WO2022025097A1 - 樹脂組成物、管渠補修材および管渠補修方法 - Google Patents

樹脂組成物、管渠補修材および管渠補修方法 Download PDF

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WO2022025097A1
WO2022025097A1 PCT/JP2021/027840 JP2021027840W WO2022025097A1 WO 2022025097 A1 WO2022025097 A1 WO 2022025097A1 JP 2021027840 W JP2021027840 W JP 2021027840W WO 2022025097 A1 WO2022025097 A1 WO 2022025097A1
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resin composition
mol
unsaturated polyester
polyester oligomer
mass
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PCT/JP2021/027840
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English (en)
French (fr)
Japanese (ja)
Inventor
尚人 岡田
直樹 後藤
健一 小林
Original Assignee
昭和電工株式会社
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Priority to CN202180042670.8A priority Critical patent/CN115698108A/zh
Priority to KR1020227042465A priority patent/KR20230009915A/ko
Priority to JP2022539516A priority patent/JP7435788B2/ja
Publication of WO2022025097A1 publication Critical patent/WO2022025097A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03F—SEWERS; CESSPOOLS
    • E03F7/00—Other installations or implements for operating sewer systems, e.g. for preventing or indicating stoppage; Emptying cesspools
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L55/00—Devices or appurtenances for use in, or in connection with, pipes or pipe systems
    • F16L55/18—Appliances for use in repairing pipes

Definitions

  • the present invention relates to a resin composition, a cured product, a method for producing a cured product, a pipe culvert repair material, and a pipe culvert repair method.
  • the present application claims priority based on Japanese Patent Application No. 2020-130660 filed in Japan on July 31, 2020, the contents of which are incorporated herein by reference.
  • thermosetting method using a thermosetting resin as a resin composition
  • photocuring method using a photocuring resin.
  • the resin composition is cured using a heat medium such as hot water or steam.
  • the photo-curing method the resin composition is cured by irradiating the pipe repair material with light such as ultraviolet light or visible light.
  • Patent Document 1 describes a thermosetting resin composition for a tube lining material containing an unsaturated polyester resin (a), a styrene monomer (b) and a silica powder (c) as essential components.
  • Patent Document 2 describes (A) a vinyl ester resin composition, (B) a urethane (meth) acrylate composition, (C) an unsaturated polyester resin composition, and (D) cumene hydroperoxide and t-butyl.
  • a resin composition for pipe repair containing a curing agent containing peroxybenzoate is described.
  • Patent Document 3 describes a tubular photocurable lining material containing a photocurable resin composition containing an unsaturated polyester resin or vinyl ester resin, styrene and a photopolymerization initiator.
  • the construction distance of the photo-curing method in the repair work of existing pipes has increased. This is because the curing speed of the resin composition is faster and the construction time is shorter than that of the thermosetting method.
  • the photo-curing method has the advantages of less curing shrinkage of the resin composition, less generation of curing defects, less heat generation of curing, and less emission of flammable gas during curing as compared with the thermosetting method. ..
  • Patent Document 4 describes a method of lining a pipe that irradiates a resin layer with light by a photocuring apparatus using a light emitting diode (LED) whose main irradiation wavelength is ultraviolet rays. LEDs generate less heat, save energy and have a long life, and are excellent as a light source.
  • LED light emitting diode
  • the present invention has been made in view of the above circumstances, and has a resin composition that is less likely to cause curing defects, provides a cured product having good heat resistance and chemical resistance, and can be preferably used as a material for pipe culvert repair materials.
  • the purpose is to provide things.
  • Another object of the present invention is to provide a cured product obtained by curing the resin composition of the present invention and having good heat resistance and chemical resistance, and a method for producing the same.
  • Another object of the present invention is to provide a pipe culvert repair material which contains a base material and the resin composition of the present invention impregnated in the base material and can obtain a repair surface having good heat resistance and chemical resistance.
  • Another object of the present invention is to provide a method for repairing a pipe using the pipe repair material of the present invention.
  • the present inventors have focused on the curing reaction of the resin composition and repeated studies.
  • a specific unsaturated polyester oligomer having a structure derived from a polyhydric alcohol component sufficiently containing neopentyl glycol, which has a wide intermolecular distance and easily transmits light having a wavelength of 315 to 460. It has been found that the resin composition may be contained. Since this resin composition has good light transmission, it is presumed that the irradiation light easily reaches not only the light irradiation surface but also the inside, and curing failure is unlikely to occur.
  • the present inventor irradiates this resin composition with only light having a peak half width of 4 to 35 nm and a center wavelength of 315 to 460 nm, which does not contain high-energy ultraviolet light having a wavelength of 200 to 314 nm. It was confirmed that a cured product having good heat resistance and chemical resistance could be obtained, and the present invention was conceived. That is, the present invention relates to the following matters.
  • (A) Unsaturated polyester oligomer and (B) Radical polymerizable monomer and (C) Including a photopolymerization initiator The structure in which the unsaturated polyester oligomer (A) is derived from the polyhydric alcohol component (a1) containing 55 to 85 mol% of neopentyl glycol with respect to 100 mol% of the total polyhydric alcohol component. Structures derived from the polybasic acid component (a2) containing isophthalic acid and / or terephthalic acid, and Containing structures derived from the unsaturated dibasic acid component (a3), including maleic anhydride and / or fumaric acid.
  • the structure derived from the polybasic acid component (a2) is 30 to 60 mol, and the structure derived from the unsaturated dibasic acid component (a3) is 100 mol with respect to 100 mol of the structure derived from the polyvalent alcohol component (a1).
  • a resin composition comprising 40 to 70 mol of.
  • the content of isophthalic acid and / or terephthalic acid in the polybasic acid component (a2) is 75 mol% or more.
  • the resin composition according to [1], wherein the content of maleic anhydride and / or fumaric acid in the unsaturated dibasic acid component (a3) is 90 mol% or more.
  • the content of the (B) radically polymerizable monomer in 100 parts by mass of the total of the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer is 20 to 60 parts by mass.
  • the content of the (C) photopolymerization initiator with respect to a total of 100 parts by mass of the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer is 0.01 to 10 parts by mass [1] to [ 3]
  • [5] [1] to [4] further contain 10 to 30 parts by mass of (D) vinyl ester resin with respect to a total of 100 parts by mass of the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer.
  • the resin composition according to any one of. [6] The resin composition according to any one of [1] to [5], wherein the (C) photopolymerization initiator is an acylphosphine-based compound and / or a benzyl ketal-based compound.
  • a pipe repair material containing a base material and the resin composition according to any one of [1] to [6] impregnated in the base material [10] The pipe repair material according to [9], wherein the base material is made of glass fiber and / or organic fiber. [11] The pipe repair material according to [9] or [10], wherein the base material is tubular. [12] The installation process of installing the pipe repair material according to any one of [9] to [11] in the existing pipe, and A method for repairing a pipe including a photocuring step of irradiating the pipe repair material with light having a peak half width of 4 to 35 nm and a center wavelength of 315 to 460 nm.
  • the resin composition of the present invention is less likely to cause curing defects, and a cured product having good heat resistance and chemical resistance can be obtained. Therefore, the resin composition of the present invention can be preferably used as a material for a pipe repair material. Further, the pipe repair material of the present invention includes a base material and the resin composition of the present invention impregnated in the base material. Therefore, by installing the pipe repair material in the existing pipe and irradiating it with light having a peak half width of 4 to 35 nm and a center wavelength of 315 to 460 nm, heat resistance and chemical resistance can be obtained. A good repair surface can be obtained.
  • FIG. 1 is a schematic perspective view for explaining an example of a pipe repair material of the present embodiment.
  • FIG. 2 is a schematic perspective view showing an example of an existing pipe that has been repaired using the pipe repair material shown in FIG.
  • the resin composition, the cured product, the method for producing the cured product, the pipe culvert repair material, and the pipe culvert repair method of the present invention will be described in detail.
  • the present invention is not limited to the embodiments shown below.
  • the resin composition of the present embodiment contains (A) an unsaturated polyester oligomer, (B) a radically polymerizable monomer, and (C) a photopolymerization initiator.
  • the resin composition of the present embodiment may further contain (D) vinyl ester resin, if necessary.
  • (A) an unsaturated polyester oligomer and a part of (B) a radically polymerizable monomer are contained as a polymer of (A) an unsaturated polyester oligomer and (B) a radically polymerizable monomer. It may have been.
  • the unsaturated polyester oligomer is copolymerized with the (B) radically polymerizable monomer to form an unsaturated polyester resin.
  • the unsaturated polyester oligomer has a structure derived from the polyvalent alcohol component (a1) containing 55 to 85 mol% of neopentyl glycol with respect to 100 mol% of the total polyhydric alcohol component, and isophthalic acid and / or terephthalic acid. It contains a structure derived from a polybasic acid component (a2) containing, and a structure derived from an unsaturated dibasic acid component (a3) containing maleic anhydride and / or fumaric acid.
  • the unsaturated polyester oligomer can be synthesized by a known method.
  • the polyhydric alcohol component (a1) used as a raw material for the unsaturated polyester oligomer contains neopentyl glycol (2,2-dimethyl-1,3-propanediol) in an amount of 55 to 85 mol%. It is preferably contained in an amount of 60 to 80 mol%, more preferably 65 to 75 mol%.
  • the two methyl groups present in the side chain of neopentyl glycol (A) widen the intermolecular distance of the unsaturated polyester oligomer to facilitate the transmission of light with wavelengths of 315 to 460.
  • the polyhydric alcohol component (a1) contains 55 mol% or more of neopentyl glycol, an unsaturated polyester oligomer (A) having good light transmission can be obtained.
  • the resin composition containing the unsaturated polyester oligomer (A) the light irradiated not only on the light-irradiated surface but also on the inside can easily reach the inside, curing defects are less likely to occur, and the photo-curing rate is high.
  • a cured product can be obtained without irradiating light in the high-energy ultraviolet region. Specifically, even if only light having a peak width at half maximum of 4 to 35 nm and a center wavelength of 315 to 460 nm is irradiated, a cured product having high density and good heat resistance can be obtained.
  • the two methyl groups present in the side chain of neopentyl glycol protect the ester bond site in the (A) unsaturated polyester oligomer synthesized using neopentyl glycol.
  • neopentyl glycol contained in the polyhydric alcohol component (a1) is 85 mol% or less, precipitates are less likely to precipitate during the reaction for synthesizing the unsaturated polyester oligomer (A), and the synthesis can be easily performed. Further, since neopentyl glycol contained in the polyhydric alcohol component (a1) is 85 mol% or less, it is difficult for precipitates derived from high crystallinity to be formed in the resin composition, and the stability over time is good. Become.
  • polyhydric alcohol component (a1) of neopentyl glycol conventionally known ones can be used. Specifically, ethylene glycol, bropyrene glycol, diethylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-Butanediol, 2-methyl-1,4-Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diol-1,5-pentanediol, 1 , 6-Hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 1,2-nonanediol, 1,4-cyclohexan
  • the other polyhydric alcohol component (a1) of neopentyl glycol includes physical properties such as strength, heat resistance and chemical resistance of the cured product obtained by curing the resin composition, glass fiber and / or organic fiber. From the viewpoint of impregnation property of the resin composition with respect to the substrate and cost, it is preferable to contain ethylene glycol and / or bropyrene glycol, and it is particularly preferable to contain bropyrene glycol.
  • the other polyhydric alcohol component (a1) of neopentyl glycol only one kind may be selected from the above and used, or two or more kinds may be used.
  • the polybasic acid component (a2) used as a raw material for the unsaturated polyester oligomer contains isophthalic acid and / or terephthalic acid.
  • the content of isophthalic acid and / or terephthalic acid in the polybasic acid component (a2) is 75 mol from the viewpoint of physical properties such as strength, heat resistance, chemical resistance, etc. of the cured product obtained by curing the resin composition and cost. % Or more, more preferably 80 mol% or more.
  • the polybasic acid component (a2) may be only isophthalic acid and / or terephthalic acid.
  • the other polybasic acid component (a2) of isophthalic acid and terephthalic acid conventionally known ones can be used. Specifically, phthalic acid anhydride, amber acid, adipic acid, sebacic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid (1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1) , 4-Cyclohexanedicarboxylic acid), naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, chlorendic acid (hetic acid), tetrabromophthalic acid, tetrahydrohydroan phthalic acid, hexahydroan phthalic acid, endomethylene tetrahydroan phthalic acid, anhydrous Amber acid, chlorendic acid anhydride, trimellitic acid anhydride, pyromelli
  • the isophthalic acid and the other polybasic acid component (a2) of terephthalic acid preferably contain phthalic anhydride from the viewpoint of the strength and cost of the cured product obtained by curing the resin composition.
  • the other polybasic acid component (a2) of isophthalic acid and terephthalic acid only one kind may be selected and used from the above, or two or more kinds may be used.
  • the unsaturated polyester oligomer (A) in the resin composition of the present embodiment has a structure derived from the polybasic acid component (a2) of 30 to 60 with respect to 100 mol of the structure derived from the polyvalent alcohol component (a1). It contains mol, preferably 40 to 50 mol. Since it contains 30 mol or more of the structure derived from the polybasic acid component (a2) with respect to 100 mol of the structure derived from the polyvalent alcohol component (a1), it is a resin curing having better strength, heat resistance and chemical resistance. You get things. Since the structure derived from the polybasic acid component (a2) is contained in an amount of 60 mol or less, the resin composition is less likely to become turbid due to the precipitation of highly crystalline acid components over time. Therefore, the photocurability of the resin composition is not easily impaired.
  • the unsaturated dibasic acid component (a3) used as a raw material for the unsaturated polyester oligomer contains maleic anhydride and / or fumaric acid.
  • the content of maleic anhydride and / or fumaric acid in the unsaturated dibasic acid component (a3) includes physical properties such as strength, heat resistance and chemical resistance of the cured product obtained by curing the resin composition, and styrene and the like.
  • the unsaturated dibasic acid component (a3) may be only maleic anhydride and / or fumaric acid.
  • the other unsaturated dibasic acid component (a3) of maleic anhydride and fumaric acid conventionally known ones can be used. Specifically, itaconic acid, citraconic acid, chloromaleic acid and the like can be used.
  • As the other unsaturated dibasic acid component (a3) of maleic anhydride and fumaric acid only one kind may be selected from the above and used, or two or more kinds may be used.
  • the unsaturated polyester oligomer (A) in the resin composition of the present embodiment has a structure derived from the unsaturated dibasic acid component (a3) 40 with respect to 100 mol of the structure derived from the polyhydric alcohol component (a1). It contains ⁇ 70 mol, preferably 45 ⁇ 65 mol. Since it contains 40 mol or more of the structure derived from the unsaturated dibasic acid component (a3) with respect to 100 mol of the structure derived from the polyhydric alcohol component (a1), the photocuring rate is high.
  • the structure derived from the unsaturated dibasic acid component (a3) since it contains 40 mol or more of a structure derived from the unsaturated dibasic acid component (a3), there is no shortage of the amount of unsaturated acid that becomes a cross-linking point (starting point of curing) during curing, and excellent strength, heat resistance, and resistance are achieved. A cured product having chemical properties can be obtained. Further, since the structure derived from the unsaturated dibasic acid component (a3) is 70 mol or less, it is possible to prevent the heat generation temperature during curing from becoming too high, and a cured product without cracks can be obtained.
  • the structure derived from the unsaturated dibasic acid component (a3) is 70 mol or less, the cured product does not become brittle due to an excessive amount of unsaturated acid, and a cured product having high toughness can be obtained. ..
  • the unsaturated polyester oligomer preferably has a polystyrene-equivalent weight average molecular weight of 1000 to 20000, more preferably 4000 to 17000, and even more preferably 7000 to 15000.
  • a cured product having better heat resistance and chemical resistance can be obtained.
  • the weight average molecular weight of the unsaturated polyester oligomer is 20000 or less, the viscosity of the resin composition due to the high molecular weight unsaturated polyester resin is unlikely to increase. Further, the unsaturated polyester oligomer having a weight average molecular weight of 20000 or less has good molecular weight uniformity. From this, it is preferable that the weight average molecular weight of the unsaturated polyester oligomer (A) is 20000 or less because a cured product having uniform characteristics can be easily obtained.
  • the content of the (A) unsaturated polyester oligomer contained in the resin composition of the present embodiment can be calculated by a method of analyzing the composition of the resin composition using a nuclear magnetic resonance (NMR) device.
  • NMR nuclear magnetic resonance
  • the structure derived from the polyvalent alcohol component (a1) contained in the (A) unsaturated polyester oligomer of the resin composition of the present embodiment, the structure derived from the polybasic acid component (a2), and the unsaturated dibasic acid component For the structure derived from a3), 1 H-NMR measurement of (A) unsaturated polyester oligomer was performed with a nuclear magnetic resonance (NMR) device, and the composition and composition ratio of the contained components were obtained from the obtained proton number and integrated value. It can be obtained by a method of calculating (molar ratio).
  • the (B) radically polymerizable monomer copolymerizes with the unsaturated bond in the molecular skeleton of the (A) unsaturated polyester oligomer to form an unsaturated polyester resin.
  • the radically polymerizable monomer is selected from an alkyl group, a nitro group, a cyano group, an amide group, a halogen group and a vinyl group at any of the ⁇ -position, ortho-position, meta-position and para-position of styrene and styrene.
  • a compound to which a substituent is bonded, a styrene-based monomer such as an ester derivative thereof, and the like can be used.
  • a styrene-based monomer such as an ester derivative thereof, and the like.
  • the radically polymerizable monomer only one kind may be selected from the above and used, or two or more kinds may be used.
  • the radically polymerizable monomer (B) since the copolymerizability with (A) unsaturated polyester oligomer is good, it is particularly preferable to use styrene among the above.
  • the content of the (B) radically polymerizable monomer in 100 parts by mass of the total of the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer is preferably 20 to 60 parts by mass, preferably 35 to 55 parts by mass. It is more preferable that it is a radical.
  • a cured product having excellent strength can be obtained as a resin composition.
  • the resin composition does not become too viscous.
  • (C) photopolymerization initiator a known intramolecular cleavage type photopolymerization initiator or the like can be used, and depending on the wavelength of the irradiation light from the light source used when curing the resin composition, 1 A species or two or more species can be appropriately selected and used.
  • the intramolecular cleavage type photopolymerization initiator include benzyldimethylketal compounds, ⁇ -hydroxyalkylphenone compounds, ⁇ -aminoalkylphenone compounds, acylphosphine compounds, and benzylketal compounds.
  • Examples of the benzyldimethylketal compound include 2,2-dimethoxy-1,2-diphenylethane-1-one and the like.
  • Examples of the ⁇ -hydroxyalkylphenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 1- [4- (2-hydroxyethoxy).
  • Examples of the ⁇ -aminoalkylphenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4).
  • -Molholinophenyl) -butanone-1 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) -1-butanone and the like can be mentioned.
  • acylphosphine compound examples include bis (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide, 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-propylphenylphosphine oxide, bis (2, 6-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like can be mentioned.
  • (C) photopolymerization initiators in particular, when the resin composition is irradiated with light having a wavelength of 315 to 460 nm, 2 is used because it absorbs light having a wavelength of 315 to 460 nm and efficiently generates an active species.
  • 2-Dimethoxy-1,2-diphenylethan-1-one, bis (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide is preferably used.
  • the content of the (C) photopolymerization initiator with respect to a total of 100 parts by mass of the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer is preferably 0.01 to 10 parts by mass, preferably 0.05. It is more preferably to 8 parts by mass, and further preferably 0.20 to 5 parts by mass.
  • the content of (C) photopolymerization initiator is 0.01 parts by mass or more, the initiation of radical polymerization of (A) unsaturated polyester oligomer and (B) radically polymerizable monomer and the polymerization rate of radical polymerization are promoted. The effect of making the radical is remarkable. Therefore, the resin composition has a high density and a cured product having good heat resistance.
  • the content of the photopolymerization initiator is 10 parts by mass or less, a rapid curing reaction and heat generation are unlikely to occur during curing of the resin composition, and a cured product without cracks and cracks can be obtained.
  • vinyl ester resin (D) examples include epoxy (meth) acrylate obtained by reacting an epoxy resin with (meth) acrylic acid.
  • the vinyl ester resin (D) it is preferable to use a bisphenol type vinyl ester resin because it is a resin composition that can obtain a cured product having better heat resistance and chemical resistance.
  • the weight average molecular weight of the (D) vinyl ester resin is preferably 500 to 6000, more preferably 1000 to 5000.
  • the weight average molecular weight is 500 or more, a cured product having better heat resistance and chemical resistance can be obtained.
  • the weight average molecular weight is 6000 or less, the viscosity of the resin composition due to the high molecular weight vinyl ester resin is unlikely to increase, which is preferable.
  • the vinyl ester resin (D) preferably contains 10 to 30 parts by mass, preferably 12 to 28 parts by mass, based on 100 parts by mass of the total of (A) unsaturated polyester oligomer and (B) radically polymerizable monomer. Is more preferable, and it is further preferable to contain 14 to 26 parts by mass.
  • the content of the vinyl ester resin (D) is 10 parts by mass or more, a cured product having better heat resistance and chemical resistance can be obtained.
  • the content of the (D) vinyl ester resin is 30 parts by mass or less, the photocurability is lowered due to the decrease in the unsaturated group concentration, and the compatibility between the (D) vinyl ester resin and the (A) unsaturated polyester oligomer is reduced.
  • the content of the (D) vinyl ester resin is 30 parts by mass or less, the viscosity increase due to the hydrogen bond due to the hydroxyl group of the side chain of the (D) vinyl ester resin is unlikely to occur, and the glass fiber and / or the organic fiber is less likely to occur. It is preferable because it is a resin composition having good impregnation property with a substrate such as.
  • the resin composition of the present embodiment may contain other additives, if necessary, as long as the effects of the present invention are not impaired.
  • the additive include an ultraviolet absorber, a coupling agent, a thickener, a colorant, a flame retardant, a filler and the like.
  • the resin composition of the present embodiment comprises (A) an unsaturated polyester oligomer, (B) a radically polymerizable monomer, (C) a photopolymerization initiator, and (D) vinyl ester resin added as needed. It can be produced by a method of mixing with other additives.
  • the resin composition of the present embodiment may be produced by the method shown below.
  • (A) unsaturated polyester oligomer and (B) radically polymerizable monomer are mixed to produce an unsaturated polyester resin in which (A) unsaturated polyester oligomer is dissolved in (B) radically polymerizable monomer.
  • it may be produced by a method of mixing the obtained unsaturated polyester resin, (C) a photopolymerization initiator, and (D) vinyl ester resin and other additives added as needed.
  • the method of mixing each component contained in the resin composition of the present embodiment is not particularly limited, and for example, a stirring blade powered by a motor, a homodisper, or the like can be used.
  • the cured product of the present embodiment is a cured product of the resin composition of the present embodiment.
  • the cured product of the present embodiment preferably has a deflection temperature under load measured in accordance with JIS A 7511 at 85 ° C. or higher, more preferably 90 ° C. or higher.
  • a resin composition in which the deflection temperature under load of the cured product is 85 ° C.
  • the cured product of the present embodiment preferably has a tensile elongation at break of 3.5% or more, more preferably 5.0% or more, as measured in accordance with JIS A 7511.
  • the pipe repair material can be used as a sewer pipe.
  • it is a pipe culvert repair material that satisfies the characteristics of tensile elongation at break in "Design and construction management guidelines for pipe rehabilitation method-2017 version-" and can obtain a repair surface with good toughness.
  • the cured product of this embodiment has a mass change rate of ⁇ 0.3% or less in a nitric acid resistance test based on a chemical resistance test of a reinforced plastic composite tube (K-2) for sewerage according to the Japan Sewerage Association standard (JSWAS). It is preferably within ⁇ 0.25%.
  • the resin composition to be impregnated in the base material of the pipe repair material the resin composition having a mass change rate of ⁇ 0.3% or less in the nitric acid resistance test of the cured product is used to strengthen the sewerage standard of the Japan Sewerage Association. It is a pipe culvert repair material that satisfies the nitric acid resistance of plastic composite pipes and provides a repair surface with good chemical resistance.
  • the method for producing the cured product of the present embodiment is not particularly limited, and a method of irradiating the resin composition of the present embodiment with light to cure the cured product can be used.
  • a light source for irradiating the resin composition of the present embodiment with light a general light emitting diode (LED) can be used. LEDs generate less heat, save energy and have a long life, and are preferable as a light source.
  • the resin composition of the present embodiment can be cured, and for example, a light source that irradiates light in a wide wavelength range such as a gallium lamp, a metal halide lamp, or a mercury lamp may be used. Even in this case, the resin composition of the present embodiment is easily cured to become a cured product.
  • the resin composition of the present embodiment is less likely to cause poor curing. Therefore, in the method for producing a cured product of the present embodiment, for example, the resin composition of the present embodiment is cured by irradiating it with only light that does not contain light in the high-energy ultraviolet region using an LED or the like.
  • the method can be used.
  • As the light that does not contain the light in the high energy ultraviolet region for example, light having a peak half width of 4 to 35 nm and a center wavelength of 315 to 460 nm can be used.
  • the central wavelength of this light is in the range from the region on the high energy side of UV-A to the indigo region of the visible light region.
  • the central wavelength of the light irradiating the resin composition can be appropriately determined according to the thickness of the target cured product (molded product).
  • the resin composition of the present embodiment can be cured by irradiating only single wavelength light having high wavelength purity. Therefore, the peak width at half maximum of light in the high-energy ultraviolet region that does not contain light may be 6 to 25 nm or 8 to 15 nm.
  • the light irradiating the resin composition of the present embodiment may be light having a peak half-value width of 4 to 35 nm and a center wavelength of 340 to 430 nm, or a peak half-value width of 4 to 35 nm and a center. It may be light having a wavelength of 350 to 405 nm.
  • the illuminance and irradiation time of the light irradiating the resin composition are appropriately determined according to the thickness of the target cured product (molded product), the wavelength of the irradiation light, and the like. Can be done, and is not particularly limited.
  • the resin composition of the present embodiment contains (A) an unsaturated polyester oligomer, (B) a radically polymerizable monomer, and (C) a photopolymerization initiator.
  • the resin composition of the present embodiment has a structure in which (A) the unsaturated polyester oligomer is derived from the polyhydric alcohol component (a1) containing 55 to 85 mol% of neopentyl glycol with respect to 100 mol% of the total polyhydric alcohol component. And a structure derived from a polybasic acid component (a2) containing isophthalic acid and / or terephthalic acid, and a structure derived from an unsaturated dibasic acid component (a3) containing maleic anhydride and / or fumaric acid.
  • the resin composition of the present embodiment has a structure derived from the polybasic acid component (a2) of 30 to 60 mol and an unsaturated dibasic acid component (unsaturated dibasic acid component) with respect to 100 mol of the structure derived from the polyvalent alcohol component (a1). It contains 40 to 70 mol of the structure derived from a3).
  • the resin composition of the present embodiment is less likely to cause curing failure, and a cured product having good heat resistance and chemical resistance can be obtained.
  • the polyhydric alcohol component (a1) contains 55 to 85 mol% of neopentyl glycol, and the polyhydric alcohol component (a1) is contained. It contains a structure derived from the polybasic acid component (a2), a structure derived from the unsaturated dibasic acid component (a3), and a structure derived from the unsaturated dibasic acid component (a3) in a specific ratio. Therefore, the unsaturated polyester oligomer (A) has good light transmission and the ester bond site is protected.
  • the resin composition of the present embodiment As a result, in the resin composition of the present embodiment, the light irradiated not only to the light irradiation surface but also to the inside can easily reach the inside, and the photocuring speed is high. Further, the cured product of the resin composition of the present embodiment has a high density and good heat resistance and chemical resistance. Therefore, the resin composition of the present embodiment can be preferably used as a material for the pipe repair material.
  • FIG. 1 is a schematic perspective view for explaining an example of a pipe repair material of the present embodiment.
  • the pipe repair material 11 of the present embodiment includes a base material 10 and a resin composition impregnated in the base material 10.
  • the base material 10 is impregnated with the resin composition of the above-described embodiment.
  • the base material 10 is made of a material having appropriate flexibility and strength that follows the shape of the inner wall of the pipe and having a gap that can be impregnated with the resin composition.
  • a base material 10 made of glass fiber and / or organic fiber.
  • the organic fiber include fibers made of polyester, polypropylene, polyethylene, vinylon, nylon, acrylic and the like.
  • the shape of the base material 10 is preferably tubular (cylindrical).
  • the pipe repair material 11 can be easily installed in an annular shape along the inner peripheral surface of the pipe.
  • a known resin film may be installed on the inner surface and / or the outer surface of the pipe repair material 11. The resin film protects the surface of the pipe repair material 11 and improves workability when the pipe repair material 11 is used to repair the pipe.
  • the resin film installed on the inner surface of the pipe repair material 11 may be removed from the pipe repair material 11 after the resin composition impregnated in the base material 10 is cured.
  • the shape of the base material 10 is not limited to the tubular shape shown in FIG. 1, and may be, for example, a sheet shape.
  • FIG. 2 is a schematic perspective view showing an example of an existing pipe that has been repaired using the pipe repair material shown in FIG.
  • reference numeral 20 indicates a pipe.
  • Examples of the pipe 20 to be repaired by using the pipe repair method of the present embodiment include existing gas pipes, water pipes, sewer pipes, sewage attachment pipes, agricultural water pipes, industrial water pipes, power pipes or communication pipes. A pipe can be mentioned.
  • the pipe repair material 11 is installed at a predetermined position in the pipe 20 in the length direction by a known method (installation step).
  • installation step for example, by applying pressure to the inner surface of the pipe repair material 11 using air, the outer surface of the pipe repair material 11 is brought into close contact with the inner surface of the pipe 20.
  • photo-curing step light is irradiated to the pipe repair material 11 from the inside of the pipe repair material 11 (photo-curing step). This cures the resin composition impregnated in the base material 10 of the pipe repair material 11.
  • the light to irradiate the pipe repair material 11 As the light to irradiate the pipe repair material 11, light having a peak half width of 4 to 35 nm and a center wavelength of 315 to 460 nm can be used. It is preferable to use a light emitting diode (LED) as a light source.
  • LED light emitting diode
  • the pipe repair material 11 of the present embodiment contains the base material 10 and the resin composition of the present embodiment impregnated with the base material 10. Therefore, the pipe repair material 11 is installed in the existing pipe 20, and the light in the high-energy ultraviolet region having a peak half-value width of 4 to 35 nm and a center wavelength of 315 to 460 nm in the pipe repair material 11. Even if the resin composition is cured by irradiating only light that does not contain the above-mentioned light, curing defects are less likely to occur, and a repair surface having good heat resistance and chemical resistance can be obtained. Therefore, when repairing the pipe 20 using the pipe repair material 11 of the present embodiment, a general light emitting diode (LED) can be used as a light source for irradiating the pipe repair material 11 with light.
  • LED general light emitting diode
  • Example 1 to Example 10 Comparative Example 1 to Comparative Example 4" Stirring (A) unsaturated polyester oligomers (UPE-1 to UPE-9) and (B) styrene as a radically polymerizable monomer powered by a motor so as to have the ratios shown in Tables 3 and 4.
  • An unsaturated polyester resin was produced by mixing and polymerizing using wings.
  • the obtained unsaturated polyester resin, the (C) photopolymerization initiator shown in Tables 3 and 4, and the (D) vinyl ester resin added as needed are mixed in the proportions shown in Tables 3 and 4.
  • the resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were obtained by a method of mixing using a stirring blade powered by a motor.
  • the content of (B) radically polymerizable monomer shown in Tables 3 and 4 is the content (parts by mass) in 100 parts by mass of the total of (A) unsaturated polyester oligomer and (B) radically polymerizable monomer. ..
  • the content of (C) photopolymerization initiator shown in Tables 3 and 4 is the content (parts by mass) with respect to a total of 100 parts by mass of (A) unsaturated polyester oligomer and (B) radically polymerizable monomer.
  • the content of (D) vinyl ester resin shown in Tables 3 and 4 is the content (parts by mass) with respect to a total of 100 parts by mass of (A) unsaturated polyester oligomer and (B) radically polymerizable monomer.
  • As the (D) vinyl ester resin a bisphenol type vinyl ester resin (Lipoxy (registered trademark) (R-806; weight average molecular weight 2400; manufactured by Showa Denko KK) was used.
  • a light emitting diode having a peak half-value width of 10 nm and a center wavelength of 385 nm (trade name; UV-LED irradiator H-4MLH84-V2-1S12-SM1) (usable wavelength) in which the resin composition is placed in a mold and used as a light source.
  • HOYA Co., Ltd. 385 nm (HOYA Co., Ltd.) is used to irradiate light with an illuminance of 40 mW / cm 2 (illuminance meter: UV illuminance meter UIT-201 manufactured by Ushio Denki) for 30 minutes, and has a plate shape of 200 mm in length, 200 mm in width, and 4 mm in thickness. The cured product of was obtained.
  • Example 9 prepare a # 450 chopped strand mat (trade name; ECM450-501 / T, manufactured by Central Glass Fiber Co., Ltd.) as a base material, and cut out 6 pieces into a square with a length of 150 mm and a width of 150 mm, totaling about 38 g.
  • the resin composition of Example 9 was impregnated with a defoaming roller to obtain a laminate.
  • the obtained laminate has a light emitting diode having a peak half-value width of 10 nm and a center wavelength of 385 nm (trade name; UV-LED irradiator H-4MLH84-V2-1S12-SM1 (usable wavelength 385 nm) HOYA Co., Ltd.
  • Example 9 of a plate-shaped plate having a length of 150 mm, a width of 150 mm, and a thickness of 5 mm by irradiating light with an illuminance of 40 mW / cm 2 (illuminance meter: UV illuminance meter UIT-201 manufactured by Usio Electric Co., Ltd.) for 3 minutes. A cured product was obtained.
  • the cured products of Examples 1 to 8 and 10 were all evaluated as “heat resistance”, “chemical resistance”, and “toughness” as ⁇ or ⁇ .
  • the cured products of Example 1 and Example 2 produced using the resin composition containing (D) vinyl ester resin were all evaluated as ⁇ in “heat resistance”, “chemical resistance” and “toughness”. ..
  • the cured product of Example 3 was evaluated as "flexural strength”.
  • the cured product of Example 9 produced by using the substrate and the same resin composition as the cured product of Example 3 was evaluated as ⁇ in "flexural strength”.
  • a comparative example using UPE-6 in which the polyvalent alcohol component (a1) contains 65 mol of the structure derived from the polybasic acid component (a2) and 35 mol of the structure derived from the unsaturated dibasic acid component (a3).
  • the cured product of No. 3 had a rating of x for "heat resistance” and "chemical resistance”.
  • a comparative example using UPE-9 in which the polyvalent alcohol component (a1) contains 25 mol of the structure derived from the polybasic acid component (a2) and 75 mol of the structure derived from the unsaturated dibasic acid component (a3). In the cured product of No. 4, cracks occurred when the resin composition was cured, and a cured product could not be obtained.

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