JP4873212B2 - Resin composition for pipe lining material and pipe lining material using the same - Google Patents

Description

  The present invention relates to a resin composition for a pipe lining material having a formaldehyde supplementing function, and a pipe lining material in which the amount of formaldehyde scattered is suppressed.

Radical polymerizable resin is liquid before curing and has excellent fluidity, so it has excellent impregnation into fiber reinforcement, etc., and its cured fiber reinforced plastic has high mechanical strength, and is also resistant to chemicals and heat. Excellent in properties. Because of these features, lining materials impregnated with radically polymerizable resin in glass fibers, carbon fibers, organic fibers, etc. are pressed into the pipes and cured by an appropriate curing method, repairing existing pipes, and corrosion resistance There are known methods for imparting an ability and forming a new tube.
A radical that polymerizes and cures such a radical polymerizable resin reacts with a polymerizable unsaturated resin having a polymerizable unsaturated double bond and a polymerizable unsaturated monomer to give a cured product, while generating formaldehyde. Is known (see, for example, Non-Patent Document 1).

Formaldehyde is a causative substance for environmental problems such as sick houses, and its emission is regulated by the Building Standards Act.
In response to this regulation, (1) a method in which the curing time after curing is prolonged until the amount of formaldehyde released decreases below a certain value, and (2) formaldehyde is forcibly stripped by post-curing at a high temperature to remain. A method of releasing formaldehyde, (3) a method of capturing formaldehyde by acetalization with alcohol under dry acid conditions, etc. have been proposed. For (1), a curing period of 7 days according to JIS K 5970 In (2) and (3), the amount of formaldehyde released cannot be reduced to the extent that it is not regulated, and (2) and (3) are still satisfactory, such as adversely affecting the curability of the resin and poor formaldehyde scavenging function. It wasn't.

Stanford Research Institute Volume1 Number 7 July, 1968; Frank R. Mayo

  When using a radical polymerizable resin as a pipe lining material, for example, since water and sewage pipes are directly connected to each household, the countermeasure against formaldehyde is particularly important.

  An object of the present invention is to provide a resin composition for a pipe lining material having a formaldehyde supplementing function and a pipe lining material in which the amount of formaldehyde scattered is suppressed.

  As a result of intensive studies on these problems, the present inventors have found that the emission of formaldehyde can be suppressed by using a compound having a specific structure, and have completed the present invention.

That is, the present invention relates to a resin (A) having an ethylenically unsaturated double bond in one molecule, a monomer (B) having an ethylenically unsaturated double bond, and ethylene urea as a compound (C). It provides the resin composition for pipe lining materials containing this.

Since the resin composition for a pipe lining material of the present invention has a good formaldehyde emission suppressing effect, it is useful for the use of a pipe lining material.

The present invention is described in further detail below.
Examples of the resin (A) [hereinafter referred to as radical curable resin (A)] having an ethylenically unsaturated double bond in one molecule used in the present invention include unsaturated polyester, epoxy (meth) acrylate, urethane ( And (meth) acrylate, polyester (meth) acrylate, and the like. The number average molecular weight of these resins is greater than 200, and those having a resin cured product of 200 to 5000 are preferred. These resins may be used alone or in combination of two or more as required.

Such unsaturated polyester is obtained from a dibasic acid containing an α, β-unsaturated dibasic acid and a polyhydric alcohol.

  Examples of the α, β-unsaturated dibasic acid that is a dibasic acid component of the unsaturated polyester used in the present invention include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like. . Examples of the saturated dibasic acid that is a dibasic acid component include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid. , Hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalene Dicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, α-terpinene, Maleic anhydride adduct, trans-piperylene It can be mentioned maleic anhydride adduct.

  Examples of the polyhydric alcohol component of the unsaturated polyester used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, and dipropylene glycol. Polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, bisphenol Adduct of A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3 -Cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexane dimethyl Nord, para-xylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, 2,7-decalin glycol, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether , Triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether Le, glycerol diallyl ether, and allyl ether compounds of polyhydric alcohols such as pentaerythritol triallyl ether.

  Furthermore, dicyclopentadiene unsaturated polyester obtained by reacting dicyclopentadiene with the above α, β-unsaturated carboxylic acid, saturated carboxylic acid and alcohol can also be used.

  The epoxy (meth) acrylate usually has a (meth) acryloyl group in one molecule, and is obtained by reacting an epoxy resin and an unsaturated monobasic acid in the presence of an esterification catalyst.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ethers of polyhydric phenols such as brominated epoxy resin, and dipropylene glycol diglycidyl. Ether, trimethylolpropane triglycidyl ether, diglycidyl ether of bisphenol A alkylene oxide adduct, glycidyl ether of polyhydric alcohols such as diglycidyl ether of hydrogenated bisphenol A, 3,4-epoxy-6-methylcyclohexyl Cycloaliphatic epoxy resins such as methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, phthalates Glycidyl esters such as diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, diglycidyl p-oxybenzoic acid, dimer acid glycidyl ester, tetraglycidyl diaminodiphenylmethane, tetraglycidyl m-xylylenediamine, triglycidyl P-aminophenol, N, Examples thereof include glycidylamines such as N-diglycidylaniline, and heterocyclic epoxy resins such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate. These epoxy resins may be used alone or in combination of two or more.

  Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethyl malate, monomethyl fumarate, monocyclohexyl fumarate, and sorbic acid. These may be used alone or in combination of two or more.

  Furthermore, the resulting epoxy (meth) acrylate is a maleic anhydride, an acid anhydride such as succinic anhydride, acetic anhydride, methacrylic anhydride, a polyisocyanate compound such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. It may be modified with

  The urethane (meth) acrylate is usually obtained by reacting a polyol, polyisocyanate and (meth) acrylate having one or more hydroxyl groups per molecule, and having a (meth) acryloyl group in the molecule. It is.

  Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, and polybutadiene polyol. The number average molecular weight of the polyol is preferably from 200 to 3,000, particularly preferably from 400 to 2,000.

  The polyether polyol includes a polyol obtained by adding the alkylene oxide to bisphenol A and bisphenol F in addition to a polyalkylene oxide such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Polyester polyol means a ring-opening polymer of a cyclic ester compound such as a condensation polymer of saturated dibasic acids and polyhydric alcohols or polycaprolactone. Examples of dibasic acids used here include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexa Hydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2, Examples include 3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof.

  Examples of polyhydric alcohols include polyhydric alcohols of the unsaturated polyester.

  Examples of the polyisocyanate include 2,4-tolylene diisocyanate and its isomer or a mixture of isomers (hereinafter referred to as TDI), diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane. Diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and the like can be mentioned, and these can be used alone or in combination of two or more. Of the above polyisocyanates, diisocyanates, particularly TDI, are preferred.

  Examples of the (meth) acrylate having one or more hydroxyl groups in one molecule used for urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxy. Mono (meth) acrylates such as butyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, pentaerythritol tri (meth) acrylate And polyvalent (meth) acrylates.

  The production method of urethane (meth) acrylate is as follows: 1) First, polyisocyanate and polyol are preferably reacted at NCO / OH = 1.3 to 2 to form a compound having a terminal isocyanate group, and then one molecule per compound. A method of reacting a (meth) acrylate having one or more hydroxyl groups therein (hereinafter referred to as a hydroxyl group-containing (meth) acrylate) so that the hydroxyl groups are substantially equivalent to the isocyanate groups, and 2) a polyisocyanate compound and a hydroxyl group Examples include a method of reacting the containing (meth) acrylate with NCO / OH = 2 or more to form a compound having an isocyanate group at one end and then adding a polyol to react.

  The polyester (meth) acrylate which is one of the radical curable resins (A) is a saturated polyester resin or an unsaturated polyester resin having two or more (meth) acryloyl groups in one molecule. A compound having a (meth) acryloyl group at the terminal of a resin or unsaturated polyester resin is reacted. The number average molecular weight of the resin is preferably 500 to 5000, more preferably 1000 to 5000.

  The saturated polyester is obtained by a condensation reaction of a saturated dibasic acid and a polyhydric alcohol, and the unsaturated polyester is a dibasic acid containing an α, β-unsaturated dibasic acid and a polyhydric alcohol. It has a functional group for introducing a compound having a (meth) acryloyl group at the terminal.

As the saturated dibasic acid herein, the above-mentioned saturated dibasic acid can be mentioned, and as the α, β-unsaturated dibasic acid, the above-mentioned unsaturated dibasic acid can be used.
Moreover, as polyhydric alcohol, the polyhydric alcohol which can be used for the said polyester polyol can be used.

  Examples of the compound having a (meth) acryloyl group used for polyester (meth) acrylate include glycidyl esters of acrylic acid or methacrylic acid. Specific examples include glycidyl (meth) acrylate.

Dibasic acids used here are, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2 , 3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof. Polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3 -Butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, an adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclo Cyclohexanedicarboxylic methanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, and 2,7-decalin glycol, and the like.

Examples of the monomer (B) having an ethylenically unsaturated double bond [hereinafter referred to as polymerizable unsaturated monomer (B)] used in the present invention include styrene, α-methylstyrene, chlorostyrene, and dichloro. Styrene, divinylbenzene, t-butylstyrene, vinyl toluene, vinyl acetate, diaryl phthalate, triaryl cyanurate, methyl methacrylate (hereinafter referred to as MMA), methyl acrylate, ethyl (meth) acrylate, (meth) acrylic acid n -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate , (Meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxyethyl Propyl, (meth) acrylic acid β-ethoxyethyl, (meth) acrylic acid 2-cyanoethyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid diethylaminoethyl, (meth) acrylic acid lauryl, (meth) acrylic acid stearyl, Examples include polycaprolactone (meth) acrylate, diethylene glycol monomethyl ether mono (meth) acrylate, dipropylene glycol monomethyl ether mono (meth) acrylate, and 2-ethylhexyl carbitol (meth) acrylate.

In addition to the above-mentioned polymerizable unsaturated monomer (B), a polymerizable compound having a hydroxyalkyl (meth) acrylate and / or phenyl group in which the alkyl group has 1 to 4 carbon atoms for the purpose of low odor. A monomer can be used individually or in combination of 2 or more types.
Examples of the hydroxyalkyl (meth) acrylate having 1 to 4 carbon atoms in the alkyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Can be mentioned.

  As the polymerizable monomer having a phenyl group, for example, an acrylic monomer having a phenyl group and having an acryloyl group having a molecular weight of 180 or more is preferably used, and a specific example of such a monomer is phenol ethylene oxide (EO) modification. Acrylate, nonylphenyl carbitol acrylate, nonylphenol EO modified acrylate, phenoxypropyl acrylate, nonylphenol PO modified acrylate, acryloyloxyethyl phthalate, phenol EO modified methacrylate, nonylphenyl carbitol methacrylate, nonylphenol EO modified methacrylate, phenoxypropyl methacrylate, phenol PO modified Methacrylate, nonylphenoxypropyl methacrylate, nonylphenol PO modified methacrylate Methacryloyloxyethyl phthalate.

  Furthermore, in addition to the polymerizable unsaturated monomer (B), various compounds can be used as long as the effects of the present invention are not impaired. Such compounds include, for example, various derivatives such as dicyclopentadiene, dicyclodecane or triazine, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate or tris (2-hydroxyethyl). ) Isocyanuric acrylate and the like.

  The present invention provides at least one of a compound having a functional group of any one of a hydrazo group, a urea bond and a urethane bond in the molecule, a compound represented by the general formula (1), and a compound represented by the general formula (2). The seed compound (C) is used. By using such a compound (C), when the resin composition for a pipe lining material is radically polymerized and cured, there is no problem such as inhibition of curing of the coating film and molded product, and the amount of formaldehyde emission can be effectively reduced. It is something that can be done.

一般式（１）中、Ｒ_１及びＲ_２は、アルキル基、アルケニル基、アルキニル基、ヒドロキシ基、アミノ基、アルコキシ基又はカルボニル基を表すものである。

In the general formula (1), R ₁ and R ₂ represent an alkyl group, an alkenyl group, an alkynyl group, a hydroxy group, an amino group, an alkoxy group, or a carbonyl group.

一般式（２）中、Ｒ_３、Ｒ_４、Ｒ_５およびＲ_６は、水素原子、アルキル基、アルケニル基、アルキニル基、ヒドロキシ基、アミノ基、アルコキシ基又はカルボニル基を表すものであり、Ｒ_３とＲ_４とは同時に水素原子ではなく、Ｒ_５とＲ_６とは同時に水素原子ではないものである。

In the general formula (2), R ₃ , R ₄ , R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a hydroxy group, an amino group, an alkoxy group or a carbonyl group, and R ₃ and R ₄ are not simultaneously hydrogen atoms, and R ₅ and R ₆ are not simultaneously hydrogen atoms.

  As the compound having any one functional group of hydrazo group, urea bond or urethane bond in the molecule, for example, a compound represented by the general formula (3) is preferable.

R ₇ -NH-Y (3)
In general formula (3), R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkyl group substituted with a hydroxyl group, an alkyl group substituted with an amino group, an amino group, an alkoxy group, a phenyl group, or a carboxyl group. Represents a monovalent functional group having a group, a urethane bond, and -NHNH-R. In this case, R is a hydrogen atom or an alkyl group. Y represents —NH—R ₂ , —CO—NH—R ₃ , or —COO—R ₄ . In this case, R ₂ , R ₃ and R ₄ are a hydrogen atom, an alkyl group, or an alkyl group substituted with a hydroxyl group. R ₁ and Y may be bonded to form a ring.

Among the compounds represented by the general formula (3), a compound in which R ₁ is an alkyl group and Y is —CO—NH—R ₃ , R ₁ is —NHNH—R, and Y is —NH It is preferable that the compound is —R ₂ and the compound in which R ₁ is a monovalent functional group having a urethane bond and Y is —COO—R ₄ .
Examples of the compound (C) represented by the general formula (3) in which R ₁ is an alkyl group and Y is —CO—NH—R ₃ include urea, monomethyl urea, monomethylol urea, dimethylol urea, dimethyl Examples include urea, diphenylurea, methyleneurea, ethyleneurea, propyleneurea, alkoxymethylurea and the like. Of these, ethylene urea is preferred because of its large formaldehyde scavenging effect.

Examples of the compound (C) represented by the general formula (3) in which R ₁ is —NHNH—R and Y is —NH—R ₂ include adipic acid dihydrazide, succinic acid dihydrazide, naphthenic acid dihydrazide, and the like. Can be mentioned.
Further, the compound (C) represented by the general formula (3) in which R ₁ is a monovalent functional group having a urethane bond and Y is —COO—R ₄ is vinyl such as urethane (meth) acrylate. A urethane compound etc. are mentioned.

  Examples of the compound represented by the general formula (1) include acetylacetone, N, N-dimethylacetoacetate, methylacetoacetate, ethylacetoacetate, acetoacetanilide and the like. Of these, acetoacetoxyethyl methacrylate is preferred.

  Examples of the compound represented by the general formula (2) include acetylacetone peroxide and methyl acetoacetate peroxide. Of these, acetylacetone peroxide is preferred in terms of curing.

  A compound having a hydrazo group, a urea bond or a urethane bond in the molecule, a compound represented by the general formula (1) and a compound represented by the general formula (2) are used as a compound (C) component as a resin for a pipe lining material. The compound which may be contained in the composition, or has a hydrazo group, a urea bond or a urethane bond in the molecule in the skeleton of the radical curable resin (A), a compound represented by the general formula (1) Alternatively, a unit having a structure similar to that of the compound represented by the general formula (2) may be introduced.

  The ratio of the radical curable resin (A), the polymerizable unsaturated monomer (B) and the compound (C) used in the present invention can be changed depending on the desired use, and is not particularly limited. (A) :( B) is desirably 10 to 80:90 to 20 by weight ratio, and more preferably 40 to 80:60 to 20 is used. Moreover, the ratio of (C) is 0.01-10 weight part with respect to a total of 100 weight part of (A) and (B), Preferably it is 0.1-10 weight part. If the amount of compound (C) added is less than 0.01% by weight, the formaldehyde scavenging ability is insufficient, and if it exceeds 10% by weight, the performance of the resulting cured product may be adversely affected.

  A curing agent, that is, a radical polymerization initiator is usually added to the pipe lining material resin composition. In addition, a curing accelerator, that is, a radical polymerization accelerator may be added.

  Examples of such curing agents include thermosetting agents and photocuring agents. Examples of thermosetting agents include organic peroxides such as diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peroxides, A publicly known thing, such as a percarbonate type, is mentioned. The addition amount of the thermosetting agent is not particularly limited as long as the object of the present invention can be achieved, but preferably it is 0.00% with respect to 100 parts by weight of the total amount of the resin used in the present invention. It is 3-5 weight part, By using it in this range, the resin composition excellent in pot life, physical properties, etc. can be obtained.

  Examples of such photocuring agents include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, and 2-hydroxy-2- Acetphenone series such as methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, thioxanthone series such as 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. Is mentioned. The addition amount of the photocuring agent is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the total amount of the resin used in the present invention.

  Examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate, vanadium acetyl acetate, cobalt acetyl acetate, iron acetylacetonate, and the like. Metal chelates, aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N- Bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m -N, N-substituted anilines such as toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, N, N-substituted-p -Amines such as toluidine and 4- (N, N-substituted amino) benzaldehyde. Of these curing accelerators, amines and metal soaps are preferred. These curing accelerators may be used alone or in combination of two or more. These curing accelerators may be added to the resin in advance or may be added at the time of use. The addition amount of the curing accelerator is not particularly limited as long as the object of the present invention can be achieved, but it is preferably 0.1% with respect to 100 parts by weight of the total amount of the resin used in the present invention. 01 to 5 parts by weight.

Furthermore, a polymerization inhibitor or the like can be used to adjust the curing rate.
Examples of the polymerization inhibitor include trihydrobenzene, toluhydroquinone, 14-naphthoquinone, parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol. Etc. The addition amount of the polymerization inhibitor is preferably 10 to 1000 ppm, more preferably 50 to 200 ppm, based on the resin used in the present invention. By using in such a range, a resin composition excellent in storage stability, workability, and strength development can be obtained.

  Furthermore, the resin composition for a pipe lining material of the present invention includes various additives such as fillers, ultraviolet absorbers, pigments, thickeners, low shrinkage agents, anti-aging agents, plasticizers, aggregates, Flame retardants, stabilizers, fiber reinforcements, waxes, thixotropic agents, coupling agents and the like can be added.

  Examples of such fillers include hydraulic silicate materials, calcium carbonate powder, clay, alumina powder, aragonite powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose-based, and cinnabar. , River sand, cold water stone, marble waste, crushed stone, and the like. These can be used alone or in combination of two or more. The filler is appropriately selected depending on the intended use. For example, when used for sewerage, aluminum hydroxide is preferred in view of chemical resistance and cost.

  Examples of the low shrinkage agent include polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene, polypropylene, poly-ε-caprolactam, saturated polyester, polyvinyl chloride, polybutadiene, styrene-acrylic acid copolymer, and styrene-acetic acid. A vinyl copolymer, an acrylonitrile-styrene copolymer, a styrene butadiene rubber, a nitrile rubber and the like can be mentioned, and these can be used alone or in combination of two or more. Further, a copolymer of a monofunctional or polyfunctional unsaturated monomer or a copolymer in which a polymerizable unsaturated group remains in part may be used. The monomer that can be used in this case is not particularly limited as long as it contains a polymerizable unsaturated group, but styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, (meta ) Acrylic acid, alkyl esters of (meth) acrylic acid, maleic anhydride, maleic acid, fumaric acid, monofunctional alcohols, polyfunctional alcohols and (meth) acrylic esters of ether glycols. The above-mentioned copolymer as a low shrinkage agent can be appropriately selected and used alone or in combination of two or more, and the blending amount thereof is (A ) + (B) can be used in the range of 30 parts by weight or less, preferably 20 parts by weight or less, based on 100 parts by weight of (B).

  Examples of the use of the resin composition for a pipe lining material of the present invention described above include, for example, lining materials for water and sewer pipes, power pipes, gas pipes, lining materials for various pipes such as factories and hot springs, and lining materials for various capile pipes Etc.

Furthermore, the pipe lining material of the present invention is a fiber reinforced material such as glass fiber, amide, aramid, vinylon, polyester, phenol, or other organic fiber, carbon fiber, metal fiber, ceramic fiber or a combination thereof. It can be obtained by impregnating. The form of the fiber reinforcing agent is not particularly limited, but usually a cylindrical or mat-like one is used.
Such a fiber reinforcing material is preferably a glass fiber or an organic fiber in view of economy. When glass fiber is used, a lining material having high strength can be obtained. It is necessary to select the kind of glass fiber according to a use, for example, when using for a sewer application, it is preferable to use acid resistant glass.

In addition, the pipe lining material is at least one side of a film or sheet for the purpose of preventing resin leakage, preventing volatilization of the polymerizable unsaturated monomer (B), and preventing curing failure when using warm water or steam as a curing medium. Is preferably covered. As the material of the film or sheet, polyethylene, polypropylene, polyamide, saturated polyester, urethane, fluorine-based polymer, or a combination thereof is used. The material of the film is preferably selected from materials that are not affected by the polymerizable unsaturated monomer (B).

The method for impregnating the fiber reinforced material with the resin composition for a pipe lining material is not particularly limited, and all known methods can be applied. For example, there is a method in which a resin is injected into a cylindrical fiber reinforcement whose outer side is covered with a cylindrical film and impregnated by applying pressure from the outside with a roller. It is preferable to remove the air inside the fiber reinforcement as much as possible. For this purpose, the film can be impregnated while reducing the pressure inside the film with a vacuum pump or the like.

Insertion of the pipe lining material obtained in this way into the pipe line is not particularly limited, but there are methods such as retraction and reversal using air pressure or water pressure. The inserted pipe lining material is inflated inside the pipe line by air pressure, water pressure, steam pressure or the like. Thereafter, the tube lining material is formed by curing by an appropriate curing method. In the case of room temperature curing, for example, it is left alone or cured by heating to some extent with a heating medium such as hot water. In the case of heat curing, for example, heat curing is performed using hot water or steam as a heat medium. Moreover, in the case of photocuring, it hardens | cures by irradiation of an ultraviolet lamp, for example.

The pipe lining material of the present invention is used for water / sewer pipes, power pipes, gas pipes, various pipes for factories and hot springs, repair of various cape pipes, chemical resistance and corrosion resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Also, “parts” in the text indicates parts by weight.

Reference Example 1 Synthesis of Unsaturated Polyester In a 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 228 parts of propylene glycol, 312 parts of neopentyl glycol, isophthalic acid 498 parts were charged and nitrogen gas flow and heating were started. A dehydration condensation reaction was performed at an internal temperature of 210 ° C. by a conventional method until the solid content acid value reached 2 mg-KOH / g. Thereafter, the resin temperature is cooled to 180 ° C., 294 parts of maleic anhydride is charged into the flask, and heating is similarly started in a nitrogen stream, and a dehydration condensation reaction is performed at an internal temperature of 200 ° C. in a conventional manner. When the viscosity is X (resin solid content / styrene = 60/40 weight ratio and the degree of condensation of the resin is confirmed) and the acid value is 12 mg KOH / g, the mixture is cooled to 180 ° C., toluhydroquinone 250 ppm, tertiary butyl 50 ppm of catechol was added. Furthermore, it cooled to 150 degreeC and obtained unsaturated polyester (henceforth UP).

[Reference Example 2] Synthesis of epoxy methacrylate In a 2-liter four-necked flask equipped with a thermometer, a stirrer, a gas inlet, and a reflux condenser, Epicron 850 [epoxy resin: reaction product of epichlorohydrin and bisphenol A: epoxy equivalent] 188, manufactured by Dainippon Ink and Chemicals, Inc.] 1000 parts, 448 parts of methacrylic acid, 0.5 part of 2,6-di-tert-butyl-4-methylphenol, and 4 parts of triethylamine were added, and nitrogen / air (flow rate) Ratio 1/1) The temperature was raised to 90 ° C. under a mixed air stream, and the reaction was performed for 2 hours. Next, the reaction temperature was raised to 105 ° C., and the reaction was continued for 15 hours. When the acid value was 7.4 and the epoxy equivalent was 11300, the reaction was cooled to 80 ° C., 50 ppm of tertiary butyl catechol was added, and an epoxy methacrylate resin ( Hereinafter referred to as EM).

Examples 1-5 and Comparative Examples 1-4
The compound (C), the curing agent and the curing accelerator are added to the radical curable resin mixture [the mixture of the radical curable resin (A) and the polymerizable unsaturated monomer (B)] obtained in Reference Example. And it mix | blended like Table-2 and produced the radical curable resin composition.
About this radical curable resin composition, the amount of formaldehyde emission was measured. The measurement method and evaluation criteria are as follows. The results are shown in Table-1 and Table-2.

<Formaldehyde emission>
Radicals obtained in each example and comparative example by creating a mold with a tube made of vinyl chloride by sandwiching a 5 mm spacer between two glass plates (40 cm square, 5 mm thickness) in a room at a temperature of 23 ° C. A curable resin composition was poured. This was immersed in a constant temperature water bath at 70 ° C. for 5 hours to obtain a cured product. After being left to cool in an environmental test chamber at a temperature of 23 ° C. and a humidity of 50% for one day, the glass plate was removed and cut into 15 cm squares to obtain test pieces.
Using this test piece, it was measured by the JIS K 5601-4-1 desiccator method. The curing period was one week.

＊； ビス(４−ｔ−ブチルシクロヘキシル)パーオキシジカーボネート、日本油脂（株）製
＊＊；ｔ−ブチルパーオキシ２エチルヘキサノエート、日本油脂（株）製

*; Bis (4-t-butylcyclohexyl) peroxydicarbonate, manufactured by NOF Corporation **; t-butylperoxy 2-ethylhexanoate, manufactured by NOF Corporation

Claims (2)

It contains a resin (A) having an ethylenically unsaturated double bond in one molecule, a monomer (B) having an ethylenically unsaturated double bond, and ethylene urea as the compound (C). Resin composition for pipe lining materials. A pipe lining material obtained by impregnating a fiber reinforcing material with the resin composition for a pipe lining material according to claim 1 .