WO2023017852A1

WO2023017852A1 - Resin composition and material for lining material

Info

Publication number: WO2023017852A1
Application number: PCT/JP2022/030702
Authority: WO
Inventors: 健一小林; 尚人岡田; 直樹後藤; 和将丸茂
Original assignee: 昭和電工株式会社
Priority date: 2021-08-13
Filing date: 2022-08-12
Publication date: 2023-02-16
Also published as: JPWO2023017852A1; TW202319420A; DE112022003933T5; KR20240033014A

Abstract

A resin composition used for a lining material for pipe rehabilitation, the resin composition containing a resin (A), an ethylenic-unsaturated-group-containing monomer (B), a thickener (C), and a photopolymerization initiator (D), the resin composition having a viscosity at 25°C of 0.1-3 Pa∙s one hour after preparation, and the resin composition having a viscosity at 25°C of 400-3500 Pa∙s two days and/or five days after preparation.

Description

Resin composition and material for lining material

The present invention relates to resin compositions and materials for lining materials.

BACKGROUND ART In recent years, deterioration of existing underground pipes such as water supply pipes, sewage pipes, and power pipes has become serious, and various methods have been proposed for repairing them.
For example, in Patent Document 1, a tubular lining material is brought into close contact with the inner wall surface of an existing pipe buried in the ground, and while compressed air is supplied to the inside of the lining material, air is introduced into the lining material. A method for repairing an existing pipe is disclosed, which includes a curing step of curing the lining material by irradiating the inner surface of the lining material with light using a mobile light irradiation device. In addition, as a material for the lining material, an impregnated substrate made of fibers or the like impregnated with a photocurable resin composition can be used. It is described that a polymerizable resin dissolved in a solvent such as styrene can be used.

Japanese Patent Application Laid-Open No. 2020-82408

In recent years, there has been an increasing demand for thin and high-strength lining materials for repairing existing pipes. For this reason, the resin composition used as the material for the lining material preferably has a low viscosity so that the substrate can be easily impregnated with the resin composition. On the other hand, when the lining material is placed on the inner surface of the existing pipe and applied, it has a viscosity that allows it to be uniformly distributed in the impregnated base material and maintained so that the resin composition is not unevenly distributed. It is required that That is, when the resin composition is impregnated into the impregnated base material, the viscosity is low, but the viscosity increases with the passage of time, and when the existing pipe is repaired, the resin composition is kept in a state that can be maintained. A resin composition having a high viscosity is desirable. However, conventional lining materials have problems such as poor impregnation of the resin composition into the base material and uneven distribution of the resin composition during application because the viscosity of the resin composition in each process is not sufficiently controlled. Was.

The present invention has been made to solve the above problems, and provides a resin composition having a low viscosity one hour after the resin composition is prepared and having an appropriately controlled thickening rate. With the goal. Another object of the present invention is to provide a lining material containing the resin composition.

That is, the present invention provides the following means.
[1] A resin composition used for a lining material for pipe rehabilitation,
a resin (A);
an ethylenically unsaturated group-containing monomer (B);
a thickener (C);
containing a photopolymerization initiator (D),
The viscosity at 25 ° C. after 1 hour from the preparation of the resin composition is 0.1 to 3.0 Pa s,
A resin composition having a viscosity of 400 to 3,500 Pa·s at 25° C. at least one of 2 days and 5 days after preparation of the resin composition.
[2] With respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B),
35 to 90 parts by mass of the resin (A),
10 to 65 parts by mass of the ethylenically unsaturated group-containing monomer (B),
0.01 to 6 parts by mass of the thickener (C),
The resin composition according to [1] above, containing 0.01 to 10 parts by mass of the photopolymerization initiator (D).
[3] With respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B),
20 to 80 parts by mass of the resin (A),
20 to 80 parts by mass of the ethylenically unsaturated group-containing monomer (B),
0.01 to 6 parts by mass of the thickener (C),
The resin composition according to [1] above, containing 0.01 to 10 parts by mass of the photopolymerization initiator (D).
[4] The resin (A) according to any one of [1] to [3] above, wherein the resin (A) contains at least one selected from a vinyl ester resin (A1) and an unsaturated polyester resin (A2). Resin composition.
[5] The vinyl ester resin (A1) includes 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) is an addition reaction product of the resin precursor (P2), which is the reaction product of 3), and the polybasic acid anhydride (a1-4),
The total amount of acid groups capable of reacting with epoxy groups derived from the polybasic acid anhydride (a1-3) is 5 to 25 mols per 100 mols of the total amount of epoxy groups in the epoxy compound (a1-1). , the resin composition according to the above [4].
[6] The vinyl ester resin (A1) is a resin precursor (P3) which is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5) and the resin composition according to [4] above, which is a reaction product of the unsaturated monobasic acid (a1-2).
[7] A resin precursor (P3) in which the vinyl ester resin (A1) is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5) , and the reaction product of the resin precursor (P4), which is the reaction product of the unsaturated monobasic acid (a1-2), and the unsaturated polybasic acid (a1-6), described in [4] above. of the resin composition.
[8] The unsaturated polyester resin (A2) is a reaction product of a diol (a2-1) and a dibasic acid (a2-2),
The diol (a2-1) contains 43 to 85 mol% of the diol (a2-1-1), which is an alkanediol having a molecular weight of 90 to 500, relative to 100 mol% of the diol (a2-1),
The dibasic acid (a2-2) includes an ethylenically unsaturated group-containing dibasic acid (a2-2-1) and an ethylenically unsaturated group-free dibasic acid (a2-2-2), the above [ 4].
[9] The resin composition according to any one of [4] to [7], wherein the vinyl ester resin (A1) has a hydroxyl value of 10 to 120 KOHmg/g.
[10] The resin according to any one of [1] to [9] above, wherein the thickener (C) is at least one selected from oxides and hydroxides of Group 2 elements. Composition.
[11] The resin according to any one of [1] to [10] above, wherein the resin composition further contains a compound (E) that is at least one selected from water and a hydroxy group-containing compound. Composition.
[12] The resin composition according to [1] or [2] above, which further contains a thixotropic agent.
[13] A lining material comprising the resin composition according to any one of [1] to [12] above and a fiber base material (F).

According to the present invention, it is possible to provide a resin composition that has a low viscosity one hour after the preparation of the resin composition and that has a moderately controlled thickening rate. Also, a material for a lining material containing the resin composition can be provided.

First, definitions and meanings of terms and notations used in this specification are shown below.
"(Meth)acrylic acid" is a generic term for acrylic acid and methacrylic acid. Similarly, "(meth)acrylate" is a generic term for acrylate and methacrylate, and "(meth)acryloyl" is a generic term for acryloyl and methacryloyl.
The "acid value" of resin (A) is the number of mg of potassium hydroxide required to neutralize 1 g of resin (A), measured by a method conforming to JIS K6901:2008. Specifically, it is measured by the method described in Examples below.
The "hydroxyl value" of resin (A) is mg of potassium hydroxide required to neutralize acetic acid generated by acetylation of 1 g of resin (A), measured by a method conforming to JIS K6901:2008. is a number. Specifically, it is measured by the method described in Examples below.
"Weight average molecular weight Mw" (hereinafter also simply referred to as "Mw") and "Number average molecular weight Mn" (hereinafter also simply referred to as "Mn") are obtained by gel permeation chromatography (GPC) measurement. It is the standard polystyrene equivalent molecular weight that is used. Specifically, it is measured by the method described in Examples below.
The "viscosity" of the resin (A) is a value obtained by measuring a mixture of the resin (A) and the ethylenically unsaturated group-containing monomer (B) using an E-type viscometer at a temperature of 25°C. is. Specifically, it is measured by the method described in Examples below.
The “viscosity” of the resin composition is a value measured at a temperature of 25° C. using a Brookfield viscometer. Specifically, it is measured by the method described in Examples below.
The term "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 the present embodiment is a resin composition used for a lining material for pipe rehabilitation, comprising a resin (A), an ethylenically unsaturated group-containing monomer (B), a thickener (C), and a photopolymerization initiator (D). Then, the viscosity at 25 ° C. 1 hour after preparing the resin composition is 0.1 to 3 Pa s, and at least one of 2 days and 5 days after preparing the resin composition. It has a viscosity of 400 to 3500 Pa·s at 25°C.
Here, the viscosity at 25 ° C. one hour after preparing the resin composition is the resin composition one hour after the resin composition is produced by mixing all the components constituting the resin composition. refers to the viscosity at 25°C. Further, the viscosity at 25 ° C. at least one of 2 days after preparing the resin composition and 5 days after preparing the resin composition, the resin (A), the ethylenically unsaturated group-containing monomer (B), and the thickener It refers to the viscosity at 25° C. at least one of 2 days and 5 days after mixing all of (C) and photopolymerization initiator (D), that is, after producing a resin composition containing all of the above components.
The resin composition has an appropriately controlled thickening rate.

The resin composition used for the lining material for pipe rehabilitation is required to have a low viscosity so as to facilitate impregnation when the fiber base material (F) described later is impregnated with the resin composition. On the other hand, when performing pipe rehabilitation, the resin composition contained in the lining material should have a viscosity that allows it to be uniformly distributed in the fiber base material (F) without being unevenly distributed. is required.
The resin composition of the present embodiment has a viscosity of 0.1 to 3.0 Pa s at 25 ° C. after 1 hour from the preparation of the resin composition, so that the resin can be The composition can efficiently and sufficiently impregnate the fiber base material (F). In addition, when the resin composition has a viscosity of 400 to 3,500 Pa s at least one of 2 days and 5 days after the preparation of the resin composition at 25 ° C., when the pipe is rehabilitated, the fiber base material in the lining material The flow of the resin composition impregnated with (F) is suppressed, the resin composition is not unevenly distributed, and the lining material has excellent shape retention. In addition, when the viscosity at 25°C of at least one of two days and five days after preparation of the resin composition is within the above range, the lining material is imparted with appropriate flexibility, and during pipe rehabilitation. Ease of construction is improved. The use of such a lining material makes it possible to suitably repair pipes.

From the viewpoint of more efficient and sufficient impregnation with the resin composition, the viscosity of the resin composition after one hour has passed is preferably 0.2 to 2.8 Pa·s, more preferably 0.3 to 2.0 Pa·s. 5 Pa·s, more preferably 0.4 to 2.3 Pa·s.
From the viewpoint of obtaining a flexible lining material with excellent shape retention, the viscosity of at least one of the resin composition after 2 days and 5 days after preparation is preferably 400 to 3,500 Pa·. s, more preferably 450 to 2,500 Pa·s, still more preferably 500 to 2,000 Pa·s.

<Resin (A)>
The resin (A) is not particularly limited, but preferably has an ethylenically unsaturated group. Examples of the resin (A) include vinyl ester resin (A1), unsaturated polyester resin (A2), urethane (meth)acrylate resin (A3), polyester (meth)acrylate resin (A4), (meth)acrylate resin ( A5) and the like. The resin (A) contains at least one selected from the vinyl ester resin (A1) and the unsaturated polyester resin (A2) from the viewpoint of moderately controlling the viscosity increase rate and the ease of pipe rehabilitation work. is preferred. These resins may be used singly or in combination of two or more.

[Vinyl ester resin (A1)]
The vinyl ester resin (A1) is not particularly limited as long as it has an ethylenically unsaturated group, and examples thereof include the following (A1-1) to (A1-5).
· Vinyl ester resin (A1-1): reaction product of epoxy compound (a1-1) having two epoxy groups in one molecule and unsaturated monobasic acid (a1-2) · Vinyl ester resin (A1- 2): A resin precursor (P1) which is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule and an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride Addition reaction product with product (a1-4) Vinyl ester resin (A1-3): epoxy compound (a1-1) having two epoxy groups in one molecule, unsaturated monobasic acid (a1-2 ), and the resin precursor (P2), which is the reaction product of the polybasic acid anhydride (a1-3), and the addition reaction product of the polybasic acid anhydride (a1-4), the vinyl ester resin (A1- 4): A resin precursor (P3) which is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5), and an unsaturated monobasic acid (a1 -2) Reaction product with vinyl ester resin (A1-5): Resin precursor (P4) which is a reaction product with resin precursor (P3) and unsaturated monobasic acid (a1-2), A reaction product with an unsaturated polybasic acid (a1-6), the resin precursor (P3) includes an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound ( a1-5) reaction product

The hydroxyl value of the vinyl ester resin (A1) is preferably 10 mg KOH/g or more, more preferably 15 mg KOH/g or more, and still more preferably 20 mg KOH/g or more, from the viewpoint of controlling the thickening rate of the resin composition. Also, from the viewpoint of efficiently thickening the resin composition, it is preferably 120 mg KOH/g or less, more preferably 110 mg KOH/g or less, and even more preferably 100 mg KOH/g or less.
These resins may be used singly or in combination of two or more.

[Vinyl ester resin (A1-1)]
The vinyl ester resin (A1-1) is a reaction product of an epoxy compound (a1-1) having two or more epoxy groups in one molecule and an unsaturated monobasic acid (a1-2).
The vinyl ester resin (A1-1) thickens the resin composition due to the interaction between the hydroxy group formed by the ring-opening of the epoxy group of the epoxy compound (a1-1) and the thickener (C).
When the resin composition contains the vinyl ester resin (A1-1), it becomes easier to control the thickening speed of the resin composition and to adjust the physical properties of the cured product of the resin composition.

The weight-average molecular weight Mw of the vinyl ester resin (A1-1) is preferably 400 or more, more preferably 600 or more, and still more preferably 800 or more, from the viewpoint of more efficient thickening. is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 1,200 or less, from the viewpoint of controlling the

The number average molecular weight Mn of the vinyl ester resin (A1-1) is preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more, from the viewpoint of efficiently thickening the resin composition. From the viewpoint of controlling the thickening speed, it is preferably 1,500 or less, more preferably 1,200 or less, and still more preferably 1,000 or less.

The Mw/Mn of the vinyl ester resin (A1-1) is preferably 1.05 or more, more preferably 1.1 or more, from the viewpoint of ease of control of the synthesis conditions. is preferably 2.0 or less, more preferably 1.7 or less, and still more preferably 1.5 or less from the viewpoint of controlling the thickening rate.
Mw/Mn is an index of molecular weight distribution, and when it is 1, it indicates a monodisperse polymer, and the larger this ratio, the wider the molecular weight distribution.

In the vinyl ester resin (A1-1), the amount of the unsaturated monobasic acid (a1-2) is the unsaturated monobasic acid (a1- The total amount of acid groups in 2) is preferably 80 mol or more, more preferably 90 mol or more, still more preferably 99 mol or more, preferably 120 mol or less, more preferably 110 mol or less, More preferably, it is 105 mol or less.
If the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 80 mol or more with respect to the total amount of epoxy groups of 100 mol of the epoxy compound (a1-1), vinyl ester resin (A1-1) Since a sufficient amount of ethylenically unsaturated groups are introduced in , the resin composition tends to exhibit good curability. In addition, from the viewpoint of controlling the viscosity increase rate and at least one of the viscosity after 2 days and 5 days after preparing the resin composition, and from the viewpoint of production stability, the vinyl ester resin (A1-1) is not used. It is preferable that the reaction epoxy group does not remain, and the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 100 mol with respect to the total amount of 100 mol of the epoxy group of the epoxy compound (a1-1). Preferably.

[Vinyl ester resin (A1-2)]
The vinyl ester resin (A1-2) is a resin precursor (P1 ) to which polybasic acid anhydride (a1-4) is further added.
When the resin composition contains the vinyl ester resin (A1-2), it becomes easier to control the thickening speed of the resin composition. In addition, it becomes easier to control the viscosity and the physical properties of the cured product after one hour from the preparation of the resin composition.

The vinyl ester resin (A1-2) is a vinyl ester resin (A1 Compared to -1), the total amount of hydroxy groups is reduced, and the viscosity is reduced 1 hour after the resin composition is prepared. As a result, as compared with the vinyl ester resin (A1-1), the impregnating property into the fiber base material (F), which will be described later, is better.
In addition, since the vinyl ester resin (A1-2) has a carboxyl group introduced by the addition of the polybasic acid anhydride (a1-4), compared to the vinyl ester resin (A1-1), the thickener (C) The interaction with is improved, and the thickening speed of the resin composition is improved.
In addition, since the vinyl ester resin (A1-2) has a wider molecular weight distribution and a higher molecular weight than the vinyl ester resin (A1-1), after 2 days and 5 days from the preparation of the resin composition At least one of the viscosity tends to be high.

The weight average molecular weight of the vinyl ester resin (A1-2) is preferably 800 or more, more preferably 900 or more, and still more preferably 1,000 or more, from the viewpoint of more efficiently thickening the resin composition. It is preferably 2,000 or less, more preferably 1,800 or less, and still more preferably 1,600 or less, from the viewpoint of controlling the viscosity and the thickening rate one hour after the composition is prepared.

The number average molecular weight (Mn) of the vinyl ester resin (A1-2) is preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more, from the viewpoint of efficiently thickening the resin composition. It is preferably 1,300 or less, more preferably 1,200 or less, and still more preferably 1,100 or less, from the viewpoint of controlling the viscosity and the thickening rate one hour after the composition is prepared.

Mw/Mn of the vinyl ester resin (A1-2) is preferably 0.6 or more, more preferably 1.0 or more, and still more preferably 1.2 or more, from the viewpoint of ease of control of the synthesis conditions. , preferably 5.0 or less, more preferably 3.0 or less, from the viewpoint of suppressing variations in the physical properties of the resin composition and controlling the viscosity and the thickening rate after 1 hour from the preparation of the resin composition, More preferably, it is 2.0 or less.

In the vinyl ester resin (A1-2), the amount of the unsaturated monobasic acid (a1-2) is the unsaturated monobasic acid (a1- The total amount of acid groups in 2) is preferably 80 mol or more, more preferably 90 mol or more, still more preferably 99 mol or more, preferably 120 mol or less, more preferably 110 mol or less, More preferably, it is 105 mol or less.
If the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 80 mol or more with respect to the total amount of epoxy groups of 100 mol of the epoxy compound (a1-1), vinyl ester resin (A1-2) Since a sufficient amount of ethylenically unsaturated groups are introduced in , the resin composition tends to exhibit good curability. In addition, from the viewpoint of controlling the viscosity increase rate and at least one of the viscosity after 2 days and 5 days after preparing the resin composition, and from the viewpoint of production stability, the vinyl ester resin (A1-2) is not used. It is preferable that no reaction epoxy groups remain, and the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 100 mol with respect to the total amount of 100 mol of the epoxy groups of the epoxy compound (a1-1). Preferably.

In the vinyl ester resin (A1-2), the polybasic acid anhydride (a1-4) is the polybasic acid anhydride (a1-4) with respect to the total amount of 100 mol of the epoxy groups of the epoxy compound (a1-1). However, the amount is preferably 3 to 60 mol, more preferably 5 to 50 mol, still more preferably 7 to 45 mol.
The amount of the polybasic acid anhydride (a1-4) is 3 mol or more with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), the amount necessary for increasing the thickening rate of the resin composition. is sufficiently introduced into the vinyl ester resin (A1-2), and the hydroxy groups generated by the ring-opening of the epoxy groups derived from the epoxy compound (a1-1) form the polybasic acid anhydride (a1- It is consumed by the addition of 4), and it is possible to suppress the increase in viscosity one hour after the resin composition is prepared. Further, when the amount of the polybasic acid anhydride (a1-4) is 60 mol or less, it becomes easy to control the thickening speed of the resin composition.

[Vinyl ester resin (A1-3)]
The vinyl ester resin (A1-3) of the present embodiment includes an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride. It is an addition reaction product between the resin precursor (P2), which is the reaction product of (a1-3), and the polybasic acid anhydride (a1-4).
By including the vinyl ester resin (A1-3) in the resin composition, it is possible to suppress an increase in viscosity one hour after the preparation of the resin composition. In addition, it is possible to improve the viscosity increasing rate and increase the viscosity at least either two days or five days after preparation of the resin composition.

The vinyl ester resin (A1-3) is obtained by reacting the epoxy group of the epoxy compound (a1-1) with the carboxyl group of the unsaturated monobasic acid (a1-2) to form the epoxy group of the epoxy compound (a1-1). is ring-opened to generate a hydroxy group, polybasic acid anhydride (a1-3) is ring-opening addition to the hydroxy group, and polybasic acid anhydride (a1-3) is generated by ring-opening addition The resulting carboxyl group further reacts with the unreacted epoxy group of the epoxy compound (a1-1) to crosslink and polymerize. Therefore, the vinyl ester resin (A1-3) has a higher molecular weight and a wider molecular weight distribution than the vinyl ester resins (A1-1) and (A1-2). Therefore, the speed of thickening is improved, and the viscosity of the resin composition tends to be high at least either two days or five days after preparation.
Further, since the polybasic acid anhydrides (a1-3) and (a1-4) are added to the hydroxy groups formed by ring-opening of the epoxy group of the epoxy compound (a1-1), the vinyl ester resin (A1-1 ) and (A1-2), the total amount of hydroxy groups is reduced, and the viscosity after 1 hour from the preparation of the resin composition is reduced. Therefore, the impregnating properties into the fiber base material (F), which will be described later, are improved.
In addition, the addition of polybasic acid anhydrides (a1-3) and (a1-4) introduces a carboxyl group, so compared to the vinyl ester resins (A1-1) and (A1-2), the thickener The interaction with (C) is further improved, and the thickening speed of the resin composition is further improved.

The weight-average molecular weight Mw of the vinyl ester resin (A1-3) is preferably 1,500 or more, more preferably 2,000 or more, still more preferably 4,000 or more, from the viewpoint of more efficient thickening. It is preferably 6,000 or more, preferably 35,000 or less, more preferably 25,000 or less, from the viewpoint of suppressing an increase in viscosity one hour after the resin composition is prepared and controlling the thickening speed. More preferably, it is 15,000 or less. In particular, when the viscosity of the resin composition two days after preparation is 400 to 3,500 Pa s, the vinyl ester resin (A1-3) preferably has a high molecular weight, preferably 5,000 or more. , more preferably 7,000 or more, and still more preferably 9,000 or more.

The number average molecular weight Mn of the vinyl ester resin (A1-3) is preferably 500 or more, more preferably 700 or more, and still more preferably 900 or more, from the viewpoint of efficiently thickening the resin composition. From the viewpoint of suppressing the increase in viscosity one hour after preparation and controlling the thickening speed, it is preferably 2,500 or less, more preferably 1,800 or less, and still more preferably 1,600 or less. In particular, when the viscosity of the resin composition two days after preparation is 400 to 3,500 Pa s, the vinyl ester resin (A1-3) preferably has a high molecular weight, preferably 900 or more, and more It is preferably 1,000 or more, more preferably 1,200 or more.

Mw/Mn of the vinyl ester resin (A1-3) is preferably 2.5 or more, more preferably 3.0 or more, and still more preferably 4.0 or more from the viewpoint of easy control of the synthesis conditions, and the resin composition From the viewpoint of suppressing variation in physical properties of the product, suppressing an increase in viscosity one hour after the preparation of the resin composition, and controlling the thickening speed, it is preferably 18 or less, more preferably 12 or less, and still more preferably 10. It is below. In particular, when the viscosity of the resin composition two days after preparation is 400 to 3,500 Pa s, it is preferably 4.0 or more, more preferably 5.0 or more, and still more preferably 6.0 or more. be.

In the vinyl ester resin (A1-3), first, an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2) and a polybasic acid anhydride (a1 A resin precursor (P2), which is the reaction product of -3), is obtained.
In the resin precursor (P2), the amount of the unsaturated monobasic acid (a1-2) is the unsaturated monobasic acid (a1-2) with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1). The total amount of acid groups in is preferably 75 to 95 mol, more preferably 77 to 93 mol, and still more preferably 79 to 91 mol.
If the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 75 mol or more with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), vinyl ester resin (A1-3) Since a sufficient amount of ethylenically unsaturated groups are introduced in , the resin composition tends to exhibit good curability. Further, when the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 95 mol or less, the reaction product of the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) The basic acid anhydride (a1-3) is sufficiently crosslinked to easily obtain a resin composition having good thickening properties.

In the resin precursor (P2), the amount of the polybasic acid anhydride (a1-3) is 100 moles of the total epoxy group of the epoxy compound (a1-1). The total amount of derived acid groups is preferably 5 to 25 mol, more preferably 7 to 23 mol, still more preferably 9 to 21 mol.
The total amount of acid groups capable of reacting with epoxy groups derived from the polybasic acid anhydride (a1-3) is 5 mol or more with respect to 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1), Crosslinking of the epoxy compound (a1-1) and the polybasic acid anhydride (a1-3) increases the molecular weight of the vinyl ester resin (A1), and can effectively thicken the resin composition. Further, when the total amount of acid groups capable of reacting with epoxy groups derived from the polybasic acid anhydride (a1-3) is 25 mol or less, the degree of crosslinking of the epoxy compound (a1-1) can be easily controlled. , the gelling during the synthesis of the vinyl ester resin (A1-3) is suppressed, and the thickening rate of the resin composition can be easily controlled.

In the resin precursor (P2), an acid group derived from the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) (the "acid group" referred to here is the polybasic acid anhydride (a1 -3) is an acid group generated by hydrolysis.For example, when the polybasic acid anhydride (a1-3) is a dibasic acid anhydride, the number of acid groups generated from one molecule is 2.) is preferably 105 to 125 mol, more preferably 107 to 123 mol, still more preferably 109 to 121 mol, per 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1). be.
The total amount of acid groups derived from the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) is 105 mol per 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1). By doing so, the amount of unreacted epoxy groups in the epoxy compound (a1-1) is reduced, making it easier to control the thickening speed of the resin composition. Further, the total amount of acid groups derived from the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) is 125 mol or less, so that the gel during synthesis of the vinyl ester resin (A1-3) conversion is suppressed, and the residual unreacted unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) in the vinyl ester resin (A1-3) is suppressed, and the resin composition It is possible to suppress the influence on the thickening speed.

In the vinyl ester resin (A1-3), by reacting the polybasic acid anhydride (a1-4) with the resin precursor (P2), a reaction mechanism similar to that of the polybasic acid anhydride (a1-3) and plays a role of cross-linking the epoxy compound (a1-1) or introducing a carboxyl group into the resin precursor (P2). That is, the polybasic acid anhydride (a1-4) is added to the hydroxy group produced by the ring-opening of the epoxy group of the epoxy compound (a1-1) and produces a carboxy group. This carboxy group reacts with the unreacted epoxy group of the epoxy compound (a1-1) to proceed with crosslinking, and after all the epoxy groups have reacted, the carboxy group derived from the polybasic acid anhydride (a1-4) is A carboxy group is introduced into the vinyl ester resin (A1-3) while remaining as it is.

The polybasic acid anhydride (a1-4) is preferably 3 to 60 mol per 100 mol of the total epoxy group of the epoxy compound (a1-1). more preferably 5 to 50 mol, still more preferably 7 to 45 mol.
If the polybasic acid anhydride (a1-4) is 3 mol or more with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), the amount necessary for increasing the viscosity thickening rate of the resin composition. The carboxy group of is introduced into the vinyl ester resin (A1-3), and the hydroxy group generated by ring-opening the epoxy group derived from the epoxy compound (a1-1) is the polybasic acid anhydride (a1-4) is consumed by the addition of , and it is possible to suppress the increase in viscosity one hour after the preparation of the resin composition. Further, when the amount of the polybasic acid anhydride (a1-4) is 60 mol or less, it becomes easy to control the thickening speed of the resin composition.

(Vinyl ester resin (A1-4))
The vinyl ester resin (A1-4) of the present embodiment is a resin precursor (a resin precursor ( P3) and the reaction product of unsaturated monobasic acid (a1-2).
By including the vinyl ester resin (A1-4) in the resin composition, it becomes easier to control the thickening speed of the resin composition and to adjust the physical properties of the cured product of the resin composition.

In the vinyl ester resin (A1-4), the resin composition thickens due to the interaction between the hydroxy group generated by the ring-opening of the epoxy group of the epoxy compound (a1-1) and the thickener (C).

The weight-average molecular weight Mw of the vinyl ester resin (A1-4) is preferably 500 or more, more preferably 600 or more, and still more preferably 800 or more, from the viewpoint of more efficient thickening. is preferably 6,000 or less, more preferably 5,000 or less, and still more preferably 4,500 or less, from the viewpoint of controlling the

The number average molecular weight Mn of the vinyl ester resin (A1-4) is preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more, from the viewpoint of efficiently thickening the resin composition. From the viewpoint of controlling the thickening speed, it is preferably 2,500 or less, more preferably 2,200 or less, and still more preferably 2,000 or less.

Mw/Mn of the vinyl ester resin (A1-4) is preferably 1.05 or more, more preferably 1.1 or more, and still more preferably 1.3 or more, from the viewpoint of ease of control of synthesis conditions. From the viewpoint of suppressing variations in physical properties of the resin composition and controlling the thickening speed, it is preferably 3.0 or less, more preferably 2.5 or less, and still more preferably 2.3 or less.
Mw/Mn is an index of molecular weight distribution, and when it is 1, it indicates a monodisperse polymer, and the larger this ratio, the wider the molecular weight distribution.

In the vinyl ester resin (A1-4), the amount of the bisphenol compound (a1-5) is the total amount of hydroxyl groups of the bisphenol compound (a1-5) with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1). is preferably 10 mol or more, more preferably 20 mol or more, still more preferably 25 mol or more, preferably 70 mol or less, more preferably 60 mol or less, further preferably 50 mol or less. be.

If the total amount of hydroxyl groups in the bisphenol compound (a1-5) is 10 mol or more with respect to the total amount of 100 mol of epoxy groups in the epoxy compound (a1-1), the molecular weight distribution of the vinyl ester resin (A1) is widened. , it becomes easier to control the ultimate viscosity of the resin composition. Further, when the total amount of the bisphenol compound (a1-5) is 70 mol or less per 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), it becomes easy to control the thickening speed of the resin composition.

In the vinyl ester resin (A1-4), the amount of the unsaturated monobasic acid (a1-2) is the unsaturated monobasic acid (a1- The total amount of acid groups in 2) is preferably 30 mol or more, more preferably 40 mol or more, still more preferably 50 mol or more, preferably 120 mol or less, more preferably 100 mol or less, More preferably, it is 80 mol or less.

If the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 30 mol or more with respect to the total amount of epoxy groups of 100 mol of the epoxy compound (a1-1), vinyl ester resin (A1-4) Since a sufficient amount of ethylenically unsaturated groups are introduced in , the resin composition tends to exhibit good curability. In addition, from the viewpoint of controlling the thickening rate, suppressing uneven distribution of the resin composition after curing, and from the viewpoint of production stability, the unsaturated The total amount of acid groups in the monobasic acid (a1-2) is preferably 120 mol or less.

(Vinyl ester resin (A1-5))
The vinyl ester resin (A1-5) is a resin precursor (P3) and a resin precursor (P4) which is a reaction product of an unsaturated monobasic acid (a1-2), and an unsaturated polybasic acid (a1- 6), wherein the resin precursor (P3) is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5) is.

In the vinyl ester resin (A1-5), the resin composition thickens due to the interaction between the compound (C) and the hydroxy group generated by ring-opening of the epoxy group of the epoxy compound (a1-1).
When the resin composition contains the vinyl ester resin (A1-5), it becomes easier to control the thickening speed of the resin composition and to adjust the physical properties of the cured product of the resin composition.

The weight-average molecular weight Mw of the vinyl ester resin (A1-5) is preferably 500 or more, more preferably 600 or more, and still more preferably 800 or more, from the viewpoint of more efficient thickening. is preferably 6,000 or less, more preferably 5,000 or less, and still more preferably 4,500 or less, from the viewpoint of controlling the

The number average molecular weight Mn of the vinyl ester resin (A1-5) is preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more, from the viewpoint of efficiently thickening the resin composition. From the viewpoint of controlling the thickening speed, it is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 1,300 or less.

Mw/Mn of the vinyl ester resin (A1-5) is preferably 1.05 or more, more preferably 1.1 or more, and still more preferably 1.3 or more, from the viewpoint of ease of control of the synthesis conditions. From the viewpoint of suppressing variations in physical properties of the resin composition and controlling the thickening speed, it is preferably 3.0 or less, more preferably 2.5 or less, and still more preferably 2.3 or less.
Mw/Mn is an index of molecular weight distribution, and when it is 1, it indicates a monodisperse polymer, and the larger this ratio, the wider the molecular weight distribution.

In the vinyl ester resin (A1-5), the amount of the bisphenol compound (a1-5) is the total amount of hydroxyl groups of the bisphenol compound (a1-5) with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1). is preferably 10 mol or more, more preferably 15 mol or more, still more preferably 20 mol or more, preferably 70 mol or less, more preferably 60 mol or less, further preferably 50 mol or less. be.

If the total amount of hydroxyl groups in the bisphenol compound (a1-5) is 10 mol or more with respect to the total amount of 100 mol of epoxy groups in the epoxy compound (a1-1), the molecular weight distribution of the vinyl ester resin (A1) is widened. , it is easy to control the ultimate viscosity of the resin composition. Further, when the total amount of hydroxyl groups in the bisphenol compound (a1-5) is 70 mol or less with respect to the total amount of 100 mol of epoxy groups in the epoxy compound (a1-1), it is easy to control the thickening rate of the resin composition. .

In the vinyl ester resin (A1-5), the amount of the unsaturated monobasic acid (a1-2) is the unsaturated monobasic acid (a1- The total amount of acid groups in 2) is preferably 30 mol or more, more preferably 40 mol or more, still more preferably 50 mol or more, preferably 120 mol or less, more preferably 100 mol or less, More preferably, it is 80 mol or less.

If the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 30 mol or more with respect to the total amount of epoxy groups of 100 mol of the epoxy compound (a1-1), vinyl ester resin (A1-5) Since a sufficient amount of ethylenically unsaturated groups are introduced in , the resin composition tends to exhibit good curability. In addition, from the viewpoint of controlling the thickening speed, suppressing the uneven distribution of the resin composition after curing, uniformly repairing the pipe, and from the viewpoint of production stability, unreacted epoxy is added to the vinyl ester resin (A1-1). It is preferable that no groups remain, and the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 120 mol or less with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1). is preferred.

The amount of the unsaturated polybasic acid (a1-6) in the vinyl ester resin (A1-5) is the unsaturated polybasic acid (a1- 6) is preferably in an amount of 0.5 mol or more, more preferably 1 mol or more, still more preferably 3 mol or more, preferably 15 mol or less, more preferably 10 mol or less, still more preferably 8 mol or less.

If the unsaturated polybasic acid (a1-6) is 0.5 mol or more with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), the vinyl ester resin (A1-5) is sufficiently Since a certain amount of ethylenically unsaturated groups are introduced, the resin composition tends to exhibit good curability. Further, from the viewpoint of controlling the thickening speed, the unsaturated polybasic acid (a1-6) is preferably 15 mol or less per 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1).　

(Epoxy compound (a1-1))
The epoxy compound (a1-1) is a compound having two epoxy groups in one molecule, and monomers, oligomers and polymers in general can be used, and the molecular weight and molecular structure are not particularly limited. The epoxy compounds (a1-1) may be used alone or in combination of two or more.
Examples of the epoxy compound (a1-1) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin; phenol novolac type epoxy resin; tert -butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic Epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, and the like. Among them, one or more selected from bisphenol-type epoxy resins and phenol novolac-type epoxy resins are preferable from the viewpoint of suppressing excessive increase in the reaching viscosity of the resin composition and controlling the thickening speed, and bisphenol A-type epoxy resins. , bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, and phenol novolak-type epoxy resin are more preferable, and bisphenol A-type epoxy resin is more preferable.

The epoxy equivalent of the epoxy compound (a1-1) is obtained without gelation of the vinyl ester resin (A1-1), and at least either 2 days or 5 days after the resin composition is prepared. From the viewpoint of controlling the viscosity and the thickening rate, it is preferably 170 to 1,000, more preferably 170 to 500, still more preferably 170 to 400, and even more preferably 170 to 300.

From the viewpoint of ease of synthesis and efficiency of the vinyl ester resin (A1), the epoxy compound (a1-1) is preferably liquid at 25° C., and preferably 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.
Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, cinnamic acid and the like. Among them, at least one selected from (meth)acrylic acid and crotonic acid is preferable from the viewpoint of versatility, reactivity during synthesis of the vinyl ester resin (A), and obtaining a resin composition having good curability. , (meth)acrylic acid is more preferred, and from the viewpoint of chemical resistance, methacrylic acid is even more preferred.

(Polybasic acid anhydride (a1-3))
The polybasic acid anhydride (a1-3) is a compound having a plurality of carboxy groups in one molecule, and at least two carboxy groups undergo dehydration condensation to form an acid anhydride. Among these, dibasic acid anhydride is used from the viewpoint of ease of synthesis of the vinyl ester resin (A1), ease of control of the molecular weight and acid value, and moderate control of the viscosity of the resin composition. preferable. Polybasic acid anhydrides (a1-3) may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides (a1-3) include maleic anhydride, phthalic anhydride, succinic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3-methyl-1,2,3, 6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, methyl-3,6-endomethylene -1,2,3,6-tetrahydrophthalic anhydride, trimellitic anhydride and the like. Among these, maleic anhydride and phthalic anhydride are preferred, and maleic anhydride is more preferred, from the viewpoints of availability, reactivity, ease of handling during synthesis, and the like.

(Polybasic acid anhydride (a1-4))
The polybasic acid anhydride (a1-4) is a compound having a plurality of carboxy groups in one molecule, and at least two carboxy groups undergo dehydration condensation to form an acid anhydride. Among them, from the viewpoint of ease of handling during synthesis of the vinyl ester resins (A1-2) and (A1-3), ease of control of molecular weight and acid value, and good viscosity characteristics of the resin composition, Dibasic anhydrides are preferred. Polybasic acid anhydrides (a1-4) may be used alone or in combination of two or more.
Specific examples of the polybasic acid anhydride (a1-4) include those similar to the polybasic acid anhydride (a1-3), and maleic anhydride is more preferred. The polybasic acid anhydride (a1-3) and the polybasic acid anhydride (a1-4) may be the same or different.

(Bisphenol compound (a1-5))
The bisphenol compound (a1-5) is not particularly limited in its molecular weight and molecular structure. The bisphenol compound (a1-5) may be used alone or in combination of two or more.
Examples of the bisphenol compound (a1-5) include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH. , bisphenol TMC, bisphenol Z, and the like. Among them, at least one or more selected from bisphenol A, bisphenol E, bisphenol F, and bisphenol S is preferable from the viewpoint of suppressing excessive increase in the reaching viscosity of the resin composition and controlling the thickening speed. , bisphenol E, and bisphenol F are more preferred, and bisphenol A is even more preferred from the viewpoint of corrosion resistance, versatility, and cost.

(Unsaturated polybasic acid (a1-6))
The unsaturated polybasic acid (a1-6) is a compound having two or more carboxyl groups and one or more unsaturated groups in one molecule, and its molecular weight and molecular structure are not particularly limited. The unsaturated polybasic acid (a1-6) may be used alone or in combination of two or more.
Examples of unsaturated polybasic acids (a1-6) include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, itaconic acid, tetrahydro phthalic acid, hexahydrophthalic acid, and the like. Among them, maleic anhydride and fumaric acid, succinic acid, glutaric acid, and adipic acid are preferred, succinic acid, fumaric acid, and maleic anhydride are more preferred, and fumaric acid is even more preferred, from the viewpoint of production costs.

If it is desired to reduce the viscosity of the resin composition one hour after preparing the resin composition, the vinyl ester resins (A1-2) and (A1-3) may be blended to appropriately control the thickening speed. If desired, the vinyl ester resin (A1-1) may be blended, and if it is desired to improve the thickening speed, the vinyl ester resin (A1-3) may be blended. Vinyl ester resin (A1-3) may be blended in order to increase the viscosity at least one of 2 days and 5 days after preparation. In this way, resins suitable for desired viscosity behavior may be used singly or in combination.

In the present embodiment, the vinyl ester resin (A1) is preferably a vinyl ester resin (A1-3), that is, the vinyl ester resin (A1) is an epoxy resin having two epoxy groups in one molecule. Compound (a1-1), resin precursor (P2) which is a reaction product of unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3), and polybasic acid anhydride (a1- 4) is preferably an addition reaction product. The total amount of acid groups derived from the polybasic acid anhydride (a1-3) is preferably 5 to 25 mols per 100 mols of the total amount of epoxy groups in the epoxy compound (a1-1).

[Unsaturated polyester resin (A2)]
As the unsaturated polyester resin, one obtained by subjecting an unsaturated dibasic acid, and optionally a dibasic acid component containing a saturated dibasic acid, to an esterification reaction with a polyhydric alcohol can be used.
Examples of the unsaturated dibasic acid and the saturated dibasic acid include those described in WO2016/171151, and these may be used alone or in combination of two or more.
Although the polyhydric alcohol is not particularly limited, examples thereof include those described in WO2016/171151, as in the case of the urethane (meth)acrylate resin.

The unsaturated polyester resin (A2) in the present embodiment contains diol (a2-1-1), which is an alkanediol having a molecular weight of 90 to 500, in an amount of 43 to 85 mol% with respect to 100 mol% of diol (a2-1). The diol (a2-1) containing an ethylenically unsaturated group-containing dibasic acid (a2-2-1) and a dibasic acid containing an ethylenically unsaturated group-free dibasic acid (a2-2-2) ( It is preferably a reaction product with a2-2).

The acid value of the unsaturated polyester resin (A2) is preferably 3 mg KOH/g or more, more preferably 5 mg KOH/g or more, and still more preferably 8 mg KOH, from the viewpoint of obtaining a lining material having flexibility while maintaining excellent shape retention. /g, and from the viewpoint of promoting thickening of the resin composition, it is preferably 25 mg KOH/g or less, more preferably 20 mg KOH/g or less, and even more preferably 16 mg KOH/g or less.

The weight-average molecular weight (Mw) of the unsaturated polyester resin (A2) is preferably 5, from the viewpoint of accelerating the thickening speed of the resin composition and obtaining a lining material having flexibility while maintaining excellent shape retention. 000 or more, more preferably 7,000 or more, and still more preferably 9,000 or more. It is preferably 20,000 or less, more preferably 17,000 or less, still more preferably 15,000 or less.

The number-average molecular weight (Mn) of the unsaturated polyester resin (A2) is preferably 1, 1, 1, 2 from the viewpoint of promoting the thickening speed of the resin composition and obtaining a flexible lining material with excellent shape retention. 000 or more, more preferably 1,500 or more, and still more preferably 2,000 or more. It is preferably 7,000 or less, more preferably 5,000 or less, and still more preferably 4,000 or less.

Although the ratio Mw/Mn between the weight average molecular weight Mw and the number average molecular weight Mn of the unsaturated polyester resin (A2) is not particularly limited, it accelerates the thickening speed, has excellent shape retention, and has flexibility. From the viewpoint of obtaining a lining material, it is preferably 15 or less, more preferably 10 or less, and still more preferably 5 or less, and from the viewpoint of productivity, it is preferably 1 or more, more preferably 1.5 or more, and still more preferably 2 or more. is.

The content ratio (molar ratio) of the structural unit derived from the diol (a2-1) contained in the unsaturated polyester resin (A2) and the structural unit derived from the dibasic acid (a2-2) is determined by dehydration condensation polymerization. It is preferably 40:60 to 60:40, more preferably 45:55 to 55:45, still more preferably 50:50, from the viewpoint of controlling the thickening speed by obtaining an unsaturated polyester having the desired molecular weight. .

When the resin composition contains the unsaturated polyester resin (A2), the content of the unsaturated polyester resin (A2) in the resin composition is the unsaturated polyester resin (A2) and the ethylenically unsaturated group-containing monomer ( It is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 40 to 65 parts by mass, based on 100 parts by mass of B).
When the content of the unsaturated polyester resin (A2) is 20 parts by mass or more, it is easy to control the thickening speed of the resin composition. Further, if the content of the unsaturated polyester resin (A2) is 80 parts by mass or less, the viscosity of the resin composition when impregnating the fiber base material (F) with the ethylenically unsaturated group-containing monomer (B) is reduced to easier to lower.

When the resin composition contains the unsaturated polyester resin (A2), the content of the unsaturated polyester resin (A2) in the resin composition is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the resin composition. parts, more preferably 30 to 70 parts by mass, and even more preferably 40 to 65 parts by mass.
When the content of the unsaturated polyester resin (A2) is 20 parts by mass or more, it is easy to control the thickening speed of the resin composition. Further, if the content of the unsaturated polyester resin (A2) is 80 parts by mass or less, the viscosity of the resin composition when impregnating the fiber base material (F) with the ethylenically unsaturated group-containing monomer (B) is more likely to be lowered.

<Diol (a2-1)>
Diol (a2-1) is a compound having two hydroxy groups in one molecule. The diol (a2-1) contains 43-85 mol % of an alkanediol (a2-1-1) having a molecular weight of 90-500.
The diol (a2-1) includes, in addition to the alkanediol (a2-1-1), an alkanediol (a2-1-2) different from the alkanediol (a2-1-1), an alkanediol (a2-1- 1) and other diols different from the alkanediol (a2-1-2).

(Alkanediol (a2-1-1))
The alkanediol (a2-1-1) is an alkanediol having a molecular weight of 90 to 500, and is a compound in which hydrogen atoms bonded to two carbon atoms of a hydrocarbon are each substituted with a hydroxy group. The alkanediol (a2-1-1) may be used alone or in combination of two or more.
Since alkanediol (a2-1-1) does not contain polar groups other than hydroxy groups or atoms with high electronegativity in the molecule, compared to polyoxyalkylene polyols with ether bonds, interaction is small. Therefore, the resin composition contains an unsaturated polyester resin (A2) which is a reaction product of the alkanediol (a2-1-1) and the dibasic acid (a2-2), thereby reducing the hygroscopicity of the resin composition. This suppresses the change in viscosity after the resin composition is thickened, resulting in excellent viscosity stability.

When the molecular weight of the alkanediol (a2-1-1) is 90 or more, the hygroscopicity of the resin composition can be reduced, and when it is less than 500, ease of production and productivity are favorable. Become. The molecular weight of the alkanediol (a2-1-1) is from the viewpoint of further reducing the hygroscopicity of the resin composition, suppressing the viscosity change after thickening the resin composition, and obtaining a resin composition having excellent viscosity stability. , preferably 95 or more, more preferably 100 or more, still more preferably 103 or more, and preferably 400 or less, more preferably 300 or less, still more preferably 250 or less from the viewpoint of ease of production and production cost.

Examples of the alkanediol (a2-1-1) include 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butanediol, 1,3-butane Diol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl -1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 1,2- nonanediol, 1,4-cyclohexanediol, 1,8-octanediol, 1,9-nonanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2, 2-di(4-hydroxycyclohexyl)propane, bisphenol A, bisphenol F and bisphenol S hydrides, and the like.
Among these, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, bisphenol A hydrides are used from the viewpoint of obtaining a resin composition having excellent viscosity stability after thickening. is preferred, and 2,2-dimethyl-1,3-propanediol is preferred from the viewpoint of availability and production cost.

The content of the alkanediol (a2-1-1) in the diol (a2-1) reduces the hygroscopicity of the resin composition more than 100 mol % of the diol (a2-1), and increases the resin composition. From the viewpoint of suppressing a change in viscosity after thickening and obtaining a resin composition having excellent viscosity stability after thickening, the amount is 43 mol% or more, preferably 45 mol% or more, and more preferably 48 mol% or more. In addition, when synthesizing the unsaturated polyester resin (A), from the viewpoint of suppressing the precipitation of crystals such as low molecular weight substances and unreacted raw materials, and further improving the impregnation of the resin composition into the fiber base material. Therefore, it is preferably 85 mol % or less, more preferably 80 mol % or less, and still more preferably 75 mol % or less.

The total content of the alkanediol (a2-1-1) in the diol (a2-1) and the later-described alkanediol (a2-1-2) is based on 100 mol% of the total amount of the diol (a2-1). , From the viewpoint of further reducing the hygroscopicity of the resin composition, suppressing the change in viscosity after thickening the resin composition, and obtaining a resin composition having excellent viscosity stability after thickening, it is preferably 70 mol% or more, More preferably 80 mol % or more, still more preferably 90 mol % or more, and even more preferably 100 mol %.

(Alkanediol (a2-1-2))
The alkanediol (a2-1-2) is an alkanediol different from the alkanediol (a2-1-1) and does not contain alkanediols with a molecular weight of 90-500.
The molecular weight of the alkanediol (a1-2) is preferably 60 or more, more preferably 65 or more, and still more preferably 70 or more, from the viewpoint of viscosity stability after thickening the resin composition. From the viewpoint of cost, it is preferably 85 or less, more preferably 80 or less, and even more preferably 78 or less.
Examples of the alkanediol (a2-1-2) include ethylene glycol and propylene glycol.
Among these, propylene glycol is more preferable from the viewpoint of viscosity stability after thickening the resin composition.
The content of the alkanediol (a2-1-2) in the diol (a2-1) is determined based on 100 mol % of the diol (a2-1) when synthesizing the unsaturated polyester resin (A2). 15 mol% or more, preferably 20 mol% or more, and more preferably 25 mol% or more. Further, from the viewpoint of further reducing the hygroscopicity of the resin composition, suppressing the change in viscosity after thickening the resin composition, and obtaining a resin composition having excellent viscosity stability after thickening, it is preferably 57 mol% or less. is 55 mol % or less, more preferably 52 mol % or less.

(other diols)
Other diols are diols different from alkanediol (a2-1-1) and alkanediol (a2-1-2).
The molecular weight of the other diol is preferably 70 or more, more preferably 85 or more, and still more preferably 100 or more from the viewpoint of production cost and good toughness of the cured product. , preferably 500 or less, more preferably 300 or less, still more preferably 150 or less.
Other diols include, for example, polyoxyalkylene polyols such as diethylene glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol.
Among these, diethylene glycol and dipropylene glycol are more preferable from the viewpoint of production cost and toughness of the cured product.

<Dibasic acid (a2-2)>
The dibasic acid (a2-2) includes an ethylenically unsaturated group-containing dibasic acid (a2-2-1) and an ethylenically unsaturated group-free dibasic acid (a2-2-2).
The dibasic acid (a2-2) may be used alone or in combination of two or more.

(Ethylenically unsaturated group-containing dibasic acid (a2-2-1))
The ethylenically unsaturated group-containing dibasic acid (a2-2-1) is a compound having two carboxy groups and one or more ethylenically unsaturated groups in one molecule, and its molecular weight and molecular structure are particularly Not limited. The ethylenically unsaturated group-containing dibasic acid (a2-2-1) may be used alone or in combination of two or more.

The content of the ethylenically unsaturated group-containing dibasic acid (a2-2-1) in the dibasic acid (a2-2) is From the viewpoint of the mechanical strength of the cured product, it is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, even more preferably 45 mol% or more, and preferably 80 mol% or less. , more preferably 75 mol % or less, still more preferably 70 mol % or less, and even more preferably 65 mol % or less.

Examples of the ethylenically unsaturated group-containing dibasic acid (a2-2-1) include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and chloromaleic acid. Among them, maleic anhydride and fumaric acid are preferred, and maleic anhydride is more preferred, from the viewpoint of production cost.

(Ethylenically unsaturated group-free dibasic acid (a2-2-2))
Ethylenically unsaturated group-free dibasic acid (a2-2-2) is a compound having two carboxy groups in one molecule and no ethylenically unsaturated group, and its molecular weight and molecular structure is not particularly limited. The ethylenically unsaturated group-free dibasic acid (a2-2-2) may be used alone or in combination of two or more.

The content of the ethylenically unsaturated group-free dibasic acid (a2-2-2) in the dibasic acid (a2-2) is 100 mol% of the dibasic acid (a2-2), the resin composition From the viewpoint of the mechanical strength of the cured product, it is preferably 20 mol% or more, more preferably 25 mol% or more, still more preferably 30 mol% or more, still more preferably 35 mol% or more, preferably 80 mol % or less, more preferably 70 mol % or less, still more preferably 60 mol % or less, and even more preferably 55 mol % or less.

Ethylenically unsaturated group-free dibasic acids (a2-2-2) include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexa Hydrophthalic acid (1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid), naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, chlorendic acid (het acid), tetrabromo Phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, succinic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, dimethylorthophthalate, dimethylisophthalate, dimethylterephthalate, etc. mentioned. Among these, isophthalic acid and terephthalic acid are preferred from the viewpoint of production cost.

In the present embodiment, the dibasic acid (a2-2) is 20 to 80 mol% of the ethylenically unsaturated group-containing dibasic acid (a2-1), and the ethylenically unsaturated group-free dibasic acid (a2- 2-2) is preferably contained in an amount of 20 to 80 mol %.

[Urethane (meth)acrylate resin (A3)]
A urethane (meth)acrylate resin is a polyurethane having a (meth)acryloyloxy group. Specifically, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, a hydroxy group-containing (meth)acrylic compound and optionally a hydroxy group-containing allyl ether compound are further added to the unreacted isocyanato groups. Obtained by reaction.

[Polyester (meth)acrylate resin (A4)]
The polyester (meth)acrylate resin is polyester having a (meth)acryloyloxy group. A polyester (meth)acrylate resin can be obtained, for example, by the method (1) or (2) shown below.
(1) A method of reacting an epoxy group-containing (meth)acrylate or a hydroxy group-containing (meth)acrylate with a carboxy-terminated polyester (2) A hydroxy-terminated polyester containing (meth)acrylic acid or an isocyanato group A method of reacting (meth)acrylate with a carboxyl-terminated polyester used as a raw material in the above method (1) is obtained from an excess amount of saturated polybasic acid and/or unsaturated polybasic acid and polyhydric alcohol. What can be obtained is mentioned.
The hydroxy-terminated polyester used as a raw material in the above method (2) includes those obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and an excess amount of a polyhydric alcohol.

[(Meth)acrylate resin (A5)]
The (meth)acrylate resin (A5) is a polymer of acrylic acid ester or methacrylic acid ester. Specific examples of the constituent monomers include those similar to the (meth)acrylates exemplified for the ethylenically unsaturated group-containing monomer (B).

The viscosity of a mixture of 65% by mass of resin (A) and 35% by mass of phenoxyethyl methacrylate is preferably 0.3 to 300 Pa s, more preferably 0.5 to 200 Pa s, from the viewpoint of ease of handling. More preferably, it is 0.8 to 150 Pa·s.

<Ethylenically unsaturated group-containing monomer (B)>
The ethylenically unsaturated group-containing monomer (B) is not particularly limited as long as it does not have a carboxy group and has an ethylenically unsaturated group, but preferably has a (meth)acryloyl group or a vinyl group. . The ethylenically unsaturated group-containing monomer (B) may be used alone or in combination of two or more.
The higher the content of the ethylenically unsaturated group-containing monomer (B), the more suppressed the increase in the viscosity after 1 hour from the adjustment of the resin composition, the thickening rate and the resin composition after 2 days from adjustment and At least one increase in viscosity after 5 days tends to be suppressed. In addition, the 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)acryloyl group include, for example, (meth)acrylates. (Meth)acrylates may be monofunctional or polyfunctional.

Monofunctional (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)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, Ethylene glycol Monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono-2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl Ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dicyclopentenyl (meth) acrylate , dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, caprolactone-modified hydroxyethyl (meth)acrylate, allyl (meth)acrylate and the like.

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

Among the ethylenically unsaturated group-containing monomers (B), other than (meth)acrylate, those having a (meth)acryloyl group include acryloylmorpholine, 2-hydroxyethyl (meth)acrylamide, 2-hydroxyethyl-N -methyl (meth)acrylamide, 3-hydroxypropyl (meth)acrylamide and the like. Examples of those having an ethylenically unsaturated group other than those having a (meth)acryloyl group include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, and t-butyl. Styrene compounds such as styrene, vinyl benzyl butyl ether, vinyl benzyl hexyl ether and divinyl benzyl ether, vinyl acetate, diallyl fumarate, diallyl phthalate, triallyl isocyanurate and the like.

Among these, as the ethylenically unsaturated group-containing monomer (B), suitable control of the thickening rate of the resin composition, curability, production cost, mechanical strength of the cured product of the resin composition, heat resistance , and chemical resistance, styrene compounds and (meth)acrylates are preferred. More specifically, styrene, methyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, diethylene glycol di(meth) At least one selected from acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and neopentyl glycol (meth)acrylate is preferred. Furthermore, from the viewpoint of odor control, at least one selected from phenoxyethyl (meth) acrylate, benzyl (meth) acrylate and diethylene glycol di (meth) acrylate, neopentyl glycol (meth) acrylate is more preferable, and curing of the resin composition At least one selected from phenoxyethyl methacrylate, benzyl methacrylate, diethylene glycol dimethacrylate, and neopentyl glycol (meth)acrylate is more preferable from the viewpoint of chemical resistance of the product.

<Thickener (C)>
Although the thickener (C) is not particularly limited, it is preferably at least one selected from group 2 element oxides and hydroxides. When the thickener (C) is at least one selected from oxides and hydroxides of Group 2 elements, the carboxyl group and hydroxyl group possessed by the resin (A), and the carboxyl groups of other component compounds It has the effect of increasing the viscosity of the resin composition over time by interacting with groups and hydroxyl groups.
The thickener (C) may be used alone or in combination of two or more.

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

<Photoinitiator (D)>
The photopolymerization initiator is not particularly limited as long as it generates radicals upon irradiation with light. For example, benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether; -methylethyl)acetophenone and other acetophenones; 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and other α-hydroxyalkylphenones; Anthraquinones such as amyl anthraquinone, 2-t-butyl anthraquinone and 1-chloroanthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Acetophenone dimethyl ketal, benzyl dimethyl ketal and the like Benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, 3,3′,4,4′-tetrakis(t-butyldioxycarbonyl)benzophenone; 2-methyl -1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1-one, 2-benzyl-2 morpholines such as -dimethylamino-1-(4-morpholinophenyl)-butan-1-one; acylphosphine oxides such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and xanthones. . These may be used singly or in combination of two or more.

From the viewpoint of reactivity, the photopolymerization initiator is preferably an intramolecular cleavage type photopolymerization initiator that does not require a hydrogen donor. In addition, since active species are generated by absorbing light with a wavelength of 315 to 460 nm, 2,2-dimethoxy-2-phenylacetophenone, phenylbis(2,4, 6-trimethylbenzoyl)phosphine oxide and 1-hydroxycyclohexylphenyl ketone, 1-hydroxycyclohexylphenyl ketone are preferred.

<Compound (E)>
At least one compound (E) selected from water and a hydroxy group-containing compound may be used in the resin composition of the present embodiment. Including the compound (E) in the resin composition makes it easier to control the thickening speed. Examples of hydroxy group-containing compounds include alcohols having a boiling point of 50° C. or higher, such as benzyl alcohol, stearyl alcohol, and isostearyl alcohol. Other examples include hydroxycarboxylic acids such as lactic acid, glycerin, polyols, and (meth)acrylates containing a hydroxy group. These may be used singly or in combination of two or more. Among these, water and alcohol are preferred, and water is more preferred, from the viewpoint of availability, cost, and the like.

<Carboxy group-containing compound>
The resin composition of this embodiment may contain a compound having at least one carboxyl group.
Examples of the carboxy group-containing compound include maleic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, fumaric acid, endomethylenetetrahydrophthalic acid, and methyltetrahydrophthalic acid. , 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4-methyl-1,2,3,6-tetrahydrophthalic acid, 3-methyl-hexahydrophthalic acid, 4-methyl-hexahydrophthalic acid , methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid, trimellitic acid, 3-dodecenylsuccinic acid, (meth)acrylic acid and the like.
Haridimer 250 (manufactured by Harima Kasei Co., Ltd.) can be mentioned as a commercially available product.
The carboxy group-containing compounds may be used singly or in combination of two or more.

When the resin (A) of the present embodiment contains the vinyl ester resin (A1), the thickening rate is controlled to prevent the resin composition from excessively thickening immediately after production of the resin composition (within 5 hours after production). From the viewpoint of suppressing the excessive increase in the ultimate viscosity of the resin composition, the carboxy group-containing compound is preferably 3-dodecenylsuccinic acid, methacrylic acid, or acrylic acid, and more preferably 3-dodecenylsuccinic acid. preferable.

When the resin (A) of the present embodiment contains the vinyl ester resin (A1) and the resin composition of the present embodiment contains a carboxyl group-containing compound, the viscosity increase rate is controlled immediately after the resin composition is produced (after production to From the viewpoint of suppressing excessive thickening of the resin composition within 5 hours) and further suppressing excessive increase in the attained viscosity of the resin composition, the vinyl ester resin (A1) and ethylenically unsaturated It is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more with respect to a total of 100 parts by mass of the group-containing monomer (B). In addition, as the content of the carboxy group-containing compound in the resin composition increases, the hygroscopicity of the resin composition increases. It is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less.

When the resin (A) of the present embodiment contains the unsaturated polyester resin (A2) and the resin composition of the present embodiment contains a carboxy group-containing compound, the carboxy group-containing compound has a lower molecular weight than the unsaturated polyester molecule. Therefore, an interaction occurs between the carboxy group or hydroxy group of the unsaturated polyester resin (A2) and the thickening agent (C), and before the resin composition thickens over time, the carboxy group-containing compound and the thickener (C) can suppress the increase in initial viscosity (within 5 hours after preparation of the resin composition).
Moreover, water is produced by the interaction between the carboxy group-containing compound and the thickener (C). The generated water accelerates the thickening of the resin composition for 24 to 48 hours after preparation, so that the target viscosity can be reached quickly. Furthermore, when the carboxy group-containing compound is contained in the resin composition, the apparent molecular weight formed by the interaction of the unsaturated polyester resin (A2), the carboxy group-containing compound, and the thickener (C) becomes low. , it is possible to suppress the attained viscosity of the resin composition from becoming excessively high.
The carboxy group-containing compounds may be used singly or in combination of two or more.

When the resin (A) of the present embodiment contains the unsaturated polyester resin (A2), the molecular weight and molecular structure of the carboxy group-containing compound are not particularly limited, but the unsaturated polyester resin (A2) and the thickener (C) The molecular weight is preferably 90 or more from the viewpoint of generating an appropriate interaction, and is preferably 500 or less, more preferably 400 or less, and still more preferably 300 or less from the viewpoint of controlling the thickening property. When the molecular weight of the carboxyl group-containing compound is 90 or more, it suppresses the decrease in the ultimate viscosity due to the inclusion of the low molecular weight compound, and the mobility is not too high, so it quickly interacts with the thickener (C) and immediately Consumption is suppressed, and an increase in initial viscosity can be suppressed. Further, when the molecular weight of the carboxy group-containing compound is 500 or less, the molecular mobility is significantly larger than that of the unsaturated polyester resin (A2), so immediately after the resin composition is prepared (within 5 hours after preparation), the resin Excessive thickening of the composition can be further suppressed, and excessive increase in the ultimate viscosity of the resin composition can be further suppressed.

When the resin (A) of the present embodiment contains the unsaturated polyester resin (A2), the carboxyl group-containing compound controls the thickening rate, and immediately after the resin composition is adjusted (within 5 hours after adjustment), the resin composition A dicarboxylic acid having two carboxy groups in one molecule is preferable from the viewpoint of suppressing excessive increase in the viscosity of the resin composition, and oxalic acid , malonic acid, succinic acid, glutaric acid, adipic acid, 3-dodecenylsuccinic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and Halidimer 250 are more preferred, and 3-dodecenylsuccinic acid and Halidimer 250 are more preferred.

When the resin (A) of the present embodiment contains the unsaturated polyester resin (A2), the content of the carboxy group-containing compound in the resin composition is immediately after preparation of the resin composition (within 5 hours after production). From the viewpoint of further suppressing the excessive increase in viscosity of the resin composition, the unsaturated polyester resin (A2) and an ethylenically unsaturated group-containing monomer It is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more, relative to 100 parts by mass of (B) in total. In addition, as the content of the carboxy group-containing compound in the resin composition increases, the hygroscopicity of the resin composition increases. It is preferably 3.5 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less.

When the resin (A) of the present embodiment contains the unsaturated polyester resin (A2), the content of the carboxy group-containing compound in the resin composition is immediately after preparation of the resin composition (within 5 hours after production). From the viewpoint of further suppressing excessive increase in the viscosity of the product and further suppressing the attained viscosity of the resin composition from becoming excessively high, it is preferably 0 with respect to the total amount of 100 parts by mass of the resin composition. 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more. In addition, as the content of the carboxy group-containing compound in the resin composition increases, the hygroscopicity of the resin composition increases. It is preferably 3.5 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less.

<Other ingredients>
Other components of the resin composition of the present embodiment include, for example, other resins, polymerization inhibitors, thixotropic agents, curing accelerators, catalysts, thickening aids, curing retardants, surfactants, surface modifiers, Additives such as wetting and dispersing agents, antifoaming agents, leveling agents, coupling agents, light stabilizers, waxes, flame retardants and plasticizers can be included. The content of the additive is not particularly limited as long as it does not impair the effects of the present invention.

(polymerization inhibitor)
A polymerization inhibitor can be used to suppress the progress of the polymerization reaction of the resin composition. The resin composition of the present embodiment preferably contains a polymerization inhibitor.
A known polymerization inhibitor can be used, and examples thereof include hydroquinone, methylhydroquinone, trimethylhydroquinone, phenothiazine, catechol, 4-t-butylcatechol, and copper naphthenate. These may be used individually by 1 type, and 2 or more types may be used together.

(thixotropic agent)
A thixotropic agent is used to adjust the mixability and fluidity of the resin composition. The thixotropic agents include organic thixotropic agents and inorganic thixotropic agents. These can be used singly or in combination of two or more.
When the resin composition of the present embodiment contains a thixotropic agent, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

Organic thixotropic agents include, for example, hydrogenated castor oil, amide, polyethylene oxide, polymerized vegetable oil, surfactant, and composites using these together. Specific examples include "Floron (registered trademark) SP-1000AF" (manufactured by Kyoeisha Chemical Co., Ltd.), "Disparon (registered trademark) 6900-20X" (Kusumoto Kasei Co., Ltd.), and the like.
Examples of inorganic thixotropic agents include hydrophobically or hydrophilically treated silica and bentonite. Specific examples of hydrophobic inorganic thixotropic agents include "Rheolosil (registered trademark) PM-20L" (manufactured by Tokuyama Corporation), "Aerosil (registered trademark) R-106" (Nippon Aerosil Co., Ltd.), "CAB-O-SIL (registered trademark)" (manufactured by Cabot Corporation) and the like. Specific examples of hydrophilic inorganic thixotropic agents include "Aerosil (registered trademark)-200" (manufactured by Nippon Aerosil Co., Ltd.). When using hydrophilic pyrogenic silica, the combination of thixotropic modifiers "BYK (registered trademark)-R605" and "BYK (registered trademark)-R606" (both manufactured by BYK) will increase the viscosity increase rate. is effective for moderate control of

<Content of each component in the resin composition>
[First embodiment]
The resin composition according to the first embodiment of this embodiment has a viscosity of 400 to 3,500 Pa·s at 25° C. two days after preparation of the resin composition.
The content of the resin (A) in the resin composition according to the first embodiment is, when the resin (A) contains the vinyl ester resin (A1), the resin (A) and the ethylenically unsaturated group-containing monomer (B ) is preferably 35 to 90 parts by mass, more preferably 40 to 80 parts by mass, and even more preferably 45 to 70 parts by mass, and the resin (A) is an unsaturated polyester resin (A2) When containing, with respect to a total of 100 parts by weight of the resin (A) and the ethylenically unsaturated group-containing monomer (B), preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, more preferably 40 to 65 parts by mass.
When the resin (A) contains the vinyl ester resin (A1), if the content of the resin (A) is 35 parts by mass or more, the resin (A) tends to moderately increase the thickening rate of the resin composition. . Further, when the resin (A) is 90 parts by mass or less, the ethylenically unsaturated group-containing monomer (B) tends to reduce the viscosity of the resin composition one hour after the preparation, and the fiber base material (F) Easier to impregnate.
When the resin (A) contains the unsaturated polyester resin (A2), if the content of the resin (A) is 20 parts by mass or more, it is easy to control the thickening speed of the resin composition. Moreover, if the resin (A) is 80 parts by mass or less, the viscosity of the resin composition after one hour from the preparation thereof can be easily reduced, and the fiber base material (F) can be easily impregnated with the resin composition.

When the resin (A) contains the vinyl ester resin (A1), the content of the resin (A) in the resin composition according to the first embodiment is preferably 35 to 90 parts by mass, more preferably 40 to 80 parts by mass, more preferably 45 to 70 parts by mass, and when the resin (A) contains the unsaturated polyester resin (A2), the total amount of the resin composition is 100 parts by mass. , preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 40 to 65 parts by mass.
When the resin (A) contains the vinyl ester resin (A1), if the content of the resin (A) is 35 parts by mass or more, the resin (A) tends to moderately increase the thickening speed of the resin composition. . Further, when the resin (A) is 90 parts by mass or less, the viscosity of the resin composition after one hour from the preparation thereof can be easily reduced, and the fiber base material (F) can be easily impregnated with the resin composition.
When the resin (A) contains the unsaturated polyester resin (A2), if the content of the resin (A) is 20 parts by mass or more, it is easy to control the thickening speed of the resin composition. Moreover, if the content of the resin (A) is 80 parts by mass or less, the viscosity of the resin composition after one hour from the preparation thereof can be easily reduced, and the fiber base material (F) can be easily impregnated with the resin composition.

When the resin (A) contains the vinyl ester resin (A1), the content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to the first embodiment is It is preferably 10 to 65 parts by mass, more preferably 20 to 60 parts by mass, and still more preferably 30 to 55 parts by mass with respect to the total of 100 parts by mass of the saturated group-containing monomer (B), and the resin (A) is unsaturated. When the saturated polyester resin (A2) is included, it is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, relative to the total 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). , more preferably 35 to 60 parts by mass.
When the resin (A) contains the vinyl ester resin (A1), if the ethylenically unsaturated group-containing monomer (B) is 10 parts by mass or more, the viscosity after 1 hour from the preparation of the resin composition can be easily reduced, It becomes easier to impregnate the fiber base material (F). When the amount of the ethylenically unsaturated group-containing monomer (B) is 65 parts by mass or less, the resin composition has better thickening properties.
When the resin (A) contains the unsaturated polyester resin (A2), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the viscosity after 1 hour from the preparation of the resin composition is easily reduced. , making it easier to impregnate the fiber base material (F). When the amount of the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, the resin composition has better thickening properties.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to the first embodiment is, when the resin (A) contains the vinyl ester resin (A1), the total amount of the resin composition is 100 parts by mass. On the contrary, it is preferably 10 to 65 parts by mass, more preferably 20 to 60 parts by mass, still more preferably 30 to 55 parts by mass, and when the resin (A) contains an unsaturated polyester resin (A2), the resin composition It is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 35 to 60 parts by mass with respect to 100 parts by mass of the total amount of.
When the resin (A) contains the vinyl ester resin (A1), if the ethylenically unsaturated group-containing monomer (B) is 10 parts by mass or more, the viscosity after 1 hour from the preparation of the resin composition can be easily reduced, It becomes easier to impregnate the fiber base material (F). When the amount of the ethylenically unsaturated group-containing monomer (B) is 65 parts by mass or less, the resin composition has better thickening properties.
When the resin (A) contains the unsaturated polyester resin (A2), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the viscosity after 1 hour from the preparation of the resin composition is easily reduced. , making it easier to impregnate the fiber base material (F). When the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, the resin composition has better thickening properties.

The content of the thickener (C) in the resin composition according to the first embodiment is preferably 0.5 parts per 100 parts by mass in total of the resin (A) and the ethylenically unsaturated group-containing monomer (B). 01 to 6 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 4 parts by mass.
If the compound (C) is 0.1 parts by mass or more, the resin composition will have better viscosity-increasing properties. When the compound (C) is 6 parts by mass or less, it becomes easy to suppress excessive thickening of the resin composition, and it becomes easy to moderately control the thickening speed.

The content of the thickener (C) in the resin composition according to the first embodiment is preferably 0.01 to 6 parts by mass, more preferably 0.05 parts by mass, with respect to 100 parts by mass of the total amount of the resin composition. to 5 parts by mass, more preferably 0.1 to 4 parts by mass.
When the thickener (C) is 0.1 parts by mass or more, the resin composition has better thickening properties. If the thickener (C) is 6 parts by mass or less, it becomes easier to suppress excessive thickening of the resin composition, and it becomes easier to moderately control the thickening speed.

The content of the photopolymerization initiator (D) in the resin composition according to the first embodiment is preferably 0 with respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 3 parts by mass.
When the content of the photopolymerization initiator (D) is 0.01 parts by mass or more, a resin composition with better curability can be obtained. If the content of the photopolymerization initiator is 10 parts by mass or less, a rapid curing reaction and heat generation are less likely to occur during curing of the resin composition, cracks are more likely to be suppressed, and strength, toughness, heat resistance, and resistance are improved. An excellent lining material can be easily obtained due to the balance of physical properties such as chemical properties.

When the resin composition according to the first embodiment contains a compound (E) that is at least one selected from water and a hydroxy group-containing compound, the content of the compound (E) in the resin composition is With respect to a total of 100 parts by mass of (A) and ethylenically unsaturated group-containing monomer (B), preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, still more preferably 0.3 to 1 part by mass.
When the compound (E) is 0.05 parts by mass or more, it becomes easy to control the thickening speed of the resin composition and suppress excessive thickening. When the compound (E) is 3 parts by mass or less, it is easy to obtain a lining material with excellent balance of physical properties such as strength, toughness, heat resistance and chemical resistance.

When the resin composition according to the first embodiment contains a compound (E) that is at least one selected from water and a hydroxy group-containing compound, the content of the compound (E) in the resin composition is It is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, still more preferably 0.3 to 1 part by mass, relative to 100 parts by mass of the total amount of the composition.
When the compound (E) is 0.05 parts by mass or more, it becomes easy to control the thickening speed of the resin composition and suppress excessive thickening. When the compound (E) is 3 parts by mass or less, it is easy to obtain a lining material with excellent balance of physical properties such as strength, toughness, heat resistance and chemical resistance.

In one aspect of the first embodiment, the resin composition contains 35 to 90 parts by mass of the resin (A) with respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). parts, 10 to 65 parts by mass of the ethylenically unsaturated group-containing monomer (B), 0.01 to 6 parts by mass of the thickener (C), and 0.01 to 10 parts by mass of the photopolymerization initiator (D) It is preferable to include parts by mass.

In another aspect of the first embodiment, the resin composition contains 20 to 80 parts by mass of the resin (A) with respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). Parts by mass, 20 to 80 parts by mass of the ethylenically unsaturated group-containing monomer (B), 0.01 to 6 parts by mass of the thickener (C), and 0.01 to 5 parts by mass of dicarboxylic acid. preferable.

[Second embodiment]
The resin composition according to the second embodiment of the present embodiment has a viscosity of 400 to 3,500 Pa·s at 25° C. after five days from the preparation of the resin composition.
The content of the resin (A) in the resin composition according to the second embodiment is, when the resin (A) contains the vinyl ester resin (A1), the resin (A) and the ethylenically unsaturated group-containing monomer (B ) is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 40 to 60 parts by mass, and the resin (A) is an unsaturated polyester resin (A2) When containing, with respect to a total of 100 parts by weight of the resin (A) and the ethylenically unsaturated group-containing monomer (B), preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, more preferably 40 to 65 parts by mass.
In the case where the resin (A) contains the vinyl ester resin (A1), if the resin (A) is 20 parts by mass or more, the resin (A) tends to moderately increase the thickening rate of the resin composition. When the resin (A) is 80 parts by mass or less, the ethylenically unsaturated group-containing monomer (B) easily reduces the viscosity one hour after the resin composition is prepared, and impregnates the fiber base material (F). becomes easier.
When the resin (A) contains the unsaturated polyester resin (A2), if the resin (A) is 20 parts by mass or more, the thickening rate of the resin composition can be easily controlled by the resin (A). When the resin (A) is 80 parts by mass or less, the ethylenically unsaturated group-containing monomer (B) easily reduces the viscosity one hour after the resin composition is prepared, and impregnates the fiber base material (F). becomes easier.

When the resin (A) contains the vinyl ester resin (A1), the content of the resin (A) in the resin composition according to the second embodiment is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, and when the resin (A) contains the unsaturated polyester resin (A2), the total amount of the resin composition is 100 parts by mass. , preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 40 to 65 parts by mass.
When the resin (A) contains the vinyl ester resin (A1), if the resin (A) is 20 parts by mass or more, the resin (A) tends to moderately increase the thickening rate of the resin composition. When the resin (A) is 80 parts by mass or less, the ethylenically unsaturated group-containing monomer (B) easily reduces the viscosity one hour after the resin composition is prepared, and impregnates the fiber base material (F). becomes easier.
When the resin (A) contains the unsaturated polyester resin (A2), if the content of the resin (A) is 20 parts by mass or more, it is easy to control the thickening speed of the resin composition. Moreover, if the content of the resin (A) is 80 parts by mass or less, the viscosity of the resin composition after one hour from the preparation thereof can be easily reduced, and the fiber base material (F) can be easily impregnated with the resin composition.

When the resin (A) contains the vinyl ester resin (A1), the content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to the second embodiment is It is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 40 to 60 parts by mass with respect to a total of 100 parts by mass of the saturated group-containing monomer (B). When the saturated polyester resin (A2) is included, it is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, relative to the total 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). , more preferably 35 to 60 parts by mass.
When the resin (A) contains the vinyl ester resin (A1), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the viscosity after 1 hour from the preparation of the resin composition can be easily reduced, Penetration into the fiber base material (F) becomes better. When the amount of the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, the resin composition has better thickening properties.
When the resin (A) contains the unsaturated polyester resin (A2), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the resin composition after 1 hour from the preparation of the resin composition The viscosity is easily reduced, and the fiber base material (F) is easily impregnated. When the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, the resin composition has better thickening properties.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to the second embodiment is, when the resin (A) contains the vinyl ester resin (A1), the total amount of the resin composition is 100 parts by mass. For, preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, and the resin (A) contains an unsaturated polyester resin (A2), the resin composition It is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, still more preferably 35 to 60 parts by mass, relative to 100 parts by mass of the total amount of the product.
When the resin (A) contains the vinyl ester resin (A1), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the viscosity after 1 hour from the preparation of the resin composition can be easily reduced, It becomes easier to impregnate the fiber base material (F). When the amount of the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, the resin composition has better thickening properties.
When the resin (A) contains the unsaturated polyester resin (A2), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the viscosity after 1 hour from the preparation of the resin composition is easily reduced. , making it easier to impregnate the fiber base material (F). When the amount of the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, the resin composition has better thickening properties.

The content of the thickener (C) in the resin composition according to the second embodiment is preferably 0.5 parts per 100 parts by mass in total of the resin (A) and the ethylenically unsaturated group-containing monomer (B). 1 to 6 parts by mass, more preferably 0.5 to 5 parts by mass, still more preferably 1 to 4 parts by mass.
When the thickener (C) is 0.1 parts by mass or more, the resin composition has better thickening properties. When the thickening agent (C) is 6 parts by mass or less, it becomes easy to suppress excessive thickening of the resin composition, and it becomes easy to moderately control the thickening speed.

The content of the thickener (C) in the resin composition according to the second embodiment is preferably 0.1 to 6 parts by mass, more preferably 0.5 parts by mass, with respect to 100 parts by mass of the total amount of the resin composition. to 5 parts by mass, more preferably 1 to 4 parts by mass.
When the thickener (C) is 0.1 parts by mass or more, the resin composition has better thickening properties. If the thickener (C) is 6 parts by mass or less, it becomes easier to suppress excessive thickening of the resin composition, and it becomes easier to moderately control the thickening speed.

The content of the photopolymerization initiator (D) in the resin composition according to the second embodiment is preferably 0 with respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 3 parts by mass.
When the content of the photopolymerization initiator (D) is 0.01 parts by mass or more, a resin composition with better curability can be obtained. If the content of the photopolymerization initiator is 10 parts by mass or less, a rapid curing reaction and heat generation are unlikely to occur during curing of the resin composition, cracks are easily suppressed, and strength, toughness, heat resistance, and resistance are improved. An excellent lining material can be easily obtained due to the balance of physical properties such as chemical properties.

The content of the photopolymerization initiator (D) in the resin composition according to the second embodiment is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, with respect to 100 parts by mass of the total amount of the resin composition. 05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.
When the content of the photopolymerization initiator (D) is 0.01 parts by mass or more, a resin composition with better curability can be obtained. If the content of the photopolymerization initiator is 10 parts by mass or less, a rapid curing reaction and heat generation are unlikely to occur during curing of the resin composition, cracks are easily suppressed, and strength, toughness, heat resistance, and resistance are improved. An excellent lining material can be easily obtained due to the balance of physical properties such as chemical properties.

When the resin composition according to the second embodiment contains at least one compound (E) selected from water and a hydroxy group-containing compound, the content of the compound (E) in the resin composition is A) and the ethylenically unsaturated group-containing monomer (B), relative to a total of 100 parts by mass, preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1.5 parts by mass, still more preferably 0.1 ~1 part by mass.
When the compound (E) is 0.05 parts by mass or more, it becomes easier to control the thickening rate of the resin composition and suppress excessive thickening. When the compound (E) is 3 parts by mass or less, it is easy to obtain a lining material having excellent balance of physical properties such as strength, toughness, heat resistance and chemical resistance.

When the resin composition according to the second embodiment contains at least one compound (E) selected from water and a hydroxy group-containing compound, the content of the compound (E) in the resin composition is It is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1.5 parts by mass, and still more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the total amount of the product.
When the compound (E) is 0.05 parts by mass or more, it becomes easier to control the thickening rate of the resin composition and suppress excessive thickening. When the compound (E) is 3 parts by mass or less, it is easy to obtain a lining material having excellent balance of physical properties such as strength, toughness, heat resistance and chemical resistance.

In one aspect of the second embodiment, the resin composition contains 35 to 90 parts by mass of the resin (A) with respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). parts, 10 to 65 parts by mass of the ethylenically unsaturated group-containing monomer (B), 0.01 to 6 parts by mass of the thickener (C), and 0.01 to 10 parts by mass of the photopolymerization initiator (D) It is preferable to include parts by mass.

In another aspect of the second embodiment, the resin composition contains 20 parts by mass of the vinyl ester resin (A1) with respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). 80 parts by mass, 20 to 80 parts by mass of the ethylenically unsaturated group-containing monomer (B), 0.01 to 6 parts by mass of the thickener (C), and 0.01 to 6 parts by mass of the photopolymerization initiator (D). It preferably contains 01 to 10 parts by mass.

In still another aspect of the second embodiment, the resin composition comprises 20 to 20 parts by mass of the resin (A) with respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). 80 parts by mass, 20 to 80 parts by mass of the ethylenically unsaturated group-containing monomer (B), 0.01 to 6 parts by mass of the thickener (C), and 0.01 of the photopolymerization initiator (D) It is preferable to contain up to 10 parts by mass.

In still another aspect of the second embodiment, the resin composition contains the unsaturated polyester resin (A2) with respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). 20 to 80 parts by mass, the ethylenically unsaturated group-containing monomer (B) 20 to 80 parts by mass, the thickener (C) 0.01 to 6 parts by mass, the dicarboxylic acid 0.01 to 5 It is preferable to include parts by mass.

[Third embodiment]
The resin composition according to the third embodiment of the present embodiment has a viscosity of 400 to 3,500 Pa·s at 25° C. two days and five days after preparation of the resin composition.
Preferred aspects of the third embodiment are the same as those of the second embodiment.

[Method for producing resin composition]
The method for producing the resin composition of the present embodiment is not particularly limited, but the resin (A), the ethylenically unsaturated group-containing monomer (B), the thickener (C), and the photopolymerization initiation A resin composition can be produced by mixing the agent (D). In addition to the resin (A), the ethylenically unsaturated group-containing monomer (B), the thickener (C), and the photopolymerization initiator (D), the compound (E), the carboxylic acid and other components described above may be optionally added. Ingredients may be mixed.

The mixing order is not particularly limited, but the thickener (C) is preferably added last from the viewpoint of facilitating viscosity control.
The mixing method is not particularly limited, and can be performed using, for example, a disper, planetary mixer, kneader, or the like. The mixing temperature is preferably 10 to 50°C, more preferably 15 to 40°C, and more preferably 20 to 30°C from the viewpoint of ease of mixing.

Further, the resin (A), the ethylenically unsaturated group-containing monomer (B), the thickener (C), and the photopolymerization initiator (D) are easily mixed uniformly, and from the viewpoint of adjusting the viscosity, the resin (A) may be diluted in advance with at least one of a solvent and a reactive diluent.

<Method for producing resin (A)>
[Method for producing vinyl ester resin (A1-1)]
Vinyl ester resin (A1-1) can be produced by reacting epoxy compound (a1-1) with unsaturated monobasic acid (a1-2).
For example, in a reaction vessel capable of being heated and stirred, the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) are optionally mixed with at least one of a solvent and a reactive diluent, and the ester It can be produced by heating with mixing at a temperature of preferably 70 to 150° C., more preferably 80 to 140° C., still more preferably 90 to 130° C., in the presence of a curing catalyst for 1 to 8 hours.
In the present embodiment, the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) are added to the total amount of 100 mol of the epoxy groups of the epoxy compound (a1-1), and the unsaturated monobasic acid The total amount of acid groups of (a1-2) is preferably 80 mol or more, more preferably 90 mol or more, still more preferably 99 mol or more.

Esterification catalysts include, for example, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol and diazabicyclooctane. Primary amines; phosphorus compounds such as triphenylphosphine and benzyltriphenylphosphonium chloride; diethylamine hydrochloride; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride; lithium chloride, lithium bromide and lithium nitrate and lithium salts such as These may be used singly or in combination of two or more. Among these, it is selected from phosphorus compounds and quaternary ammonium salts from the viewpoint of moderately promoting the synthesis reaction rate of vinyl ester resins, suppressing gelation, and facilitating moderate control of the molecular weight distribution. At least one is preferred, and at least one selected from quaternary ammonium salts is more preferred.

The amount of the esterification catalyst used is the amount of the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) from the viewpoint of suppressing the thickening of the vinyl ester resin (A1-1) while promoting the reaction. It is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass in total.

A solvent and a reactive diluent are used as necessary from the viewpoint of facilitating uniform mixing of the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2). The mixing method is not particularly limited, and can be performed by a known method.
The solvent is not particularly limited as long as it is inert to the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2). Examples thereof include known solvents having a boiling point of 70 to 150° C. at 1 atm, such as methyl isobutyl ketone. A solvent may be used individually by 1 type, and may use 2 or more types together.
As the reactive diluent, an ethylenically unsaturated group-containing monomer (B) inert to the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) is preferred.

A polymerization inhibitor may be added from the viewpoint of suppressing the progress of the polymerization reaction of the vinyl ester resin (A1-1). As the polymerization inhibitor, those described in the section <Other components> above are preferably used. When adding a polymerization inhibitor, the amount added is, for example, 0.0001 to 10 parts by mass with respect to a total of 100 parts by mass of the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2). preferably 0.001 to 1 part by mass.

[Method for producing vinyl ester resin (A1-2)]
The vinyl ester resin (A1-2) is a resin precursor (P1) which is a reaction product of an epoxy compound (a1-1) and an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride (a1- It can be produced by further adding 4).
For example, in a reaction vessel capable of being heated and stirred, the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) are optionally mixed with at least one of a solvent and a reactive diluent, and the ester A resin precursor (P1) is produced by heating with mixing at preferably 70 to 150° C., more preferably 80 to 140° C., still more preferably 90 to 130° C. for 1 to 8 hours in the presence of a curing catalyst. . Subsequently, the polybasic acid anhydride (a1-4) is added to the reaction vessel in which the resin precursor (P1) was synthesized, and the temperature is maintained at 70 to 150°C, preferably 80 to 140°C, in the presence of an esterification catalyst. More preferably, the vinyl ester resin (A1-2) is obtained by reacting at 90 to 130° C. for 30 minutes to 4 hours.

In the present embodiment, the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) are added to the total amount of 100 mol of the epoxy groups of the epoxy compound (a1-1), and the unsaturated monobasic acid The total amount of acid groups of (a1-2) is preferably 80 mol or more, more preferably 90 mol or more, still more preferably 99 mol or more.
Further, the polybasic acid anhydride (a1-4) is 3 to 60 moles per 100 moles of the total epoxy group of the epoxy compound (a1-1). more preferably 5 to 50 mol, still more preferably 7 to 45 mol.

Examples of the esterification catalyst used for producing the vinyl ester resin (A1-2) include those similar to the esterification catalysts used for producing the vinyl ester resin (A1-1).
The amount of the esterification catalyst used is 100 in total for the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) from the viewpoint of suppressing thickening of the resin precursor (P1) while promoting the reaction. It is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, still more preferably 0.1 to 3 parts by mass.

Examples of the solvent and reactive diluent used for producing the vinyl ester resin (A1-2) include the same solvents and reactive diluents as those used for producing the vinyl ester resin (A1-1). The same applies to preferred embodiments.

A polymerization inhibitor may be added from the viewpoint of suppressing the progress of the polymerization reaction of the vinyl ester resin (A1-2). As the polymerization inhibitor, those described in the section <Other components> above are preferably used. When adding a polymerization inhibitor, the amount added is, for example, 0.0001 to 10 parts by mass with respect to a total of 100 parts by mass of the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2). preferably 0.001 to 1 part by mass.

[Method for producing vinyl ester resin (A1-3)]
Vinyl ester resin (A1-3) is an epoxy compound (a1-1) having two epoxy groups in one molecule, unsaturated monobasic acid (a1-2), and polybasic acid anhydride (a1-3 ) can be produced by further adding polybasic acid anhydride (a1-4) to the resin precursor (P2) which is the reaction product of ).
For example, in a reaction vessel capable of heating and stirring, epoxy compound (a1-1), unsaturated monobasic acid (a1-2), and polybasic acid anhydride (a1-3), if necessary, a solvent and At least one of the reactive diluents is mixed, and in the presence of an esterification catalyst, preferably at 70 to 150° C., more preferably 80 to 140° C., still more preferably 90 to 130° C., for 1 to 8 hours while mixing. A resin precursor (P2) is produced by heating. Subsequently, the polybasic acid anhydride (a1-4) is added to the reaction vessel in which the resin precursor (P2) was synthesized, and the temperature is maintained at 70 to 150°C, preferably 80 to 140°C, in the presence of an esterification catalyst. More preferably, the vinyl ester resin (A1-3) is obtained by reacting at 90 to 130° C. for 30 minutes to 4 hours.

In the production of the resin precursor (P2) according to the present embodiment, the total amount of acid groups of the unsaturated monobasic acid (a1-2) is It is preferable to react so as to obtain 75 to 95 mol, more preferably 77 to 93 mol, still more preferably 79 to 91 mol.

In the production of the resin precursor (P2) according to the present embodiment, the epoxy groups derived from the polybasic acid anhydride (a1-3) are reacted with the total amount of 100 mol of the epoxy groups of the epoxy compound (a1-1). The total amount of acid groups to be obtained is preferably 5 to 25 mol, more preferably 7 to 23 mol, still more preferably 9 to 21 mol.

In the production of the resin precursor (P2) according to the present embodiment, the acid group derived from the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) (here, the "acid group" is Acid groups produced by hydrolysis of polybasic acid anhydride (a1-3) For example, when the polybasic acid anhydride (a1-3) is a dibasic acid anhydride, the number of acid groups produced from one molecule is 2.) is preferably 105 to 125 mol, more preferably 107 to 123 mol, and further It is preferably 109 to 121 mol.

In the production of the vinyl ester resin (A1-3) according to the present embodiment, the polybasic acid anhydride (a1-4) is 3- It is preferable to carry out the reaction so as to obtain 60 mol, more preferably 5 to 50 mol, still more preferably 7 to 45 mol.

Examples of the esterification catalyst used for producing the vinyl ester resin (A1-3) include those similar to the esterification catalysts used for producing the vinyl ester resin (A1-1). Further, the esterification catalyst used in producing the resin precursor (P2) and the esterification catalyst used in producing the vinyl ester resin (A1-3) from the resin precursor (P2) may be the same or different. good.
The amount of the esterification catalyst used is, from the viewpoint of suppressing the thickening of the resin precursor (P2) while promoting the reaction, the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2) and the polybasic It is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, still more preferably 0.1 to 3 parts by mass, relative to the total 100 parts by mass of the acid anhydride (a1-3). .

Examples of the solvent and reactive diluent used to produce the vinyl ester resin (A1-3) include the same solvents and reactive diluents used to produce the vinyl ester resin (A1-1). The same applies to preferred embodiments.

A polymerization inhibitor may be added from the viewpoint of suppressing the progress of the polymerization reaction of the vinyl ester resin (A1-3). As the polymerization inhibitor, those described in the section <Other components> above are preferably used. When the polymerization inhibitor is added, the amount added is, for example, the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) with respect to a total of 100 parts by mass. 0.0001 to 10 parts by mass, preferably 0.001 to 1 part by mass.

<Method for producing vinyl ester resin (A1-4)>
A method for producing a vinyl ester resin (A1-4) comprises reacting an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5) to obtain a resin precursor (P3). and a step of reacting the resin precursor (P3) and the unsaturated monobasic acid (a1-2) to obtain a vinyl ester resin (A1-4).

The step of obtaining a resin precursor (P3) includes reacting an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5) to obtain a resin precursor (P3). It is a process of obtaining
In the step of obtaining the resin precursor (P3), from the viewpoint of widening the molecular weight distribution of the vinyl ester resin (A1-4) and controlling the ultimate viscosity of the resin composition, an epoxy compound having two epoxy groups per molecule is used. (a1-1) and the bisphenol compound (a1-5) are preferably combined so that the total amount of hydroxyl groups of the bisphenol compound (a1-5) is It is preferable to carry out the reaction so as to obtain 10 to 70 mol, more preferably 20 to 60 mol, still more preferably 25 to 50 mol.

The step of obtaining the resin precursor (P3) includes, for example, adding a solvent and a reactive diluent to the epoxy compound (a1-1) and the bisphenol compound (a1-5) in a reaction vessel capable of being heated and stirred. Mixing with at least one of the resin precursors and heating in the presence of an esterification catalyst at a temperature of preferably 70 to 160° C., more preferably 80 to 155° C., still more preferably 90 to 150° C. for 1 to 3 hours while mixing. body (P3) can be obtained.

Examples of esterification catalysts include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, and cyazabicyclooctane. Phosphorus compounds such as primary amines, triphenylphosphine and benzyltriphenylphosphonium chloride, diethylamine hydrochloride, trimethylbenzylammonium chloride, lithium chloride and the like. These can be used singly or in combination of two or more. Among these, from the viewpoints of slowing the reaction rate, preventing gelation of the resin, and facilitating control of the molecular weight distribution, phosphorus-based and ammonium salt-based catalysts are preferred, and ammonium salts are more preferred.

The amount of the esterification catalyst used is, from the viewpoint of suppressing the thickening of the vinyl ester resin (A1-4) while promoting the reaction, the epoxy compound (a1-1), the bisphenol compound (a1-5), and the unsaturated It is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, still more preferably 0.1 to 3 parts by mass, relative to the total 100 parts by mass of the monobasic acid (a1-2). .

A solvent and a reactive diluent are used as necessary from the viewpoint of facilitating uniform mixing of the epoxy compound (a1-1), the bisphenol compound (a1-5) and the unsaturated monobasic acid (a1-2). . The mixing method is not particularly limited, and can be performed by a known method.
The solvent is not particularly limited as long as it is inert to the epoxy compound (a1-1), bisphenol compound (a1-5) and unsaturated monobasic acid (a1-2). Examples thereof include known solvents having a boiling point of 70 to 150° C. at 1 atm, such as methyl isobutyl ketone. A solvent may be used individually by 1 type, and may use 2 or more types together.
Preferred reactive diluents include epoxy compounds (a1-1), bisphenol compounds (a1-5), and ethylenically unsaturated group-containing monomers (B) inert to unsaturated monobasic acids (a1-2). .

A polymerization inhibitor may be added from the viewpoint of suppressing the progress of the polymerization reaction of the resin precursor (P3). As the polymerization inhibitor, those described in the section <Other components> above are preferably used. When adding a polymerization inhibitor, the amount added is, for example, the epoxy compound (a1-1), the bisphenol compound (a1-5) and the unsaturated monobasic acid (a1-2) with respect to a total of 100 parts by mass, 0 0.0001 to 10 parts by weight, preferably 0.001 to 1 part by weight.

The step of obtaining the vinyl ester resin (A1-4) is a step of reacting the resin precursor (P3) and the unsaturated monobasic acid (a1-2) to obtain the vinyl ester resin (A1-4).
In the step of obtaining the vinyl ester resin (A1-4), from the viewpoint of controlling the thickening rate, suppressing uneven distribution of the resin composition after curing, and from the viewpoint of production stability, the epoxy of the epoxy compound (a1-1) The total amount of acid groups of the unsaturated monobasic acid (a1-2) is preferably 30 to 120 mol, more preferably 40 to 100 mol, and still more preferably 50 to 80 mol with respect to 100 mol of the total amount of groups. It is preferable to react as follows.

The step of obtaining the vinyl ester resin (A1-4) includes, for example, adding an unsaturated monobasic acid (a1-2) in the presence of an esterification catalyst into the reaction vessel in which the resin precursor (P3) was synthesized, The vinyl ester resin (A1-4) can be produced by heating with mixing at 70 to 150°C, preferably 80 to 140°C, more preferably 90 to 130°C for 30 minutes to 4 hours.

Examples of the esterification catalyst used in the step of obtaining the vinyl ester resin (A1-4) include those similar to those used in the step of obtaining the resin precursor (P3). Further, the esterification catalyst used in producing the resin precursor (P3) and the esterification catalyst used in producing the vinyl ester resin (A1-4) from the resin precursor (P3) may be the same or different. good.
In the step of obtaining the vinyl ester resin (A1-4), as in the step of obtaining the resin precursor (P3), if necessary, at least one of a solvent, a reactive diluent, and a polymerization inhibitor is added. good too. The mixing method can also be performed by a known method similarly to the step of obtaining the resin precursor (P3). The same applies to preferred embodiments.
When adding a reactive diluent to the vinyl ester resin (A1-4) for the purpose of lowering the viscosity of the vinyl ester resin (A1-4), the reactive diluent is added after synthesis of the vinyl ester resin (A1-4). It is preferable to mix in addition, and when a reactive diluent is added for the purpose of facilitating the synthesis of the vinyl ester resin (A1-4), the reactive diluent is added during the synthesis of the vinyl ester resin (A1-4). It is preferable to add and mix the reactive diluent and other components after the synthesis of the vinyl ester resin (A1-4).

A polymerization inhibitor may be added from the viewpoint of suppressing the progress of the polymerization reaction of the vinyl ester resin (A1-4). As the polymerization inhibitor, those described in the section <<other components>> above are preferably used. The amount of the polymerization inhibitor added is, for example, the epoxy compound (a1-1), the bisphenol compound (a1-5), and the unsaturated monobasic acid (a1-2) with respect to a total of 100 parts by mass, It can be 0.0001 to 10 parts by mass, preferably 0.001 to 1 part by mass.

<Method for producing vinyl ester resin (A1-5)>
A method for producing a vinyl ester resin (A1-5) includes reacting an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5) to obtain a resin precursor (P3 ), reacting the resin precursor (P3) and the unsaturated monobasic acid (a1-2) to obtain the resin precursor (P4), the resin precursor (P4) and the unsaturated polybasic It has a step of reacting the acid (a1-6) to obtain a vinyl ester resin (A1-5).

The step of obtaining a resin precursor (P3) includes reacting an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5) to obtain a resin precursor (P3). It is a process of obtaining

The step of obtaining the resin precursor (P3) includes the same method as the step of obtaining the resin precursor (P3) in the method for producing the vinyl ester resin (A1-4), and preferred embodiments are also the same.

In the step of obtaining the resin precursor (P3), from the viewpoint of controlling the thickening speed of the resin composition, an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5 ), the total amount of hydroxyl groups of the bisphenol compound (a1-5) is preferably 10 to 70 mol, more preferably 15 to 60 mol, per 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), More preferably, the reaction is carried out so that the amount becomes 20 to 50 mol.

The step of obtaining the resin precursor (P4) is a step of reacting the resin precursor (P3) and the unsaturated monobasic acid (a1-2) to obtain the resin precursor (P4).

The step of obtaining the resin precursor (P4) includes the same method as the step of obtaining the vinyl ester resin (A1-4) in the method for producing the vinyl ester resin (A1-4), and preferred embodiments are also the same.

In the step of obtaining the resin precursor (P4), the epoxy group of the epoxy compound (a1-1) is controlled from the viewpoint of controlling the thickening rate, suppressing uneven distribution of the resin composition after curing, and manufacturing stability. The total amount of acid groups of the unsaturated monobasic acid (a1-2) is preferably 40 to 120 mol, more preferably 50 to 100 mol, still more preferably 60 to 80 mol, relative to the total amount of 100 mol. It is preferable to react.

The step of obtaining the vinyl ester resin (A1-5) is a step of reacting the resin precursor (P4) and the unsaturated polybasic acid (a1-6) to obtain the vinyl ester resin (A1-5).

The step of obtaining the vinyl ester resin (A1-5) includes, for example, adding an unsaturated polybasic acid (a1-6) in the presence of an esterification catalyst into the reaction vessel in which the resin precursor (P4) was synthesized, The vinyl ester resin (A1-5) can be produced by heating with mixing at 70 to 150°C, preferably 80 to 140°C, more preferably 90 to 130°C for 30 minutes to 4 hours.

In the step of obtaining the vinyl ester resin (A1-5), from the viewpoint of controlling the thickening rate, the unsaturated polybasic acid (a1-6) is added to the total amount of 100 mol of the epoxy groups of the epoxy compound (a1-1). is preferably 0.5 to 15 mol, more preferably 1 to 10 mol, still more preferably 3 to 8 mol.

Examples of the esterification catalyst used in the step of obtaining the vinyl ester resin (A1-5) include those similar to those used in the step of obtaining the resin precursor (P3). Further, the esterification catalyst used in producing the resin precursor (P4) and the esterification catalyst used in producing the vinyl ester resin (A1-5) from the resin precursor (P4) may be the same or different. good.
In the step of obtaining the vinyl ester resin (A1-5), similarly to the step of obtaining the resin precursors (P3) and (P4), if necessary, at least one of a solvent, a reactive diluent, and a polymerization inhibitor. may be added. The mixing method can also be performed by a known method similarly to the step of obtaining the resin precursor (P3). The same applies to preferred embodiments.
When adding a reactive diluent to the vinyl ester resin (A1-5) for the purpose of lowering the viscosity of the vinyl ester resin (A1-5), the reactive diluent is added after synthesis of the vinyl ester resin (A1-5). It is preferable to mix in addition, and when a reactive diluent is added for the purpose of facilitating the synthesis of the vinyl ester resin (A1-5), the reactive diluent is added during the synthesis of the vinyl ester resin (A1-5). It is preferable to add and mix the reactive diluent and other components after the synthesis of the vinyl ester resin (A1-5).

[Method for producing unsaturated polyester resin (A2)]
The unsaturated polyester resin (A2) includes a diol (a2-1), an ethylenically unsaturated group-containing dibasic acid (a2-2-1), and an ethylenically unsaturated group-free dibasic acid (a2-2- 2) can be produced by dehydration condensation polymerization.
For example, in a reaction vessel capable of being heated and stirred, a diol (a2-1), an ethylenically unsaturated group-containing dibasic acid (a2-2-1) and an ethylenically unsaturated group-free dibasic acid (a2-2- 2) at 150 to 250° C., preferably 170 to 240° C., more preferably 180 to 230° C., for 8 to 15 hours.
In the present embodiment, from the viewpoint of the mechanical strength of the cured product of the resin composition, the molar ratio of the diol (a2-1) and the ethylenically unsaturated group-free dibasic acid (a2-2-2) (diol ( a2-1): Ethylenically unsaturated group-free dibasic acid (a2-2-2)) is preferably reacted at 50:50 to 85:15, more preferably 55:45 to 80: 20, more preferably 60:40 to 75:25.

[Material for lining material]
The material for lining material in the present embodiment includes a fiber base material (F) impregnated with the resin composition described above (hereinafter also referred to as a resin-impregnated base material).
As the material for the lining material, it is preferable to impregnate the fiber base material (F) with the resin composition and store (cured) it for a certain period of time to thicken it. By using such a lining material, a lining material having excellent shape retention can be obtained.

When a pipe is to be rehabilitated, the pipe is repaired by irradiating with ultraviolet rays, visible light, or the like to cure the resin composition in the lining material. Therefore, the cured product of the lining material obtained by curing the resin composition is required to have mechanical strength to the extent that the pipe can be repaired.
For example, in the lining material using glass fiber as the fiber base material (F), generally, the bending strength of the cured product (FRP) of the lining material is preferably 100 to 1000 MPa, more preferably 120 to 900 MPa, more preferably 150 to 800 MPa. Further, the bending elastic modulus of FRP is preferably 5 to 40 GPa, more preferably 7 to 35 GPa, still more preferably 8 to 30 GPa.
The bending strength and bending elastic modulus values are measured values according to JIS K7171:2016.

The content of the resin composition in the base material impregnated with the resin composition is preferably 20-95% by mass, more preferably 25-85% by mass, and even more preferably 25-75% by mass. When the content of the resin composition is 20% by mass or more, the lining material can be imparted with appropriate flexibility, and workability during pipe rehabilitation is improved. When the content of the resin composition is 85% by mass or less, sufficient strength can be imparted to the lining material after photocuring.

The content of the fiber base material (F) in the resin composition-impregnated base material is preferably 5 to 80% by mass, more preferably 15 to 75% by mass, and even more preferably 25 to 75% by mass. When the content of the fiber base material (F) is 5% by mass or more, sufficient strength can be imparted to the lining material after photocuring. When the content of the fiber base material (F) is 80% by mass or less, the lining material can be imparted with appropriate flexibility, and workability during pipe rehabilitation is improved.

<Fibrous base material (F)>
As the fiber material of the fiber base material (F), from the viewpoint of mechanical strength, for example, synthetic fibers such as amide, nylon, aramid, vinylon, polyester and phenolic resin, carbon fiber, glass fiber, metal fiber, ceramic fiber and so-called reinforcing fibers, and composite fibers thereof. These may be used singly or in combination of two or more. Among these, aramid fiber, carbon fiber, and glass fiber are preferred, and glass fiber is more preferred from the viewpoints of strength, hardness, availability, price, and the like. In particular, from the viewpoint of photocuring the resin composition with which the fiber base material (F) is impregnated, light-transmitting glass fibers and polyester fibers are preferable.
For example, in the case of glass fibers, the commonly used filament diameter is preferably 1-15 μm, more preferably 3-10 μm.

Examples of the form of the fiber base material (F) include sheet, chopped strand, chop, milled fiber and the like. As the sheet, for example, a sheet formed by arranging a plurality of reinforcing fibers in one direction, bidirectional fabrics such as plain weaves and twill weaves, multiaxial fabrics, non-crimp fabrics, nonwoven fabrics, mats, knits, braids, reinforcing fibers, etc. and the like. The fiber base material (F) may be used singly or in combination of two or more types, and may be a single layer or a laminate of multiple layers.
From the viewpoint of the impregnating property of the resin composition, the thickness of the sheet is preferably 0.01 to 5 mm in the case of a single layer, and preferably the total thickness in the case of a multilayer lamination. 1 to 20 mm, more preferably 1 to 15 mm.

<Lining material>
The lining material is used for repairing pipes such as existing pipes. Pipe repair is performed by arranging the lining material along the inner circumference of the inner surface of the pipe, crimping the lining material to the inner surface of the pipe, and then irradiating light such as ultraviolet rays or visible light to remove the resin composition contained in the lining material. It is done by curing the material. In this specification, the lining material is arranged along the inner circumference of the inner surface of the pipe, and after the lining material is crimped to the inner surface of the pipe, the lining material is irradiated with ultraviolet rays or visible light. Curing the resin composition is also referred to as performing pipe rehabilitation.

The lining material has a cylindrical shape and includes a lining material in which a fiber base material (F) is impregnated with a resin composition.
The lining material has an inner film as the innermost layer on the inner surface, an outer film as the outermost layer on the outer surface, and a composite material layer containing a lining material between the inner film and the outer film from the viewpoint of ease of pipe rehabilitation work. Alternatively, it is preferable to have an outer film as the innermost layer on the inner surface, an inner film as the outermost layer on the outer surface, and a composite material layer containing a lining material between the inner film and the outer film. In addition, the lining material having an outer film as the innermost layer on the inner surface, an inner film as the outermost layer on the outer surface, and a composite material layer containing the material for the lining material between the inner film and the outer film is applied to the inner surface of the pipe while the lining material is turned over. It is preferable to use it for the inversion construction method to pull in.
The lining material may have other layers as desired. Moreover, each layer may be a single layer, or a plurality of layers may be laminated.

It is preferable that the lining material has a cylindrical shape having approximately the same diameter as the diameter of the inner surface of the pipe. This improves the strength of the pipe after repair.
The inner diameter of the lining material is not particularly limited, but is preferably 100 to 1500 mm, more preferably 130 to 1200 mm, still more preferably 150 to 1000 mm.
When the inner diameter of the lining material is 100 mm or more, light curing is easy.

[inner film]
As the inner film, for example, a resin film such as polyethylene film, polypropylene film, polyethylene terephthalate film can be used. The inner film needs to be transparent to the light emitted from the light irradiation device during pipe rehabilitation. As a result, the lining material can be cured efficiently, and the pipe can be properly rehabilitated. The inner film may be peeled off after curing the lining material.

Although the thickness of the inner film is not particularly limited, it is preferably 50-200 μm, more preferably 80-170 μm. If the thickness of the inner film is 50 μm or more, sufficient strength can be imparted to the pipe without the inner film being damaged or wrinkled during or before pipe rehabilitation. If the thickness of the inner film is 200 µm or less, the lining material can be easily manufactured, and workability during pipe rehabilitation work is good.

[Outer film]
As the outer film, a resin film can be used like the inner film. The outer film preferably has light shielding properties. As a result, it is possible to suppress the hardening of the lining material due to light from the outside before the construction of pipe rehabilitation.
In addition, at the time of construction of pipe rehabilitation, it is possible to suppress the transmission of irradiated light through the lining material, so that the lining material can be efficiently photo-cured. As the light-shielding outer film, for example, a laminated film having a yellow or other colored film layer between two transparent polyethylene films can be used.

Although the thickness of the outer film is not particularly limited, it is preferably 5 to 100 μm, more preferably 10 to 90 μm. If the thickness of the outer film is 5 μm or more, sufficient strength can be imparted to the pipe without the outer film being damaged or wrinkled prior to light irradiation during pipe rehabilitation. If the thickness of the outer film is 100 μm or less, the lining material can be easily manufactured, and workability during pipe rehabilitation work is good.

[Manufacturing method of lining material]
A conventionally known manufacturing method can be used for the manufacturing method of the lining material.
When manufacturing a lining material after manufacturing a lining material using the resin composition according to the above-described first embodiment, the following steps 1 and 2 are preferably included.
Further, when manufacturing a lining material after manufacturing a lining material using the resin composition according to the first embodiment, it is preferable to include the following steps 1 to 3.

(Step 1)
Step 1 is a step of impregnating a fiber base material (F) with a resin composition to obtain a resin composition-impregnated base material. In step 1, the fiber base material (F) in which the inner film and the outer film are not laminated on the fiber base material (F) may be impregnated with the resin composition, and the inner film and the outer film are laminated on the surface. A fiber base material (F) may be used.
When the fiber base material (F) having the inner film and the outer film laminated on the surface is used, the resin composition is impregnated into the fiber base material (F) through at least one of the inner film and the outer film. be.

The fiber base material (F) used in step 1 may be cylindrical, sheet-like, or tape-like.
When using the resin composition according to the first embodiment described above, the fiber base material (F) preferably has a cylindrical shape, and the resin composition according to the second embodiment and the third embodiment described above When using, the fiber base material (F) is preferably sheet-like or tape-like.

In step 1, the viscosity of the resin composition at 25°C when the fiber base material (F) is impregnated with the resin composition is preferably 0.1 to 3 Pa·s. That is, it is preferably the same as the viscosity at 25° C. after 1 hour from the preparation of the resin composition. When the viscosity of the resin composition is within the above range, impregnation failure of the fiber base material (F) with the resin composition is reduced, and a resin composition-impregnated base material uniformly impregnated with the resin composition is easily obtained. The viscosity of the resin composition at 25° C. when impregnating the fiber base material (F) with the resin composition is more preferably 0.2 from the viewpoint of further reducing impregnation defects and more uniformly impregnating the resin composition. to 2.5 Pa·s, more preferably 0.5 to 2.0 Pa·s.

The time for impregnating the fiber base material (F) with the resin composition is preferably 0.5 to 24 hours, more preferably 1 to 10 hours, from the viewpoint of reducing poor impregnation and uniformly impregnating the resin composition. More preferably, it is 1.5 to 5 hours.
After the resin composition is prepared, that is, after the resin composition is produced, the time until the impregnation of the resin composition is completed is preferably 1 to 30 hours, more preferably 2 to 24 hours, and still more preferably 5 to 10 hours. .

(Step 2)
Step 2 is a step of laminating the inner film and the outer film on the fiber base material (F).
The method for laminating the inner film and the outer film is not particularly limited. F) or a method of laminating on a resin composition-impregnated base material, a method of directly laminating a film on a fiber base material (F) or a resin composition-impregnated base material, and the like. The inner film and the outer film may be laminated using different methods, or may be laminated using the same method.
The inner film and the outer film may be independently laminated before or after impregnation of the fiber base material (F) with the resin composition. Moreover, it may be performed before or after step 3, which will be described later.

(Step 3)
Step 3 is a step of processing into a cylindrical shape. In addition, when the fiber base material (F) which is already cylindrical is used, it is not necessary to carry out step 3, and it is carried out when the sheet-like or tape-like fiber base material (F) is used.
In step 3, the resin composition-impregnated base material is wound around a mandrel having a diameter approximately the same as the diameter of the inner surface of the tube, and is held together by the resin composition contained in the resin-impregnated base material, thereby forming a cylindrical shape.
Specifically, when the resin composition-impregnated base material is in the form of a sheet, the resin composition contained in the resin composition-impregnated base material is obtained by overlapping two sides in the longitudinal direction of about 1 to 10 cm after winding it around a mandrel. Tie with. Further, when the resin composition-impregnated base material is tape-shaped, the resin composition-impregnated base material is spirally wound while being overlapped by about 1 to 10 cm, and the overlapping portion is the resin composition contained in the resin composition-impregnated base material. Tie with.

In step 3, if the resin composition-impregnated base material is wound with the inner film already arranged on the mandrel, there is no need to laminate the inner film on the fiber base material (F) or the resin composition-impregnated base material, and the resin composition This is preferable because it also facilitates removal of the mandrel after winding the material-impregnated substrate.
Moreover, from the viewpoint of productivity, it is preferable to laminate the outer film after processing into a cylindrical shape.

In step 3, the overlapping portions of the resin composition-impregnated base material are held together with the resin composition. Therefore, the viscosity of the resin composition contained in the resin composition-impregnated base material at this time is preferably a viscosity with moderate stickiness, preferably 30 to 1,500 Pa s, more preferably 40 to 1 ,000 Pa·s, more preferably 50 to 500 Pa·s.
If the viscosity of the resin composition contained in the resin composition-impregnated base material is 30 Pa s or more, the resin composition has appropriate adhesiveness and the resin composition is unevenly distributed in the resin composition-impregnated base material. can maintain a uniformly contained state. Also, if the viscosity of the resin composition is 1,500 Pa·s or less, it is easy to process into a cylindrical shape.

The method of manufacturing the lining material may have a curing step in addition to the above steps 1 to 3.
The curing step is a step for appropriately increasing the viscosity of the resin composition until it reaches a viscosity suitable for each step. It is preferably provided after the fiber base material (F) is impregnated with the resin composition or before pipe rehabilitation is performed.
The curing temperature in the curing step is preferably 10 to 40°C, more preferably 15 to 30°C, still more preferably 20 to 30°C. The curing temperature can be appropriately adjusted according to the target viscosity of the resin composition, the curing time, and the like.

When manufacturing a lining material using the resin composition according to the first embodiment, it is preferable to provide a curing step between after the above steps 1 and 2 and before the execution of pipe rehabilitation. The curing time is preferably 6 hours to 3.5 days, more preferably 12 hours to 3 days, still more preferably 1 to 2 days.

When a lining material is produced using the resin compositions according to the second and third embodiments, it is preferable to provide a curing step immediately after step 1, and pipe rehabilitation is performed after step 3. It is preferable to provide a curing step in between.
The curing time immediately after step 1 is preferably 12 hours to 3 days, more preferably 1 day to 2.5 days, still more preferably 1.5 to 2 days. When the curing time is within the above range, the resin composition exhibits appropriate adhesiveness, and the overlapping portions of the resin composition-impregnated base material can be held together with sufficient strength.
The curing time between step 3 and execution of pipe rehabilitation is preferably 6 hours to 3.5 days, more preferably 12 hours to 3 days, still more preferably 1 to 2 days.

The storage period of the lining material that has completed the curing step and the viscosity of the resin composition has reached 400 to 3,500 Pa s is preferably 1 to 6 months, more preferably 2 to 5 months, from the viewpoint of quality stability. for months.

<Pipe rehabilitation>
A lining material obtained using the resin composition according to the present embodiment can be suitably used for pipe rehabilitation.
Pipe rehabilitation is performed, for example, by arranging a lining material along the inner periphery of the inner surface of the pipe, crimping the lining material to the inner surface of the pipe, and then irradiating the lining material with ultraviolet light or visible light to photo-cure the lining material. .
In general, the lining material is folded in a folded state for easy transportation and transported to the place where pipe rehabilitation is to be carried out. At this time, it is preferable that the resin composition in the lining material does not leak out and hang down or is unevenly distributed in the lining material, and that the lining material has appropriate flexibility. From such a point of view, the viscosity of the resin composition in the lining material at a temperature of 25 ° C. during pipe rehabilitation is preferably 400 to 3,500 Pa s, more preferably 450 to 2,500 Pa s, and further It is preferably 500 to 2,000 Pa·s. That is, it is preferably the same as the viscosity at 25° C. at least either 2 days or 5 days after preparation of the resin composition.

For the work of introducing the lining material into the existing pipe, it is possible to pull the lining material as it is from a manhole or the like.
Since the diameter-expanding operation of the lining material is performed by blowing air into the inner cavity of the lining material, end packers are provided at both ends of the lining material for sealing the lining material. By blowing air from the end packer side of one end, the pressure in the inner cavity of the lining material increases, and the diameter of the lining material expands so as to adhere to the inner peripheral surface of the existing pipe.

The diameter-expanded lining material is irradiated with ultraviolet light, visible light, or the like on the inner surface of the lining material by a mobile light irradiation device, whereby the resin composition contained in the lining material is cured, and the inner surface of the existing pipe is , the resin composition is coated with a cured lining material. Although the radiation intensity of the light irradiation device is not particularly limited, it is preferably 0.0008 to 0.03 W/mm ² .

If the radiation intensity is 0.0008 W/mm ² or more, work efficiency is good and sufficient strength can be imparted to the pipe. Further, if the radiation intensity is 0.03 W/mm ² or less, local excessive irradiation of the inner surface layer of the lining material can be suppressed, and deterioration and reduction in strength of the lining material can be suppressed.

As the light irradiation device, a light source that emits light in the ultraviolet to visible region (usually, wavelengths of 200 to 800 nm) can be used. Examples of light sources include metal halide lamps such as gallium lamps, mercury lamps, chemical lamps, xenon lamps, halogen lamps, mercury halogen lamps, carbon arc lamps, incandescent lamps, laser beams, and LEDs.
From the viewpoint of work efficiency at the time of construction of pipe rehabilitation, at least one of ultraviolet rays and visible light irradiation devices having a peak wavelength in the wavelength range of 350 to 450 nm is preferable, and from the viewpoint of efficiently curing the resin composition, gallium Lamps and LEDs are more preferred, and gallium lamps are even more preferred.

The light irradiation device is not particularly limited as long as it has one or more irradiation units, but it preferably has a lamp assembly configured by connecting a plurality of light irradiation lamps in series. By having the lamp coupler, it is possible to efficiently perform pipe rehabilitation.

When a lining material is produced using the resin composition according to the first embodiment of the present embodiment, the number of days elapsed from after the resin composition is prepared (after the resin composition is produced) to when pipe rehabilitation is performed is preferably is 1-4 days, more preferably 1-3 days, more preferably 1-2 days.

When a lining material is produced using the resin compositions according to the second embodiment and the third embodiment of the present embodiment, after the resin composition is prepared (after the resin composition is produced) until pipe rehabilitation is performed. is preferably 2 to 7 days, more preferably 3 to 6 days, still more preferably 4 to 5 days.

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Synthesis of resin (A)]
First, resins for preparing resin compositions were synthesized according to the following Synthesis Examples and Comparative Synthesis Examples.
The details of the epoxy compounds used for synthesizing the resin (A) in the Synthesis Examples and Comparative Synthesis Examples are shown below.
Epoxy compound (1): bisphenol A type epoxy resin; "Epomic (registered trademark) R140P" manufactured by Mitsui Chemicals, Inc., epoxy equivalent 188
- Epoxy compound (2): bisphenol A type epoxy resin; "jER (registered trademark) 834", manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 245
Epoxy compound (3): phenolic novolak type epoxy resin; "EPICLON (registered trademark) N-740" manufactured by DIC Corporation, epoxy equivalent 172
In addition, an epoxy equivalent is the value measured based on JISK7236:2001.

<Synthesis of vinyl ester resin (A1)>
[Synthesis Example 1]
2068 g of epoxy compound (1), 1.2 g of methylhydroquinone as a polymerization inhibitor (epoxy compound (1), and 0.04 parts by mass with respect to a total of 100 parts by mass of methacrylic acid), and 2,4,6-tris (dimethylaminomethyl) phenol ("Seikuol TDMP", manufactured by Seiko Kagaku Co., Ltd., purity 95 mass as an esterification catalyst. %) (0.3 parts by mass with respect to the total of 100 parts by mass of the epoxy compound and methacrylic acid) was added and heated to 110°C. Then, 946 g of methacrylic acid (acid group of methacrylic acid is 100 mol per 100 mol of total epoxy group of epoxy compound (1)) as unsaturated monobasic acid (a1-2) is added dropwise over about 30 minutes. , 120° C. and allowed to react for about 3 hours to produce a vinyl ester resin (A1-1a).
Table 3 shows the blending amount of each component.

[Synthesis Example 2]
1260 g of epoxy compound (1) and 0.74 g of methylhydroquinone as a polymerization inhibitor (epoxy compound (1) and methacrylic acid described later) were placed in a 5 L four-necked separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube and a thermometer. 0.04 parts by mass with respect to a total of 100 parts by mass), as a catalyst tetradecyldimethylbenzyl-ammonium chloride (“Nissan Cation (registered trademark) M ₂ -100R” (manufactured by NOF Corporation), purity greater than 90% by mass ) 5.6 g (0.3 parts by mass with respect to a total of 100 parts by mass of the epoxy compound (1) and methacrylic acid described later) is added and heated to 110 ° C., as an unsaturated monobasic acid (a1-2) After 577 g of methacrylic acid (100 mol of acid groups per total of 100 mol of epoxy groups in epoxy compound (1)) was added dropwise over about 30 minutes, the mixture was allowed to react for about 4 hours to form a resin precursor (P1-1). was synthesized. Then, 132 g of maleic anhydride (20 mol of maleic anhydride with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1)) is added as a polybasic acid anhydride (a1-4), and the reaction is continued for about 2 hours. A vinyl ester resin (A1-2a) was obtained by reaction.
Table 3 shows the blending amount of each component.

[Synthesis Examples 3 to 5]
Vinyl ester resins (A1-2b) to (A1-2d) were obtained in the same manner as in Synthesis Example 2, except that the raw materials and compounding ratios shown in Table 3 were used.
Table 3 shows the blending amount of each component.

[Synthesis Example 6]
In a 5 L four-necked separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube and a thermometer, 1260 g of epoxy compound (1) and 0.74 g of methyl hydroquinone as a polymerization inhibitor (epoxy compound (1), methacrylic acid , and 0.04 parts by mass with respect to a total of 100 parts by mass of maleic anhydride used as the polybasic acid anhydride (a1-3) described later), and tetradecyldimethylbenzylammonium chloride as a catalyst (“Nissan Cation (registered trademark) M ₂ -100R” (manufactured by NOF Corporation), purity greater than 90% by mass) 5.6 g (epoxy compound (1), methacrylic acid described later, and anhydride used as polybasic acid anhydride (a1-3) described later 0.3 parts by mass with respect to a total of 100 parts by mass of maleic acid (a1-3)) is added and heated to 110 ° C., and 519 g of methacrylic acid (epoxy compound (1 ) and 66 g of maleic anhydride as the polybasic acid anhydride (a1-3) (per 100 mol of the total epoxy group of the epoxy compound (1) , the total amount of maleic anhydride-derived acid groups is 10 mol) was added dropwise over about 30 minutes, followed by reaction for about 4 hours to synthesize a resin precursor (P1-1). Then, 263 g of maleic anhydride (40 mol of maleic anhydride with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1)) is added as a polybasic acid anhydride (a1-4), and the reaction is continued for about 2 hours. A vinyl ester resin (A1-3a) was obtained by reaction.
Table 3 shows the blending amount of each component.

[Synthesis Examples 7 to 9]
Vinyl ester resins (A1-3b) to (A1-3d) were obtained in the same manner as in Synthesis Example 6, except that the raw materials and compounding ratios shown in Table 3 were used.
Table 3 shows the blending amount of each component.

[Comparative Synthesis Examples 1 to 4]
Synthesis was performed in the same manner as in Synthesis Example 6, except that the raw materials and blending ratios shown in Table 4 were used. As a result, the resin precursor gelled, making it impossible to proceed with subsequent synthetic operations, and no resin was obtained.
Table 4 shows the blending amount of each component.

[Synthesis Example 10]
1512 g of epoxy compound (1) and 429 g of bisphenol A (bisphenol per 100 mol of total epoxy groups in epoxy compound (1)) were placed in a 5 L four-necked separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube and a thermometer. The total amount of hydroxyl groups of A is 47 mol) was added and heated to 80°C. Then, 3.9 g of triethylamine (manufactured by Daicel Co., Ltd.) as a catalyst (epoxy compound (a1-1), bisphenol (a1-5), and unsaturated monobasic acid (a1-2) for a total of 100 parts by mass) .2 parts by mass) was added, heated to 145° C., and reacted for 1 hour to synthesize a resin precursor (P3). Then, after cooling to 110 ° C., 429 g of styrene as a reactive diluent (10% by mass based on the total mass of ingredients), 0.04 g of 5% copper naphthenate as a polymerization inhibitor (epoxy compound (a1-1), bisphenol ( a1-5) and unsaturated monobasic acid (a1-2) total 100 parts by mass), 1.3 g of trimethylhydroquinone (epoxy compound (a1-1), bisphenol (a1-5) and 0.056 parts by mass with respect to a total of 100 parts by mass of the unsaturated monobasic acid (a1-2)) and 2,4,6-tris (dimethylaminomethyl) phenol ("Seikuol TDMP", Seiko as an esterification catalyst Chemical Co., Ltd., purity greater than 95% by mass) 6.9 g (epoxy compound (a1-1), bisphenol (a1-5) and unsaturated monobasic acid (a1-2) for a total of 100 parts by mass) 3 parts by mass) was added and heated to 110°C. Then, 365 g of methacrylic acid (the total amount of acid groups of methacrylic acid is 53 mols per 100 mols of the total amount of epoxy groups of the epoxy compound (1)) as the unsaturated monobasic acid (a1-2) is added dropwise over about 30 minutes. After that, the mixture was heated to 130° C. and reacted for about 2 hours to produce a vinyl ester resin (A1-4a).
This reaction product was cooled to 90° C., and 0.13 g of hydroquinone as a polymerization inhibitor (0.003 parts by mass with respect to a total of 100 parts by mass of all ingredients), a reactive diluent (ethylenically unsaturated group-containing monomer As (B)), 1546 g of styrene (36% by mass based on the total mass of compounding components) was added to obtain a mixture of 54% by mass of vinyl ester resin (based on the total mass of compounding components) and 46% by mass of styrene.
Table 5 shows the blending amount of each component.

[Synthesis Example 11]
In a 5 L four-necked separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube and a thermometer, 1795 g of epoxy compound (1) and 271 g of bisphenol A (bisphenol A per 100 mol of total epoxy groups in epoxy compound (1) (total amount of hydroxyl groups of 25 mol) was added and heated to 80°C. Next, 3.1 g of triethylamine (manufactured by Daicel Co., Ltd.) as a catalyst (0.15 parts by mass with respect to the total of 100 parts by mass of the epoxy compound (a1-1) and bisphenol (a1-5)) was added, and the temperature was raised to 145 ° C. The mixture was heated and reacted for 1 hour to synthesize a resin precursor (P3). Then, after cooling to 110 ° C., 496 g of styrene as a reactive diluent (10% by mass based on the total mass of ingredients), 0.05 g of 5% copper naphthenate as a polymerization inhibitor (epoxy compound (a1-1), bisphenol ( a1-5) and unsaturated monobasic acid (a1-2) total 100 parts by mass 0.0019 parts by mass), methyl hydroquinone 1.0 g (epoxy compound (a1-1), bisphenol (a1-5) , and 0.04 parts by mass with respect to a total of 100 parts by mass of unsaturated monobasic acid (a1-2)), 1.5 g of trimethylhydroquinone (epoxy compound (a1-1), bisphenol (a1-5) and unsaturated 0.057 parts by mass with respect to a total of 100 parts by mass of the monobasic acid (a1-2)), 2,4,6-tris (dimethylaminomethyl) phenol ("Seikuol TDMP", Seiko Kagaku Co., Ltd. as an esterification catalyst Made, purity over 95% by mass) 8.0 g (0.3 parts by mass per 100 parts by mass of epoxy compound (a1-1), bisphenol (a1-5) and unsaturated monobasic acid (a1-2) ) is added and heated to 110° C., and 564 g of methacrylic acid as unsaturated monobasic acid (a1-2) (the total amount of acid groups of methacrylic acid is 69 per 100 mol of the total amount of epoxy groups in epoxy compound (1). mol) was added dropwise over about 30 minutes, followed by reaction for about 2 hours to synthesize a resin precursor (P4). Next, 33 g of fumaric acid (6 moles of fumaric acid per 100 moles of total epoxy groups of epoxy compound (1)) is added as unsaturated polybasic acid (a1-6) and reacted for about 1 hour to give vinyl. An ester resin (A1-5a) was obtained.
This reaction product was cooled to 90° C., 1784 g of styrene (36% by mass based on the total mass of ingredients) was added as a reactive diluent (ethylenically unsaturated group-containing monomer (B)), and 54 masses of vinyl ester resin was added. % (based on total weight of compounding components) and 46% by weight of styrene.
Table 5 shows the blending amount of each component.

[Synthesis Example 12]
In a 5 L four-necked separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube and a thermometer, 1950 g of epoxy compound (1) was heated to 80° C., and 407 g of styrene as a reactive diluent (based on the total mass of the blending components 10% by mass), 0.04 g of 5% copper naphthenate as a polymerization inhibitor (0.0014 parts by mass with respect to a total of 100 parts by mass of the epoxy compound (a1-1) and unsaturated monobasic acid (a1-2)) , 0.9 g of methyl hydroquinone (0.03 parts by mass with respect to a total of 100 parts by mass of the epoxy compound (a1-1) and unsaturated monobasic acid (a1-2)), 1.6 g of trimethyl hydroquinone (epoxy compound (a1 -1), 0.057 parts by mass with respect to a total of 100 parts by mass of the unsaturated monobasic acid (a1-2)), 2,4,6-tris (dimethylaminomethyl) phenol as an esterification catalyst ("SEIQOL TDMP ”, manufactured by Seiko Chemical Co., Ltd., purity greater than 95% by mass) 8.5 g (epoxy compound (a1-1) and unsaturated monobasic acid (a1-2) 0.3 parts by mass with respect to a total of 100 parts by mass ) is added and heated to 100° C., and 891 g of methacrylic acid as unsaturated monobasic acid (a1-2) (the total amount of acid groups of methacrylic acid is 100 per 100 mol of the total amount of epoxy groups of epoxy compound (1). mol) was added dropwise over about 30 minutes, followed by reaction for about 2 hours to obtain a vinyl ester resin (A1-1b).
This reaction product was cooled to 90° C., 815 g of styrene (20% by mass based on the total mass of ingredients) was added as a reactive diluent (ethylenically unsaturated group-containing monomer (B)), and 70 masses of vinyl ester resin was added. % (based on total weight of compounding components) and 30% by weight of styrene.
Table 5 shows the blending amount of each component.

[Synthesis Examples 13 and 14]
Vinyl ester resins (A1-1c) and (A1-1d) were obtained in the same manner as in Synthesis Example 10, except that the composition shown in Table 5 was used. In Synthesis Example 15, "Nissan Cation (registered trademark) M ₂ -100R" (manufactured by NOF Corporation, purity of more than 90% by mass) was used as the catalyst.
For the vinyl ester resin (A1-1c), after cooling to 90 ° C., 1222 g of styrene was added as a reactive diluent (ethylenically unsaturated group-containing monomer (B)), and 70% by mass of the vinyl ester resin (compounding component A mixture of 30% by weight of styrene and 30% by weight of styrene was obtained.
For the vinyl ester resin (A1-1d), after cooling to 90 ° C., 1543 g of phenoxyethyl methacrylate was added as a reactive diluent (ethylenically unsaturated group-containing monomer (B)), and 65% by mass of the vinyl ester resin ( A mixture of 35% by weight of styrene and 35% by weight of styrene was obtained.
Table 5 shows the blending amount of each component.

<Synthesis of unsaturated polyester resin (A2)>
[Synthesis Example 15]
224.6 g of propylene glycol as diol (a2-1) (per 100 mol% of diol (a2-1) 27.5 mol%) and 810.5 g of 2,2-dimethyl-1,3-propanediol (72.5 mol% with respect to 100 mol% of diol (a2-1)), an ethylenically unsaturated group As non-containing dibasic acid (a2-2-2), 472.6 g of isophthalic acid (26.5 mol% with respect to 100 mol% of diol (a2-1)) and 356.6 g of terephthalic acid (diol (a2- 1) 20.0 mol% with respect to 100 mol%), as the ethylenically unsaturated group-containing dibasic acid (a2-2-1), 563.1 g of maleic anhydride (diol (a2-1) 100 mol% 53.5 mol % of the total amount) was charged, and condensation reaction was performed at 215° C. for 10 hours to obtain an unsaturated polyester resin (A2-a).
Table 6 shows the blending amount of each component.

[Synthesis Examples 16 to 23]
Synthesis was carried out in the same manner as in Synthesis Example 17 except that the raw materials and compounding ratios shown in Table 6 were used to obtain unsaturated polyester resins (A2-b) to (A2-i).
Table 6 shows the blending amount of each component.

[Measurement evaluation of resin (A)]
Vinyl ester resins (A1-1a) to (A1-1f), (A1-2a) to (A1-2d), (A1-3a) to (A1-3d), (A1-4a) obtained in the above synthesis examples ), and (A1-5a), and the unsaturated polyester resins (A2-a) to (A2-i) were measured and evaluated for the following items. These measurement evaluation results are summarized in Tables 3, 5 and 6 below.

<Acid value>
The acid value of resin (A) is vinyl ester resin (A1-1a) ~ (A1-1f), (A1-2a) ~ ( A1-2d), (A1-3a) to (A1-3d), (A1-4a), and (A1-5a), and acids contained in unsaturated polyester resins (A2-a) to (A2-i) The mass of potassium hydroxide required to neutralize the components was measured to determine the acid value.
The vinyl ester resin (A1) is a mixture obtained by diluting the vinyl ester resin (A1) with phenoxyethyl methacrylate (manufactured by Showa Denko Materials Co., Ltd.) or styrene, which is an ethylenically unsaturated group-containing monomer (B). (Vinyl ester resin (A1) 54 to 70% by mass), and in the unsaturated polyester resin (A2), the unsaturated polyester resin (A2) is diluted with styrene, which is an ethylenically unsaturated group-containing monomer (B). The resulting mixture (unsaturated polyester resin (A2) 57-65% by mass) was used as a measurement sample. The acid value of resin (A) was obtained from the measured value of the measurement sample. "Autoburette UCB-2000" (manufactured by Hiranuma Sangyo Co., Ltd.) was used as the titrator, and a mixed indicator of bromothymol blue and phenol red was used as the indicator.
Table 1 shows details of the mixture (measurement sample) containing the vinyl ester resin (A1) obtained in each synthesis example and the mixture (measurement sample) containing the unsaturated polyester resin (A2).

<Hydroxyl value>
The hydroxyl value of the resin (A) is vinyl ester resin (A1-1b) ~ (A1-1d), (A1-2b), (A1-2b), ( A1-2d), (A1-4a) and (A1-5a) were measured for the mass of potassium hydroxide required to neutralize the acetic acid generated by the acetylation of 1 g, and the hydroxyl value was determined.
In the vinyl ester resin (A1), a mixture (vinyl Ester resin (A1) 65% by mass) and two mixtures (vinyl ester resin (A1) 70% by mass and 54% by mass) obtained by diluting vinyl ester resin (A1) with styrene were used as measurement samples. The hydroxyl value of resin (A) was obtained from the measured value of the measurement sample. Neutralization titration was performed manually using 1% phenolphthalein (ethanol solution) as an indicator.
Table 1 shows the details of the mixture (measurement sample) containing the vinyl ester resin (A1) obtained in each synthesis example.

<Weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw/Mn>
The weight-average molecular weight Mw and number-average molecular weight Mn of the resin (A) were measured by gel permeation chromatography (GPC) under the following conditions and determined as standard polystyrene equivalent molecular weights. Mw/Mn was calculated from the values of Mn and Mw.
・ Apparatus: "Shodex (registered trademark) GPC-101" (manufactured by Showa Denko Co., Ltd.)
・ Column: “Shodex (registered trademark) LF-804” (manufactured by Showa Denko KK)
・ Detector: Differential refractometer “Shodex (registered trademark) RI-71S” (manufactured by Showa Denko Co., Ltd.)
・Column temperature: 40°C
・Sample: 0.2% by mass tetrahydrofuran solution of resin (A) ・Developing solvent: tetrahydrofuran ・Flow rate: 1.0 mL/min

<Viscosity>
In the vinyl ester resin (A1), a mixture of 65% by mass of the vinyl ester resin (A1) and 35% by mass of phenoxyethyl methacrylate, a mixture of 70% by mass of the vinyl ester resin (A1) and 30% by mass of styrene, or a vinyl ester The viscosity of a mixture of 54% by mass of resin (A1) and 46% by mass of styrene was measured using an E-type viscometer ("RE-85U" (manufactured by Toki Sangyo Co., Ltd.), cone plate type, cone rotor: 1°34' ×R24, rotation speed: 50 rpm to 0.5 rpm), and measured at a temperature of 25°C.
The mixture (measurement sample) containing the vinyl ester resin (A1) obtained in each Synthesis Example was the same as the mixture used in the hydroxyl value measurement.

Further, the rotational speed of the cone rotor according to the measured viscosity was set as follows.
When the viscosity of the mixture was more than 0 Pa·s and 1.0 Pa·s or less, the measurement was performed at a rotation speed of 50 rpm.
When the viscosity of the mixture was more than 1.0 Pa·s and 2.0 Pa·s or less, the measurement was performed at a rotation speed of 20 rpm.
When the viscosity of the mixture was over 2.0 Pa·s and 4.0 Pa·s or less, the measurement was performed at a rotation speed of 10 rpm.
When the viscosity of the mixture was more than 4.0 Pa·s and 8.0 Pa·s or less, the measurement was performed at a rotation speed of 5 rpm.
When the viscosity of the mixture was more than 8.0 Pa·s and 18.0 Pa·s or less, the measurement was performed at a rotation speed of 2.5 rpm.
When the viscosity of the mixture was greater than 18.0 Pa·s and less than or equal to 45.0 Pa·s, the measurement was performed at a rotation speed of 1.0 rpm.
When the viscosity of the mixture was more than 45.0 Pa·s and less than or equal to 100.0 Pa·s, the measurement was performed at a rotational speed of 0.5 rpm.

Table 2 below shows the rotation speed of the cone rotor according to the measured viscosity.

[Production of resin composition]
The details of the thixotropic agents used in the production of the resin compositions in the following examples and comparative examples are shown below.
・Thixotropic agent (1): Organic thixotropic agent; “Floronon SP-1000AF”, manufactured by Kyoeisha Chemical Co., Ltd. ・Thixotropic agent (2): Hydrophobic silica; “Reolosil PM-20L”, manufactured by Tokuyama Corporation

<Example 1>
A mixture (1) of 26 parts by mass of a vinyl ester resin (A1-1a) and 14 parts by mass of phenoxyethyl methacrylate as an ethylenically unsaturated group-containing monomer (B), and 26 parts by mass of a vinyl ester resin (A1-3c) and 14 parts by mass of phenoxyethyl methacrylate as an ethylenically unsaturated group-containing monomer (B) to prepare a mixture (2).
Subsequently, 40 parts by mass of the mixture (1), 40 parts by mass of the mixture (2), 12 parts by mass of benzyl methacrylate, 8 parts by mass of diethylene glycol dimethacrylate, 0.2 parts by mass of water, and 1.7 parts by mass of thixotropic agent (1). parts by mass, and 0.2 parts by mass of 2,2-dimethoxy-2-phenylacetophenone and 0.2 parts by mass of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide as a polymerization initiator (D), Mixing was performed for 20 minutes at 2000 to 3000 rpm using a disper (high-speed dispersing group "Homo Disper 2.5 type" manufactured by Primix Co., Ltd.). To this, 1.5 parts by mass of magnesium oxide (“Magmicron MD-4AM-2”, manufactured by Mikuni-Color Co., Ltd., magnesium oxide content 30% by mass (estimated); hereinafter the same) was added as a compound (C). , and further mixed for about 1 minute to obtain a resin composition (X-1).

<Examples 2 to 16, Comparative Examples 1 to 8>
In Example 1, resin compositions (X-2) to (X-16) and (X'-1) to ( X'-8) was obtained.

<Example 17>
A mixture of 54 parts by mass of a vinyl ester resin (A1-4a) and 46 parts by mass of styrene as an ethylenically unsaturated group-containing monomer (B) was added with 2,2-dimethoxy-2-phenyl as a photopolymerization initiator (D). 0.2 parts by mass of acetophenone and 0.2 parts by mass of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.1 parts by mass of water as compound (E), and an organic thixotropic agent (thixotropic Agent (1), "Furnon SP-1000AF", manufactured by Kyoeisha Chemical Co., Ltd.) 1.0 parts by mass is added, and disper (high-speed dispersing group "Homodisper 2.5 type" manufactured by Primix Co., Ltd.) is used to 2000 to 2000. Mixed for 20 minutes at 3000 rpm. To this, as a thickener (C), magnesium oxide (“Magmicron MD-4AM-2”, manufactured by Mikuni-Color Co., Ltd., magnesium oxide content 30% by mass (estimated); hereinafter the same.) 1.2 parts by mass ( Magnesium oxide content of 0.36 parts by mass) was added and further mixed for about 1 minute to obtain a resin composition (X-17).

<Examples 18, 19, 21-27, 29, 30, 33-38>
In Example 17, resin compositions (X-18), (X-19), (X-21) to (X -27), (X-29), (X-30) and (X-33) to (X-38).

<Examples 20, 28, 31 and 32>
In Example 17, the mixture of the resin (A) and styrene as the ethylenically unsaturated group-containing monomer (B) was further added with 3-dodecenylsuccinic acid as the carboxy group-containing compound at the compounding ratio shown in Tables 8 and 9. Others were prepared in the same manner except that the raw materials and blending ratios shown in Tables 12 and 13 were used, and resin compositions (X-20), (X-28), (X-31) and (X -32) was obtained.

<Example 39>
A mixture (1) was prepared by dissolving 54.74 parts by mass of the unsaturated polyester resin (A2-a) as the ethylenically unsaturated group-containing monomer (B) in 44.63 parts by mass of styrene. Further, as a carboxy group-containing compound, 0.63 parts by mass of 3-dodecenylsuccinic acid was dissolved in 0.63 parts by mass of styrene to prepare a mixture (2). 99.37 parts by mass of the mixture (1), 1.26 parts by mass of the mixture (2), 0.20 parts by mass of water as the compound (E), and phenylbis(2, 0.11 parts by mass of 4,6-trimethylbenzoyl)phosphine oxide and 0.11 parts by mass of 2,2-dimethoxy-2-phenylacetophenone are added, and disper (high-speed dispersing group "Homodisper 2.5 type" Primix stock company) at 2000-3000 rpm for about 10 minutes. Furthermore, as a thickener (C), magnesium oxide (Magmicron MD-4AM-2, manufactured by Mikuni-Color Co., Ltd., estimated content of magnesium oxide 30% by mass) 0.96 parts by mass (0.29 parts by mass in terms of magnesium oxide ) was added and mixed for about 1 minute at 2000 to 3000 rpm using a disper to obtain a resin composition (X-39).

<Examples 40 to 66, Comparative Examples 9 to 14>
In Example 39, resin compositions (X-40) to (X-66) and (X'-9) to were prepared in the same manner except that the raw materials and blending ratios shown in Tables 14 to 17 were used. (X'-14) was obtained.

[Measurement evaluation of resin composition]
Regarding the resin compositions (X-1) to (X-66) and (X'-1) to (X'-14) obtained in the above examples and comparative examples, the viscosity, impregnating property, tackiness, staining We measured and evaluated the ease of extraction, bending, and rehabilitation of simulated pipes. These measurement evaluation results are shown in Tables 9 to 17 below.

<Viscosity>
Immediately after preparation, 280 g of resin compositions (X-1) to (X-38) were placed in a 300 ml container, sealed, and left to stand at 25° C. and normal humidity for storage.
For resin compositions (X-39) to (X-66), (X'-9), (X'-10), (X'-13), and (X'-14), immediately after adjustment, 500 g was placed in a 500 mL polypropylene container and covered with aluminum foil. This was placed in a bag (410 mm × 280 mm, material: polyethylene, film thickness: 30 µm), sealed by thermocompression, and left statically in an environment of 25°C and 50% RH or 25°C and 80% RH. placed and stored.
Immediately after preparation, the resin compositions (X'-11) and (X'-12) were placed in 500 mL metal round cans, covered with metal lids, and placed in an environment of 23 ° C. and 50% RH. placed.

For the stationary resin compositions (X-1) to (X-4), (X-17) to (X-27) and (X-39) to (X-51), 1 after resin composition adjustment The viscosity at 25° C. after the passage of time and the viscosity at 25° C. after 2 days from the preparation of the resin composition were measured.
Resin compositions (X-5) to (X-16), (X-28) to (X-38), (X-52) to (X-66) and (X'-1) to (X'- Regarding 14), the viscosity at 25 ° C. after 1 hour from the preparation of the resin composition, the viscosity at 25 ° C. after 2 days from the preparation of the resin composition, and the viscosity at 25 ° C. after 5 days from the preparation of the resin composition was measured. According to the viscosity range, the following two types of instruments were appropriately selected and measured at a temperature of 25°C.

(1) "RB80 type viscometer" (manufactured by Toki Sangyo Co., Ltd.; rotor No. 3 to 4)
When the viscosity of the resin composition is more than 0 Pa·s and 1.0 Pa·s or less, rotor No. 3 and measured at a rotation speed of 60 rpm.
When the viscosity of the resin composition is more than 1.0 Pa·s and 5.0 Pa·s or less, rotor No. 4 and measured at a rotation speed of 60 rpm.
When the viscosity of the resin composition is more than 5.0 Pa·s and 25.0 Pa·s or less, rotor No. 4 and measured at a rotation speed of 12 rpm.
When the viscosity of the resin composition is more than 25.0 Pa·s and 50.0 Pa·s or less, rotor No. 4 and measured at a rotation speed of 6 rpm.
When the viscosity of the resin composition is more than 50.0 Pa·s and 100.0 Pa·s or less, rotor No. 4 and measured at a rotation speed of 3 rpm.
Table 7 below shows the rotor used and the number of revolutions according to the measured viscosity.

(2) "HBDVE type viscometer" (manufactured by Eiko Seiki Co., Ltd.; T-bar spindle TA to TD, rotation speed: 1 rpm)
T-bar spindle TA was used when the viscosity of the resin composition was more than 100.0 Pa·s and 800.0 Pa·s or less.
T-bar spindle TB was used when the viscosity of the resin composition was more than 800.0 Pa·s and 1600.0 Pa·s or less.
A T-bar spindle TC was used when the viscosity of the resin composition was more than 1600.0 Pa·s and 4000.0 Pa·s or less.
T-bar spindle TD was used when the viscosity of the resin composition was more than 4000.0 Pa·s and 10000.0 Pa·s or less.
The T-bar spindles used according to the measured viscosity are shown in Table 8 below.

<Impregnability>
Cut out 3 squares of 100 mm × 100 mm from glass fiber chopped strand mat ("MC 450A", manufactured by Nitto Boseki Co., Ltd.), stack the 3 sheets, and place a stainless steel ring with an inner diameter of 50 mm and a height of 20 mm. After that, 10 g of the resin composition prepared in Examples and Comparative Examples 1 hour after adjustment was poured into a stainless steel ring, and the time for the resin composition to permeate to the bottom glass fiber was measured.
The impregnating property was determined to be good when the poured resin composition permeated the bottom layer of glass fibers in less than 5 minutes. In the column of impregnating properties in Tables 9 to 17, "◯" indicates good impregnating properties, and "X" indicates other cases.

<Tackiness>
280 g of the resin composition was placed in a 300 ml disposable cup, left to stand and stored for 2 days under room temperature and normal humidity (dark place), and then the surface of the resin composition was touched with a finger. At that time, when there was stickiness and the resin composition adhered to the finger, it was determined that the tackiness was good. In the column of tackiness in Tables 9 to 17, "O" indicates good tackiness, and "X" indicates no stickiness and the resin composition does not adhere to fingers.
When producing a lining material using a sheet-like or tape-like fiber base material (F), a resin composition exhibiting good tackiness in this evaluation can be suitably used.

<Exudation>
Cut out 3 pieces of glass fiber chopped strand mat ("MC 450A", manufactured by Nitto Boseki Co., Ltd.) into 200 mm × 200 mm squares, stack the 3 pieces, and impregnate about 51 g of the resin composition with a defoaming roller. , to obtain a laminate (glass content about 50%). The laminate was sandwiched between polyethylene terephthalate films cut out to a size of 250 mm×250 mm, and allowed to stand at room temperature and normal humidity (dark place) for curing to obtain a lining material. In addition, when using the resin compositions (X-1) to (X-4), (X-17) to (X-27) and (X-39) to (X-51), they were cured for 2 days. , resin compositions (X-5) to (X-16), (X-28) to (X-38), (X-52) to (X-66) and (X'-1) to (X' -14) was cured for 5 days. After curing, a cut of about 50 mm is made with scissors, and the presence or absence of the resin composition exuding (resin dripping) is checked from the cross section. If the resin composition does not exude from the cross section, it is judged to be in good condition bottom. In the exudation property column of Tables 5 to 12, the case where there was no exudation was indicated as "◯", and the case where exudation was present was indicated as "x".

<Bending evaluation>
A material for lining material was obtained in the same manner as in the evaluation of exudation property. In addition, when using the resin compositions (X-1) to (X-4), (X-17) to (X-27) and (X-39) to (X-51), they were cured for 2 days. , resin compositions (X-5) to (X-16), (X-28) to (X-38), (X-52) to (X-66) and (X'-1) to (X' -14) was cured for 5 days. After curing, the laminate is bent 180°, and after returning it, the presence or absence of bending marks and the presence or absence of peeling of the resin and fibers are checked. Judged. In the bending evaluation column of Tables 9 to 17, the presence or absence of bending marks and the absence of peeling of the resin and fibers are indicated by "○", and the presence or absence of bending marks and peeling of the resin and fibers are indicated. "A" indicates the case, and "x" indicates the presence or absence of bending traces and peeling of resin and fiber.

<Evaluation of simulated pipe rehabilitation>
An aluminum plate with a width of 220 mm, a length of 1000 mm, and a thickness of 4 mm, whose edges were curved with R2, was coated with a polyethylene film (manufactured by Ise Kasei Kogyo Co., Ltd.) having a length of 1,400 mm and a thickness of 100 μm as an inner film. It was wrapped and heat-sealed using Vinylade (manufactured by Hakko Co., Ltd.) at the wrap portion. Then, from above the inner film, a glass fiber chopped strand mat (“MC 450A”, manufactured by Nitto Boseki Co., Ltd.) with a length of 800 mm, which is the fiber base material (F), is wound, and at the same time as it is wound, a defoaming roller is used to make the resin composition. A substrate impregnated with a resin composition (four layers: thickness 3.0 mm, glass fiber content 40%) was obtained.
Further, the resin composition-impregnated substrate was covered with a polyethylene film of 1400 mm length×100 μm thickness as an outer film, and the wrap portion was adhered and fixed with a masking tape of 50 mm width (manufactured by 3M Japan Ltd.). Subsequently, the aluminum plate was pulled out to obtain a lining material.
After curing the lining material at 25° C. for 2 days, it was pulled into an acrylic pipe, which is a simulated pipe with an inner diameter of 150 mm and a length of 1000 mm. Both ends of the lining material were bound with binding bands to seal, and air was injected from one end at 4 L/sec to expand the diameter of the lining material and press it against the inner surface of the acrylic pipe. After that, both ends of the lining material are fixed to the acrylic pipe, one end is installed with a cap with an air injection hole, and the other end is an ultraviolet LED fluorescent lamp type light "NS365-FTL-C30" ( (manufactured by Nitride Semiconductor) was installed. While injecting air from a cap with an air injection hole at 4 L/sec, using an ultraviolet illuminometer “UIT-201” (Ushio Inc.), illuminance 10 mW / cm ² , sensitivity wavelength range 330 to 490 nm, irradiation time The simulated pipe was rehabilitated by photocuring the lining material for 60 minutes.
When air was blown into the lining material and the diameter could be expanded without any problem, it was determined that the diameter could be expanded.
Furthermore, using a UVLED fluorescent lamp type light "NS365-FTL-C30" (manufactured by Nitride Semiconductor), the lining material was photocured at an illuminance of 10 mW/cm ² for an irradiation time of 60 minutes, and then the inner film was removed. The thickness of the hardened layer of the lining material was confirmed. The thickness of the hardened layer of the lining material was measured at 4 points on the cross section of the pipe, 12 points in total, at 3 points, 200 mm from the center and both ends of the simulated pipe. When the lower limit of the thickness is 3.0 mm or more and the upper limit is within 3.0 mm + 20% (within 3.6 mm), uneven distribution of the resin composition in the lining material is well suppressed, and the appearance is good. I judged. In the column of simulated pipe rehabilitation evaluation in Tables 5 to 12, "○" indicates that the lining material can be expanded and the thickness of the hardened layer of the lining material is 3.0 to 3.6 mm, and the lining material is expanded. When the thickness of the cured layer of the lining material was not within the range of 3.0 to 3.6 mm, or both of them, it was evaluated as "x".

As shown in Tables 9, 12 and 14, in Examples 1 to 4, 17 to 27 and 39 to 51, the viscosity after 1 hour from the preparation of the resin composition was 0.1 to 3 Pa s, and the resin Since the viscosity was 400 to 3500 Pa·s two days after the preparation of the composition, it can be seen that a resin composition with an appropriately controlled thickening rate was obtained.
Further, as shown in Tables 10, 13, 15 and 16, in Examples 5 to 16, 28 to 38 and 52 to 66, the viscosity after 1 hour from the preparation of the resin composition was 0.1 to 3 Pa s. , and the viscosity was 400 to 3500 Pa·s 5 days after the preparation of the resin composition, indicating that a resin composition with an appropriately controlled thickening rate was obtained.
On the other hand, in Comparative Examples 1 to 4 and 10, the impregnability was low because the viscosity was high one hour after the resin composition was prepared. In Comparative Examples 5, 9, and 11 to 14, although the viscosity was appropriate one hour after the resin composition was prepared, the rate of thickening was low, and the resin composition did not seep out even after curing for 5 days. be seen. Further, in Comparative Examples 6 to 8, although the viscosity was appropriate one hour after the resin composition was prepared, the viscosity was very high five days after the resin composition was prepared, and the resin composition did not seep out. Although not visible, traces of bending and peeling of resin and fibers were observed.

[Evaluation of cured product (cast product, FRP)]
The resin composition (X-5) obtained in Example 5 was irradiated with light for 60 minutes using a 250 W metal halide lamp (peak wavelength: 420 nm, illuminance: 20 mW/cm ² ) to obtain a 170 mm × 170 mm, 4 mm thick A cured product (cast product) was obtained. The illuminance was measured using an illuminance meter "IL1400A" (manufactured by International Light Technologies, photodetector model SEL005, measurement wavelength range: 380 to 450 nm, median value: 415 nm).
In addition, a glass fiber chopped strand mat ("MC 450A", manufactured by Nitto Boseki Co., Ltd.) was impregnated with the resin composition (X-5) obtained in Example 5, and three sheets were stacked at 25 ° C. for 5 days. After curing, a material for lining material was obtained. The material for the lining material is irradiated with light for 30 minutes using a 250 W metal halide lamp (peak wavelength 420 nm, illuminance 25 mW/cm ² ), and a cured product (FRP: glass fiber content 31% by mass) was obtained.
Subsequently, each cured product was cut to a length of 80 mm and a width of 10 mm, and cured for 24 hours under an environment of a temperature of 23° C. and a relative humidity of 50% to obtain test pieces for measurement evaluation.

<Bending strength and bending elastic modulus>
In accordance with JIS K7171: 2016, using a universal material testing machine ("Tensilon UCT-1T", manufactured by Orientec Co., Ltd.; distance between fulcrums 48 mm, test speed 1.3 mm / min), temperature 23 ° C., humidity 50% The flexural strength and flexural modulus were measured under the environment of
For the cured product (cast product), the measured values of 5 test pieces (N = 5), and for the cured product (FRP), the average values of the measured values of 3 test pieces (N = 3) were calculated. flexural strength and flexural modulus.
The cured product (cast product) of the resin composition (X-5) has a bending strength of 101 MPa and a bending elastic modulus of 3.3 GPa, and the cured product (FRP) has a bending strength of 162 MPa and a bending elastic modulus of 8.5 GPa. Met.

<Load Deflection Temperature>
For cured products (cast products), in accordance with JIS K7191-1: 2015 and JIS K7191-1: 2015, load deflection temperature (HDT) measuring device ("HDT Tester S-3M", manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to measure the deflection temperature under load, and the average value of the measured values of 3 test pieces (N = 3) was taken as the deflection temperature under load of the cured product.
The deflection temperature under load of the cured product (cast product) of the resin composition (X-5) was 90°C.

<Barcol hardness>
Regarding the cured product (cast product) and cured product (FRP), in accordance with JIS K7060: 1995, using a Barcol hardness tester ("GYZJ 934-1", manufactured by Barber-Coleman), each test piece for measurement evaluation The back surface of 10 light-irradiated surfaces was measured, and the average value was taken as the Barcol hardness of the cured product.
The cured product (FRP) of the resin composition (X-5) had a Barcol hardness of 46.

The bending strength, bending elastic modulus, and deflection temperature under load of the cured product of the resin composition were measured and evaluated, and it was found that the obtained cured product had sufficient mechanical strength.
Furthermore, from the results of evaluation of diameter expansion of the lining material and uneven distribution of the resin composition in the lining material, it was found that the lining material produced by impregnating the resin composition has properties suitable for pipe rehabilitation.

According to the present embodiment, there is provided a resin composition used as a lining material for pipe rehabilitation, which has a low viscosity one hour after the resin composition is prepared and a moderately controlled thickening rate. A lining material using the resin composition according to the present embodiment has good workability and excellent strength.

Claims

A resin composition used for a lining material for pipe rehabilitation,
a resin (A);
an ethylenically unsaturated group-containing monomer (B);
a thickener (C);
containing a photopolymerization initiator (D),
The viscosity at 25 ° C. after 1 hour from the preparation of the resin composition is 0.1 to 3.0 Pa s,
A resin composition having a viscosity of 400 to 3,500 Pa·s at 25° C. at least one of 2 days and 5 days after preparation of the resin composition.
With respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B),
35 to 90 parts by mass of the resin (A),
10 to 65 parts by mass of the ethylenically unsaturated group-containing monomer (B),
0.01 to 6 parts by mass of the thickener (C),
The resin composition according to claim 1, comprising 0.01 to 10 parts by mass of the photopolymerization initiator (D).
With respect to a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B),
20 to 80 parts by mass of the resin (A),
20 to 80 parts by mass of the ethylenically unsaturated group-containing monomer (B),
0.01 to 6 parts by mass of the thickener (C),
The resin composition according to claim 1, comprising 0.01 to 10 parts by mass of the photopolymerization initiator (D).
The resin composition according to claim 1 or 2, wherein the resin (A) contains at least one selected from vinyl ester resin (A1) and unsaturated polyester resin (A2).
The vinyl ester resin (A1) is 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). It is an addition reaction product of the resin precursor (P2), which is a reaction product, and the polybasic acid anhydride (a1-4),
The total amount of acid groups capable of reacting with epoxy groups derived from the polybasic acid anhydride (a1-3) is 5 to 25 mols per 100 mols of the total amount of epoxy groups in the epoxy compound (a1-1). The resin composition according to claim 4.
The vinyl ester resin (A1) is a resin precursor (P3) which is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5), and an The resin composition according to claim 4, which is a reaction product with a saturated monobasic acid (a1-2).
The vinyl ester resin (A1) is a resin precursor (P3) which is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5), and an inorganic The resin composition according to claim 4, which is a reaction product of a resin precursor (P4), which is a reaction product of a saturated monobasic acid (a1-2), and an unsaturated polybasic acid (a1-6). .
The unsaturated polyester resin (A2) is a reaction product of diol (a2-1) and dibasic acid (a2-2),
The diol (a2-1) contains 43 to 85 mol% of the diol (a2-1-1), which is an alkanediol having a molecular weight of 90 to 500, relative to 100 mol% of the diol (a2-1),
The claim that the dibasic acid (a2-2) comprises an ethylenically unsaturated group-containing dibasic acid (a2-2-1) and an ethylenically unsaturated group-free dibasic acid (a2-2-2). 4. The resin composition according to 4.
The resin composition according to claim 4, wherein the resin (A) has a hydroxyl value of 10 to 120 KOHmg/g.
The resin composition according to claim 1 or 2, wherein the thickener (C) is at least one selected from group 2 element oxides and hydroxides.
The resin composition according to claim 1 or 2, further comprising at least one compound (E) selected from water and a hydroxy group-containing compound.
The resin composition according to claim 1 or 2, further comprising a thixotropic agent.
A lining material comprising the resin composition according to claim 1 or 2 and a fiber base material (F).