KR20230009915A - Resin composition, conduit repair material and conduit repair method - Google Patents

Abstract

(A) an unsaturated polyester oligomer, (B) a radically polymerizable monomer, and (C) a photopolymerization initiator, and (A) the unsaturated polyester oligomer contains 55% neopentyl glycol based on 100 mol% of all polyhydric alcohol components. to 85 mol% of a structure derived from a polyhydric alcohol component (a1), a structure derived from a polybasic acid component (a2) containing isophthalic acid and/or terephthalic acid, and an unsaturated di-salt containing maleic anhydride and/or fumaric acid. 30 to 60 moles of the structure derived from the polybasic acid component (a2), including the structure derived from the base acid component (a3), relative to 100 moles of the structure derived from the polyhydric alcohol component (a1), unsaturated dibasic acid component (a3) A resin composition containing 40 to 70 moles of a structure derived from

Description

Resin composition, conduit repair material and conduit repair method

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

This application claims priority based on Japanese Patent Application No. 2020-130660 for which it applied in Japan on July 31, 2020, and uses the content here.

Conventionally, as a method of repairing existing conduits such as gas pipes, water pipes, sewage pipes, agricultural water pipes, etc., there is a method of using a conduit repair material in which a resin composition is impregnated into a base material made of fibers. Specifically, after installing a conduit repair material at a predetermined position in an existing conduit, the conduit is repaired by curing the resin composition contained in the conduit repair material. In this method, there are a thermosetting method using a thermosetting resin as the resin composition and a photocuring method using a photocuring resin. In the thermal curing method, a resin composition is cured using a heat medium such as hot water or steam. In the photocuring method, the conduit repair material is irradiated with light such as ultraviolet light or visible light to cure the resin composition.

Patent Literature 1 describes a thermosetting resin composition for a pipe lining material comprising an unsaturated polyester resin (a), a styrene monomer (b) and a silica powder (c) as essential components.

Further, in Patent Document 2, (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 peroxybenzo A resin composition for conduit repair containing a curing agent comprising an ate is disclosed.

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

In recent years, the construction distance of the light curing method in the repair work of existing conduits is increasing. This is because the curing rate of the resin composition is fast and the construction time is short compared to the thermosetting method. In addition, the photocuring method has the advantages of less curing shrinkage of the resin composition, less curing defects, less curing heat generation, and less emission of combustible gases during curing compared to the thermal curing method.

In the photocuring method, a gallium lamp, a metal halide lamp, a mercury lamp or the like is used as a light source. Further, Patent Document 4 describes a pipe lining method in which a resin layer is irradiated with light by a photocuring device using a light emitting diode (LED) whose main irradiation wavelength is ultraviolet rays. LED generates little heat, saves energy and has a long life, and is excellent as a light source.

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

However, in the prior art, even if light is irradiated to a conduit repair material used in a photocuring method, a repair surface having good heat resistance and chemical resistance may not be obtained.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition that is less likely to cause curing failure, obtains a cured product having good heat resistance and chemical resistance, and can be suitably used as a material for conduit repair material. .

Another object of the present invention is to provide a cured product obtained by curing the resin composition of the present invention having good heat resistance and chemical resistance, and a method for producing the same.

Another object of the present invention is to provide a conduit repair material comprising a base material and the resin composition of the present invention impregnated into the base material, from which a repair surface having excellent heat resistance and chemical resistance is obtained.

Further, an object of the present invention is to provide a conduit repair method using the conduit repair material of the present invention.

In order to solve the above problems, the inventors of the present invention paid attention to the curing reaction of the resin composition and repeated studies.

As a result, a resin composition containing a specific unsaturated polyester oligomer having a wide intermolecular distance and easy transmission of light with a wavelength of 315 to 460 by including a structure derived from a polyhydric alcohol component sufficiently containing neopentyl glycol. I figured out what to do. Since this resin composition has good light transmittance, it is estimated that the irradiation light easily reaches not only the light irradiated surface but also the inside, so that curing defects are less likely to occur.

The present inventors discovered that the resin composition was irradiated with only light having a peak half-width of 4 to 35 nm and a central wavelength of 315 to 460 nm, not including high-energy ultraviolet light with a wavelength of 200 to 314 nm, thereby improving heat resistance and resistance. It was confirmed that a cured product having good chemical properties could be obtained, and the present invention was considered.

That is, the present invention relates to the following matters.

[1] (A) an unsaturated polyester oligomer,

(B) a radically polymerizable monomer;

(C) a photopolymerization initiator;

The (A) 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;

A structure derived from a polybasic acid component (a2) containing isophthalic acid and/or terephthalic acid;

comprising a structure derived from an unsaturated dibasic acid component (a3) comprising maleic anhydride and/or fumaric acid;

It contains 30 to 60 moles of the structure derived from the polybasic acid component (a2) and 40 to 70 moles of the structure derived from the unsaturated dibasic acid component (a3), relative to 100 moles of the structure derived from the polyhydric alcohol component (a1). A resin composition characterized in that to do.

[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 (A) unsaturated polyester oligomer has a weight average molecular weight of 1000 to 20000.

[4] The content of the (B) radically polymerizable monomer in the total of 100 parts by mass of the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer is 20 to 60 parts by mass,

According to any one of [1] to [3], wherein the content of the (C) photopolymerization initiator is 0.01 to 10 parts by mass relative to 100 parts by mass of the total of the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer. resin composition.

[5] Based on the total of 100 parts by mass of the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer, (D) further comprising 10 to 30 parts by mass of a vinyl ester resin, [1] to [4 ] The resin composition described in any one of them.

[6] The resin composition according to any one of [1] to [5], wherein the photopolymerization initiator (C) is an acylphosphine compound and/or a benzylketal compound.

[7] It is a cured product of the resin composition according to any one of [1] to [6], and the deflection temperature under load measured in accordance with JIS A 7511 is 85 ° C. or higher, and the chemical resistance of the reinforced plastic composite pipe for sewage according to the Japanese Sewerage Association standard A cured product whose mass change rate in the nitric acid resistance test based on the test is within ±0.3%.

[8] A method for producing a cured product in which the resin composition according to any one of [1] to [6] is cured by irradiation with light having a peak half-value width of 4 to 35 nm and a center wavelength of 315 to 460 nm.

[9] A conduit 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 conduit repair material according to [9], wherein the substrate is made of glass fiber and/or organic fiber.

[11] The conduit repair material according to [9] or [10], wherein the substrate is tubular.

[12] An installation step of installing the conduit repair material according to any one of [9] to [11] in an existing conduit;

A conduit repair method comprising a photocuring step of irradiating the conduit 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 prone to curing failure and yields a cured product having excellent heat resistance and chemical resistance. Therefore, the resin composition of the present invention can be preferably used as a material for a conduit repair material.

Further, the conduit repair material of the present invention includes a base material and the resin composition of the present invention impregnated into the base material. For this reason, a repair surface with good heat resistance and chemical resistance is obtained by installing a conduit repair material in an existing conduit and irradiating, for example, light with a peak half-width of 4 to 35 nm and a center wavelength of 315 to 460 nm.

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

Hereinafter, the resin composition of the present invention, a cured product, a method for producing a cured product, a conduit repair material, and a conduit repair method will be described in detail. In addition, this invention is not limited only to embodiment described below.

[Resin composition]

The resin composition of this embodiment contains (A) an unsaturated polyester oligomer, (B) a radically polymerizable monomer, and (C) a photoinitiator. The resin composition of this embodiment may further contain (D) vinyl ester resin as needed.

In the resin composition of the present embodiment, part of (A) unsaturated polyester oligomer and (B) radically polymerizable monomer may be contained as a polymer of (A) unsaturated polyester oligomer and (B) radically polymerizable monomer. .

<(A) Unsaturated polyester oligomer>

(A) The unsaturated polyester oligomer copolymerizes with the (B) radically polymerizable monomer to form an unsaturated polyester resin.

(A) The unsaturated polyester oligomer contains a structure derived from the 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. A structure derived from a polybasic acid component (a2) and a structure derived from an unsaturated dibasic acid component (a3) containing maleic anhydride and/or fumaric acid are included.

(A) An 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), and contains 60 to 80 It is preferable to include mol%, and it is more preferable to include 65 to 75 mol%.

The two methyl groups present in the side chain of neopentyl glycol (A) widen the intermolecular distance of the unsaturated polyester oligomer and make it easier to transmit light with a wavelength of 315 to 460. When 55 mol% or more of neopentyl glycol is contained in the polyhydric alcohol component (a1), an unsaturated polyester oligomer (A) having good light transmittance is obtained. The resin composition containing the (A) unsaturated polyester oligomer is easily reached by light irradiated not only to the light-irradiated surface but also to the inside, hard to cause curing failure, and has a high photocuring speed. Therefore, a hardened|cured material is obtained even if it does not irradiate the light of a 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 having high density and good heat resistance is obtained. In addition, the two methyl groups present in the side chain of neopentyl glycol protect the ester bond site in the unsaturated polyester oligomer (A) synthesized using neopentyl glycol. For this reason, when the resin composition containing the unsaturated polyester oligomer (A) synthesized using the polyhydric alcohol component (a1) containing 55 mol% or more of neopentyl glycol is cured, a cured product having good chemical resistance is obtained. .

In addition, since the neopentyl glycol contained in the polyhydric alcohol component (a1) is 85 mol% or less, it is difficult to precipitate during the reaction for synthesizing the unsaturated polyester oligomer (A), and the composition can be easily synthesized. In addition, since neopentyl glycol contained in the polyhydric alcohol component (a1) is 85 mol% or less, precipitates derived from high crystallinity are not easily formed in the resin composition, and stability over time is improved.

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-hexane diol, 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, 2-di(4-hydroxycyclohexyl)propane {hydrogenated bisphenol A}, dihydric alcohols such as polyethylene glycol and polypropylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. can be used

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

(A) The polybasic acid component (a2) used as a raw material for an 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 preferably 75 mol% or more, and preferably 80 mol% or more, from the viewpoint of physical properties such as strength, heat resistance, chemical resistance and cost of a cured product obtained by curing the resin composition. it is more preferable The polybasic acid component (a2) may be only isophthalic acid and/or terephthalic acid.

As the other polybasic acid component (a2) of 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 acid, 1,4-cyclohexanedicarboxylic acid), naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, chlorendic acid (hetic acid), tetrabromophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride , endomethylenetetrahydrophthalic anhydride, succinic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, dimethyl orthophthalate, dimethyl isophthalate, dimethyl terephthalate and the like can be used.

Among these, it is preferable that the other polybasic acid component (a2) of isophthalic acid and terephthalic acid contains phthalic anhydride from the viewpoint of the strength, physical properties and cost of a cured product obtained by curing the resin composition. As the other polybasic acid component (a2) of isophthalic acid and terephthalic acid, only one type may be selected and used from the above, or two or more types may be used.

The (A) unsaturated polyester oligomer in the resin composition of the present embodiment contains 30 to 60 mol of the structure derived from the polybasic acid component (a2) with respect to 100 mol of the structure derived from the polyhydric alcohol component (a1), and 40 It is preferable to include 50 moles. Since 30 mol or more of the structure derived from the polybasic acid component (a2) is included with respect to 100 mol of the structure derived from the polyhydric alcohol component (a1), a cured resin having superior strength, heat resistance and chemical resistance is obtained. Since 60 mol or less of the structure derived from the polybasic acid component (a2) is included, turbidity of the resin composition due to precipitation of a highly crystalline acid component with time is unlikely to occur. 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) determines the physical properties of the cured product obtained by curing the resin composition, such as strength, heat resistance and chemical resistance, and copolymerizability with (B) radically polymerizable monomers such as styrene. And from a viewpoint of cost, it is preferable that it is 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 and the like can be used. As the other unsaturated dibasic acid component (a3) of maleic anhydride and fumaric acid, only one type may be selected and used from the above, or two or more types may be used.

The (A) unsaturated polyester oligomer in the resin composition of the present embodiment contains 40 to 70 moles of the structure derived from the unsaturated dibasic acid component (a3) with respect to 100 moles of the structure derived from the polyhydric alcohol component (a1). , It is preferable to include 45 to 65 moles. Since 40 mol or more of the structure derived from the unsaturated dibasic acid component (a3) is included with respect to 100 mol 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 the structure derived from the unsaturated dibasic acid component (a3), there is no shortage in the amount of the unsaturated acid serving as a crosslinking point (originating point of curing) during curing, and it has excellent strength, heat resistance and chemical resistance. cargo is obtained. In addition, since the structure derived from the unsaturated dibasic acid component (a3) is 70 moles or less, the exothermic temperature at the time of curing can be prevented from becoming excessively high, and a cured product without cracks is obtained. In addition, since the structure derived from the unsaturated dibasic acid component (a3) is 70 mol or less, the cured product does not become brittle when the amount of the unsaturated acid is excessive, and a cured product having high toughness is obtained.

(A) The unsaturated polyester oligomer preferably has a weight average molecular weight of 1000 to 20000 in terms of polystyrene, more preferably 4000 to 17000, still more preferably 7000 to 15000. (A) When the weight average molecular weight of the unsaturated polyester oligomer is 1000 or more, a cured product having better heat resistance and chemical resistance is obtained. (A) When the weight average molecular weight of the unsaturated polyester oligomer is 20000 or less, it is difficult to increase the viscosity of the resin composition due to the high molecular weight unsaturated polyester resin. Moreover, the (A) unsaturated polyester oligomer whose weight average molecular weight is 20000 or less has favorable molecular weight uniformity. From this point of view, when the weight average molecular weight of the (A) unsaturated polyester oligomer is 20000 or less, a cured product having uniform properties can be easily obtained and is preferable.

Content of (A) unsaturated polyester oligomer contained in the resin composition of this embodiment is computable by the method of analyzing the composition of a resin composition using a nuclear magnetic resonance (NMR) apparatus.

The structure derived from the polyhydric alcohol component (a1) contained in the (A) unsaturated polyester oligomer of the resin composition of the present embodiment, the structure derived from the polybasic acid component (a2), and the structure derived from the unsaturated dibasic acid component (a3) , can be determined by a method in which ¹ H-NMR measurement of (A) an unsaturated polyester oligomer is performed with a nuclear magnetic resonance (NMR) apparatus, and the composition and composition ratio (molar ratio) of the components are calculated from the obtained proton numbers and integral values. there is.

<(B) radically polymerizable monomer>

(B) The radical polymerizable monomer copolymerizes with the unsaturated bond in the molecular skeleton of the (A) unsaturated polyester oligomer to form an unsaturated polyester resin. (B) The radical polymerizable monomer is a compound having an ethylenic carbon double bond (C=C).

(B) As the radically polymerizable monomer, a substituent selected from an alkyl group, a nitro group, a cyano group, an amide group, a halogen group, and a vinyl group is bonded to any of the α-position, ortho-position, meta-position, and para-position of styrene or styrene. Styrene-based monomers, such as a compound and its ester derivative, etc. can be used. (B) As a radically polymerizable monomer, you may select and use only 1 type from the above, and may use 2 or more types. (B) As the radically polymerizable monomer, since copolymerizability with (A) unsaturated polyester oligomer is good, it is particularly preferable to use styrene among the above.

The content of the (B) radically polymerizable monomer in the 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 more preferably 35 to 55 parts by mass. desirable. (B) It becomes a resin composition from which the hardened|cured material which has excellent intensity|strength is obtained when content of a radically polymerizable monomer is 20 mass parts or more. (B) When the content of the radically polymerizable monomer is 60 parts by mass or less, the resin composition does not have an excessively high viscosity. Therefore, for example, when used as a resin composition to be impregnated into a substrate of a pipe repair material, the resin composition has good wettability and permeability to the substrate and excellent workability is obtained, so it is preferable.

<(C) photopolymerization initiator>

(C) As the photopolymerization initiator, known intramolecular cleavage type photopolymerization initiators and the like can be used, and one type or two or more types can be appropriately selected and used according to the wavelength of irradiation light from a light source used when curing the resin composition. can

Examples of the intramolecular cleavage type photopolymerization initiator include benzyldimethylketal compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine compounds, and benzylketal compounds.

As a benzyl dimethyl ketal type compound, 2, 2- dimethoxy- 1, 2- diphenylethan- 1-one etc. are mentioned, for example.

As an α-hydroxyalkylphenone compound, for example, 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), etc. can be heard

As an α-aminoalkylphenone compound, for example, 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 the acylphosphine compound include bis(2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-phenylphosphine oxide, and bis(2,6-dichlorobenzoyl). )-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-ethoxyphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc. are mentioned.

Among these (C) photopolymerization initiators, since they absorb light with a wavelength of 315 to 460 nm and efficiently generate active species, when the resin composition is irradiated with light with a wavelength of 315 to 460 nm, 2,2-dimethoxy It is preferable to use -1,2-diphenylethane-1-one or bis(2,4,6-trimethylbenzoyl)-diphenylphosphine oxide.

The content of the photopolymerization initiator (C) relative to the total of 100 parts by mass of the (A) unsaturated polyester oligomer and the radical polymerizable monomer (B) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and 0.20 to 5 parts by mass is more preferred. (C) When the content of the photopolymerization initiator is 0.01 parts by mass or more, the effect of accelerating the initiation of radical polymerization between (A) unsaturated polyester oligomer and (B) radically polymerizable monomer and the polymerization rate of radical polymerization becomes remarkable. For this reason, it becomes a resin composition from which a hardened|cured material with high density and favorable heat resistance is obtained. (C) When the content of the photopolymerization initiator is 10 parts by mass or less, a rapid curing reaction and heat generation are less likely to occur during curing of the resin composition, and a cured product without cracks or cracks is obtained.

<(D) vinyl ester resin>

(D) As vinyl ester resin, the epoxy (meth)acrylate obtained by making (meth)acrylic acid react with an epoxy resin, etc. are mentioned, for example. (D) As the vinyl ester resin, it is preferable to use a bisphenol-type vinyl ester resin because it becomes a resin composition from which a cured product having better heat resistance and chemical resistance can be obtained.

(D) It is preferable that it is 500-6000, and, as for the weight average molecular weight of vinyl ester resin, it is more preferable that it is 1000-5000. When the weight average molecular weight is 500 or more, it becomes a resin composition from which a cured product having better heat resistance and chemical resistance can be obtained. When the weight average molecular weight is 6000 or less, the increase in viscosity of the resin composition due to the high molecular weight vinyl ester resin is less likely to occur, which is preferable.

(D) The vinyl ester resin is preferably contained in an amount of 10 to 30 parts by mass, and preferably in an amount of 12 to 28 parts by mass, based on 100 parts by mass in total of the unsaturated polyester oligomer (A) and the radical polymerizable monomer (B). It is more preferable, and it is even more preferable to include 14 to 26 parts by mass. (D) When the content of the vinyl ester resin is 10 parts by mass or more, it becomes a resin composition from which a cured product having better heat resistance and chemical resistance is obtained. (D) When the content of the vinyl ester resin is 30 parts by mass or less, a decrease in photocurability due to a decrease in the concentration of unsaturated groups and turbidity accompanying a decrease in compatibility between the (D) vinyl ester resin and (A) unsaturated polyester oligomer There is no occurrence of deterioration of photocurability due to generation of For this reason, a cured product having better heat resistance and chemical resistance is obtained. Further, (D) When the content of the vinyl ester resin is 30 parts by mass or less, the increase in viscosity due to the hydrogen bond due to the side chain hydroxyl group of the (D) vinyl ester resin is less likely to occur, and the base material such as glass fiber and/or organic fiber It is preferable because it is a resin composition having good impregnating properties.

The resin composition of the present embodiment may contain other additives as needed within a range not impairing the effects of the present invention. As an additive, a ultraviolet absorber, a coupling agent, a thickener, a coloring agent, a flame retardant, a filler etc. are mentioned, for example.

<Method for producing resin composition>

The resin composition of the present embodiment is a mixture of (A) an unsaturated polyester oligomer, (B) a radically polymerizable monomer, (C) a photopolymerization initiator, and (D) a vinyl ester resin and other additives added as necessary. It can be manufactured by the method of

You may manufacture the resin composition of this embodiment by the method shown below.

For example, (A) unsaturated polyester oligomer and (B) radically polymerizable monomer are mixed, and (A) unsaturated polyester oligomer is dissolved in (B) radically polymerizable monomer to prepare an unsaturated polyester resin.

Then, you may manufacture by the method of mixing the obtained unsaturated polyester resin, (C) photoinitiator, and (D) vinyl ester resin and other additives added as needed.

The method of mixing each component contained in the resin composition of this embodiment is not specifically limited, For example, it can perform using the stirring blade which used a motor as power, a homodisper, etc.

[cured material]

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

It is preferable that the deflection temperature under load measured according to JIS A 7511 of the hardened|cured material of this embodiment is 85 degreeC or more, and it is more preferable that it is 90 degreeC or more. As a resin composition impregnated into the base material of the conduit repair material, by using a resin composition in which the cured product has a deflection temperature under load of 85 ° C. or more, for example, when the conduit repair material is used for rehabilitation of sewage pipes, “Design in conduit rehabilitation method” ·Construction Management Guidelines -2017 Edition-", which satisfies the characteristics of load deflection temperature and becomes a conduit repair material capable of obtaining a repair surface with good heat resistance.

The cured product of the present embodiment preferably has a tensile elongation at break of 3.5% or more, more preferably 5.0% or more, as measured in accordance with JIS A 7511. As a resin composition impregnated into the base material of the conduit repair material, by using a resin composition having a tensile elongation rate of 3.5% or more at the time of breakage of the cured product, for example, when the conduit repair material is used for rehabilitation of sewage pipes, “in the conduit rehabilitation method It is a conduit repair material that satisfies the characteristics of tensile elongation at break in the Design and Construction Management Guidelines -2017 Edition- and provides a repair surface with good toughness.

The cured product of the present embodiment preferably has a mass change rate within ±0.3% in a nitric acid resistance test based on the chemical resistance test of a reinforced plastic composite pipe for sewage (K-2) of the Japanese Sewerage Association Standard (JSWAS), It is preferable that it is within ±0.25%. As a resin composition to be impregnated into the base material of the conduit repair material, the nitric acid resistance property in the reinforced plastic composite pipe for sewage according to the Japanese Sewerage Association standard is obtained by using a resin composition whose mass change rate in the nitric acid resistance test of the cured product is within ±0.3%. It satisfies and becomes a conduit repair material from which a repair surface with good chemical resistance can be obtained.

[Method for producing cured product]

The method for producing the cured product of the present embodiment is not particularly limited, and a method of irradiating light to the resin composition of the present embodiment to cure it can be used.

As a light source for irradiating light to the resin composition of the present embodiment, a general light emitting diode (LED) can be used. The LED generates little heat, saves energy and has a long life, and is suitable as a light source.

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

In the resin composition of the present embodiment, curing failure is less likely to occur. For this reason, in the method for producing the cured product of the present embodiment, for example, a method of curing the resin composition of the present embodiment by irradiating only light that does not contain light in the high energy ultraviolet region using an LED or the like. can be used.

As light that does not contain light in the high-energy ultraviolet region, for example, light having a peak half-value width of 4 to 35 nm and a center wavelength of 315 to 460 nm can be used. The central wavelength of this light is within a 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 to the resin composition can be appropriately determined according to the thickness of the target cured product (molded product).

In addition, the resin composition of the present embodiment can be cured by irradiating only single wavelength light with high wavelength purity. Accordingly, the peak half-value width of light that does not contain 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 having a peak half value width of 4 to 35 nm and a center wavelength of 340 to 430 nm, or a peak half value width of 4 to 35 nm and a center wavelength of 350 to 405 nm. It may be light.

In the method for producing a cured product of the present embodiment, the illuminance and irradiation time of the light applied to the resin composition can be appropriately determined depending on the thickness of the target cured product (molded product), the wavelength of the irradiated light, and the like, and is not particularly limited.

The resin composition of this embodiment contains (A) an unsaturated polyester oligomer, (B) a radically polymerizable monomer, and (C) a photoinitiator. The resin composition of the present embodiment includes (A) a structure derived from a polyhydric alcohol component (a1) in which the unsaturated polyester oligomer contains 55 to 85 mol% of neopentyl glycol with respect to 100 mol% of the total polyhydric alcohol component; It includes a structure derived from a polybasic acid component (a2) containing phthalic 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) and the structure derived from the unsaturated dibasic acid component (a3) with respect to 100 moles of the structure derived from the polyhydric alcohol component (a1). 40 to 70 moles.

For this reason, in the resin composition of this embodiment, hardening failure does not occur easily, and a hardened|cured material with favorable heat resistance and chemical resistance is obtained. More specifically, in the (A) unsaturated polyester oligomer in the resin composition of the present embodiment, the polyhydric alcohol component (a1) contains 55 to 85 mol% of neopentyl glycol, and the structure is derived from the polyhydric alcohol component (a1). and 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 (A) unsaturated polyester oligomer has good light transmittance, and furthermore, the ester bond site is protected. As a result, in the resin composition of the present embodiment, light irradiated not only to the light irradiation surface but also to the inside easily reaches, and the photocuring speed is high. In addition, the cured resin composition of the present embodiment has a high density and has good heat resistance and chemical resistance.

Therefore, the resin composition of this embodiment can be suitably used as a material for a conduit repair material.

[Conduit repair material]

1 : is a schematic perspective view for demonstrating an example of the conduit repair material of this embodiment.

The conduit repair material 11 of the present embodiment includes a base material 10 and a resin composition impregnated into the base material 10 . In the conduit repair material 11 of the present embodiment, the base material 10 is impregnated with the resin composition of the above-described embodiment.

The substrate 10 is made of a material that has appropriate flexibility and strength that conforms to the shape of the inner wall of the conduit and has a gap into which the resin composition can be impregnated. Specifically, as the substrate 10, it is preferable to use glass fibers and/or organic fibers. As an organic fiber, the fiber etc. which consist of polyester, polypropylene, polyethylene, vinylon, nylon, acrylic etc. are mentioned, for example.

As shown in FIG. 1, the shape of the base material 10 is preferably tubular (cylindrical). If the substrate 10 is tubular, the conduit repair material 11 can be easily installed in an annular shape along the inner circumferential surface of the conduit.

A known resin film may be provided on the inner surface and/or outside of the conduit repair material 11. The resin film improves workability at the time of repairing a conduit using the conduit repair material 11 while protecting the surface of the conduit repair material 11 . The resin film provided on the inner surface of the conduit repair material 11 may be peeled off and removed from the conduit repair material 11 after curing the resin composition impregnated into the base material 10 .

The shape of the substrate 10 is not limited to the tubular shape shown in FIG. 1, and may be, for example, a sheet shape.

[Conduit repair method]

Next, as an example of the conduit repair method of the present embodiment, a case of repairing a conduit using the conduit repair material 11 shown in FIG. 1 will be described as an example.

2 is a schematic perspective view showing an example of an existing conduit repaired using the conduit repair material shown in FIG. 1 . In Fig. 2, reference numeral 20 denotes a conduit. Examples of the conduit 20 repaired using the conduit repair method of the present embodiment include existing conduits such as gas pipes, water pipes, sewer pipes, sewage installation pipes, agricultural water pipes, industrial water pipes, electric power pipes, or communication pipes. .

As a method of repairing the conduit 20 using the conduit repair material 11 shown in FIG. 1, the method shown below can be used, for example. The conduit repair material 11 is installed at a predetermined position in the longitudinal direction in the conduit 20 using a known method (installation step). Next, the outer surface of the conduit repair material 11 is brought into close contact with the inner surface of the conduit 20 by applying pressure to the inner surface of the conduit repair material 11 using, for example, air. Then, the conduit repair material 11 is irradiated with light from the inside of the conduit repair material 11 using a known light irradiation device (photocuring step). In this way, the resin composition impregnated in the substrate 10 of the conduit repair material 11 is cured. In this embodiment, as the light irradiated to the conduit repair material 11, light having a peak half-value width of 4 to 35 nm and a center wavelength of 315 to 460 nm can be used. As a light source, it is preferable to use a light emitting diode (LED).

The conduit repair material 11 of the present embodiment includes a base material 10 and the resin composition of the present embodiment impregnated into the base material 10 . For this reason, the conduit repair material 11 is installed in the existing conduit 20, and light in the high-energy ultraviolet region having a peak half-width at half maximum of 4 to 35 nm and a central wavelength of 315 to 460 nm is emitted to the conduit repair material 11. Even if the resin composition is cured by irradiating only light not contained therein, curing failure is less likely to occur, and a repair surface having excellent heat resistance and chemical resistance is obtained. Therefore, when repairing the conduit 20 using the conduit repair material 11 of this embodiment, as a light source for irradiating light to the conduit repair material 11, a general light emitting diode (LED) can be used.

Example

Hereinafter, the present invention will be described in more detail by examples and comparative examples. In addition, this invention is not limited only to the following example.

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

(1) polyhydric alcohol and (2) polybasic acid shown in Tables 1 and 2 were charged into a four-necked flask equipped with a thermometer, a stirrer, an inert gas blowing pipe, and a reflux condenser at the ratios shown in Tables 1 and 2. . And the polymerization reaction was performed at 215 degreeC for 10 hours, blowing nitrogen gas into a 4-necked flask. Thereafter, the reaction solution was cooled to 150°C.

To the cooled reaction solution, (3) unsaturated dibasic acids shown in Tables 1 and 2 were added 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, (A) precipitates are precipitated and turbidity is generated by a reaction for synthesizing an unsaturated polyester oligomer, and (A) unsaturated polyester oligomers are synthesized. No ester oligomer was obtained.

(A) About the unsaturated polyester oligomer (UPE-1 - UPE-9), the weight average molecular weight was investigated by the method shown below. The results are shown in Table 1 and Table 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: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko)

Column temperature: 40°C

Sample: (A) 0.2% tetrahydrofuran of unsaturated polyester oligomer

Solution Developing Solvent: Tetrahydrofuran

Detector: Differential refractometer (Shodex RI-71S) (manufactured by Showa Denko) Flow rate: 1 mL/min

"Examples 1 to 10, Comparative Examples 1 to 4"

(A) unsaturated polyester oligomers (UPE-1 to UPE-9) and (B) styrene as a radically polymerizable monomer were prepared in the ratios shown in Tables 3 and 4 using motor-powered stirring blades. Mixing and polymerization were performed to prepare an unsaturated polyester resin.

The obtained unsaturated polyester resin, (C) photopolymerization initiator shown in Tables 3 and 4, and (D) vinyl ester resin added as necessary were added at the ratios shown in Tables 3 and 4, and the motor was powered by power. The resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were obtained by a method of mixing using a stirring blade.

Content of (B) radically polymerizable monomer shown in Table 3 and Table 4 is content (mass part) in 100 mass parts of total of (A) unsaturated polyester oligomer and (B) radically polymerizable monomer.

Content of (C) photoinitiator shown in Table 3 and Table 4 is content (mass part) with respect to 100 mass parts of total of (A) unsaturated polyester oligomer and (B) radically polymerizable monomer.

Content of (D) vinyl ester resin shown in Table 3 and Table 4 is content (mass part) with respect to 100 mass parts of total of (A) unsaturated polyester oligomer and (B) radically polymerizable monomer. Moreover, as (D) vinyl ester resin, bisphenol-type vinyl ester resin (Lipoxy (registered trademark) (R-806; weight average molecular weight 2400; Showa Denko Co., Ltd. make) was used.

Next, the resin compositions of Examples 1 to 8 and 10 and Comparative Examples 1 to 4 were cured by the methods shown below, respectively, to obtain cured products.

The resin composition was placed in a mold, and as a light source, a light emitting diode having a peak half-width at half maximum and a center wavelength of 385 nm (trade name: UV-LED irradiator H-4MLH84-V2-1S12-SM1 (available wavelength: 385 nm) manufactured by HOYA ) was used, and light with an illuminance of 40 mW/cm 2 (illuminance meter: UV illuminance meter UIT-201 manufactured by Ushio Denki Co., Ltd.) was irradiated for 30 minutes to obtain a plate-shaped cured product having a length of 200 mm, a width of 200 mm and a thickness of 4 mm.

For the obtained cured products of Examples 1 to 8 and 10 and Comparative Examples 1 to 4, respectively, "deflection temperature under load (heat resistance)" and "tensile elongation at break (toughness)" were obtained in accordance with JIS A 7511. )” was measured and evaluated according to the criteria shown in Tables 3 and 4.

In addition, with respect to the cured products of Examples 1 to 8 and 10 and Comparative Examples 1 to 4, respectively, in accordance with the Japanese Sewerage Association Standard (JSWAS) chemical resistance test of reinforced plastic composite pipe for sewage (K-2) "Nitric acid resistance (chemical resistance)" was measured and evaluated according to the criteria shown in Tables 3 and 4. Their 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, a #450 chopped strand mat (trade name: ECM450-501/T, manufactured by Central Glass Fiber Co., Ltd.) was prepared as a base material, and 6 sheets were cut into squares of 150 mm in length and 150 mm in width. The resin composition of 9 was impregnated with a defoaming roller to obtain a laminate. A light emitting diode (trade name: UV-LED irradiator H-4MLH84-V2-1S12-SM1 (available wavelength: 385 nm) manufactured by HOYA) having a peak half-width at half maximum and a center wavelength of 385 nm was used for the obtained laminate, Light with an illuminance of 40 mW/cm 2 (illuminance meter: UV illuminance meter UIT-201 manufactured by Ushio Denki Co., Ltd.) was irradiated for 3 minutes to obtain a plate-shaped cured product of Example 9 having a length of 150 mm, a width of 150 mm and a thickness of 5 mm.

The cured product of Example 9 and the cured product of Example 3 thus obtained were respectively measured for "bending strength" in accordance with JIS A 7511, and evaluated according to the criteria shown below.

The results are shown in Table 3.

(standard)

○; 100 to 149 MPa

◎; ≥150MPa

As shown in Table 3, the cured products of Examples 1 to 8 and 10 had evaluations of "heat resistance", "chemical resistance" and "toughness" of ○ or ◎. In particular, (D) the cured products of Examples 1 and 2 prepared using a resin composition containing a vinyl ester resin were rated as ◎ in terms of “heat resistance,” “chemical resistance,” and “toughness.”

In addition, as shown in Table 3, the cured product of Example 3 had an evaluation of "bending strength" of ○. In addition, the evaluation of "bending strength" of the cured product of Example 9 manufactured using the base material and the same resin composition as the cured product of Example 3 was ◎.

On the other hand, as shown in Table 4, the cured product of Comparative Example 1 using UPE-3 in which the polyhydric alcohol component (a1) contains 50 mol% of neopentyl glycol had a "chemical resistance" evaluation of △.

In addition, the evaluation of "chemical resistance" of the cured product of Comparative Example 2 using UPE-4 containing 20 mol% of neopentyl glycol was x.

In addition, the cured product of Comparative Example 3 using UPE-6 in which the polyhydric alcohol component (a1) contains 65 mol of the structure derived from the polybasic acid component (a2) and 35 mol of the structure derived from the unsaturated dibasic acid component (a3) Evaluation of "heat resistance" and "chemical resistance" was x.

In addition, the cured product of Comparative Example 4 using UPE-9 in which the polyhydric alcohol component (a1) contains 25 mol of the structure derived from the polybasic acid component (a2) and 75 mol of the structure derived from the unsaturated dibasic acid component (a3) , Cracks occurred during curing of the resin composition, and a cured product was not obtained.

10: registration
11: conduit repair material
20: Conduit

Claims (12)

(A) an unsaturated polyester oligomer;
(B) a radically polymerizable monomer;
(C) a photopolymerization initiator;
The (A) 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;
A structure derived from a polybasic acid component (a2) containing isophthalic acid and/or terephthalic acid;
comprising a structure derived from an unsaturated dibasic acid component (a3) comprising maleic anhydride and/or fumaric acid;
It contains 30 to 60 moles of the structure derived from the polybasic acid component (a2) and 40 to 70 moles of the structure derived from the unsaturated dibasic acid component (a3), relative to 100 moles of the structure derived from the polyhydric alcohol component (a1). A resin composition characterized in that to do. According to claim 1,
The content of isophthalic acid and/or terephthalic acid in the polybasic acid component (a2) is 75 mol% or more,
The resin composition whose content of maleic anhydride and/or fumaric acid in the said unsaturated dibasic acid component (a3) is 90 mol% or more. According to claim 1 or 2,
The resin composition whose weight average molecular weight of said (A) unsaturated polyester oligomer is 1000-20000. According to any one of claims 1 to 3,
The content of the (B) radically polymerizable monomer in the total of 100 parts by mass of the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer is 20 to 60 parts by mass,
The resin composition whose content of said (C) photoinitiator is 0.01-10 mass parts with respect to 100 mass parts of the total of said (A) unsaturated polyester oligomer and said (B) radically polymerizable monomer. According to any one of claims 1 to 4,
A resin composition further comprising 10 to 30 parts by mass of a vinyl ester resin (D) based on 100 parts by mass in total of the unsaturated polyester oligomer (A) and the radical polymerizable monomer (B). According to any one of claims 1 to 5,
The resin composition in which the photoinitiator (C) is an acylphosphine-based compound and/or a benzylketal-based compound. It is a cured product of the resin composition according to any one of claims 1 to 6, and the deflection temperature under load measured in accordance with JIS A 7511 is 85 ° C. or higher, Japan Sewerage Association Standard Chemical resistance test of a reinforced plastic composite pipe for sewage A cured product having a mass change rate within ±0.3% in a nitric acid resistance test based on A method for producing a cured product in which the resin composition according to any one of claims 1 to 6 is cured by irradiation with light having a peak half width of 4 to 35 nm and a central wavelength of 315 to 460 nm. A conduit repair material comprising a base material and the resin composition according to any one of claims 1 to 6 impregnated into the base material. According to claim 9,
A conduit repair material in which the base material is made of glass fiber and/or organic fiber. The method of claim 9 or 10,
A conduit repair material in which the base material is tubular. An installation step of installing the conduit repair material according to any one of claims 9 to 11 in an existing conduit;
A conduit repair method comprising a photocuring step of irradiating the conduit 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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