JP2001335612A - 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 curing material for covering or repairing the inside face of a tubular molded product wherein a stabilized reaction in a short time is regarded as B stage state and stabilized and rapid curing is possible over a long time. SOLUTION: A resin composition, which contains (A) an unsaturated polyester resin and/or vinyl ester resin 100 pts.wt., for example (B1) at least two sorts of photopolymerization initiator 0.01 to 10 pts.wt. which is the combination of the initiator with a photosensitivity to visible light >=500 nm wavelength or near infrared light region and the initiator with a photosensitivity to a visible light <=500 wavelength and/or ultraviolet region and (c) an inorganic or organic filler 0-200 pts.wt., is immersed in a fiber layer-form substance, it is irradiated with a light of wavelength >=500 nm, a part of radical polymerizable unsaturated group in the composition is prepolymerized and a photopolymerization initiator and a part of radical polymerizable unsaturated group with at least photosensitivity to a light having <500 nm wavelength are remained.

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, a steel pipe, a vinyl chloride pipe and the like, and a method for coating the same. More specifically, irradiation of visible light and / or ultraviolet light having a wavelength of 500 nm or less, which is prepolymerized by irradiating the fiber layered body impregnated with the resin composition with visible light and / or near-infrared light having a wavelength of 500 nm or more. Also, the present invention relates to a photocurable material for coating or repairing an inner surface of a tubular molded body, an inner surface of a square tube, an inner surface of a human hole, etc., which can be cured by heating, and a method of coating the same.

[0002]

2. Description of the Related Art Concrete, steel, stainless steel, vinyl chloride, pottery and the like are used as pipe materials for water and sewage, crude oil, chemicals, city gas and the like. In the water supply and sewer systems, concrete fume pipes are mainly used, but in addition to physical damage due to long-term burial use, especially in the sewer systems, sulfur dioxide gas is generated due to decomposition of contaminants by sulfate-reducing bacteria and sulfur oxidation and sulfur oxidation. Corrosion, aging, cracks, etc. occur from the inside of the concrete pipe due to the generation of sulfate ions by bacteria, and displacement of joints, uneven settlement, infiltration of groundwater and earth and sand, etc. have become problems, and existing pipes need to be updated. Sex had increased. However, the roads where the sewer pipes are buried are also buried with electricity, gas, water, etc., making it difficult to renew the sewer pipes by open-cutting methods.
Excavation work that requires a longer period of time requires a method that can be performed without excavation in order to cause traffic obstacles and the like.

[0003] As a means for solving these requirements, a tubular fibrous body impregnated with a thermosetting resin such as an unsaturated polyester resin and a thixotropic agent added thereto is inserted into a tube and pressure-bonded, and then heated with hot water or hot air. Curing method (Japanese Patent Publication 1-15)
No. 374, etc.) and a method in which ultraviolet or visible light is used as a curing means using a tubular composite material obtained by impregnating an unsaturated polyester resin or vinyl ester resin into a glass mat, glass cloth, or the like to increase the viscosity. No. 2,210,981). This enabled efficient sewer pipe repair without cutting, but with only thixotropic materials, resin leaked out of the fibrous body during storage,
There have been problems such as the occurrence of bias and the failure to obtain uniform fiber content. In addition, in the method of thickening after impregnating the fibrous body, a conventional thickening method of a thermosetting resin, which is a known technique, for example, metal thickening with magnesium oxide of an unsaturated polyester resin or isocyanate thickening of a vinyl ester resin. The thickening method requires a long time to thicken, and it is difficult to stabilize the thickened state, and the reactive diluent such as styrene monomer in the resin increases the viscosity of vinyl ester resin or unsaturated polyester resin. Is not involved in
Problems such as the resin flowing out of the fibrous base material during storage have not been solved.

[0004]

SUMMARY OF THE INVENTION In view of the above situation, the present invention is capable of achieving a B-stage state by a stabilized reaction in a short time, and a resin flowing out of a fibrous base material during storage. It is an object of the present invention to provide a curable material for coating or repairing the inner surface of a tubular molded body which is stable for a long period of time and can be cured more quickly, and a method for coating the same. Here, the B-stage state refers to a stage in which the reaction of the initial raw material prepolymer is further advanced to increase the molecular weight and the melt viscosity.

[0005]

According to the present invention, there are provided (A) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin, and (B1) photosensitivity in a visible light or near infrared light region having a wavelength of 500 nm or more. 0.01 to 10 parts by weight of at least two photopolymerization initiators which are a combination of a photopolymerization initiator and a photopolymerization initiator having photosensitivity in a visible light region and / or an ultraviolet region of less than 500 nm; Alternatively, a fibrous layered body is impregnated with a resin composition containing 0 to 200 parts by weight of an organic filler, and a wavelength of 50
Irradiate light of 0 nm or more to prepolymerize some of the radically polymerizable unsaturated groups in the composition, and at least a photopolymerization initiator and a radically polymerizable unsaturated group photosensitive to light having a wavelength of less than 500 nm. (A) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin, (B2) visible light having a wavelength of 500 nm or more or near red. 0.01 to 10 parts by weight of at least two kinds of polymerization initiators which are a combination of a photopolymerization initiator having photosensitivity in an external light region and a thermal polymerization initiator, and (C) an inorganic or organic filler of 0 to 200 parts by weight Part is impregnated into a fibrous layered body, and irradiated with light having a wavelength of 500 nm or more to partially polymerize radically polymerizable unsaturated groups in the composition, and Curable material for coating or repairing the inner surface of a tubular molded body in which a thermal polymerization initiator and a part of a radically polymerizable unsaturated group remain, and a fibrous layered material is selected from sheet, roll, tubular, and tubular shapes One or more curable materials for coating or repairing the inner surface of the tubular molded body according to the above or the above, and a photopolymerization initiator having photosensitivity to visible light or near infrared light having a wavelength of 500 nm or more is represented by the general formula (1) ^{) D + · a - ··· (} 1) ( wherein, D ⁺ is methine having photosensitivity in a visible light region or infrared light region, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane, or pyrylium A-is a dye cation, and A ^- represents various anions.) A cationic dye having photosensitivity in the visible light region or near-infrared light region represented by the general formula (2):

[0006]

Embedded image

(Wherein Z ⁺ represents an arbitrary cation;
¹ , R ² , R ³ and R ⁴ are each independently an alkyl group, aryl group, acyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, halogen atom, substituted alkyl group, substituted aryl group , A substituted acyl group,
It represents a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group. The curable material for coating or repairing the inner surface of a tubular molded product according to any one of the above, which is a combination of an organoboron compound represented by the following: a photopolymerization initiator having photosensitivity from an ultraviolet light region to a visible light region. The curable material for coating or repairing the inner surface of a tubular molded product according to any one of the above or any one of the above, wherein one kind is an acylphosphine oxide-based compound; Is closed, the tubular body is inserted into the tubular molded body, and gas is blown into the tubular body to inflate the tubular molded body so as to be pressed against the inner surface of the tubular molded body. Then, the tubular body material is cured by irradiation with ultraviolet light and / or visible light or heating. A method for coating the inner surface of a tubular molded body, characterized in that the curable sheet-like material according to any one of the above or the like is wound around a rubber sleeve provided with a light source and a heater therein, A method for coating the inside surface of a tubular molded body, comprising applying a rubber gas to the inside of a tubular molded body, inflating a rubber sleeve with a compressed gas and pressing the rubber sleeve, and then irradiating or heating ultraviolet light and / or visible light or heating the tubular material. ,
Is provided.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Among the unsaturated polyester resins or vinyl ester resins used in the present invention (hereinafter, both resins may be collectively referred to as resins, etc.), the unsaturated polyester used as a raw material is as follows. May be produced by a known method, and specifically, a saturated polybase having no polymerizable unsaturated bond such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. An acid or its anhydride and an unsaturated polybasic acid or its anhydride having an active unsaturated bond such as fumaric acid, maleic anhydride, maleic acid, and itaconic acid as an acid component, and ethylene glycol, Propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pen Tandiool, 1,6-hexanediol, 2-methyl-1,3-propanediol,
Polyvalent alcohols such as 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A In which alcohol is reacted as an alcohol component.

The vinyl ester used as a raw material for the vinyl ester resin (epoxy acrylate resin) is produced by a known method, and is obtained by reacting an unsaturated monobasic acid such as acrylic acid or methacrylic acid with the epoxy resin. Α, β-unsaturated carboxylic acid ester to epoxy (meth) acrylate obtained by the reaction or saturated polyester or unsaturated polyester having a terminal carboxyl group obtained from saturated dicarboxylic acid and / or unsaturated dicarboxylic acid and polyhydric alcohol And a polyester (meth) acrylate of a saturated polyester or an unsaturated polyester obtained by using an epoxy compound having a group as a component. Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether, its high-molecular-weight homologues, and novolak-type polyglycidyl ethers.

As the saturated dicarboxylic acid used for the terminal carboxyl polyester (vinyl ester raw material), dicarboxylic acids 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. Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol.
1,2-butanediol, 1,3-butanediol
1,5-pentaneddiol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2
Polyhydric alcohols such as -dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A. As an epoxy compound containing an α, β-unsaturated carboxylic acid ester group used in the production of vinyl esters, glycidyl methacrylate is a typical example.

The unsaturated polyester or vinyl ester as the raw material of the component (A) preferably has a relatively high degree of unsaturation, and has an unsaturated group equivalent (molecular weight per unsaturated group) of about 100 to 800. Is preferred. If the unsaturated group equivalent is less than 100, it cannot be synthesized, and if the unsaturated group equivalent exceeds 800, a cured product having high hardness cannot be obtained. The unsaturated polyester resin or vinyl ester resin as the component (A) is usually obtained by blending a monomer having an unsaturated group represented by a styrene monomer (a reactive diluent) with the above unsaturated polyester or vinyl ester. . The monomer having an unsaturated group enhances the kneading and impregnating properties with the fiber reinforcement and filler when producing a composite material, and the hardness, strength, and
Styrene monomers are important for improving chemical resistance, weather resistance and the like, and styrene monomers are particularly effective for improving corrosion resistance. The amount of the monomer having an unsaturated group is 10 to 250 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the unsaturated polyester or vinyl ester. If the amount is less than 10 parts by weight, workability, impregnation, and corrosion resistance deteriorate due to high viscosity.
If the amount exceeds 50 parts by weight, sufficient strength and heat resistance cannot be obtained, which is not preferable as a matrix of the corrosion-resistant FRP. When a styrene monomer is used as a monomer having an unsaturated group, part or all of the styrene monomer is converted into a styrene-based monomer such as chlorostyrene, vinyltoluene, divinylbenzene, methyl (meth) acrylate, ethyl (meth) acrylate, Ethylene glycol di (meth)
Other polymerizable monomers such as acrylates can be substituted for and used within a range that does not impair the gist of the present invention.

[0012] (B1) as the component and (B2) a photopolymerization initiator having photosensitivity in a visible light or near infrared light region longer than the wavelength 500nm according to the component of the general formula ^{(1) D + · A -} ·· - (1) (wherein, D ⁺ is the visible light region or methine having photosensitivity in the near infrared region, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane, or pyrylium dyes cation, a ^- Represents various anions.) A cationic dye having photosensitivity in the visible light region or the near infrared light region represented by the general formula (2):

[0013]

Embedded image

(Wherein, Z ⁺ represents an arbitrary cation;
¹ , R ² , R ³ and R ⁴ are each independently an alkyl group, aryl group, acyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, halogen atom, substituted alkyl group, substituted aryl group , A substituted acyl group,
It represents a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group. The photoinitiator which combined the organic boron compound represented by ()) is preferable.

A ⁻ , which is a counter anion of the cationic dye represented by the general formula (1), is any anion such as p-toluenesulfonate ion, organic carboxylate ion, perchlorate ion and halide ion. , General formula (3)

[0016]

Embedded image

(Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent an alkyl group, an aryl group, an acyl 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 acyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted silyl group, or a substituted heterocyclic group.). .

Examples of the cation “Z ⁺ ” in the general formula (2) include a quaternary ammonium cation, a quaternary pyridinium cation, and a quaternary quinolinium cation which are insensitive to visible light or near infrared light. Ions, diazonium cations, tetrazolium cations, sulfonium cations, oxosulfonium cations, metal cations such as sodium, potassium, lithium, magnesium and calcium, and cation charges on oxygen atoms such as flavylium and pyranium salts ( Organic) compounds, carbon cations such as tropylium and cyclopropylium, halogenium cations such as iodonium, and cations of metal compounds such as arsenic, cobalt, palladium, chromium, titanium, tin and antimony. In the present invention, the composition ratio between the organic boron compound and the near-infrared light or visible light-absorbing cationic dye is preferably from 1/5 to 1 / 0.05 by weight (organic boron compound / cationic dye), Particularly preferably 1/1
１ ／ 1 / 0.1. In general, it is preferable to use a larger amount of the organic boron compound than the cationic dye from the viewpoints of the decoloring reaction of the dye and the radical generation efficiency.

By combining the organic boron compound represented by the general formula (2) with a cationic dye having a photosensitive wavelength in the visible light or near-infrared light region, the dye irradiated with light having a wavelength in the photosensitive region can be used. When excited and exchange electrons with the organic boron compound, the dye is decolorized and radicals are generated to cause a polymerization reaction of the coexisting polymerizable unsaturated compound. In this polymerization reaction, unlike a conventional ultraviolet polymerization reaction or the like, generated radicals can be easily controlled, and a part of unsaturated groups in the resin can be easily stopped at the time of radical polymerization. Further, since a long wavelength in the visible light or near infrared region is used, the reaction can be easily promoted even in a system to which a filler, a pigment or the like is added.

Examples of combinations of the above cationic dyes and boron compounds are described in JP-A-3-111402, JP-A-3-179003, JP-A-4-146905, JP-A-4-261405, JP-A-4-26
There is a detailed description in JP-A No. 1406, JP-A-5-194609 and the like. Specific examples of "D ⁺ " in the cationic dye are shown in Tables 1 and 2. Among these cationic dyes, cyanine-based, styryl-based cationic dyes and triarylmethane-based dyes are preferably used. Cyanine-based and styryl-based cationic dyes are preferable in that the electron transfer with an organic boron-based compound generally occurs easily and the reaction of the present invention easily occurs.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

Examples of visible light polymerization initiators having photosensitivity in the visible light region include, for example, Yamaoka et al., “Surface”, 27 (7), 5
48 (1989), Sato et al., "Summary of the 3rd Polymer Material Forum", IBP18 (1994), camphorquinone, benzyltrimethylbenzoyldiphenylphosphine oxide, methylthioxanthone,
In addition to a single visible light polymerization initiator such as dicyclopentadienyltitanium di (pentafluorophenyl), an organic peroxide / dye system, a diphenyliodonium salt / dye, an imidazole / keto compound, a hexaarylbiimidazole compound / Known complex initiator systems such as hydrogen-donating compounds, mercaptobenzothiazole / thiopyrylium salts, metal arenes / cyanine dyes, and hexaarylbiimidazole / radical generators described in JP-B-45-37377. . Further, an acylphosphine oxide compound is effective as an initiator having photosensitivity from the ultraviolet light to the visible light region. Specific examples thereof include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and 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) -2,2-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -dodecylphosphine oxide,
Bis (2,6-dichlorobenzoyl) -4-octylphenylphosphine 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-dichloro-
3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1)
-Naphthoyl) -2,5-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-methyl-1-naphthoyl) -4-methoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)
-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-diphenylbenzoyl-
Diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,
3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, 2-phenyl-6-methylbenzoyl-diphenylphosphine Oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,8-dimethylnaphthalene-
1-carbonyl-diphenylphosphine oxide,
1,3-dimethoxynaphthalene-2-carbonyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester,
2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl-phenylphosphinic acid methyl ester and the like can be mentioned.

Commercially available initiators having photosensitivity from ultraviolet light to visible light range include, for example, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one (trade name: D
arocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl)
75% of 2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.)
Trade name Irgacure-1 mixed at a ratio of% / 25%
700 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (Ciba Special) Tea Chemicals Co., Ltd.
(Trade name) Irgacure 1800 (Ciba Specialty Chemicals Co., Ltd.) mixed at a ratio of 75% / 25%, and Irgacure 1850 (Ciba Specialty) mixed at a ratio of 50% / 50% Chemicals Co., Ltd.), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, Ciba Specialty Chemicals Co., Ltd.), 2,4,6-trimethylbenzoyl-diphenyl Phosphine oxide (trade name Lucirin)
TPO, manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Da)
rocur1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name Lucirin)
Darocur 4265 (trade name) obtained by mixing TPO and BASF (trade name) at a ratio of 50% / 50%.
The visible light initiator may be any photopolymerization initiator having photosensitivity in a wavelength range of 380 to 780 nm, and the component (B1) may be a combination of a component having a wavelength of 500 nm or more and a component having a wavelength of less than 500 nm. Yes, (B2)
A component having a wavelength of 500 nm or more is used.
Known polymerization initiators such as acetophenone, benzyl ketal, and (bis) acyl phosphine oxides can be used as the ultraviolet polymerization initiator for the component (B1). Since the composition has low light transmittance, it has photosensitivity in a relatively long wavelength region, preferably in a wavelength region of 300 nm or more (bis).
It is preferable to use an ultraviolet polymerization initiator such as an acylphosphine oxide.

The thermal polymerization initiator relating to the component (B2) is, for example, an organic peroxide catalyst or an azo compound which generates a radical upon heating, such as benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, or the like.
Ditertiary butyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,
5-dimethyl-2,5-bis (t-butylperoxy)
Hexin-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl)
Peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3
5-trimethylhexanoyl peroxide, lauryl peroxide, azobisisobutyronitrile, azobiscarbonamide and the like can be used. Dicumyl peroxide, ditertiary butyl peroxide, t-butyl hydroperoxide and the like are particularly effective because of good storage stability.

A photopolymerization initiator having photosensitivity in the visible light or near infrared light region having a wavelength of 500 nm or more;
The amount of at least two types of photopolymerization initiators (component (B1)), which is a combination of photopolymerization initiators having photosensitivity in the visible light and / or ultraviolet light region of less than 100% by weight of the resin (A) Part to 0.01 to 20 parts by weight,
Preferably it is 0.05 to 15 parts by weight. If the amount of the photopolymerization initiator is less than 0.01 part by weight, the thickening reaction or polymerization after the thickening tends to be insufficient, and if the amount exceeds 20 parts by weight, the strength of the cured product is insufficient. A photopolymerization initiator having a sensitivity in the visible light or near-infrared light region having a wavelength of 500 nm or more for a prepolymerization reaction for bringing into a B-stage state; a visible light of less than 500 nm and / or a main curing of the prepolymerized reaction product; Alternatively, when a photopolymerization initiator having photosensitivity in the ultraviolet region is used in combination, the composition ratio is 0.1 / 5 to 5 / 0.5 by weight.
1, preferably 0.5 / 5 to 5 / 0.5. When the ratio of the photopolymerization initiator for prepolymerization to the photopolymerization initiator for main curing is less than 0.1 / 5, the light of the photosensitive wavelength (500 to 1200 nm) of the photopolymerization initiator for prepolymerization for bringing into the B-stage state. Even if irradiation is performed, the prepolymerization reaction may not proceed, while if the ratio is more than 5 / 0.1, the prepolymerization reaction may proceed too much.

Use of at least two kinds of photopolymerization initiators (component (B2)) which are a combination of a photopolymerization initiator having a photosensitivity in the visible light or near-infrared light region having a wavelength of 500 nm or more and a thermal polymerization initiator. The amount is 100 parts of the resin (A).
The amount is 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight based on parts by weight. Use of a photopolymerization initiator having photosensitivity in the visible light or near-infrared light region having a wavelength of 500 nm or more for a prepolymerization reaction for bringing into a B-stage state and a thermal polymerization initiator for fully curing the prepolymerized reaction product. In this case, the composition ratio is 0.1 / 5 to 5 / 0.1 by weight, preferably 0.5 / 5 to 5 / 0.5. If the ratio of the photopolymerization initiator for prepolymerization and the thermal polymerization initiator for main curing is less than 0.1 / 5,
Irradiation of the photopolymerization initiator for prepolymerization at the photosensitive wavelength (500 to 1200 nm) to bring it into the B-stage state may not advance the prepolymerization reaction in some cases.
If the amount exceeds 0.1, the prepolymerization reaction may proceed too much. As the polymerization initiator when the pre-polymerized product is fully cured, a photopolymerization initiator having photosensitivity in a visible light and / or ultraviolet light region having a wavelength of less than 500 nm and a thermal polymerization initiator may be used in combination.

The inorganic or organic filler as the component (C) includes an inorganic filler, an organic filler and a polymer. As the inorganic filler, for example, known ones such as aluminum hydroxide, calcium carbonate, talc, clay, glass powder, silica, barium sulfate, titanium oxide, and cement are used. When providing, aluminum hydroxide is effective. These inorganic fillers can be used in combination of two or more kinds. The amount of the inorganic filler is 0 to 200 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the resin as the component (A). It is. When the amount of the inorganic filler is more than 200 parts by weight, the viscosity is too high, and the workability is reduced, and the foam tends to remain, and the strength is reduced. Further, in the present invention, thixotropic may be imparted by a known method. As the thixotropic agent, for example, silica powder (aerosil type), mica powder, casium carbonate powder or the like is used as the resin (A) in 100% by weight. 0.1 to 50 parts by weight per part.

As the organic filler or polymer, for example, known polystyrene, which is also effective as a low shrinkage agent,
Polyvinyl acetate, polymethyl methacrylate, polyethylene, polyvinylidene chloride microballoons, polyacrylonitrile microballoons and the like can be used. When used as a low shrinkage agent, the amount of resin (A) used is 10
0 to 200 parts by weight, preferably 0 to 5 parts by weight per 0 parts by weight
0 parts by weight. Further, in the present invention, a pigment can be used. There is no particular limitation on the type, and organic pigments or inorganic pigments can be used. The amount of the pigment
The amount is at most 20 parts by weight, preferably up to 10 parts by weight, based on 100 parts by weight of the resin as the component (A).

The shape of the fiber layer in the present invention includes sheet, roll, tube, and tube. Types of fiber reinforcement for reinforcing these fiber layered bodies include organic and / or inorganic fibers such as glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber, amide fiber, Roving of metal fiber, ceramic fiber, etc.
Known materials such as cloths, mats, and nonwoven fabrics are used. Of course, two or more of these fibers may be used in combination. Among these reinforcing materials, glass fibers and organic fibers are particularly desirable in the present invention, and cloth-like and mat-like ones are preferable in view of workability and the like. Also,
In particular, where corrosive gas is generated, it is also preferable to use acid-resistant glass fiber as the glass fiber.

In the present invention, ultraviolet light means 280-38.
0 nm, visible light refers to light rays in a wavelength range of 380 to 780 nm, and near infrared light refers to light rays in a wavelength range of 780 to 1200 nm. In the present invention, the light source used in the prepolymerization reaction for bringing the resin of the component (A) into the B-stage state may be a light source having a spectral distribution in the photosensitive wavelength region of the photopolymerization initiator. An infrared lamp, a sodium lamp, a halogen lamp, a fluorescent lamp, a metal halide lamp, or the like can be used. In addition, it is also possible to select a wavelength necessary for the prepolymerization reaction and irradiate the lamp by combining these lamps or light of a wide wavelength range with a light source and a wavelength cut filter. The wavelength used for the prepolymerization reaction is desirably long-wavelength light having a low energy level. In particular, when near-infrared light is used, the B-stage reaction can be easily controlled.

The irradiation time of the lamp for pre-polymerization to bring it into the B-stage state cannot be specified unconditionally because the effective wavelength range, output power, irradiation distance, thickness of the composition and the like of the light source are different. The time is at least 01 hour, preferably at least 0.05 hour. The curable material for coating or repairing the inner surface of the tubular molded body thus produced can be quickly and completely cured by light irradiation and / or heating with the remaining photopolymerization initiator and / or thermal polymerization initiator. The light source for light irradiation may be any light source having a spectral distribution in the photosensitive wavelength region of the remaining photopolymerization initiator, such as sunlight, a metal halide lamp, a halogen lamp, an ultraviolet lamp, and a fluorescent lamp.

In the method of coating the inner surface of a tubular molded article with the curable 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 closed. Then, the tubular body is inserted into the tubular molded body, inflated by blowing air or the like into the tubular body, brought into close contact with the inner surface of the tubular molded body, and irradiated with light or blown with hot air to cure the material. The cured film may be peeled off if necessary. Further, as another method, a known method is provided in which a film is provided on the outside of a cylindrical body, and when the cylindrical body is inserted into a tubular molded body, the film is inserted while the front and back of the cylindrical body are reversed (for example, Japanese Patent Application Laid-Open No. Hei 5-138738, JP-A-8-1779) can also be adopted. As a method of locally repairing the inner surface of the tubular molded body, there is a commercially available device provided with a light source and a heater in a rubber sleeve, and this can be used. The resin-impregnated sheet of the present invention is wound around the outside of the rubber sleeve, applied to the repaired portion, and the rubber sleeve is inflated with compressed air or the like and pressed, and then cured by light irradiation or heating.

Examples of pipes that can be coated or repaired in the present invention include concrete fume pipes, steel pipes, stainless steel pipes, vinyl chloride pipes, pottery pipes, square pipes (culverts), and vertical pile pipes such as manholes. The sewage pipe can include a main pipe, a branch pipe, a fitting pipe, and the like.
In the case of poor adhesion such as a vinyl chloride pipe or a ceramic pipe, it is also an effective means to provide a primer layer between the pipe body and cover or repair it. Compounding a urethane resin used as a water-stopping agent and a (meth) acrylic acid ester containing a photoinitiator having no functional group which reacts with isocyanate such as a hydroxyl group, and a prepolymerization method of the present invention It is also an effective means to further use a polymer preliminarily polymerized in the above.

[0037]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, “parts” in each example indicates parts by weight. Example 1 To 100 parts of unsaturated polyester resin Rigolac M-543 (manufactured by Showa Polymer Co., Ltd.) was added 1.0 part of triethylamine,
1,1,5,5-tetrakis (p-diethylaminophenyl) -2,4-pentadienyl triphenyl-n-butyl borate (shown by Showa Denko: I shown in Table 3)
Abbreviated as RB. 0.03 parts of a near-infrared light absorbing cationic dye) and tetra-n-butylammonium triphenyl-n-
Near-infrared photopolymerization initiator for B-stage combining with 0.15 parts of butyl borate (manufactured by Showa Denko; hereinafter abbreviated as P3B; boron compound), photosensitive from UV light to visible light region to fully cure B-staged product Bisacylphosphine oxide-based polymerization initiator having the following (trade name, Irgacure 18)
00: Ciba Specialty Chemicals Co., Ltd., hereinafter abbreviated as I-1800) to obtain a curable resin composition. Next, a 30 cm x 50 cm # 450 chopped strand glass mat (made by Asahi Fiber Glass Co., Ltd.)
Three sheets were impregnated with a fiber content of 25% by weight and covered with a transparent PET film.
A 2 kW halogen lamp which is a light source including a wavelength range of 0 nm and a SC-
50 (manufactured by Fuji Film Co., Ltd.) was used, and irradiation was performed at a distance of 30 cm. The stage was changed to the B-stage in 1 minute, and the B-stage state was not changed even after one spectral irradiation was continued. Then, the thing of the B stage state after light irradiation for 2 minutes is used as the photocurable material for coating or repairing the inner surface of the tubular molded body, at 30 ° C.
When the storage stability in a dark place was examined, the hardness of the prepreg did not change for 6 months or more. The photocurable material stored at 30 ° C. in a dark place for 6 months was cured by placing it at a distance of 15 cm under a 250 W metal halide lamp and irradiating with light for 10 minutes. When the mechanical strength of the cured product in JIS K 6911 was measured, the cured product reached the level of curing by peroxide. The results are shown in Table 3.

Example 2 Except that Irgacure 1800 of the present curing agent of Example 1 was changed to 1.0 part of an organic peroxide catalyst t-butylperoxybenzoate (manufactured by NOF Corporation, hereinafter abbreviated as perbutyl Z). When the same operation as in Example 1 was performed, 30
As for the storage stability in a dark place at ℃, the hardness of the prepreg did not change for one month or more. After storage at 30 ° C. for one month in a dark place, the thermosetting material is heated at 80 ° C. for 1 hour + 120 ° C. for 1 hour 250
After W curing, the same mechanical strength as in Example 1 was examined.
The results are shown in Table 3. Comparative Example 1 Unsaturated polyester resin Rigolac M-543 100
In a part, 1 part of magnesium oxide trade name Magmic (manufactured by Kyowa Chemical Industry Co., Ltd.), which is a known thickener, and 1.0 part of perbutyl Z for fully curing the B-staged product were mixed to obtain a curable resin composition. Was. Next, the thermosetting resin composition is 30 cm × 30 c.
m # 450 chopped strand glass mat (made by Asahi Fiberglass Co., Ltd.)
5% by weight was covered with a transparent PET film and allowed to stand at 40 ° C.
It is in the stage state, it is used as a photocurable material for coating or repairing the inner surface of the tubular molded body, and the storage stability in a dark place at 30 ° C is examined. Did not.

[0039]

[Table 5]

Example 3 Vinyl ester resin Lipoxy R-802 (Showa Kobunshi
100 parts, 0.03 parts IRB and 0.1 parts P3B
Near-infrared photopolymerization initiator for B-stage formation combining 5 parts, Irgacure 819 for fully curing B-staged product
1.5 parts were mixed to obtain a curable resin composition. Next, the curable resin composition was coated with a # 450 chopped strand glass mat (manufactured by Asahi Fiberglass Co., Ltd.) of 80 cm × 30 cm.
Sheets, polyester non-woven fabric (trade name: Sontara 8005)
H, manufactured by DuPont) and impregnated with a single fiber so that the fiber content becomes 25% by weight.
AL-spotlight (ALF-1) which is a light source covered with an ET film and including a wavelength range of 380 to 1200 nm.
0) Irradiation was performed at a distance of 20 cm using 1 kW with SC-50, which is a wavelength cut filter of 500 nm or less, to form a B-stage in 2 minutes, and then the B-stage state did not change even if one spectral irradiation was continued. Then, the thing of the B stage state after light irradiation for 3 minutes was used as the photocurable material for coating or repairing the inner surface of the tubular molded body, and the storage stability in a dark place at 30 ° C. was examined. No change. Next, this material was wound around the outside of a repair tool equipped with four 36W blue fluorescent lamps in a silicon tube, placed in a concrete fume tube having an inner diameter of 250 mm, and the silicon tube was inflated and compressed by compressed air. When irradiated with light, it was completely cured in 20 minutes. Barcol hardness (type 934-1) of the cured surface is 40
This was the complete curing level. Example 4 The curable resin composition used in Example 1 was impregnated into a # 350 glass cloth (trade name: FW350, manufactured by Nitto Boseki Co., Ltd.) and Sontara 8005H, each of which was sewn one by one. The coated material was applied to the 2 kW halogen lamp used in Example 1 and SC-50 (Fuji Film), a wavelength cut filter of 500 nm or less.
(Made by Co., Ltd.) are combined and two are arranged side by side.
After passing at a speed of m / min, the stage was in the B stage. This was sewn into a tube of 150 mm diameter and the end was closed to obtain a photocurable material for coating or repairing the inner surface of the tubular molded body. This material was introduced into a 150 mm diameter concrete fume tube and pressed. An ultraviolet irradiation lamp equipped with four 1 kW high-pressure mercury lamps was moved at a speed of 10 cm per minute while being pressed against the inner surface of the concrete fume tube with air, and cured. Barcol hardness of hardened surface (Type 934-1)
Was a full cure level above 40.

[0041]

According to the present invention, the B-stage state can be obtained by a stabilized reaction in a short time, and the resin does not flow out of the fibrous base material during storage, and is stable for a long time. Further, a curable material for coating or repairing the inner surface of the tubular molded body which can be cured quickly can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 2/50 C08F 2/50 4J027 C08J 5/24 CFC C08J 5/24 CFC 4J038 CFE CFE 7/04 CEV 7 / 04 CEVA C08K 3/00 C08K 3/00 5/00 5/00 7/02 7/02 C08L 63/10 C08L 63/10 67/06 67/06 C09D 133/04 C09D 133/04 167/07 167 / 07 F16L 1/00 F16L 1/00 J // B29K 31:00 B29K 31:00 67:00 67:00 105: 08 105: 08 105: 16 105: 16 105: 24 105: 24 B29L 23:00 B29L 23 : 00 F term (reference) 4F006 AA17 AB16 AB24 AB34 AB42 AB54 AB74 AB76 BA05 BA16 EA03 EA05 4F072 AB04 AB05 AB06 AB08 AB09 AB10 AB11 AB28 AB29 AB30 AD34 AD38 AD55 AE01 AF03 AF05 AF06 AG02 AG03 AH02 AJ22 AK05 AL03 AL17 AB2 1 AD08 AD12 AD16 AD32 AG03 AG08 SA13 SC03 SD01 SD04 SD06 SH06 SH21 SH24 SJ01 SP12 SP21 SP27 4J002 BC031 CD201 CF221 DE138 DE148 DE238 DG048 DJ018 DJ038 DJ048 DL008 DM008 EE036 EL096 EL106 EN136 ER006 EU026 EU056 EU186 EV296 EV306J01 FD 018 EB EV 018 FD 018 CA01 CA02 CA03 CA05 CB02 CC02 CC04 CC10 PA03 PA07 PA09 PA13 PA15 PA16 PA64 PA65 PA66 PA68 PA69 PA88 PA96 PB04 PB07 PB08 PB22 PC02 PC08 QA09 QB12 QB19 SA80 SA82 SA83 SA84 SA88 UA01 UA06 UA07 UA08 AB05 AB05 AB02 AB02 AB02 AB02 AB02 AB05 AB05 AB05 AB17 AB18 AE02 AJ08 BA05 CA14 CA18 CA19 CA34 CA36 CA38 CB10 CC02 CC04 CC05 CD08 CD09 4J038 CB022 CC032 CC061 CD082 CF022 CG141 CG142 CG162 CH171 CJ031 CJ051 DD181 GA01 GA07 HA216 HA266 HA376 HA446 HA466 J526 JBAJ27 JA66 JC38 KA03 KA04 KA08 KA12 KA21 NA26

Claims (7)

[Claims] (A1) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin; (B1) a photopolymerization initiator having photosensitivity in a visible light or near infrared light region having a wavelength of 500 nm or more;
0.01 to 10 parts by weight of at least two kinds of photopolymerization initiators which are a combination of photopolymerization initiators having photosensitivity in the visible light and / or ultraviolet light region of less than 0.01 and (C) an inorganic or organic filler 0 to The fiber composition is impregnated with a resin composition containing 200 parts by weight of
Irradiating light having a wavelength of at least 00 nm to partially polymerize the radically polymerizable unsaturated groups in the composition, and at least a photopolymerization initiator and a radically polymerizable unsaturated group which are photosensitive to light having a wavelength of less than 500 nm. Curable material for covering or repairing the inner surface of the tubular molded body, with a part of the material remaining. 2. (A) 100 parts by weight of an unsaturated polyester resin and / or vinyl ester resin. (B2) a photopolymerization initiator having photosensitivity in a visible light or near infrared light region having a wavelength of 500 nm or more, and thermal polymerization initiation. At least two polymerization initiators 0.01 to
A fibrous layered body is impregnated with a resin composition containing 10 parts by weight and (C) 0 to 200 parts by weight of an inorganic or organic filler, and a wavelength of 5
A tubular molded body formed by irradiating light of not less than 00 nm and preliminarily polymerizing a part of the radically polymerizable unsaturated group in the composition and leaving a thermal polymerization initiator and a part of the radically polymerizable unsaturated group. Curable material for surface coating or repair. 3. The curable material for coating or repairing the inner surface of a tubular molded body according to claim 1, wherein the fibrous layered body is at least one selected from a sheet shape, a roll shape, a tubular shape and a tubular shape. 4. A photopolymerization initiator having photosensitivity in a wavelength of not less than 500nm visible light or near infrared light, the general formula ^{(1) D + · A -} ··· (1) ( wherein, D ⁺ is A methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane or pyrylium dye cation having photosensitivity in the visible light region or near-infrared light region, and A ^- represents various anions.) A cationic dye having photosensitivity in the visible light region or the near infrared light region, and a compound represented by the general formula (2): (In the formula, Z ⁺ represents an arbitrary cation, and R ¹ , R ² , R
³ and R ⁴ are each independently an alkyl group, aryl group, acyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, halogen atom, substituted alkyl group, substituted aryl group, substituted acyl group, substituted It represents an aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group. The curable material for coating or repairing the inner surface of a tubular molded product according to any one of claims 1 to 3, which is a combination of an organic boron compound represented by the formula (1). 5. The method according to claim 1, wherein one of the photopolymerization initiators having photosensitivity from an ultraviolet light region to a visible light region is an acylphosphine oxide-based compound. Curable material for repair. 6. An end of a cylinder made of the curable material according to any one of claims 1 to 5, the end is closed, the cylinder is inserted into a tubular molded body, and gas is blown into the cylinder to inflate. A method for coating the inner surface of a tubular molded body, which comprises pressing the inner surface of the tubular molded body, and then irradiating or heating ultraviolet light and / or visible light or heating the cylindrical body material. 7. The sheet-shaped curable material according to claim 1 is wound around a rubber sleeve provided with a light source and a heater therein, applied to the inner surface of the tubular molded body, and compressed gas is applied. A method for coating the inner surface of a tubular molded body, comprising: inflating and pressing a rubber sleeve according to the method described above, and then curing the cylindrical material by irradiation or heating with ultraviolet light and / or visible light.