameter: 600 mm)

Using the same material as in Example 2, with the short-circuit meter of the feeder of the centrifugal molding device turned on, 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.

(2) Light curing while supplying material (nominal diameter 100 mm)

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.

With the same configuration as 2, 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, and the inner protective layer is 3 minutes. The material was charged and continuously cured, and finally irradiated with light for another 10 minutes to be cured, whereby a composite tube similar to that of Example 2 (5) was formed. Test example

For each of the composite pipes obtained in Examples 2 to 4, an external pressure test and an internal pressure test of the internal pressure pipe (Class 4) were performed in accordance with JIS A530. Table 1 shows the results. Table 1 [External pressure test and internal pressure test of internal pressure pipe (Class 4)]

Test condition

External pressure test

Nominal diameter 600 Attack Standard deflection: 31 mm External pressure of test: 44.6 KN / m Nominal diameter 1000 Maraud Standard deflection: 5 Imra External pressure of test: 74.3 KN / ra Internal pressure test

Nominal diameter 600 Maraud Design internal pressure: 0.5 KN / ffl Test internal pressure: 1.0 KN / ra Nominal diameter 1000 Awake Design internal pressure: 0.5 KN / m Test internal pressure: No 0 KN / m Industrial applicability

According to the present invention, by combining centrifugal molding and light irradiation, In addition, it is possible to form a multi-layered tubular member in a short time, and it is not necessary to cure after forming, so that the molding cycle can be greatly improved.

Claims

The scope of the claims

1. A curable resin or a molding material containing a curable resin and an inorganic filler and / or a fiber reinforced material is poured into a rotating centrifugal mold for a pipe member, and irradiated with light under a centrifugal force. A method for producing a pipe member, characterized in that the pipe member is cured by the following method.

2. The pipe member is made of an outer protective layer, an outer FRP layer, a molar 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. 2. The method for producing a pipe member according to claim 1, comprising an inner surface protective layer obtained by curing a molding material as a main component, and forming each layer by applying light while being subjected to a centrifugal force.

3. The pipe member is formed by curing a molding material containing a curable resin and an inorganic filler and / or a fiber reinforced material. The outer protective layer, the outer FRP layer, the mole layer, the inner FRP layer, and the curable resin. The method for manufacturing a pipe member according to claim 1, comprising an inner protective layer formed by curing a molding material as a main component, and forming all layers by applying a single light irradiation while applying a centrifugal force. .

4. The pipe member is formed by curing a molding material containing a curable resin and an inorganic filler and / or a fiber reinforced material. The outer protective layer, the outer FRP layer, the mole layer, the inner FRP layer, and the curable resin. A method comprising forming an inner surface protective layer obtained by curing a molding material as a main component, charging the molding material into a rotating centrifugal molding die for a pipe member while irradiating light, and curing the molding material. Item 4. The method for producing a pipe member according to Item 1.

5. 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 R

Z + B (I)

R ² R

(Wherein, 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.) Compound and optionally used general formula (によ)

(Wherein L ¹ , L ² and L ³ each independently represent an aryl group) A polymerization initiator comprising a combination with a hexarylubimidazole compound represented by, and (c) an organic peroxide catalyst The resin is at least one resin selected from unsaturated polyester resins containing at least one polymerization initiator selected from the group consisting of unsaturated polyester resins, vinyl ester resins, and urethane (meth) acrylate resins. The method for producing a pipe member according to any one of 1 to 4.

6. The pipe according to any one of claims 1 to 5, wherein the inorganic filler is sand and / or calcium carbonate, and the fiber reinforcing material is at least one selected from glass fiber, carbon fiber, and aramide fiber. Method of manufacturing components.

7. The method for producing a tube member according to claim 1, wherein the irradiation light has a wavelength in a range from visible light to near-infrared light.

8. The method for producing a tube member according to claim 1, wherein the light source for light irradiation is a metal halide lamp and / or a halogen lamp.

9. When a resin containing an organic boron compound represented by the general formula (I) is used as the curable resin, the centrifugal molding die for pipe members is used without mixing the organic boron compound alone in the resin in advance. The method for producing a pipe member according to any one of claims 5 to 8, wherein the mixture is charged and mixed with a resin.

10. The method for producing a tube member according to any one of claims 1 to 9, wherein the curing is promoted by heating simultaneously with light irradiation.

11. A pipe member obtained by the method according to any one of claims 1 to 10.

10. A centrifugal molding device used in the method according to any one of claims 1 to 10, wherein the tube member has a mechanism for supplying each component constituting the molding material and a light irradiation mechanism. For manufacturing equipment.