Resin composition, pipe and channel repair materials and pipe and channel repair methods

Abstract

A resin composition comprising (A) an unsaturated polyester oligomer, (B) a free radical polymerizable monomer, and (C) a photopolymerization initiator, wherein (A) the unsaturated polyester oligomer comprises a structure derived from a polyol component (a1) comprising 55 to 85 mol% neopentyl glycol relative to 100 mol% of the total polyol component, a structure derived from a polyacid component (a2) comprising isophthalic acid and / or terephthalic acid, and a structure derived from an unsaturated diacid component (a3) ​​comprising maleic anhydride and / or fumaric acid, wherein relative to 100 mol of the structure derived from the polyol component (a1), the structure derived from the polyacid component (a2) comprises 30 to 60 mol of the structure derived from the polyacid component (a2) and the structure derived from the unsaturated diacid component (a3) ​​comprises 40 to 70 mol of the structure derived from the unsaturated diacid component (a3).

Description

Technical Field

[0001] This invention relates to resin compositions, cured products, methods for manufacturing cured products, pipe and channel repair materials, and methods for pipe and channel repair.

[0002] This application asserts priority based on Japanese Patent Application No. 2020-130660 filed on July 31, 2020, the contents of which are incorporated herein by reference. Background Technology

[0003] Traditionally, methods for repairing existing pipework such as gas pipes, water pipes, sewer pipes, and agricultural water pipes have involved using pipe repair materials that impregnate a resin composition with a fiber-based substrate. Specifically, the pipe repair material is applied to a predetermined location within the existing pipework, and then the resin composition contained within the material is cured to repair the pipework. This method includes thermosetting methods using thermosetting resins and light-curing methods using light-curing resins. In thermosetting methods, the resin composition is cured using a heat medium such as warm water or steam. In light-curing methods, the resin composition is cured by irradiating the pipe repair material with ultraviolet or visible light.

[0004] Patent Document 1 describes a thermosetting resin composition for pipe lining materials, which uses unsaturated polyester resin (a), styrene monomer (b), and silica powder (c) as essential components.

[0005] Furthermore, Patent Document 2 describes a pipe repair resin composition containing (A) a vinyl ester resin composition, (B) a urethane (meth) acrylate composition, (C) an unsaturated polyester resin composition, and (D) a curing agent comprising isopropylbenzene hydroperoxide and tert-butyl peroxide benzoate.

[0006] Furthermore, Patent Document 3 describes a tubular photocurable lining material containing a photocurable resin composition comprising an unsaturated polyester resin or vinyl ester resin, styrene, and a photopolymerization initiator.

[0007] In recent years, the construction distance for UV-curing methods in the repair of existing pipelines has increased. This is because, compared with thermosetting methods, the resin composition cures faster and the construction time is shorter. In addition, compared with thermosetting methods, UV-curing methods also have advantages such as less curing shrinkage of the resin composition, less likelihood of poor curing, less heat generation during curing, and less emission of flammable gases during curing.

[0008] In photocuring construction methods, gallium lamps, metal halide lamps, and mercury lamps are used as light sources. Furthermore, Patent Document 4 describes a method for lining pipes that uses a photocuring device employing a light-emitting diode (LED) with ultraviolet light as its primary irradiation wavelength to irradiate the resin layer. LEDs generate little heat, are energy-efficient, and have a long lifespan, making them excellent light sources.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent No. 4055300

[0012] Patent Document 2: Japanese Patent No. 6460999

[0013] Patent Document 3: Japanese Patent No. 6095278

[0014] Patent Document 4: Japanese Patent Application Publication No. 2008-142996 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] However, with existing technologies, even when light is irradiated onto the pipe repair materials used in light-curing construction methods, it is sometimes impossible to obtain a repair surface with good heat resistance and chemical resistance.

[0017] The present invention is made in view of the above circumstances, and its object is to provide a resin composition that is not prone to poor curing, yields a cured product with good heat resistance and chemical resistance, and is preferably used as a material for pipe and channel repair.

[0018] Furthermore, the object of the present invention is to provide a cured product with good heat resistance and chemical resistance, which cures the resin composition of the present invention, and a method thereof.

[0019] Furthermore, the object of the present invention is to provide a pipe repair material comprising a substrate and a resin composition of the present invention impregnated in the substrate, which can provide a repair surface with good heat resistance and chemical resistance.

[0020] Furthermore, the purpose of this invention is to provide a pipe repair method using the pipe repair material of this invention.

[0021] Methods for solving problems

[0022] In order to solve the above-mentioned problems, the inventors focused on the curing reaction of the resin composition and conducted repeated research.

[0023] The results showed that a resin composition containing specific unsaturated polyester oligomers with wide intermolecular distances and easily transmittable wavelengths of light (315–460 nm) can be prepared by using a structure containing a polyol component derived from neopentyl glycol. It is presumed that due to the good light transmittance of this resin composition, irradiated light can easily reach not only the irradiated surface but also the interior, thus reducing the likelihood of poor curing.

[0024] The inventors discovered that by irradiating the resin composition with light that does not contain high-energy ultraviolet light in the wavelength range of 200–314 nm, has a full width at half maximum (FWHM) of 4–35 nm, and a center wavelength of 315–460 nm, a cured product with good heat resistance and chemical resistance can be obtained, and thus conceived of the present invention.

[0025] That is, the present invention relates to the following matters.

[0026] [1] A resin composition, characterized in that it comprises:

[0027] (A) Unsaturated polyester oligomers;

[0028] (B) Free radical polymerizable monomers; and

[0029] (C) Photopolymerization initiator,

[0030] The above-mentioned (A) unsaturated polyester oligomer includes:

[0031] The structure is derived from the polyol component (a1), which contains 55 to 85 mol% neopentyl glycol relative to 100 mol% of the total polyol components;

[0032] The structure is derived from the polybasic acid component (a2), which comprises isophthalic acid and / or terephthalic acid; and

[0033] The structure is derived from the unsaturated dicarboxylic acid component (a3), which comprises maleic anhydride and / or fumaric acid.

[0034] Of which, relative to the above-mentioned 100 moles of the structure derived from the polyol component (a1), there are 30 to 60 moles of the structure derived from the polyacid component (a2) and 40 to 70 moles of the structure derived from the unsaturated dicarboxylic acid component (a3).

[0035] [2] According to the resin composition described in [1], the content of isophthalic acid and / or terephthalic acid in the above-mentioned polybasic acid component (a2) is 75 mol% or more.

[0036] The content of maleic anhydride and / or fumaric acid in the above-mentioned unsaturated dicarboxylic acid component (a3) ​​is 90 mol% or more.

[0037] [3] According to the resin composition of [1] or [2], the weight-average molecular weight of the unsaturated polyester oligomer of (A) is 1,000 to 20,000.

[0038] [4] In any one of the resin compositions according to [1] to [3], the content of the free radical polymerizable monomer (B) in 100 parts by mass of the total of the unsaturated polyester oligomer (A) and the free radical polymerizable monomer (B) is 20 to 60 parts by mass.

[0039] The content of the above-mentioned (C) photopolymerization initiator relative to the total of 100 parts by mass of the above-mentioned (A) unsaturated polyester oligomer and the above-mentioned (B) free radical polymerizable monomer is 0.01 to 10 parts by mass.

[0040] [5] The resin composition according to any one of [1] to [4] further comprises 10 to 30 parts by weight of (D) vinyl ester resin relative to 100 parts by weight of the total of the above-mentioned (A) unsaturated polyester oligomer and the above-mentioned (B) free radical polymerizable monomer.

[0041] [6] In any one of the resin compositions according to [1] to [5], the above (C) photopolymerization initiator is an acylphosphine compound and / or a benzoyl ketal compound.

[0042] [7] A cured product is a cured product of the resin composition described in any one of [1] to [6], having a load flexural temperature of 85°C or higher as determined by JIS A7511, and a mass change rate of ±0.3% or less in the nitric acid resistance test of the chemical resistance test for reinforced plastic composite pipes for sewers according to the specifications of the Japan Sewerage Association.

[0043] [8] A method for manufacturing a cured product, wherein a resin composition described in any one of [1] to [6] is irradiated with light having a half-width of 4 to 35 nm and a center wavelength of 315 to 460 nm to cure it.

[0044] [9] A pipe repair material comprising a substrate and a resin composition impregnated therein in any one of [1] to [6].

[0045]

[10] According to the pipe repair material described in [9], the substrate is composed of glass fiber and / or organic fiber.

[0046]

[11] The base material of the pipe repair material according to [9] or

[10] is tubular.

[0047]

[12] A method for repairing pipes and channels, comprising the following steps:

[0048] The installation process of placing the pipe repair material as described in any one of [9] to

[11] into an existing pipe channel; and

[0049] A photocuring process in which the above-mentioned pipe repair material is irradiated with light having a half-width of 4 to 35 nm and a center wavelength of 315 to 460 nm.

[0050] The effects of the invention

[0051] The resin composition of the present invention is less prone to poor curing and yields a cured product with good heat resistance and chemical resistance. Therefore, the resin composition of the present invention is preferably used as a material for pipe and channel repair.

[0052] Furthermore, the pipe repair material of the present invention comprises a substrate and a resin composition of the present invention impregnated in the substrate. Therefore, by placing the pipe repair material in an existing pipe, for example by irradiating it with light having a half-width of 4 to 35 nm and a center wavelength of 315 to 460 nm, a repair surface with good heat resistance and chemical resistance can be obtained. Attached Figure Description

[0053] Figure 1 This is a schematic perspective view illustrating an example of the pipe repair material used in this embodiment.

[0054] Figure 2 For display purposes Figure 1 The diagram shows a schematic perspective view of an existing pipework repaired with the provided repair materials. Detailed Implementation

[0055] The resin composition, cured product, method for manufacturing the cured product, pipe repair material, and pipe repair method of the present invention will be described in detail below. Furthermore, the present invention is not limited to the embodiments shown below.

[0056] [Resin Composition]

[0057] The resin composition of this embodiment comprises (A) an unsaturated polyester oligomer, (B) a free radical polymerizable monomer, and (C) a photopolymerization initiator. The resin composition of this embodiment may further comprise (D) a vinyl ester resin if desired.

[0058] In the resin composition of this embodiment, (A) unsaturated polyester oligomer and (B) free radical polymerizable monomer may be contained as a polymer of (A) unsaturated polyester oligomer and (B) free radical polymerizable monomer.

[0059] <(A) Unsaturated polyester oligomers>

[0060] (A) Unsaturated polyester oligomers are copolymerized with (B) free radical polymerizable monomers to form unsaturated polyester resins.

[0061] (A) The unsaturated polyester oligomer comprises: a structure derived from a polyol component (a1), wherein the polyol component (a1) comprises 55 to 85 mol% neopentyl glycol per 100 mol% of the total polyol component; a structure derived from a polyacid component (a2), wherein the polyacid component (a2) comprises isophthalic acid and / or terephthalic acid; and a structure derived from an unsaturated dicarboxylic acid component (a3), wherein the unsaturated dicarboxylic acid component (a3) ​​comprises maleic anhydride and / or fumaric acid.

[0062] (A) Unsaturated polyester oligomers can be synthesized by known methods.

[0063] The polyol component (a1) used as a raw material for (A) unsaturated polyester oligomers contains 55 to 85 mol% neopentyl glycol (2,2-dimethyl-1,3-propanediol), preferably 60 to 80 mol%, more preferably 65 to 75 mol%.

[0064] The two methyl groups present in the side chain of neopentyl glycol increase the intermolecular distance of the (A) unsaturated polyester oligomer, making it easier for light with wavelengths of 315–460 nm to pass through. If neopentyl glycol is included in the polyol component (a1) at a level of 55 mol% or more, a (A) unsaturated polyester oligomer with good light transmittance can be obtained. Resin compositions containing this (A) unsaturated polyester oligomer are easily illuminated, allowing light to reach not only the irradiated surface but also the interior, reducing the likelihood of poor curing and resulting in rapid photocuring. Therefore, cured products can be obtained even without irradiation in the high-energy ultraviolet region. Specifically, even with only irradiation of light with a half-width of 4–35 nm and a center wavelength of 315–460 nm, a cured product with high density and good heat resistance can be obtained. Furthermore, the two methyl groups present in the side chain of neopentyl glycol protect the ester bond sites in the (A) unsaturated polyester oligomer synthesized using neopentyl glycol. Therefore, if a resin composition containing an (A) unsaturated polyester oligomer synthesized using a polyol component (a1) comprising more than 55 mol% neopentyl glycol is cured, a cured product with good chemical resistance can be obtained.

[0065] Furthermore, since the neopentyl glycol contained in the polyol component (a1) is less than 85 mol%, precipitates are not easily formed during the synthesis of the (A) unsaturated polyester oligomer, making synthesis easy. Additionally, since the neopentyl glycol contained in the polyol component (a1) is less than 85 mol%, highly crystalline precipitates are not easily formed in the resin composition, resulting in good stability over time.

[0066] As the polyol component (a1) other than neopentyl glycol, conventionally known substances can be used. Specifically, ethylene glycol, propylene 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-diethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, and 2,5-dimethyl-2,5-hexanediol can be used. Diols, 1,2-octanediol, 1,2-nonanediol, 1,4-cyclohexanediol, 1,8-octanediol, 1,9-nonanediol, 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol, bisphenol A and bisphenol F, bisphenol S, 2,2-bis(4-hydroxycyclohexyl)propane {hydrogenated bisphenol A}, polyethylene glycol, polypropylene glycol and other diols, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, etc.

[0067] Among these, from the viewpoints of the strength, heat resistance, chemical resistance, and other physical properties of the cured product obtained by curing the resin composition, the impregnation properties of the resin composition on substrates such as glass fibers and / or organic fibers, and cost, the polyol component (a1) other than neopentyl glycol preferably includes ethylene glycol and / or propylene glycol, and particularly preferably includes propylene glycol. As the polyol component (a1) other than neopentyl glycol, only one of the above can be selected and used, or two or more can be used.

[0068] The polybasic acid component (a2) used as a raw material for the (A) unsaturated polyester oligomer includes isophthalic acid and / or terephthalic acid. From the viewpoint of the strength, heat resistance, chemical resistance, and other physical properties of the cured product obtained by curing the resin composition, as well as cost, the content of isophthalic acid and / or terephthalic acid in the polybasic acid component (a2) is preferably 75 mol% or more, more preferably 80 mol% or more. The polybasic acid component (a2) may consist solely of isophthalic acid and / or terephthalic acid.

[0069] As the polybasic acid component (a2) other than isophthalic acid and terephthalic acid, conventionally known substances can be used. Specifically, phthalic anhydride, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, inner methylene tetrahydrophthalic acid, hexahydrophthalic acid (1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid), naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, chloroplastric acid, tetrabromophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, inner methylene tetrahydrophthalic anhydride, succinic anhydride, chloroplastric anhydride, trimellitic anhydride, pyromellitic anhydride, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, etc., can be used.

[0070] Among these, from the viewpoint of the strength and cost of the cured product obtained by curing the resin composition, the polybasic acid component (a2) other than isophthalic acid and terephthalic acid preferably includes phthalic anhydride. As the polybasic acid component (a2) other than isophthalic acid and terephthalic acid, only one of the above can be selected and used, or two or more can be used.

[0071] In this embodiment, the (A) unsaturated polyester oligomer in the resin composition contains 30 to 60 moles of the structure derived from the polyol component (a1), preferably 40 to 50 moles, relative to 100 moles of the structure derived from the polyacid component (a2). Since it contains 30 or more moles of the structure derived from the polyacid component (a2) relative to 100 moles of the structure derived from the polyol component (a1), a cured resin with superior strength, heat resistance, and chemical resistance can be obtained. Since it contains 60 or fewer moles of the structure derived from the polyacid component (a2), turbidity of the resin composition caused by the time-induced precipitation of highly crystalline acid components is less likely to occur. Therefore, the photocurability of the resin composition is less likely to be impaired.

[0072] The unsaturated diacid component (a3) ​​used as a raw material for (A) unsaturated polyester oligomers comprises maleic anhydride and / or fumaric acid. From the viewpoints of strength, heat resistance, chemical resistance, copolymerization with (B) free radical polymerizable monomers such as styrene, and cost, the content of maleic anhydride and / or fumaric acid in the unsaturated diacid component (a3) ​​is preferably 90 mol% or more. The unsaturated diacid component (a3) ​​may consist solely of maleic anhydride and / or fumaric acid.

[0073] As an unsaturated dicarboxylic acid component (a3) ​​other than maleic anhydride and fumaric acid, conventionally known substances can be used. Specifically, itaconic acid, citraconic acid, chloromaleic acid, etc., can be used. As an unsaturated dicarboxylic acid component (a3) ​​other than maleic anhydride and fumaric acid, only one of the above can be selected, or two or more can be used.

[0074] In this embodiment, the (A) unsaturated polyester oligomer in the resin composition contains 40 to 70 moles of the unsaturated diacid component (a3), preferably 45 to 65 moles, relative to 100 moles of the structure derived from the polyol component (a1). Since it contains 40 or more moles of the structure derived from the unsaturated diacid component (a3) ​​relative to 100 moles of the structure derived from the polyol component (a1), the photocuring speed is fast. Furthermore, since it contains 40 or more moles of the structure derived from the unsaturated diacid component (a3), the amount of unsaturated acid that becomes the crosslinking point (the starting point of curing) during curing is not insufficient, resulting in a cured product with excellent strength, heat resistance, and chemical resistance. Furthermore, since the amount of the structure derived from the unsaturated diacid component (a3) ​​is 70 moles or less, excessively high curing temperatures can be prevented, resulting in a cured product without cracks. Moreover, since the amount of the structure derived from the unsaturated diacid component (a3) ​​is 70 moles or less, the excess amount of unsaturated acid prevents the cured product from becoming brittle, resulting in a cured product with high toughness.

[0075] The weight-average molecular weight (MA) of the polystyrene-based unsaturated polyester oligomer (A) is preferably 1,000 to 20,000, more preferably 4,000 to 17,000, and even more preferably 7,000 to 15,000. If the MA of the unsaturated polyester oligomer (A) is 1,000 or more, a cured product with better heat resistance and chemical resistance can be obtained. If the MA of the unsaturated polyester oligomer (A) is 20,000 or less, the viscosity increase of the resin composition due to the high molecular weight of the unsaturated polyester resin is less likely to occur. Furthermore, the uniformity of the molecular weight of the unsaturated polyester oligomer (A) with a MA of 20,000 or less is good. Therefore, if the MA of the unsaturated polyester oligomer (A) is 20,000 or less, a cured product with uniform properties is easily obtained, which is preferred.

[0076] The content of (A) unsaturated polyester oligomers in the resin composition of this embodiment can be calculated by analyzing the composition of the resin composition using a nuclear magnetic resonance (NMR) apparatus.

[0077] The structures derived from the polyol component (a1), the polyacid component (a2), and the unsaturated diacid component (a3) ​​in the (A) unsaturated polyester oligomer of the resin composition of this embodiment can be analyzed using a nuclear magnetic resonance (NMR) apparatus. 1 The composition and composition ratio (molar ratio) of the components are determined by ¹H-NMR determination, which uses the number of protons and the integral value obtained.

[0078] <(B) Free radical polymerizable monomers>

[0079] (B) Free radical polymerizable monomers copolymerize with the unsaturated bonds in the molecular backbone of (A) unsaturated polyester oligomers to form unsaturated polyester resins. (B) Free radical polymerizable monomers are compounds with alkene carbon-carbon double bonds (C=C).

[0080] As the (B) radical polymerizable monomer, styrene, compounds obtained by combining substituents selected from alkyl, nitro, cyano, amide, halogen, and vinyl groups at any of the α, ortho, meta, and para positions of styrene, and their ester derivatives, etc., can be used. Only one of the above can be selected as the (B) radical polymerizable monomer, or two or more can be used. As the (B) radical polymerizable monomer, styrene is particularly preferred above for good copolymerization with the (A) unsaturated polyester oligomer.

[0081] The content of (B) free radical polymerizable monomer in a total of 100 parts by mass of (A) unsaturated polyester oligomer and (B) free radical polymerizable monomer is preferably 20 to 60 parts by mass, more preferably 35 to 55 parts by mass. If the content of (B) free radical polymerizable monomer is 20 parts by mass or more, it becomes a resin composition in which a cured product with excellent strength can be obtained. If the content of (B) free radical polymerizable monomer is 60 parts by mass or less, the resin composition will not become excessively viscous. Therefore, for example, when used as a resin composition for impregnating a base material of a pipe repair material, it becomes a resin composition with good wettability and penetration into the base material, and excellent workability can be obtained, which is therefore preferred.

[0082] <(C) Photopolymerization Initiator>

[0083] As (C) photopolymerization initiator, known intramolecular cleavage type photopolymerization initiators can be used, and one or more can be appropriately selected according to the wavelength of the irradiation light from the light source used to cure the resin composition.

[0084] Examples of intramolecularly fractured photopolymerization initiators include benzoyl dimethyl ketal compounds, α-hydroxyalkyl phenyl ketone compounds, α-aminoalkyl phenyl ketone compounds, acylphosphine compounds, and benzoyl ketal compounds.

[0085] Examples of benzoyladium dimethyl ketal compounds include, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0086] Examples of α-hydroxyalkylphenyl ketone compounds include, for example, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]-phenyl}-2-methyl-propane-1-one, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone), etc.

[0087] Examples of α-aminoalkylphenyl ketone compounds include, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, etc.

[0088] Examples of acylphosphine compounds include, for instance, bis(2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-ethoxyphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0089] Among these (C) photopolymerization initiators, in particular, in order to efficiently generate active species by absorbing light with a wavelength of 315 to 460 nm, 2,2-dimethoxy-1,2-diphenylethane-1-one and bis(2,4,6-trimethylbenzoyl)-diphenylphosphine oxide are preferred when irradiating the resin composition with light with a wavelength of 315 to 460 nm.

[0090] The content of (C) photopolymerization initiator relative to 100 parts by mass of the total amount of (A) unsaturated polyester oligomer and (B) free radical polymerizable monomer is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and even more preferably 0.20 to 5 parts by mass. If the content of (C) photopolymerization initiator is 0.01 parts by mass or more, the effect of promoting the initiation of free radical polymerization of (A) unsaturated polyester oligomer and (B) free radical polymerizable monomer and the polymerization rate of free radical polymerization becomes significant. Therefore, a resin composition with high density and good heat resistance is obtained. If the content of (C) photopolymerization initiator is 10 parts by mass or less, rapid curing reaction and heat generation are less likely to occur during the curing of the resin composition, and a cured product without cracks or fissures can be obtained.

[0091] <(D) Vinyl ester resin>

[0092] Examples of (D) vinyl ester resins include, for instance, epoxy (meth)acrylates obtained by reacting (meth)acrylic acid with an epoxy resin. As a (D) vinyl ester resin, a bisphenol-type vinyl ester resin is preferred in order to obtain a resin composition with better heat resistance and chemical resistance in the cured product.

[0093] (D) The weight-average molecular weight of the vinyl ester resin is preferably 500 to 6000, more preferably 1000 to 5000. If the weight-average molecular weight is 500 or more, it becomes a resin composition from which a cured product with better heat resistance and chemical resistance can be obtained. If the weight-average molecular weight is 6000 or less, the viscosity increase of the resin composition due to the high molecular weight vinyl ester resin is less likely to occur, and therefore it is preferred.

[0094] The (D) vinyl ester resin preferably comprises 10 to 30 parts by mass relative to 100 parts by mass of the total (A) unsaturated polyester oligomer and (B) free radical polymerizable monomer. More preferably, it comprises 12 to 28 parts by mass, and even more preferably, it comprises 14 to 26 parts by mass. If the content of (D) vinyl ester resin is 10 parts by mass or more, it becomes a resin composition from which a cured product with better heat resistance and chemical resistance can be obtained. If the content of (D) vinyl ester resin is 30 parts by mass or less, the decrease in photocurability due to the decrease in the concentration of unsaturated groups and the decrease in photocurability due to the occurrence of turbidity accompanying the decrease in the compatibility between (D) vinyl ester resin and (A) unsaturated polyester oligomer will not occur. Therefore, a cured product with better heat resistance and chemical resistance can be obtained. Furthermore, if the content of (D) vinyl ester resin is 30 parts by mass or less, the increase in viscosity due to the hydrogen bonds formed by the hydroxyl groups of the side chain of (D) vinyl ester resin is less likely to occur, making it a resin composition with good impregnation properties for substrates such as glass fibers and / or organic fibers, which is preferred.

[0095] The resin composition of this embodiment may contain other additives as needed, without impairing the effects of the present invention. Examples of additives include, for instance, ultraviolet absorbers, coupling agents, thickeners, colorants, flame retardants, and fillers.

[0096] <Method for manufacturing resin composition>

[0097] The resin composition of this embodiment can be manufactured by mixing (A) an unsaturated polyester oligomer, (B) a free radical polymerizable monomer, (C) a photopolymerization initiator, (D) a vinyl ester resin added as needed, and other additives.

[0098] The resin composition of this embodiment can be manufactured by the method shown below.

[0099] For example, an unsaturated polyester resin in which an (A) unsaturated polyester oligomer is dissolved in a (B) radically polymerizable monomer is produced by mixing the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer.

[0100] Then, it can be produced by a method of mixing the obtained unsaturated polyester resin, a (C) photoinitiator, a (D) vinyl ester resin and other additives added as needed.

[0101] The method of mixing the components contained in the resin composition of the present embodiment is not particularly limited. For example, it can be carried out using a stirring blade powered by an electric motor, a homogenizer, etc.

[0102] [Cured product]

[0103] The cured product of the present embodiment is obtained by curing the resin composition of the present embodiment.

[0104] The heat deflection temperature of the cured product of the present embodiment measured according to JIS A 7511 is preferably 85°C or higher, more preferably 90°C or higher. By using a resin composition in which the heat deflection temperature of the cured product is 85°C or higher as the resin composition for impregnating the substrate of the pipe channel repair material, for example, in the case of using the pipe channel repair material for the renovation of sewer pipes, it meets the heat deflection temperature characteristics in the "Design / Construction Management Guidelines for Pipe Channel Renovation Construction Methods - 2017 Edition - (Design and Construction Management Guidelines for Pipe Renovation Methods - 2017 Edition -)", and becomes a pipe channel repair material that can obtain a repair surface with good heat resistance.

[0105] The tensile elongation at break of the cured product of the present embodiment measured according to JIS A 7511 is preferably 3.5% or higher, more preferably 5.0% or higher. By using a resin composition in which the tensile elongation at break of the cured product is 3.5% or higher as the resin composition for impregnating the substrate of the pipe channel repair material, for example, in the case of using the pipe channel repair material for the renovation of sewer pipes, it meets the tensile elongation at break characteristics in the "Design / Construction Management Guidelines for Pipe Channel Renovation Construction Methods - 2017 Edition - (Design and Construction Management Guidelines for Pipe Renovation Methods - 2017 Edition -)", and becomes a pipe channel repair material that can obtain a repair surface with good toughness.

[0106] In this embodiment, the mass change rate of the cured material in the nitric acid resistance test, according to the Japan Sewerage Association Standard (JSWAS) for reinforced plastic composite pipes (K-2) for sewers, is preferably within ±0.3%, and more preferably within ±0.25%. By using a resin composition whose mass change rate in the nitric acid resistance test of the cured material is within ±0.3% as the base material for impregnating the pipe repair material, the nitric acid resistance characteristics of reinforced plastic composite pipes for sewers according to the Japan Sewerage Association Standard are met, resulting in a pipe repair material that provides a repair surface with good chemical resistance.

[0107] [Method for manufacturing cured products]

[0108] The method for producing the cured product of this embodiment is not particularly limited, and a method of curing the resin composition of this embodiment by irradiating it with light can be used.

[0109] As the light source for irradiating the resin composition of this embodiment, a general light-emitting diode (LED) can be used. LEDs generate little heat, are energy-efficient, and have a long lifespan, making them a preferred light source.

[0110] As a light source, any light source capable of curing the resin composition of this embodiment can be used, such as a gallium lamp, a metal halide lamp, or a mercury lamp, which illuminates a wide wavelength range. In this case, the resin composition of this embodiment can also be easily cured into a cured product.

[0111] The resin composition of this embodiment is less prone to poor curing. Therefore, in the method of manufacturing the cured product of this embodiment, for example, a method can be used to cure the resin composition of this embodiment by irradiating it with light such as an LED that does not contain the high-energy ultraviolet region.

[0112] As light that does not contain the high-energy ultraviolet region, light with a full width at half maximum (FWHM) of 4–35 nm and a center wavelength of 315–460 nm can be used, for example. The center wavelength of this light is within the range from the high-energy side of UV-A to the blue region of the visible light spectrum. The center wavelength of the light irradiating the resin composition can be appropriately determined based on the thickness of the cured product (molded article) to which the target is to be irradiated.

[0113] Furthermore, the resin composition of this embodiment can also be cured by irradiating it with only a single wavelength of light with high wavelength purity. Therefore, the full width at half maximum (FWHM) of the light, which does not contain the high-energy ultraviolet region, can be 6–25 nm or 8–15 nm.

[0114] The light irradiating the resin composition of this embodiment can be light with a half-width of 4 to 35 nm and a center wavelength of 340 to 430 nm, or light with a half-width of 4 to 35 nm and a center wavelength of 350 to 405 nm.

[0115] In the method for manufacturing the cured product according to this embodiment, the illuminance and irradiation time of the light irradiating the resin composition can be appropriately determined according to the thickness of the cured product (molded article) as the target and the wavelength of the irradiated light, and there are no particular limitations.

[0116] The resin composition of this embodiment comprises (A) an unsaturated polyester oligomer, (B) a free radical polymerizable monomer, and (C) a photopolymerization initiator. The (A) unsaturated polyester oligomer of the resin composition of this embodiment comprises a structure derived from a polyol component (a1) containing 55-85 mol% neopentyl glycol relative to 100 mol% of the total polyol component, a structure derived from a polyacid component (a2) containing isophthalic acid and / or terephthalic acid, and a structure derived from an unsaturated diacid component (a3) ​​containing maleic anhydride and / or fumaric acid. The resin composition of this embodiment comprises, relative to 100 mol of the structure derived from the polyol component (a1), 30-60 mol of the structure derived from the polyacid component (a2) and 40-70 mol of the structure derived from the unsaturated diacid component (a3).

[0117] Therefore, the resin composition of this embodiment is less prone to poor curing, and a cured product with good heat resistance and chemical resistance can be obtained. More specifically, the polyol component (a1) of the (A) unsaturated polyester oligomer in the resin composition of this embodiment contains 55-85 mol% neopentyl glycol, and contains structures derived from the polyol component (a1), the polyacid component (a2), and the unsaturated diacid component (a3) ​​in a specific proportion. Therefore, the (A) unsaturated polyester oligomer has good light transmittance, and the ester bond sites are protected. As a result, with respect to the resin composition of this embodiment, irradiated light can easily reach not only the light-irradiated surface but also the interior, and the light curing speed is fast. Furthermore, the cured product of the resin composition of this embodiment has high density and good heat resistance and chemical resistance.

[0118] Therefore, the resin composition of this embodiment is preferably used as a material for pipe and channel repair.

[0119] Pipeline repair materials

[0120] Figure 1 This is a schematic perspective view illustrating an example of the pipe repair material used in this embodiment.

[0121] The pipe repair material 11 of this embodiment includes a substrate 10 and a resin composition impregnated in the substrate 10. In the pipe repair material 11 of this embodiment, the resin composition of the above embodiment is impregnated in the substrate 10.

[0122] The substrate 10 is made of a material that has moderate flexibility and strength, following the shape of the inner wall of the pipe, and has gaps that allow the resin composition to be impregnated. Specifically, as the substrate 10, a material made of glass fiber and / or organic fiber is preferably used. Examples of organic fibers include fibers made of polyester, polypropylene, polyethylene, vinylon, nylon, acrylic fibers, etc.

[0123] The shape of the substrate 10 is as follows Figure 1 As shown, it is preferably tubular (cylindrical). If the substrate 10 is tubular, the pipe repair material 11 can be easily arranged in a ring along the inner circumferential surface of the pipe.

[0124] A known resin film may be applied to the inner and / or outer surfaces of the pipe repair material 11. The resin film protects the surface of the pipe repair material 11 and improves workability when repairing pipes using the pipe repair material 11. The resin film applied to the inner surface of the pipe repair material 11 can be peeled off from the pipe repair material 11 after the resin composition impregnated in the substrate 10 has cured.

[0125] The shape of the substrate 10 is not limited to Figure 1 The tubular shape shown can, for example, be sheet-like.

[0126] [Methods for repairing pipes and ditches]

[0127] Next, as an example of the pipe repair method of this embodiment, we will give an example of using... Figure 1 The pipe repair material 11 shown is used to illustrate the situation of repairing pipes and channels as an example.

[0128] Figure 2 For display purposes Figure 1 The diagram shows a schematic perspective view of an existing pipework repaired with the provided repair materials. Figure 2 In this text, the symbol 20 represents a pipe or channel. Examples of pipes or channels 20 that can be repaired using the pipe and channel repair method of this embodiment include, for example, gas pipes, water pipes, sewer pipes, sewer connection pipes, agricultural water pipes, industrial water pipes, power pipes, or communication pipes that are already installed.

[0129] As a use Figure 1The method for repairing pipe 20 using the pipe repair material 11 shown can be, for example, as described below. The pipe repair material 11 is placed at a predetermined position along the length of the pipe 20 using a known method (placement step). Next, for example, pressure is applied to the inner surface of the pipe repair material 11 using air, thereby causing the outer surface of the pipe repair material 11 to adhere tightly to the inner surface of the pipe 20. Then, light is irradiated onto the pipe repair material 11 from the inside using a known light irradiation device (photocuring step). This causes the resin composition impregnated in the substrate 10 of the pipe repair material 11 to cure. In this embodiment, light with a half-width of 4–35 nm and a center wavelength of 315–460 nm can be used as the light irradiating the pipe repair material 11. A light-emitting diode (LED) is preferably used as the light source.

[0130] The pipe repair material 11 of this embodiment includes a substrate 10 and a resin composition of this embodiment impregnated in the substrate 10. Therefore, when the pipe repair material 11 is placed within an existing pipe 20, and light with a half-width of 4–35 nm and a center wavelength of 315–460 nm, excluding the high-energy ultraviolet region, is irradiated onto the pipe repair material 11, poor curing is less likely to occur even when the resin composition cures, resulting in a repair surface with good heat resistance and chemical resistance. Therefore, when repairing the pipe 20 using the pipe repair material 11 of this embodiment, a general light-emitting diode (LED) can be used as the light source for irradiating the pipe repair material 11.

[0131] Example

[0132] The present invention will be further described in detail below through examples and comparative examples. However, the present invention is not limited to the following examples.

[0133] <(A) Synthesis of Unsaturated Polyester Oligomers (UPE-1 to UPE-10)>

[0134] In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet tube, and reflux cooling tube, (1) polyol and (2) polyacid, as shown in Tables 1 and 2, were added in the proportions shown in Tables 1 and 2. The polymerization reaction was then carried out at 215°C for 10 hours while nitrogen was blown into the four-necked flask. The reaction mixture was then cooled to 150°C.

[0135] In the cooled reaction solution, the unsaturated dicarboxylic acid (3) shown in Tables 1 and 2 was added in the proportions shown in Tables 1 and 2, and the temperature was raised to 215°C for 10 hours for condensation reaction.

[0136] Through the above processes, (A) unsaturated polyester oligomers (UPE-1 to UPE-9) were obtained.

[0137] Regarding the polyol component (a1), which contains 90 mol% of neopentyl glycol UPE-10, the reaction of synthesizing (A) unsaturated polyester oligomers results in the precipitation of precipitates and turbidity, thus failing to yield (A) unsaturated polyester oligomers.

[0138] Table 1

[0139]

[0140] Table 2

[0141]

[0142] For (A) unsaturated polyester oligomers (UPE-1 to UPE-9), the weight-average molecular weight was investigated using the method shown below. The results are presented in Tables 1 and 2.

[0143] The weight-average molecular weights shown in Tables 1 and 2 are converted weight-average molecular weights of standard polystyrene determined using gel permeation chromatography (GPC) under the following conditions.

[0144] Pillar: Show Dex (registered trademark) LF-804+LF-804 (manufactured by Showa Denko Co., Ltd.)

[0145] Column temperature: 40℃

[0146] Sample: (A) 0.2% tetrahydrofuran solution of unsaturated polyester oligomers

[0147] Developing solvent: Tetrahydrofuran

[0148] Detector: Differential refractometer (Showa Denko RI-71S) (manufactured by Showa Denko Co., Ltd.)

[0149] Flow rate: 1 mL / min

[0150] Examples 1 to 10, Comparative Examples 1 to 4

[0151] Unsaturated polyester resin was produced by mixing (A) unsaturated polyester oligomers (UPE-1 to UPE-9) and styrene as (B) free radical polymerizable monomers in the proportions shown in Tables 3 and 4 using an electric motor-powered stirring blade.

[0152] The obtained unsaturated polyester resin, the photopolymerization initiator (C) shown in Tables 3 and 4, and the vinyl ester resin (D) added as needed were added 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 mixing with stirring blades powered by an electric motor.

[0153] The content of (B) free radical polymerizable monomers shown in Tables 3 and 4 is the content (parts by mass) in 100 parts by mass of the total of (A) unsaturated polyester oligomers and (B) free radical polymerizable monomers.

[0154] The content of (C) photopolymerization initiator described in Tables 3 and 4 is the content (parts by mass) relative to a total of 100 parts by mass of (A) unsaturated polyester oligomer and (B) free radical polymerizable monomer.

[0155] The content of (D) vinyl ester resin shown in Tables 3 and 4 is the content (parts by mass) relative to a total of 100 parts by mass of (A) unsaturated polyester oligomer and (B) free radical polymerizable monomer. Furthermore, as (D) vinyl ester resin, a bisphenol type vinyl ester resin (RIPOKIS (registered trademark) (R-806; weight average molecular weight 2400; manufactured by Showa Denko Co., Ltd.)) was used.

[0156]

[0157] Table 4

[0158]

[0159] Next, the resin compositions of Examples 1 to 8, 10 and Comparative Examples 1 to 4 were cured by the methods shown below to prepare cured products.

[0160] The resin composition was added to the mold frame as a light source, using a light-emitting diode (trade name: UV-LED Irradiator H-4MLH84-V2-1S12-SM1 (usable wavelength 385nm) manufactured by HOYA Co., Ltd.) with a half-width of 10nm and a center wavelength of 385nm, and an irradiance of 40mW / cm². 2 After 30 minutes of exposure to light (UT-201 UV illuminometer), a plate-shaped cured material with dimensions of 200mm in length, 200mm in width, and 4mm in thickness was obtained.

[0161] Regarding the cured products of Examples 1 to 8, 10 and Comparative Examples 1 to 4, the "flexural temperature under load (heat resistance)" and "elongation at break (toughness)" were measured according to JIS A7511 and evaluated using the criteria shown in Tables 3 and 4.

[0162] Furthermore, the cured products of Examples 1 to 8, 10, and Comparative Examples 1 to 4 were tested for "nitric acid resistance (chemical resistance)" according to the Japan Sewerage Association Standard (JSWAS) for reinforced plastic composite pipes (K-2) used in sewers, and evaluated using the standards shown in Tables 3 and 4. The results are shown in Tables 3 and 4. The numerical values ​​(mass change rate) of the nitric acid resistance of JSWAS K-2 shown in Tables 3 and 4 are absolute values.

[0163] Next, using #450 chopped strand mat (trade name: ECM450-501 / T, manufactured by Central Grasp Factory Co., Ltd.) as the substrate, six square pieces with dimensions of 150mm in length and 150mm in width were cut out. Approximately 38g of the resin composition from Example 9 was then impregnated with a degassing roller to obtain a laminate. The resulting laminate was then irradiated with an illuminant (trade name: UV-LED irradiator H-4MLH84-V2-1S12-SM1 (usable wavelength 385nm), manufactured by HOYA Co., Ltd.) with a half-width of 10nm and a center wavelength of 385nm, at an illuminance of 40mW / cm². 2 A cured product of Example 9, measuring 150 mm in length, 150 mm in width, and 5 mm in thickness, was obtained by shining light (UT-201 UV illuminometer) for 3 minutes.

[0164] The cured products of Example 9 and Example 3 obtained by such operation were evaluated according to JIS A 7511, with their "flexural strength" measured and assessed using the criteria shown below.

[0165] The results are shown in Table 3.

[0166] (Benchmark)

[0167] ○; 100~149MPa

[0168] ◎;≥150MPa

[0169] As shown in Table 3, the evaluations of "heat resistance", "chemical resistance", and "toughness" of the cured products of Examples 1 to 8 and 10 are all ○ or ◎. In particular, the evaluations of "heat resistance", "chemical resistance", and "toughness" of the cured products of Examples 1 and 2, which were manufactured using a resin composition containing (D) vinyl ester resin, are all ◎.

[0170] Furthermore, as shown in Table 3, the "flexural strength" of the cured product of Example 3 was evaluated as ○. Further, the "flexural strength" of the cured product of Example 9, manufactured using the same substrate and resin composition as the cured product of Example 3, was evaluated as ◎.

[0171] In contrast, as shown in Table 4, the "chemical resistance" of the cured product of Comparative Example 1, which uses polyol component (a1) containing 50 mol% neopentyl glycol of UPE-3, was rated as △.

[0172] Furthermore, the "chemical resistance" of the cured product of Comparative Example 2, which uses 20 mol% of UPE-4 containing neopentyl glycol, was rated as ×.

[0173] Furthermore, the "heat resistance" and "chemical resistance" of the cured product of Comparative Example 3, which used (A) unsaturated polyester oligomer containing 65 moles of structure derived from polybasic acid component (a2) and 35 moles of structure derived from unsaturated dibasic acid component (a3), were rated as ×.

[0174] Furthermore, the cured product of Comparative Example 4, which used (A) unsaturated polyester oligomer containing 25 moles of the structure derived from the polybasic acid component (a2) and 75 moles of the structure derived from the unsaturated dibasic acid component (a3), cracked during the curing of the resin composition and the cured product could not be obtained.

[0175] Explanation of symbols

[0176] 10···Base material, 11···Pipe and ditch repair material, 20···Pipe and ditch.

Claims

1. A resin composition, characterized in that, Include: (A) Unsaturated polyester oligomers; (B) Free radical polymerizable monomers; and (C) Photopolymerization initiator, The (A) unsaturated polyester oligomer comprises: The structure is derived from the polyol component (a1), which contains 55-85 mol% neopentyl glycol per 100 mol% of the total polyol component. The structure is derived from the polybasic acid component (a2), which comprises isophthalic acid and / or terephthalic acid; and The structure is derived from the unsaturated dicarboxylic acid component (a3), which comprises maleic anhydride and / or fumaric acid. Of which, relative to 100 moles of the structure derived from the polyol component (a1), there are 40-50 moles of the structure derived from the polyacid component (a2) and 45-65 moles of the structure derived from the unsaturated dicarboxylic acid component (a3). The polystyrene equivalent weight-average molecular weight of the unsaturated polyester oligomer in (A) is 7000–15000. The polyol components mentioned above, excluding neopentyl glycol, are ethylene glycol, propylene glycol, or mixtures thereof. The resin composition further comprises 10 to 30 parts by weight of (D) vinyl ester resin relative to a total of 100 parts by weight of the (A) unsaturated polyester oligomer and the (B) free radical polymerizable monomer.

2. The resin composition according to claim 1, wherein the content of isophthalic acid and / or terephthalic acid in the polybasic acid component (a2) is 75 mol% or more. The content of maleic anhydride and / or fumaric acid in the unsaturated dicarboxylic acid component (a3) ​​is 90 mol% or more.

3. The resin composition according to claim 1 or 2, wherein the content of the free radical polymerizable monomer (B) in a total of 100 parts by weight of the unsaturated polyester oligomer (A) and the free radical polymerizable monomer (B) is 20 to 60 parts by weight. The content of the photopolymerization initiator (C) relative to the total of 100 parts by mass of the unsaturated polyester oligomer (A) and the free radical polymerizable monomer (B) is 0.01 to 10 parts by mass.

4. The resin composition according to claim 1 or 2, wherein the photopolymerization initiator (C) is an acylphosphine compound and / or a benzoyl ketal compound.

5. A cured product, which is a cured product of the resin composition according to any one of claims 1 to 4, having a load flexural temperature of 85°C or higher as determined according to JIS A7511, and a mass change rate of within ±0.3% in the nitric acid resistance test of the chemical resistance test for reinforced plastic composite pipes for sewers according to the Japan Sewerage Association specifications.

6. A method for manufacturing a cured product, comprising irradiating the resin composition of any one of claims 1 to 4 with light having a half-width of 4 to 35 nm and a center wavelength of 315 to 460 nm to cure it.

7. A pipe repair material comprising a substrate and a resin composition impregnated therein according to any one of claims 1 to 4.

8. The pipe repair material according to claim 7, wherein the substrate is composed of glass fiber and / or organic fiber.

9. The pipe repair material according to claim 7 or 8, wherein the substrate is tubular.

10. A method for repairing pipes and channels, comprising the following steps: The installation process of placing the pipe repair material as described in any one of claims 7 to 9 into an existing pipe channel; and A photocuring process in which the pipe repair material is irradiated with light having a half-width of 4–35 nm and a center wavelength of 315–460 nm.

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