JPH11210981A - Photo-curing material for covering or repairing inside face of tubular molded product and its covering method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material for covering or repairing a tubular molded product by a photo-curing composition curable by the light of a long wavelength having permeability even using a heat source. SOLUTION: In this material, a fiber layer-form substance, such as a cylinder body or a sheet, is impregnated-with a resin composition consisting of 100 pts.wt. unsaturated polyester resin and/or vinyl ester resin and 0.01-20 pts.wt. bissacyl phosphin oxide compound represented by a formula, wherein R1 -R3 respectively independently indicate an alkyl group, an aryl group, an aryl group, an aralkyl group, an alkynil group, an alkenyl group, alkynil group, a heterocyclic group, a substitution alkyl group, a substitution aryl group, a substitution allyl group, a substitution aralkyl group, a substitution alkenyl group, a substitution alkinyl group, or a substitution heterocyclic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable material for coating or repairing the inner surface of a tubular molded body such as a concrete pipe or a steel pipe. More specifically, it is characterized in that a fiber layered material such as felt is impregnated with a composition obtained by adding a specific compound to a polyester resin or the like as a photocurable material.

[0002]

2. Description of the Related Art Except for sea transportation of tankers and the like, gas, liquid or granular materials are mostly transported by pipelines, not only for short distances but also for long distances. As the pipe material, concrete, steel, stainless steel, plastic, etc. are used, and they are used for supplying a wide range of utilities such as water and sewage, crude oil, chemicals, city gas, etc. It is invisible. However, for example, steel pipes are mainly used in the transportation of crude oil, but corrosive impurities and stray currents contained in petroleum may cause corrosion of the pipes, resulting in leakage of crude oil. In addition, concrete fume pipes are mainly used in water supply and sewerage systems, but in addition to physical damage due to external pressure due to long-term burial use, especially in sewerage systems, sulfur dioxide gas is generated due to decomposition of contaminants such as sulfate-reducing bacteria. Corrosion and aging of concrete pipes have been a problem due to the generation of sulfur ions by sulfur oxidizing bacteria, and measures to improve the corrosion resistance of new pipes and the development of efficient repair methods for existing pipes are urgently needed. It is a problem.

[0003] In order to improve the corrosion resistance of new pipes and repair local corrosion of existing pipes, the inside of the pipes is also provided with a corrosion coating or lining using, for example, a pig or the like. There is a limit, and it does not compensate for the strength of the piping. There is also a method of newly inserting a corrosion-resistant plastic pipe into an old pipe in consideration of strength and durability, but repairing an existing pipe involves significant construction restrictions and has a problem in terms of cost.

[0004] One of the most noticeable repair methods that can be carried out on site is a FRP prepreg cylinder impregnated with a thermosetting resin in which a thixotropic agent has been added in advance, and is inserted into an aged pipe by pressure bonding. Or a method of curing with hot air (P. Chaneliere, U. Bultjer,
Diegrabenrose Sanierungv
on Abbasserleitungen. Ein
interescantes Einsatzgeb
ie fur ungesattigtePolye
starharze. Composites 3,18
(1992); Johnson et al. ,
45th. SPI, 12-D (1990), Tokuhei 1-
No. 15374). The prepreg used in this method is a tubular felt or a tubular woven fabric obtained by laminating reinforcing fibers such as chopped strand mats, swirl mats, and nonwoven fabrics on one surface of an extensible film that is not attacked by the impregnated resin composition. A film impregnated with an unsaturated polyester, vinyl ester resin, or epoxy resin is a composite material having an outer surface of a cylindrical body. This is a method in which the tubular body is pressed against the pipe wall with water pressure or air pressure while turning over the inside of the pipe, and then the inner surface is blown with hot water or hot air to cure the composite material. According to this method, since the tubular fibrous body is flexible,
It can be installed on site and cures in a state of being pressed against the pipe wall, so it has the performance of reinforcing hardening in addition to corrosion prevention hardening, but it is a radical hardening type thermosetting resin containing organic peroxide or hardening Since the epoxy resin containing the agent is used, the pot life or storage time as a prepreg is short. Further, there is a problem that a large amount of heat medium and a large amount of heat are required for curing.

A method of using ultraviolet light as a curing means by using a tubular composite material in which an unsaturated polyester resin is impregnated into glass fiber or glass mat (Kunstst)
off German Plastics. 83 (1
0), 55 (1993) are also being studied. When this method is used, the heat medium and the amount of heat are not required, but when the FRP layer is thickened to improve the anticorrosion property, it becomes difficult for ultraviolet rays to pass therethrough, and it is easy to cause insufficient curing, or cracks are caused due to a difference in curing speed. It has a drawback that it is likely to occur and reduces the corrosion resistance. Furthermore, in order to ensure ultraviolet transmittance, only a small amount of a specific filler can be added, and thus there are restrictions on the dimensional stability and cost of the cured product.

[0006] As described above, the conventional thermosetting resin composition has a problem in the pot life or storage stability as a prepreg. Since it is necessary to secure a heat medium, there are naturally restrictions on the length and diameter of the pipe that can be constructed. On the other hand, in the case of using the thermosetting resin composition, the ultraviolet curing resin composition does not require a large heat source, which is indispensable when using the thermosetting resin composition, or an auxiliary facility for making the heat distribution uniform, but presupposes the ultraviolet curability. And more
The thickness and the curable resin are naturally limited, and it has been difficult to secure the thickness of the FRP layer necessary for corrosion resistance. JP-A-8-323860 describes a method of coating the inner surface of a tubular molded article using a combination of a cationic dye compound sensitive to near-infrared light, an organic boron salt compound, and a compound sensitive to ultraviolet to visible light. However, the deep curing property, the curing speed, and the storage stability are insufficient, and further improvement has been desired.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a photocurable composition which is rich in storage stability and which can be cured by long-wavelength light which is transparent so that the coating thickness can be freely determined without using a heat source. The purpose of the present invention is to develop a material for covering the inner surface of a tubular molded article by using the method described above, or a material for repairing a partial coating of the inner surface by using a patchwork tube.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, instead of using a conventionally used ultraviolet light initiator, a specific material having absorption in a longer wavelength region has been specified. It has been found that the above problem can be solved by using a photopolymerization initiator having the structure of formula (1), and the present invention has been completed. The present invention basically includes the following inventions. (1) (A) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin (B) 0.01 to 20 parts by weight of a bisacylphosphine oxide compound represented by the following general formula (1);

Embedded image (Wherein, R _{1 to} R ₃ each independently represent an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a substituted alkyl group, a substituted aryl group, a substituted allyl group, a substituted aralkyl Or a substituted alkenyl group, a substituted alkynyl group or a substituted heterocyclic group). A photocurable material for coating or repairing the inner surface of a tubular molded product obtained by impregnating a fibrous layered body with a resin composition containing a resin composition as an essential component. (2) The photocurable material according to (1), wherein at least one surface of the fibrous layered body is transparent in a wavelength region of 380 nm or more and is covered with an extensible film that is not affected by the impregnated resin composition.

(3) The resin composition described in the above (1) or (2) is further used as a photopolymerization initiator by the following general formula (2)
A photocurable material for coating or repairing the inner surface of a tubular molded product obtained by impregnating a fibrous layered body with a resin composition containing a cationic dye represented by the following formula and an organic boron compound represented by the following general formula (3). Formula ^{(2); D + · A} - ( wherein, D ⁺ is a cation having an absorption in the desired wavelength region of from visible light to near infrared light, A ^- represents various anions) General Formula (3);

Embedded image (Wherein, R _{4 to} R ₇ each independently represent an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, a substituted alkyl group, a substituted aryl group, A substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a cation. (4) The above (1) to (3) in which the cover film is inside.
After closing the end of the cylindrical body made of the photocurable material described above, inserting the cylindrical body into the tubular molded body, blowing air into the cylindrical body to inflate and press-fit the inner surface of the tubular molded body, and then 380 to 12
A method for coating the inner surface of a tubular molded body, comprising curing the tubular material with light having a wavelength of 00 nm.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition used for the photocurable material of the present invention is obtained by photopolymerizing an unsaturated polyester resin or a vinyl ester resin with a bisacylphosphine oxide compound represented by the above general formula (1). It is characterized by being comprised as an agent added. The photopolymerization initiator represented by the general formula (1) is more sensitive to a longer wavelength region than the conventional UV initiator, is excellent in light transmittance, and is cleaved by light irradiation to produce an acyl radical and a phosphino acid. Since it generates yl radicals, the polymerization initiation efficiency is said to be higher than conventional UV initiators.

Specific examples of the bisacylphosphine oxide compound of the general formula (1) used in the present invention include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide and bis (2,6-dichlorobenzoyl). −
2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylphosphine oxide, bis (2,6- Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2 6-dichlorobenzoyl)
-4-chlorophenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -decylphosphine oxide, bis (2,6-di Chlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2 4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6 -Dichlor-3,4
5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethyl Phenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-biphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxybiphenylphosphine oxide, bis (2-methyl-1-naphthoyl)- 2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methoxy- 1-naphthoyl) -4-ethoxy Phenylphosphine oxide, bis (2-methoxy-1-naphthoyl) -4-biphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) −2,4
Examples thereof include 4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

The object of the present invention can be achieved by using 0.01 to 20 parts by weight of these initiators based on 100 parts by weight of the total amount of the unsaturated polyester resin and / or vinyl ester resin. If it is less than this, polymerization may not be sufficiently performed. Preferably 0.03 to 20
It is in the range of parts by weight. More preferably 0.05 to 15
It is in the range of parts by weight. It is not preferable to use too much in terms of physical properties of the cured product and from an economic viewpoint. The initiator may be used alone or in combination of two or more. Methods for synthesizing these bisacylphosphine oxide compounds are described in JP-A-61-130296 and JP-A-6-2.
No. 98818 and Japanese Patent Publication No. 05-29234 describe the synthesis method. Further, another feature of the present invention is that a photopolymerization initiator represented by the general formula (1) and a compound having photosensitivity in the visible to near-infrared light region represented by the general formula (2) can be used in combination. . By selecting D ⁺ , the polymerization initiator having photosensitivity in the visible to near-infrared light region has photosensitivity in a long wavelength region as compared with the initiator represented by the general formula (1). From, because the light transmittance is more excellent,
The limitations on the thickness of the photocurable material and the amount of the inorganic filler added as needed are greatly relaxed. The compound represented by the general formula (2) is dyed by irradiation with light containing a wavelength at which the compound represented by the general formula (2) is sensitive in the presence of a four-coordinate boron anion represented by the general formula (3). Is discolored, radicals are generated, and polymerization is started. The decolorization reaction of the cationic dye is an irreversible reaction, and the color of the cationic dye does not impair the hue of the polymer.

The cationic dye of the general formula (2) may be a dye having absorption in an arbitrary wavelength region from visible light to near infrared light, and specifically, an arbitrary wavelength region in the range of 380 nm to 1200 nm. It is only necessary to have absorption. Preferred examples of the cation (D ⁺ ) of the present invention include methine, polymethine, indoline, cyanine, xanthene, oxazine, thiazine, diarylmethane, triarylmethane, and cations of pyrylium-based cation dyes. Among them, cationic dyes having absorption in the near-infrared light region are particularly preferable in consideration of light transmittance, equipment safety, light stability of the initiator, operability, and the like. The cation having an absorption in the near-infrared light region here is a cation having an absorption in a wavelength region of 740 nm or more, preferably 78 nm.
It is a compound having absorption in a wavelength region of 0 nm or more. Representative examples of such cationic dyes having absorption in the visible to near-infrared light region include, for example, cations shown in Table 1.

[0014]

[Table 1]

A ^{− as a} counter anion is an arbitrary anion, and a 4-coordinate boron anion similar to the anion portion of the organic boron compound of the general formula (3) is particularly preferable. Specific examples include n-butyl triphenyl boron ion, n-octyl triphenyl boron ion, triphenylsilyl triphenyl boron ion, di-n-dodecyl diphenyl boron ion, tetraphenyl boron ion, triphenyl naphthyl boron ion, tetrabutyl Examples thereof include a boron ion and tri-n-butyl (dimethylphenylsilyl) boron ion, and more specifically, an anion described in JP-A-6-75374.

Specific examples of the boron ion of the organic boron compound of the general formula (3) include n-butyltriphenylboron ion, n-octyltriphenylboron ion, triphenylsilyltriphenylboron ion, n -Butyl trianisyl boron ion, n-butyl tri (p-fluorophenyl) boron ion, n-butyl tri (p-trifluoromethyl phenyl) boron ion, di-n-dodecyl diphenyl boron ion, tetraphenyl boron ion, triphenyl naphthyl boron Ion, tetrabutylboron ion, and tri-n-butyl (dimethylphenylsilyl) boron ion.
The cation (Z ⁺ ) described in the formula is a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a diazonium cation, a tetrazolium cation, a phosphonium cation, or an (oxo) sulfonium cation. Metal cations such as sodium, potassium, lithium, magnesium and calcium, organic oxygen cations such as flavylium and pyranium salts, carbon cations such as tropylium and cyclopropylium, halogenium cations such as iodonium, arsenic, cobalt and palladium And cations of metal compounds such as chromium, titanium, tin, and antimony, and the like, which are described in detail in JP-A-6-75374. These cationic dyes and boron compounds can be used alone or in combination of two or more.

When the cationic dye of the general formula (2) and the organic boron compound of the general formula (3) are used in combination with the compound of the general formula (1), the cationic dye of the general formula (2) is The amount is suitably 20.0 parts by weight or less based on 100 parts by weight of the total amount of the unsaturated polyester resin and / or vinyl ester resin. Preferably it is 0.01 to 10.0 parts by weight. More preferably, it is 0.01 to 5.0 parts by weight.
If the amount of the cationic dye is less than 0.01 parts by weight, the effect of adding the cationic dye is not sufficiently exhibited. When the amount of the cationic dye is more than 20.0 parts by weight based on 100 parts by weight of the total amount of the unsaturated polyester resin and / or the vinyl ester resin, the radical generation amount becomes extremely large, and the cured product having high hardness is obtained. Is not obtained, and it is not preferable from an economic viewpoint. The cationic dye may be used alone or in combination of two or more.
The proportion of the cationic dye represented by the general formula (2) to the organic boron salt represented by the general formula (3) is generally from 1/20 to 10:
/ 1 (weight ratio). Preferably 1/10 to 1
/ 1, more preferably 1/5 to 1/2. Considering the decolorization reaction of the cationic dye, the efficiency of generating the polymerization initiation radical, and the like, it is preferable to add a relatively large amount of the organic boron compound. Examples of the combination of the cationic dye and the boron salt compound are described in JP-A-3-111402, JP-A-3-179003, and JP-A-4-146.
905, JP-A-4-261405, JP-A-4-261406, JP-A-5-194609 and the like have detailed descriptions.

The resins in the resin composition used in the present invention are unsaturated polyester resins and vinyl ester resins. The reason why these resins are suitable for the present invention is that not only the unsaturated polyester resin is inexpensive, but also the vinyl ester resin is excellent in corrosion resistance, in addition to having a reaction site which is cured by a photoreaction. In both cases, the hardness required for coating and repair (Barcol hardness tester; Type 93
(40 or more in 4-1), the time required for curing, and the degree of freedom in selecting a resin that requires less irradiation energy. The unsaturated polyester resin is
Polyester resin handbook, published by Nikkan Kogyo Shimbun, published in 1988, prepared by dissolving unsaturated polyester obtained by heat-esterifying glycol with unsaturated polybasic acid or saturated polybasic acid in monomers such as copolymerizable styrene. And the like. The unsaturated polyester may be produced by a known method, and specifically has an active unsaturated bond such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. No dicarboxylic acid and fumaric acid, maleic anhydride, maleic acid, a dicarboxylic acid having an active unsaturated bond such as itaconic acid as a component, ethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4 -Dimethanol, ethylene oxide adduct of bisphenol A, propylene of bisphenol A Polyalcohols oxide adduct is obtained as the alcohol component.

The vinyl ester resin used in the present invention is also called an epoxy acrylate resin, and is generally a polymerizable double resin formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group such as acrylic acid. It is a resin having a bond, and represents a resin described in detail in, for example, a coating glossary published by the Color Material Association published in 1993 or published in 1988 by the Polyester Resin Handbook published by Nikkan Kogyo Shimbun. Specifically, an epoxy (meth) acrylate obtained by using an epoxy resin and acrylic acid or methacrylic acid as components, or a polyester having a terminal carboxyl group obtained from a saturated dicarboxylic acid and / or an unsaturated dicarboxylic acid and a polyhydric alcohol has α,
A polyester (meth) acrylate obtained by reacting an epoxy compound containing a β-unsaturated carboxylic acid ester group.

Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether, its high molecular weight homologues, and novolak type polyglycidyl ethers. Examples of the saturated dicarboxylic acid include dicarboxylic acids having no active unsaturated group, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples of the dicarboxylic acid having an active unsaturated group include fumaric acid, maleic anhydride, maleic acid, and itaconic acid. As the polyhydric alcohol, for example, ethylene glycol, propylene glycol, dipropylene glycol, 1,2-
Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-
1,3-propanediol, cyclohexane-1,4-
Polyhydric alcohols such as dimethanol, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A are exemplified. As an epoxy compound containing an α, β-unsaturated carboxylic acid ester group, glycidyl methacrylate is a typical example.

The unsaturated polyester or vinyl ester used for the resin or the like is preferably one having a high degree of unsaturation, and has an unsaturated group equivalent (molecular weight per unsaturated group) of 1 or less.
100 to 800 parts by weight of resin, etc.
Use up to 90 parts by weight. Those having an unsaturated group equivalent of less than 100 cannot be synthesized. If the unsaturated group equivalent exceeds 800, a cured product having high hardness cannot be obtained. If the amount of the unsaturated polyester or vinyl ester in the resin or the like is less than 30 parts by weight, the curability and moldability will decrease. If the amount exceeds 90 parts by weight, a cured product with high hardness will not be obtained. The monomer having an unsaturated group typified by the styrene monomer to be blended with the resin of the present invention enhances the kneadability and impregnation with a fiber reinforcing material and a filler when producing an FRP molding material, and enhances the molded product. It is important for improving hardness, strength, chemical resistance, water resistance, etc., and is 10 to 70 parts by weight, preferably 15 parts by weight, per 100 parts by weight of the unsaturated polyester resin or vinyl ester resin.
５０50 parts by weight are used. If the amount is less than 10 parts by weight, the curability is inferior. If the amount exceeds 70 parts by weight, a product having high hardness cannot be obtained, and the heat resistance is insufficient, which is not preferable as an FRP material. In this case, as the monomer having an unsaturated group other than the styrene monomer, there are polymerizable monomers such as chlorostyrene, methyl methacrylate, and ethylene glycol dimethacrylate, and it is possible to substitute and use within a range that does not impair the gist of the present invention. is there.

A thixotropic agent and a thickener can be added to the resin composition used in the present invention. If necessary, other additives can be used. As the thixotropic agent, for example, 0.1 to 20 parts by weight of a known thixotropic agent such as silica powder (aerosil type), mica powder, and calcium carbonate powder is preferably added. Examples of the thickener include, for example, magnesium oxide, magnesium hydroxide, calcium oxide, alkaline earth metal compounds such as calcium hydroxide, organic metal compounds such as aluminum alcoholate, toluylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, Isocyanates such as diphenylmethane diisocyanate, aziridine compounds and the like are used in an amount of 0.2 to 30 parts by weight based on 100 parts by weight of the resin and the like. When the amount of the thickener is less than 0.2 parts by weight, the effect of thickening is substantially reduced, while when the amount exceeds 30 parts by weight, the viscosity becomes extremely high and the production of the sheet becomes difficult.

Also, these thixotropic agents and thickeners may be used in combination. As the inorganic filler used as necessary, for example, known ones such as calcium carbonate, talc, clay, glass powder, silica, aluminum hydroxide, barium sulfate, and titanium oxide are used. Of course, these inorganic fillers can be used in combination, and the amount used is 0 to 50 parts by weight, preferably 0 to 40 parts by weight, based on 100 parts by weight of the resin. When the amount of the filler is more than 50 parts by weight, the impregnating property is reduced, bubbles are likely to remain, the fluidity during molding is poor, and it is difficult to adhere to the mold. In addition, in the present invention, it is also possible to further use a low-shrinking agent. As the low-shrinking agent, known polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene and the like can be used.
0 to 20 parts by weight, preferably 0 to 1 part by weight, per 100 parts by weight
5 parts by weight. If the amount of the low-shrinkage agent exceeds 20 parts by weight, the viscosity becomes too high, and the moldability decreases, and depending on the type of the low-shrinkage agent, the chemical resistance of the cured product decreases. Further, for the purpose of accelerating curing and obtaining a cured product having high hardness in the composition of the present invention, a thermal polymerization initiator can also be added,
Specific examples include various peroxides such as t-butyl peroxypivalate and lauroyl peroxide, and lipophilic azobis compounds such as azobisisobutyronitrile.

The composition of the present invention may further contain a leveling agent, a plasticizer, an antifoaming agent, a polymerization inhibitor, an antioxidant, etc., which are generally used as paint additives, if necessary. Can be added to such an extent as not to impair. The above resin composition is impregnated into a fibrous layered body. As the layered body, felt, nonwoven fabric, woven fabric and the like are used, which may be a single layer or a multilayer. The shape of the layered body is generally a cylinder or a sheet. The wall thickness of the tubular body and the thickness of the sheet depend on the diameter of the tubular molded body to be covered or repaired.
The thickness of about 10 to 20 mm in a 0 mm tubular molded body,
It is appropriate in consideration of reinforcement strength and workability. In order to secure this thickness, a single fiber or a plurality of fibers may be superposed. Fibers include glass fiber, polyester fiber, polyethylene fiber, polypropylene fiber,
Acrylic fiber or the like is used. After impregnating the fibrous layered body with the resin composition, at least one surface thereof is covered with a heat extensible material (cover film) that is transparent in a wavelength region of 380 nm or more and is not affected by the impregnated resin composition. The heat-extensible film is necessary for pressing the photocurable composition into the molded body tube by gas pressure, and is impermeable,
In addition, since the composition is light-cured, the composition has excellent transparency in a wavelength region of 380 nm or more, and is not affected by the impregnated resin composition and does not transmit the monomers contained in the resin. What is necessary is just to have the property and the heat extensibility of a film. Depending on the type of the monomer, for example, the thickness of polyamide up to about 100 μm, similar to those used in the conventional composite material composition,
Saturated polyester, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyurethane, vinylon,
Partially saponified ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, plasticized polyvinyl alcohol and the like can be used. As used herein, the film may be formed into a film in advance, or may be a film obtained by spraying or painting (coating) the resin. In the present invention, these two are called films.

The wavelength of light used in the present invention is 380-380.
This is a wavelength region of 1200 nm. If only the light having a wavelength shorter than 380 nm is used, the light transmittance is extremely deteriorated, which is not preferable for safety. Further, only light having a wavelength longer than 1200 nm is not preferable because there is no photosensitivity of the bisacylphosphine oxide compound represented by the general formula (1) and the cationic dye represented by the general formula (2). Examples of the light source having the above wavelength include a halogen lamp, a xenon lamp, a mercury lamp, a metal halide lamp, and sunlight. Above all, a metal halide lamp or a halogen lamp for visible light is preferable because it emits a wavelength effective for decomposing the initiator of the present invention, and at the same time, the temperature of the irradiated object is increased by the action of heat rays to accelerate the curing reaction. Further, the metal halide lamp or the halogen lamp for visible light has a wide variety of products from small to large bulb diameters, and it is easy to design an irradiator according to the tubular molded article to be covered or repaired. For a description of this lamp, see "Optical Engineering Handbook" (Asakura Shoten, 1986), p.
462-463. In addition, two or more light sources can be used in combination in order to match the photosensitive wavelength of the photopolymerization initiator. The light intensity required for curing the tubular molding inner surface coating material of the present invention varies depending on the photosensitivity (photosensitivity) of the initiator, the curability and the amount of the unsaturated polyester resin or vinyl ester resin, etc., but is generally 10 mJ / cm. The light intensity is ² or more, preferably 100 mJ / cm ² or more. If the light intensity is too low, the photoreaction does not proceed sufficiently, and a cured product having high hardness may not be obtained. Further, in order to accelerate the polymerization reaction, a curing step can be performed by heating.

In the method of coating the inner surface of a tubular molded article with the photocurable material of the present invention, a film is provided on the inner surface of a cylindrical body made of the material, a light irradiation device is provided in the cylindrical body, and both ends of the cylindrical body are coated. Close and insert the cylinder into the tubular molding,
There is a method in which the material is inflated by blowing air or the like into the cylinder, brought into close contact with the inner wall of the tubular molded body, and irradiated with light to cure the material (FIG. 1). The cured film may be peeled off if necessary. As another method, a known method is provided in which a film is provided on the outside of a cylindrical body, and the cylindrical body is inserted while being turned upside down when the cylindrical body is inserted into the tubular molded body (for example, Japanese Patent Application Laid-Open Nos. Hei 5-138738 and Hei 8-13838). -1779) can also be employed. As a method for locally repairing the inner surface of the tubular molded body, there is a commercially available repairing tool provided with a light source in a silicon tube, and this can be used. The resin-impregnated sheet of the present invention is wound around the outside of the tube, applied to the repaired portion, and the silicon tube is inflated and compressed by compressed air, and then irradiated with light.

[0027]

The present invention will be described in detail below with reference to examples and comparative examples. “Parts” and “%” in each example are based on weight. [Synthesis Example 1] (Synthesis of unsaturated polyester resin UP-1) In a 40-liter reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, and a thermometer, 40 mol of neopentyl glycol, 60 mol of diethylene glycol, 45 mol of isophthalic acid and 55 mol of fumaric acid were charged, and 2
The reaction was carried out at 00 ° C. until the acid value reached 15. Thereafter, 0.015 parts of hydroquinone was added to 100 parts of the obtained unsaturated polyester, and after cooling to 160 ° C., a styrene monomer was mixed so as to be 35% of the resin, and the unsaturated polyester resin ( UP-1) was obtained.

[Synthesis Example 2] (Vinyl ester resin VE-
Synthesis of 1) A reactor equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, and a thermometer was charged with 1 equivalent (189) of Epicoat 828 (manufactured by Yuka Shell Co., Ltd., epoxy resin, epoxy equivalent 189).
g), bisphenol A (0.5 equivalent based on the epoxy group) and 0.3 parts of triethylamine were charged and reacted at 150 ° C. for 2 hours under a nitrogen atmosphere. After cooling to 110 ° C., 1 equivalent of methacrylic acid was added to 1 equivalent of epoxy (8 equivalents).
6 g), 0.3 part of tris (dimethylaminomethyl) phenol, 0.03 part of hydroquinone, and ス チ レ ン of the total amount of the styrene monomer were charged.
The reaction was carried out at 10 to 130 ° C. for 3 to 4 hours, and the reaction was terminated when the acid value became 5 or less. The remaining 3/4 of the styrene monomer was added to obtain a vinyl ester resin VE-1 such that the total styrene monomer content was 35%.

EXAMPLE 1 Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, a photopolymerization initiator, was added to 100 parts of the unsaturated polyester resin (UP-1) obtained in Synthesis Example 1. 1.0 part and 0.8 parts of Aerogel 200 (Nippon Aerogel Co., Ltd.) were mixed as a thixotropic agent to obtain a photocurable resin composition. 10m made of polyester fiber coated on one side with transparent polyurethane
The felt layer was impregnated with a roller at a ratio of 10 parts of an m-thick felt-like fabric (trade name: Coating Felt, manufactured by Nippon Valqua Industries, Ltd.) and defoamed to obtain a photocurable material having a thickness of 10 mm. The photocurable material was irradiated from the polyurethane-coated surface with a 2 kW metal halide lamp (trade name: Dynabeam 2: manufactured by Toshiba Lighting & Technology Corp.) at a distance of 1 m, and was completely cured to the back surface in 7 minutes.
When the cured product was measured by Barcol hardness (using type 934-1), a value of 35 or more was shown on both sides.

(Example 2) The vinyl ester resin (VE-1) obtained in Synthesis Example 2 was used in place of the unsaturated polyester resin used in Example 1, and terrene was used instead of Aerogel 200 as a thixotropic agent. Except for using 2 parts of 72000-20 (manufactured by Kyoeisha Chemical Co., Ltd.) and performing high-speed stirring, the same operation as in Example 1 was performed to obtain a cured product having a thickness of 10 mm completely cured to the back surface in 5 minutes. . When the Barcol hardness of the cured product was measured in the same manner as in Example 1, both sides showed a value of 35 or more.

Example 3 Of the composition used in Example 1, 1 part of magnesium oxide (trade name: Magmic, manufactured by Kyowa Chemical Industry Co., Ltd.) as a thickener instead of Aerogel 200 as a thixotropic agent Was added to obtain a photocurable resin composition. This photocurable resin composition was used as a # 350 glass cloth [trade name: FW350, manufactured by Nitto Boseki Co., Ltd.]
And polyester nonwoven fabric [Product name: Sontara 8005H,
DuPont Co., Ltd.] 12 sets each sewn by 1 ply are impregnated with a roller and laminated so that the resin content becomes 75 wt% while defoaming.
A thickening reaction was performed for 8 hours to obtain a photocurable material having a thickness of 10 mm. Light irradiation was performed in the same manner as in Example 1 to obtain a cured product having a thickness of 10 mm which was cured to the back surface in an irradiation time of 7 minutes. When the Barcol hardness of the cured product was measured in the same manner as in Example 1, it showed a value of 40 or more on both sides.

Example 4 101.8 parts of the photo-curable resin composition used in Example 1 was further added with aluminum hydroxide [trade name: Heidilite H-320, Showa Denko KK]
10 parts) and 1 part of magnesium oxide (trade name: Magmic, manufactured by Kyowa Chemical Industry Co., Ltd.) as a thickener were added to obtain a photocurable resin composition. Next, this photocurable resin composition is impregnated with # 350 glass cloth [trade name: FW350, manufactured by Nitto Boseki Co., Ltd.] with a roller and defoamed so that the resin content becomes 70 wt% and the thickness is 2 mm. Of the photocurable material. This photocurable material was subjected to the same light irradiation operation as in Example 1 to obtain a cured product having a thickness of 2 mm, which was cured to the back surface in an irradiation time of 4 minutes. When the Barcol hardness of the cured product was measured in the same manner as in Example 1, both sides showed a value of 40 or more.

(Example 5) Of the photocurable resin compositions used in Example 2, Tarlene 720 used as a thixotropic agent
Instead of 00-20, diphenylmethane diisocyanate [trade name: ISONATE143L, Mitsubishi Dow Co., Ltd.]
The composition obtained by adding 4 parts was used as a photocurable resin composition.
Next, two layers of this photocurable resin composition are impregnated with a roller so that the resin content becomes 90 wt%, and defoamed, and two layers of polyester nonwoven fabric (trade name: Sontara 8005H, manufactured by DuPont Co., Ltd.) are laminated. For 24 hours to obtain a photocurable material having a thickness of 2 mm. This photocurable material was subjected to the same light irradiation operation as in Example 1 for an irradiation time of 5 hours.
In 2 minutes, a cured product having a thickness of 2 mm was cured to the back surface. When the Barcol hardness of the cured product was measured in the same manner as in Example 1, both sides showed a value of 40 or more.

Example 6 The photopolymerization initiator used in Example 1 was bis (2,4,6-trimethylbenzoyl)-
Other than changing to 1 part of phenylphosphine oxide,
When exactly the same operation as in Example 1 was performed, an irradiation time of 7
In minutes. When the hardness of the obtained cured product was measured by Barcol hardness, it showed a value of 40 or more on both sides.

Example 7 To 102 parts of the photocurable resin composition used in Example 3 was added 1,1,5,5-tetrakis (p-diethylaminophenyl) -2,4-pentadienyl triphenyl n 0.1 parts of butyl borate (manufactured by Showa Denko KK, hereinafter abbreviated as IRB) and 0.5 parts of tetra n-butyl ammonium triphenyl n-butyl borate (manufactured by Showa Denko KK, abbreviated as P3B) And 10 parts of calcium carbonate [trade name: Softon 1200, manufactured by Bihoku Powder Chemical Industry Co., Ltd.] were mixed and added to obtain a photocurable resin composition. Next, this photocurable resin composition was sewn with # 350 glass cloth [trade name: FW350, manufactured by Nitto Boseki Co., Ltd.] and polyester non-woven fabric [trade name: Sontara 8005H, manufactured by Dupont Co., Ltd.] 1 each. The set is impregnated with a roller and defoamed, resulting in a resin content of 75w
The reaction was carried out at 80 ° C. for 48 hours to obtain a photocurable material having a thickness of 2 mm. This photocurable material is used as a halogen lamp (ADS), A
Light irradiation at a distance of 30 cm with LF-10 (1 kW) completely cured the back surface in 5 minutes. The Barcol hardness of the cured product was measured in the same manner as in Example 1.
The above values were shown.

(Example 8) In addition to 103 parts of the photocurable resin composition used in Example 2, 0.1 part of IRB and P3B
0.5 parts, calcium carbonate [Product name: Softon 120]
0, Bihoku Powder Chemical Industry Co., Ltd.] 10 parts, diphenylmethane diisocyanate as a thickener [trade name: ISONAT]
E143L, manufactured by Mitsubishi Dow Co., Ltd.] was used as the photocurable resin composition. Next, this photocurable resin composition was sewn with # 350 glass cloth [trade name: FW350, manufactured by Nitto Boseki Co., Ltd.] and polyester non-woven fabric [trade name: Sontara 8005H, manufactured by Dupont Co., Ltd.] 1 each. The set is impregnated with a roller and defoamed so that the resin content becomes 75 wt%.
A time thickening reaction was performed to obtain a photocurable material having a thickness of 2 mm. When this photocurable material was irradiated with the same light as in Example 6, it was completely cured to the back surface in 6 minutes. The Barcol hardness of the cured product was measured in the same manner as in Example 1.
The above values were shown.

(Comparative Example 1) A photocurable resin composition in which the photopolymerization initiator used in Example 1 was replaced with 5 parts of an ultraviolet polymerization initiator Darocure 1173 (manufactured by Ciba Specialty Chemical Co.) was used. Similarly, 10m made of polyester fiber
A m-thick felt-like fabric (trade name: Coating Felt, manufactured by Nippon Valqua Industry Co., Ltd.) is impregnated and defoamed using a roller, and a 2 kW ultra-high pressure water-cooled mercury lamp (hydro Cure 2
000 (manufactured by Oak Manufacturing Co., Ltd.) for 20 minutes, but only the surface layer was cured, and the inside and the back were uncured. Therefore, the hardness of the cured product could not be measured.

(Comparative Example 2) A photocurable resin composition in which the photopolymerization initiator used in Example 2 was replaced by 5 parts of an ultraviolet polymerization initiator Irgacure 184 (manufactured by Ciba Specialty Chemicals) was used. Similarly, the felt-like woven fabric is impregnated and defoamed using a roller, and 30
Irradiation was performed for 20 minutes with a 2 kW ultra-high pressure water-cooled mercury lamp (HydroCure 2000, manufactured by Oak Manufacturing Co., Ltd.) at a distance of 20 cm. The curing was only on the surface layer, and the inside and the back were uncured. Therefore, the hardness of the cured product could not be measured.

(Comparative Example 3) Instead of the photopolymerization initiator used in Example 3, a visible light polymerization initiator lucilin TPO (B
The same operation as in Example 3 was performed except that the amount was changed to 1 part (manufactured by ASF), but it took 15 minutes to completely cure the back surface. When the hardness of the cured product was measured by Barcol hardness, both sides showed a value of 40 or more.

Comparative Example 4 The photopolymerization initiator used in Example 1 was replaced with a visible light polymerization initiator, lucilin TPO (BASF
Except that the procedure was changed to 1 part, the same operation as in Example 1 was performed, but it took 10 minutes to completely cure to the back surface. When the hardness of the cured product was measured by Barcol hardness, both sides showed a value of 40 or more.

(Comparative Example 5) Instead of the photopolymerization initiator used in Example 5, a visible light polymerization initiator lucilin TPO (B
The same operation as in Example 5 was performed, except that the amount was changed to 1 part (manufactured by ASF).
It took a minute. When the hardness of the cured product was measured by Barcol hardness, both sides showed a value of 40 or more.

(Embodiment 9) An embodiment of an actual coating method will be described with reference to FIGS. Figure 1 shows the 150 to be repaired
Inside the fume tube with a diameter of 1 mm (reference numeral 1), the photocurable material used in Example 5 was covered on both sides with a polyurethane film and sewn into a 150 mm diameter tube (reference numeral 2) in an uncured state. FIG. One end of the photocurable material 2 is provided with a bobbin (reference numeral 3) having a function of discharging air out of the system in order to appropriately adjust the air pressure when pressing with compressed air, and The bobbin 3 is provided with a rope (reference numeral 4) as traction means for simultaneously introducing the photocurable material 2 into the fume tube 1 and a light irradiation device described later, and the rope is operated by a traction mechanism (reference numeral 5). It has become. FIG. 2 shows that after the photocurable material 2 is introduced into the fume tube 1, the other end of the photocurable material 2 is squeezed, and the compressed air inlet (reference numeral 6) and the compressed air inlet tube (reference numeral 7) are connected. A figure in which compressed air of 1 kgf / cm ² is introduced, and the photo-curing material is pressed against the inner surface of the fume tube and cured while the light irradiation device (reference numeral 8) is moved by the traction mechanism 5 at a speed of 10 cm per minute. It is.
At this time, the rope 4 provided on the bobbin 3 moves only the light irradiation device 8 and the connection between the light-curable material 2 and the rope 4 is released so that the light-curable material 2 is not pulled. As shown in FIG. 3, the light irradiation device used here is a device in which a plurality of Ushio Electric's QIR100V-400WIR (reference numeral 9) fixed to a jig (reference numeral 10) are connected to each other, and are smoothly pulled. A rotatable roller (reference numeral 12) is attached to a telescopic arm (reference numeral 11). Barcoal hardness of the light-irradiated surface of the photocurable material of the fume tube coated with the photocurable material in the same manner as in Example 1 was measured.
It showed a value of 0 or more.

[0043]

The photocurable material used in the method for coating the inner surface of a tubular molded article according to the present invention is easy to produce, has little restrictions on the types and amounts of fillers and reinforcing materials, and has a low storage stability. It is excellent, and the one with a thick coating layer is easy to manufacture. Since no heat is required during construction, there is no need for a heat medium, a heat source, or auxiliary equipment for equalizing heat, regardless of the material of the pipe to be covered, and when the pipe diameter is small. Even if the diameter is large, there is no problem, and the inner surface of the tubular molded body to be coated with the resin can be easily coated in a short time. Further, it can be used for repairing an already laid pipeline, and coating can be performed which is extremely effective in improving the corrosion resistance and strength of the pipeline.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing a method of introducing a photocurable material in a coating method of the present invention, and a light irradiation device, a pulling mechanism, and the like.

FIG. 2 is a diagram schematically showing pressure bonding and light curing.

FIG. 3 is a diagram schematically showing a light irradiation device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Fume tube 2 Photocurable material 3 Bobbin 4 Rope 5 Traction mechanism 6 Compressed air inlet 7 Compressed air inlet tube 8 Light irradiation device 9 Lamp body 10 Jig 11 Arm 12 Roller

[Table 1]

[Table 1]

[Table 1]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08K 5/5397 C08K 5/5397 C08L 67/06 C08L 67/06 C09J 7/02 C09J 7/02 Z (72) Inventor Shuichi Sugita 1-1-1, Onodai, Midori-ku, Chiba-shi, Chiba, Japan Showa Denko KK Research Institute (72) Kazuo Otani 673-8 Kuboshima, Kumagaya-shi, Saitama (72) Tomio Yamamoto 13-Yomota, Honjo-shi, Saitama ( 72) Inventor Hideki Chiyo 618-1 Mizonokuchi, Takatsu-ku, Kawasaki City, Kanagawa Prefecture

Claims (7)

[Claims] (A) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin (B) 0.01 to 20 parts by weight of a bisacylphosphine oxide compound represented by the following general formula (1) ); (Wherein, R _{1 to} R ₃ each independently represent an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a substituted alkyl group, a substituted aryl group, a substituted allyl group, a substituted aralkyl Or a substituted alkenyl group, a substituted alkynyl group or a substituted heterocyclic group). A photocurable material for coating or repairing the inner surface of a tubular molded product obtained by impregnating a fibrous layered body with a resin composition containing a resin composition as an essential component. 2. The photocurable material according to claim 1, wherein the fibrous layered body is a cylindrical body. 3. The method according to claim 1, wherein at least one surface of the fibrous layered body has 380
The photocurable material according to claim 1, wherein the photocurable material is transparent in a wavelength region of at least nm and is covered with an extensible film that is not affected by the impregnated resin composition. 4. The resin composition according to claim 1, further comprising, as a photopolymerization initiator, a cationic dye represented by the following general formula (2) and an organic compound represented by the following general formula (3): A photocurable material for coating or repairing the inner surface of a tubular molded body obtained by impregnating a fiber composition with a resin composition containing a boron compound. Formula ^{(2); D + · A} - ( wherein, D ⁺ is a cation having an absorption in the desired wavelength region of from visible light to near infrared light, A ^- represents various anions) General Formula (3); (Wherein, R _{4 to} R ₇ each independently represent an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, a substituted alkyl group, a substituted aryl group, Represents a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a cation. 5. A method for coating a fibrous layered body with a resin composition according to claim 1, which comprises a filler and / or a thickener and / or a thixotropic agent. Repair photocurable material. 6. The end of a cylindrical body made of the photocurable material according to claim 2 wherein the cover film is inside, the cylindrical body is inserted into a tubular molded body, and air is introduced into the cylindrical body. After blowing and inflating the inner surface of the tubular molded body,
A method for coating the inner surface of a tubular molded body, wherein the tubular material is cured with light having a wavelength of 380 to 1200 nm. 7. The method for coating the inner surface of a tubular molded body according to claim 4, wherein the curing of the cylindrical body material is performed using a metal halide lamp for visible light or a halogen lamp.