TW202321330A - Resin composition and method for producing same, and composite material - Google Patents

Abstract

A resin composition comprising (A) a vinyl ester resin, (B) a monomer containing an ethylenically unsaturated group, (C) at least one compound selected from an alkaline earth metal oxide and an alkaline earth metal hydroxide, and (D) at least one compound selected from water and a compound containing a hydroxy group, in which the vinyl ester resin (A) comprises a vinyl ester resin (A1), and the vinyl ester resin (A1) has a weight average molecular weight (Mw) of 1,500 or more and a molecular weight distribution (Mw/Mn) of 2.0 or more.

Description

Resin composition, its production method and composite material

The present invention relates to a resin composition containing a vinyl ester resin, a method for producing the same, and a composite material.

In recent years, the aging of existing pipelines buried in the ground such as water supply pipes, sewage pipes, and power pipes has become more serious, and various methods of repairing these have been proposed. For example, Patent Document 1 discloses that the inner wall surface of the existing pipeline buried in the ground is closely adhered to the tubular lining material, and the mobile light irradiation device is supplied with compressed air inside the lining material and introduced into the lining material. A method of repairing existing pipes in a hardening step in which the lining material is irradiated with light to harden the lining material. In addition, as the material of the lining material, a photocurable resin composition impregnated into an impregnated base material made of fibers or the like can be used, or as the aforementioned photocurable resin composition, an unsaturated polyester resin or vinyl resin can be used. Polymer resins such as ester resins are dissolved in solvents such as styrene. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2020-82408

[Problem solved by the invention]

As a resin composition used as a lining material for repairing existing pipelines, it is preferable to have a low viscosity that can be easily impregnated with the resin composition when the impregnation base is impregnated with the resin composition. On the other hand, it is also desirable to have a viscosity such that the resin composition is not unevenly distributed and can maintain a uniformly distributed state in the impregnated base material. That is, even if the impregnation base material is impregnated with a resin composition, it has a low viscosity, and the viscosity increases over time. When repairing an existing pipeline, it is preferable to become a high-viscosity resin composition to the extent that the state of the resin composition can be maintained. . However, conventional resin compositions have problems such as low viscosity and difficulty in controlling the speed of viscosity increase. In order to solve the above problems, the present invention aims to provide a resin composition whose viscosity (hereinafter also referred to as initial viscosity) is low immediately after manufacture, increases with time, and is easy to control the rate of viscosity increase. Moreover, it aims at providing the composite material containing the said resin composition, and the manufacturing method of the said resin composition. [means to solve the problem]

That is, the present invention provides the following means. [1] A resin composition comprising an alkenyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), and at least 1 element selected from oxides and hydroxides of metals belonging to Group 2 elements. A compound (C), and at least one compound (D) selected from water and hydroxyl-containing compounds, the aforementioned vinyl ester resin (A) contains a vinyl ester resin (A1), and the aforementioned vinyl ester resin (A1) The weight average molecular weight (Mw) is 1,500 or more, and the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is 2.0 or more. [2] The resin composition according to the above [1], wherein the vinyl ester resin (A1) has a weight average molecular weight (Mw) of 35,000 or less. [3] The resin composition according to the above [1] or [2], wherein the vinyl ester resin (A1) has a molecular weight distribution (Mw/Mn) of 18 or less. [4] The resin composition according to any one of the above [1] to [3], wherein the vinyl ester resin (A1) has an acid value of 5 KOHmg/g or more. [5] The resin composition according to any one of the above [1] to [4], wherein the vinyl ester resin (A1) has an acid value of 100 KOHmg/g or less. [6] The resin composition as described in [1] above, wherein the vinyl ester resin (A1) is an addition reaction product of a resin precursor (P1) and a polybasic acid anhydride (a1-4), and the resin precursor (P1) is an epoxy compound (a1-1) having two epoxy groups in one molecule, A reaction product obtained by reacting unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) until the total amount of acid groups derived from the polybasic acid anhydride (a1-3) becomes 5 to 25 moles. [7] The epoxy compound (a1-1) is the resin composition described in the above [6] of the bisphenol-type epoxy resin. [8] The unsaturated monobasic acid (a1-2) is the resin composition described in the above [6] or [7] that is at least one selected from (meth)acrylic acid and crotonic acid. [9] The polybasic acid anhydride (a1-3) is the resin composition described in any one of the above [6] to [8] of the dibasic acid anhydride. [10] The polybasic acid anhydride (a1-4) is the resin composition described in any one of the above [6] to [9] of the dibasic acid anhydride. [11] The vinyl ester resin (A) further contains a vinyl ester resin (A2), and the vinyl ester resin (A2) is an epoxy compound having two or more epoxy groups in one molecule (a2-1 ) and the resin composition described in any one of [6] to [10] above, which is a reaction product of an unsaturated monobasic acid (a2-2). [12] With respect to a total of 100 parts by mass of the vinyl ester resin (A1) and the vinyl ester resin (A2), the vinyl ester resin (A1) is 35 to 90 parts by mass, and the vinyl ester resin (A2 ) is 10 to 65 parts by mass of the resin composition described in [11] above. [13] The aforementioned compound (C) is the resin composition described in any one of the aforementioned [1] to [12] of magnesium oxide. [14] The resin composition described in any one of the above [1] to [13] that further contains a polymerization initiator (E). [15] The polymerization initiator (E) is the resin composition described in any one of the above [1] to [14] of the photopolymerization initiator. [16] Containing 20 to 80 parts by mass of the vinyl ester resin (A) relative to the total of 100 parts by mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B), The aforementioned [1]~[ 15] the resin composition described in any one. [17] A method for producing a resin composition comprising a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), and oxides and hydroxides of metals belonging to Group 2 elements At least one compound (C), and at least one compound (D) selected from water and hydroxyl-containing compounds, the aforementioned vinyl ester resin (A) contains vinyl ester resin (A1), which contains the following steps The manufacturing method of the resin composition of 1~3; Step 1: react epoxy compound (a1-1), unsaturated monobasic acid (a1-2), and polybasic acid anhydride (a1-3) with 2 epoxy groups in one molecule until, relative to the aforementioned ring For 100 moles of the total amount of epoxy groups in the oxygen compound (a1-1), the total amount of the acid groups from the aforementioned polybasic acid anhydride (a1-3) becomes 5 to 25 moles to obtain the resin precursor (P1). step, Step 2: the step of obtaining the aforementioned vinyl ester resin (A1) after the addition reaction of the aforementioned resin precursor (P1) and the polybasic acid anhydride (a1-4), Step 3: a step of mixing the aforementioned vinyl ester resin (A), the aforementioned ethylenically unsaturated group-containing monomer (B), the aforementioned compound (C) and the aforementioned compound (D) to obtain a resin composition. [18] A composite material comprising the resin composition described in any one of the above [1] to [16] and a fibrous base sheet (F). [19] The composite material described in [18] above for pipe repair. [Effect of Invention]

According to the present invention, it is possible to provide a resin composition having a low initial viscosity, which increases in viscosity over time, and whose rate of viscosity increase is easy to control, and a method for producing the same. Moreover, a composite material containing the aforementioned resin composition can also be provided.

[Types of implementing the invention]

First, the definitions and meanings of the terms and symbols used in this specification are as follows. The term "(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)acryl" is a general term for acryl and methacryl. "Weight average molecular weight Mw" (hereinafter may be simply referred to as "Mw") and "number average molecular weight Mn" (hereinafter may also be simply referred to as "Mn") are measured by gel permeation chromatography (GPC) And obtain the standard polystyrene conversion molecular weight. Specifically, it was measured by the method described in the Examples described later. The so-called "acid value" of vinyl ester resin indicates the value measured according to JIS K6901:2008 using a mixed solution of bromothymol blue and phenol red as an indicator, which is necessary to neutralize 1 g of vinyl ester resin The mg of potassium hydroxide. Specifically, it was measured by the method described in the Examples described later. The "viscosity" of the vinyl ester resin means the viscosity of a mixture of 65% by mass of vinyl ester resin and 35% by mass of phenoxyethyl methacrylate. The value measured at a temperature of 25° C. using an E-type viscometer. Specifically, it was measured by the method described in the Examples described later. The "viscosity" of the resin composition is a value measured at a temperature of 23° C. using a B-type viscometer. Specifically, it was measured by the method described in the Examples described later. The "initial viscosity" means the viscosity measured within one hour immediately after the production of the resin composition. "An acid group derived from a polybasic acid anhydride" means a free acid group generated from a polybasic acid anhydride unless otherwise specified.

[Resin composition] The resin composition of this embodiment contains a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), and at least one compound selected from oxides and hydroxides of metals belonging to Group 2 elements (C) and at least one compound (D) selected from water and hydroxyl-containing compounds. Then, the vinyl ester resin (A) contains a vinyl ester resin (A1) having a weight average molecular weight Mw of 1,500 or more and a ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 2.0 or more. With such a constitution, the initial viscosity of the resin composition is low, the viscosity increases with time, and it becomes easy to control the rate of viscosity increase.

The resin composition of this embodiment contains a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C) and a compound (D), and may also contain other components described below, but From the viewpoint of obtaining the effect of the present invention well, the vinyl ester resin (A), ethylenically unsaturated group-containing monomer (B), compound (C) and compound (D) in the resin composition The total content is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, more preferably 95 to 100% by mass.

＜Vinyl ester resin (A)＞ The vinyl ester resin (A) of this embodiment contains a vinyl ester resin (A1). Vinyl ester resin (A1) may be used individually by 1 type, and may use 2 or more types together. Moreover, the vinyl ester resin (A2) mentioned later may be contained in vinyl ester resin (A) as needed.

[vinyl ester resin (A1)] The weight average molecular weight (Mw) of the vinyl ester resin (A1) of this embodiment is 1,500 or more, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.0 or more. When the weight average molecular weight (Mw) of the vinyl ester resin (A1) is 1,500 or more, the resin composition can be thickened more efficiently. The weight-average molecular weight (Mw) of the vinyl ester resin (A1) is preferably 2,000 or more, more preferably 4,000 or more, and more preferably 6,000 or more from the viewpoint of more efficient thickening. From the viewpoint of reducing the initial viscosity of the product to an appropriate range and controlling the viscosity increase rate, it is preferably 35,000 or less, more preferably 25,000 or less, more preferably 15,000 or less.

When the molecular weight distribution index of Mw/Mn is 1, it means a monodisperse polymer, and a larger ratio means a wider molecular weight distribution. Mw/Mn of the vinyl ester resin (A1) is a wide range of 2.0 or more, and the optimization of various production conditions at the time of synthesis of the vinyl ester resin (A1) can be facilitated. The Mw/Mn of the vinyl ester resin (A1) is preferably 2.5 or more, more preferably 3.0 or more, and more preferably 4.0 or more from the viewpoint of making it easier to optimize various production conditions. From the standpoint of dispersion of physical properties, reduction of initial viscosity to an appropriate range, and control of viscosity increase rate, 18 or less is preferable, more preferably 12 or less, more preferably 10 or less.

The number average molecular weight (Mn) of the vinyl ester resin (A1) is preferably 500 or more, more preferably 700 or more, and more preferably 900 or more from the viewpoint of efficiently making the resin composition more viscous. From the viewpoint of reducing the initial viscosity of the resin composition to an appropriate range and controlling the viscosity increase rate, it is preferably 2,500 or less, more preferably 1,800 or less, more preferably 1,600 or less.

The acid value of the vinyl ester resin (A1) is preferably 5KOHmg/g or more, more preferably 10KOHmg/g or more, more preferably 15KOHmg/g or more, from the viewpoint of increasing the viscosity-increasing rate of the resin composition. More preferably above 25KOHmg/g, from the point of view of controlling the viscosity increase rate of the resin composition, preferably below 100KOHmg/g, preferably below 90KOHmg/g, more preferably below 80KOHmg/g, more preferably below 80KOHmg/g Below 70KOHmg/g.

Vinyl ester resin (A1) is preferably used to adjust the viscosity by using a solvent or a reactive diluent from the viewpoint of moderate control of the initial viscosity of the resin composition and ease of mixing. The viscosity is preferably adjusted to 1~400Pa·s, more preferably 10~300Pa·s, more preferably 20~150Pa·s.

Vinyl ester resin (A1) is a reaction product of epoxy compound (a1-1) having two epoxy groups in one molecule, unsaturated monobasic acid (a1-2), and polybasic acid anhydride (a1-3) The addition reaction product of the resin precursor (P1) and polybasic acid anhydride (a1-4) is preferable. By using such a vinyl ester resin (A1), the initial viscosity of the resin composition can be reduced to a more suitable range, and the effect of the compound (C) can make the resin composition more efficient over time to thicken.

(Resin Precursor (P1)) The resin precursor (P1) is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride (a1-3). Resin precursor (P1) from the point of view of stably producing vinyl ester resin (A), and from the point of view of expanding the Mw/Mn of vinyl ester resin (A1) moderately and accelerating the viscosity increase rate of the resin composition See, relative to the total amount of 100 moles of epoxy groups of the aforementioned epoxy compound (a1-1), the reaction of the aforementioned epoxy compound (a1-1), the aforementioned unsaturated monobasic acid (a1-2), and the aforementioned The polybasic acid anhydride (a1-3) to the total amount of the acid groups from the aforementioned polybasic acid anhydride (a1-3) is preferably a reaction product obtained by 5 to 25 moles, preferably 7 to 23 moles, more preferably 9~21 moles. For example, when the aforementioned polybasic acid anhydride (a1-3) is a dibasic acid anhydride, at first by the reaction of the epoxy group of the epoxy compound (a1-1) and the carboxyl group of the unsaturated monobasic acid (a1-2), the epoxy The epoxy group of the compound (a1-1) generates a hydroxyl group through ring opening, and the dibasic acid anhydride of the polybasic acid anhydride (a1-3) is ring-opening addition to the hydroxyl group. Next, the carboxyl group generated by the ring-opening addition of the dibasic acid anhydride further reacts with the unreacted epoxy group of the epoxy compound (a1-1). Therefore, when the said polybasic acid anhydride (a1-3) is a dibasic acid anhydride, it can react with the epoxy group contained in 1 molecular unit of a dibasic acid anhydride, and the number of the acid group originating in a dibasic acid anhydride is 1.

(epoxy compound (a1-1)) The epoxy compound (a1-1) is a compound having two epoxy groups in one molecule, and any monomer, oligomer, or polymer can be used, and the molecular weight and molecular structure are not particularly limited. An epoxy compound (a1-1) may be used individually by 1 type, and may use 2 or more types together. Examples of the epoxy compound (a1-1) include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AF type epoxy resins. Epoxy resin; tert-butyl catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl ester type epoxy resin, biphenyl type ring Oxygen resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexanedimethanol ring Oxygen resin, naphthylene ether type epoxy resin, etc. Among them, from the viewpoint of suppressing the initial viscosity increase of the resin composition and controlling the viscosity increasing speed, bisphenol epoxy resins are preferred, and bisphenol A epoxy resins and bisphenol F epoxy resins are preferred. , bisphenol S type epoxy resin, and bisphenol AF type epoxy resin are preferred, and bisphenol A type epoxy resin is more preferred.

The epoxy equivalent of the epoxy compound (a1-1) can be obtained when the vinyl ester resin (A1) is not gelled, and from the viewpoint of suppressing the increase of the initial viscosity of the resin composition and moderately controlling the viscosity increase rate Look, 170~1000 is better, more preferably 170~500, more preferably 170~400, and more preferably 170~300.

From the viewpoint of the efficiency and ease of synthesizing vinyl ester resin (A), the epoxy compound (a1-1) to be used is liquid at 25°C and has an epoxy equivalent of 300 or less. .

(unsaturated monobasic acid (a1-2)) The unsaturated monobasic acid (a1-2) is preferably a monocarboxylic acid having an ethylenically unsaturated group, and may be used alone or in combination of two or more. As unsaturated monobasic acid, (meth)acrylic acid, crotonic acid, cinnamic acid, etc. are mentioned, for example. Among them, at least 1 selected from (meth)acrylic acid and crotonic acid can be obtained from the viewpoint of obtaining a resin composition having general versatility, reactivity during synthesis of vinyl ester resin (A), and good curability. Among them, (meth)acrylic acid is preferred, and methacrylic acid is more preferred from the viewpoint of chemical resistance.

The amount of unsaturated monobasic acid (a1-2) is relative to the epoxy group total amount 100 mole of epoxy compound (a1-1), reacts to the acid group total amount of unsaturated monobasic acid (a1-2) becomes 75-95 moles is preferred, more preferably 77-93 moles, more preferably 79-91 moles. When the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 75 moles or more relative to 100 moles of the total amount of epoxy groups of the aforementioned epoxy compound (a1-1), the vinyl ester resin In (A1), since a sufficient amount of ethylenically unsaturated groups is introduced, the resin composition tends to exhibit good curability. Also, when the total amount of the acid groups of the unsaturated monobasic acid (a1-2) is 95 moles or less with respect to the total amount of 100 moles of the epoxy groups of the aforementioned epoxy compound (a1-1), the ring The reaction product of the oxygen compound (a1-1) and the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) can be sufficiently cross-linked to easily obtain a resin composition with good thickening properties.

(polyanhydride (a1-3)) The polybasic acid anhydride (a1-3) is an acid anhydride formed by dehydration condensation of at least two carboxyl groups in a compound having a plurality of carboxyl groups in one molecule. Among these, dibasic acid anhydrides are preferred from the viewpoints of ease of synthesis of vinyl ester resin (A1), ease of control of molecular weight or acid value, and ability to control the viscosity of the resin composition within an appropriate range. . The polybasic acid anhydride (a1-3) may be used individually by 1 type, and may use 2 or more types together. Examples of the polybasic acid anhydride (a1-3) include maleic anhydride, phthalic anhydride, succinic anhydride, terminal methylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3-methanoic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride Acid anhydride, 4-methyl-hexahydrophthalic anhydride, methyl-3,6-end methylene-1,2,3,6-tetrahydrophthalic anhydride, trimellitic anhydride, etc. These may be used individually, and may use 2 or more types. Among them, maleic anhydride and phthalic anhydride are preferred, and maleic anhydride is preferred from the viewpoints of availability, reactivity during synthesis of vinyl ester resin (A1), and ease of handling during synthesis. better.

The polybasic acid anhydride (a1-3) has the role of crosslinking the reaction product of an epoxy compound (a1-1) and a hydroxyl group, and polymerizing a vinyl ester resin (A1). The mechanism of polymerization of the vinyl ester resin (A1) is estimated as follows. By the reaction of the epoxy group of the epoxy compound (a1-1) and the carboxyl group of the unsaturated monobasic acid (a1-2), the epoxy group of the epoxy compound (a1-1) generates a hydroxyl group through ring opening, for this Hydroxyl ring-opening addition of polybasic acid anhydride (a1-3). Then, the carboxyl group generated by the ring-opening addition of the polybasic acid anhydride (a1-3) further reacts with the unreacted epoxy group of the epoxy compound (a1-1) to crosslink and polymerize. By polymerizing the vinyl ester resin (A1) in this way, the viscosity increase rate of the resin composition can be increased because the molecular weight distribution shifts to the polymer side.

The amount of polybasic acid anhydride (a1-3) is relative to the total amount of 100 moles of epoxy groups of the aforementioned epoxy compound (a1-1), and the total amount of the acid group that is reacted to come from polybasic acid anhydride (a1-3) becomes 5-25 moles is preferred, more preferably 7-23 moles, more preferably 9-21 moles. By reacting until the total amount of acid groups derived from polybasic acid anhydride (a1-3) becomes 5 moles or more relative to the total amount of epoxy groups of the aforementioned epoxy compound (a1-1) 100 moles, the epoxy The crosslinking of the compound (a1-1) and the polybasic anhydride (a1-3) increases the molecular weight of the vinyl ester resin (A1), which can effectively increase the viscosity of the resin composition. Also, by reacting until the total amount of the acid groups from the polybasic acid anhydride (a1-3) becomes 25 moles or less with respect to the total amount of 100 moles of the epoxy groups of the aforementioned epoxy compound (a1-1), the control The amount of crosslinking of the aforementioned epoxy compound (a1-1) becomes easier, the gelation during synthesis of the vinyl ester resin (A1) is suppressed, and the rate of thickening of the resin composition becomes easier to control.

For this embodiment, the acid group from unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) is reacted to 100 moles of the total amount of epoxy groups relative to epoxy compound (a1-1). (The so-called "acid group" refers to the acid group produced by hydrolysis of the polybasic acid anhydride (a1-3). For example, when the polybasic acid anhydride (a1-3) is a binary acid anhydride, the number of acid groups generated from one molecule is 2.) The total amount is preferably 105~125 moles, more preferably 107~123 moles, more preferably 109~121 moles. By reacting to the total amount of acid groups from unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) relative to the total amount of epoxy groups of the aforementioned epoxy compound (a1-1) 100 moles When it becomes 105 mol or more, the amount of unreacted epoxy group derived from the said epoxy compound (a1-1) is suppressed, and the control of the thickening rate of a resin composition becomes easy. Also, by reacting until the total amount of acid groups from unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) relative to the total amount of epoxy groups of the aforementioned epoxy compound (a1-1) is 100 mo If it is less than 125 moles, the reaction without gelation can be controlled, and the remaining unreacted unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) in the vinyl ester resin (A1) can be reduced. It is suppressed, and can suppress the influence on the viscosity increasing speed of the resin composition.

(polyanhydride (a1-4)) The polybasic acid anhydride (a1-4) is not particularly limited as long as it is a compound having a plurality of carboxyl groups in one molecule, and at least two carboxyl groups can be dehydrated and condensed to form an acid anhydride. For example, the same ones as polybasic acid anhydrides (a1-3) can be mentioned, among them, the ease of controlling the molecular weight and acid value of the vinyl ester resin (A1), the ease of handling during synthesis, and the good viscosity characteristics of the resin composition From other viewpoints, dibasic acid anhydrides are preferred. The polybasic acid anhydride (a1-4) may be used individually by 1 type, and may use 2 or more types together. Specific examples of the polybasic acid anhydride (a1-4) include the same ones as the polybasic acid anhydride (a1-3), and maleic anhydride is preferred. The polybasic acid anhydride (a1-3) and the polybasic acid anhydride (a1-4) may use the same thing, and may use a different thing.

The polybasic acid anhydride (a1-4) acts as one of the reaction products obtained by successively reacting the aforementioned epoxy compound (a1-1), the aforementioned unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3). The resin precursor (P1) reacts to continue to cross-link the aforementioned polybasic acid anhydride (a1-3) with the epoxy compound (a1-1) through the same reaction mechanism, or to introduce carboxyl groups into the resin precursor (P1). That is, the polybasic acid anhydride (a1-4) is added to the hydroxyl group derived from the ring-opening of the epoxy group of the epoxy compound (a1-1), and a carboxyl group is generated. Then, the generated carboxyl group reacts with the unreacted epoxy group from the epoxy compound (a1-1) and cross-links. After all the epoxy groups are reacted, the carboxyl group from the polybasic anhydride (a1-4) is removed The above remains without being cross-linked, and carboxyl groups are introduced into the vinyl ester resin (A1).

Reaction until polybasic acid anhydride (a1-4) relative to epoxy compound (a1-1) epoxy group total amount 100 moles, polybasic acid anhydride (a1-4) becomes 3~60 moles preferably, preferably 5-50 moles, more preferably 7-45 moles. By reacting polybasic acid anhydride (a1-4) to 3 moles or more with respect to the total amount of epoxy groups of the aforementioned epoxy compound (a1-1) 100 moles, by inhibiting vinyl ester resin (A1 ) of the unreacted epoxy group remains, the initial viscosity increase of the resin composition can be suppressed, and by the introduction of the carboxyl group, a sufficient amount of carboxyl group necessary to increase the viscosity of the resin composition is introduced into the vinyl ester Resin (A1), and the hydroxyl group generated by the ring-opening of the epoxy group from the epoxy compound (a1-1) is consumed by the addition of polybasic anhydride (a1-4), which can reduce the initial stage of the resin composition. viscosity. In addition, by reacting the polybasic acid anhydride (a1-4) to 60 moles or less with respect to the total amount of epoxy groups of the epoxy compound (a1-1) of 100 moles, the viscosity of the resin composition can be increased. Speed becomes easy to control.

[vinyl ester resin (A2)] Said vinyl ester resin (A2) is the reaction product of the epoxy compound (a2-1) which has 2 or more epoxy groups in 1 molecule, and an unsaturated monobasic acid (a2-2). When the resin composition contains the vinyl ester resin (A2), it becomes easier to control the viscosity increase rate of the resin composition. In addition, the initial viscosity of the resin composition and the physical properties of the cured product can also be adjusted.

The weight average molecular weight (Mw) of the vinyl ester resin (A2) is preferably 500-6,000, more preferably 500-5,000, more preferably 500-4,500. When the weight average molecular weight (Mw) is 500 or more, the mechanical strength of the cured product of the resin composition can be easily improved. In addition, if the weight average molecular weight (Mw) is 6,000 or less, other components contained in the resin composition can be easily dissolved when used as a resin composition, and handling becomes easier. The weight average molecular weight (Mw) of vinyl ester resin (A2) can be measured by the method similar to vinyl ester resin (A1).

The number average molecular weight Mn of the vinyl ester resin (A2) is preferably 400 or more, more preferably 500 or more, and more preferably 600 or more from the viewpoint of efficiently making the resin composition more viscous. From the viewpoint of the viscosity increasing rate of the composition, it is preferably 1,500 or less, more preferably 1,200 or less, more preferably 1,000 or less.

The Mw/Mn of the vinyl ester resin (A2) is preferably 1.05 or more, more preferably 1.1 or more from the viewpoint of the ease of control of the synthesis conditions, because it suppresses the dispersion of the physical properties of the resin composition and controls the viscosity increasing rate. From a viewpoint, it is preferably 2.0 or less, more preferably 1.7 or less, more preferably 1.5 or less. In addition, Mw/Mn represents an index of molecular weight distribution, and when it is 1, it represents a monodisperse polymer, and the larger the ratio, the wider the molecular weight distribution.

(epoxy compound (a2-1)) As the epoxy compound (a2-1), a compound having two or more epoxy groups in one molecule can be used, and all monomers, oligomers, and polymers can be used, and the molecular weight and molecular structure are not particularly limited. The said epoxy compound (a2-1) may have 2 or 3 or more epoxy groups in 1 molecule. An epoxy compound (a2-1) may be used individually by 1 type, and may use 2 or more types together. Examples of the aforementioned epoxy compound (a2-1) include the same ones as the epoxy compound (a1-1) used in the aforementioned vinyl ester resin (A1), stilbene-type epoxy resins; novolac-type epoxy resins; Resin; Multifunctional epoxy resin; Phenol aralkyl type epoxy resin; Epoxy resin containing triazine nucleus; Denatured phenolic epoxy resin with bridged cyclic hydrocarbon compound; Glycidyl ester type epoxy resin; Epoxy resins with oxazolidone rings, etc.

(unsaturated monobasic acid (a2-2)) The unsaturated monobasic acid (a2-2) is preferably a monocarboxylic acid having an ethylenically unsaturated group, and may be used alone or in combination of two or more. Known ones can be used as the unsaturated monobasic acid (a2-2). For example, the same thing as (a1-1) used for the said vinyl ester resin (A1) can be used, and (meth)acrylic acid, crotonic acid, cinnamic acid, etc. are mentioned. Among these, (meth)acrylic acid is also preferable.

Reaction of unsaturated monobasic acid (a2-2) until the total amount of acid groups of unsaturated monobasic acid (a2-2) becomes 80 moles relative to the total amount of epoxy groups of epoxy compound (a2-1) 100 moles ~100 moles is preferred, more preferably 90~100 moles, more preferably 99~100 moles. By reacting the total amount of the acid groups of the unsaturated monobasic acid (a2-2) to become 80 moles or more with respect to the total amount of 100 moles of the epoxy groups of the aforementioned epoxy compound (a2-1), in The reaction between the unreacted epoxy group contained in the vinyl ester resin (A2) and the carboxyl group contained in the vinyl ester resin (A1) can easily prevent the viscosity increase rate of the resin composition from becoming too high. Also, from the viewpoint of controlling the viscosity increasing rate and the viscosity of the resin composition 2 days and/or 5 days after preparation, and from the viewpoint of production stability, no unreacted rings remain in the vinyl ester resin (A2). Oxygen group is preferably, relative to the total amount of 100 moles of the epoxy group of epoxy compound (a2-1), the total amount of the acid group of unsaturated monobasic acid (a2-2) is with 100 moles. good.

When the resin composition contains a vinyl ester resin (A2), the content of the vinyl ester resin (A1) is 100 parts by mass of the total of the vinyl ester resin (A1) and the vinyl ester resin (A2), The vinyl ester resin (A1) is preferably 35-90 parts by mass, more preferably 40-85 parts by mass, more preferably 45-80 parts by mass. The content of the vinyl ester resin (A2) is preferably set at 10 to 65 parts by mass with respect to the total of 100 parts by mass of the vinyl ester resin (A1) and the vinyl ester resin (A2), preferably 10 to 65 parts by mass, more preferably 15-60 parts by mass, more preferably 20-55 parts by mass. When the vinyl ester resin (A1) and vinyl ester resin (A2) in the above-mentioned range are contained in the resin composition, it becomes easy to further control the thickening speed of the resin composition.

The content of the vinyl ester resin (A) in the resin composition is 20 to 80 parts by mass relative to the total of 100 parts by mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B) described later. Parts by mass are preferred, preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass. When the vinyl ester resin (A) is 20 parts by mass or more, the thickening rate of the resin composition can be easily accelerated by the vinyl ester resin (A1). When the vinyl ester resin (A) is 80 parts by mass or less, the initial viscosity of the resin composition is easily reduced by the ethylenically unsaturated group-containing monomer (B).

The content of the vinyl ester resin (A) in the resin composition is preferably 20 to 75 parts by mass, more preferably 30 to 65 parts by mass, more preferably 30 to 65 parts by mass, relative to 100 parts by mass of the total amount of the resin composition 40 to 60 parts by mass. When the vinyl ester resin (A) is at least 20 parts by mass, the vinyl ester resin (A1) can easily and favorably accelerate the rate of thickening of the resin composition. When the vinyl ester resin (A) is 75 parts by mass or less, the initial viscosity of the resin composition can be easily reduced by the ethylenically unsaturated group-containing monomer (B).

<Ethylenically unsaturated group-containing monomer (B)> The aforementioned ethylenically unsaturated group-containing monomer (B) is not particularly limited as long as it has an ethylenically unsaturated group, but preferably has a (meth)acryl group or a vinyl group. The more the ethylenically unsaturated group-containing monomer (B) contains, the more the initial viscosity increase of the resin composition is suppressed, which has an effect on controlling the viscosity increasing speed or the direction of the viscosity after increasing the viscosity. In addition, hardness, strength, chemical resistance, water resistance, etc. of composite materials containing the resin composition described later can be improved.

Among the ethylenically unsaturated group-containing monomers (B), those having a (meth)acryl group include, for example, (meth)acrylic acid, (meth)acrylate, and the like. (Meth)acrylate may be monofunctional or polyfunctional.

Examples of monofunctional (meth)acrylates include meth (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, base) acrylate, t-butyl (meth)acrylate, 2-ethylhexyl, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, Stearyl (meth)acrylate, tridecyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethyl Glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, ethylene glycol monohexyl ether (methyl) ) 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, bicyclic Pentenyl (meth)acrylate, Dicyclopentenyloxyethyl (meth)acrylate, Tricyclodecanyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate , Diethylaminoethyl (meth)acrylate, caprolactone-modified hydroxyalkyl (meth)acrylate, allyl (meth)acrylate, etc.

Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, ) acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate etc. (meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate Polyoxyalkylene glycol di(meth)acrylate such as acrylate, polyethylene glycol di(meth)acrylate and polytetramethylene glycol di(meth)acrylate, and trimethylolpropane Di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol diacrylate monostearate, 1,3-bis((meth)acryloxy )-2-hydroxypropane, ethoxylated bisphenol A di(meth)acrylate, ginseng-(2-(meth)acryloxyethyl)isocyanurate, etc.

Among the ethylenically unsaturated group-containing monomers (B), those having (meth)acryl groups other than (meth)acrylates include, for example, acryloylmorpholine, 2-hydroxyethyl ( Meth)acrylamide, 2-hydroxyethyl-N-methyl(meth)acrylamide, 3-hydroxypropyl(meth)acrylamide, and the like. In addition to those having a (meth)acryl group, examples of those having a vinyl group include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinyl Benzene, t-butylstyrene, vinyl acetate, diallyl fumarate, triallyl isocyanurate, vinyl benzyl butyl ether, vinyl benzyl Vinyl benzyl compounds such as hexyl ether, vinyl benzyl octyl ether, and divinyl benzyl ether.

Among these, it is also from the viewpoints of the control of the viscosity increase rate of the resin composition, curability, drying, etc., and from the viewpoints of the strength, toughness, heat resistance, chemical resistance, etc. of the composite material containing the resin composition, and From the point of view of cost, it is selected from styrene, methyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate base) acrylate, dicyclopentenyloxyethyl (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate At least one of (meth)acrylate and neopentyl glycol (meth)acrylate is preferred. From the viewpoint of odor suppression, it is selected from phenoxyethyl (meth)acrylate, Benzyl (meth)acrylate, and at least one of diethylene glycol di(meth)acrylate and neopentyl glycol (meth)acrylate are preferred, and the resistance of the cured product of the resin composition is From the point of view of drug properties, selected from phenoxyethyl methacrylate, benzyl (meth)acrylate, diethylene glycol dimethacrylate, neopentyl glycol (meth)acrylic acid At least one kind of ester is more preferable.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition is based on 20 parts by mass of the total of vinyl ester resin (A) and ethylenically unsaturated group-containing monomer (B). Preferably ~80 parts by mass, more preferably 30~70 parts by mass, more preferably 40~60 parts by mass. When the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the initial viscosity of the resin composition can be easily reduced, and workability can be improved. When the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, it becomes a resin composition with better thickening properties.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 20 to 75 parts by mass, more preferably 30 to 65 parts by mass relative to 100 parts by mass of the total amount of the resin composition. parts by mass, more preferably 40 to 60 parts by mass. When the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the initial viscosity of the resin composition tends to decrease, and workability becomes favorable. When the ethylenically unsaturated group-containing monomer (B) is 75 parts by mass or less, it becomes a resin composition with better thickening properties.

＜Compound (C)＞ The compound (C) may be at least one kind selected from oxides and hydroxides of metals belonging to Group 2 elements, and may be used alone or in combination of two or more kinds. The compound (C) interacts with the carboxyl group and hydroxyl group of the vinyl ester resin (A) and the compound having the carboxyl group and hydroxyl group as other additives, and has the effect of increasing the viscosity of the resin composition over time.

Examples of oxides of metals belonging to Group 2 elements include magnesium oxide, calcium oxide, barium oxide, and the like. Examples of hydroxides of metals belonging to Group 2 elements include hydroxides of magnesium, calcium, barium, and the like. Among them, magnesium oxide is preferable from the viewpoints of thickening effect, versatility, and cost.

The content of the compound (C) in the resin composition is preferably 0.01 to 6 parts by mass relative to the total of 100 parts by mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). , preferably 0.05 to 5 parts by mass, more preferably 0.1 to 4 parts by mass. When the compound (C) is at least 0.01 parts by mass, the thickening property of the resin composition can be further improved. By setting the compound (C) at 6 parts by mass or less, excessive thickening of the resin composition can be easily suppressed, and the rate of thickening over time can be easily controlled, allowing more sufficient time to be secured.

The content of the compound (C) in the resin composition is preferably 0.01 to 6 parts by mass, more preferably 0.05 to 5 parts by mass, more preferably 0.1 to 4 parts by mass relative to 100 parts by mass of the total amount of the resin composition. parts by mass. When the compound (C) is 0.01 mass part or more, the thickening property of a resin composition will become more favorable. When the compound (C) is 6 parts by mass or less, excessive thickening of the resin composition can be easily suppressed, and the rate of thickening over time can be easily controlled, allowing more sufficient time to be secured.

＜Compound (D)＞ The compound (D) is at least one or more selected from water and hydroxyl-containing compounds. The compound (D) is used for the purpose of controlling the thickening speed with respect to the change in the thickening speed with the lapse of time. Examples of the hydroxyl group-containing compound include alcohols having a boiling point of 50° C. or higher such as benzyl alcohol, stearyl alcohol, and isostearyl alcohol. Moreover, others include hydroxycarboxylic acids such as lactic acid, glycerin, polyhydric alcohols, hydroxyl group-containing (meth)acrylates, and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, water and alcohol are preferable from the viewpoints of availability and cost, and water is more preferable.

The content of the compound (D) in the resin composition is preferably 0.01 to 3 parts by mass relative to the total of 100 parts by mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). Preferably, it is 0.05-2 mass parts, More preferably, it is 0.1-1 mass parts. When the compound (D) is 0.01 parts by mass or more, the thickening rate of the resin composition becomes easy to control, and excessive thickening becomes easy to suppress. When the compound (D) is 3 parts by mass or less, the composite material containing the resin composition will have better physical properties such as strength, toughness, heat resistance, and chemical resistance.

The content of the compound (D) in the resin composition is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 parts by mass. When the compound (D) is 0.01 parts by mass or more, the thickening rate of the resin composition becomes easy to control, and excessive thickening becomes easy to suppress. When the compound (D) is 3 parts by mass or less, the composite material containing the resin composition will have better physical properties such as strength, toughness, heat resistance, and chemical resistance.

＜Polymerization initiator (E)＞ The resin composition may further contain a polymerization initiator (E). In the polymerization initiator (E), any one of a photopolymerization initiator and a thermal polymerization initiator can also be used. From the viewpoint of ensuring the control of the viscosity increasing speed and the time for increasing the viscosity to a predetermined viscosity, it is preferable that the resin composition contains a photopolymerization initiator.

When a photopolymerization initiator is used as the polymerization initiator (E), the content of the photopolymerization initiator in the resin composition is relative to the vinyl ester resin (A) and the monoethylenically unsaturated group-containing 0.01-10 mass parts is preferable with respect to a total of 100 mass parts of body (B), More preferably, it is 0.05-5 mass parts, More preferably, it is 0.1-3 mass parts. When the content of the photopolymerization initiator is 0.01 parts by mass or more, a resin composition with better curability can be obtained. When the content of the photopolymerization initiator is 10 parts by mass or less, the resin composition is less likely to undergo rapid curing reaction and heat generation during curing, and it becomes easier to suppress cracks, and the resulting composite material becomes stronger in strength, toughness, and heat resistance. , and the balance of physical properties such as chemical resistance is better.

When a photopolymerization initiator is used as the polymerization initiator (E), the content of the photopolymerization initiator in the resin composition is 0.01 to 10 parts by mass relative to 100 parts by mass of the total amount of the resin composition. Parts by mass are preferred, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass. When the content of the photopolymerization initiator is 0.01 parts by mass or more, a resin composition with better curability can be obtained. When the content of the photopolymerization initiator is 10 parts by mass or less, the resin composition is less likely to undergo rapid curing reaction and heat generation during curing, and it becomes easier to suppress cracks, and the resulting composite material becomes stronger in strength, toughness, and heat resistance. , and the balance of physical properties such as chemical resistance is better.

When a thermal polymerization initiator is used as the polymerization initiator (E), the content of the thermal polymerization initiator in the resin composition is relative to the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer The total of 100 parts by mass of (B) is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, more preferably 0.5 to 5 parts by mass. When the content of the thermal polymerization initiator is 0.05 parts by mass or more, a resin composition with better curability can be obtained. When the content of the thermal polymerization initiator is 10 parts by mass or less, the composite material containing the resin composition has a better balance of physical properties such as strength, toughness, heat resistance, and chemical resistance.

When a thermal polymerization initiator is used as the polymerization initiator (E), the content of the thermal polymerization initiator in the resin composition is 0.05 to 10 parts by mass relative to 100 parts by mass of the total amount of the resin composition. Parts are preferred, preferably 0.1 to 8 parts by mass, more preferably 0.5 to 5 parts by mass. When the content of the thermal polymerization initiator is 0.05 parts by mass or more, a resin composition with better curability can be obtained. When the content of the thermal polymerization initiator is 10 parts by mass or less, the composite material containing the resin composition has a better balance of physical properties such as strength, toughness, heat resistance, and chemical resistance.

The photopolymerization initiator is not particularly limited as long as it can generate free radicals by light irradiation, for example, benzoin, benzoin methyl ether, benzoin ethyl ether and other benzoin and its alkyl ethers; benzene Ethanone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl) Acetophenones such as acetophenone; α-hydroxyalkylphenones such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one; Anthraquinones such as base anthraquinone, 2-pentyl anthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone and other thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone, 4-(1 -t-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4'-tetra(t-butyldioxycarbonyl)benzophenone and other benzophenones Class; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. Phylines; Acylphosphine oxides such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; Xanthones, etc. These can be used individually by 1 type or in combination of 2 or more types.

As the photopolymerization initiator, it is preferable to use an intramolecular cleavage type photopolymerization initiator that does not require a hydrogen donor from the viewpoint of reactivity. Also, from the viewpoint of generating active species by absorbing light with a wavelength of 315 to 460 nm, 2,2-dimethoxy-2-phenylacetophenone and benzene can more efficiently generate active species in the aforementioned wavelength range. Bis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone and 1-hydroxy cyclohexyl phenyl ketone are preferred.

The thermal polymerization initiator is not particularly limited, and known radical polymerization initiators can be used. Examples of the thermal polymerization initiator include organic peroxides, azo compounds, persulfates, redox compounds, and the like. Among these, organic peroxides are also preferred. Examples of organic peroxides include ketone peroxide, perbenzoate, hydrogen peroxide, diacyl peroxide, peroxyketal, hydrogen peroxide, diallyl peroxide, peroxide Oxygen esters and peroxydicarbonates, etc. More specifically, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl perbenzoate, 2-ethylhexane peroxy acid 1,1,3,3-tetramethyl butyl, dibenzoyl peroxide (also known as benzoyl peroxide), benzoyl m-methylbenzoyl peroxide, m-toluyl peroxide, diiso Propylbenzene peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, 1,1-bis(t-butyl peroxy)-3 ,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3,3-isopropyl perhydroxide, t- Butyl perhydroxide, dicumyl perhydroxide, acetyl peroxide, bis(4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isopropylperoxydicarbonate Butyl peroxide, 3,3,5-trimethylhexyl peroxide, lauryl peroxide, etc. These can be used individually by 1 type or in combination of 2 or more types.

Among them, from the viewpoint of ease of hardening control, availability, or ease of handling, bis(4-t-butylcyclohexyl)peroxydicarbonate, 2-ethylhexane peroxyacid 1, 1,3,3-tetramethylbutyl, dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluyl peroxide, methyl ethyl ketone peroxide Oxide, and t-butyl peroxybenzoate are preferred.

＜Other ingredients＞ The resin composition of this embodiment may contain, as other components, other resins, catalysts, thickening aids, polymerization inhibitors, thixotropic agents, hardening accelerators, hardening retarders, surfactants, interface modifiers, Wetting and dispersing agent, defoaming agent, leveling agent, coupling agent, light stabilizer, wax, flame retardant, plasticizer, filler, internal release agent, low shrinkage agent, toner, viscosity reducer, separation prevention Additives such as agents and compatibilizers. The content of the aforementioned additives is not particularly limited as long as it does not interfere with the effects of the present invention.

(other resins) The resin composition in this embodiment has a radically polymerizable unsaturated group in one molecule from the viewpoint of further controlling the thickening rate, and may contain other resins different from the aforementioned vinyl ester resin (A) . Examples of other resins include urethane (meth)acrylate resins, polyester (meth)acrylate resins, (meth)acrylate resins, and unsaturated polyester resins. These other resins may be used alone or in combination of two or more.

The said urethane (meth)acrylate resin means the polyurethane which has a (meth)acryloxy group. Specifically, after reacting polyisocyanate with polyhydroxy compounds or polyols, reacting unreacted isocyanate groups with hydroxyl-containing (meth)acrylic compounds and optionally hydroxyl-containing allyl ether compounds The obtained oligomer containing a radically polymerizable unsaturated group.

The aforementioned polyester (meth)acrylate resin is a polyester having a (meth)acryloxy group. Polyester (meth)acrylate resin can be obtained by the method of (1) or (2) shown below, for example. (1) A method of reacting a carboxyl-terminated polyester with an epoxy-containing (meth)acrylate or a hydroxyl-containing (meth)acrylate (2) Method of reacting hydroxyl-terminated polyester with (meth)acrylic acid or isocyanate group-containing (meth)acrylate The carboxyl-terminated polyester used as a raw material in the method (1) above includes one obtained from an excess amount of saturated polybasic acid and/or unsaturated polybasic acid and polyhydric alcohol. The hydroxyl-terminated polyester used as a raw material in the method (2) above includes one obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and an excess amount of polyhydric alcohol.

The aforementioned unsaturated polyester resin is an unsaturated dibasic acid, and a dibasic acid component optionally containing a saturated dibasic acid is obtained by esterification with a polyhydric alcohol.

As other resins, urethane (meth)acrylate resins, polyester (meth)acrylate resins, and (meth)acrylate resins are preferable from the viewpoint of further controlling the thickening rate. When the resin composition of this embodiment contains other resins, the content of the other resins in the resin composition is based on 100 mass of the total of vinyl ester resin (A) and ethylenically unsaturated group-containing monomer (B). In terms of parts, preferably 1 to 45 parts by mass, more preferably 5 to 40 parts by mass, more preferably 10 to 35 parts by mass.

(polymerization inhibitor) A polymerization inhibitor can be used to inhibit the polymerization reaction of the resin composition. Known ones can be used as the polymerization inhibitor, and examples thereof include hydroquinone, methylhydroquinone, phenothiazine, catechol, 4-t-butylcatechol, and the like. These may be used individually by 1 type, and may use 2 or more types together. When the resin composition of this embodiment contains a polymerization inhibitor, the content of the polymerization inhibitor in the resin composition is relative to the epoxy compound (a1-1), unsaturated monobasic acid (a1-2) and polybasic acid anhydride ( The total of 100 parts by mass of a1-3) is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, more preferably 0.03 to 3 parts by mass.

(thixotropic agent) The resin composition in this embodiment may contain a thixotropic agent as necessary. Thixotropic agents are used to adjust the mixing or fluidity of resin compositions. Examples of the thixotropic agent include organic thixotropic agents and inorganic thixotropic agents. These can be used individually by 1 type or in combination of 2 or more types. When the resin composition of the present embodiment contains a thixotropic agent, the content is 0.01 parts by mass relative to the total of 100 parts by mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). ~10 parts by mass is better, more preferably 0.1~5 parts by mass.

Examples of organic thixotropic agents include hydrogenated castor oil, amide-based, acidified polyethylene-based, vegetable oil polymerized oil-based, surfactant-based, and composite systems using these in combination. Specific examples thereof include "Flonon (registered trademark) SP-1000AF" (manufactured by Kyoeisha Chemical Co., Ltd.), "Disparon (registered trademark) 6900-20X" (Kusumoto Chemical Co., Ltd.), and the like. As an inorganic type thixotropic agent, the silica and bentonite etc. which were hydrophobically treated or hydrophilically treated are mentioned, for example. Specific examples of the hydrophobic inorganic thixotropic agent include "Leoroseal (registered trademark) PM-20L" (manufactured by Tokuyama Co., Ltd.), "AEROSIL (registered trademark) R-106" (Nippon Aerosil Co., Ltd.), "CAB-O-SIL (registered trademark)" (manufactured by Cabot Corporation) and the like. Specific examples of the hydrophilic inorganic thixotropic agent include "AEROSIL (registered trademark)-200" (manufactured by Nippon Aerosil Co., Ltd.). And when using hydrophilic fired silica, the combined use of thixotropic modifiers "BYK (registered trademark)-R605" and "BYK (registered trademark)-R606" (both manufactured by BYK Corporation) can effectively Moderately control the speed of viscosity increase.

(hardening accelerator) Hardening accelerators can be used to adjust the hardening speed. The hardening accelerator is not particularly limited. For example, known organometallic compounds such as organometallic salts, amine compounds, β-diketones, and the like can be used. These may be used alone or in combination of two or more. When the resin composition in this embodiment contains a hardening accelerator, the content is 100 parts by mass of the total of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). It is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, more preferably 0.1 to 3 parts by mass. When the content is within the above range, the adjustment of curability can be facilitated.

Examples of the organometallic compound include copper compounds such as copper naphthenate; cobalt compounds such as cobalt octylate, cobalt naphthenate, and cobalt hydroxide; zinc compounds such as zinc hexanoate; and manganese compounds such as manganese octylate. Examples of amine compounds include anilines, toluidines, benzaldehydes, triethanolamine, diethylenetriamine, pyridine, phenmorpholine, piperidine, 2,4,6-paraffin (dimethylamine methyl)phenol, N,N-dimethylbenzylamine, etc. Examples of β-diketones include acetylacetone, ethyl acetylacetate, α-acetyl-γ-butyrolactone, N-pyrazinoacetylacetamide, N,N-dimethylacetate Acetamide, etc.

The resin composition in this embodiment contains 20 to 80 mass parts of vinyl ester resin (A) with respect to the total of 100 mass parts of vinyl ester resin (A) and ethylenically unsaturated group-containing monomer (B). Parts, including 20-80 parts by mass of monomer (B) containing ethylenically unsaturated groups, containing 0.01-6 parts by mass of compound (C), containing at least one compound (D) selected from water and compounds containing hydroxyl groups 0.01 to 3 parts by mass is preferred.

The initial viscosity of the resin composition is preferably 0.1-3.0 Pa·s, more preferably 0.2-2.5 Pa·s, more preferably 0.5-2.0 Pa·s. When the initial viscosity is within the above range, a composite material in which the resin composition is efficiently and sufficiently impregnated into the fibrous base sheet (G) described later and has no resin-free parts (no resin-extracted parts) can be obtained.

From the manufacture of the resin composition to 2 days later, preferably 5 days later, the viscosity (after increasing the viscosity) is preferably 100~2,200Pa·s, preferably 200~2,000Pa·s, more preferably 400~1,800Pa·s, more preferably 500~1,500Pa·s. When the viscosity after thickening is within the above range, the resin composition becomes difficult to flow when applied as a composite material. That is, it is preferable to obtain that the resin composition and the fiber base sheet (G) will not be separated, and the resin composition will not be unevenly distributed in the fiber base sheet (G), and the resin composition and the fiber base A composite material excellent in the adhesiveness of the material sheet (G).

[Manufacturing method of resin composition] The so-called method for producing the resin composition in this embodiment means that a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), an oxide of a metal selected from the group 2 elements, and hydrogen A method for producing a resin composition of at least one compound (C) of an oxide and at least one compound (D) selected from water and a compound containing a hydroxyl group, comprising steps 1-3. And said vinyl ester resin (A) contains vinyl ester resin (A1) at least.

＜Step 1＞ The so-called step 1 in this embodiment means that the epoxy compound (a1-1), unsaturated monobasic acid (a1-2), and polybasic acid anhydride (a1-3) having 2 epoxy groups in 1 molecule are reacted to With respect to the total amount of 100 moles of the epoxy groups of the aforementioned epoxy compound (a1-1), the total amount of the acid groups from the aforementioned polybasic acid anhydride (a1-3) is 5 to 25 moles, and the resin precursor The step of object (P1). As step 1, for example, in a reaction vessel that can be heated and stirred, in the presence of an esterification catalyst, epoxy compound (a1-1), unsaturated monobasic acid (a1-2), and epoxy compound ( The epoxy group of a1-1) is 100 moles, and the polybasic acid anhydride (a1-3) is dissolved in a solvent or The reactive diluent is reacted at 70-150°C, preferably at 80-140°C, more preferably at 90-130°C for 1-8 hours to obtain the resin precursor (P1).

(catalyst) Examples of esterification catalysts include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, 2,4,6-paraffin (di Methylaminomethyl)phenol, and tertiary amines such as diazabicyclooctane, triphenylphosphine, and phosphorus compounds such as benzyltriphenylphosphonium chloride or diethylamine hydrochloride, triphenylphosphonium chloride, etc. Tolyl benzyl ammonium chloride, lithium chloride, etc. These may be used individually by 1 type, or may use 2 or more types together. Among these, phosphorus-based and ammonium-based catalysts are preferred, and ammonium-based catalysts are preferred, from the standpoint of slowing down the reaction rate to prevent gelation of the resin and enabling easy control of the molecular weight distribution.

The amount of catalyst used is from the point of view of promoting the reaction and inhibiting the viscosity of the resin precursor (P1), the epoxy compound (a1-1) is relatively ) to a total of 100 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, more preferably 0.1 to 3 parts by mass.

From the viewpoint of being able to mix epoxy compound (a1-1), unsaturated monobasic acid (a1-2), polybasic acid anhydride (a1-3), and polybasic acid anhydride (a1-4) easily and uniformly, if necessary Dilution with solvents and/or reactive diluents. As a solvent, as long as it is inert to the epoxy compound (a1-1), unsaturated monobasic acid (a1-2), polybasic acid anhydride (a1-3), and polybasic acid anhydride (a1-4) is inert. None Particularly limited, for example, known solvents such as methyl isobutyl ketone (MIBK) having a boiling point of 70 to 150° C. at 1 atmosphere can be used alone or in combination of two or more.

As a reactive diluent, an ethylenic non The monomer (B) of a saturated group is preferable. Although the mixing method is particularly limited, it can be performed by a known method.

In Step 1, a polymerization inhibitor may be added from the viewpoint of inhibiting the progress of the polymerization reaction of the resin precursor (P1). Polymerization inhibitors can also be applied to those described in the item of the above <Other Components>. When adding a polymerization inhibitor, the addition amount may be 0.0001, for example, with respect to a total of 100 parts by mass of the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3). ~10 parts by mass, preferably 0.001~1 part by mass.

＜Step 2＞ The so-called step 2 in this embodiment means the step of making the resin precursor (P1) and the polybasic acid anhydride (a1-4) undergo an addition reaction to obtain the vinyl ester resin (A1). As step 2, for example, in the reaction vessel of the synthetic resin precursor (P1), in the presence of a catalyst, add polybasic acid anhydride (a1-4), at 70~150°C, preferably at 80~140°C , more preferably at 90-130° C. for 30 minutes to 4 hours to react to obtain the vinyl ester resin (A1).

As the catalyst, it can be applicable to those described in the item of the above-mentioned <step 1> (catalyst), and can also continue to use the catalyst used in the synthesis of the resin precursor (P1) in step 1, and add polybasic acid anhydride ( In the case of a1-4), it is also possible to newly add the same thing or the different thing added in step 1. Also in step 2, similarly to step 1, a solvent and/or a reactive diluent, and a polymerization inhibitor may be added as necessary. The mixing method is also performed by a known method in the same manner as step 1.

In the following step 3, from the viewpoint of easily mixing the vinyl ester resin (A), the ethylenically unsaturated group-containing monomer (B) and the metal compound (C) uniformly to adjust the viscosity, it is also possible to adjust the viscosity by Dilute with vinyl ester resin (A1) solvent and/or reactive diluent. The viscosity of vinyl ester resin (A1) (adjusted by solvent and/or reactive diluent) is preferably 1~400Pa·s, more preferably 10~300Pa·s, more preferably 20~150Pa·s .

(Manufacture of vinyl ester resin (A2)) When the vinyl ester resin (A) contains the vinyl ester resin (A2), as the production method of the vinyl ester resin (A2), for example, in a reaction vessel that can be heated and stirred, in the esterification catalyst In the presence of epoxy compound (a2-1) and unsaturated monobasic acid (a2-2) may be dissolved in solvent or reactive diluent if necessary, at 70~150°C, preferably at 80~140°C, more preferably at 90°C The method of carrying out the reaction at ~130°C for 1~8 hours. As the catalyst, the same one as in step 1 can be used, and similarly to step 1, a solvent and/or a reactive diluent and a polymerization inhibitor may be added as necessary. The mixing method can also be performed by a known method in the same manner as in step 1.

＜Step 3＞ The so-called step 3 in this embodiment means that the vinyl ester resin (A) containing the vinyl ester resin (A1), the monomer (B) containing an ethylenically unsaturated group, and the metal selected from the group 2 elements are mixed. A step of obtaining a resin composition with at least one compound (C) of oxides and hydroxides, and at least one compound (D) selected from water and hydroxyl-containing compounds. In Step 3, in addition to vinyl ester resin (A), ethylenically unsaturated group-containing monomer (B), compound (C) and compound (D), polymerization initiator (E), Catalyst, and any other ingredients mentioned above. In Step 3, the order of mixing is not limited. For example, vinyl ester resin (A) is produced by using ethylenically unsaturated group-containing monomer (B) as a reactive diluent, and then additional ethylene-containing A method in which the monomer (B), the compound (C), the compound (D) of a sexually unsaturated group, and the aforementioned optional components are mixed together. From the viewpoint of easy viscosity control, it is preferable to add the compound (C) last. The mixing method is not particularly limited, and it can be performed using, for example, a dispersant, a planetary mixer, a kneader, or the like. The kneading temperature is preferably 10 to 40°C, more preferably 15 to 30°C, and more preferably 20 to 30°C from the viewpoint of ease of mixing.

[composite material] The composite material in this embodiment contains the said resin composition and a fibrous base material sheet (F). As a composite material, for example, it is preferable to impregnate a fiber base material with a resin composition and store (cure) it for a certain period of time to increase its viscosity. Such a composite material can obtain a hardened product (molded product) having good shape retention and excellent mechanical strength.

The composite material containing the resin composition and the fibrous base sheet (F) can be used in the construction of structures as materials such as preforms, prepregs, and lining materials for pipe repairs such as reinforcement or repair of existing pipes. Among these, it is also preferred to be used as lining materials and other materials. That is, the composite material is preferable for repairing pipes. When a composite material is used as a backing material, various known methods can be applied. Specifically, a cylindrical light-hardening composite material is directly pulled in as a lining material, and the lining material is reversed from the tip side, and pushed into the existing pipeline by pushing it into the existing pipeline, so that After the inner surface of the existing pipeline is adhered to the lining material by air pressure, etc., the inner surface of the lining material is irradiated with ultraviolet light or visible light by the mobile light irradiation device introduced into the lining material to harden the lining material, and then the existing pipeline can be repaired. Piping is reinforced and repaired.

The content of the resin composition in the composite material is preferably 20 to 95% by mass, more preferably 25 to 85% by mass, more preferably 25 to 75% by mass, relative to 100% by mass of the composite material. When the content of the resin composition is 20% by mass or more, the workability of the composite material can be improved. When the content of the resin composition is 95% by mass or less, the content of the fibrous base sheet (F) can be sufficiently secured, and sufficient strength as a cured product of the composite material can be easily obtained.

The content of the fiber base sheet (F) in the composite material is preferably 5 to 80% by mass, more preferably 15 to 75% by mass, more preferably 25 to 75% by mass relative to 100% by mass of the composite material %. When the content of the fibrous base material sheet (F) is 5% by mass or more, it is easy to obtain sufficient strength as a cured product of the composite material. When the content of the fibrous base material sheet (F) is 80% by mass or less, the content of the resin composition can be sufficiently ensured, and the workability of the composite material becomes better.

＜Fibrous Base Sheet (F)＞ Examples of the fibrous base sheet (F) include organic fibers such as amide, alanide, vinylon, polyester, and phenol, carbon fibers, glass fibers, and metals from the viewpoint of mechanical strength. So-called reinforcing fibers such as fibers and ceramic fibers, and such composite fibers. Among these, aramid fibers, carbon fibers, and glass fibers are also preferable, and glass fibers are more preferable from the viewpoints of strength, availability, and price. Especially in the case of photocuring the resin composition impregnated into the fiber substrate, glass fibers or polyester fibers having light transmission properties are preferable. The fibrous base sheet (F) may be used alone or in combination of two or more. For example, in the case of glass fibers, the diameter of the yarn used in general is preferably 1 to 15 μm, more preferably 3 to 10 μm.

As a form of a fibrous base material, a sheet, chopped strand, chopped, ground fiber, etc. are mentioned, for example. Examples of the sheet include those in which a plurality of reinforcing fibers are arranged in one direction, bidirectional fabrics such as plain weave or twill weave, multiaxial fabrics, non-crimped fabrics, nonwoven fabrics, mats, knits, weaves, reinforcing fibers, etc. Paper made from paper, etc. One type of fiber base material may be used alone, or two or more types may be used in combination, and it may be a single layer or may be laminated in plural layers. The thickness of the fibrous base sheet (F) is preferably 0.01 to 5mm in the case of a single layer from the viewpoint of the impregnation property of the resin composition, and in the case of laminating multiple layers, the total thickness is 1 ~20mm is preferred, more preferably 1~15mm. These fibrous base sheets (F) may contain a known size agent in a known content.

The mechanical strength required for hardened composite materials (fiber-reinforced plastic: FRP) varies depending on the purpose of use. For example, composite materials using glass fiber substrates are generally used as FRP The bending strength is preferably 100~1000MPa, more preferably 150~800MPa. Also, the flexural modulus of FRP is preferably 5 to 40 GPa, more preferably 7 to 35 GPa, more preferably 8 to 30 GPa. In addition, the values of the aforementioned flexural strength and flexural modulus are measured values based on JIS K7171:2016.

[Manufacturing method of composite material] As a method for producing a composite material, impregnating the fibrous base material sheet (F) with a resin composition, laminating a film on both sides of the fibrous base material sheet (F) impregnated with the resin composition, It is a method of curing and making the resin composition viscous until the resin composition reaches the target viscosity and is a constructable material. Such as storage temperature or target viscosity as recorded in the item of resin composition. As a storage method, a method of storing the sheet-shaped composite material by accordion folding or coiling is mentioned. [Example]

Hereinafter, the present invention will be described in more detail by examples and comparative examples, but the present invention is not limited to the following examples.

[Synthesis of vinyl ester resin] First, the vinyl ester resin to prepare the resin composition was synthesized by the following synthesis example and comparative synthesis example.

The details of the epoxy compound used in the synthesis of the vinyl ester resin in the following synthesis examples and comparative synthesis examples are as follows. ・Epoxy compound (1): bisphenol A type epoxy resin; "Epomic (registered trademark) R140P", epoxy equivalent 188 manufactured by Mitsui Chemicals Co., Ltd. ・Epoxy compound (2): bisphenol A epoxy resin; "jER (registered trademark) 834", epoxy equivalent 245 manufactured by Mitsubishi Chemical Corporation ・Epoxy compound (3): Phenol novolac type epoxy resin; "EPICLON (registered trademark) N-740", epoxy equivalent 172 manufactured by DIC Co., Ltd. In addition, epoxy equivalent is the value measured based on JISK7236:2001.

[Synthesis Example 1] In a 5 L separable flask with a stirrer, a reflux cooling pipe, a gas introduction pipe and a thermometer, 1260 g of epoxy compound (1) and 0.74 g of methylhydroquinone as a polymerization inhibitor (relatively 0.04 parts by mass based on a total of 100 parts by mass of epoxy compound (1), methacrylic acid described later, and maleic anhydride used as polybasic acid anhydride (a1-3) described later), tetradecane as an esterification catalyst Dimethylbenzyl-ammonium chloride (“Nissan Cationic (registered trademark) M ₂ -100R” (manufactured by NOF Corporation), purity exceeding 90% by mass) 5.6 g (relative to epoxy compound (1) , the methacrylic acid described later, and the total of 100 parts by mass of maleic anhydride used as the polybasic acid anhydride (a1-3) described below is 0.3 parts by mass), heated to 110°C, and the unsaturated monobasic acid (a1-2) 519g of methacrylic acid (relative to the total amount of 100 moles of epoxy groups in the epoxy compound (1), the acid group of methacrylic acid is 90 moles), and as the polybasic acid anhydride (a1-3) Maleic anhydride 66g (relative to the epoxy group total amount 100 moles of epoxy compound (1), the total amount of acid groups from maleic anhydride is 10 moles) after about 30 minutes and dropwise, carry out about 4 Hour reaction to synthesize the resin precursor (P1-1). Next, add maleic anhydride 263g (relative to the epoxy group total amount 100 moles of epoxy compound (a1-1), maleic anhydride is 40 moles) as polybasic acid anhydride (a1-4), carry out about After 2 hours of reaction, vinyl ester resin (A1-1) was obtained. Table 2 shows the compounding quantity of each component.

[Synthesis Examples 2~4, Comparative Synthesis Examples 1~8] In Synthesis Example 1, the synthesis was carried out in the same manner except that the raw materials and compounding ratios described in Table 2 were set. As a result, vinyl ester resins (A1-2) to (A1-4) were obtained in Synthesis Examples 2 to 4, and vinyl ester resins (A1'-1) to (A1') were obtained in Comparative Synthesis Examples 5 to 8. -4), in Comparative Synthesis Examples 1-4, the resin precursor was gelled and the synthesis operation could not be continued and vinyl ester resin could not be obtained.

[Determination and Evaluation of Resin Composition] For the vinyl ester resins (A1-1)~(A1-4) and (A1'-1)~(A1'-4) obtained in the above synthesis examples and comparative synthesis examples, the following items were measured and evaluated . The results of these measurement evaluations are summarized in Table 1 below.

＜Acid value＞ The acid value of vinyl ester resin is determined according to JIS K6901: 2008 "Partial acid value (indicator titration method)", which is intended to be compared with (A1-1)~(A1-4) and (A1'- 1) The mass of potassium hydroxide required to neutralize the acid components of (A1'-4), and obtain vinyl ester resins (A1-1)~(A1-4), and (A1'-1)~ Acid value of (A1'-4). Specifically, in order to make the content of the vinyl ester resin obtained in the above-mentioned synthesis examples and comparative synthesis examples 65% by mass, phenoxyethylmethyl methacrylate was used as the ethylenically unsaturated group-containing monomer (B). Acrylate (manufactured by Showa Denko Materials Co., Ltd.) was diluted to prepare a mixture, and the required mass of potassium hydroxide to neutralize the acid component contained in the mixture was measured. Then, convert the measured value into the original value to obtain the acid value of the vinyl ester resin. "Automatic buret UCB-2000" (manufactured by Hiranuma Sangyo Co., Ltd.) was used as the titration device, and a mixed indicator of bromothymol blue and phenol red was used as the indicator.

<Weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw/Mn> Mw and Mn were measured by GPC under the following measurement conditions, and Mw/Mn was computed from these measured values. (measurement conditions) ・Device: "showdex (registered trademark) GPC-101" (manufactured by Showa Denko Co., Ltd.) ・Column: "showdex (registered trademark) LF-804" (manufactured by Showa Denko Co., Ltd.) ・Detector: Differential refractometer "showdex (registered trademark) RI-71S" (manufactured by Showa Denko Co., Ltd.) ・Column temperature: 40°C ・Sample: 0.2% by mass tetrahydrofuran solution of vinyl ester resin ・Developing solvent: Tetrahydrofuran ・Flow rate: 1.0mL/min ・Sample injection volume: 20μL ・Standard sample: polystyrene

＜Viscosity＞ The viscosity of the mixture of 65% by mass of vinyl ester resin and 35% by mass of phenoxyethyl methacrylate obtained in the above synthesis example and comparative synthesis example was measured using an E-type viscometer "RE-85U" (Toki Sangyo Co., Ltd. Co., Ltd., cone-plate type, conical rotor 1°34'×R24, rotation speed: 50rpm~0.5rpm), measured at a temperature of 25°C. Corresponding to the measurement of viscosity, the number of revolutions of the conical rotor was set as shown in Table 1 below.

[Manufacture of resin composition] Details of the thixotropic agent used in the production of the resin composition in the following examples and comparative examples are as follows. ・Thixotropic agent (1): Organic thixotropic agent; "Flonon SP-1000AF", manufactured by Kyoeisha Chemical Co., Ltd. ・Thixotropic agent (2): Hydrophobic silica; "Leoroseal PM-20L", manufactured by Tokuyama Co., Ltd.

[Synthesis of vinyl ester resin (A2)] Vinyl ester resin (A2) used in the following examples and comparative examples was synthesized as shown below. Equipped with a 5 L separable flask with a stirrer, a reflux cooling tube, a gas inlet tube and a thermometer, 2068 g of epoxy compound (1) and 1.2 g of methyl hydroquinone as a polymerization inhibitor (relative to the epoxy compound, 0.04 parts by mass based on 100 parts by mass of methacrylic acid in total), and 2,4,6-ginseng(dimethylaminomethyl)phenol ("SequallTDMP", manufactured by Seiko Chemicals Co., Ltd.) as a catalyst The purity exceeds 95 mass %) 9.0g (0.3 mass parts with respect to a total of 100 mass parts of epoxy compounds and methacrylic acid), and heated to 110 degreeC. Then, 946 g of methacrylic acid as an unsaturated monobasic acid (acid group is 100 moles relative to the total amount of epoxy groups of epoxy compound (1) 100 moles) was dropped for about 30 minutes. After heating at 120° C. for about 3 hours and reacting, a resin composition was obtained. This reaction product was cooled to 90° C., and 1628 g of phenoxyethyl methacrylate was added as a reactive diluent (ethylenically unsaturated group-containing monomer (B)) to prepare a vinyl ester resin of 65 mass % (Based on the mass of the total ingredients) and 35% by mass of phenoxyethyl methacrylate is a vinyl ester resin (A2) of a mixture.

[Example 1] A mixture (1) of 25 parts by mass of vinyl ester resin (A1-1), 13.5 parts by mass of phenoxyethyl methacrylate as an ethylenically unsaturated group-containing monomer (B), and ethylene Mixture (2) of 25 parts by mass of base ester resin (A2) and 13.5 parts by mass of phenoxyethyl methacrylate as an ethylenically unsaturated group-containing monomer (B). 38.5 parts by mass of the aforementioned mixture (1), 38.5 parts by mass of the aforementioned mixture (2), 10 parts by mass of methyl benzyl methacrylate, 13 parts by mass of diethylene glycol dimethacrylate, 0.5 parts by mass of water, and thixotropic 1.7 parts by mass of agent (1), and 0.2 parts by mass of 2,2-dimethoxy-2-phenylacetophenone and phenylbis(2,4,6-trimethyl 0.2 parts by mass of benzoyl)phosphine oxide, and mixed at 2000-3000 rpm for 20 minutes using a dispersant (high-speed dispersant "homodispersant type 2.5" manufactured by Primix Co., Ltd.). Next, add 3 parts by mass of magnesium oxide (magmicron MD-4AM-2, the estimated content of magnesium oxide produced by Yukuni Color Co., Ltd.: 30% by mass) as compound (C), and use the above-mentioned dispersant at 2000~3000rpm for 1 minute Resin composition (X-1) was obtained after mixing to a certain degree.

[Examples 2-18, Comparative Examples 1-14] In Example 1, it was manufactured in the same manner except that it was set to the raw materials and compounding ratios listed in Tables 5 and 6, to obtain resin compositions (X-2)~(X-18), and (X'-1)~( X'-14).

[Determination and Evaluation of Resin Composition] For the resin compositions (X-1) to (X-18) and (X'-1) to (X'-14) obtained in the above-mentioned Examples and Comparative Examples, the following items were measured and evaluated. These measurement and evaluation results are summarized in Tables 5 and 6 below.

＜Viscosity＞ Immediately after production, 280 g of each resin composition was placed in a 300 mL poly container, and the initial viscosity was measured at a temperature of 25° C. with a B-type viscometer. Thereafter, the aforementioned poly container was placed in a closed state at a temperature of 25° C., and the viscosity was measured in the same manner after 2 days and 5 days. The B-type viscometer is used to suitably select any one of the following two types in order to match the measurement viscosity range. (1) "RB80 type viscometer", manufactured by Toki Sangyo Co., Ltd.; used with rotor No.3~4 to measure viscosity, the used rotor and the number of rotations are set as shown in Table 3 below.

(2)「HBDVE型黏度計」，英弘精機股份有限公司製；T棒錠T-A~T-D，轉動速度：1rpm 配合測定黏度，使用如下述表4所示T棒錠。

(2) "HBDVE type viscometer", manufactured by Hideo Seiki Co., Ltd.; T-bar ingots TA~TD, rotation speed: 1rpm to measure viscosity, using T-bar ingots as shown in Table 4 below.

＜Evaluation of Viscosity＞ According to the measurement results of the above viscosity, those whose initial viscosity is below 3Pa·s and the viscosity after 5 days are within the range of 100-2,200Pa·s are evaluated as those with good viscosity-increasing properties. In the column of the thickening property of Table 5 and Table 6, when the thickening property was good, it was evaluated as "◯", and in other cases, it was indicated with "×".

As shown in Table 5 and Table 6, in Examples 1 to 18, the viscosity (initial viscosity) of the resin composition after manufacture is low, and the viscosity will increase with time, and the viscosity after 5 days after the resin composition is manufactured When the viscosity is in an appropriate range, it is known that a resin composition that does not increase too much in viscosity can be obtained. On the other hand, in the resin compositions of Comparative Examples 1 to 5 that did not contain water in the resin composition, although the immediate viscosity (initial viscosity) of the resin composition after manufacture was low, the viscosity increasing rate was high, which was obtained from the resin composition. The viscosity of the composition was very large after 5 days from manufacture. In addition, it was found that in Comparative Examples 6-14 using vinyl ester resins whose Mw was less than 1,500 and whose Mw/Mn was less than 2.0, the initial viscosity was too high, or the rate of viscosity increase was low, and the viscosity after 5 days did not reach the appropriate range. resin composition.

[Manufacture of hardened resin composition] [Example 19] For the resin composition (X-1) produced in Example 1, a 250W metal halide lamp (absorption peak wavelength 420nm, illuminance 20mW/cm ² ), Irradiate with light for 60 minutes to obtain hardened product 1 (cast product) with a size of 170 mm×170 mm and a thickness of 4 mm. In addition, the above-mentioned illuminance was measured using an illuminance meter "IL1400A" (manufactured by International Optical Technology Co., Ltd., receiver type SEL005, measurement wavelength range: 380 to 450 nm, median value: 415 nm).

[Example 20] In Example 19, except that the resin composition described in Table 4 was added instead of the resin composition (X-1), a resin composition (Y-2) containing a photopolymerization initiator was obtained in the same manner, and a cured product was obtained. 2.

[Example 21] For fiberglass chopped strand mat (fiberglass chopped strand mat; "MC 450A", manufactured by Nitto Industries Co., Ltd.), the resin composition (X-1) produced in Example 1 was impregnated, and 3 layers were stacked. After curing for 5 days at 23°C, a 250W metal halide lamp (absorption peak wavelength 420nm, illuminance 25mW/cm ² ) was used to obtain a hardened product 3 with a thickness of 170mm×170mm and a thickness of 3.1mm (FRP: glass fiber content 31% by mass).

[Example 22] In Example 21, except that the resin composition (X-15) produced in Example 15 was used instead of the resin composition (X-1), a cured product 4 was obtained in the same manner.

[Measurement and evaluation of cured product of resin composition] For the cured products obtained in Examples 19 to 22 above, measurement and evaluation of the following items were performed. The results of these measurement evaluations are shown in Tables 7 and 8 below. As for the test piece for measurement and evaluation, each hardened product was cut into length 80mm, width 10mm, and then cured for 24 hours at a temperature of 25°C and a relative humidity of 50%.

＜Bending Strength＞ According to JIS K7171:2016, using a universal material testing machine ("TensilonUCT-1T", manufactured by Dongfang Technology Co., Ltd., the distance between the fulcrums is 48mm, and the test speed is 1.3mm/min), in an environment with a temperature of 23°C and a humidity of 50%. The measurement was performed on 5 test pieces for measurement and evaluation, and the average value was taken as the flexural strength of the cured product of the resin composition.

＜Bending modulus＞ According to JIS K7171:2016, using a universal material testing machine ("TensilonUCT-1T", manufactured by Dongfang Technology Co., Ltd., the distance between the fulcrums is 48mm, and the test speed is 1.3mm/min), in an environment with a temperature of 23°C and a humidity of 50%. The measurement was performed on 5 test pieces for measurement and evaluation, and the average value was taken as the flexural modulus of the cured product of the resin composition.

＜Load deflection temperature＞ For hardened products 1 and 2 (cast products) obtained in Examples 19 and 20, a load deflection temperature (HDT) measuring device ("HDT tester S-3M", Toyo Co., Ltd.) was used according to JIS K7191-1:2015 Seiki Seisakusho Co., Ltd.) was measured on 3 test pieces for measurement and evaluation, and the average value was taken as the load deflection temperature of the cured product of the resin composition.

＜Barcol Hardness＞ For hardened products 3 and 4 (FRP) obtained in Examples 21 and 22, a Barcol hardness tester ("GYZJ 934-1", manufactured by Barber Coleman Ltd.) was used in accordance with JIS K7060: 1995, and the test piece for measurement and evaluation was used. The measurement was performed on the back of the light-irradiated surface of 10 sheets, and the average value was taken as the Barcol hardness of the cured product.

From the measurement and evaluation results of the flexural strength, flexural modulus, load deflection temperature, and Barcol hardness of the cured product of the resin composition, it can be seen that the obtained cured product has sufficient mechanical strength. [industrial availability]

According to this embodiment, there is provided a resin composition whose initial viscosity is low and which can be increased over time. Also, a composite material is provided in which a fibrous base sheet is impregnated with the resin composition. This composite material has a resin composition capable of retaining its shape by thickening, and a cured product with good workability and excellent strength can be obtained. Therefore, it is suitable for the reinforcement or repair of fixed structures, and can be preferably used as prepreg, preform, lining material, lining material, etc.

Claims (19)

A resin composition comprising a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), at least one compound selected from oxides and hydroxides of metals belonging to group 2 elements ( C), and at least one compound (D) selected from water and hydroxyl-containing compounds, the aforementioned vinyl ester resin (A) contains vinyl ester resin (A1), the weight average molecular weight of the aforementioned vinyl ester resin (A1) (Mw) is 1,500 or more, and the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is 2.0 or more. The resin composition according to claim 1, wherein the weight average molecular weight (Mw) of the vinyl ester resin (A1) is 35,000 or less. The resin composition according to claim 1 or 2, wherein the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of the vinyl ester resin (A1) is 18 or less. The resin composition according to claim 1 or 2, wherein the acid value of the above-mentioned vinyl ester resin (A1) is 5KOHmg/g or more. The resin composition according to claim 1 or 2, wherein the acid value of the above-mentioned vinyl ester resin (A1) is 100KOHmg/g or less. The resin composition according to claim 1 or 2, wherein the aforementioned vinyl ester resin (A1) is an addition reaction product of the resin precursor (P1) and polybasic acid anhydride (a1-4), and the aforementioned resin precursor (P1) is , with respect to the total amount of epoxy groups of the aforementioned epoxy compound (a1-1) 100 moles, the epoxy compound (a1-1) having two epoxy groups in one molecule, the unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) react until the total amount of the acid group derived from the said polybasic acid anhydride (a1-3) becomes 5-25 mol and the reaction product obtained. The resin composition according to claim 6, wherein the epoxy compound (a1-1) is a bisphenol epoxy resin. The resin composition according to claim 6, wherein the unsaturated monobasic acid (a1-2) is at least one selected from (meth)acrylic acid and crotonic acid. The resin composition according to claim 6, wherein the polybasic acid anhydride (a1-3) is a dibasic acid anhydride. The resin composition according to claim 6, wherein the polybasic acid anhydride (a1-4) is a dibasic acid anhydride. The resin composition according to claim 6, wherein the vinyl ester resin (A) further contains a vinyl ester resin (A2), and the vinyl ester resin (A2) is a ring having two or more epoxy groups in one molecule. A reaction product of an oxygen compound (a2-1) and an unsaturated monobasic acid (a2-2). The resin composition according to claim 11, wherein the vinyl ester resin (A1) is 35 to 90 parts by mass relative to the total of 100 parts by mass of the vinyl ester resin (A1) and the vinyl ester resin (A2) parts, the aforementioned vinyl ester resin (A2) is 10 to 65 parts by mass. The resin composition according to claim 1 or 2, wherein the aforementioned compound (C) is magnesium oxide. The resin composition according to claim 1 or 2, further comprising a polymerization initiator (E). The resin composition according to claim 1 or 2, wherein the polymerization initiator (E) is a photopolymerization initiator. The resin composition according to claim 1 or 2, wherein said vinyl ester resin is contained with respect to a total of 100 parts by mass of said vinyl ester resin (A) and said ethylenically unsaturated group-containing monomer (B) (A) 20 to 80 parts by mass, containing 20 to 80 parts by mass of the aforementioned ethylenically unsaturated group-containing monomer (B), containing 0.01 to 6 parts by mass of the aforementioned compound (C), and containing 0.01 to 3 parts by mass of the aforementioned compound (D) parts by mass. A method for producing a resin composition comprising a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), and at least A method for producing a resin composition of a compound (C) and at least one compound (D) selected from water and hydroxyl-containing compounds, wherein the vinyl ester resin (A) contains a vinyl ester resin (A1 ), which is a method for producing a resin composition comprising the following steps 1 to 3; Step 1: react epoxy compound (a1-1), unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) with 2 epoxy groups in 1 molecule until, relative to the aforementioned epoxy The total amount of epoxy groups in compound (a1-1) is 100 moles, and the total amount of acid groups derived from polybasic acid anhydride (a1-3) is 5-25 moles to obtain the resin precursor (P1), Step 2: the step of obtaining the aforementioned vinyl ester resin (A1) after the aforementioned resin precursor (P1) and polybasic acid anhydride (a1-4) undergo an addition reaction, Step 3: a step of mixing the aforementioned vinyl ester resin (A), the aforementioned ethylenically unsaturated group-containing monomer (B), the aforementioned compound (C) and the aforementioned compound (D) to obtain a resin composition. A composite material, which contains the resin composition according to any one of claims 1 to 16 and a fibrous substrate sheet (F). Such as the composite material of claim 18, which is used for repairing pipes.