JP7435788B2 - Resin composition, pipe repair material, and pipe repair method - Google Patents

Description

The present invention relates to a resin composition, a cured product, a method for producing a cured product, a pipe repair material, and a pipe repair method.
This 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.

Conventionally, as a method for repairing existing pipes such as gas pipes, water pipes, sewer pipes, agricultural water pipes, etc., there is a method of using a pipe repair material in which a base material made of fiber is impregnated with a resin composition. Specifically, after the pipe repair material is installed at a predetermined position within the existing pipe pipe, the pipe repair material is cured by curing the resin composition contained in the pipe repair material. This method includes a thermosetting method using a thermosetting resin as a resin composition and a photocuring method using a photocuring resin. In the thermosetting method, a resin composition is cured using a heat medium such as hot water or steam. In the photocuring 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 pipe lining material, which contains an unsaturated polyester resin (a), a styrene monomer (b), and a silica powder (c) as essential components.
Further, 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 pipe repair resin composition containing a curing agent containing peroxybenzoate is described.
Further, 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.

In recent years, the distance covered by the light curing method in repair work for existing pipes has been increasing. This is because the curing speed of the resin composition is faster and the construction time is shorter than in the thermosetting method. Additionally, compared to thermosetting methods, the photocuring method has the advantages of less curing shrinkage of the resin composition, less curing defects, less curing heat generation, and less release of flammable gas during curing. .

In the light curing method, a gallium lamp, metal halide lamp, mercury lamp, etc. are used as a light source. Further, Patent Document 4 describes a method for lining a pipe in which a resin layer is irradiated with light using a photocuring device using a light emitting diode (LED) whose main irradiation wavelength is ultraviolet light. LEDs generate less heat, are energy saving, have a long lifespan, and are excellent as light sources.

Patent No. 4055300 Patent No. 6460999 Patent No. 6095278 Japanese Patent Application Publication No. 2008-142996

However, with conventional techniques, even when light is irradiated onto the pipe repair material used in the photocuring method, a repaired surface with good heat resistance and chemical resistance may not be obtained.

The present invention has been made in view of the above circumstances, and provides a resin composition that is less likely to cause curing defects, provides a cured product with good heat resistance and chemical resistance, and can be preferably used as a material for pipe repair materials. The purpose is to provide something.
Another object of the present invention is to provide a cured product having good heat resistance and chemical resistance, obtained by curing the resin composition of the present invention, and a method for producing the same.
Another object of the present invention is to provide a pipe repair material that includes a base material and the resin composition of the present invention impregnated into the base material, and can provide a repair surface with good heat resistance and chemical resistance. shall be.
Another object of the present invention is to provide a pipe repair method using the pipe repair material of the present invention.

In order to solve the above problems, the present inventors focused on the curing reaction of the resin composition and conducted repeated studies.
As a result, we developed a specific unsaturated polyester oligomer that contains a structure derived from a polyhydric alcohol component that contains a sufficient amount of neopentyl glycol, and has a wide intermolecular distance, making it easy for light with a wavelength of 315 to 460 to pass through. It has been found that it is sufficient to create a resin composition containing the following. Since this resin composition has good light transmittance, the irradiated light easily reaches not only the light irradiated surface but also the inside, and it is presumed that curing defects are less likely to occur.
The present inventor discovered that by irradiating 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 with a wavelength of 200 to 314 nm. It was confirmed that a cured product with 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.

[1] (A) unsaturated polyester oligomer;
(B) a radically polymerizable monomer;
(C) a photopolymerization initiator;
The unsaturated polyester oligomer (A) has a structure derived from a polyhydric alcohol component (a1) containing 55 to 85 mol% of neopentyl glycol based on 100 mol% of the total polyhydric alcohol component;
A structure derived from a polybasic acid component (a2) containing isophthalic acid and/or terephthalic acid,
A structure derived from an unsaturated dibasic acid component (a3) containing maleic anhydride and/or fumaric acid,
For 100 moles of the structure derived from the polyhydric alcohol component (a1), 30 to 60 moles of the structure derived from the polybasic acid component (a2), and the structure derived from the unsaturated dibasic acid component (a3). A resin composition comprising 40 to 70 moles of.

[2] 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.
[3] The resin composition according to [1] or [2], wherein the unsaturated polyester oligomer (A) has a weight average molecular weight of 1,000 to 20,000.

[4] The content of the radically polymerizable monomer (B) in the total of 100 parts by mass of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B) is 20 to 60 parts by mass,
The content of the photopolymerization initiator (C) is 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B) [1] to [ 3]. The resin composition according to any one of [3].
[5] Further containing 10 to 30 parts by mass of (D) vinyl ester resin based on the total of 100 parts by mass of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B) [1] to [4] ] The resin composition according to any one of the above.
[6] The resin composition according to any one of [1] to [5], wherein the photopolymerization initiator (C) is an acylphosphine compound and/or a benzyl ketal compound.

[7] A cured product of the resin composition according to any one of [1] to [6], which has a deflection temperature under load measured in accordance with JIS A 7511 of 85°C or higher, and which meets the standards of the Japan Sewage Works Association. A cured product whose mass change rate is within ±0.3% in a nitric acid resistance test based on a chemical resistance test for reinforced plastic composite pipes for use in industrial applications.
[8] Production of a cured product by irradiating the resin composition according to any one of [1] to [6] with light having a peak half-width of 4 to 35 nm and a center wavelength of 315 to 460 nm. Method.

[9] A pipe repair material comprising a base material and the resin composition according to any one of [1] to [6] impregnated into 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] An installation step of installing the pipe repair material according to any one of [9] to [11] in an existing pipe;
A method for repairing pipes, comprising 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 suffer from poor curing and provides a cured product with good heat resistance and chemical resistance. Therefore, the resin composition of the present invention can be preferably used as a material for pipe repair materials.
Moreover, the pipe repair material of the present invention includes a base material and the resin composition of the present invention impregnated into the base material. Therefore, by installing pipe repair materials inside existing pipes and irradiating them 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 improved. A good repair surface can be obtained.

FIG. 1 is a schematic perspective view for explaining an example of the pipe repair material of this embodiment. FIG. 2 is a schematic perspective view showing an example of an existing pipe repaired using the pipe repair material shown in FIG. 1.

Hereinafter, the resin composition, cured product, method for producing the cured product, pipe repair material, and pipe repair method of the present invention will be explained in detail. Note that the present invention is not limited only to the embodiments shown below.

[Resin composition]
The resin composition of this embodiment includes (A) an unsaturated polyester oligomer, (B) a radically polymerizable monomer, and (C) a photopolymerization initiator. The resin composition of this embodiment may further contain (D) a vinyl ester resin, if necessary.
In the resin composition of this embodiment, part of (A) the unsaturated polyester oligomer and (B) the radically polymerizable monomer is contained as a polymer of the (A) unsaturated polyester oligomer and (B) the radically polymerizable monomer. may have been done.

<(A) Unsaturated polyester oligomer>
(A) The unsaturated polyester oligomer is copolymerized with the (B) radically polymerizable monomer to form an unsaturated polyester resin.
(A) The unsaturated polyester oligomer has a structure derived from a polyhydric alcohol component (a1) containing 55 to 85 mol% of neopentyl glycol based on 100 mol% of the total polyhydric alcohol component, and isophthalic acid and/or terephthalic acid. and a structure derived from an unsaturated dibasic acid component (a3) containing maleic anhydride and/or fumaric acid.
(A) The unsaturated polyester oligomer can be synthesized by a known method.

(A) The polyhydric alcohol component (a1) used as a raw material for the unsaturated polyester oligomer contains 55 to 85 mol% of neopentyl glycol (2,2-dimethyl-1,3-propanediol), 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 chains of neopentyl glycol widen the intermolecular distance of the unsaturated polyester oligomer (A), making it easier to transmit light with a wavelength of 315 to 460. When the polyhydric alcohol component (a1) contains 55 mol% or more of neopentyl glycol, the unsaturated polyester oligomer (A) with good light transmittance can be obtained. In the resin composition containing the unsaturated polyester oligomer (A), the irradiated light can easily reach not only the light irradiated surface but also the inside, hardening defects are less likely to occur, and the photocuring speed is fast. Therefore, a cured product can be obtained without irradiation with light in the high-energy ultraviolet region. Specifically, even if only light having a peak half-width of 4 to 35 nm and a center wavelength of 315 to 460 nm is irradiated, a cured product with high density and good heat resistance can be obtained. Furthermore, the two methyl groups present in the side chains of neopentyl glycol protect the ester bonding site in the unsaturated polyester oligomer (A) synthesized using neopentyl glycol. Therefore, when a resin composition containing (A) unsaturated polyester oligomer synthesized using a polyhydric alcohol component (a1) containing 55 mol% or more of neopentyl glycol is cured, a cured product with good chemical resistance can be obtained. is obtained.

Furthermore, since the neopentyl glycol contained in the polyhydric alcohol component (a1) is 85 mol % or less, precipitates are difficult to form during the reaction for synthesizing the unsaturated polyester oligomer (A), and the synthesis can be facilitated. In addition, since neopentyl glycol contained in the polyhydric alcohol component (a1) is 85 mol% or less, precipitates due to high crystallinity are unlikely to be formed in the resin composition, and stability over time is good. Become.

As the other polyhydric alcohol component (a1) of neopentyl glycol, conventionally known ones 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, 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 1,2-nonanediol, 1,4-cyclohexanediol , 1,8-octanediol, 1,9-nonanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, bisphenol A and bisphenol F, bisphenol S, 2, Dihydric alcohols such as 2-di(4-hydroxycyclohexyl)propane {hydrogenated bisphenol A}, polyethylene glycol, polypropylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. can be used. .

Among these, the other polyhydric alcohol component (a1) of neopentyl glycol improves physical properties such as strength, heat resistance, and chemical resistance of the cured product obtained by curing the resin composition, and improves the properties of the cured product such as glass fiber and/or organic fiber. From the viewpoint of impregnating the resin composition into the base material and cost, it is preferable that ethylene glycol and/or propylene glycol is included, and it is particularly preferable that propylene glycol is included. As the other polyhydric alcohol component (a1) of neopentyl glycol, only one type may be selected from the above, or two or more types may be used.

(A) 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, and chemical resistance 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.

As the polybasic acid component (a2) other than isophthalic acid and terephthalic acid, conventionally known ones can be used. Specifically, phthalic anhydride, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid (1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid), naphthalene dicarboxylic acid, trimellitic acid, pyromellitic acid, chlorendic acid (het acid), tetrabromophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, anhydride Succinic acid, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, dimethyl orthophthalate, dimethyl isophthalate, dimethyl terephthalate, etc. can be used.
Among these, the polybasic acid component (a2) other than isophthalic acid and terephthalic acid preferably contains phthalic anhydride from the viewpoint of the strength and physical properties of the cured product obtained by curing the resin composition and the cost. As the polybasic acid component (a2) other than isophthalic acid and terephthalic acid, only one type may be selected from the above, or two or more types may be used.

The unsaturated polyester oligomer (A) in the resin composition of this embodiment has 30 to 60 moles of structure derived from the polybasic acid component (a2) per 100 moles of structure derived from the polyhydric alcohol component (a1). It contains 40 to 50 moles, preferably 40 to 50 moles. Cured resin with superior strength, heat resistance, and chemical resistance because it contains 30 moles or more of the structure derived from the polybasic acid component (a2) per 100 moles of the structure derived from the polyhydric alcohol component (a1). You can get things. Since the resin composition contains 60 moles or less of the structure derived from the polybasic acid component (a2), the resin composition is less likely to become cloudy due to precipitation of the highly crystalline acid component over time. Therefore, the photocurability of the resin composition is less likely to be impaired.

(A) 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) is determined by physical properties such as strength, heat resistance, and chemical resistance of the cured product obtained by curing the resin composition, and ( B) From the viewpoint of copolymerizability with the radically polymerizable monomer and cost, the content is preferably 90 mol% or more. The unsaturated dibasic acid component (a3) may be only maleic anhydride and/or fumaric acid.

As 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, etc. can be used. As the unsaturated dibasic acid component (a3) other than maleic anhydride and fumaric acid, only one type may be selected from the above, or two or more types may be used.

The unsaturated polyester oligomer (A) in the resin composition of this embodiment has 40 moles of structure derived from the unsaturated dibasic acid component (a3) per 100 moles of the structure derived from the polyhydric alcohol component (a1). It contains 70 moles, preferably 45 to 65 moles. Since the composition contains 40 moles or more of the structure derived from the unsaturated dibasic acid component (a3) per 100 moles of the structure derived from the polyhydric alcohol component (a1), the photocuring rate is fast. In addition, since it contains 40 moles or more of a structure derived from the unsaturated dibasic acid component (a3), there is no shortage of unsaturated acid that becomes a crosslinking point (curing starting point) during curing, and it has excellent strength, heat resistance, and A cured product with chemical properties is obtained. Further, since the structure derived from the unsaturated dibasic acid component (a3) is 70 moles or less, the exothermic temperature during curing can be prevented from becoming too high, and a cured product without cracks can be obtained. In addition, since the structure derived from the unsaturated dibasic acid component (a3) is 70 moles or less, the cured product does not become brittle due to an excessive amount of unsaturated acid, and a cured product with high toughness can be obtained. .

(A) The unsaturated polyester oligomer preferably has a weight average molecular weight in terms of polystyrene of 1,000 to 20,000, more preferably 4,000 to 17,000, and even more preferably 7,000 to 15,000. (A) When the weight average molecular weight of the unsaturated polyester oligomer is 1000 or more, a cured product with better heat resistance and chemical resistance can be obtained. (A) When the weight average molecular weight of the unsaturated polyester oligomer is 20,000 or less, the viscosity of the resin composition is unlikely to increase due to the high molecular weight unsaturated polyester resin. Further, the unsaturated polyester oligomer (A) having a weight average molecular weight of 20,000 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 20,000 or less, since a cured product with uniform properties can be easily obtained.

The content of the unsaturated polyester oligomer (A) contained in the resin composition of this embodiment can be calculated by a method of analyzing the composition of the resin composition using a nuclear magnetic resonance (NMR) apparatus.
The structure derived from the polyhydric alcohol component (a1) contained in the unsaturated polyester oligomer (A) of the resin composition of this embodiment, the structure derived from the polybasic acid component (a2), the unsaturated dibasic acid component ( The structure derived from a3) was determined by performing ¹ H-NMR measurement of (A) unsaturated polyester oligomer using a nuclear magnetic resonance (NMR) device, and from the obtained proton number and integral value, the composition and composition ratio of the contained components. (molar ratio).

<(B) Radical polymerizable monomer>
(B) The radically polymerizable monomer copolymerizes with the unsaturated bonds in the molecular skeleton of the unsaturated polyester oligomer (A) to form an unsaturated polyester resin. (B) The radically polymerizable monomer is a compound having an ethylenic carbon-carbon double bond (C=C).
(B) The radically polymerizable monomer is selected from styrene, an alkyl group, a nitro group, a cyano group, an amide group, a halogen group, and a vinyl group at the alpha, ortho, meta, or para positions of styrene. Compounds with substituents bonded thereto, styrene monomers such as ester derivatives thereof, and the like can be used. (B) As the radically polymerizable monomer, only one type may be selected from the above, or two or more types may be used. As the radically polymerizable monomer (B), it is particularly preferable to use styrene among the above because it has good copolymerizability with the unsaturated polyester oligomer (A).

The content of the radically polymerizable monomer (B) in a total of 100 parts by mass of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B) is preferably 20 to 60 parts by mass, and preferably 35 to 55 parts by mass. It is more preferable that it is part. (B) When the content of the radically polymerizable monomer is 20 parts by mass or more, the resin composition provides a cured product with excellent strength. (B) When the content of the radically polymerizable monomer is 60 parts by mass or less, the resin composition does not have too high a viscosity. Therefore, for example, when used as a resin composition to be impregnated into a base material of a pipe repair material, the resin composition has good wettability and permeability to the base material, and excellent workability can be obtained, which is preferable.

<(C) Photopolymerization initiator>
(C) As the photopolymerization initiator, a known intramolecular cleavage type photopolymerization initiator can be used, and depending on the wavelength of the irradiation light from the light source used when curing the resin composition, One species or two or more species can be appropriately selected and used.
Examples of the intramolecular cleavage type photopolymerization initiator include benzyl dimethyl ketal compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine compounds, and benzyl ketal compounds.

Examples of benzyl dimethyl ketal compounds include 2,2-dimethoxy-1,2-diphenylethan-1-one.
Examples of α-hydroxyalkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy) )-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl} -2-methyl-propan-1-one, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone), and the like.

Examples of α-aminoalkylphenone compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)-butanone-1, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, and the like.

Examples of acylphosphine compounds include 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, bis(2, Examples include 6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

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

The content of the photopolymerization initiator (C) is preferably 0.01 to 10 parts by mass, and 0.05 parts by mass based on a total of 100 parts by mass of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B). The amount is more preferably 8 parts by weight, and even more preferably 0.20 to 5 parts by weight. (C) When the content of the photopolymerization initiator is 0.01 part by mass or more, initiation of radical polymerization between (A) unsaturated polyester oligomer and (B) radically polymerizable monomer and the polymerization rate of radical polymerization are promoted. The effect of This results in a resin composition from which a cured product with high density and good heat resistance can be obtained. When the content of the photopolymerization initiator (C) is 10 parts by mass or less, rapid curing reactions and heat generation are less likely to occur during curing of the resin composition, and a cured product without cracks or cracks can be obtained.

<(D) Vinyl ester resin>
Examples of the vinyl ester resin (D) include epoxy (meth)acrylate obtained by reacting an epoxy resin with (meth)acrylic acid. (D) As the vinyl ester resin, it is preferable to use a bisphenol type vinyl ester resin, since this results in a resin composition that yields a cured product with better heat resistance and chemical resistance.

The weight average molecular weight of the vinyl ester resin (D) is preferably from 500 to 6,000, more preferably from 1,000 to 5,000. When the weight average molecular weight is 500 or more, the resin composition provides a cured product with better heat resistance and chemical resistance. It is preferable that the weight average molecular weight is 6000 or less because the viscosity of the resin composition is less likely to increase due to the high molecular weight vinyl ester resin.

(D) Vinyl ester resin preferably contains 10 to 30 parts by mass, and preferably contains 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 even more preferable to contain 14 to 26 parts by mass. (D) When the content of the vinyl ester resin is 10 parts by mass or more, the resin composition provides a cured product with better heat resistance and chemical resistance. (D) If the content of vinyl ester resin is 30 parts by mass or less, photocurability decreases due to a decrease in unsaturated group concentration, and compatibility between (D) vinyl ester resin and (A) unsaturated polyester oligomer decreases. There is no decrease in photocurability due to the occurrence of turbidity accompanying the decrease. Therefore, a cured product with better heat resistance and chemical resistance can be obtained. In addition, when the content of (D) vinyl ester resin is 30 parts by mass or less, viscosity increase due to hydrogen bonding due to the hydroxyl group in the side chain of (D) vinyl ester resin is difficult to occur, and glass fiber and/or organic fiber This is preferable because it provides a resin composition with good impregnation properties for substrates such as.

The resin composition of the present embodiment may contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of additives include ultraviolet absorbers, coupling agents, thickeners, colorants, flame retardants, and fillers.

<Method for manufacturing resin composition>
The resin composition of this embodiment includes (A) an unsaturated polyester oligomer, (B) a radically polymerizable monomer, (C) a photopolymerization initiator, and (D) a vinyl ester resin added as necessary. It can be manufactured by mixing with other additives.

The resin composition of this embodiment may be manufactured by the method shown below.
For example, (A) an unsaturated polyester oligomer and (B) a radically polymerizable monomer are mixed to produce an unsaturated polyester resin in which the (A) unsaturated polyester oligomer is dissolved in (B) the radically polymerizable monomer.
Thereafter, it may be manufactured by a method of mixing the obtained unsaturated polyester resin, (C) a photopolymerization initiator, and (D) a vinyl ester resin and other additives added as necessary.

The method for mixing the components contained in the resin composition of the present embodiment is not particularly limited, and can be carried out using, for example, a stirring blade powered by a motor, a homodisper, or the like.

[Cured product]
The cured product of this embodiment is obtained by curing the resin composition of this embodiment.
The cured product of this embodiment preferably has a deflection temperature under load of 85°C or higher, more preferably 90°C or higher, as measured in accordance with JIS A 7511. By using a resin composition with which the deflection temperature under load of the cured product is 85°C or higher as the resin composition impregnated into the base material of the pipe repair material, for example, when the pipe repair material is used for rehabilitation of sewer pipes, " It is a pipe repair material that satisfies the characteristics of deflection temperature under load in the Design and Construction Management Guidelines for Pipe Rehabilitation Methods - 2017 Edition, and provides a repaired surface with good heat resistance.

The cured product of this embodiment preferably has a tensile elongation at break measured in accordance with JIS A 7511 of 3.5% or more, more preferably 5.0% or more. By using a resin composition with which the cured product has a tensile elongation rate of 3.5% or more at break as the resin composition impregnated into the base material of the pipe repair material, for example, the pipe repair material can be used as a base material for sewer pipes. When used for rehabilitation, it satisfies the characteristics of tensile elongation at break in the "Design and Construction Management Guidelines for Pipe Rehabilitation Methods - 2017 Edition" and is a pipe repair material that can provide a repaired surface with good toughness.

The cured product of this embodiment has a mass change rate within ±0.3% in a nitric acid resistance test based on the Japanese Sewage Works Association Standards (JSWAS) chemical resistance test for reinforced plastic composite pipes for sewers (K-2). is preferably within ±0.25%. By using a resin composition with which the base material of the pipe repair material is impregnated, the mass change rate of the cured product is within ±0.3% in the nitric acid resistance test, thereby achieving reinforcement for sewerage according to the Japan Sewage Works Association standards. This is a pipe repair material that satisfies the nitric acid resistance properties of plastic composite pipes and provides a repair surface with good chemical resistance.

[Method for producing cured product]
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.
A general light emitting diode (LED) can be used as a light source that irradiates the resin composition of this embodiment with light. LEDs are preferable as light sources because they generate less heat, save energy, and have a long life.

The light source may be any light source as long as it can cure the resin composition of this embodiment, and for example, a light source that irradiates light in a wide wavelength range such as a gallium lamp, metal halide lamp, or mercury lamp may be used. Even in this case, the resin composition of this embodiment is easily cured to become a cured product.

The resin composition of this embodiment is less likely to suffer from poor curing. Therefore, in the method for producing the cured product of the present embodiment, for example, the resin composition of the present embodiment is cured by irradiating only light that does not include light in the high-energy ultraviolet region using an LED or the like. A method can be used.
As the light that does not include 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 center wavelength of this light is within the range from the high energy region of UV-A to the indigo region of the visible light region. The center wavelength of the light irradiated onto the resin composition can be appropriately determined depending on the thickness of the intended cured product (molded product).

Further, the resin composition of the present embodiment can be cured even by irradiating only single wavelength light with high wavelength purity. Therefore, the peak half-width of light that does not include light in the high-energy ultraviolet region may be 6 to 25 nm or 8 to 15 nm.
The light irradiated to the resin composition of the present embodiment may be light with a peak half-width of 4 to 35 nm and a center wavelength of 340 to 430 nm, or light with a peak half-width of 4 to 35 nm and a center wavelength of 340 to 430 nm. The light may have a wavelength of 350 to 405 nm.

In the method for producing a cured product of the present embodiment, the illuminance and irradiation time of the light irradiated onto the resin composition may be appropriately determined depending on the thickness of the intended cured product (molded product), the wavelength of the irradiation light, etc. is possible, but there are no particular limitations.

The resin composition of this embodiment includes (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 a polyhydric alcohol component (a1) containing 55 to 85 mol% of neopentyl glycol based on 100 mol% of the total polyhydric alcohol component. , 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 contains 30 to 60 moles of the structure derived from the polybasic acid component (a2) per 100 moles of the structure derived from the polyhydric alcohol component (a1), and the unsaturated dibasic acid component ( Contains 40 to 70 moles of a structure derived from a3).

Therefore, the resin composition of this embodiment is less likely to suffer from poor curing, and a cured product with good heat resistance and chemical resistance can be obtained. More specifically, in the unsaturated polyester oligomer (A) in the resin composition of the present embodiment, the polyhydric alcohol component (a1) contains 55 to 85 mol% of neopentyl glycol, and the polyhydric alcohol component (a1) contains 55 to 85 mol% of neopentyl glycol. It contains a structure derived from the polybasic acid component (a2), and a structure derived from the unsaturated dibasic acid component (a3) in a specific ratio. Therefore, the unsaturated polyester oligomer (A) has good light transmittance and has protected ester bond sites. As a result, in the resin composition of this embodiment, the irradiated light easily reaches not only the light irradiated surface but also the inside, and the photocuring speed is fast. Furthermore, the cured product of the resin composition of this embodiment has high density and good heat resistance and chemical resistance.
Therefore, the resin composition of this embodiment can be preferably used as a material for pipe repair materials.

[Pipe repair material]
FIG. 1 is a schematic perspective view for explaining an example of the pipe repair material of this embodiment.
The pipe repair material 11 of this embodiment includes a base material 10 and a resin composition with which the base material 10 is impregnated. In the pipe repair material 11 of this embodiment, the base material 10 is impregnated with the resin composition of the embodiment described above.
The base material 10 is made of a material that has appropriate flexibility and strength to follow the shape of the inner wall of the pipe, and has gaps that can be impregnated with the resin composition. Specifically, it is preferable to use a material made of glass fiber and/or organic fiber as the base material 10. Examples of organic fibers include fibers made of polyester, polypropylene, polyethylene, vinylon, nylon, acrylic, and the like.

As shown in FIG. 1, the shape of the base material 10 is preferably tubular (cylindrical). When the base material 10 is tubular, 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 repairing the pipe using the pipe repair material 11. The resin film installed on the inner surface of the pipe repair material 11 may be peeled off and removed from the pipe repair material 11 after curing the resin composition impregnated into the base material 10.
The shape of the base material 10 is not limited to the tubular shape shown in FIG. 1, but may be, for example, a sheet shape.

[Pipe repair method]
Next, as an example of the pipe repair method of this embodiment, a case will be described in which a pipe is repaired using the pipe repair material 11 shown in FIG. 1.
FIG. 2 is a schematic perspective view showing an example of an existing pipe repaired using the pipe repair material shown in FIG. 1. In FIG. 2, reference numeral 20 indicates a pipe conduit. Examples of the pipe 20 to be repaired using the pipe repair method of the present embodiment include existing pipes such as gas pipes, water pipes, sewer pipes, sewage attachment pipes, agricultural water pipes, industrial water pipes, power pipes, and communication pipes. An example is a culvert.

As a method for repairing the pipe culvert 20 using the pipe repair material 11 shown in FIG. 1, the following method can be used, for example. The pipe repair material 11 is installed at a predetermined position in the length direction within the pipe culvert 20 using a known method (installation step). Next, 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. Then, using a known light irradiation device, light is irradiated onto the pipe culvert repair material 11 from inside the pipe culvert repair material 11 (photo-curing step). By this, the resin composition impregnated into the base material 10 of the pipe repair material 11 is cured. In this embodiment, as the light irradiated to 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 the light source.

The pipe repair material 11 of this embodiment includes a base material 10 and the resin composition of this embodiment impregnated into the base material 10. For this purpose, the pipe repair material 11 is installed inside the existing pipe pipe 20, and the pipe repair material 11 is exposed to high-energy ultraviolet light having a peak half width of 4 to 35 nm and a center wavelength of 315 to 460 nm. Even if the resin composition is cured by irradiating only light that does not contain , curing defects are unlikely to occur and a repaired surface with good heat resistance and chemical resistance can be obtained. 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 a light source that irradiates the pipe repair material 11 with light.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to the following examples.

<(A) Synthesis of unsaturated polyester oligomers (UPE-1 to UPE-10)>
Into a four-necked flask equipped with a thermometer, stirrer, inert gas blowing tube, and reflux condenser, (1) polyhydric alcohol and (2) polybasic acid shown in Tables 1 and 2 were added. It was prepared in the proportion shown. Then, a polymerization reaction was carried out at 215° C. for 10 hours while blowing nitrogen gas into the four-necked flask. Thereafter, the reaction solution was cooled to 150°C.
The unsaturated dibasic acid (3) shown in Tables 1 and 2 was added to the cooled reaction solution in the proportions shown in Tables 1 and 2, and the temperature was raised to 215°C to conduct a condensation reaction for 10 hours.
Through the above steps, (A) unsaturated polyester oligomers (UPE-1 to UPE-9) were obtained.

Regarding UPE-10, in which the polyhydric alcohol component (a1) contains 90 mol% of neopentyl glycol, precipitates precipitate out due to the reaction to synthesize (A) unsaturated polyester oligomer, resulting in turbidity, and (A) unsaturated No polyester oligomer was obtained.

(A) The weight average molecular weights of the unsaturated polyester oligomers (UPE-1 to UPE-9) were examined by the method shown below. The results are shown in Tables 1 and 2.
The weight average molecular weights shown in Tables 1 and 2 are standard polystyrene equivalent weight average molecular weights measured using gel permeation chromatography (GPC) under the following conditions.
Column: Showdex (registered trademark) LF-804+LF-804 (manufactured by Showa Denko K.K.)
Column temperature: 40℃
Sample: (A) 0.2% tetrahydrofuran solution of unsaturated polyester oligomer Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Showdex RI-71S) (manufactured by Showa Denko K.K.) Flow rate: 1 mL/min

"Example 1 to Example 10, Comparative Example 1 to Comparative Example 4"
(A) unsaturated polyester oligomers (UPE-1 to UPE-9) and (B) styrene as a radically polymerizable monomer were stirred using a motor so that the proportions shown in Tables 3 and 4 were obtained. The mixture was mixed and polymerized using a blade to produce an unsaturated polyester resin.
The obtained unsaturated polyester resin, the photopolymerization initiator (C) shown in Tables 3 and 4, and the vinyl ester resin (D) added as necessary were added in the proportions shown in Tables 3 and 4. In addition, resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were obtained by 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 (A) unsaturated polyester oligomer and (B) radically polymerizable monomer. .
The content of the photopolymerization initiator (C) shown in Tables 3 and 4 is the content (parts by mass) based on the total of 100 parts by mass of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B).
The content of the vinyl ester resin (D) shown in Tables 3 and 4 is the content (parts by mass) based on 100 parts by mass of the total of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B). Furthermore, as the vinyl ester resin (D), a bisphenol type vinyl ester resin (Lipoxy (registered trademark) (R-806; weight average molecular weight 2400; manufactured by Showa Denko K.K.) was used.

Next, the resin compositions of Examples 1 to 8 and 10 and Comparative Examples 1 to 4 were each cured to obtain cured products by the methods shown below.
The resin composition was placed in a mold, and as a light source, a light emitting diode (trade name: UV-LED irradiator H-4MLH84-V2-1S12-SM1 (available wavelength 385 nm) manufactured by HOYA Co., Ltd.) and irradiated with light from an illuminance of 40 mW/cm ² (illuminance meter: Ushio Inc. ultraviolet illuminometer UIT-201) for 30 minutes. A cured product was obtained.

The obtained cured products of Examples 1 to 8, 10 and Comparative Examples 1 to 4 were evaluated for "deflection temperature under load (heat resistance)" and "tension at break" in accordance with JIS A 7511. The "elongation rate (toughness)" was measured and evaluated according to the criteria shown in Tables 3 and 4.
In addition, the cured products of Examples 1 to 8 and 10 and Comparative Examples 1 to 4 comply with the chemical resistance test of reinforced plastic composite pipes for sewers (K-2) of the Japan Sewage Works Association Standards (JSWAS). "Nitric acid resistance (chemical resistance)" was measured and evaluated according to the criteria shown in Tables 3 and 4. The results are shown in Tables 3 and 4. The nitric acid resistance values (mass change rate) of JSWAS K-2 shown in Tables 3 and 4 are absolute values.

Next, prepare a #450 chopped strand mat (product name: ECM450-501/T, manufactured by Central Glass Fiber Co., Ltd.) as a base material and cut out 6 pieces into 150 mm long and 150 mm wide squares, giving a total of about 38 g. A laminate was obtained by impregnating the resin composition of Example 9 with a defoaming roller. A light emitting diode (product name: UV-LED irradiator H-4MLH84-V2-1S12-SM1 (usable wavelength 385 nm) HOYA Co., Ltd.) having a peak half-width of 10 nm and a center wavelength of 385 nm was added to the obtained laminate. A plate of Example 9 measuring 150 mm long, 150 mm wide, and 5 mm thick was irradiated with light from an illuminance of 40 mW/cm ² (illuminance meter: Ushio Inc. ultraviolet illuminometer UIT-201) for 3 minutes. A cured product was obtained.

The "bending strength" of the cured product of Example 9 and the cured product of Example 3 thus obtained was measured in accordance with JIS A 7511, and evaluated according to the criteria shown below.
The results are shown in Table 3.
(standard)
○; 100-149MPa
◎；≧150MPa

As shown in Table 3, the cured products of Examples 1 to 8 and 10 were all evaluated as ○ or ◎ in terms of "heat resistance,""chemicalresistance," and "toughness." In particular, the cured products of Examples 1 and 2 produced using resin compositions containing (D) vinyl ester resin were all rated ◎ in terms of "heat resistance,""chemicalresistance," and "toughness." .
Furthermore, as shown in Table 3, the cured product of Example 3 was evaluated as ○ in terms of "bending strength." Furthermore, the cured product of Example 9, which was produced using the base material and the same resin composition as the cured product of Example 3, was evaluated as ◎ in terms of "bending strength."

On the other hand, as shown in Table 4, the cured product of Comparative Example 1 using UPE-3 whose polyhydric alcohol component (a1) contains 50 mol% of neopentyl glycol had a "chemical resistance" evaluation of △. there were.
Furthermore, the cured product of Comparative Example 2 using UPE-4 containing 20 mol % of neopentyl glycol was evaluated as "poor" in terms of "chemical resistance."

In addition, a comparative example using UPE-6 in which the polyhydric alcohol component (a1) contains 65 moles of a structure derived from a polybasic acid component (a2) and 35 moles of a structure derived from an unsaturated dibasic acid component (a3) The cured product of No. 3 was evaluated as × in “heat resistance” and “chemical resistance”.
In addition, a comparative example using UPE-9 in which the polyhydric alcohol component (a1) contains 25 moles of a structure derived from a polybasic acid component (a2) and 75 moles of a structure derived from an unsaturated dibasic acid component (a3) In No. 4, a cured product could not be obtained because cracks occurred during curing of the resin composition.

10... Base material, 11... Pipe repair material, 20... Pipe culvert.

Claims (12)

(A) an unsaturated polyester oligomer;
(B) a radically polymerizable monomer;
(C) a photopolymerization initiator;
The unsaturated polyester oligomer (A) has a structure derived from a polyhydric alcohol component (a1) containing 55 to 85 mol% of neopentyl glycol based on 100 mol% of the total polyhydric alcohol component;
A structure derived from a polybasic acid component (a2) containing isophthalic acid and/or terephthalic acid,
A structure derived from an unsaturated dibasic acid component (a3) containing maleic anhydride and/or fumaric acid,
For 100 moles of the structure derived from the polyhydric alcohol component (a1), 30 to 60 moles of the structure derived from the polybasic acid component (a2), and the structure derived from the unsaturated dibasic acid component (a3). Contains 40 to 70 moles of
A resin composition that can be cured by irradiation with light having a peak half-width of 4 to 35 nm and a center wavelength of 315 to 460 nm . 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 claim 1, wherein the content of maleic anhydride and/or fumaric acid in the unsaturated dibasic acid component (a3) is 90 mol% or more. The resin composition according to claim 1 or 2, wherein the unsaturated polyester oligomer (A) has a weight average molecular weight of 1,000 to 20,000. The content of the radically polymerizable monomer (B) in the total of 100 parts by mass of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B) is 20 to 60 parts by mass,
Claims 1 to 3, wherein the content of the photopolymerization initiator (C) is 0.01 to 10 parts by mass based on a total of 100 parts by mass of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B). The resin composition according to any one of Item 3. Any one of claims 1 to 4, further comprising 10 to 30 parts by mass of (D) vinyl ester resin, based on a total of 100 parts by mass of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B). The resin composition according to item (1). The resin composition according to any one of claims 1 to 5, wherein the photopolymerization initiator (C) is an acylphosphine compound and/or a benzyl ketal compound. A cured product of the resin composition according to any one of claims 1 to 6, which has a deflection temperature under load of 85°C or higher as measured in accordance with JIS A 7511, and is a cured product for use in sewers according to the Japan Sewage Works Association. A cured product whose mass change rate is within ±0.3% in a nitric acid resistance test based on a chemical resistance test for reinforced plastic composite pipes. A method for producing a cured product, comprising curing the resin composition according to any one of claims 1 to 6 by irradiating the resin composition with light having a peak half-width of 4 to 35 nm and a center wavelength of 315 to 460 nm. . A pipe repair material comprising a base material and the resin composition according to any one of claims 1 to 6 impregnated into the base material. The pipe repair material according to claim 9, wherein the base material is made of glass fiber and/or organic fiber. The pipe repair material according to claim 9 or 10, wherein the base material is tubular. an installation step of installing the pipe repair material according to any one of claims 9 to 11 in an existing pipe;
A method for repairing pipes, comprising 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.

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