Resin composition and lining material

Abstract

To provide a resin composition that exhibits good viscosity even in low-temperature environments. [Solution] A resin composition comprising an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C) which is at least one selected from oxides of group 2 elements and hydroxides of group 2 elements, a dicarboxylic acid (D), water (E), and a compound (F) which is a hydroxyl group-containing compound, wherein the content of water (E) is 0.15 to 0.60% by mass with respect to 100% by mass of the total of the ethylenically unsaturated group-containing resin (A), the ethylenically unsaturated group-containing monomer (B), the dicarboxylic acid (D), the water (E), and the compound (F), and the content of compound (F) is 0.01 to 3.00 parts by mass with respect to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

Description

Technical Field

[0001] The present invention relates to a resin composition and a lining material.

Background Art

[0002] In recent years, the aging of existing pipes buried underground, such as water supply pipes, sewer pipes, and power pipes, has become serious, and various methods for repairing them have been proposed. For example, in Patent Document 1, a tubular lining material is adhered to the inner wall surface of an existing pipe buried underground, and while supplying compressed air to the inside of the lining material, a mobile light irradiation device introduced into the inside of the lining material irradiates light on the inner surface of the lining material to cure the lining material. A method for repairing an existing pipe including a curing step is disclosed. Further, as a material for the lining material, a material obtained by impregnating an impregnated base material made of fibers or the like with a photocurable resin composition can be used, and as the photocurable resin composition, a polymerizable resin such as an unsaturated polyester resin or a vinyl ester resin dissolved in a solvent such as styrene can be used.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In recent years, for the rehabilitation of existing pipes, there has been a demand for higher strength of the pipes, thinner lining materials for pipe rehabilitation, higher efficiency when arranging the lining material on the inner surface of the existing pipe and curing it, etc. Consequently, the fibrous substrates that make up lining materials tend to become thinner and denser. For this reason, resin compositions used to impregnate the fibrous substrates as lining materials are preferred to have low viscosity to facilitate impregnation. On the other hand, in the process from storing the manufactured lining material to on-site construction, the resin composition must not be unevenly distributed within the fibrous substrate and must have a viscosity sufficient to allow the lining material to expand appropriately during construction. To solve this, a technique is used in which a thickening agent such as magnesium oxide is added to the resin composition before impregnation into the fibrous substrate. This results in a resin composition that is initially low viscosity but increases in viscosity over time, maintaining a specific high viscosity state when the lining material is placed inside the existing pipe.

[0005] However, with conventional technology, the rate of thickening over time is slow in low-temperature environments (below 16°C), and in winter or in regions with low temperatures, it was necessary to control the temperature of the storage environment or adjust the temperature of the resin composition in order to speed up the rate of thickening of the resin composition.

[0006] This invention was made under these circumstances and aims to provide a resin composition that exhibits good viscosity even in low-temperature environments (below 16°C). [Means for solving the problem]

[0007] The present invention is based on the discovery that a resin composition containing an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C), a dicarboxylic acid (D), water (E), and a specific compound (F), exhibits good viscosity even in low-temperature environments by setting the content of water (E) and compound (F) in the resin composition to specific amounts.

[0008] The present invention provides the following means. [1] A resin containing ethylenically unsaturated groups (A), A monomer containing an ethylenically unsaturated group (B), A compound (C) which is at least one selected from oxides of Group 2 elements and hydroxides of Group 2 elements, Dicarboxylic acid (D) and, Water (E) and, A resin composition containing compound (F), which is a hydroxyl group-containing compound, The water (E) content is 0.150 to 0.600% by mass relative to 100% by mass of the total of the ethylenically unsaturated group-containing resin (A), the ethylenically unsaturated group-containing monomer (B), the dicarboxylic acid (D), the water (E), and the compound (F). A resin composition in which the content of the compound (F) is 0.01 to 3.00 parts by mass per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B). [2] The resin composition according to claim 1, wherein the ethylenically unsaturated group-containing resin (A) is at least one selected from unsaturated polyester resin (A-1) and vinyl ester resin (A-2). [3] The resin composition according to [1] or [2] above, wherein the ethylenically unsaturated group-containing resin (A) is an unsaturated polyester resin (A-1). [4] The resin composition according to any one of [1] to [3] above, wherein the compound (F) is a glycol compound. [5] The resin composition according to any one of [1] to [4] above, wherein the water (E) content is 0.300 to 0.500% by mass with respect to 100% by mass of the total of the ethylenically unsaturated group-containing resin (A), the ethylenically unsaturated group-containing monomer (B), the dicarboxylic acid (D), the water (E), and the compound (F). [6] The resin composition according to any one of [1] to [5] above, wherein the content of compound (F) is 0.10 to 1.00 parts by mass with respect to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B). [7] The resin composition according to any one of [1] to [6] above, wherein the content of compound (C) is 0.01 to 3.00 parts by mass with respect to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B). [8] The resin composition according to any one of [1] to [7] above, wherein compound (C) is at least one selected from magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide. [9] The resin composition according to any one of [1] to [8] above, wherein the compound (C) is magnesium oxide.

[10] The resin composition according to any one of [1] to [9] above, wherein the content of compound (D) is 0.01 to 3.00 parts by mass with respect to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

[11] The resin composition according to [3] above, wherein the weight-average molecular weight Mw of the unsaturated polyester resin (A-1) is 5,000 to 20,000.

[12] The resin composition according to [3] or

[11] above, wherein the number average molecular weight Mn of the unsaturated polyester resin (A-1) is 1,000 to 7,000.

[13] The resin composition according to [3],

[11] or

[12] above, wherein the acid value of the unsaturated polyester resin (A-1) is 8.0 to 20.0 KOH mg / g.

[14] A lining material comprising a composite material (H) containing the resin composition and fiber base material (h) described in any of [1] to

[13] above. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a resin composition that exhibits good viscosity even in low-temperature environments. The resin composition of the present invention can be suitably used as a lining material for pipe rehabilitation. [Modes for carrying out the invention]

[0010] The definitions and meanings of terms and notations used in this specification are given below. The preferred numerical range can be any combination of preferred lower and upper limits. (Meth)acrylic acid is a general term for acrylic acid and methacrylic acid. Similarly, (meth)acrylate is a general term for acrylate and methacrylate, and (meth)acryloyl is a general term for acryloyl and methacryloyl. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) are standard polystyrene-equivalent molecular weights determined by gel permeation chromatography (GPC). Specifically, they are measured by the method described in the examples below. The molecular weight distribution is the calculated value of Mw / Mn. A low-temperature environment means an environment below 16°C, but it may also be an environment below 15°C or an environment above 0°C. The initial viscosity of a resin composition refers to the viscosity of the resin composition from the time of manufacture up to 5 hours later. The acid value of vinyl ester resins and unsaturated polyester resins is the amount of potassium hydroxide (KOH) [mg] required to neutralize 1 g of vinyl ester resin or unsaturated polyester resin, measured according to the method in accordance with JIS K6901:2008. Specifically, it is measured by the method described in the examples below.

[0011] [Resin composition] The resin composition according to an embodiment of the present invention (hereinafter also referred to as "this embodiment") is a resin composition containing an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C) which is at least one selected from oxides of group 2 elements and hydroxides of group 2 elements, a dicarboxylic acid (D), water (E), and a compound (F) which is a hydroxyl group-containing compound, wherein the water (E) content is 0.15 to 0.60% by mass with respect to 100% by mass of the total of the ethylenically unsaturated group-containing resin (A), the ethylenically unsaturated group-containing monomer (B), the dicarboxylic acid (D), the water (E), and the compound (F), and the compound (F) content is 0.01 to 3.00 parts by mass with respect to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

[0012] The resin composition contains an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C), a dicarboxylic acid (D), water (E), and a compound (F). By setting the contents of water (E) and the compound (F) in the resin composition to specific amounts, it exhibits good thickening properties even in a low-temperature environment.

[0013] The thickening rate of the resin composition in a low-temperature environment can be increased by increasing the amount of the compound (C). However, with an increase in the amount of the compound (C), the final viscosity of the resin composition also increases. Therefore, it is possible to increase the amount of the compound (C) to make the thickening rate of the resin composition in a low-temperature environment the desired rate, but the final viscosity of the resin composition becomes excessively high, making it difficult to use the resin composition for lining material applications. On the other hand, in this embodiment, since the resin composition contains a specific amount of water (E), water (E) promotes thickening even in a low-temperature environment, and the resin composition thickens well without a decrease in the thickening rate. Further, since the resin composition contains the compound (F), an interaction occurs between the compound (F) and the compound (C), suppressing the formation of a three-dimensional structure between polymers and suppressing the excessive increase in the final viscosity of the resin composition. For these reasons, the resin composition according to this embodiment exhibits good thickening properties even in a low-temperature environment.

[0014] [Ethylenically unsaturated group-containing resin (A)] The ethylenically unsaturated group-containing resin (A) of this embodiment is a resin having polymerizability due to an ethylenically unsaturated group. Examples of the ethylenically unsaturated group-containing resin (A) include unsaturated polyester resins (A-1), vinyl ester resins (A-2), (meth)acrylic resins (A-3), urethane (meth)acrylate resins (A-4), and the like. The ethylenically unsaturated group-containing resin (A) may be used alone or in combination of two or more. Among these, from the viewpoint of exhibiting better thickening properties in a low-temperature environment, unsaturated polyester resins (A-1), vinyl ester resins (A-2), and urethane (meth)acrylate (A-4) resins are preferred, unsaturated polyester resins (A-1) and vinyl ester resins (A-2) are more preferred, and unsaturated polyester resins (A-1) are even more preferred.

[0015] The content of the ethylenically unsaturated group-containing resin (A) in the resin composition is preferably 20.00 parts by mass or more, more preferably 30.00 parts by mass or more, and even more preferably 40.00 parts by mass or more, from the viewpoint of suppressing the decrease in the initial viscosity of the resin composition, with respect to a total of 100 parts by mass of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B). From the viewpoint of suppressing a sharp increase in the initial viscosity of the resin composition, it is preferably 80.00 parts by mass or less, more preferably 70.00 parts by mass or less, and even more preferably 60.00 parts by mass or less. That is, the content of the ethylenically unsaturated group-containing resin (A) in the resin composition is preferably 20.00 to 80.00 parts by mass, more preferably 30.00 to 70.00 parts by mass, and even more preferably 40.00 to 60.00 parts by mass, with respect to a total of 100 parts by mass of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

[0016] The content of the ethylenically unsaturated group-containing resin (A) in the resin composition is preferably 20.00% by mass or more, more preferably 30.00% by mass or more, and even more preferably 40.0% by mass or more, from the viewpoint of suppressing a decrease in the initial viscosity of the resin composition, and preferably 80.00% by mass or less, more preferably 70.00% by mass or less, and even more preferably 60.00% by mass or less, from the viewpoint of suppressing a rapid increase in the initial viscosity of the resin composition. In other words, the content of the ethylenically unsaturated group-containing resin (A) in the resin composition is preferably 20.00 to 80.00% by mass, more preferably 30.00 to 70.00% by mass, and even more preferably 40.00 to 60.00% by mass.

[0017] <Unsaturated polyester resin (A-1)> The unsaturated polyester resin (A-1) is preferably a reaction product of a diol (a1-1) and a dibasic acid (a1-2), and the dibasic acid (a1-2) more preferably includes an ethylenically unsaturated group-containing dibasic acid (a1-2-1) and an ethylenically unsaturated group-free dibasic acid (a1-2-2). The unsaturated polyester resin (A-1) can be produced using a diol (a1-1) and a dibasic acid (a1-2) as reaction raw materials by applying a known synthesis method involving a condensation reaction.

[0018] The acid value of the unsaturated polyester resin (A-1) is preferably 8.0 KOH mg / g or higher, more preferably 10.0 KOH mg / g or higher, and even more preferably 12.0 KOH mg / g or higher, from the viewpoint of exhibiting better viscosity in low-temperature environments, and preferably 20.0 KOH mg / g or lower, more preferably 18.0 KOH mg / g or lower, and even more preferably 16.0 KOH mg / g or lower, from the viewpoint of ease of handling of the resin composition. In other words, the acid value of the unsaturated polyester resin (A-1) is preferably 8.0 to 20.0 KOH mg / g, more preferably 10.0 to 18.0 KOH mg / g, and even more preferably 12.0 to 16.0 KOH mg / g.

[0019] The weight-average molecular weight (Mw) of the unsaturated polyester resin (A-1) is preferably 5,000 or more, more preferably 6,000 or more, even more preferably 7,000 or more, and even more preferably 8,000 or more, from the viewpoint of exhibiting better viscosity in low-temperature environments, and preferably 20,000 or less, more preferably 18,000 or less, even more preferably 16,000 or less, and even more preferably 15,000 or less, from the viewpoint of ease of handling of the resin composition. In other words, the weight-average molecular weight (Mw) of the unsaturated polyester resin (A-1) is preferably 5,000 to 20,000, more preferably 6,000 to 18,000, even more preferably 7,000 to 16,000, and even more preferably 8,000 to 15,000.

[0020] The number-average molecular weight (Mn) of the unsaturated polyester resin (A-1) is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more, from the viewpoint of exhibiting better viscosity in low-temperature environments, and preferably 7,000 or less, more preferably 6,000 or less, and even more preferably 5,000 or less, from the viewpoint of ease of handling of the resin composition. In other words, the number-average molecular weight (Mn) of the unsaturated polyester resin (A-1) is preferably 1,000 to 7,000, more preferably 2,000 to 6,000, and even more preferably 3,000 to 5,000.

[0021] The molecular weight distribution (Mw / Mn) of the unsaturated polyester resin (A-1) is preferably 1.00 or higher, more preferably 1.50 or higher, and even more preferably 2.00 or higher, from the viewpoint of ease of manufacture, and preferably 15.00 or lower, more preferably 10.00 or lower, and even more preferably 5.00 or lower, from the viewpoint of exhibiting better viscosity in low-temperature environments. In other words, the molecular weight distribution (Mw / Mn) of the unsaturated polyester resin (A-1) is preferably 1.00 to 15.00, more preferably 1.50 to 10.00, and even more preferably 2.00 to 5.00.

[0022] <Diol (a1-1)> The diol (a1-1), which is a reaction raw material for the unsaturated polyester resin (A-1), is a compound having two hydroxyl groups in one molecule. From the viewpoint of ease of manufacture, mechanical strength, and manufacturing cost, for example, alkanediols and glycol ethers are preferably used. Diol (a1-1) may be used alone or in combination of two or more. When using a diol (a1-1) with a melting point of 25°C or higher (for example, neopentyl glycol, 1,4-cyclohexanediol, bisphenol A, etc.) alone, precipitates may form during manufacturing, and the unsaturated polyester resin (A-1) may not be obtained. Therefore, it is preferable to use two or more diols in combination, including one with a melting point of less than 25°C. Examples of alkanediols include ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 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, and 2- Examples include 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, 2,2-di(4-hydroxycyclohexyl)propane, and hydrides of bisphenol A, bisphenol F, and bisphenol S. Examples of glycol ethers include diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol. Of these, from the viewpoint of availability, ease of handling of the resin composition, and manufacturing cost, 2-methyl-1,3-propanediol, ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, and bisphenol A hydrogenates are preferred, 2-methyl-1,3-propanediol, propylene glycol, neopentyl glycol, and bisphenol A hydrogenates are more preferred, and propylene glycol and neopentyl glycol are even more preferred.

[0023] <Dibasic acid (a1-2)> The dibasic acid (a1-2), which is a reaction raw material for the unsaturated polyester resin (A-1), preferably contains both an ethylenically unsaturated group-containing dibasic acid (a1-2-1) and an ethylenically unsaturated group-free dibasic acid (a1-2-2). Note that the dibasic acid (a1-2) also includes acid anhydrides.

[0024] Since the unsaturated polyester resin (A-1) is obtained by the reaction of 1 mole of hydroxyl group of diol (a1-1) and 1 mole of carboxyl group of dibasic acid (a1-2) to form an ester bond, the total amount of dibasic acid (a1-2) blended when producing the unsaturated polyester resin (A-1) is preferably 80.0 mol% or more, more preferably 85.0 mol% or more, even more preferably 90.0 mol% or more, preferably 120.0 mol% or less, more preferably 110.0 mol% or less, and even more preferably 100.0 mol% or less, relative to 100 mol% of diol (a1-1). In other words, the total amount of dibasic acid (a1-2) blended when producing the unsaturated polyester resin (A-1) is 80.0 to 120.0 mol%, more preferably 85.0 to 110.0 mol%, and even more preferably 90.0 to 100.0 mol%, relative to 100 mol% of diol (a1-1).

[0025] ≪Dibasic acid containing ethylenically unsaturated groups (a1-2-1)≫ Ethylene-unsaturated group-containing dibasic acids (a1-2-1) are compounds having two carboxyl groups (including acid anhydrides) and at least one ethylenically unsaturated group in one molecule. Ethylene-unsaturated group-containing dibasic acids (a1-2-1) may be used alone or in combination of two or more types. Examples of ethylenically unsaturated group-containing dibasic acids (a1-2-1) include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and chloromaleic acid. Of these, maleic anhydride and fumaric acid are preferred from the viewpoint of availability, ease of handling of the resin composition, and manufacturing cost, with maleic anhydride being more preferred.

[0026] When producing the unsaturated polyester resin (A-1), the amount of ethylenically unsaturated group-containing dibasic acid (a1-2-1) blended is preferably 30.0 mol% or more, more preferably 40.0 mol% or more, even more preferably 45.0 mol% or more, preferably 80.0 mol% or less, more preferably 70.0 mol% or less, and even more preferably 65.0 mol% or less, based on 100 mol% of diol (a1-1), from the viewpoint of ease of production, mechanical strength, and production cost. In other words, when producing the unsaturated polyester resin (A-1), the amount of ethylenically unsaturated group-containing dibasic acid (a1-2-1) blended is preferably 30.0 to 80.0 mol%, more preferably 40.0 to 70.0 mol%, and even more preferably 45.0 to 65.0 mol%, based on 100 mol% of diol (a1-1).

[0027] The content of ethylenically unsaturated group-containing dibasic acid (a1-2-1) in dibasic acid (a1-2) is preferably 20.0 mol% or more, more preferably 30.0 mol% or more, even more preferably 40.0 mol% or more, and even more preferably 45.0 mol% or more, with respect to 100 mol% of dibasic acid (a1-2), from the viewpoint of ease of manufacture, mechanical strength, and manufacturing cost. In other words, the content of ethylenically unsaturated group-containing dibasic acid (a1-2-1) in dibasic acid (a1-2) is preferably 20.0 to 80.0 mol%, more preferably 30.0 to 75.0 mol%, even more preferably 40.0 to 70.0 mol%, and even more preferably 45.0 to 65.0 mol%, with respect to 100 mol% of dibasic acid (a1-2).

[0028] ≪Dibasic acid (a1-2-2) without ethylenically unsaturated groups≫ Ethylene-unsaturated group-free dibasic acids (a1-2-2) are compounds that have two carboxyl groups (including acid anhydrides) in one molecule and do not contain an ethylenically unsaturated group. Ethylene-unsaturated group-free dibasic acids (a1-2-2) may be used alone or in combination of two or more types. Examples of ethylenically unsaturated group-free dibasic acids (a1-2-2) include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid (1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid), naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, chlorendic acid (hettic acid), tetrabromophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, succinic anhydride, chlorendic acid anhydride, trimellitic anhydride, pyromellitic anhydride, 4-methylphthalic acid, 5-methylisophthalic acid, and 5-methylterephthalic acid. Of these, isophthalic acid and terephthalic acid are preferred from the viewpoint of availability, ease of handling of the resin composition, and manufacturing cost.

[0029] When producing the unsaturated polyester resin (A-1), the amount of ethylenically unsaturated group-free dibasic acid (a1-2-2) blended is preferably 20.0 mol% or more, more preferably 30.0 mol% or more, more preferably 35.0 mol% or more, preferably 70.0 mol% or less, more preferably 60.0 mol% or less, and even more preferably 55.0 mol% or less, based on 100 mol% of diol (a1-1), from the viewpoint of ease of production, mechanical strength, and production cost. In other words, when producing the unsaturated polyester resin (A-1), the amount of ethylenically unsaturated group-free dibasic acid (a1-2-2) blended is preferably 20.0 to 70.0 mol%, more preferably 30.0 to 60.0 mol%, and even more preferably 35.0 to 55.0 mol%, based on 100 mol% of diol (a1-1).

[0030] The content of ethylenically unsaturated group-free dibasic acid (a1-2-2) in dibasic acid (a1-2) is preferably 20.0 mol% or more, more preferably 25.0 mol% or more, even more preferably 30.0 mol% or more, and even more preferably 35.0 mol% or more, preferably 80.0 mol% or less, more preferably 70.0 mol% or less, even more preferably 60.0 mol% or less, and even more preferably 55.0 mol% or less, relative to 100 mol% of dibasic acid (a1-2), from the viewpoint of ease of manufacture, mechanical strength, and manufacturing cost. In other words, the content of ethylenically unsaturated group-free dibasic acid (a1-2-2) in dibasic acid (a1-2) is preferably 20.0 to 80.0 mol%, more preferably 25.0 to 70.0 mol%, even more preferably 30.0 to 60.0 mol%, and even more preferably 35.0 to 55.0 mol%, based on 100 mol% of dibasic acid (a1-2).

[0031] <Vinyl ester resin (A-2)> The vinyl ester resin (A-2) is preferably a reaction product of an epoxy compound (a2-1) and an unsaturated monobasic acid (a2-2). The vinyl ester resin (A-2) may also be a reaction product of reaction raw materials including the epoxy compound (a2-1) and the unsaturated monobasic acid (a2-2), and optionally a bisphenol compound, an unsaturated polybasic acid, etc. The vinyl ester resin (A-2) can be produced using an epoxy compound (a2-1) and an unsaturated monobasic acid (a2-2) as reaction raw materials by applying a known synthesis method by addition reaction. The obtained vinyl ester resin (A-2) may be diluted with an ethylenically unsaturated group-containing monomer (B) as needed. The vinyl ester resin (A-2) may be a single type or a combination of two or more types.

[0032] <Epoxy compound (a2-1)> The epoxy compound (a2-1), which is a reaction raw material for the vinyl ester resin (A-2), is a compound having at least two, preferably two, epoxy groups in one molecule. The epoxy compound (a2-1) may be used alone or in combination of two or more types. Examples of epoxy compounds (a2-1) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiroring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, and the like. Of these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin are preferred from the viewpoint of availability, ease of handling of the resin composition, and manufacturing cost, and bisphenol A type epoxy resin is more preferred.

[0033] The epoxy equivalent of epoxy compound (a2-1) is preferably 170 or more, preferably 1,000 or less, more preferably 500 or less, and even more preferably 300 or less, from the viewpoint of ease of synthesis. That is, the epoxy equivalent of epoxy compound (a2-1) is preferably 170 to 1,000, more preferably 170 to 500, and even more preferably 170 to 300.

[0034] <Unsaturated monobasic acid (a2-2)> The unsaturated monobasic acid (a2-2) is preferably a monocarboxylic acid having an ethylenically unsaturated group. The unsaturated monobasic acid (a2-2) may be used alone or in combination of two or more types. Examples of unsaturated monobasic acids (a2-2) include (meth)acrylic acid, crotonic acid, and cinnamic acid. Of these, (meth)acrylic acid and crotonic acid are preferred from the viewpoint of ease of synthesis, (meth)acrylic acid is more preferred, and methacrylic acid is even more preferred from the viewpoint of chemical resistance.

[0035] When vinyl ester resin (A-2) is a reaction product of epoxy compound (a2-1) and unsaturated monobasic acid (a2-2), it is obtained by the reaction of 1 mole of epoxy group of epoxy compound (a2-1) and 1 mole of carboxyl group of unsaturated monobasic acid (a2-2) to form an ester bond. When producing vinyl ester resin (A-2), the amount of unsaturated monobasic acid (a2-2) to be blended is preferably 30.0 moles or more, more preferably 40.0 moles or more, and even more preferably 50.0 moles or more of carboxyl groups of the unsaturated monobasic acid per 100 moles of epoxy groups of epoxy compound (a2-1), from the viewpoint of exhibiting better viscosity in low-temperature environments. Furthermore, from the viewpoint of making the resin composition easy to handle, it is preferably 120.0 moles or less, more preferably 110.0 moles or less, and even more preferably 105.0 moles or less. In other words, the amount of unsaturated monobasic acid (a2-2) to be blended when producing vinyl ester resin (A-2) is preferably 30.0 to 120.0 moles, more preferably 40.0 to 110.0 moles, and even more preferably 50.0 to 105.0 moles.

[0036] (Bisphenol compounds (a2-3)) The vinyl ester resin (A-2) may contain a bisphenol compound (a2-3) as a reaction raw material. The bisphenol compound (a2-3) may be used alone or in combination of two or more types. Examples of bisphenol compounds (a2-3) include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z. Of these, bisphenol A, bisphenol E, bisphenol F, and bisphenol S are preferred from the viewpoint of availability, manufacturing cost, and making the resin composition easy to handle, bisphenol A, bisphenol E, and bisphenol F are more preferred, and bisphenol A is even more preferred from the viewpoint of corrosion resistance, versatility, and price.

[0037] When a bisphenol compound (a2-3) is included as a reaction raw material for vinyl ester resin (A-2), the total amount of unsaturated monobasic acid (a2-2) and bisphenol compound (a2-3) blended when producing vinyl ester resin (A-2) is preferably 80.0 moles or more, more preferably 90.0 moles or more, even more preferably 95.0 moles or more, preferably 120.0 moles or less, more preferably 110.0 moles or less, and even more preferably 105.0 moles or less, per 100 moles of epoxy groups of epoxy compound (a2-1), from the viewpoint of ease of production and mechanical strength. In other words, the total amount of unsaturated monobasic acid (a2-2) and bisphenol compound (a2-3) blended when producing vinyl ester resin (A-2) is preferably 80.0 to 120.0 moles, more preferably 90.0 to 110.0 moles, and even more preferably 95.0 to 105.0 moles, per 100 moles of epoxy groups of epoxy compound (a2-1).

[0038] When a bisphenol compound (a2-3) is included as a reaction raw material for vinyl ester resin (A-2), the amount of bisphenol compound (a2-3) to be blended when producing vinyl ester resin (A-2) is preferably 10.0 moles or more, more preferably 20.0 moles or more, even more preferably 25.0 moles or more, preferably 70.0 moles or less, more preferably 60.0 moles or less, and even more preferably 50.0 moles or less, per 100 moles of epoxy groups of epoxy compound (a2-1), from the viewpoint of mechanical strength. In other words, the amount of bisphenol compound (a2-3) to be blended when producing vinyl ester resin (A-2) is preferably 10.0 to 70.0 moles, more preferably 20.0 to 60.0 moles, and even more preferably 25.0 to 50.0 moles, per 100 moles of epoxy groups of epoxy compound (a2-1).

[0039] The vinyl ester resin (A-2) may contain an unsaturated polybasic acid (a2-4) as a reaction raw material. Unsaturated polybasic acids (a2-4) are compounds having at least two carboxyl groups (including acid anhydrides) and at least one unsaturated group in one molecule. Unsaturated polybasic acids (a2-4) may be used individually or in combination of two or more types. Examples of unsaturated polybasic acids (a2-4) include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, itaconic acid, tetrahydrophthalic acid, and hexahydrophthalic acid. Of these, maleic anhydride, fumaric acid, succinic acid, glutaric acid, and adipic acid are preferred from the viewpoint of availability, ease of handling of the resin composition, and manufacturing cost, succinic acid, fumaric acid, and maleic anhydride are more preferred, and fumaric acid is even more preferred.

[0040] When an unsaturated polybasic acid (a2-4) is included as a reaction raw material for vinyl ester resin (A-2), the amount of unsaturated polybasic acid blended when producing vinyl ester resin (A-2) is preferably 0.5 moles or more, more preferably 1.0 mole or more, even more preferably 3.0 moles or more, preferably 15.0 moles or less, more preferably 10.0 moles or less, and even more preferably 8.0 moles or less, per 100 moles of epoxy groups of epoxy compound (a2-1), from the viewpoint of exhibiting better viscosity in a low-temperature environment. In other words, the amount of unsaturated polybasic acid blended when producing vinyl ester resin (A-2) is preferably 0.5 to 15.0 moles, more preferably 1.0 to 10.0 moles, and even more preferably 3.0 to 8.0 moles, per 100 moles of epoxy groups of epoxy compound (a2-1).

[0041] The acid value of vinyl ester resin (A-2) is preferably 3.0 KOH mg / g or higher, more preferably 5.0 KOH mg / g or higher, and even more preferably 10.0 KOH mg / g or higher, from the viewpoint of ease of handling of the resin composition and exhibiting better viscosity in low-temperature environments. From the viewpoint of ease of handling of the resin composition, it is preferably 50.0 KOH mg / g or lower, more preferably 40.0 KOH mg / g or lower, and even more preferably 35.0 KOH mg / g or lower. In other words, the acid value of vinyl ester resin (A-2) is preferably 3.0 to 50.0 KOH mg / g, more preferably 5.0 to 40.0 KOH mg / g, and even more preferably 10.0 to 35.0 KOH mg / g.

[0042] The weight-average molecular weight (Mw) of the vinyl ester resin is preferably 300 or more, more preferably 500 or more, and even more preferably 700 or more, from the viewpoint of exhibiting better viscosity in low-temperature environments, and preferably 20,000 or less, more preferably 10,000 or less, and even more preferably 5,000 or less, from the viewpoint of ease of handling of the resin composition. In other words, the weight-average molecular weight (Mw) of the vinyl ester resin is preferably 300 to 20,000, more preferably 500 to 10,000, and even more preferably 700 to 5,000.

[0043] The number-average molecular weight (Mn) of the vinyl ester resin is preferably 200 or more, more preferably 400 or more, and even more preferably 600 or more, from the viewpoint of exhibiting better viscosity in low-temperature environments, and preferably 15,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less, from the viewpoint of ease of handling of the resin composition. In other words, the number-average molecular weight (Mn) of the vinyl ester resin is preferably 200 to 15,000, more preferably 400 to 5,000, and even more preferably 600 to 3,000.

[0044] From a similar viewpoint, the molecular weight distribution (Mw / Mn) of the vinyl ester resin is preferably 1.00 or higher, more preferably 1.50 or higher, and even more preferably 2.00 or higher, from the viewpoint of ease of manufacture, and preferably 15.00 or lower, more preferably 10.00 or lower, and even more preferably 5.00 or lower, from the viewpoint of exhibiting better viscosity in low-temperature environments. That is, the molecular weight distribution (Mw / Mn) of the unsaturated polyester resin (A-1) is preferably 1.00 to 15.00, more preferably 1.50 to 10.00, and even more preferably 2.00 to 5.00.

[0045] [Monomers containing ethylenically unsaturated groups (B)] The ethylenically unsaturated group-containing monomer (B) is a monomer that is polymerizable due to the ethylenically unsaturated group. Preferably, the ethylenically unsaturated group of the ethylenically unsaturated group-containing monomer (B) is at least one selected from vinyl groups (including allyl groups) and (meth)acryloyl groups. The monomer (B) containing an ethylenically unsaturated group may be used alone or in combination of two or more types.

[0046] Examples of monomers having a vinyl group include styrene derivatives such as styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, tert-butylstyrene, vinylbenzylbutyl ether, vinylbenzylhexyl ether, and divinylbenzyl ether; vinyl acetate, diallyl fumarate, diallyl phthalate, and triallyl isocyanurate.

[0047] Examples of monomers having a (meth)acryloyl group include (meth)acrylic acid, monofunctional (meth)acrylate, polyfunctional (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylamide, 2-hydroxyethyl-N-methyl (meth)acrylamide, and 3-hydroxypropyl (meth)acrylamide.

[0048] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, and ethylene glycol monohexyl Examples include sil ether (meth)acrylate, ethylene glycol mono-2-ethylhexyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monohexyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, and allyl (meth)acrylate.

[0049] Examples of polyfunctional (meth)acrylates include alkane diol di(meth)acrylates such as ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate. Examples include polyoxyalkylene glycol di(meth)acrylates, as well as trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol diacrylate monostearate, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethoxylated bisphenol A di(meth)acrylate, tris-(2-(meth)acryloxyethyl) isocyanurate, etc.

[0050] Of these, the monomers containing ethylenically unsaturated groups (B) are selected from the viewpoint of availability, manufacturing cost, and better viscosity in low-temperature environments, and include styrene, vinyltoluene, methyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and trimethyl Iolpropane tri(meth)acrylate and ethoxylated bisphenol A di(meth)acrylate are preferred, styrene, vinyltoluene, phenoxyethyl(meth)acrylate, benzyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ethoxylated bisphenol A di(meth)acrylate are more preferred, styrene and phenoxyethyl(meth)acrylate are even more preferred, and styrene is even more preferred.

[0051] The content of ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 20.00 parts by mass or more, more preferably 30.00 parts by mass or more, and even more preferably 35.00 parts by mass or more, per 100 parts by mass of the total of ethylenically unsaturated group-containing resin (A) and ethylenically unsaturated group-containing monomer (B), from the viewpoint of suppressing a rapid increase in the initial viscosity of the resin composition, and preferably 70.00 parts by mass or less, more preferably 60.00 parts by mass or less, and even more preferably 35.00 parts by mass or less, from the viewpoint of suppressing a decrease in the initial viscosity of the resin composition. In other words, the content of ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 20.00 to 70.00 parts by mass, more preferably 30.00 to 60.00 parts by mass, and even more preferably 35.00 to 55.00 parts by mass, per 100 parts by mass of the total of ethylenically unsaturated group-containing resin (A) and ethylenically unsaturated group-containing monomer (B).

[0052] The content of ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 20.00% by mass or more, more preferably 30.00% by mass or more, and even more preferably 35.00% by mass or more, from the viewpoint of suppressing a rapid increase in the initial viscosity of the resin composition, and preferably 70.00% by mass or less, more preferably 60.00% by mass or less, and even more preferably 55.00% by mass or less, from the viewpoint of suppressing a decrease in the initial viscosity of the resin composition. In other words, the content of ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 20.00 to 70.00% by mass, more preferably 30.00 to 60.00% by mass, and even more preferably 35.00 to 55.00% by mass.

[0053] [Compound (C)] The compound (C) of this embodiment is at least one selected from oxides of Group 2 elements and hydroxides of Group 2 elements. Compound (C) may be a single compound or a combination of two or more compounds. Compound (C) interacts with the carboxyl groups and hydroxyl groups of the ethylenically unsaturated group-containing resin (A), thereby increasing the viscosity of the resin composition over time.

[0054] Examples of oxides of Group 2 elements include magnesium oxide, calcium oxide, and barium oxide. Examples of hydroxides of Group 2 elements include magnesium hydroxide, calcium hydroxide, and barium hydroxide. Among these, magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide are preferred from the viewpoint of thickening effect, versatility, and cost, and magnesium oxide is more preferred.

[0055] The content of compound (C) in the resin composition is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.10 parts by mass or more, per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B), from the viewpoint of efficiently thickening the resin composition, and preferably 3.00 parts by mass or less, more preferably 2.00 parts by mass or less, and even more preferably 1.00 part by mass or less, from the viewpoint of further suppressing the attainment viscosity of the resin composition from becoming excessively high. In other words, the content of compound (C) in the resin composition is preferably 0.01 to 3.00 parts by mass, more preferably 0.05 to 2.00 parts by mass, and even more preferably 0.10 to 1.00 parts by mass, per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

[0056] The content of compound (C) in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.10% by mass or more, from the viewpoint of efficiently increasing the viscosity of the resin composition, and preferably 3.00% by mass or less, more preferably 2.00% by mass or less, and even more preferably 1.00% by mass or less, from the viewpoint of further suppressing the attainment viscosity of the resin composition from becoming excessively high. In other words, the content of compound (C) in the resin composition is preferably 0.01 to 3.00% by mass, more preferably 0.05 to 2.00% by mass, and even more preferably 0.10 to 1.00% by mass.

[0057] [Dicarboxylic acid (D)] The dicarboxylic acid (D) in this embodiment is a compound having two carboxyl groups in one molecule. The dicarboxylic acid (D) interacts with compound (C) and the carboxyl groups, hydroxyl groups, etc., present in the ethylenically unsaturated group-containing resin (A). This interaction occurs before the resin composition thickens over time, thus suppressing a rapid increase in viscosity immediately after the preparation of the resin composition (within 5 hours after preparation). Furthermore, water is generated due to the interaction between the dicarboxylic acid (D) and compound (C). This generated water promotes the thickening of the resin composition from 5 hours after preparation. In addition, when the resin composition contains dicarboxylic acid (D), the formation of a three-dimensional structure between polymers formed by the interaction between the ethylenically unsaturated group-containing resin (A), compound (C), and dicarboxylic acid (D) is suppressed, which can prevent the resin composition from reaching an excessively high viscosity. The dicarboxylic acid (D) may be a single type or a combination of two or more types.

[0058] Examples of dicarboxylic acids (D) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 3-dodecenylsuccinic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. Among these, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 3-dodecenylsuccinic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, with 3-dodecenylsuccinic acid being more preferred, from the viewpoint of controlling the viscosity increase rate and suppressing excessive viscosity of the resin composition immediately after preparation (within 5 hours after preparation), thereby further suppressing excessive viscosity of the resin composition.

[0059] The content of dicarboxylic acid (D) in the resin composition is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.10 parts by mass or more, per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B), from the viewpoint of further suppressing the attainment viscosity of the resin composition becoming excessively high, and preferably 3.00 parts by mass or less, more preferably 2.50 parts by mass or less, and even more preferably 2.00 parts by mass or less, from the viewpoint of suppressing the attainment viscosity of the resin composition becoming excessively low. In other words, the content of dicarboxylic acid (D) in the resin composition is preferably 0.01 to 3.00 parts by mass, more preferably 0.05 to 2.00 parts by mass, and even more preferably 0.10 to 2.00 parts by mass, per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

[0060] The content of dicarboxylic acid (D) in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.10% by mass or more, from the viewpoint of further suppressing the attainment viscosity of the resin composition from becoming excessively high, and preferably 3.00% by mass or less, more preferably 2.50% by mass or less, and even more preferably 2.00% by mass or less, from the viewpoint of further suppressing the attainment viscosity of the resin composition from becoming excessively low. That is, the content of dicarboxylic acid (D) in the resin composition is preferably 0.01 to 3.00% by mass, more preferably 0.05 to 2.00% by mass, and even more preferably 0.10 to 2.00% by mass.

[0061] [Water (E)] In this embodiment, the water (E) content in the resin composition is 0.15 to 0.60% by mass relative to 100% by mass of the total of the ethylenically unsaturated group-containing resin (A), ethylenically unsaturated group-containing monomer (B), dicarboxylic acid (D), water (E), and compound (F). Because the water (E) content in the resin composition is within this range, the resin composition exhibits good viscosity even in low-temperature environments. Furthermore, as described above, when the resin composition contains water (E), the formation of a three-dimensional structure between polymers formed by the interaction between the ethylenically unsaturated group-containing resin (A), the compound (C), and the dicarboxylic acid (D) is suppressed, thereby preventing the resin composition from reaching an excessively high viscosity.

[0062] The content of compound (E) in the resin composition is preferably 0.010% by mass or more, more preferably 0.100% by mass or more, even more preferably 0.200% by mass or more, and even more preferably 0.300% by mass or more, based on 100% by mass of the total of the ethylenically unsaturated group-containing resin (A), ethylenically unsaturated group-containing monomer (B), dicarboxylic acid (D), water (E), and compound (F), from the viewpoint of exhibiting better viscosity even in low-temperature environments. From the viewpoint of further suppressing the attainment viscosity of the resin composition from becoming excessively low, it is preferably 3.000% by mass or less, more preferably 2.000% by mass or less, even more preferably 1.000% by mass or less, and even more preferably 0.500% by mass or less. In other words, the content of compound (E) is preferably 0.010 to 3.000% by mass, more preferably 0.100 to 2.000% by mass, even more preferably 0.200 to 1.000% by mass, and even more preferably 0.300 to 0.500% by mass, based on 100% by mass of the total of the ethylenically unsaturated group-containing resin (A), ethylenically unsaturated group-containing monomer (B), dicarboxylic acid (D), water (E), and compound (F).

[0063] [Compound (F)] Compound (F) in this embodiment is a hydroxyl group-containing compound and does not contain water. Compound (F) interacts with compound (C), suppressing the formation of a three-dimensional polymer structure. As a result, it is possible to prevent the resin composition from reaching an excessively high viscosity.

[0064] Compound (F) can be a monohydric alcohol or a polyhydric alcohol. Compound (F) may also be a combination of a monohydric alcohol and a polyhydric alcohol. Examples of monohydric alcohols include benzyl alcohol, stearyl alcohol, isostearyl alcohol, and other alcohols with a boiling point of 50°C or higher. Examples of polyhydric alcohols include glycol compounds and trihydric or higher alcohols, such as ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 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, and 2-ethyl-1,3-hexa Examples include bisphenol diol, 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, 2,2-di(4-hydroxycyclohexyl)propane, bisphenol A, bisphenol F, bisphenol S hydrides, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and the like. These may be used individually or in combination of two or more. Among these, from the viewpoint of availability, cost, etc., polyhydric alcohols are preferred, more preferably glycol compounds, even more preferably ethylene glycol, 2-methyl-1,3-propanediol, propylene glycol, neopentyl glycol, diethylene glycol, and dipropylene glycol, and even more preferably ethylene glycol and propylene glycol.

[0065] The content of compound (F) in the resin composition is 0.01 to 3.00 parts by mass per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B). The content of compound (F) in the resin composition is preferably 0.05 parts by mass or more, more preferably 0.08 parts by mass or more, and even more preferably 0.10 parts by mass or more, based on 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B), from the viewpoint of exhibiting better viscosity even in low-temperature environments, and preferably 2.00 parts by mass or less, more preferably 1.50 parts by mass or less, and even more preferably 1.00 parts by mass or less, from the viewpoint of suppressing the attainment viscosity of the resin composition from becoming excessively low. In other words, the content of compound (F) in the resin composition is preferably 0.05 to 0.20 parts by mass, more preferably 0.08 to 1.50 parts by mass, and even more preferably 0.10 to 1.00 parts by mass, based on 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

[0066] The content of compound (F) in the resin composition is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, and even more preferably 0.10% by mass or more, from the viewpoint of exhibiting better viscosity even in low-temperature environments, and preferably 2.00% by mass or less, more preferably 1.50% by mass or less, and even more preferably 1.00% by mass or less, from the viewpoint of suppressing the attainment viscosity of the resin composition from becoming excessively low. That is, the content of di-compound (F) in the resin composition is preferably 0.05 to 0.20% by mass, more preferably 0.08 to 1.50% by mass, and even more preferably 0.10 to 1.00% by mass.

[0067] [Photopolymerization initiator (G)] The resin composition of this embodiment may further contain a photopolymerization initiator (G). As the photopolymerization initiator (G), known intramolecular cleavage type photopolymerization initiators can be used, and one or more types can be appropriately selected and used depending on the wavelength of the irradiation light from the light source used when curing the resin composition. A resin composition containing a photopolymerization initiator (G) becomes a cured product when irradiated with a light source having an emission wavelength corresponding to the absorption wavelength of the photopolymerization initiator (G).

[0068] The photopolymerization initiator (G) is not particularly limited as long as it generates radicals upon light irradiation, but examples include: benzoin, benzoin methyl ether and its alkyl ethers such as benzoin, benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; α-hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; and 2,4-dimethylthioxanthone and 2,4-diisopropylthioxanthone. Examples include thioxanthones such as oxanthones and 2-chlorothioxanthones; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; morpholines such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1-one; acylphosphine oxides such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and xanthones.

[0069] From the viewpoint of reactivity, it is preferable to use an intramolecular cleavage type photopolymerization initiator (G) that does not require a hydrogen donor. Furthermore, since it absorbs light with a wavelength of 315 to 460 nm to generate active species, 2,2-dimethoxy-2-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and 1-hydroxycyclohexylphenyl ketone are preferred, and 2,2-dimethoxy-2-phenylacetophenone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide are more preferred.

[0070] The content of the photopolymerization initiator (G) in the resin composition is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more, per 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B), from the viewpoint of curability, and preferably 3.00 parts by mass or less, more preferably 2.00 parts by mass or less, and even more preferably 1.00 part by mass or less, from the viewpoint of suppressing heat generation and cracking during curing of the resin composition, and from the viewpoint of balancing the physical properties such as strength, toughness, heat resistance, and chemical resistance of the cured resin composition. In other words, the content of the photopolymerization initiator (G) in the resin composition is preferably 0.01 to 3.00 parts by mass, more preferably 0.03 to 2.00 parts by mass, and even more preferably 0.05 to 1.00 parts by mass.

[0071] The content of the photopolymerization initiator (G) in the resin composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.05% by mass or more, from the viewpoint of curability, and from the viewpoint of suppressing heat generation, cracking, etc. during curing of the resin composition, and from the viewpoint of balancing the physical properties such as strength, toughness, heat resistance, and chemical resistance of the cured resin composition, it is preferably 3.00% by mass or less, more preferably 2.00% by mass or less, and even more preferably 1.00% by mass or less. That is, the content of the ethylenically unsaturated group-containing resin (B) in the resin composition is preferably 0.01 to 3.00% by mass, more preferably 0.03 to 2.00% by mass, and even more preferably 0.05 to 1.00% by mass.

[0072] [Other ingredients] The resin composition of this embodiment may contain, as other components, additives such as other resins, polymerization inhibitors, thixotropes, curing accelerators, catalysts, thickening aids, curing retarders, surfactants, interface modifiers, wetting and dispersing agents, defoaming agents, leveling agents, coupling agents, light stabilizers, waxes, flame retardants, plasticizers, fillers, internal release agents, low-shrinkage agents, toners, viscosity reducers, separation inhibitors, compatibilizers, and dyes. The content of the additives is not particularly limited as long as it does not hinder the effects of the present invention.

[0073] Switotheramps can be used to adjust the miscibility and fluidity of resin compositions. Examples of switotheramps include organic and inorganic switotheramps. These can be used individually or in combination of two or more. If the resin composition of this embodiment contains a thixotrope, its content is preferably 0.01 to 5.00% by mass, more preferably 0.1 to 3.00% by mass, of the resin composition.

[0074] Examples of organic thixotropes include hydrogenated castor oil-based, amide-based, oxidized polyethylene-based, polymerized vegetable oil-based, surfactant-based, and composite systems using these in combination. Specifically, examples include "Flonon® SP-1000AF" (manufactured by Kyoeisha Chemical Co., Ltd.) and "Disparon® 6900-20X" (manufactured by Kusumoto Kasei Co., Ltd.). Examples of inorganic thixotropes include hydrophobic or hydrophilic silica and bentonite. Specific examples of hydrophobic inorganic thixotropes include "Rheorosil (registered trademark) PM-20L" (manufactured by Tokuyama Corporation), "Aerosil (registered trademark) R-106" (Nippon Aerosil Co., Ltd.), and "CAB-O-SIL (registered trademark)" (manufactured by Cabot Corporation). Specific examples of hydrophilic inorganic thixotropes include "Aerosil (registered trademark)-200" (manufactured by Nippon Aerosil Co., Ltd.). When using hydrophilic calcined silica, the combined use of the thixotropy modifiers "BYK (registered trademark)-R605" and "BYK (registered trademark)-R606" (both manufactured by BYK Corporation) is effective in appropriately controlling the viscosity increase rate.

[0075] [Viscosity of resin compositions] The viscosity of the resin composition immediately after preparation (within 1 hour of preparation) at 15°C is preferably 0.1 to 10.0 Pa·s, more preferably 0.5 to 5.0 Pa·s, and even more preferably 1.0 to 1.5 Pa·s, from the viewpoint of impregnation into the fibrous substrate. The viscosity of the resin composition at 15°C 24 hours after preparation is preferably 30-300 Pa·s, more preferably 50-250 Pa·s, and even more preferably 80-200 Pa·s, from the viewpoint of thickening properties. The viscosity of the resin composition at 15°C 168 hours, 336 hours, 504 hours, and 840 hours after preparation is preferably 300 to 2,500 Pa·s, more preferably 450 to 2,000 Pa·s, and even more preferably 600 to 1,300 Pa·s, from the viewpoint of thickening properties.

[0076] [Method for producing resin composition] The resin composition according to this embodiment can be produced by mixing an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C), a dicarboxylic acid (D), water (E), and a compound (F) which is a hydroxyl group-containing compound. The other components may be added and mixed as needed.

[0077] The mixing order is not particularly limited. For example, a resin composition can be obtained by mixing and dissolving an ethylenically unsaturated group-containing resin (A) with an ethylenically unsaturated group-containing monomer (B), and then adding and mixing compound (C), dicarboxylic acid (D), water (E), and optionally other components. The mixing method is not particularly limited and can be carried out using, for example, a disper, planetary mixer, kneader, etc. The mixing temperature is preferably 10 to 40°C, more preferably 15 to 30°C, and even more preferably 20 to 30°C from the viewpoint of ease of mixing.

[0078] [Uses of resin compositions] The resin composition of this embodiment can also be used as a composite material (H) with a fibrous substrate (h) described later to obtain a cured product with good strength, making it suitable for lining material applications.

[0079] [Composite material (H)] The composite material in this embodiment includes a fibrous substrate (h) impregnated with the above-described resin composition (hereinafter also referred to as the resin-impregnated substrate), and is a material for a lining. As the composite material (H), it is preferable to impregnate a fibrous base material (h) with a resin composition and allow it to thicken by storing (curing) it for a certain period of time. Using such a composite material (H) yields a lining material with excellent shape retention.

[0080] From the viewpoint of mechanical strength and other factors, the types of fibers used in the fiber base material (h) include, for example, organic fibers such as amide, aranid, vinylon, polyester, and phenol, as well as so-called reinforcing fibers such as carbon fibers, glass fibers, metal fibers, and ceramic fibers, and composite fibers thereof. The fiber base material (h) may be a single type or two or more types may be used in combination. Of these, aramid fibers, carbon fibers, and glass fibers are preferred, and from the viewpoint of strength, availability, and price, glass fibers are more preferred, and glass fibers or polyester fibers that have light transmittance are even more preferred. For example, in the case of glass fibers, the filament diameter commonly used is preferably 1 to 15 μm, and more preferably 3 to 10 μm.

[0081] Examples of the fibrous base material (h) include roving, chopped strand, yarn, and milled fiber. Furthermore, it is preferable to process the fibrous base material of the above form into a sheet-like shape such as a plain weave or twill weave, a multiaxial weave, or a nonwoven fabric, thereby forming it into a mat or cloth. Among these, roving cloth, chopped strand mat, and glass cloth are preferred, and from the viewpoint of strength, roving cloth and chopped strand mat are more preferred. The fibrous base material (d) may be used alone or in combination of two or more types. In the case of sheet materials such as roving cloth, chopped strand mat, or glass cloth, it may be used as a single layer or in multiple layers, but it is preferable to laminate multiple layers from the viewpoint of obtaining a cured lining material with higher mechanical strength.

[0082] The content of the resin composition in the composite material (H) is preferably 20 to 95% by mass, more preferably 25 to 85% by mass, and even more preferably 25 to 75% by mass. If the content of the resin composition is 20% by mass or more, the lining material can be given appropriate flexibility, resulting in good workability during pipe rehabilitation. If the content of the resin composition is 95% by mass or less, the cured product of the lining material can be given sufficient strength.

[0083] The content of the fibrous base material (h) in the composite material (H) is preferably 5 to 80% by mass, more preferably 15 to 75% by mass, and even more preferably 25 to 75% by mass. If the content of the fibrous base material (h) is 5% by mass or more, sufficient strength can be imparted to the cured product of the lining material, and if the content of the fibrous base material (h) is 80% by mass or less, appropriate flexibility can be imparted to the lining material.

[0084] The total content of the resin composition and the fibrous base material (h) in the composite material (H) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, and may be 100% by mass, from the viewpoint of imparting sufficient strength to the cured product of the lining material.

[0085] [Lining material] A lining material is used for repairing existing pipes and other pipes. Pipe repair is carried out by placing the lining material along the inner circumference of the inner surface of the pipe, pressing the lining material against the inner surface of the pipe, and then curing the resin composition contained in the lining material by irradiating it with light such as ultraviolet light or visible light. In this specification, the process of placing the lining material along the inner circumference of the inner surface of the pipe, pressing the lining material against the inner surface of the pipe, and then curing the resin composition contained in the lining material by irradiating it with ultraviolet light or visible light is also referred to as performing pipe rehabilitation.

[0086] The lining material is cylindrical in shape and includes a composite material (H) in which a resin composition is impregnated into a fibrous base material (h). From the viewpoint of ease of pipe rehabilitation construction, it is preferable that the lining material has an inner film as the innermost layer on the inner surface, an outer film as the outermost layer on the outer surface, and a composite material layer containing composite material (H) between the inner and outer films, or an outer film as the innermost layer on the inner surface, an inner film as the outermost layer on the outer surface, and a composite material layer containing composite material (H) between the inner and outer films. Furthermore, a lining material having an outer film as the innermost layer on the inner surface, an inner film as the outermost layer on the outer surface, and a composite material layer containing composite material (H) between the inner and outer films is preferably used in an inversion method in which the lining material is pulled into the inner surface of the pipe while being inverted. The lining material may have other layers as needed. Each layer may be a single layer or multiple layers may be laminated together.

[0087] The lining material is preferably cylindrical in shape with a diameter approximately the same as the diameter of the inner surface of the pipe. This improves the strength of the pipe after repair. The inner diameter of the lining material is not particularly limited, but is preferably 100 to 1500 mm, more preferably 130 to 1200 mm, and even more preferably 150 to 1000 mm. If the inner diameter of the lining material is 100 mm or more, light curing is easy to perform, and if the inner diameter of the lining material is 1500 mm or less, the workability during pipe rehabilitation is good.

[0088] [Inner film] As the inner film, resin films such as polyethylene film, polypropylene film, polyethylene terephthalate film, polyamide film, and cellophane film can be used. The inner film needs to be transparent to light irradiated from the light irradiation device during pipe rehabilitation work. This allows the lining material to harden efficiently and pipe rehabilitation to be carried out properly. The inner film may be peeled off after the lining material has hardened.

[0089] The thickness of the inner film is not particularly limited, but is preferably 50 to 200 μm, and more preferably 80 to 170 μm. If the inner film thickness is 50 μm or more, the inner film will not be damaged or wrinkled during or before pipe rehabilitation work, and sufficient strength can be imparted to the pipe. If the inner film thickness is 200 μm or less, the manufacturing of the lining material becomes easier, and the workability during pipe rehabilitation work is good.

[0090] [Outer film] Similar to the inner film, a resin film can be used as the outer film. The outer film preferably has light-blocking properties. This prevents the lining material from hardening due to external light before the pipe rehabilitation work is completed. Furthermore, during pipe rehabilitation work, the light irradiated onto the lining material can be suppressed from passing through, allowing the lining material to be photocured efficiently. As an outer film with light-shielding properties, for example, a laminated film having a colored coating layer, such as yellow, between two transparent polyethylene films can be used.

[0091] The thickness of the outer film is not particularly limited, but is preferably 5 to 100 μm, more preferably 10 to 90 μm. If the outer film thickness is 5 μm or more, the outer film will not be damaged or wrinkled before light irradiation during pipe rehabilitation work, and sufficient strength can be imparted to the pipe. If the outer film thickness is 100 μm or less, the manufacturing of the lining material becomes easier, and the workability during pipe rehabilitation work is good.

[0092] [Method for manufacturing lining material] The method for manufacturing the lining material can be a conventionally known method, but it is preferable to use the first or second embodiment described below. The method for manufacturing the lining material in the first embodiment of the present invention includes the following steps 1 and 2. The method for manufacturing the lining material in the second embodiment of the present invention includes the following steps 1 to 3.

[0093] [Process 1] Step 1 is a step of impregnating a fibrous substrate (h) with a resin composition to obtain a composite material (H) (resin composition impregnated substrate). In Step 1, the resin composition may be impregnated into a fibrous substrate (h) in which the inner film and outer film are not laminated on the fibrous substrate (h), or a fibrous substrate (h) in which the inner film and outer film are laminated on the surface may be used. Furthermore, when a fibrous substrate (h) with an inner film and an outer film laminated on its surface is used, the resin composition is impregnated into the fibrous substrate (h) by being poured between the inner film and the outer film.

[0094] The fibrous base material (h) used in step 1 may be cylindrical, sheet-like, or tape-like. In the first embodiment, the fibrous base material (h) is preferably cylindrical, and in the second embodiment, the fibrous base material (h) is preferably sheet-like or tape-like.

[0095] The time for impregnating the fibrous substrate (h) with the resin composition is preferably 0.5 to 24 hours, more preferably 1 to 10 hours, and even more preferably 1.5 to 5 hours, from the viewpoint of reducing impregnation defects and ensuring uniform impregnation of the resin composition. The time from the preparation of the resin composition, that is, from the manufacturing of the resin composition until the impregnation of the resin composition is completed, is preferably 1 to 30 hours, more preferably 2 to 24 hours, and even more preferably 5 to 10 hours.

[0096] [Process 2] Step 2 is the process of laminating the inner film and the outer film onto the fibrous substrate (h). There are no particular limitations on the method of laminating the inner film and the outer film, but examples include a method of laminating by applying and curing a liquid film composition onto a fibrous substrate (h), a method of laminating the film onto a fibrous substrate (h) or composite material (H) via an adhesive layer, and a method of directly laminating the film onto a fibrous substrate (h) or composite material (H). The inner film and the outer film may be laminated using different methods, or they may be laminated using the same method. The inner film and the outer film may be laminated independently before or after impregnation of the resin composition into the fiber substrate (h). Furthermore, this process may be performed before or after step 3, which is described later.

[0097] [Step 3] Step 3 is the process of processing the material into a cylindrical shape. Note that if a fibrous material (h) that is already cylindrical is used, it is not necessary to perform step 3. This step is performed only when a sheet-like or tape-like fibrous material (h) is used. In step 3, the lining material is wrapped around a mandrel having a diameter approximately the same as the inner diameter of the pipe, and then bound together with the resin composition contained in the resin-impregnated substrate to form a cylindrical shape. Specifically, if the composite material (H) is in sheet form, it is wrapped around a mandrel, and then two of its longitudinal sides are overlapped by about 1 to 10 cm and bonded together with the resin composition contained in the composite material (H). If the composite material (H) is in tape form, the composite material (H) is wrapped spirally, overlapping by about 1 to 10 cm, and the overlapping portion is bonded together with the resin composition contained in the composite material (H).

[0098] In step 3, if the composite material (h) is wrapped around the mandrel with the inner film already placed on it, it is preferable because there is no need to laminate the inner film onto the fiber base material (h) or composite material (H), and the mandrel can be easily removed after the composite material (H) has been wrapped around it. Furthermore, from a productivity standpoint, it is preferable to laminate the outer film after processing the material into a cylindrical shape.

[0099] In step 3, the overlapping portions of the composite material (H) are bonded together with the resin composition. Therefore, the viscosity of the resin composition contained in the composite material (H) at 15°C is preferably such that it has moderate tackiness, preferably 300 to 2,000 Pa·s, more preferably 450 to 1,500 Pa·s, and even more preferably 600 to 1,000 Pa·s. If the viscosity of the resin composition contained in the composite material (H) is 300 Pa·s or higher, the resin composition will have appropriate tackiness and will remain uniformly contained within the composite material (H) without being unevenly distributed. Furthermore, if the viscosity of the resin composition is 2,000 Pa·s or lower, it will be easy to process into a cylindrical shape.

[0100] The method for manufacturing the lining material may include a curing step in addition to steps 1 to 3 described above. The curing process is a step to appropriately thicken the resin composition until it reaches a viscosity suitable for each process. It is preferable to perform this step after impregnating the fibrous substrate (h) with the resin composition or before the pipe rehabilitation work. The curing temperature in the curing process is preferably 0 to 40°C, more preferably 10 to 35°C, and even more preferably 15 to 30°C. The curing temperature can be appropriately adjusted depending on the target viscosity of the resin composition, the curing time, etc.

[0101] In the first embodiment, it is preferable to include a curing step between steps 1 and 2 and the pipe rehabilitation work. The curing time is preferably 6 hours to 3.5 days, more preferably 12 hours to 3 days, and even more preferably 1 to 2 days.

[0102] In the second embodiment, it is preferable to provide a curing step immediately after step 1, and also preferable to provide a curing step between step 3 and the pipe rehabilitation work. The curing time immediately after step 1 is preferably 12 hours to 3 days, more preferably 1 day to 2.5 days, and even more preferably 1.5 to 2 days. If the curing time is within the above range, the resin composition will develop appropriate tackiness and the overlapping portions of the composite material (H) will be bonded together with sufficient strength. The curing time between step 3 and the pipe rehabilitation work is preferably 6 hours to 3.5 days, more preferably 12 hours to 3 days, and even more preferably 1 to 2 days.

[0103] After the curing process is complete and the viscosity of the resin composition reaches 50 to 1,500 Pa·s at 15°C, the storage period for the lining material is preferably 1 to 6 months, more preferably 2 to 5 months, from the viewpoint of quality stability. [Examples]

[0104] The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples.

[0105] [Synthesis of ethylenically unsaturated group-containing resin (A)] As the ethylenically unsaturated group-containing resin (A), an unsaturated polyester resin (A-1a) was synthesized. The method for measuring the physical properties of unsaturated polyester resin (A-1a) is as follows. The measurement results are shown in Table 1.

[0106] [Acid value] In accordance with JIS K6901:2008 "Partial Acid Value (Indicator Titration Method)", the acid value was determined by measuring the mass of potassium hydroxide required to neutralize the acidic components in the sample using an "Autoburette UCB-2000" (manufactured by Hiranuma Sangyo Co., Ltd.) with a mixed indicator of bromothymol blue and phenol red.

[0107] [Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the unsaturated polyester resin (A-1a) were measured by gel permeation chromatography (GPC) under the following measurement conditions and determined as standard polystyrene equivalent molecular weight. The molecular weight distribution (Mw / Mn) was calculated from the values ​​of the number-average molecular weight (Mn) and the weight-average molecular weight (Mw).

[0108] <Measurement conditions> • Equipment: High-performance liquid chromatograph "Prominence®" (manufactured by Shimadzu Corporation) • Column: "Showdex (registered trademark) LF-804" (manufactured by Resonac Co., Ltd.) • Detector: Differential refractometer "SHOWDEX® RI-71S" (manufactured by RESONAC Corporation) Column temperature: 40°C • Sample: 0.2% by mass solution of unsaturated polyester resin in tetrahydrofuran • Developing solvent: tetrahydrofuran ·Flow rate: 1.0mL / min

[0109] [Synthesis Example 1] In a 3L four-neck separable flask equipped with a thermometer, stirrer, gas inlet tube, and reflux condenser, 181g of propylene glycol (27.5 mol%) of the total 100 mol% of diols (a1-1) and 652g of neopentyl glycol (2,2-dimethyl-1,3-propanediol) (72.5 mol%) of the total 100 mol% of diols (a1-1) were added as diol (a1-1), and malean anhydride was added as ethylenically unsaturated polybasic acid (a1-2-1). 453 g of acid (53.5 mol% relative to a total of 100 mol% of diol (a1-1)) and 380 g of isophthalic acid (26.5 mol% relative to a total of 100 mol% of diol (a1-1)) and 287 g of terephthalic acid (20.0 mol% relative to a total of 100 mol% of diol (a1-1)) as ethylenically unsaturated polybasic acids (a1-2-2) were charged together and condensed at 215°C for 10 hours under a nitrogen gas atmosphere to obtain unsaturated polyester resin (A-1a).

[0110] [Table 1]

[0111] [Manufacturing of resin compositions] A resin composition was prepared using the ethylenically unsaturated group-containing resin (A) obtained in the above synthesis example. Details of the compounds used in the following examples and comparative examples are shown below. (Compound (C)) • Magnesium oxide: Magmicron MD-4AM-2 (magnesium oxide content 40% by mass (estimated), manufactured by Mikuni Pigment Co., Ltd.) (Photopolymerization initiator (G)) BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide DMPA: 2,2-dimethoxy-2-phenylacetophenone

[0112] [Example 1] After mixing 50.63 parts by mass of an unsaturated polyester resin (A-1a) as an ethylenically unsaturated group-containing resin (A) and 49.37 parts by mass of styrene as an ethylenically unsaturated group-containing monomer (B), 1.27 parts by mass of 3-dodecenylsuccinic acid as a dicarboxylic acid (D), 0.42 parts by mass of ethylene glycol as a compound (F), 0.06 parts by mass of BAPO and 0.08 parts by mass of DMPA as photopolymerization initiators (G), and water (E) in amounts such that the final resin composition contains 0.409% by mass, the mixture was then mixed for 20 minutes at 2,000 to 3,000 rpm using a disperser (high-speed dispersant "Homodisperser 2.5 type", manufactured by Primix Corporation). The mixture was left standing in a constant temperature bath set to 15°C, and after adjusting the temperature of the mixture to 15°C and leaving it for 24 hours, Magmicron MD-4AM-2 (manufactured by Mikuni Pigment Co., Ltd.) was added in an amount equal to 0.56 parts by mass of magnesium oxide (compound (C)), and the mixture was mixed for a further minute to obtain resin composition (X-1).

[0113] [Examples 2 and 3, and Comparative Examples 1-7] Resin compositions (X-2), (X-3), and (Y-1) to (Y-7) were obtained in the same manner as in Example 1, except that the raw materials and mixing ratios were as listed in Table 4.

[0114] [Measurement and evaluation of resin compositions] The resin compositions (X-1) to (X-3) and (Y-1) to (Y-7) obtained in the above examples and comparative examples were measured and evaluated for the following items. The results of these measurements and evaluations are shown in Table 4 below.

[0115] 〔viscosity〕 The obtained resin compositions (X-1) to (X-3) and (Y-1) to (Y-7) were each placed in 500 ml containers at a rate of 500 g, immediately after production (within 1 hour of production), and their viscosity at 15°C was measured. After measurement, the containers were sealed and stored in a constant temperature bath set to 15°C. Subsequently, the viscosity at 15°C was measured 24 hours, 168 hours, 336 hours, 504 hours, and 840 hours after the production of the resin compositions. For viscosity measurement, two types of instruments, (1) and (2) below, were appropriately selected depending on the viscosity range of the resin composition. (1) "RB80 type viscometer" (manufactured by Toki Sangyo Co., Ltd.; rotors No. 3 and 4) Table 2 below shows the rotors and rotation speeds to be used according to the viscosity of the resin composition.

[0116] [Table 2]

[0117] (2) "HBDVE type viscometer" (manufactured by Eiko Seiki Co., Ltd.; T-bar spindle TA~TD, rotation speed: 1 rpm) Table 3 below shows the T-bar spindles used according to the viscosity of the resin composition.

[0118] [Table 3]

[0119] 〔comprehensive evaluation〕 The resin compositions were evaluated according to the following criteria. G: The viscosity at each time interval is within the target viscosity range. B: At least one viscosity at each time interval is outside the target viscosity range.

[0120] [Table 4]

[0121] The resin composition contains an ethylenically unsaturated group-containing resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C), a dicarboxylic acid (D), water (E), and a compound (F). It was confirmed that by setting the content of water (E) and compound (F) in the resin composition to specific amounts, good viscosity is exhibited even in low-temperature environments. The resin composition of this embodiment is suitable for use as a lining material.

Claims

1. A resin containing ethylenically unsaturated groups, A monomer containing an ethylenically unsaturated group (B), A compound (C) which is at least one selected from oxides of Group 2 elements and hydroxides of Group 2 elements, Dicarboxylic acid (D) and, Water (E) and A resin composition containing compound (F), which is a hydroxyl group-containing compound, The water (E) content is 0.150 to 0.600% by mass with respect to 100% by mass of the total of the ethylenically unsaturated group-containing resin (A), the ethylenically unsaturated group-containing monomer (B), the dicarboxylic acid (D), the water (E), and the compound (F). A resin composition in which the content of the compound (F) is 0.01 to 3.00 parts by mass with respect to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

2. The resin composition according to claim 1, wherein the ethylenically unsaturated group-containing resin (A) is at least one selected from unsaturated polyester resin (A-1) and vinyl ester resin (A-2).

3. The resin composition according to claim 1 or 2, wherein the ethylenically unsaturated group-containing resin (A) is an unsaturated polyester resin (A-1).

4. The resin composition according to claim 1 or 2, wherein the compound (F) is a glycol compound.

5. The resin composition according to claim 1 or 2, wherein the water (E) content is 0.300 to 0.500% by mass with respect to 100% by mass of the total of the ethylenically unsaturated group-containing resin (A), the ethylenically unsaturated group-containing monomer (B), the dicarboxylic acid (D), the water (E), and the compound (F).

6. The resin composition according to claim 1 or 2, wherein the content of the compound (F) is 0.10 to 1.00 parts by mass with respect to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

7. The resin composition according to claim 1 or 2, wherein the content of compound (C) is 0.01 to 3.00 parts by mass with respect to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

8. The resin composition according to claim 1 or 2, wherein the compound (C) is at least one selected from magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide.

9. The resin composition according to claim 1 or 2, wherein the compound (C) is magnesium oxide.

10. The resin composition according to claim 1 or 2, wherein the content of compound (D) is 0.01 to 3.00 parts by mass with respect to 100 parts by mass of the total of the ethylenically unsaturated group-containing resin (A) and the ethylenically unsaturated group-containing monomer (B).

11. The resin composition according to claim 3, wherein the weight-average molecular weight Mw of the unsaturated polyester resin (A-1) is 5,000 to 20,000.

12. The resin composition according to claim 3, wherein the number average molecular weight Mn of the unsaturated polyester resin (A-1) is 1,000 to 7,000.

13. The resin composition according to claim 3, wherein the acid value of the unsaturated polyester resin (A-1) is 8.0 to 20.0 KOH mg / g.

14. A lining material comprising a composite material (H) containing the resin composition and fibrous base material (h) according to claim 1 or 2.

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