KR20240029781A - How to rehabilitate a pipe - Google Patents

Abstract

A step (I) of preparing a resin composition, a step (II) of impregnating a fiber base (F) with the resin composition to obtain a resin composition-impregnated base material, and a process (III) of obtaining a lining material containing the resin composition-impregnated base material. ) and a step (IV) of placing the lining material in the pipe and photocuring it, wherein the resin composition includes a resin (A), an ethylenically unsaturated group-containing monomer (B), and a thickener ( C) and a photopolymerization initiator (D), the viscosity of the resin composition in step (II) at 25°C is 0.1 to 3 Pa·s, and in step (IV), the lining material is A method of rehabilitating a pipe wherein the resin composition has a viscosity of 400 to 3,500 Pa·s at 25°C when placed in the pipe.

Description

How to rehabilitate a pipe

The present invention relates to a method for rehabilitating pipes.

Recently, the deterioration of existing pipes buried in the ground, such as water pipes, sewage pipes, and power pipes, has become increasingly serious, and various methods for rehabilitating these pipes have been proposed.

For example, in Patent Document 1, a tubular lining material is brought into close contact with the inner wall of an existing pipe buried in the ground, and compressed air is supplied to the inside of the lining material while a movable light irradiation device introduced inside the lining material is used. A method for repairing existing pipes is disclosed, which includes a curing process of hardening the lining material by irradiating light to the inner surface of the lining material. Additionally, as a material for the lining material, a photocurable resin composition impregnated into an impregnated base made of fiber or the like can be used. As the photocurable resin composition, a polymerizable resin such as unsaturated polyester resin or vinyl ester resin can be used, such as styrene. It is described that one dissolved in a solvent can be used.

Japanese Patent Publication No. 2020-82408

Recently, rehabilitation of existing pipes requires increased pipe strength, thinner lining materials for pipe rehabilitation, and higher efficiency when arranging and hardening the lining material on the inner surface of existing pipes.

In line with this, the fiber base material constituting the lining material tends to become thinner and more dense. For this reason, the resin composition used as a material for the lining material by impregnating the fiber base material is preferably of low viscosity so that it can be easily impregnated. On the other hand, when placing a lining material in an existing pipe and curing it, the resin composition is required to have a viscosity that allows it to be uniformly distributed and maintained in the fiber base material without being unevenly distributed. Additionally, from the viewpoint of workability when placing the lining material in an existing pipe, it is also required to have a viscosity sufficient to provide flexibility to the lining material. That is, when impregnating a fiber base with a resin composition, the viscosity is low, but the viscosity increases over time, and when the lining material is placed in an existing pipe, the resin composition can be maintained in a maintained state and also provides flexibility to the lining material. A resin composition that has a sufficiently high viscosity is preferred. However, the thickening rate of the resin composition from production of the resin composition to placement of the lining material in the existing pipe could not be said to be sufficiently controlled. As a result, there were problems such as cases where pipes were not repaired uniformly or repairs could not be made efficiently.

The present invention was made to solve the above problems, and its purpose is to provide a pipe rehabilitation method that can uniformly and efficiently repair pipes.

That is, the present invention provides the following means.

[1] A step (I) of preparing a resin composition, a step (II) of impregnating a fiber base (F) with the resin composition to obtain a resin composition-impregnated base material, and obtaining a lining material containing the resin composition-impregnated base material. A pipe rehabilitation method comprising a step (III) and a step (IV) of disposing the lining material in the pipe and photocuring it, wherein the resin composition includes a resin (A), an ethylenically unsaturated group-containing monomer (B), and , a thickener (C) and a photopolymerization initiator (D), the viscosity of the resin composition in step (II) at 25°C is 0.1 to 3 Pa·s, and in step (IV), the lining A method of rehabilitating a pipe wherein the resin composition has a viscosity of 400 to 3,500 Pa·s at 25°C when the material is placed in the pipe.

[2] The pipe rehabilitation method according to [1] above, wherein the resin (A) contains at least one selected from vinyl ester resin (A1) and unsaturated polyester resin (A2).

[3] The vinyl ester resin (A1) is a resin that is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride (a1-3). It is an addition reaction product of a precursor (P2) and a polybasic acid anhydride (a1-4), and reacts with an epoxy group derived from the polybasic acid anhydride (a1-3) with respect to 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1). The pipe rehabilitation method described in [2] above, wherein the total amount of acid radicals that can be used is 5 to 25 mol.

[4] The vinyl ester resin (A1) is a resin precursor (P3) which is a reaction product of an epoxy compound (a1-1) and a bisphenol compound (a1-5) having two epoxy groups in one molecule, and an unsaturated monobasic acid. The pipe rehabilitation method described in [2] above, which is the reaction product of (a1-2).

[5] The vinyl ester resin (A1) is a resin precursor (P3) which is a reaction product of an epoxy compound (a1-1) and a bisphenol compound (a1-5) having two epoxy groups in one molecule, and an unsaturated monobasic acid. The pipe rehabilitation method described in [2] above, which is a reaction product of a resin precursor (P4), which is a reaction product of (a1-2), and an unsaturated polybasic acid (a1-6).

[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 diol (a2-1-1), which is an alkanediol with a molecular weight of 90 to 500, based on 100 mol% of the diol (a2-1),

The dibasic acid (a2-2) is of the tube described in [2] above, including a dibasic acid (a2-2-1) containing an ethylenically unsaturated group and a dibasic acid (a2-2-2) not containing an ethylenically unsaturated group. How to be rehabilitated.

[7] The pipe rehabilitation method according to any one of the above [1] to [6], wherein the number of days from completion of step (I) to completion of step (III) or curing process is at least 1 day and within 4 days.

[8] The resin (A) includes the vinyl ester resin (A1), and the resin composition contains the vinyl ester resin (A1), based on 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 ester resin (A1), 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 6 parts by mass of the photopolymerization initiator (D). The pipe rehabilitation method according to any one of [2] to [5] above, comprising 10 parts by mass.

[9] The resin (A) includes the unsaturated polyester resin (A2), and the unsaturated polyester resin (A2) and the ethylenically unsaturated group-containing monomer (B) total 100 parts by mass. 20 to 80 parts by mass of the polyester resin (A2), 20 to 80 parts by mass of the ethylenically unsaturated group-containing monomer (B), 0.01 to 6 parts by mass of the above thickener (C), and 0.01 to 5 parts by mass of the above carboxyl group-containing compound. The pipe rehabilitation method according to [2] or [6] above, comprising a mass part.

[10] The pipe rehabilitation method according to [1] or [2], wherein the resin composition in step (III) has a viscosity of 30 to 1,500 Pa·s at 25°C.

[11] The pipe rehabilitation method described in [10] above, wherein the number of days from the completion of the process (I) to the completion of the process (III) or the curing process is at least 3 days and within 6 days.

[12] The resin (A) includes the vinyl ester resin (A1), and the resin composition contains the vinyl ester resin (A1), based on 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 ester resin (A1), 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). The pipe rehabilitation method according to [10] or [11] above, comprising 10 parts by mass.

[13] The resin (A) contains the unsaturated polyester resin (A2), and the unsaturated polyester resin (A2) and the ethylenically unsaturated group-containing monomer (B) total 100 parts by mass. 20 to 80 parts by mass of the polyester resin (A2), 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 the carboxyl group-containing compound. The pipe rehabilitation method according to [10] or [11] above, comprising:

[14] The pipe rehabilitation method according to any one of [1] to [13] above, wherein the thickener (C) is at least one selected from oxides and hydroxides of Group 2 elements.

[15] The pipe rehabilitation method according to any one of [1] to [14] above, wherein the resin composition further contains at least one compound (E) selected from water and a hydroxy group-containing compound.

[16] The pipe rehabilitation method according to any one of [1] to [5] above, wherein the resin composition further contains a thixotropic agent.

[17] The pipe rehabilitation method according to any one of claims 2 to 5, wherein the vinyl ester resin (A1) has a hydroxyl value of 10 to 120 KOHmg/g.

According to the present invention, it is possible to provide a pipe rehabilitation method that can repair pipes uniformly and efficiently.

First, the definitions and meanings of terms and notations in this specification are shown below.

“(Meth)acrylic acid” is a general term for acrylic acid and methacrylic acid. Likewise, “(meth)acrylate” is a general term for acrylate and methacrylate, and “(meth)acryloyl” is a general term for acryloyl and methacryloyl.

The “acid value” of the resin (A) is the number of mg of potassium hydroxide required to neutralize 1 g of the resin (A), measured by a method based on JIS K6901: 2008. Specifically, it is measured by the method described in the Examples described later.

The “hydroxyl value” of resin (A) is the number of mg of potassium hydroxide required to neutralize acetic acid generated in the acetylation of 1 g of resin (A), measured by a method based on JIS K6901: 2008. Specifically, it is measured by the method described in the Examples described later.

“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. This is the molecular weight equivalent to standard polystyrene. Specifically, it is measured by the method described in the Examples described later.

The “viscosity” of the resin (A) is a value converted from the value measured at a temperature of 25°C for a mixture of the resin (A) and the monomer (B) containing an ethylenically unsaturated group using an E-type viscometer. Specifically, it is measured by the method described in the Examples described later.

The “viscosity” of the resin composition is a value measured at a temperature of 25°C using a B-type viscometer. Specifically, it is measured by the method described in the Examples described later.

“Acid group derived from polybasic acid anhydride” means a free acid group derived from a polybasic acid anhydride, unless otherwise specified.

[How to rehabilitate the coffin]

The pipe rehabilitation method of the present embodiment includes a step (I) of preparing a resin composition, a step (II) of impregnating a fiber substrate (F) with the resin composition to obtain a resin composition-impregnated substrate, and the resin composition-impregnated substrate. It includes a step (III) of obtaining the containing lining material, and a step (IV) of placing the lining material in a pipe and photocuring it. And, the resin composition contains a resin (A), an ethylenically unsaturated group-containing monomer (B), a thickener (C), and a photopolymerization initiator (D), and the The viscosity at 25°C is 0.1 to 3.0 Pa·s, and in step (IV), the viscosity of the resin composition at 25°C when the lining material is placed in the pipe is 400 to 3,500 Pa·s.

In this way, steps (I) to (IV) are included, the resin composition contains the above components, the viscosity of the resin composition in step (II), and the lining material in step (IV) are disposed in the pipe. When the viscosity of the resin composition is within a specific range, the pipe can be repaired uniformly and efficiently.

〔Process (I)〕

Process (I) of this embodiment is a process of preparing a resin composition.

Preparing a resin composition means mixing all the components constituting the resin composition to prepare the resin composition.

The preparation method of the resin composition of this embodiment is not particularly limited, but the resin composition is prepared by mixing the resin (A), the ethylenically unsaturated group-containing monomer (B), the thickener (C), and the photopolymerization initiator (D). It can be manufactured. Additionally, in addition to the resin (A), the ethylenically unsaturated group-containing monomer (B), the thickener (C), and the photopolymerization initiator (D), arbitrary components such as compound (E) and other components may be mixed.

The mixing order is not particularly limited, but from the viewpoint of facilitating viscosity control, it is preferable to add the thickener (C) last.

The mixing method is not particularly limited and can be performed using, for example, a disper, planetary mixer, kneader, etc. 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.

In addition, from the viewpoint of making it easier to uniformly mix the resin (A), the ethylenically unsaturated group-containing monomer (B), the thickener (C), the photopolymerization initiator (D), and other components, and adjusting the viscosity, the resin ( A) may be diluted in advance with at least one of a solvent and a reactive diluent.

<Resin composition>

The resin composition of this embodiment contains a resin (A), an ethylenically unsaturated group-containing monomer (B), a thickener (C), and a photopolymerization initiator (D).

≪Suzy (A)≫

The resin (A) is not particularly limited, but preferably has an ethylenically unsaturated group. As the resin (A), for example, vinyl ester resin (A1), unsaturated polyester resin (A2), urethane (meth)acrylate resin (A3), polyester (meth)acrylate resin (A4), (meth) ) Acrylate resin (A5), etc. can be mentioned. From the viewpoint of appropriately controlling the thickening rate and the workability of step (IV), it is preferable that the resin (A) contains at least one type selected from vinyl ester resin (A1) and unsaturated polyester resin (A2). . These resins may be used singly or in combination of two or more types.

<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 (A1-1) to (A1-5) below.

Vinyl ester resin (A1-1): reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule and an 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 (a1) Addition reaction product of -4)

Vinyl ester resin (A1-3): a resin precursor that is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride (a1-3) Addition reaction product of (P2) and polybasic acid anhydride (a1-4)

Vinyl ester resin (A1-4): a resin precursor (P3) that is a reaction product of an epoxy compound (a1-1) and a bisphenol compound (a1-5) having two epoxy groups in one molecule, and an unsaturated monobasic acid (a1) -2) Reaction product

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

These resins may be used singly or in combination of two or more types.

The acid value of the vinyl ester resin (A1) is preferably 1 KOH mg/g or more, more preferably 5 KOH mg/g or more, even more preferably 8 KOH mg/g or more, from the viewpoint of more efficiently thickening the resin composition. It is more than 10KOHmg/g. Additionally, from the viewpoint of controlling the thickening rate of the resin composition, it is preferably 100 KOH mg/g or less, more preferably 90 KOH mg/g or less, further preferably 80 KOH mg/g or less, and even more preferably 85 KOH mg/g or less. .

The hydroxyl value of the vinyl ester resin (A1) is preferably 10 KOH mg/g or more, more preferably 15 KOH mg/g or more, and even more preferably 20 KOH mg/g or more from the viewpoint of controlling the thickening rate of the resin composition. Moreover, from the viewpoint of efficiently thickening the resin composition, it is preferably 120 KOH mg/g or less, more preferably 110 KOH mg/g or less, and even more preferably 100 KOH mg/g or less.

(Vinyl ester resin (A1-1))

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 by the interaction between the hydroxy group formed by ring opening of the epoxy group of the epoxy compound (a1-1) and the thickener (C).

When the resin composition contains vinyl ester resin (A1-1), it becomes easy to control the thickening rate of the resin composition and also easy to adjust the mechanical strength of the lining material after photocuring.

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 efficiently thickening the resin composition, and the thickening rate of the resin composition From the viewpoint of controlling, it is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,200 or less.

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, and the thickening rate of the resin composition From the viewpoint of controlling, it is preferably 1,500 or less, more preferably 1,200 or less, and even more preferably 1,000 or less.

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 synthesis conditions, suppresses variation in the physical properties of the resin composition, and increases the thickening rate. From the viewpoint of control, it is preferably 2.0 or less, more preferably 1.7 or less, and even more preferably 1.5 or less.

In addition, Mw/Mn is an indicator of molecular weight distribution, and when it is 1, it indicates that it is a monodisperse polymer, and the larger this ratio, the wider the molecular weight distribution is.

In the vinyl ester resin (A1-1), the amount of unsaturated monobasic acid (a1-2) is 100 moles of the total amount of epoxy groups of epoxy compound (a1-1). The total amount is preferably 80 mol or more, more preferably 90 mol or more, further preferably 99 mol or more, preferably 120 mol or less, more preferably 110 mol or less, even more preferably 105 mol or more. It is less than a mole.

If the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 80 mol or more relative to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), a sufficient amount of ethylenically unsaturated acid in the vinyl ester resin (A1-1) Because the group is introduced, the resin composition is likely to exhibit good curability. Additionally, from the viewpoint of controlling the thickening rate of the resin composition and from the viewpoint of manufacturing stability, it is preferable that no unreacted epoxy groups remain in the vinyl ester resin (A1-1), and the epoxy group of the epoxy compound (a1-1) It is preferable that the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 100 moles relative to the total amount of 100 moles.

(Vinyl ester resin (A1-2))

Vinyl ester resin (A1-2) is a polybasic acid anhydride (a1- It is a reaction product obtained by further adding 4).

When the resin composition contains vinyl ester resin (A1-2), it becomes easier to control the thickening rate of the resin composition.

Vinyl ester resin (A1-2) adds polybasic acid anhydride (a1-4) to the hydroxy group formed by ring opening of the epoxy group of epoxy compound (a1-1), so the total amount of hydroxy groups is lower than that of vinyl ester resin (A1-1). decreases. Therefore, when vinyl ester resin (A1-2) is used, the viscosity of the resin composition in step (II) decreases compared to when vinyl ester resin (A1-1) is used. As a result, when vinyl ester resin (A1-2) is used, the impregnation property into the fiber base material (F) is better than when vinyl ester resin (A1-1) is used.

Additionally, a carboxyl group is introduced into the vinyl ester resin (A1-2) by addition of a polybasic acid anhydride (a1-4). Therefore, when vinyl ester resin (A1-2) is used, the interaction with the thickener (C) is improved compared to when vinyl ester resin (A1-1) is used, and the thickening rate of the resin composition is improved.

Additionally, vinyl ester resin (A1-2) has a wider molecular weight distribution and higher molecular weight than vinyl ester resin (A1-1). Therefore, when vinyl ester resin (A1-2) is used, the thickening speed is improved compared to when vinyl ester resin (A1-1) is used, and in step (IV), when placing the lining material in the pipe, The viscosity of the resin composition in the lining material is also high. As a result, the resin composition can be distributed and maintained more uniformly, and the pipe can be rehabilitated more uniformly and more efficiently.

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, and in step (II) From the viewpoint of further lowering the viscosity of the resin composition and appropriately controlling the thickening rate of the resin composition, it is preferably 2,000 or less, more preferably 1,800 or less, and even more preferably 1,600 or less.

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, and step (II) ), from the viewpoint of further lowering the viscosity of the resin composition, and from the viewpoint of appropriately controlling the thickening rate of the resin composition, it is preferably 1,300 or less, more preferably 1,200 or less, and even more preferably 1,100 or less.

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 controlling the synthesis conditions, and in step (II) From the viewpoint of further reducing the viscosity of the resin composition, suppressing variation in the physical properties of the resin composition, and controlling the thickening rate, it is preferably 5.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less. .

In the vinyl ester resin (A1-2), first, a resin precursor (P1), which is a reaction product of an epoxy compound (a1-1) having two epoxy groups per molecule and an unsaturated monobasic acid (a1-2), is obtained.

In the resin precursor (P1), the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 80 mol based on 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1). The amount is preferably mole or more, more preferably 90 mole or more, further preferably 99 mole or more, preferably 120 mole or less, more preferably 110 mole or less, and even more preferably 105 mole or less.

If the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 80 mol or more relative to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), a sufficient amount of ethylenically unsaturated acid in the vinyl ester resin (A1-2) Because the group is introduced, the resin composition is likely to exhibit good curability. Additionally, from the viewpoint of controlling the thickening rate of the resin composition and from the viewpoint of manufacturing stability, it is preferable that no unreacted epoxy groups remain in the vinyl ester resin (A1-2), and the epoxy group of the epoxy compound (a1-1) It is preferable that the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 100 moles relative to the total amount of 100 moles.

In the vinyl ester resin (A1-2), the epoxy compound (a1-1) is crosslinked by reacting the polybasic acid anhydride (a1-4) with the resin precursor (P1), or a carboxyl group is introduced into the resin precursor (P1). etc. plays a role. That is, the polybasic acid anhydride (a1-4) adds to the hydroxy group formed by ring opening of the epoxy group of the epoxy compound (a1-1) and generates a carboxyl group. This carboxyl group reacts with the unreacted epoxy group of the epoxy compound (a1-1), and crosslinking proceeds. After all of the epoxy groups have reacted, the carboxyl group derived from the polybasic acid anhydride (a1-4) remains as is, and the vinyl ester resin ( A carboxyl group is introduced into A1-2).

In the vinyl ester resin (A1-2), the polybasic acid anhydride (a1-4) is preferably 3 to 60 moles based on 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1). The amount is preferably 5 to 50 mol, and even more preferably 7 to 45 mol.

If the polybasic acid anhydride (a1-4) is 3 mol or more based on 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), the amount of carboxyl groups necessary to increase the thickening rate of the resin composition is added to the vinyl ester resin (A1-2). The hydroxy group that is sufficiently introduced and formed by ring-opening of the epoxy group derived from the epoxy compound (a1-1) is consumed by the addition of the polybasic acid anhydride (a1-4). As a result, an increase in the viscosity of the resin composition in step (II) can be suppressed. Moreover, when the polybasic acid anhydride (a1-4) is 60 mol or less, it becomes easy to control the thickening rate of the resin composition.

(Vinyl ester resin (A1-3))

The vinyl ester resin (A1-3) of this embodiment is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride (a1-3). It is an addition reaction product of a resin precursor (P2) and a polybasic acid anhydride (a1-4).

When the resin composition contains vinyl ester resin (A1-3), an increase in the viscosity of the resin composition in step (II) can be suppressed. Additionally, the thickening speed can be improved and the viscosity of the resin composition in the lining material can be increased when the lining material is placed in the pipe in step (IV).

Vinyl ester resin (A1-3) is formed by adding polybasic acid anhydrides (a1-3) and (a1-4) to the hydroxy group formed by ring-opening of the epoxy group of epoxy compound (a1-1). and (A1-2), the total amount of hydroxy groups is reduced. As a result, when the resin composition contains vinyl ester resin (A1-3), compared to the case where it contains vinyl ester resin (A1-1) or vinyl ester resin (A1-2), in step (II) The viscosity of the resin composition decreases, and the impregnation property into the fiber base (F) in step (II) becomes good.

In addition, since the vinyl ester resin (A1-3) has a carboxyl group introduced by the addition of polybasic acid anhydride (a1-3) and (a1-4), if the resin composition contains the vinyl ester resin (A1-3), the vinyl ester resin (A1-3) Compared to the case where ester resin (A1-1) or vinyl ester resin (A1-2) is included, the interaction with the thickener (C) is further improved, and the thickening rate of the resin composition is further improved.

In addition, the vinyl ester resin (A1-3) is ring-opened by the epoxy group of the epoxy compound (a1-1) reacting with the carboxyl group of the unsaturated monobasic acid (a1-2). A hydroxy group is generated, a polybasic acid anhydride (a1-3) is ring-opening added to the hydroxy group, and the carboxyl group created by the ring-opening addition of the polybasic acid anhydride (a1-3) is an unreacted epoxy group of the epoxy compound (a1-1). It crosslinks by further reacting with and polymerizes. Therefore, vinyl ester resin (A1-3) has a higher molecular weight and a wider molecular weight distribution than vinyl ester resins (A1-1) and (A1-2). Therefore, when the resin composition contains vinyl ester resin (A1-3), the thickening rate of the resin composition improves compared to the case where it contains vinyl ester resin (A1-1) or vinyl ester resin (A1-2). , in step (IV), the viscosity of the resin composition in the lining material when the lining material is placed in the pipe is also high. As a result, the resin composition can be distributed and maintained more uniformly, and the pipe can be rehabilitated more uniformly and more efficiently.

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, further preferably 4,000 or more, and even more preferably 6,000 from the viewpoint of efficiently thickening the resin composition. or more, and from the viewpoint of suppressing the increase in viscosity of the resin composition in step (II) and controlling the thickening rate, it is preferably 35,000 or less, more preferably 25,000 or less, and even more preferably 15,000 or less. In particular, in the case of the resin composition according to the first embodiment described later, the vinyl ester resin (A1-3) preferably has a high molecular weight, preferably 5,000 or more, more preferably 7,000 or more, even more preferably 9,000 or more. am.

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, and in step (II) From the viewpoint of suppressing the increase in viscosity of the resin composition and controlling the thickening rate, it is preferably 2,500 or less, more preferably 1,800 or less, and even more preferably 1,600 or less. In particular, in the case of the resin composition according to the first embodiment described later, the vinyl ester resin (A1-3) preferably has a high molecular weight, preferably 900 or more, more preferably 1,000 or more, even more preferably 1,200 or more. am.

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 is adjusted to account for the deviation of the physical properties of the resin composition. From the viewpoint of suppressing the increase in viscosity of the resin composition in step (II) and controlling the thickening rate, it is preferably 18 or less, more preferably 12 or less, and still more preferably 10 or less. . In particular, in the case of the resin composition according to the first embodiment described later, it is preferably 4.0 or more, more preferably 5.0 or more, and even more preferably 6.0 or more.

In the vinyl ester resin (A1-3), first, it is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride (a1-3). Obtain a resin precursor (P2).

In the resin precursor (P2), the total amount of acid groups of unsaturated monobasic acid (a1-2) is 75 mol based on 100 mol of the total amount of epoxy groups of epoxy compound (a1-1). The amount is preferably ∼95 mol, more preferably 77 to 93 mol, and even 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 relative to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), a sufficient amount of ethylenically unsaturated acid in the vinyl ester resin (A1-3) Because the group is introduced, the resin composition is likely to exhibit good curability. In addition, if 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) and the polybasic acid anhydride (a1-3) It is easy to obtain a resin composition that is sufficiently crosslinked and has good thickening properties.

In the resin precursor (P2), the amount of the polybasic acid anhydride (a1-3) is an acid group that can react with the epoxy group derived from the polybasic acid anhydride (a1-3), relative to 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1). The total amount is preferably 5 to 25 mol, more preferably 7 to 23 mol, and even more preferably 9 to 21 mol.

With respect to 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1), the total amount of acid groups that can react with the epoxy group derived from the polybasic acid anhydride (a1-3) is 5 moles or more, so that the epoxy compound (a1-1) and the polybasic acid By crosslinking the anhydride (a1-3), the molecular weight increases and the resin composition can be thickened efficiently. In addition, since the total amount of acid groups derived from the polybasic acid anhydride (a1-3) that can react with the epoxy group is 25 mol or less, it is easy to control the degree of crosslinking of the epoxy compound (a1-1), and the vinyl ester resin (A1- 3) Gelation during synthesis is suppressed, and it becomes easier to control the thickening rate of the resin composition.

In the resin precursor (P2), an acid group derived from an unsaturated monobasic acid (a1-2) and a polybasic acid anhydride (a1-3) (the "acidic group" referred to here is an acid group formed by hydrolysis of the polybasic acid anhydride (a1-3). For example, when the polybasic acid anhydride (a1-3) is a dibasic acid anhydride, the number of acid groups formed from one molecule is 2. The total amount of epoxy group (a1-1) is 100 moles. , the amount is preferably 105 to 125 mol, more preferably 107 to 123 mol, and even more preferably 109 to 121 mol.

When the total amount of acid groups derived from unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) is 105 mol or more with respect to 100 mol of total epoxy groups of the epoxy compound (a1-1), the epoxy compound (a1- The amount of unreacted epoxy groups in 1) is reduced, making it easier to control the thickening rate of the resin composition. In addition, when the total amount of acid groups derived from unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) is 125 mol or less, gelation during synthesis of vinyl ester resin (A1-3) is suppressed, and vinyl ester resin (A1-3) is synthesized. Remaining of unreacted unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) in the resin (A1-3) is suppressed, and the influence on the thickening rate of the resin composition can be suppressed.

In the vinyl ester resin (A1-3), the polybasic acid anhydride (a1-4) is reacted with the resin precursor (P2) to form an epoxy compound (a1-1) using the same reaction mechanism as for the polybasic acid anhydride (a1-3). It plays a role such as crosslinking or introducing a carboxyl group into the resin precursor (P2). That is, the polybasic acid anhydride (a1-4) adds to the hydroxy group formed by ring opening of the epoxy group of the epoxy compound (a1-1) and generates a carboxyl group. This carboxyl group reacts with the unreacted epoxy group of the epoxy compound (a1-1), and crosslinking proceeds. After all of the epoxy groups have reacted, the carboxyl group derived from the polybasic acid anhydride (a1-4) remains as is, and the vinyl ester resin ( A carboxyl group is introduced into A1-3).

The polybasic acid anhydride (a1-4) is preferably used in an amount of 3 to 60 moles, more preferably 5 moles, based on 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1). ~50 mol, more preferably 7-45 mol.

If the polybasic acid anhydride (a1-4) is 3 mol or more based on 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1), the amount of carboxyl groups necessary to increase the thickening rate of the resin composition is added to the vinyl ester resin (A1-3). In addition, the hydroxy group formed by ring opening of the epoxy group derived from the epoxy compound (a1-1) is consumed by the addition of the polybasic acid anhydride (a1-4), thereby increasing the viscosity of the resin composition in step (II). It can be suppressed. In addition, when the polybasic acid anhydride (a1-4) is 60 mol or less, it becomes easy to control the thickening rate of the resin composition.

(Vinyl ester resin (A1-4))

The vinyl ester resin (A1-4) of the present embodiment is a resin precursor (P3) which is a reaction product of an epoxy compound (a1-1) and a bisphenol compound (a1-5) having two epoxy groups in one molecule, and an unsaturated monobasic group. It is a reaction product of acid (a1-2).

When the resin composition contains the vinyl ester resin (A1-4), it becomes easier to control the thickening rate of the resin composition and to adjust the physical properties of the cured product of the resin composition.

The vinyl ester resin (A1-4) thickens the resin composition by the interaction between the hydroxy group formed by 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, and controls the thickening rate of the resin composition. From this point of view, it is preferably 6,000 or less, more preferably 5,000 or less, and even more preferably 4,500 or less.

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, and the thickening rate of the resin composition From the viewpoint of controlling, it is preferably 2,500 or less, more preferably 2,200 or less, and even 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 even more preferably 1.3 or more from the viewpoint of ease of control of synthesis conditions, and the physical properties of the resin composition From the viewpoint of suppressing variation and controlling the thickening rate, it is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.3 or less.

In addition, Mw/Mn is an indicator of molecular weight distribution, and when it is 1, it indicates that it is a monodisperse polymer, and the larger this ratio, the wider the molecular weight distribution is.

In the vinyl ester resin (A1-4), the amount of the bisphenol compound (a1-5) is 10 moles of the total amount of hydroxyl groups of the bisphenol compound (a1-5) relative to 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1). The amount is preferably 20 mol or more, more preferably 25 mol or more, preferably 70 mol or less, more preferably 60 mol or less, and even more preferably 50 mol or less.

If the total amount of hydroxyl groups in the bisphenol compound (a1-5) is 10 mol or more relative to the total amount of 100 moles of epoxy groups in the epoxy compound (a1-1), the molecular weight distribution of the vinyl ester resin (A1) widens, and the resin composition is reached. It becomes easier to control viscosity. Additionally, if the total amount of the bisphenol compound (a1-5) is 70 mol or less relative to the total amount of 100 mol of epoxy groups in the epoxy compound (a1-1), it becomes easy to control the thickening rate of the resin composition.

In the vinyl ester resin (A1-4), the amount of unsaturated monobasic acid (a1-2) is 100 moles of the total amount of epoxy groups of epoxy compound (a1-1). The total amount 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, even more preferably 80 mol. It is as follows.

If the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 30 mol or more relative to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), a sufficient amount of ethylenically unsaturated acid in the vinyl ester resin (A1-4) Because the group is introduced, the resin composition is likely to exhibit good curability. In addition, from the viewpoint of controlling the thickening rate, suppressing uneven distribution of the resin composition after curing, and manufacturing stability, the unsaturated monobasic acid (a1-2) is added to the total amount of 100 moles of epoxy groups in the epoxy compound (a1-1). It is preferable that the total amount of acid groups is 120 mol or less.

(Vinyl ester resin (A1-5))

Vinyl ester resin (A1-5) is a reaction product of a resin precursor (P4), which is a reaction product of a resin precursor (P3) and an unsaturated monobasic acid (a1-2), and an unsaturated polybasic acid (a1-6), and the resin The 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).

The vinyl ester resin (A1-5) thickens the resin composition by the interaction between the compound (C) and the hydroxy group formed by ring opening of the epoxy group of the epoxy compound (a1-1).

When the resin composition contains a vinyl ester resin (A1-5), it becomes easier to control the thickening rate of the resin composition and also easier 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, and controls the thickening rate of the resin composition. From this point of view, it is preferably 6,000 or less, more preferably 5,000 or less, and even more preferably 4,500 or less.

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, and the thickening rate of the resin composition From the viewpoint of controlling, it is preferably 2,000 or less, more preferably 1,500 or less, and even 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 synthesis conditions, and the physical properties of the resin composition From the viewpoint of suppressing variation and controlling the thickening rate, it is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.3 or less.

In addition, Mw/Mn is an indicator of molecular weight distribution, and when it is 1, it indicates that it is a monodisperse polymer, and the larger this ratio, the wider the molecular weight distribution is.

In the vinyl ester resin (A1-5), the amount of the bisphenol compound (a1-5) is 10 moles of the total amount of hydroxyl groups of the bisphenol compound (a1-5) relative to 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1). The amount is preferably 15 mol or more, more preferably 20 mol or more, preferably 70 mol or less, more preferably 60 mol or less, and even more preferably 50 mol or less.

If the total amount of hydroxyl groups in the bisphenol compound (a1-5) is 10 mol or more relative to the total amount of 100 moles of epoxy groups in the epoxy compound (a1-1), the molecular weight distribution of the vinyl ester resin (A1) widens, and the resin composition is reached. It becomes easier to control viscosity. Additionally, if the total amount of hydroxyl groups in the bisphenol compound (a1-5) is 70 mol or less relative to the total amount of 100 moles of epoxy groups in the epoxy compound (a1-1), it becomes easy to control the thickening rate of the resin composition.

In the vinyl ester resin (A1-5), the amount of unsaturated monobasic acid (a1-2) is 100 moles of the total amount of epoxy groups of epoxy compound (a1-1). The total amount 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, even more preferably 80 mol. It is as follows.

If the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 30 mol or more relative to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), a sufficient amount of ethylenically unsaturated acid in the vinyl ester resin (A1-5) Because the group is introduced, the resin composition is likely to exhibit good curability. In addition, from the viewpoint of controlling the thickening rate, suppressing uneven distribution of the resin composition after curing, uniformly repairing the pipe, and manufacturing stability, more unreacted epoxy groups remain in the vinyl ester resin (A1-1). It is preferable that the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 120 mol or less relative to the total amount of 100 mol of epoxy groups of the epoxy compound (a1-1).

The amount of unsaturated polybasic acid (a1-6) in the vinyl ester resin (A1-5) is preferably 0.5 mol or more of unsaturated polybasic acid (a1-6) based on 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1). It is more preferably 1 mol or more, further preferably 3 mol or more, preferably 15 mol or less, more preferably 10 mol or less, and even more preferably 8 mol or less.

If the unsaturated polybasic acid (a1-6) is 0.5 mol or more based on 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1), a sufficient amount of ethylenically unsaturated groups will be introduced into the vinyl ester resin (A1-5), so that the resin The composition is likely to develop good curing properties. Additionally, from the viewpoint of controlling the thickening rate, it is preferable that the unsaturated polybasic acid (a1-6) is 15 mol or less with respect to 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 its molecular weight and molecular structure are not particularly limited. The epoxy compound (a1-1) may be used alone or in combination of two or more types.

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 with a butadiene structure, alicyclic Formulated epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, etc. can be mentioned. Among them, from the viewpoint of suppressing excessive increase in the viscosity achieved by the resin composition and controlling the thickening rate, at least one selected from bisphenol type epoxy resin and phenol novolac type epoxy resin is preferable, and bisphenol A type epoxy resin, One or more types selected from bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, and phenol novolac-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 the vinyl ester resin (A1-1) gelling, and the viscosity of the resin composition when the lining material in step (IV) is placed in the pipe, And from the viewpoint of controlling the thickening rate, it is preferably 170 to 1,000, more preferably 170 to 500, further 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 in a liquid state under conditions of 25°C, and an epoxy equivalent of 300 or less is preferably used.

(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 types.

Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, and cinnamic acid. Among them, at least one selected from (meth)acrylic acid and crotonic acid is preferred from the viewpoint of obtaining a resin composition having versatility, reactivity during synthesis of the vinyl ester resin (A), and good curability, and (meth)acrylic acid is More preferable is methacrylic acid from the viewpoint of chemical resistance.

(polybasic acid anhydride (a1-3))

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

Examples of the polybasic acid anhydride (a1-3) include maleic anhydride, phthalic anhydride, succinic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and 3-methyl-1,2,3,6-tetrahydro. Phthalic 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, etc. Among these, maleic anhydride and phthalic anhydride are preferable, and maleic anhydride is more preferable from the viewpoint of ease of availability, reactivity, ease of handling during synthesis, etc.

(polybasic acid anhydride (a1-4))

Polybasic acid anhydride (a1-4) is a compound having a plurality of carboxyl groups in one molecule, and at least two carboxyl groups undergo dehydration condensation to form an acid anhydride. Among them, dibasic acid anhydrides are preferable from the viewpoints of ease of handling during synthesis of 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. . The polybasic acid anhydride (a1-4) may be used singly or in combination of two or more types.

Specific examples of polybasic acid anhydride (a1-4) include polybasic acid anhydride (a1-3), and maleic anhydride is more preferable. The polybasic acid anhydride (a1-3) and the polybasic acid anhydride (a1-4) may be the same or different.

(Bisphenol compound (a1-5))

The molecular weight and molecular structure of the bisphenol compound (a1-5) are not particularly limited. The bisphenol compound (a1-5) may be used singly or in combination of two or more types.

As bisphenol compounds (a1-5), for example, 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, etc. can be mentioned. Among them, from the viewpoint of suppressing the resin composition's ultimate viscosity from becoming excessively high and controlling the thickening rate, at least one selected from bisphenol A, bisphenol E, bisphenol F, and bisphenol S is preferable, and bisphenol A and bisphenol E are preferred. , bisphenol F is more preferable, and bisphenol A is more preferable from the viewpoints 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 types.

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, and tetrahydrocytic acid. Phthalic acid, hexahydrophthalic acid, etc. can be mentioned. Among them, from the viewpoint of production cost, maleic anhydride, fumaric acid, succinic acid, glutaric acid, and adipic acid are preferable, succinic acid, fumaric acid, and maleic anhydride are more preferable, and fumaric acid is still more preferable.

When it is desired to lower the viscosity of the resin composition in step (II), vinyl ester resins (A1-2) and (A1-3) may be mixed, and when the thickening rate is desired to be appropriately controlled, vinyl ester resins (A1-2) and (A1-3) may be mixed. Ester resins (A1-1) and (A1-2) may be mixed, and if it is desired to improve the thickening rate, vinyl ester resin (A1-3) may be mixed, and the lining material in step (IV) If it is desired to increase the viscosity when placed in the pipe, vinyl ester resin (A1-3) may be added. In this way, resins according to desired viscosity behavior may be used individually or in combination.

In this embodiment, the vinyl ester resin (A1) is preferably a vinyl ester resin (A1-3), that is, the vinyl ester resin (A1) is an epoxy compound (a1-1) having two epoxy groups in one molecule. , it is preferably the addition reaction product of the resin precursor (P2), which is a reaction product of an unsaturated monobasic acid (a1-2) and a polybasic acid anhydride (a1-3), and a polybasic acid anhydride (a1-4). And, with respect to the total amount of 100 moles of epoxy groups of the epoxy compound (a1-1), it is preferable that the total amount of acid groups that can react with the epoxy groups derived from the polybasic acid anhydride (a1-3) is 5 to 25 moles.

<Unsaturated polyester resin (A2)>

The unsaturated polyester resin can be one obtained by esterifying a dibasic acid component containing an unsaturated dibasic acid and, if necessary, a saturated dibasic acid, and a polyhydric alcohol.

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.

There is no particular limitation on the polyhydric alcohol, but for example, as in the case of urethane (meth)acrylate resin, those described in Publication WO2016/171151 can be mentioned.

The unsaturated polyester resin (A2) in the present embodiment contains 43 to 85 mol% of diol (a2-1-1), which is an alkanediol with a molecular weight of 90 to 500, based on 100 mol% of diol (a2-1). A dibasic acid (a2-2) comprising the diol (a2-1), a dibasic acid (a2-2-1) containing an ethylenically unsaturated group, and a dibasic acid (a2-2-2) without an ethylenically unsaturated group. It is preferable that it is a reaction product of.

The acid value of the unsaturated polyester resin (A2) is preferably 3 KOHmg from the viewpoint of making the lining material high enough to maintain a uniformly distributed state in the fiber base when placing the lining material in the pipe in step (IV). /g or more, more preferably 5KOHmg/g or more, further preferably 8KOHmg/g or more, and from the viewpoint of promoting thickening of the resin composition, preferably 25KOHmg/g or less, more preferably 20KOHmg/g or less, More preferably, it is 16KOHmg/g or less.

The weight average molecular weight (Mw) of the unsaturated polyester resin (A2) is high enough to accelerate the thickening rate of the resin composition and maintain a uniform distribution in the fiber base when placing the lining material in the pipe. From this point of view, it is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 9,000 or more, and is preferable from the viewpoint of suppressing the decrease in viscosity due to moisture absorption of the resin composition and obtaining a resin composition with excellent viscosity stability after thickening. Preferably it is 20,000 or less, more preferably 17,000 or less, and even more preferably 15,000 or less.

The number average molecular weight (Mn) of the unsaturated polyester resin (A2) promotes the thickening rate of the resin composition and is high enough to maintain a uniform distribution in the fiber base when the lining material is placed in the pipe. From this point of view, it is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more, from the viewpoint of suppressing the decrease in viscosity of the resin composition due to moisture absorption and obtaining a resin composition with excellent viscosity stability after thickening. Preferably it is 7,000 or less, more preferably 5,000 or less, and even more preferably 4,000 or less.

The ratio Mw/Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the unsaturated polyester resin (A2) is not particularly limited, but is distributed uniformly in the fiber base material to accelerate the thickening rate and when disposing the lining material in the pipe. From the viewpoint of making the viscosity high enough to maintain the viscosity, it is preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less, and from the viewpoint of productivity, it is preferably 1 or more, more preferably It is 1.5 or more, more preferably 2 or more.

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

When the resin composition contains an unsaturated polyester resin (A2), the content of the unsaturated polyester resin (A2) in the resin composition is the total of the unsaturated polyester resin (A2) and the ethylenically unsaturated group-containing monomer (B) 100. With respect to parts by mass, it is 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.

If the content of the unsaturated polyester resin (A2) is 20 parts by mass or more, it is easy to control the thickening rate of the resin composition. Moreover, if the content of the unsaturated polyester resin (A2) is 80 parts by mass or less, the viscosity of the resin composition in step (II) is more likely to be reduced by the ethylenically unsaturated group-containing monomer (B).

When the resin composition contains an unsaturated polyester resin (A2), the content of the unsaturated polyester resin (A2) in the resin composition is preferably 20 to 80 parts by mass, more preferably 20 to 80 parts by mass, based on 100 parts by mass of the total amount of the resin composition. is 30 to 70 parts by mass, more preferably 40 to 65 parts by mass.

If the content of the unsaturated polyester resin (A2) is 20 parts by mass or more, it is easy to control the thickening rate of the resin composition. Moreover, if the content of the unsaturated polyester resin (A2) is 80 parts by mass or less, an increase in the initial viscosity of the resin composition is likely to be suppressed by the ethylenically unsaturated group-containing monomer (B).

<Dior (a2-1)>

Diol (a2-1) is a compound that has two hydroxy groups in one molecule. And diol (a2-1) contains 43 to 85 mol% of alkanediol (a2-1-1) with a molecular weight of 90 to 500.

Diol (a2-1), in addition to alkanediol (a2-1-1), is an alkanediol (a2-1-2) different from alkanediol (a2-1-1), or alkanediol (a2-1-1). and other diols different from alkanediol (a2-1-2).

(alkanediol(a2-1-1))

Alkanediol (a2-1-1) is an alkanediol with a molecular weight of 90 to 500, and is a compound in which one hydrogen atom bonded to two carbon atoms of a hydrocarbon is replaced with a hydroxy group. Alkanediol (a2-1-1) may be used singly or in combination of two or more types.

Since alkanediol (a2-1-1) does not contain polar groups or highly electronegative atoms other than the hydroxy group in the molecule, its interaction with water molecules is small compared to polyoxyalkylene polyols that have ether bonds. . Therefore, when the resin composition contains an unsaturated polyester resin (A2), which is a reaction product of an alkanediol (a2-1-1) and a dibasic acid (a2-2), the hygroscopicity of the resin composition is reduced, and the viscosity after thickening of the resin composition is reduced. Changes are suppressed, resulting in excellent viscosity stability.

When the molecular weight of 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 manufacture and productivity become good. The molecular weight of the alkanediol (a2-1-1) is preferably 95 or more, more preferably 95 or more, from the viewpoint of further reducing the hygroscopicity of the resin composition, suppressing the viscosity change after thickening of the resin composition, and obtaining a resin composition with excellent viscosity stability. Preferably it is 100 or more, more preferably 103 or more, and from the viewpoint of ease of manufacture and manufacturing cost, preferably 400 or less, more preferably 300 or less, and even more preferably 250 or less.

Examples of alkanediol (a2-1-1) include 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butanediol, and 1,3-butanediol. , 1,4-butanediol, 2,3-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1, 5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 1,2-nonanediol, 1,4-cyclohexanediol, 1,8-octanediol, 1,9-nonanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2 , 2-di(4-hydroxycyclohexyl)propane, and hydrides of bisphenol A, bisphenol F, and bisphenol S, etc.

Among these, from the viewpoint of obtaining a resin composition with excellent viscosity stability after thickening, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and the hydride of bisphenol A are more preferable, From the viewpoint of availability and production cost, 2,2-dimethyl-1,3-propanediol is preferred.

The content of alkanediol (a2-1-1) in diol (a2-1) reduces the hygroscopicity of the resin composition compared to 100 mol% of diol (a2-1), suppresses the viscosity change after thickening of the resin composition, and thickens the resin composition. From the viewpoint of obtaining a resin composition with excellent later viscosity stability, it 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, it is preferable is 85 mol% or less, more preferably 80 mol% or less, and even more preferably 75 mol% or less.

The total content of alkanediol (a2-1-1) and alkanediol (a2-1-2) described later in diol (a2-1) determines the hygroscopicity of the resin composition relative to 100 mol% of the total amount of diol (a2-1). From the viewpoint of reducing the viscosity change after thickening of the resin composition and obtaining a resin composition with excellent viscosity stability after thickening, the amount is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mole. % or more, more preferably 100 mol%.

(alkanediol(a2-1-2))

Alkanediol (a2-1-2) is an alkanediol different from alkanediol (a2-1-1), and does not include alkanediols with a molecular weight of 90 to 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 of the resin composition, and from the viewpoint of ease of manufacture and manufacturing cost. , Preferably it is 85 or less, more preferably 80 or less, and even more preferably 78 or less.

Examples of 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 of the resin composition.

The content of alkanediol (a2-1-2) in diol (a2-1) is determined based on 100 mol% of diol (a2-1) when synthesizing unsaturated polyester resin (A2), such as low molecular weight substances and unreacted raw materials. From the viewpoint of suppressing precipitation of crystals and the like and further improving the impregnability of the resin composition into the fiber base, it is 15 mol% or more, preferably 20 mol% or more, and more preferably 25 mol% or more. In addition, from the viewpoint of further lowering the hygroscopicity of the resin composition, suppressing the viscosity change after thickening of the resin composition, and obtaining a resin composition with excellent viscosity stability after thickening, 57 mol% or less, preferably 55 mol% or less, more preferably is 52 mol% or less.

(Other Dior)

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 manufacturing cost and good toughness of the cured product, and from the viewpoint of ease of manufacture and manufacturing cost, it is preferably is 500 or less, more preferably 300 or less, and even more preferably 150 or less.

Examples of other diols include 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 manufacturing cost and improving the toughness of the cured product.

<Dibasic acid (a2-2)>

The dibasic acid (a2-2) includes a dibasic acid (a2-2-1) containing an ethylenically unsaturated group and a dibasic acid (a2-2-2) without an ethylenically unsaturated group.

One type of dibasic acid (a2-2) may be used alone, or two or more types may be used in combination.

(Dibasic acid containing ethylenically unsaturated group (a2-2-1))

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

The content of dibasic acid (a2-2-1) containing an ethylenically unsaturated group in dibasic acid (a2-2) is preferably from the viewpoint of the mechanical strength of the cured product of the resin composition relative to 100 mol% of dibasic acid (a2-2). is 20 mol% or more, more preferably 30 mol% or more, further preferably 40 mol% or more, even more preferably 45 mol% or more, preferably 80 mol% or less, more preferably 75 mol% Below, more preferably 70 mol% or less, 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, from the viewpoint of production cost, maleic anhydride and fumaric acid are preferable, and maleic anhydride is more preferable.

(Dibasic acid (a2-2-2) without ethylenically unsaturated group)

The ethylenically unsaturated group-free dibasic acid (a2-2-2) is a compound that has two carboxyl groups in one molecule and does not have an ethylenically unsaturated group, and its molecular weight and molecular structure are not particularly limited. The dibasic acid (a2-2-2) not containing an ethylenically unsaturated group may be used singly or in combination of two or more types.

The content of dibasic acid (a2-2-2) without an ethylenically unsaturated group in dibasic acid (a2-2) is preferable from the viewpoint of mechanical strength of the cured product of the resin composition relative to 100 mol% of dibasic acid (a2-2). Preferably it is 20 mol% or more, more preferably 25 mol% or more, even more preferably 30 mol% or more, even more preferably 35 mol% or more, preferably 80 mol% or less, more preferably 70 mol%. Below, more preferably 60 mol% or less, even more preferably 55 mol% or less.

Examples of dibasic acids (a2-2-2) not containing an ethylenically unsaturated group include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, and hexahydrophthalic acid (1, 2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid), naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, chlorendic acid ( hetic acid), tetrabromophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, succinic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, dimethyl orthophthalate, dimethyl iso. Phthalate, dimethyl terephthalate, etc. can be mentioned. Among these, isophthalic acid and terephthalic acid are preferable from the viewpoint of manufacturing cost.

In this embodiment, the dibasic acid (a2-2) is composed of 20 to 80 mol% of the dibasic acid (a2-1) containing an ethylenically unsaturated group and the dibasic acid (a2-2-2) without an ethylenically unsaturated group. It is preferable to contain 20 to 80 mol%.

<Urethane (meth)acrylate resin (A3)>

Urethane (meth)acrylate resin is polyurethane having a (meth)acryloyloxy group. Specifically, it is obtained by reacting polyisocyanate with a polyhydroxy compound or polyhydric alcohol, and then reacting with a (meth)acrylic compound containing a hydroxy group and, if necessary, an allyl ether compound containing a hydroxy group in addition to the unreacted isocyanato group. Lose.

<Polyester (meth)acrylate resin (A4)>

The polyester (meth)acrylate resin is a polyester having a (meth)acryloyloxy group. Polyester (meth)acrylate resin is obtained, for example, by the method (1) or (2) shown below.

(1) Method of reacting epoxy group-containing (meth)acrylate or hydroxy group-containing (meth)acrylate with polyester having a carboxyl group at the terminal.

(2) A method of reacting (meth)acrylic acid or isocyanato group-containing (meth)acrylate with polyester having a hydroxyl group at the terminal.

Examples of the polyester having a carboxyl group at the terminal used as a raw material in the method (1) above include those obtained from an excessive amount of saturated polybasic acid and/or unsaturated polybasic acid and polyhydric alcohol.

Examples of the polyester having a hydroxyl group at the terminal used as a raw material in the method (2) above include those obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and an excess amount of polyhydric alcohol.

<(meth)acrylate resin (A5)>

(Meth)acrylate resin (A5) is a polymer of acrylic acid ester or methacrylic acid ester. Specific examples of the constituent monomer include (meth)acrylate as exemplified by the ethylenically unsaturated group-containing monomer (B).

The viscosity of the 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) does not have a carboxyl group and is not particularly limited as long as it has an ethylenically unsaturated group, but it is preferred to have 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 types.

The greater the content of the ethylenically unsaturated group-containing monomer (B), the viscosity and thickening rate of the resin composition in step (II), and the viscosity of the resin composition when placing the lining material in the pipe in step (IV). The rise tends to be suppressed. Additionally, the hardness, strength, chemical resistance, water resistance, etc. of the lining material after photocuring can be improved.

Among the ethylenically unsaturated group-containing monomers (B), examples of those having a (meth)acryloyl group include (meth)acrylate. (meth)acrylate 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, and t-butyl (meth)acrylate. ) Acrylate, 2-ethylhexyl, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, phenoxy Ethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate Rate, ethylene glycol monohexyl ether (meth)acrylate, ethylene glycol mono2-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 mono2-ethylhexyl ether (meth)acrylate, dicyclopentenyl (meth)acrylate, Dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, caprolactone-modified hydroxyethyl (meth)acrylate, allyl (meth)acrylate, etc. can be mentioned.

Examples of polyfunctional (meth)acrylate include ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1 Alkanediol di(meth)acrylates such as 4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate, and diethylene glycol di. (Meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate and polytetramethylene glycol di. Polyoxyalkylene glycol di(meth)acrylate such as (meth)acrylate, also trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethyl All-propane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythate Ritold diacrylate monostearate, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethoxylated bisphenol A di(meth)acrylate, tris-(2-(meth)acryloxy) Ethyl) isocyanurate, etc. can be mentioned.

Among the ethylenically unsaturated group-containing monomers (B), in addition to (meth)acrylate, those having a (meth)acryloyl group include acryloylmorpholine, 2-hydroxyethyl (meth)acrylamide, and 2-hydroxyethyl. -N-methyl (meth)acrylamide, 3-hydroxypropyl (meth)acrylamide, etc. are mentioned. In addition to having a (meth)acryloyl group, examples of those having an ethylenically unsaturated 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, and triallyl isocyanurate are included.

Among these, the ethylenically unsaturated group-containing monomer (B) is a styrene compound 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)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and neopentyl glycol (meth)acrylate are preferred. Furthermore, from the viewpoint of suppressing odor, at least one selected from phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, diethylene glycol di(meth)acrylate, and neopentyl glycol (meth)acrylate is more preferable. And, from the viewpoint of chemical resistance of the lining material after photocuring, at least one selected from phenoxyethyl methacrylate, benzyl methacrylate, diethylene glycol dimethacrylate, and neopentyl glycol (meth)acrylate is more preferable. .

≪Thickener (C)≫

The thickener (C) is not particularly limited, but is preferably at least one selected from oxides and hydroxides of Group 2 elements. When the thickener (C) is at least one selected from the oxides and hydroxides of Group 2 elements, the resin composition due to interaction with the carboxyl group and hydroxyl group of the resin (A) and the carboxyl group and hydroxyl group of the other component compounds. It has the effect of increasing the intensity over time.

One type of thickener (C) may be used alone, or two or more types may be used in combination.

Examples of oxides of Group 2 elements include magnesium oxide, calcium oxide, and barium oxide.

Examples of hydroxides of Group 2 elements include magnesium hydroxide, calcium hydroxide, and barium hydroxide.

Among these, magnesium oxide is preferable from the viewpoint of thickening effect, versatility, cost, etc.

≪Photopolymerization initiator (D)≫

The photopolymerization initiator is not particularly limited as long as it generates radicals by light irradiation. For example, benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; α-hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; Thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 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- Morpholines such as 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; Acylphosphine oxides such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; Xanthons, etc. can be mentioned. These may be used alone or in combination of two or more types.

From the viewpoint of reactivity, it is preferable to use an intramolecular cleavage type photopolymerization initiator that does not require a hydrogen donor. In addition, since it generates active species by absorbing light with a wavelength of 315 to 460 nm, 2,2-dimethoxy-2-phenylacetophenone and phenylbis(2,4,6) efficiently generate active species in the above wavelength range. -Trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenylketone, and 1-hydroxycyclohexylphenylketone are preferred.

≪Compound (E)≫

The resin composition of this embodiment may use at least one compound (E) selected from water and a hydroxy group-containing compound. When the resin composition contains compound (E), it becomes easier to control the thickening rate. Examples of the hydroxy group-containing compound include alcohols with a boiling point of 50°C or higher, such as benzyl alcohol, stearyl alcohol, and isostearyl alcohol. In addition, hydroxycarboxylic acids such as lactic acid, glycerin, polyols, and (meth)acrylates containing a hydroxy group can be mentioned. These may be used alone or in combination of two or more types. Among these, from the viewpoint of availability, cost, etc., water and alcohol are preferred, and water is more preferred.

≪Compounds containing carboxyl groups≫

The resin composition of this embodiment may contain a compound having at least one carboxyl group.

Examples of the carboxyl group-containing compounds include maleic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, fumaric acid, endomethylenetetrahydrophthalic acid, 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, Examples include 6-endomethylene-1,2,3,6-tetrahydrophthalic acid, trimellitic acid, 3-dodecenylsuccinic acid, and (meth)acrylic acid.

Commercially available products include Haridimer 250 (manufactured by Harima Kasei Co., Ltd.).

One type of carboxyl group-containing compound may be used alone, or two or more types may be used in combination.

When the resin (A) of the present embodiment contains the vinyl ester resin (A1), the thickening rate is controlled and excessive thickening of the resin composition immediately after production (within 5 hours after production) is suppressed, From the viewpoint of further suppressing excessive increase in the achieved viscosity of the resin composition, 3-dodecenylsuccinic acid, methacrylic acid, and acrylic acid are preferable as the carboxyl group-containing compound, and 3-dodecenylsuccinic acid is more preferable.

When the resin (A) of the present embodiment contains a vinyl ester resin (A1) and the resin composition of the present embodiment contains a carboxyl group-containing compound, the thickening rate is controlled and immediately after production of the resin composition (up to 5 hours after production). 100 mass in total of the vinyl ester resin (A1) and the ethylenically unsaturated group-containing monomer (B) from the viewpoint of suppressing excessive thickening of the resin composition and further suppressing the attained viscosity of the resin composition from excessively increasing. Part by mass, it is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and even more preferably 0.1 part by mass or more. In addition, as the content of the carboxyl group-containing compound in the resin composition increases, the hygroscopicity of the resin composition increases. Therefore, from the viewpoint of suppressing the hygroscopicity of the resin composition, the amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less. , more preferably 1 part by mass or less, and even more preferably 0.5 part by mass or less.

When the resin (A) of the present embodiment contains an unsaturated polyester resin (A2) and the resin composition of the present embodiment contains a carboxyl group-containing compound, the carboxyl group-containing compound has a lower molecular weight than the unsaturated polyester molecule, so that the unsaturated polyester resin (A2) is contained. An interaction occurs between the carboxyl group or hydroxy group of the polyester resin (A2) and the thickener (C), and before the resin composition thickens over time, an interaction occurs between the carboxyl group-containing compound and the thickener (C), and the initial viscosity The rise (within 5 hours after preparation of the resin composition) can be suppressed.

Additionally, water is generated as a result of interaction between the carboxyl group-containing compound and the thickener (C). This generated water promotes thickening of the resin composition 24 to 48 hours after preparation, allowing the target viscosity to be reached quickly. In addition, when a carboxyl group-containing compound is included in the resin composition, the apparent molecular weight formed by the interaction of the unsaturated polyester resin (A2), the carboxyl group-containing compound, and the thickener (C) is lowered, and the ultimate viscosity of the resin composition becomes excessive. The rise can be suppressed.

The carboxyl group-containing compound may be used alone or in combination of two or more types.

When the resin (A) of the present embodiment contains an unsaturated polyester resin (A2), the molecular weight and molecular structure of the carboxyl group-containing compound are not particularly limited, but the unsaturated polyester resin (A2) and the thickener (C) can be used as appropriate. From the viewpoint of generating interaction, the molecular weight is preferably 90 or more, and from the viewpoint of controlling viscosity, it is preferably 500 or less, more preferably 400 or less, and even more preferably 300 or less. If the molecular weight of the carboxyl group-containing compound is 90 or more, a decrease in the achieved viscosity due to the inclusion of a low molecular weight compound is suppressed, and since the mobility is not too high, rapid interaction with the thickener (C) and immediate consumption is suppressed, and the initial viscosity is suppressed. The increase in viscosity can be suppressed. In addition, if the molecular weight of the carboxyl group-containing compound is 500 or less, the molecular mobility is significantly greater than that of the unsaturated polyester resin (A2), so the resin is used immediately after step (I) (immediately after preparing the resin composition (within 5 hours after adjustment)) Excessive thickening of the composition can be further suppressed, and the attained viscosity of the resin composition can be further suppressed from excessively increasing.

When the resin (A) of the present embodiment contains an unsaturated polyester resin (A2), the thickening rate is controlled as the carboxyl group-containing compound, and is used immediately after step (I) (immediately after adjusting the resin composition (within 5 hours after preparation)) ), from the viewpoint of suppressing the resin composition from excessively thickening and further suppressing the attained viscosity of the resin composition from becoming excessively high, dicarboxylic acids having two carboxyl groups in one molecule are preferred, oxalic acid, malonic acid, and succinic acid. , glutaric acid, adipic acid, 3-dodecenylsuccinic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and Haridimer 250 are more preferred, and 3-dodecenylsuccinic acid and Haridimer 250 are more preferred.

When the resin (A) of the present embodiment contains an unsaturated polyester resin (A2), the content of the carboxyl group-containing compound in the resin composition is determined immediately after step (I) (immediately after adjusting the resin composition (within 5 hours after preparation)). From the viewpoint of being able to further suppress excessive thickening of the resin composition and further suppressing excessive increase in the ultimate viscosity of the resin composition, the total of the unsaturated polyester resin (A2) and the ethylenically unsaturated group-containing monomer (B) is 100. With respect to parts by mass, it is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more. Additionally, as the content of the carboxyl group-containing compound in the resin composition increases, the hygroscopicity of the resin composition increases. Therefore, from the viewpoint of suppressing the hygroscopicity of the resin composition, the amount is preferably 5 parts by mass or less, more preferably 3.5 parts by mass or less. , more preferably 2 parts by mass or less, and even more preferably 1 mass part or less.

When the resin (A) of the present embodiment contains an unsaturated polyester resin (A2), the content of the carboxyl group-containing compound in the resin composition is determined immediately after step (I) (immediately after adjusting the resin composition (within 5 hours after preparation)). From the viewpoint of being able to further suppress excessive thickening of the resin composition and further suppressing the attained viscosity of the resin composition from becoming excessively high, the amount is preferably 0.01 parts by mass or more, based on 100 parts by mass of the total amount of the resin composition. Preferably it is 0.05 parts by mass or more, more preferably 0.1 parts by mass or more. Additionally, as the content of the carboxyl group-containing compound in the resin composition increases, the hygroscopicity of the resin composition increases. Therefore, from the viewpoint of suppressing the hygroscopicity of the resin composition, the amount is preferably 5 parts by mass or less, more preferably 3.5 parts by mass or less. , more preferably 2 parts by mass or less, and even more preferably 1 mass part or less.

≪Other ingredients≫

The resin composition of the present embodiment contains other components, for example, other resins, polymerization inhibitors, thixotropic agents, curing accelerators, catalysts, thickening aids, curing retarders, surfactants, surfactants, wetting and dispersing agents, anti-foaming agents, It is possible to contain additives such as leveling agents, coupling agents, light stabilizers, waxes, flame retardants, and plasticizers. The content of the additive is not particularly limited as long as it does not impair the effect of the present invention.

<Polymerization inhibitor>

A polymerization inhibitor can be used to inhibit the progress of the polymerization reaction of the resin composition. It is preferable that the resin composition of this embodiment contains a polymerization inhibitor.

Known polymerization inhibitors can be used, and examples include hydroquinone, methylhydroquinone, trimethylhydroquinone, phenothiazine, catechol, 4-t-butylcatechol, and copper naphthenate. These may be used individually, or two or more types may be used together.

<Thixotropic agent>

When the resin composition in this embodiment contains vinyl ester resin (A1) as the resin (A), it is preferable to contain a thixotropic agent. A thixotropic agent is used to adjust the miscibility or fluidity of the resin composition. Examples of thixotropic agents include organic thixotropic agents and inorganic thixotropic agents. These can be used individually or in combination of two or more types.

When the resin composition of the present embodiment contains a thixotropic agent, the content is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, based on a total of 100 parts by mass of the resin (A) and the monomer (B) containing an ethylenically unsaturated group. Typically, it is 0.1 to 5 parts by mass.

Examples of organic thixotropic agents include hydrogenated castor oil-based, amide-based, oxidized polyethylene-based, vegetable oil polymerized oil-based, surfactant-based, and complex systems using these in combination. Specifically, “Plonon (registered trademark) SP-1000AF” (manufactured by Kyoeisha Kagaku Co., Ltd.), “Disparon (registered trademark) 6900-20X” (Kusumoto Kasei Co., Ltd.), etc. You can.

Examples of inorganic thixotropic agents include hydrophobically or hydrophilically treated silica and bentonite. As hydrophobic inorganic thixotropic agents, specifically, "Leorosil (registered trademark) PM-20L" (manufactured by Tokuyama Corporation), "Aerosil (registered trademark) R-106" (Nippon Aero Jill Co., Ltd.), “CAB-O-SIL (registered trademark)” (manufactured by Cabot Corporation), and the like. As a hydrophilic inorganic thixotropic agent, specific examples include “Aerosil (registered trademark)-200” (manufactured by Nippon Aerosil Co., Ltd.). Additionally, when using hydrophilic calcined silica, the combined use of thixotropic modifiers “BYK (registered trademark)-R605” and “BYK (registered trademark)-R606” (both manufactured by BYK) is effective in appropriately controlling the thickening speed.

<Content of each component in the resin composition>

Although the content of each component constituting the resin composition of this embodiment is not limited, it is preferable that it is the following 1st Embodiment and 2nd Embodiment.

[Resin composition according to the first embodiment]

The content of resin (A) in the resin composition according to the first embodiment is 100 mass in total of resin (A) and ethylenically unsaturated group-containing monomer (B) when resin (A) contains vinyl ester resin (A1). Part by mass, it 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, when the resin (A) contains an unsaturated polyester resin (A2). , 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, based on a total of 100 parts by mass of the resin (A) and the monomer (B) containing an ethylenically unsaturated group. It is wealth.

When the resin (A) contains a vinyl ester resin (A1), if the content of the resin (A) is 35 parts by mass or more, the thickening rate of the resin composition is likely to be appropriately increased by the resin (A). Moreover, if the resin (A) is 90 parts by mass or less, it is easy to reduce the viscosity of the resin composition in step (II), and it becomes easy to impregnate the fiber base material (F).

When the resin (A) contains an unsaturated polyester resin (A2), it is easy to control the thickening rate of the resin composition if the content of the resin (A) is 20 parts by mass or more. Moreover, if the content of the resin (A) is 80 parts by mass or less, it is easy to reduce the viscosity of the resin composition in step (II), and it becomes easy to impregnate the fiber base material (F).

The content of resin (A) in the resin composition according to the first embodiment is preferably 35 to 90 parts by mass with respect to 100 parts by mass of the total amount of the resin composition when the resin (A) contains vinyl ester resin (A1). , more preferably 40 to 80 parts by mass, still more preferably 45 to 70 parts by mass, and when the resin (A) contains an unsaturated polyester resin (A2), it is preferable relative to the total amount of 100 parts by mass of the resin composition. Preferably it is 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 a vinyl ester resin (A1), if the content of the resin (A) is 35 parts by mass or more, it is easy to appropriately increase the thickening rate of the resin composition with the resin (A). Moreover, if the resin (A) is 90 parts by mass or less, it is easy to reduce the viscosity of the resin composition in step (II), and it becomes easy to impregnate the fiber base material (F).

When the resin (A) contains an unsaturated polyester resin (A2), it is easy to control the thickening rate of the resin composition if the content of the resin (A) is 20 parts by mass or more. Moreover, if the content of the resin (A) is 80 parts by mass or less, it is easy to reduce the viscosity of the resin composition in step (II), and it becomes easy to impregnate the fiber base material (F).

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to the first embodiment is the ratio of the resin (A) and the ethylenically unsaturated group-containing monomer (B) when the resin (A) contains a vinyl ester resin (A1). ) is preferably 10 to 65 parts by mass, more preferably 20 to 60 parts by mass, and even more preferably 30 to 55 parts by mass, based on a total of 100 parts by mass, and the resin (A) is an unsaturated polyester resin (A2). ), preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, based on a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). is 35 to 60 parts by mass.

When the resin (A) contains a vinyl ester resin (A1), if the ethylenically unsaturated group-containing monomer (B) is 10 parts by mass or more, it is easy to reduce the viscosity of the resin composition in step (II), and the fiber substrate (F) becomes easier to impregnate. If the ethylenically unsaturated group-containing monomer (B) is 65 parts by mass or less, a resin composition with better thickening properties will be obtained.

When the resin (A) contains an unsaturated polyester resin (A2), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, it is easy to reduce the viscosity of the resin composition in step (II), It becomes easier to impregnate the fiber substrate (F). If the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, a resin composition with better thickening properties will be obtained.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to the first embodiment is preferably, when the resin (A) contains the vinyl ester resin (A1), with respect to 100 parts by mass of the total amount of the resin composition. 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 total amount of the resin composition is 100 parts by mass. Part by mass, it is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 35 to 60 parts by mass.

When the resin (A) contains a vinyl ester resin (A1), if the ethylenically unsaturated group-containing monomer (B) is 10 parts by mass or more, it is easy to reduce the viscosity of the resin composition in step (II), and the fiber substrate (F) becomes easier to impregnate. If the ethylenically unsaturated group-containing monomer (B) is 65 parts by mass or less, a resin composition with better thickening properties will be obtained.

When the resin (A) contains an unsaturated polyester resin (A2), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, it is easy to reduce the viscosity of the resin composition in step (II), It becomes easier to impregnate the fiber substrate (F). If the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, a resin composition with better thickening properties will be obtained.

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, based on a total of 100 parts by mass of the resin (A) and the monomer (B) containing an ethylenically unsaturated group. is 0.05 to 5 parts by mass, more preferably 0.1 to 4 parts by mass.

When the thickener (C) is 0.1 part by mass or more, the thickening properties of the resin composition become better. When the thickener (C) is 6 parts by mass or less, it becomes easy to suppress excessive thickening of the resin composition, and it also becomes easy to appropriately control the thickening rate.

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 to 5 parts by mass, and still more preferably 0.1, based on 100 parts by mass of the total amount of the resin composition. ~4 parts by mass.

When the thickener (C) is 0.1 part by mass or more, the thickening properties of the resin composition become better. When the thickener (C) is 6 parts by mass or less, it becomes easy to suppress excessive thickening of the resin composition, and it also becomes easy to appropriately control the thickening rate.

The content of the photopolymerization initiator (D) in the resin composition according to the first embodiment is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, based on a total of 100 parts by mass of the resin (A) and the monomer (B) containing an ethylenically unsaturated group. It is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

If the content of the photopolymerization initiator (D) is 0.01 parts by mass or more, a resin composition with better curability can be obtained. When the content of the photopolymerization initiator is 10 parts by mass or less, rapid curing reaction and heat generation are unlikely to occur during curing of the resin composition, cracks are easily suppressed, and the balance of physical properties such as strength, toughness, heat resistance, and chemical resistance is maintained. It is easy to obtain a better lining material.

The content of the photopolymerization initiator (D) in the resin composition according to the first embodiment is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 100 parts by mass of the total amount of the resin composition. It is 0.1 to 3 parts by mass.

If the content of the photopolymerization initiator (D) is 0.01 parts by mass or more, a resin composition with better curability can be obtained. When the content of the photopolymerization initiator is 10 parts by mass or less, rapid curing reaction and heat generation are unlikely to occur during curing of the resin composition, cracks are easily suppressed, and the balance of physical properties such as strength, toughness, heat resistance, and chemical resistance is maintained. It is easy to obtain a better lining material.

When the resin composition according to the first embodiment contains at least one compound (E) selected from water and a hydroxy group-containing compound, the content of compound (E) in the resin composition is based on the resin (A) and the ethylenically unsaturated group-containing monomer. With respect to a total of 100 parts by mass of (B), the amount is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and even more preferably 0.3 to 1 part by mass.

If the compound (E) is 0.05 parts by mass or more, it becomes easy to control the thickening rate of the resin composition and suppress excessive thickening. If the compound (E) is 3 parts by mass or less, a lining material with a better balance of physical properties such as strength, toughness, heat resistance, and chemical resistance can be easily obtained.

When the resin composition according to the first embodiment contains at least one compound (E) selected from water and a hydroxy group-containing compound, the content of compound (E) in the resin composition is preferably based on 100 parts by mass of the total amount of the resin composition. Preferably it is 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and still more preferably 0.3 to 1 part by mass.

If the compound (E) is 0.05 parts by mass or more, it becomes easy to control the thickening rate of the resin composition and suppress excessive thickening. If the compound (E) is 3 parts by mass or less, a lining material with a better balance of physical properties such as strength, toughness, heat resistance, and chemical resistance can be easily obtained.

In one form of this embodiment, the resin composition contains 35 to 90 parts by mass of the vinyl ester resin (A1), based on a total of 100 parts by mass of the resin (A) and the monomer (B) containing an ethylenically unsaturated group. It is preferable to include 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).

In another form of this embodiment, the resin composition contains 20 to 80 parts by mass of the unsaturated polyester resin (A2) relative to a total of 100 parts by mass of the resin (A) and the monomer (B) containing an ethylenically unsaturated group. , it is preferable to include 20 to 80 parts by mass of the ethylenically unsaturated group-containing monomer (B), 0.01 to 6 parts by mass of the above-mentioned thickener (C), and 0.01 to 5 parts by mass of the above-mentioned carboxyl group-containing compound.

[Resin composition according to the second embodiment]

The content of resin (A) in the resin composition according to the second embodiment is 100 mass in total of resin (A) and ethylenically unsaturated group-containing monomer (B) when resin (A) contains vinyl ester resin (A1). Part by mass, it is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 40 to 60 parts by mass, when the resin (A) contains an unsaturated polyester resin (A2). , 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, based on a total of 100 parts by mass of the resin (A) and the monomer (B) containing an ethylenically unsaturated group. It is wealth.

When the resin (A) contains a vinyl ester resin (A1), if the resin (A) is 20 parts by mass or more, the thickening rate of the resin composition is likely to be appropriately increased by the resin (A). If the resin (A) is 80 parts by mass or less, the viscosity of the resin composition in step (II) can be easily reduced by the ethylenically unsaturated group-containing monomer (B), and the fiber base material (F) can be easily impregnated.

When the resin (A) contains an unsaturated polyester resin (A2), it is easy to control the thickening rate of the resin composition if the content of the resin (A) is 20 parts by mass or more. Moreover, if the content of the resin (A) is 80 parts by mass or less, it is easy to reduce the viscosity of the resin composition in step (II), and it becomes easy to impregnate the fiber base material (F).

The content of resin (A) in the resin composition according to the second embodiment is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the resin composition when the resin (A) contains vinyl ester resin (A1). , more preferably 30 to 70 parts by mass, further preferably 40 to 60 parts by mass, and when the resin (A) contains an unsaturated polyester resin (A2), it is preferable relative to the total amount of 100 parts by mass of the resin composition. Preferably it is 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 a vinyl ester resin (A1), if the resin (A) is 20 parts by mass or more, it is easy to appropriately increase the thickening rate of the resin composition with the resin (A). If the resin (A) is 80 parts by mass or less, the viscosity of the resin composition in step (II) can be easily reduced by the ethylenically unsaturated group-containing monomer (B), and the fiber base material (F) can be easily impregnated.

When the resin (A) contains an unsaturated polyester resin (A2), it is easy to control the thickening rate of the resin composition if the content of the resin (A) is 20 parts by mass or more. Moreover, if the content of the resin (A) is 80 parts by mass or less, it is easy to reduce the viscosity of the resin composition in step (II), and it becomes easy to impregnate the fiber base material (F).

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to the second embodiment is the ratio of the resin (A) and the ethylenically unsaturated group-containing monomer (B) when the resin (A) contains a vinyl ester resin (A1). ) 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, based on a total of 100 parts by mass, and the resin (A) is an unsaturated polyester resin (A2). ), preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, based on a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). is 35 to 60 parts by mass.

When the resin (A) contains a vinyl ester resin (A1), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, it is easy to reduce the viscosity of the resin composition in step (II), and the fiber substrate (F) becomes easier to impregnate. If the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, a resin composition with better thickening properties will be obtained.

When the resin (A) contains an unsaturated polyester resin (A2), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, it is easy to reduce the viscosity of the resin composition in step (II), and the fiber It becomes easier to impregnate the substrate (F). If the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, a resin composition with better thickening properties will be obtained.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to the second embodiment is preferably, when the resin (A) contains the vinyl ester resin (A1), with respect to 100 parts by mass of the total amount of the resin composition. 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, still more preferably 40 to 60 parts by mass, and when the resin (A) contains an unsaturated polyester resin (A2), the total amount of the resin composition is 100 parts by mass. Part by mass, it is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 35 to 60 parts by mass.

When the resin (A) contains a vinyl ester resin (A1), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, it is easy to reduce the viscosity of the resin composition in step (II), and the fiber substrate (F) becomes easier to impregnate. If the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, a resin composition with better thickening properties will be obtained.

When the resin (A) contains an unsaturated polyester resin (A2), if the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, it is easy to reduce the viscosity of the resin composition in step (II), and the fiber It becomes easier to impregnate the substrate (F). If the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, a resin composition with better thickening properties will be obtained.

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, based on a total of 100 parts by mass of the resin (A) and the ethylenically unsaturated group-containing monomer (B). is 0.5 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 thickening properties of the resin composition become better. When the thickener (C) is 6 parts by mass or less, it becomes easy to suppress excessive thickening of the resin composition, and it also becomes easy to appropriately control the thickening rate.

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 to 5 parts by mass, and still more preferably 1 part by mass, based on 100 parts by mass of the total amount of the resin composition. ~4 parts by mass.

When the thickener (C) is 0.1 parts by mass or more, the thickening properties of the resin composition become better. If the thickener (C) is 6 parts by mass or less, it becomes easy to suppress excessive thickening of the resin composition and it becomes easy to appropriately control the thickening rate.

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, based on a total of 100 parts by mass of the resin (A) and the monomer (B) containing an ethylenically unsaturated group. It is preferably 0.05 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 is obtained. When the content of the photopolymerization initiator is 10 parts by mass or less, rapid curing reaction and heat generation are unlikely to occur during curing of the resin composition, cracks are easily suppressed, and the balance of physical properties such as strength, toughness, heat resistance, and chemical resistance is maintained. It is easy to obtain a better lining material.

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 0.05 to 5 parts by mass, and still more preferably 100 parts by mass of the total amount of the resin composition. It is 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 is obtained. When the content of the photopolymerization initiator is 10 parts by mass or less, rapid curing reaction and heat generation are unlikely to occur during curing of the resin composition, cracks are easily suppressed, and the balance of physical properties such as strength, toughness, heat resistance, and chemical resistance is maintained. It is easy to obtain a better lining material.

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 compound (E) in the resin composition is based on the resin (A) and the ethylenically unsaturated group-containing monomer. With respect to a total of 100 parts by mass of (B), the amount is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1.5 parts by mass, and even more preferably 0.1 to 1 part by mass.

If the compound (E) is 0.05 parts by mass or more, it becomes easy to control the thickening rate of the resin composition and suppress excessive thickening. If the compound (E) is 3 parts by mass or less, a lining material with a better balance of physical properties such as strength, toughness, heat resistance, and chemical resistance can be easily obtained.

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 compound (E) in the resin composition is preferably based on 100 parts by mass of the total amount of the resin composition. It is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1.5 parts by mass, and even more preferably 0.1 to 1 part by mass.

If the compound (E) is 0.05 parts by mass or more, it becomes easy to control the thickening rate of the resin composition and suppress excessive thickening. If the compound (E) is 3 parts by mass or less, a lining material with a better balance of physical properties such as strength, toughness, heat resistance, and chemical resistance can be easily obtained.

In another form of this embodiment, the resin composition contains 20 to 80 parts by mass of the vinyl ester resin (A1), based on a total of 100 parts by mass of the resin (A) and the monomer (B) containing an ethylenically unsaturated group. It is preferable to include 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 10 parts by mass of the photopolymerization initiator (D).

In another form of this embodiment, the resin composition contains 20 to 80 parts by mass of the unsaturated polyester resin (A2) relative to a total of 100 parts by mass of the resin (A) and the monomer (B) containing an ethylenically unsaturated group. , 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 the dicarboxylic acid.

≪Method for producing resin (A)≫

<Method for producing vinyl ester resin (A1-1)>

Vinyl ester resin (A1-1) can be produced by reacting an epoxy compound (a1-1) with an unsaturated monobasic acid (a1-2).

For example, in a reaction vessel capable of heating and stirring, at least one of a solvent and a reactive diluent is mixed with the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2), if necessary, and an esterification catalyst is present. It can be prepared by heating while mixing for 1 to 8 hours, preferably at 70 to 150°C, more preferably at 80 to 140°C, and even more preferably at 90 to 130°C.

In this embodiment, the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) are added to the unsaturated monobasic acid (a1-2) relative to 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1). It is preferable to react so that the total amount of acid groups is 80 mol or more, more preferably 90 mol or more, and even 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. tertiary amines such as; Phosphorus compounds such as triphenylphosphine and benzyltriphenylphosphonium chloride; diethylamine hydrochloride; Quaternary ammonium salts such as trimethylbenzylammonium chloride and tetradecyldimethylbenzylammonium chloride; and lithium salts such as lithium chloride, lithium bromide, and lithium nitrate. These may be used alone or in combination of two or more types. Among these, at least one selected from phosphorus compounds and quaternary ammonium salts is preferred from the viewpoints of gently promoting the synthesis reaction rate of the vinyl ester resin, suppressing gelation, and easily controlling the molecular weight distribution, etc. , at least one type selected from quaternary ammonium salts is more preferable.

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

At least one of the solvent and the reactive diluent is used as needed 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 carried out by known methods.

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). For example, known solvents having a boiling point of 70 to 150°C at 1 atm, such as methyl isobutyl ketone, can be mentioned. One type of solvent may be used individually, and two or more types may be used together.

As a reactive diluent, an epoxy compound (a1-1) and an ethylenically unsaturated group-containing monomer (B) that are inactive to an unsaturated monobasic acid (a1-2) are preferable.

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

<Method for producing vinyl ester resin (A1-2)>

Vinyl ester resin (A1-2) can be prepared by further adding a polybasic acid anhydride (a1-4) to the resin precursor (P1), which is a reaction product of an epoxy compound (a1-1) and an unsaturated monobasic acid (a1-2). You can.

For example, in a reaction vessel capable of heating and stirring, the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) are mixed with at least one of a solvent and a reactive diluent as needed, and an esterification catalyst is present. The resin precursor (P1) is prepared by heating while mixing for 1 to 8 hours, preferably at 70 to 150°C, more preferably at 80 to 140°C, and even more preferably at 90 to 130°C. Subsequently, polybasic acid anhydride (a1-4) is added to the reaction vessel in which the resin precursor (P1) was synthesized, and in the presence of an esterification catalyst, the reaction temperature is 70 to 150°C, preferably 80 to 140°C, more preferably. Vinyl ester resin (A1-2) is obtained by reacting at 90 to 130°C for 30 minutes to 4 hours.

In this embodiment, the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) are added to the unsaturated monobasic acid (a1-2) relative to 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1). It is preferable to react so that the total amount of acid groups is 80 mol or more, more preferably 90 mol or more, and even more preferably 99 mol or more.

In addition, the polybasic acid anhydride (a1-4) is preferably reacted so that the amount of polybasic acid anhydride (a1-4) is 3 to 60 mol per 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), and more preferably 5. ~50 mol, more preferably 7-45 mol.

Examples of the esterification catalyst used in the production of vinyl ester resin (A1-2) include the same esterification catalyst used in the production of vinyl ester resin (A1-1).

The amount of the esterification catalyst used is preferably 100 parts by mass of the total of the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) from the viewpoint of promoting the reaction and suppressing the thickening of the resin precursor (P1). 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.

Examples of at least one of the solvent and reactive diluent used in producing vinyl ester resin (A1-2) include the same solvent and reactive diluent used in producing vinyl ester resin (A1-1). Also, the preferred form is the same.

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

<Method for producing vinyl ester resin (A1-3)>

Vinyl ester resin (A1-3) is a resin precursor ( It can be produced by further adding polybasic acid anhydride (a1-4) to P2).

For example, in a reaction vessel capable of heating and stirring, at least one of a solvent and a reactive diluent is added to the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2), and the polybasic acid anhydride (a1-3) as needed. A resin precursor (P2) is obtained by mixing and heating in the presence of an esterification catalyst, preferably at 70 to 150°C, more preferably at 80 to 140°C, and even more preferably at 90 to 130°C for 1 to 8 hours. ) is manufactured. Subsequently, polybasic acid anhydride (a1-4) is added to the reaction vessel in which the resin precursor (P2) was synthesized, and in the presence of an esterification catalyst, the reaction temperature is 70 to 150°C, preferably 80 to 140°C, more preferably. 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 75 to 95 moles relative to 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1). It is preferable to react, more preferably 77 to 93 mol, and even more preferably 79 to 91 mol.

In the production of the resin precursor (P2) according to the present embodiment, the total amount of acid groups that can react with the epoxy group derived from the polybasic acid anhydride (a1-3) is It is preferable to react so that the amount is 5 to 25 mol, more preferably 7 to 23 mol, and even more preferably 9 to 21 mol.

In the production of the resin precursor (P2) according to the present embodiment, an acid group derived from an unsaturated monobasic acid (a1-2) and a polybasic acid anhydride (a1-3) (the "acid group" herein is a polybasic acid anhydride (a1-3) (It is an acid group formed by hydrolysis. For example, when the polybasic acid anhydride (a1-3) is a dibasic acid anhydride, the number of acid groups formed from one molecule is 2.) The total amount of the epoxy group of the epoxy compound (a1-1) is It is preferable to react so that the total amount of 100 moles is 105 to 125 moles, more preferably 107 to 123 moles, and even more preferably 109 to 121 moles.

In the production of the vinyl ester resin (A1-3) according to the present embodiment, the polybasic acid anhydride (a1-4) is reacted in an amount of 3 to 60 mol based on 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1). It is preferable, more preferably 5 to 50 mol, and even more preferably 7 to 45 mol.

Examples of the esterification catalyst used in the production of vinyl ester resin (A1-3) include the same esterification catalyst used in the production of vinyl ester resin (A1-1). In addition, the esterification catalyst used when producing the resin precursor (P2) and the esterification catalyst used when producing the vinyl ester resin (A1-3) from the resin precursor (P2) may be the same or different.

The amount of the esterification catalyst used is that of the epoxy compound (a1-1), unsaturated monobasic acid (a1-2), and polybasic acid anhydride (a1-3) from the viewpoint of promoting the reaction and suppressing the thickening of the resin precursor (P2). For a total of 100 parts by mass, the amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass.

Examples of at least one of the solvent and reactive diluent used in producing vinyl ester resin (A1-3) include the same solvent and reactive diluent used in producing vinyl ester resin (A1-1). Also, the preferred form is the same.

From the viewpoint of suppressing the progress of the polymerization reaction of the vinyl ester resin (A1-3), a polymerization inhibitor may be added. As for the polymerization inhibitor, those described in the above “Other Components” section are preferably used. When adding a polymerization inhibitor, the addition amount is, for example, 0.0001 to 10 parts by mass based on a total of 100 parts by mass of the epoxy compound (a1-1), unsaturated monobasic acid (a1-2), and polybasic acid anhydride (a1-3). It can be in parts by mass, and is preferably 0.001 to 1 part by mass.

<Method for producing vinyl ester resin (A1-4)>

The method for producing vinyl ester resin (A1-4) includes the steps of reacting an epoxy compound (a1-1) and a bisphenol compound (a1-5) having two epoxy groups in one molecule to obtain a resin precursor (P3), and There is a process to obtain vinyl ester resin (A1-4) by reacting the precursor (P3) and unsaturated monobasic acid (a1-2).

The process for obtaining the resin precursor (P3) is a process for obtaining the resin precursor (P3) by reacting an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5).

In the process of obtaining the resin precursor (P3), from the viewpoint of broadening the molecular weight distribution of the vinyl ester resin (A1-4) and controlling the achieved viscosity of the resin composition, an epoxy compound (a1-1) having two epoxy groups in one molecule and , the total amount of hydroxyl groups of the bisphenol compound (a1-5) is preferably 10 to 70 mol, more preferably, based on 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1). It is preferable to react so that it is 20 to 60 mol, more preferably 25 to 50 mol.

The process of obtaining the resin precursor (P3) is, for example, in a reaction vessel capable of heating and stirring, mixing the epoxy compound (a1-1) and the bisphenol compound (a1-5) with at least one of a solvent and a reactive diluent as needed. Resin precursor (P3) is mixed and heated in the presence of an esterification catalyst, preferably at 70 to 160°C, more preferably at 80 to 155°C, and even more preferably at 90 to 150°C for 1 to 3 hours while mixing. can be obtained.

Esterification catalysts include, for example, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, and diazabicyclo. Tertiary amines such as octane, phosphorus compounds such as triphenylphosphine and benzyltriphenylphosphonium chloride, diethylamine hydrochloride, trimethylbenzylammonium chloride, and lithium chloride. These can be used individually or in combination of two or more types. Among these, catalysts such as phosphorus-based and ammonium salt-based catalysts are preferable, and ammonium salts are more preferable from the viewpoint of slowing the reaction rate to prevent gelation of the resin and facilitating control of molecular weight distribution.

The amount of the esterification catalyst used is epoxy compound (a1-1), bisphenol compound (a1-5), and unsaturated monobasic acid (a1) from the viewpoint of promoting the reaction and suppressing the thickening of the vinyl ester resin (A1-4). For a total of 100 parts by mass of -2), the amount 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.

Solvents and reactive diluents are used as needed from the viewpoint of facilitating uniform mixing of the epoxy compound (a1-1), bisphenol compound (a1-5), and unsaturated monobasic acid (a1-2). The mixing method is not particularly limited and can be carried out by known methods.

The solvent is not particularly limited as long as it is a solvent that is inert to the epoxy compound (a1-1), bisphenol compound (a1-5), and unsaturated monobasic acid (a1-2). For example, known solvents having a boiling point of 70 to 150°C at 1 atm, such as methyl isobutyl ketone, can be mentioned. One type of solvent may be used individually, and two or more types may be used together.

As the reactive diluent, an epoxy compound (a1-1), a bisphenol compound (a1-5), and an ethylenically unsaturated group-containing monomer (B) that is inactive to an unsaturated monobasic acid (a1-2) are preferable.

From the viewpoint of suppressing the progress of the polymerization reaction of the resin precursor (P3), a polymerization inhibitor may be added. The polymerization inhibitor described in the section <Other components> above is preferably used. When adding a polymerization inhibitor, the addition amount is, for example, 0.0001 to 10 parts by mass based on a total of 100 parts by mass of the epoxy compound (a1-1), bisphenol compound (a1-5), and unsaturated monobasic acid (a1-2). It can be 0.001 to 1 part by mass, preferably 0.001 to 1 part by mass.

The process for obtaining vinyl ester resin (A1-4) is a process for obtaining vinyl ester resin (A1-4) by reacting a resin precursor (P3) and an unsaturated monobasic acid (a1-2).

In the process 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 manufacturing stability, the total amount of epoxy groups of the epoxy compound (a1-1) is 100 mol. In contrast, it is preferable to react so that 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 even more preferably 50 to 80 mol.

The process of obtaining the vinyl ester resin (A1-4) is, for example, adding an unsaturated monobasic acid (a1-2) in the presence of an esterification catalyst to a reaction vessel in which the resin precursor (P3) was synthesized, Vinyl ester resin (A1-4) can be produced by heating while mixing at ℃, preferably 80 to 140℃, more preferably 90 to 130℃, for 30 minutes to 4 hours.

The esterification catalyst used in the process of obtaining the vinyl ester resin (A1-4) may be the same as the esterification catalyst used in the process of obtaining the resin precursor (P3). In addition, the esterification catalyst used when producing the resin precursor (P3) and the esterification catalyst used when producing the vinyl ester resin (A1-4) from the resin precursor (P3) may be the same or different.

In the process of obtaining the vinyl ester resin (A1-4), as in the process of obtaining the resin precursor (P3), at least one of a solvent, a reactive diluent, and a polymerization inhibitor may be added as needed. The mixing method can also be performed by a known method, similar to the step of obtaining the resin precursor (P3). Also, the preferred form is the same.

When adding a reactive diluent to vinyl ester resin (A1-4) for the purpose of lowering the viscosity of vinyl ester resin (A1-4), it is better to add and mix the reactive diluent after synthesizing vinyl ester resin (A1-4). Preferably, 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), and the vinyl ester resin (A1-4) is added. After the synthesis in 4), it is preferable to add and mix the reactive diluent and other ingredients.

From the viewpoint of suppressing the progress of the polymerization reaction of the vinyl ester resin (A1-4), a polymerization inhibitor may be added. As for the polymerization inhibitor, those described in the above “Other Components” section are preferably used. When adding a polymerization inhibitor, the addition amount is, for example, 0.0001 to 10 parts by mass based on a total of 100 parts by mass of the epoxy compound (a1-1), the bisphenol compound (a1-5), and the unsaturated monobasic acid (a1-2). It can be in parts by mass, and is preferably 0.001 to 1 part by mass.

<Method for producing vinyl ester resin (A1-5)>

The method for producing vinyl ester resin (A1-5) includes the steps of reacting an epoxy compound (a1-1) and a bisphenol compound (a1-5) having two epoxy groups in one molecule to obtain a resin precursor (P3), (P3) and an unsaturated monobasic acid (a1-2) are reacted to obtain a resin precursor (P4), and the resin precursor (P4) and an unsaturated polybasic acid (a1-6) are reacted to obtain a vinyl ester resin (A1-5). There is a process for obtaining .

The step of obtaining the resin precursor (P3) is a step of obtaining the resin precursor (P1) by reacting an epoxy compound (a1-1) having two epoxy groups in one molecule and a bisphenol compound (a1-5).

The process for obtaining the resin precursor (P3) may be the same as the process for obtaining the resin precursor (P3) in the method for producing the vinyl ester resin (A1-4), and the preferred form is also the same.

In the process of obtaining the resin precursor (P3), from the viewpoint of controlling the thickening rate of the resin composition, an epoxy compound (a1-1) having two epoxy groups per molecule and a bisphenol compound (a1-5) are added to the epoxy compound (a1). The total amount of hydroxyl groups in the bisphenol compound (a1-5) is preferably 10 to 70 mol, more preferably 15 to 60 mol, and still more preferably 20 to 50 mol, relative to 100 mol of the total amount of epoxy groups in -1). It is desirable to react as much as possible.

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

The process for obtaining the resin precursor (P4) may be the same as the process for obtaining the vinyl ester resin (A1-4) in the method for producing the vinyl ester resin (A1-4), and the preferred form is also the same.

In the process of obtaining the resin precursor (P4), from the viewpoint of controlling the thickening rate, suppressing the uneven distribution of the resin composition after curing, and manufacturing stability, the process of obtaining the resin precursor (P4) is unsaturated with respect to 100 moles of the total amount of epoxy groups in the epoxy compound (a1-1). It is preferable to react so that the total amount of acid groups in the monobasic acid (a1-2) is preferably 40 to 120 mol, more preferably 50 to 100 mol, and even more preferably 60 to 80 mol.

The process of obtaining vinyl ester resin (A1-5) is a process of obtaining vinyl ester resin (A1-5) by reacting a resin precursor (P4) and an unsaturated polybasic acid (a1-6).

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

In the process of obtaining the vinyl ester resin (A1-5), from the viewpoint of controlling the thickening rate, the unsaturated polybasic acid (a1-6) is preferably added at 0.5 to 15% per 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1). It is preferable to react so that the amount is mol, more preferably 1 to 10 mol, and even more preferably 3 to 8 mol.

The esterification catalyst used in the process of obtaining the vinyl ester resin (A1-5) may be the same as the esterification catalyst used in the process of obtaining the resin precursor (P3). In addition, the esterification catalyst used when producing the resin precursor (P4) and the esterification catalyst used when producing the vinyl ester resin (A1-5) from the resin precursor (P4) may be the same or different.

In the process of obtaining the vinyl ester resin (A1-5), as in the process of obtaining the resin precursors (P3) and (P4), at least one of a solvent, a reactive diluent, and a polymerization inhibitor may be added as needed. The mixing method can also be performed by a known method, similar to the step of obtaining the resin precursor (P3). Also, the preferred form is the same.

When adding a reactive diluent to vinyl ester resin (A1-5) for the purpose of lowering the viscosity of vinyl ester resin (A1-5), it is better to add and mix the reactive diluent after synthesizing vinyl ester resin (A1-5). Preferably, 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), and the vinyl ester resin (A1-5) is added. After the synthesis in 5), it is preferable to add and mix the reactive diluent and other ingredients.

<Method for producing unsaturated polyester resin (A2)>

Unsaturated polyester resin (A2) is a dehydration condensation of diol (a2-1), dibasic acid (a2-2-1) containing an ethylenically unsaturated group, and dibasic acid (a2-2-2) without an ethylenically unsaturated group. It can be produced by polymerization.

For example, in a reaction vessel capable of heating and stirring, diol (a2-1), dibasic acid containing an ethylenically unsaturated group (a2-2-1), and dibasic acid not containing an ethylenically unsaturated group (a2-2-2) It can be produced by reacting at 150 to 250°C, preferably 170 to 240°C, more preferably 180 to 230°C for 8 to 15 hours.

In this embodiment, from the viewpoint of the mechanical strength of the cured product of the resin composition, the molar ratio of diol (a2-1) and dibasic acid (a2-2-2) not containing an ethylenically unsaturated group (diol (a2-1): ethylene It is preferable to react so that the dibasic acid (a2-2-2)) not containing a dibasic unsaturated group is 50:50 to 85:15, more preferably 55:45 to 80:20, and even more preferably 60:40. It is ~75:25.

The mixing timing of the diol (a2-1), the dibasic acid (a2-2-1) containing an ethylenically unsaturated group, and the dibasic acid (a2-2-2) without an ethylenically unsaturated group is not particularly limited, It can be done by any known method.

〔Process (II)〕

Process (II) of this embodiment is a process of obtaining a resin composition-impregnated base material by impregnating the fiber base material (F) with a resin composition. And the viscosity of the resin composition in step (II) at 25°C (hereinafter also referred to as the viscosity of the resin composition in step (II)) is 0.1 to 3 Pa·s.

The viscosity of the resin composition in step (II) refers to the viscosity of the resin composition at 25°C from the start of impregnation of the resin composition into the fiber base material (F) until the impregnation is completed. That is, the viscosity of the resin composition at 25°C is 0.1 to 3 Pa·s from the time impregnation of the resin composition into the fiber base (F) begins until the impregnation is completed.

When the viscosity of the resin composition in step (II) is 0.1 to 3 Pa·s, the resin composition can be efficiently and sufficiently impregnated into the fiber substrate (F) in a homogeneous state with no portion not impregnated with the resin composition. .

The viscosity of the resin composition in step (II) is preferably 0.2 to 2.8 Pa·s, more preferably 0.3 to 2.5 Pa·s, and still more preferably from the viewpoint of more efficient and sufficient impregnation of the resin composition. It is 0.4 to 2.3 Pa·s.

The time for impregnating the fiber base (F) with the resin composition is not particularly limited, but is preferably 0.5 to 24 hours, more preferably 1 to 10 hours, and still more preferably from the viewpoint of efficient and sufficient impregnation of the resin composition. is 1.5 to 5 hours.

Moreover, the time from the start of process (I) until completion of process (II) is preferably 1 to 30 hours, more preferably 2 to 24 hours, and even more preferably 5 to 10 hours.

The lining material preferably includes an inner film and an outer film, which will be described later, and an inner film, which will be described later, is laminated on one side of the fiber base (F) impregnated with the resin composition, and an outer film, which will be described later, is laminated on the other side. desirable.

In step (II), the resin composition may be impregnated in a state in which an inner film, described later, is laminated on one side of the fiber substrate (F), and an outer film, described later, is laminated on the other side. Among the inner film and the outer film, The resin composition may be impregnated in a laminated state on either side, or the fiber base material (F) may be impregnated directly.

In addition, when a fiber base (F) having at least one of an inner film and an outer film laminated on the surface is used, the resin composition is impregnated into the fiber base (F) through at least one of the inner film and the outer film.

There are no particular limitations on the impregnation method, including a method of impregnating by a dipping method, a method of impregnating by dropping or injecting a resin composition under atmospheric pressure, a method of impregnating by dropping or injecting a resin composition under reduced pressure, and a method of impregnating by dropping or injecting a resin composition under pressure. Alternatively, a method of impregnating by injection may be used.

In this embodiment, it is preferable to impregnate according to the first and second embodiments in the following process (II).

<Process (II): First embodiment>

The first embodiment in step (II) uses the resin composition according to the above-described first embodiment and a cylindrical fiber base material (F), and an inner film is placed on one side of the fiber base material (F), A resin composition-impregnated base material is obtained by impregnating the other side with the resin composition while an outer film is laminated on the other side.

In the first embodiment in step (II), it is preferable to impregnate the resin composition with one type selected from the following (i) to (iii).

(i) A method of impregnating the fiber base material (F) with the resin composition by dropping or injecting the resin composition from one end of the fiber base material (F) and reducing pressure from the other end.

(ii) A method of impregnating the fiber base (F) by dropping or injecting a resin composition from one end and pressurizing from the end onto which the resin composition was dropped or injected toward the other end.

(iii) Method combining (i) and (ii)

Among these, from the viewpoint of productivity, it is preferable to impregnate the resin composition by (iii).

The first embodiment in step (II) has the advantage that the time required for steps (I) to (IV) can be shortened and pipe rehabilitation can be performed efficiently.

Additionally, in the first embodiment in step (II), the lining material is obtained when step (II) is completed. In other words, when process (II) is completed, process (III) is also completed.

<Process (II): Second Embodiment>

The second embodiment in step (II) uses the resin composition according to the above-described second embodiment and a sheet-shaped or tape-shaped fiber base material (F), and directly impregnates the fiber base material (F) with the resin composition. , to obtain a base material impregnated with a resin composition.

In the second embodiment in step (II), a method of impregnating by a dipping method and a method of impregnating while dropping the resin composition are preferable.

The first embodiment in step (II) has the advantage of being easy to apply to pipes of various sizes.

≪Fiber base material (F)≫

As the fiber material of the fiber base (F), from the viewpoint of mechanical strength, etc., for example, synthetic fibers such as amide, nylon, aramid, vinylon, polyester, and phenol resin, carbon fiber, glass fiber, metal fiber, and ceramic fiber. So-called reinforcing fibers such as these, and composite fibers thereof can be mentioned. These may be used alone or in combination of two or more types. Among these, aramid fiber, carbon fiber, and glass fiber are preferable, and glass fiber is more preferable from viewpoints of strength, hardness, availability, price, etc. In particular, from the viewpoint of photocuring the resin composition impregnated in the fiber base (F), glass fibers or polyester fibers having light transparency are preferable.

For example, in the case of glass fiber, the generally used filament diameter is preferably 1 to 15 μm, more preferably 3 to 10 μm.

Examples of the form of the fiber base (F) include sheet, ?h strand, ?h, milled fiber, etc. Sheets include, for example, those formed by arranging a plurality of reinforcing fibers in one direction, two-way fabrics such as plain weave or twill weave, multiaxial fabrics, non-crimped fabrics, non-woven fabrics, mats, knits, braids, reinforcing fibers, etc. You can hold one piece of paper, etc. The fiber base material (F) may be used individually, or two or more types may be used together, and may be a single layer or may be laminated in multiple layers.

From the viewpoint of the impregnability of the resin composition, for example, in the case of a single layer, the thickness of the sheet is preferably 0.01 to 5 mm, and in the case of multiple layers laminated, the total thickness is preferably 1 to 20 mm, more preferably. is 1 to 15 mm.

The shape of the fiber base material (F) includes cylindrical shape, sheet shape, tape shape, etc.

When the fiber base material (F) has a cylindrical shape, the cylindrical shape is made into a cylindrical shape by partially overlapping the sheet-like or tape-shaped base material, and the overlapping parts are glued together with adhesive, sewn with thread, or punched together with a needle punch. It can be connected or in one form.

When using a cylindrical fiber base (F), it is preferable that the diameter of the fiber base (F) is the same as the inner diameter of the pipe to be rehabilitated.

When using a sheet-like base material, it is preferable that the length of the short side of the sheet be slightly larger than the inner circumference of the pipe to be rehabilitated, taking into account the polymerization of the sheet (part to be glued) during the production of the lining material.

When using a tape-shaped substrate, it is not particularly limited, but it is preferably 1/8 to 1/3 of the width of the inner circumference of the pipe to be rehabilitated.

<Substrate impregnated with resin composition>

The resin composition-impregnated substrate is obtained by impregnating the fiber substrate (F) with the above-described resin composition.

The pipe is rehabilitated by irradiating the lining material with ultraviolet rays or visible light and curing the resin composition in the lining material, that is, the resin composition in the resin composition-impregnated base material contained in the lining material. Therefore, the lining material obtained by hardening the resin composition is required to have a mechanical strength sufficient to repair the pipe.

For example, when glass fiber is used as the fiber substrate (F), the bending strength of the cured product (FRP) of the resin composition-impregnated substrate is preferably 100 to 1000 MPa, more preferably 120 to 900 MPa, and even more preferably 150 MPa. It is ~800MPa. Additionally, the bending elastic modulus of FRP is preferably 5 to 40 GPa, more preferably 7 to 35 GPa, and still more preferably 8 to 30 GPa.

In addition, the values of the bending strength and bending elastic modulus are measured values based on JIS K7171:2016.

The content of the resin composition in the resin composition-impregnated base material is preferably 20 to 95 mass%, more preferably 25 to 85 mass%, and even more preferably 25 to 75 mass%. When the content of the resin composition is 20% by mass or more, appropriate flexibility can be provided to the lining material, and workability in step (IV) becomes good. If the content of the resin composition is 85% by mass or less, sufficient strength can be provided 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. If the content of the fiber base material (F) is 5% by mass or more, sufficient strength can be provided to the lining material after photocuring. If the content of the fiber base (F) is 80% by mass or less, appropriate flexibility can be provided to the lining material, and workability in step (IV) becomes good.

〔Process (III)〕

Process (III) of the present embodiment is a process of obtaining a lining material containing the resin composition-impregnated base material.

Additionally, the lining material used for pipe rehabilitation needs to be cylindrical, and step (III) is also a process for obtaining a cylindrical lining material.

Although conventionally known methods can be used to obtain the lining material, it is preferable to obtain the lining material according to the first and second embodiments in the process (III) below.

<Process (III): First embodiment>

The first embodiment in step (III) uses the resin composition according to the above-described first embodiment and a cylindrical fiber substrate (F), and forms an inner film on one side of the fiber substrate (F), A lining material containing a base material impregnated with a resin composition obtained by impregnating a resin composition with an outer film laminated on the other side is obtained. That is, it is a process of obtaining a lining material containing the resin composition-impregnated base material obtained by the first embodiment of process (II). However, in the first embodiment of process (II), a cylindrical fiber base material (F) is used. Because the resin composition is impregnated, it already has a cylindrical shape at the time the first embodiment in step (II) is completed, and also has a configuration as a lining material. Therefore, in the first embodiment in step (III), when step (II) is completed, step (III) is also completed.

<Process (III): Second Embodiment>

The second embodiment in step (III) uses the resin composition according to the above-described second embodiment and a sheet-shaped or tape-shaped fiber base material (F), and directly impregnates the fiber base material (F) with the resin composition. A lining material containing a base material impregnated with the obtained resin composition is obtained. That is, in the process of obtaining a lining material containing the resin composition-impregnated base material obtained by the second embodiment in step (II), a cylindrical lining material is obtained using a sheet-shaped or tape-shaped resin composition-impregnated base material. It's fair.

In the second embodiment of the process (III), the resin composition-impregnated base material obtained by the second embodiment of the process (II) is wound around a mandrel having a diameter approximately the same as the inner diameter of the pipe for pipe rehabilitation, and the resin composition is applied to the second embodiment of the process (III). It is processed into a cylindrical shape by binding it with the resin composition contained in the composition-impregnated base material, and if necessary, an outer film is laminated to obtain a lining material.

Specifically, when the resin composition-impregnated base material is in the form of a sheet, it is wound on a mandrel, then the two sides in the longitudinal direction are overlapped by about 1 to 10 cm, and bound with the resin composition contained in the resin composition-impregnated base material. Additionally, when the resin composition-impregnated base material is in the form of a tape, the resin composition-impregnated base material is wound in a spiral shape with an overlap of about 1 to 10 cm, and the overlapping portion is tied with the resin composition contained in the resin composition-impregnated base material.

When obtaining a lining material in which an inner film is laminated, it is preferable to wind the resin composition-impregnated base material with the inner film already placed on the mandrel. By arranging an inner film on the mandrel in advance, it becomes easy to separate the mandrel after winding the resin composition-impregnated base material, and there is no need to laminate a separate inner film, thereby improving productivity.

Additionally, from the viewpoint of productivity, it is preferable to laminate the outer film after processing it into a cylindrical shape.

In step (III), the overlapping portions of the resin composition-impregnated substrate are bound with the resin composition as described above. Therefore, when the fiber substrate (F) contained in the resin-impregnated base material is sheet-shaped, the viscosity of the resin composition contained in the resin composition-impregnated base material is preferably a viscosity having appropriate adhesiveness, and is preferably 30 to 1,500 Pa·s. , more preferably 40 to 1,000 Pa·s, and even more preferably 50 to 500 Pa·s.

If the viscosity of the resin composition contained in the resin composition-impregnated base material is 40 Pa·s or more, the resin composition has appropriate adhesiveness, is not distributed in the resin composition-impregnated base material, and can maintain a uniformly contained state. Additionally, if the viscosity of the resin composition is 1,500 Pa·s or less, it is easy to process it into a cylindrical shape.

≪Lining material≫

Lining material is used for rehabilitation of pipes such as existing pipes.

The lining material has a cylindrical shape and contains a resin composition-impregnated base material in which a fiber base material (F) is impregnated with a resin composition.

Then, the lining material is placed in the pipe, and the resin composition in the resin composition-impregnated base material contained in the lining material is photocured, thereby curing the lining material and rehabilitating the pipe.

From the viewpoint of ease of construction for pipe rehabilitation, 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 base material impregnated with a resin composition between the inner film and the outer film, or 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 resin composition-impregnated base 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 a resin composition-impregnated base material between the inner film and the outer film is introduced into the inner surface of the pipe while inverting the lining material. It is desirable to use it in the inversion method.

The lining material may have other layers as needed. Additionally, each layer may be a single layer, or multiple layers may be laminated.

The lining material preferably has a diameter that is approximately the same as the inner diameter of the pipe through which rehabilitation is performed. Thereby, the strength of the pipe after rehabilitation is improved.

The inner diameter of the lining material is not particularly limited, but is preferably 100 to 1500 mm, more preferably 130 to 1200 mm, and still more preferably 150 to 1000 mm.

If the inner diameter of the lining material is 100 mm or more, light curing construction is easy, and if the inner diameter of the lining material is 1500 mm or less, workability during pipe rehabilitation construction is good.

[Inner film]

As the inner film, for example, resin films such as polyethylene film, polypropylene film, and polyethylene terephthalate film can be used. When photocuring the inner film in step (IV), it is necessary to have transparency to the light irradiated from the light irradiation device. As a result, the lining material can be cured efficiently and pipe rehabilitation can be performed appropriately. Additionally, the inner film may be peeled off after curing the lining material.

The thickness of the inner film is not particularly limited, but is preferably 50 to 200 μm, more preferably 80 to 170 μm. If the thickness of the inner film is 50 μm or more, damage to the inner film or wrinkles can be suppressed during or before step (IV), and sufficient strength can be provided to the pipe. If the thickness of the inner film is 200 μm or less, the production of the lining material becomes easy and the workability of pipe rehabilitation is good.

The inner film may be laminated before impregnating the fiber base material (F) with the resin composition, or may be laminated on the fiber base material (F) impregnated with the resin composition (resin composition impregnated base material).

The method of laminating the inner film is not particularly limited, but for example, a method of applying a liquid film composition to a fiber substrate (F), curing it and laminating it, impregnating the film with the fiber substrate (F) or a resin composition through an adhesive layer. Examples include a method of laminating a film to a substrate, a method of laminating a film to a fiber substrate (F) or a resin composition-impregnated substrate, and the like. The inner film and the outer film may be laminated using different methods, respectively, or may be laminated using the same method.

〔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 curing of the resin composition in the resin composition-impregnated base material contained in the lining material by light from the outside before step (IV). In other words, hardening of the lining material before step (IV) can be suppressed.

Additionally, in step (IV), penetration of irradiated light through the lining material can be suppressed, and the resin composition can be efficiently photocured. As an outer film having light-shielding properties, for example, a laminated film having a colored coating layer such as yellow between two transparent polyethylene films can be used.

The thickness of the outer film is not particularly limited, but is preferably 5 to 100 μm, more preferably 10 to 90 μm. If the thickness of the outer film is 5 μm or more, the outer film is not damaged or wrinkled before photocuring in step (IV), and sufficient strength can be provided to the pipe. If the thickness of the outer film is 100 μm or less, the production of the lining material becomes easy and the constructability of step (IV) becomes good.

The outer film may be laminated before impregnating the fiber base material (F) with the resin composition, or may be laminated on the fiber base material (F) impregnated with the resin composition (resin composition impregnated base material).

The method of laminating the outer film on the fiber base (F) is not particularly limited, but includes the same method as the method of laminating the inner film.

[curing process]

In this embodiment, a curing step of appropriately thickening the resin composition until it reaches the desired viscosity may be included. It is desirable to prepare it after completing process (II) but before carrying out process (III), or after completing process (III) but before carrying out process (VI).

The curing temperature in the curing process is preferably 10 to 40°C, more preferably 15 to 30°C, and even more preferably 20 to 30°C. The curing temperature can be adjusted appropriately depending on the target viscosity of the resin composition, curing time, etc.

In this embodiment, the curing process is preferably performed according to the first and second embodiments below.

<Curing process: first embodiment>

The first embodiment of the curing process is a curing process of the lining material obtained by the first embodiment of the process (III). That is, it is a curing process of a lining material containing a resin-impregnated base material in which a cylindrical fiber base material (F) is impregnated with a resin composition. In this case, a curing process is prepared after completing process (III) but before carrying out process (VI). It is desirable. The curing time is preferably 6 hours to 3.5 days, more preferably 12 hours to 3 days, and even more preferably 1 to 2 days.

The storage period of the lining material after the curing process is completed and the viscosity of the resin composition reaches 400 to 3,500 Pa·s is preferably 1 to 6 months, more preferably 2 to 5 months, from the viewpoint of quality stability.

When the lining material is obtained by the first embodiment of process (III), the number of days from completion of process (I) to completion of process (III) or curing process is preferably at least 1 day and within 4 days, more preferably. is at least 1 day and within 3 days, more preferably at least 1 day and within 2 days.

A method of controlling the number of days from completion of process (I) to completion of process (III) or curing process within the above range includes, for example, resin (A), ethylenically unsaturated group-containing monomer (B), thickener (C), And it can be controlled by selection of the type of photopolymerization initiator (D), adjustment of each compounding amount, selection of the type of fiber base material (F), temperature setting in the curing process, etc.

<Curing process: second embodiment>

The second embodiment of the curing process is a curing process of the lining material obtained by the second embodiment of process (III). That is, it is a curing process of a lining material comprising a resin impregnated base material in which a sheet or tape-like fiber base material (F) is impregnated with a resin composition. In this case, it is preferable to provide a curing process immediately after completing process (III), and further, It is desirable to prepare a curing process after completing process (III) but before carrying out process (IV).

When a curing process is provided immediately after completion of process (III), the curing time is preferably 12 hours to 3 days, more preferably 1 day to 2.5 days, and even more preferably 1.5 days to 2 days. If the curing time is within the above range, the resin composition can develop appropriate adhesion and the overlapping portion of the resin composition-impregnated substrate can be bound with sufficient strength.

When a curing process is provided after completing process (III) but before carrying out process (IV), the curing time is preferably 6 hours to 3.5 days, more preferably 12 hours to 3 days, and even more preferably 1 to 3.5 days. It's 2 days.

The storage period of the lining material after the curing process is completed and the viscosity of the resin composition reaches 400 to 3,500 Pa·s is preferably 1 to 6 months, more preferably 2 to 5 months, from the viewpoint of quality stability.

When the lining material is obtained by the second embodiment of process (III), the number of days from completion of process (I) to completion of process (III) or curing process is preferably 2 days or more and 7 days or less, more preferably. is 3 to 6 days, more preferably 4 to 5 days.

A method of controlling the number of days from completion of process (I) to completion of process (III) or curing process within the above range includes, for example, resin (A), ethylenically unsaturated group-containing monomer (B), thickener (C), And it can be controlled by selection of the type of photopolymerization initiator (D), adjustment of each compounding amount, selection of the type of fiber base material (F), temperature setting in the curing process, etc.

〔Process IV〕

Process (IV) of this embodiment is a process of placing a lining material in a pipe and photocuring it. And, in step (IV), the viscosity of the resin composition at 25°C when the lining material is placed in the pipe is 400 to 3,500 Pa·s.

The pipe is rehabilitated by placing the lining material obtained in step (III) inside the pipe and photocuring the lining material. From the viewpoint of providing excellent strength to the pipe, it is preferable to arrange the lining material along the inner circumference of the inner surface of the pipe, and it is also preferable to irradiate the lining material with ultraviolet rays or visible light after pressing it to the inner surface of the pipe.

Additionally, in order to facilitate transportation, the lining material is generally transported in a folded state to a location where pipe rehabilitation is performed (a location for light hardening), and the folded lining material is inserted into the existing pipe and expanded. At this time, it is desirable that the resin composition in the lining material does not leak or run down or is unevenly distributed in the lining material, and that the lining material has appropriate flexibility. From that point of view, in step (IV), the viscosity of the resin composition at 25°C when the lining material is placed in the pipe, that is, the temperature of the resin composition in the resin composition impregnated base material contained in the lining material at 25°C The viscosity is 400 to 3,500 Pa·s, preferably 450 to 2,500 Pa·s, and more preferably 500 to 2,000 Pa·s.

The work of introducing the lining material into the existing pipe can be done by inserting the lining material as is from a manhole or the like, but an inversion method in which the lining material is pushed into the existing pipe while being reversed from the tip side is also preferably used.

Since the diameter expansion operation of the lining material is generally performed by blowing air into the lumen of the lining material, it is desirable to have end packers at both ends of the lining material to seal the lining material. By having an end packer, when air is blown in from the end packer side of one end, the pressure inside the lining material increases, and the diameter of the lining material can be expanded so as to come into close contact with the inner peripheral surface of the existing pipe.

The enlarged lining material is cured by irradiating ultraviolet rays or visible light to the inner surface of the lining material using, for example, a portable light irradiation device, so that the resin composition contained in the lining material is hardened, and the inner surface of the existing pipe is a lining in which the resin composition has hardened. covered with ashes The radiation intensity by the light irradiation device is not particularly limited, but is preferably 0.0008 to 0.03 W/mm ² .

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

As a light irradiation device, a light source that emits light in the ultraviolet to visible light range (usually wavelength 200 to 800 nm) can be adopted. 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 operational efficiency of the process (IV), at least one of ultraviolet 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, a gallium lamp and an LED is more preferable, and a gallium lamp is more preferable.

There is no particular limitation on the light irradiation device as long as it has one or more irradiation units, but it is preferable to have a lamp connection body composed of a plurality of light irradiation lamps connected in series. By having a lamp connector, photocuring can be performed efficiently.

Example

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

[Synthesis of Resin (A)]

First, a resin for preparing a resin composition was synthesized according to the following synthesis examples and comparative synthesis examples.

Details of the epoxy compound used in the synthesis of resin (A) in the following 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 Co., Ltd., 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): Phenol novolac type epoxy resin; “EPICLON (registered trademark) N-740”, manufactured by DIC Corporation, epoxy equivalent 172

In addition, the epoxy equivalent is a value measured based on JIS K7236:2001.

[Synthesis of vinyl ester resin (A1)]

<Synthesis Example 1>

In a 5 L four-necked separable flask equipped with a stirrer, reflux condenser, gas inlet pipe, and thermometer, 2068 g of epoxy compound (1), 1.2 g of methylhydroquinone (epoxy compound (1)) as a polymerization inhibitor, and methacryl (described later) 0.04 parts by mass based on a total of 100 parts by mass of acid), and 2,4,6-tris(dimethylaminomethyl)phenol (“Seikuol TDMP”, manufactured by Seiko Chemical Co., Ltd., purity 95% by mass) as an esterification catalyst. Excess) 9.0 g (0.3 parts by mass relative to a total of 100 parts by mass of the epoxy compound and methacrylic acid described later) was added and heated to 110°C. Then, 946 g of methacrylic acid (100 moles of acid groups relative to 100 moles of the total amount of epoxy groups of epoxy compound (1)) as an unsaturated monobasic acid (a1-2) was added dropwise over about 30 minutes, and then heated to 120°C. , and reacted for about 3 hours to prepare vinyl ester resin (A1-1a).

Table 3 shows the mixing amount of each component.

<Synthesis Example 2>

In a 5 L four-necked separable flask equipped with a stirrer, reflux condenser, gas inlet pipe, and thermometer, 1260 g of epoxy compound (1) and 0.74 g of methylhydroquinone as a polymerization inhibitor (epoxy compound (1) and methacrylic acid described later) 0.04 parts by mass based on a total of 100 parts by mass), tetradecyldimethylbenzyl-ammonium chloride as a catalyst (“Nissan Cation (registered trademark) M ₂ -100R” (manufactured by Nichiyu Corporation), purity exceeding 90% by mass) 5.6 g (0.3 parts by mass based on a total of 100 parts by mass of the epoxy compound (1) and methacrylic acid described later) was added and heated to 110°C, and 577 g of methacrylic acid (epoxy compound) was added as the unsaturated monobasic acid (a1-2). A resin precursor (P1-1) was synthesized by adding 100 mol of acid groups to the total amount of 100 mol of epoxy groups of compound (1) dropwise over about 30 minutes and reacting for about 4 hours. Next, 132 g of maleic anhydride (20 moles of maleic anhydride relative to 100 moles of the total amount of epoxy groups of epoxy compound (1)) was added as the polybasic acid anhydride (a1-4), and the reaction was carried out for about 2 hours to form a vinyl ester resin ( A1-2a) was obtained.

Table 3 shows the mixing amount of each component.

<Synthesis Examples 3 to 5>

In Synthesis Example 2, 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 mixing ratios shown in Table 3 were used.

Table 3 shows the mixing amount of each component.

<Synthesis Example 6>

1260 g of epoxy compound (1), 0.74 g of methylhydroquinone as a polymerization inhibitor (epoxy compound (1), methacrylic acid described later, and 0.04 parts by mass based on a total of 100 parts by mass of maleic anhydride, which is a polybasic acid anhydride (a1-3) described later), and tetradecyldimethylbenzylammonium chloride (“Nissan Cation (registered trademark) M ₂ -100R” (ni) as a catalyst. (manufactured by Chiyu Co., Ltd.), purity exceeding 90% by mass) 5.6 g (0.3 parts by mass for a total of 100 parts by mass of epoxy compound (1), methacrylic acid described later, and maleic anhydride, which is a polybasic acid anhydride (a1-3) described later. parts by mass) and heated to 110°C, 519 g of methacrylic acid as an unsaturated monobasic acid (a1-2) (90 moles of acid groups relative to 100 moles of the total amount of epoxy groups of the epoxy compound (1)), and a polybasic acid anhydride ( As a1-3), 66 g of maleic anhydride (the total amount of acid groups derived from maleic anhydride is 10 moles relative to the total amount of 100 moles of epoxy groups of epoxy compound (1)) was added dropwise over about 30 minutes, and then reacted for about 4 hours. The resin precursor (P1-1) was synthesized. Next, 263 g of maleic anhydride (40 moles of maleic anhydride relative to 100 moles of the total amount of epoxy groups of the epoxy compound (a1-1)) was added as the polybasic acid anhydride (a1-4), and the reaction was carried out for about 2 hours to form vinyl ester. Resin (A1-3a) was obtained.

Table 3 shows the mixing amount of each component.

<Synthesis Examples 7 to 9>

In Synthesis Example 6, 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 mixing ratios shown in Table 3 were used.

Table 3 shows the mixing amount of each component.

<Comparative synthesis examples 1 to 4>

In Synthesis Example 6, synthesis was performed in the same manner except that the raw materials and mixing ratios shown in Table 4 were used. As a result, the resin precursor gelled, and the subsequent synthesis operation could not proceed, making it impossible to obtain a resin.

Table 4 shows the mixing amount of each component.

<Synthesis Example 10>

1512 g of epoxy compound (1) and 429 g of bisphenol A were added to a 5L 4-necked separable flask equipped with a stirrer, reflux condenser, gas inlet pipe, and thermometer (the ratio of the hydroxyl group of bisphenol A relative to 100 moles of the total amount of epoxy groups of epoxy compound (1)). (total amount: 47 mol) was added and heated to 80°C. Next, as a catalyst, triethylamine (manufactured by Daicel Co., Ltd.) was added to 3.9 g (a total of 100 parts by mass of epoxy compound (a1-1), bisphenol (a1-5), and unsaturated monobasic acid (a1-2). 0.2 parts by mass with respect to the mixture) was added, heated to 145°C, and reacted for 1 hour to synthesize a resin precursor (P3). Next, after cooling to 110°C, 429 g of styrene (10% by mass based on the total mass of blended components) as a reactive diluent and 0.04 g of 5% copper naphthenate (epoxy compound (a1-1), bisphenol (a1) as a polymerization inhibitor were added. -5) and 0.0019 parts by mass based on a total of 100 parts by mass of unsaturated monobasic acid (a1-2)), 1.3 g of trimethylhydroquinone (epoxy compound (a1-1), bisphenol (a1-5) and unsaturated monobasic acid (0.056 parts by mass based on a total of 100 parts by mass of (a1-2)) and 2,4,6-tris(dimethylaminomethyl)phenol (“Seikuol TDMP”, manufactured by Seiko Chemical Co., Ltd., purity) as an esterification catalyst. Add 6.9 g (more than 95% by mass) (0.3 parts by mass based on a total of 100 parts by mass of epoxy compound (a1-1), bisphenol (a1-5), and unsaturated monobasic acid (a1-2)) and heat to 110°C. did. Then, 365 g of methacrylic acid (total amount of acid groups of methacrylic acid is 53 moles relative to 100 moles of total amount of epoxy groups of epoxy compound (1)) as unsaturated monobasic acid (a1-2) was added dropwise over about 30 minutes. , heated to 130°C, and reacted for about 2 hours to prepare 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 based on a total of 100 parts by mass of all ingredients) and 1546 g of styrene as a reactive diluent (monomer (B) containing an ethylenically unsaturated group) were added. (36% by mass based on the total mass of blended components) was added to obtain a mixture of 54% by mass of vinyl ester resin (based on the total mass of blended components) and 46% by mass of styrene.

Table 5 shows the mixing amount of each component.

<Synthesis Example 11>

1795 g of epoxy compound (1) and 271 g of bisphenol A were added to a 5L 4-necked separable flask equipped with a stirrer, reflux condenser, gas inlet pipe, and thermometer (the ratio of the hydroxyl group of bisphenol A relative to 100 moles of the total amount of epoxy groups of epoxy compound (1)). A total amount 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 based on a total of 100 parts by mass of epoxy compound (a1-1) and bisphenol (a1-5)) was added, and the temperature was heated to 145°C. It was heated and reacted for 1 hour to synthesize a resin precursor (P3). Next, after cooling to 110°C, 496 g of styrene (10% by mass based on the total mass of blended components) as a reactive diluent and 0.05 g of 5% copper naphthenate (epoxy compound (a1-1), bisphenol (a1) as a polymerization inhibitor were added. -5) and 0.0019 parts by mass based on a total of 100 parts by mass of unsaturated monobasic acid (a1-2)), 1.0 g of methylhydroquinone (epoxy compound (a1-1), bisphenol (a1-5), and unsaturated monobasic acid 0.04 parts by mass based on a total of 100 parts by mass of acid (a1-2)), 1.5 g of trimethylhydroquinone (sum of epoxy compound (a1-1), bisphenol (a1-5), and unsaturated monobasic acid (a1-2) 0.057 parts by mass per 100 parts by mass), 8.0 g of 2,4,6-tris(dimethylaminomethyl)phenol (“Seikuol TDMP”, manufactured by Seiko Chemical Co., Ltd., purity exceeding 95% by mass) as an esterification catalyst. (0.3 parts by mass based on a total of 100 parts by mass of the epoxy compound (a1-1), bisphenol (a1-5), and unsaturated monobasic acid (a1-2)) was added and heated to 110°C, and the unsaturated monobasic acid (a1-2) was added and heated to 110°C. As a1-2), 564 g of methacrylic acid (total amount of acid groups of methacrylic acid is 69 moles relative to 100 moles of epoxy groups of epoxy compound (1)) was added dropwise over about 30 minutes, and then reacted for about 2 hours to form a resin. The precursor (P4) was synthesized. Next, 33 g of fumaric acid (6 moles of fumaric acid relative to 100 moles of the total amount of epoxy groups of the epoxy compound (1)) as an unsaturated polybasic acid (a1-6) was added, and the reaction was carried out for about 1 hour to form a vinyl 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 blended components) was added as a reactive diluent (monomer (B) containing an ethylenically unsaturated group), and 54% by mass of vinyl ester resin (mixed components) was added. A mixture of (total mass basis) and 46% by mass of styrene was obtained.

Table 5 shows the mixing amount of each component.

<Synthesis Example 12>

1950 g of epoxy compound (1) was heated to 80°C in a 5L 4-necked separable flask equipped with a stirrer, reflux condenser, gas inlet pipe, and thermometer, and 407 g of styrene (10% by mass based on the total mass of blended components) was added as a reactive diluent. , 0.04 g of 5% copper naphthenate as a polymerization inhibitor (0.0014 parts by mass based on a total of 100 parts by mass of the epoxy compound (a1-1) and unsaturated monobasic acid (a1-2)), 0.9 g of methylhydroquinone (epoxy compound) (0.03 parts by mass based on a total of 100 parts by mass of (a1-1) and unsaturated monobasic acid (a1-2)), 1.6 g of trimethylhydroquinone (epoxy compound (a1-1), unsaturated monobasic acid (a1-2) 0.057 parts by mass based on a total of 100 parts by mass), 2,4,6-tris(dimethylaminomethyl)phenol (“Seikuol TDMP”, manufactured by Seiko Chemical Co., Ltd., purity exceeding 95% by mass) as an esterification catalyst. 8.5 g (0.3 parts by mass based on a total of 100 parts by mass of the epoxy compound (a1-1) and unsaturated monobasic acid (a1-2)) was added, heated to 100°C, and unsaturated monobasic acid (a1-2) was added. As a result, 891 g of methacrylic acid (total amount of acid groups of methacrylic acid is 100 moles relative to 100 moles of epoxy groups of epoxy compound (1)) was added dropwise over about 30 minutes, and then reacted for about 2 hours to obtain vinyl ester resin (A1). -1b) was obtained.

This reaction product was cooled to 90°C, 815 g of styrene (20% by mass based on the total mass of blended components) was added as a reactive diluent (monomer (B) containing an ethylenically unsaturated group), and 70% by mass of vinyl ester resin (mixed component) was added. (based on total mass) and 30% by mass of styrene were obtained.

Table 5 shows the mixing amount of each component.

<Synthesis Examples 13 and 14>

In Synthesis Example 10, the synthesis was performed in the same manner except that the composition shown in Table 5 was used to obtain vinyl ester resins (A1-1c) and (A1-1d). In addition, in Synthesis Example 15, “Nissan Cation (registered trademark) M ₂ -100R” (manufactured by Nichiyu Corporation, purity exceeding 90% by mass) was used as a catalyst.

For the vinyl ester resin (A1-1c), after cooling to 90°C, 1222 g of styrene was added as a reactive diluent (monomer (B) containing an ethylenically unsaturated group), and 70% by mass of vinyl ester resin (based on the total mass of blended components) was added. A mixture of 30% by mass 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 (monomer (B) containing an ethylenically unsaturated group), and 65% by mass of vinyl ester resin (compounded A mixture of (based on the total mass of components) and 35% by mass of styrene was obtained.

Table 5 shows the mixing amount of each component.

[Synthesis of unsaturated polyester resin (A2)]

<Synthesis Example 15>

224.6 g of propylene glycol as diol (a2-1) (27.5 mol% based on 100 mol% of diol (a2-1)) and 2 , 810.5 g of 2-dimethyl-1,3-propanediol (72.5 mol% based on 100 mol% of diol (a2-1)), isophthalic acid 472.6 as dibasic acid (a2-2-2) without an ethylenically unsaturated group. g (26.5 mol% based on 100 mol% of diol (a2-1)) and 356.6 g of terephthalic acid (20.0 mol% based on 100 mol% of diol (a2-1)) were added, and nitrogen gas was added to a 3L four-necked separable flask. While blowing, a polymerization reaction was performed at 215°C for 10 hours. After that, the reaction solution was cooled to 150°C.

To the cooled reaction liquid, 563.1 g of maleic anhydride (53.5 mol% based on 100 mol% of diol (a2-1)) was added as dibasic acid (a2-2-1) containing an ethylenically unsaturated group, and 10 mol% was added at 215°C. A time condensation reaction was performed to obtain an unsaturated polyester resin (A2-a).

Table 6 shows the mixing amount of each component.

<Synthesis Examples 16 to 23>

In Synthesis Example 17, the synthesis was performed in the same manner except that the raw materials and mixing ratios shown in Table 6 were used, and unsaturated polyester resins (A2-b) to (A2-i) were obtained.

Table 6 shows the mixing amount of each component.

[Measurement evaluation of resin (A)]

Vinyl ester resins (A1-1a) to (A1-1f), (A1-2a) to (A1-2d) and (A1-3a) to (A1-3d), (A1-4a) obtained in the above synthesis examples, and (A1-5a), and unsaturated polyester resins (A2-a) to (A2-i) were measured and evaluated for the items shown below. The results of these measurement evaluations are summarized in Tables 3, 5, and 6 below.

<Sanga>

The acid value of the resin (A) is based on JIS K6901:2008 “Partial acid value (indicator titration method)” and is as follows: vinyl ester resin (A1-1a) to (A1-1f), (A1-2a) to (A1-2d), To neutralize the acid components contained in (A1-3a) to (A1-3d), (A1-4a), and (A1-5a), and unsaturated polyester resins (A2-a) to (A2-i). The mass of potassium hydroxide required was measured and the acid value was determined.

In addition, in the vinyl ester resin (A1), the vinyl ester resin (A1) is prepared using phenoxyethyl methacrylate (manufactured by Showa Denko Materials Co., Ltd.) or styrene, which is an ethylenically unsaturated group-containing monomer (B). The diluted mixture (54 to 70% by mass of vinyl ester resin (A1)) was prepared by mixing the unsaturated polyester resin (A2) with styrene, which is an ethylenically unsaturated group-containing monomer (B). The diluted mixture (57 to 65% by mass of unsaturated polyester resin (A2)) was used as a measurement sample. The acid value of the resin (A) was determined from the measured value of the measurement sample. As a titrator, “Auto Burette UCB-2000” (manufactured by Hiranuma Sangyo Co., Ltd.) was used, and as an indicator, a mixed indicator of bromothymol blue and phenol red was used.

Table 1 shows the details of the mixture (measurement sample) containing the vinyl ester resin (A1) and the mixture (measurement sample) containing the unsaturated polyester resin (A2) obtained in each synthesis example.

<hydroxyl value>

The hydroxyl value of resin (A) is based on JIS K6901:2008 “Hydroxyl value (neutralization titration method)” for vinyl ester resins (A1-1b) to (A1-1d), (A1-2b), and (A1-2d). , (A1-4a) and (A1-5a), the mass of potassium hydroxide required to neutralize the acetic acid generated by 1 g of acetylation was measured, and the hydroxyl value was determined.

In addition, in the vinyl ester resin (A1), the vinyl ester resin (A1) was diluted using phenoxyethyl methacrylate (manufactured by Showa Denko Materials Co., Ltd.), which is an ethylenically unsaturated group-containing monomer (B). One mixture (65% by mass of vinyl ester resin (A1)) and two mixtures (70% by mass and 54% by mass of vinyl ester resin (A1)) of vinyl ester resin (A1) diluted with styrene were used as measurement samples. . From the measured value of the measurement sample, the hydroxyl value of the resin (A) was determined. Neutralization titration was performed manually, and 1% phenolphthalein (ethanol solution) was used as an indicator.

Table 1 shows details of the mixture (measurement sample) containing 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 were obtained as standard polystyrene equivalent molecular weight. Mw/Mn was calculated from the values of Mn and Mw.

・Device: “Shodex (registered trademark) GPC-101” (manufactured by Showa Denko Kabushiki Kaisha)

Column: “Shodex (registered trademark) LF-804” (manufactured by Showa Denko Kabushiki Kaisha)

・Detector: Parallax refractometer “Shodex (registered trademark) RI-71S” (manufactured by Showa Denko Kabushiki Kaisha)

·Column temperature: 40℃

Sample: 0.2% by mass tetrahydrofuran solution of resin (A)

·Developing solvent: tetrahydrofuran

·Flow rate: 1.0mL/min

<Viscosity>

In the vinyl ester resin (A1), a mixture of 65% by mass of vinyl ester resin (A1) and 35% by mass of phenoxyethyl methacrylate, a mixture of 70% by mass of vinyl ester resin (A1) and 30% by mass of styrene, or vinyl ester. The viscosity of the 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, rotating. Number: 50 rpm to 0.5 rpm) and measured at a temperature of 25°C.

In addition, the mixture (measurement sample) containing the vinyl ester resin (A1) obtained in each synthesis example was the same as the mixture used during the measurement of the hydroxyl group.

Additionally, the rotation speed of the cone rotor according to the measured viscosity was set as follows.

When the viscosity of the mixture was greater than 0 Pa·s but less than 1.0 Pa·s, it was measured at a rotation speed of 50 rpm.

When the viscosity of the mixture was greater than 1.0 Pa·s and less than 2.0 Pa·s, it was measured at a rotation speed of 20 rpm.

When the viscosity of the mixture was more than 2.0 Pa·s and less than 4.0 Pa·s, it was measured at a rotation speed of 10 rpm.

When the viscosity of the mixture was more than 4.0 Pa·s and less than 8.0 Pa·s, it was measured at a rotation speed of 5 rpm.

When the viscosity of the mixture was more than 8.0 Pa·s and less than 18.0 Pa·s, it was measured at a rotation speed of 2.5 rpm.

When the viscosity of the mixture was more than 18.0 Pa·s and less than 45.0 Pa·s, it was measured at a rotation speed of 1.0 rpm.

When the viscosity of the mixture was greater than 45.0 Pa·s and less than 100.0 Pa·s, it was measured at a rotation speed of 0.5 rpm.

The rotation speed of the cone rotor according to the measured viscosity is shown in Table 2 below.

[Manufacture of resin composition]

Details of the thixotropic agent used in the production of the resin composition in the following examples and comparative examples are shown below.

·Thixotropic agent (1): Organic thixotropic agent; “Plonon SP-1000AF”, manufactured by Kyoeisha Kagaku Co., Ltd.

·Thixotropic agent (2): hydrophobic silica; “Leorosil PM-20L”, manufactured by Tokuyama Co., Ltd.

<Example 1>

A mixture (1) of 26 parts by mass of vinyl ester resin (A1-1a), 14 parts by mass of phenoxyethyl methacrylate as an ethylenically unsaturated group-containing monomer (B), and 26 parts by mass of vinyl ester resin (A1-3c). , a mixture (2) containing 14 parts by mass of phenoxyethyl methacrylate was prepared as the ethylenically unsaturated group-containing monomer (B).

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 thixotropic agent (1). 1.7 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) were added, and disper was added. It was mixed for 20 minutes at 2000 to 3000 rpm using a high-speed disperser "Homo Disper 2.5 type" manufactured by Primix Co., Ltd. Here, 1.5 parts by mass of magnesium oxide (“Magmicron MD-4AM-2”, manufactured by Mikuni Shikiso Co., Ltd., magnesium oxide content 30% by mass (estimated); hereinafter, the same) was added as compound (C), and additionally 1. It was prepared by mixing for about a minute to obtain a resin composition (X-1).

<Examples 2 to 16, Comparative Examples 1 to 8>

Resin compositions (X-2) to (X-16) and (X'-1) to (X'-8) were prepared in the same manner as in Example 1, except that the raw materials and mixing ratios shown in Tables 9 to 11 were used. ) was obtained.

<Example 17>

In a mixture of 54 parts by mass of vinyl ester resin (A1-4a) and 46 parts by mass of styrene as an ethylenically unsaturated group-containing monomer (B), 0.2 mass of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator (D) 0.2 parts by mass of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.1 part by mass of water as compound (E), and organic thixotropic agent as a thixotropic agent (thixotropic agent (1), “Flonon SP-1000AF”) , manufactured by Kyoeisha Kagaku Co., Ltd.) was added, and mixed for 20 minutes at 2000 to 3000 rpm using Disper (high-speed disperser “Homo Disper 2.5 type” manufactured by Primix Co., Ltd.). Here, as a thickener (C), 1.2 parts by mass of magnesium oxide (“Magmicron MD-4AM-2”, manufactured by Mikuni Shikiso, magnesium oxide content 30% by mass (estimated); hereinafter, the same) (magnesium oxide content 0.36% by mass) (part) was added and mixed for an additional minute to prepare a resin composition (X-17).

<Examples 18, 19, 21 to 27, 29, 30, 33 to 38>

In Example 17, resin compositions (X-18), (X-19), (X-21) to (X-27) were prepared in the same manner as in Example 17, except that the raw materials and mixing ratios shown in Tables 12 and 13 were used. (X-29), (X-30), and (X-33) to (X-38) were obtained.

<Examples 20, 28, 31 and 32>

In Example 17, 3-dodecenylsuccinic acid as a carboxyl group-containing compound was further added to a mixture of resin (A) and styrene as an ethylenically unsaturated group-containing monomer (B) in the mixing ratios shown in Tables 8 and 9, The rest was prepared in the same manner except that the raw materials and mixing ratios shown in Tables 12 and 13 were used, and resin compositions (X-20), (X-28), (X-31), and (X-32) were obtained.

<Example 39>

Mixture (1) was prepared by dissolving 54.74 parts by mass of unsaturated polyester resin (A2-a) in 44.63 parts by mass of styrene as an ethylenically unsaturated group-containing monomer (B). Additionally, as a carboxyl group-containing compound, 0.63 parts by mass of 3-dodecenylsuccinic acid was dissolved in 0.63 parts by mass of styrene to prepare mixture (2). 99.37 parts by mass of mixture (1), 1.26 parts by mass of mixture (2), 0.20 parts by mass of water as compound (E), and 0.11 parts by mass of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide as photopolymerization initiator (D). parts by mass, and 0.11 parts by mass of 2,2-dimethoxy-2-phenylacetophenone were added, and the disper (high-speed disperser "Homo Disper 2.5 type" manufactured by Primix Co., Ltd.) was added at about 10% at 2000 to 3000 rpm. Mixed for a minute. Additionally, as a thickener (C), 0.96 parts by mass (0.29 parts by mass in terms of magnesium oxide) of magnesium oxide (Magmicron MD-4AM-2, manufactured by Mikuni Shikiso, estimated magnesium oxide content of 30% by mass) was added, and Disper was mixed for about 1 minute at 2000 to 3000 rpm 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 (X'-14) were prepared in the same manner except that the raw materials and mixing ratios shown in Tables 14 to 17 were used. ) 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, viscosity, impregnation, tackiness, seepage, and bending , and measurements and evaluations of simulated pipe rehabilitation were performed. The results of these measurement evaluations are shown in Tables 9 to 17 below.

<Viscosity>

Regarding the resin compositions (X-1) to (X-38), 280 g were placed in each 300 ml container immediately after preparation, and left to stand and stored in a sealed state at 25°C and normal humidity.

For resin compositions (X-39) to (X-66), (X'-9), (X'-10), (X'-13) and (X'-14), 500 mL of each was added immediately after adjustment. 500 g was placed in a 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 heat compression, and left and stored in an environment of 25°C and 50%RH, or in an environment of 25°C and 80%RH. .

Resin compositions (X'-11) and (X'-12) were placed in 500 mL metal round cans immediately after adjustment, covered with metal lids, and left to stand in an environment of 23°C and 50%RH.

For the resin compositions (X-1) to (X-4), (X-17) to (X-27) and (X-39) to (X-51) that were allowed to stand, 1 hour has elapsed after adjusting the resin composition. The viscosity at 25°C (viscosity at 25°C of the resin composition in step (II)) and the viscosity at 25°C 2 days after preparing the resin composition were measured. In addition, the thickening rate is the same whether the resin composition is impregnated into the fiber base (F) or when it is left standing only with the resin composition without impregnation, and the viscosity at 25° C. 2 days after preparing the resin composition is also same. Therefore, the viscosity at 25°C 2 days after preparing the resin composition means 25°C of the resin composition in the lining material when the lining material in step (IV) is placed in the pipe on the 2nd day after preparing the resin composition. Corresponds to viscosity at °C.

For the resin compositions (X-5) to (X-16), (X-28) to (X-38) and (X-52) to (X-66) that were allowed to stand, 1 hour has elapsed after adjusting the resin composition. Measure the viscosity at 25°C (viscosity of the resin composition in step (II)), the viscosity at 25°C 2 days after preparing the resin composition, and the viscosity at 25°C 5 days after preparing the resin composition. did. In addition, as described above, the thickening rate is the same whether the resin composition is impregnated into the fiber base (F) or when it is left standing only with the resin composition without being impregnated, and 25% at 5 days after preparation of the resin composition. The viscosity at °C is also the same. Therefore, the viscosity at 25°C 5 days after preparing the resin composition means 25% of the resin composition in the lining material when the lining material in step (IV) is placed in the pipe on the 5th day after preparing the resin composition. Corresponds to viscosity at °C.

For (X'-1) to (X'-14), viscosity at 25°C 1 hour after adjusting the resin composition (viscosity of the resin composition in step (II)), 2 days after preparing the resin composition The viscosity at 25°C over time and the viscosity at 25°C 5 days after preparation of the resin composition were measured. In addition, the viscosity at 25°C 2 days and 5 days after preparing the resin composition refers to the viscosity when the lining material in step (IV) is placed in the pipe on the 2nd and 5th days after preparing the resin composition. , corresponds to the viscosity at 25°C of the resin composition in the lining material.

For viscosity measurement, the following two types of equipment were appropriately selected depending on the viscosity range.

(1) “RB80 type viscometer” (manufactured by Toki Sangyo Co., Ltd.; rotor No. 3 to 4)

When the viscosity of the resin composition was more than 0 Pa·s and less than 1.0 Pa·s, it was measured at a rotation speed of 60 rpm using rotor No. 3.

When the viscosity of the resin composition was more than 1.0 Pa·s and less than 5.0 Pa·s, it was measured at a rotation speed of 60 rpm using rotor No. 4.

When the viscosity of the resin composition was more than 5.0 Pa·s and less than 25.0 Pa·s, it was measured using rotor No. 4 at a rotation speed of 12 rpm.

When the viscosity of the resin composition was more than 25.0 Pa·s and less than 50.0 Pa·s, it was measured using rotor No. 4 at a rotation speed of 6 rpm.

When the viscosity of the resin composition was more than 50.0 Pa·s and less than 100.0 Pa·s, it was measured using rotor No. 4 at a rotation speed of 3 rpm.

The rotor used and rotation speed according to the measured viscosity are shown in Table 7 below.

(2) “HBDVE type viscometer” (manufactured by Eiko Seiki Co., Ltd.; T-bar spindle T-A to T-D, rotation speed: 1 rpm)

When the viscosity of the resin composition was more than 100.0 Pa·s and less than 800.0 Pa·s, the T bar spindle T-A was used.

When the viscosity of the resin composition was more than 800.0 Pa·s and less than 1600.0 Pa·s, the T-bar spindle T-B was used.

When the viscosity of the resin composition was more than 1600.0 Pa·s and less than 4000.0 Pa·s, the T-bar spindle T-C was used.

When the viscosity of the resin composition was more than 4000.0 Pa·s and less than 10000.0 Pa·s, a T-bar spindle T-D was used.

The T-bar spindle used according to the measured viscosity is shown in Table 8 below.

<Impregnability>

A glass fiber ?h strand mat (“MC 450A”, manufactured by Nitto Boseki Co., Ltd.) was cut into three 100 mm × 100 mm squares, and a stainless steel ring with an inner diameter of 50 mm and a height of 20 mm was placed on top of the three sheets. Then, 10 g of the resin composition prepared in the examples and comparative examples 1 hour after adjustment was poured into a stainless steel ring, and the time for the resin composition to penetrate into the glass fibers of the lowest layer was measured.

When the poured resin composition penetrated into the lowest layer glass fiber in less than 5 minutes, the impregnation property was judged to be good. In the columns for impregnability in Tables 9 to 17, cases where impregnationability is good are indicated as “○”, and other cases are indicated as “×”.

<Taekseong>

280 g of the resin composition was placed in a 300 ml disposable cup, left to stand at room temperature and humidity (dark place) for 2 days, and then the surface of the resin composition was touched. 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 tackiness column of Tables 9 to 17, cases where tackiness is good are indicated with “○”, and cases where there is no stickiness and the resin composition does not adhere to fingers are indicated with “×”.

In addition, when manufacturing a lining material using a sheet-like or tape-shaped fiber base material (F), a resin composition having good tackiness in this evaluation can be preferably used.

<oozing out>

Cut three sheets of glass fiber ?h strand mat (“MC 450A”, manufactured by Nitto Boseki Co., Ltd.) into a square of 200 mm × 200 mm, stack the three sheets, and impregnate them with about 51 g of resin composition using a defoaming roller. This gave a laminate (glass content of about 50%). The laminate was sandwiched with a polyethylene terephthalate film cut to 250 mm x 250 mm, left to cure at room temperature and normal humidity (in the dark), and a resin composition-impregnated base material was obtained. In addition, when resin compositions (X-1) to (X-4), (X-17) to (X-27) and (X-39) to (X-51) are used, curing is performed for 2 days and the resin composition Compositions (X-5) to (X-16), (X-28) to (X-38), (X-52) to (X-66) and (X'-1) to (X'-14) When used, it was cured for 5 days. After curing, a cut of about 50 mm was made with scissors, and the presence or absence of oozing of the resin composition (resin flowing) was checked from the cross section. If there was no oozing of the resin composition from the cross section, it was judged to be in good condition. In the oozing column of Tables 5 to 13, cases where there is no oozing are indicated as “○”, and cases where there is oozing are indicated as “×”.

If the resin composition does not seep out, the lining material can be used suitably because the resin composition does not leak out or run down or become uneven in the lining material when placed in the pipe in step (IV).

<Bending evaluation>

In the same manner as the evaluation of seepage properties, a material for lining material was obtained. In addition, when resin compositions (X-1) to (X-4), (X-17) to (X-27) and (X-39) to (X-51) are used, curing is performed for 2 days and the resin composition Compositions (X-5) to (X-16), (X-28) to (X-38), (X-52) to (X-66) and (X'-1) to (X'-14) When used, it was cured for 5 days. After curing, the laminate was bent 180° and returned to check the presence or absence of bending marks and peeling of the resin and fibers. If there were no bending marks or peeling of the resin and fibers, it was judged to be in good condition. In the bending evaluation column of Tables 9 to 17, “○” indicates the presence or absence of bending traces and no peeling of the resin and fiber, and “△” indicates the presence or absence of bending traces or peeling of the resin and fiber. 」, the presence or absence of bending traces, and the presence of both resin and fiber peeling are indicated as 「×」.

<Evaluation of simulation officer rehabilitation>

A 220 mm wide x 1000 mm long x 4 mm thick aluminum plate with the edges treated with R2 in a curved shape is wrapped with a 1400 mm long x 100 μm thick polyethylene film (manufactured by Ise Kasei Kogyo Co., Ltd.) as an inner film, and the plastic wrap is wrapped at the wrap portion. A heat seal was performed using Raid (made by Hakko Corporation). Next, from the inner film, a glass fiber ?h strand mat (“MC 450A”, manufactured by Nitto Boseki Co., Ltd.) with a length of 800 mm as the fiber base material (F) is wound, and at the same time as it is wound, a defoaming roller is used to form a resin composition. was impregnated to obtain a resin composition-impregnated base material (4 sheets overlapping: thickness 3.0 mm, glass fiber content 40%).

Additionally, a polyethylene film with a length of 1400 mm and a thickness of 100 μm was covered as an outer film from the resin composition-impregnated substrate, and the wrap portion was adhered and fixed with a 50 mm wide masking tape (manufactured by 3M Japan Co., Ltd.). Subsequently, the aluminum plate was drawn to obtain a lining material.

After curing the lining material at 25°C and normal humidity for 2 days, it was introduced into an acrylic pipe, which is a simulated pipe with an inner diameter of 150 mm x a length of 1000 mm. Both ends of the lining material were tied with a binding band and sealed, air was injected from one end at 4 L/sec, the lining material was enlarged and pressed against the inner surface of the acrylic pipe. After that, both ends of the lining material are fixed to the acrylic pipe, a cap with an air injection hole is installed on one end, and an ultraviolet LED fluorescent lamp type light "NS365-FTL-C30" (Nitride Semi) is installed on the other end. A cap containing a conductor (made of conductor) was installed. While injecting air at 4 L/sec from a cap with an air injection hole, use an ultraviolet illuminance meter "UIT-201" (Ushio Denki Co., Ltd.) at an illuminance of 10 mW/cm ² , a sensitivity wavelength range of 330 to 490 nm, and an irradiation time of 60 mW/cm 2 . Pipe rehabilitation of the simulated pipe was performed by photocuring the lining material.

In cases where the diameter could be expanded without problems by blowing air into the lining material, it was determined that expansion was possible.

Additionally, after curing the lining material, the inner film was removed and the thickness of the cured layer of the lining material was confirmed. The thickness of the lining hardened layer was measured at 4 points on the top, bottom, left, and right sides of the cross section of the pipe at 3 locations in the center of the simulation pipe, each 200 mm from both ends, for a total of 12 points. When the lower limit of the thickness was 3.0 mm or more and the upper limit was within 3.0 mm + 20% (within 3.6 mm), uneven distribution of the resin composition in the lining material was well suppressed, and the appearance was judged to be good. In the mock pipe rehabilitation evaluation column of Tables 5 to 12, “○” is given when the lining material can be expanded and the thickness of the lining material hardened layer is 3.0 to 3.6 mm, and when the lining material cannot be expanded or the lining material is hardened. When the layer thickness was outside the range of 3.0 to 3.6 mm, or both, it was designated as “×”.

As shown in Tables 9, 12, and 14, in Examples 1 to 4, 17 to 27, and 39 to 51, the viscosity 1 hour after preparing the resin composition (viscosity of the resin composition in step (II)) Since is 0.1 to 3 Pa·s, and the viscosity 2 days after preparing the resin composition (viscosity of the resin composition when placing the lining material in step (IV) into the pipe) is 400 to 3,500 Pa·s, It can be seen that a resin composition with an appropriately controlled thickening rate was obtained.

In addition, as shown in Tables 10, 13, 15 and 16, in Examples 5 to 16, 28 to 38 and 52 to 66, the viscosity 1 hour after preparation of the resin composition (resin in step (II) The viscosity of the composition is 0.1 to 3 Pa·s, and the viscosity of the resin composition 5 days after preparation (viscosity of the resin composition when placing the lining material in step (IV) within the pipe) is 400 to 3500 Pa·s. Because of this, it can be seen that a resin composition with an appropriately controlled thickening rate was obtained.

On the other hand, in Comparative Examples 1 to 4 and 10, it can be seen that the impregnability is low because the viscosity 1 hour after preparation of the resin composition (viscosity of the resin composition in step (II)) is large. Additionally, in Comparative Examples 5, 9, and 11 to 14, the viscosity 1 hour after preparing the resin composition (viscosity of the resin composition in step (II)) was appropriate, but the thickening rate was low, so even after curing for 5 days. The viscosity is low and oozing of the resin composition is visible. Additionally, in Comparative Examples 6 to 8, the viscosity 1 hour after preparing the resin composition (viscosity of the resin composition in step (II)) was appropriate, but the viscosity 5 days after preparing the resin composition was very high. No oozing of the resin composition was seen, but traces of bending and peeling of the resin and fibers were visible.

[Evaluation of hardened product (cast product, FRP)]

The resin composition (X-1) obtained in Example 1 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 molded product of 170 mm × 170 mm and a thickness of 4 mm. The cargo (mould) was obtained. In addition, the above illuminance was measured using an illuminance meter "IL1400A" (manufactured by International Light Technologies, receiver model SEL005, measurement wavelength range: 380 to 450 nm, median value: 415 nm).

Additionally, about 51 g of the resin composition (X-1) obtained in Example 1 was impregnated into a ?h strand mat of glass fiber (“MC 450A”, manufactured by Nitto Boseki Co., Ltd.), and three sheets were stacked for 5 minutes at 25°C. After curing for one day, a base material impregnated with the resin composition was obtained. The resin composition-impregnated substrate was 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 of 170 mm × 170 mm and a thickness of 3.1 mm (FRP: glass fiber content of 31% by mass) was obtained. got it

Subsequently, each cured product was cut into 80 mm in length and 10 mm in width, and cured for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50% to obtain test pieces for measurement and evaluation.

<Bending strength and bending modulus>

In accordance with JIS K7171:2016, using a universal material testing machine (“Tensilon UCT-1T”, manufactured by Orientek Co., Ltd.; distance between support points 48 mm, test speed 1.3 mm/min), temperature 23°C, humidity 50%. The bending strength and bending elastic modulus were measured under the following conditions.

The average value of the measured values of 5 test pieces (N=5) for the cured product (cast product) and the measured values of 3 test pieces (N=3) for the cured product (FRP) are the bending strength and bending of each cured material. It was determined by the elastic modulus.

The bending strength of the cured product (cast product) of the resin composition (X-1) was 101 MPa and the bending elastic modulus was 3.3 GPa, and the bending strength of the cured product (FRP) was 162 MPa and the bending elastic modulus was 8.5 GPa.

<Load bending temperature>

For hardened products (cast products), in accordance with JIS K7191-1:2015 and JIS K7191-1:2015, a load deflection temperature (HDT) measuring device (“HDT Tester S-3M”, Toyo Seiki Seiki Co., Ltd. The load deflection temperature was measured using a (Sakusho product), and the average value of the measured values of three test pieces (N=3) was taken as the load deflection temperature of the cured product.

The load deflection temperature of the cured product (cast product) of the resin composition (X-1) was 90°C.

<Bacol hardness>

For the cured product (cast product) and the cured product (FRP), 10 test pieces for each measurement and evaluation were measured using a Bacall hardness meter (“GYZJ 934-1”, manufactured by Barber-Coleman) in accordance with JIS K7060:1995. The back side of the light irradiation surface was measured, and the average value was taken as the Barcol hardness of the cured product.

The Barcol hardness of the cured product (FRP) of the resin composition (X-1) was 46.

From the measurement and evaluation results of the bending strength, bending modulus, and load bending temperature of the cured product of the resin composition, it was found that the obtained cured product had sufficient mechanical strength. Therefore, a lining material containing a resin-impregnated base material impregnated with the resin composition of the present embodiment can provide sufficient strength to the pipe.

According to this embodiment, a resin composition used in a lining material for pipe rehabilitation is provided, which has a low viscosity 1 hour after preparation of the resin composition and an appropriately controlled thickening rate. The lining material using the resin composition according to this embodiment has good workability and excellent strength.

Claims (17)

A step (I) of preparing a resin composition,
A step (II) of impregnating a fiber substrate (F) with the resin composition to obtain a resin composition-impregnated substrate,
Step (III) of obtaining a lining material containing the resin composition impregnated base material,
A pipe rehabilitation method comprising the step (IV) of placing the lining material in the pipe and photocuring it,
The resin composition is,
Suzy (A),
A monomer (B) containing an ethylenically unsaturated group,
A thickener (C),
Contains a photopolymerization initiator (D),
The viscosity of the resin composition in step (II) at 25°C is 0.1 to 3 Pa·s,
In step (IV), a pipe rehabilitation method wherein the viscosity of the resin composition at 25°C when the lining material is placed in the pipe is 400 to 3,500 Pa·s. According to claim 1,
A pipe rehabilitation method wherein the resin (A) contains at least one selected from vinyl ester resin (A1) and unsaturated polyester resin (A2). According to claim 2,
The vinyl ester resin (A1) is a resin precursor (P2) which is a reaction product of an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride (a1-3). ) and the addition reaction product of polybasic acid anhydride (a1-4),
A pipe rehabilitation method wherein the total amount of acid groups capable of reacting with the epoxy groups derived from the polybasic acid anhydride (a1-3) is 5 to 25 moles, relative to the total amount of 100 moles of epoxy groups of the epoxy compound (a1-1). According to claim 2,
The vinyl ester resin (A1) is a resin precursor (P3) which is a reaction product of an epoxy compound (a1-1) and a bisphenol compound (a1-5) having two epoxy groups in one molecule, and an unsaturated monobasic acid (a1- 2) Rehabilitation method for pipes that are the reaction products. According to claim 2,
The vinyl ester resin (A1) is a resin precursor (P3) which is a reaction product of an epoxy compound (a1-1) and a bisphenol compound (a1-5) having two epoxy groups in one molecule, and an unsaturated monobasic acid (a1- A method of rehabilitating a pipe that is a reaction product of a resin precursor (P4), which is the reaction product of 2), and an unsaturated polybasic acid (a1-6). According to claim 2,
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 diol (a2-1-1), which is an alkanediol with a molecular weight of 90 to 500, based on 100 mol% of the diol (a2-1),
The dibasic acid (a2-2) is a pipe rehabilitation method comprising a dibasic acid (a2-2-1) containing an ethylenically unsaturated group and a dibasic acid (a2-2-2) not containing an ethylenically unsaturated group. The method of claim 1 or 2,
A pipe rehabilitation method in which the number of days from the completion of the above process (I) to the completion of the process (III) or the curing process is 1 day or more and less than 4 days. According to claim 2,
The resin (A) includes the vinyl ester resin (A1),
The resin composition contains 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 vinyl ester resin (A1),
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),
A pipe rehabilitation method comprising 0.01 to 10 parts by mass of the photopolymerization initiator (D). According to claim 2,
The resin (A) includes the unsaturated polyester resin (A2),
For a total of 100 parts by mass of the unsaturated polyester resin (A2) and the ethylenically unsaturated group-containing monomer (B),
20 to 80 parts by mass of the unsaturated polyester resin (A2),
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),
A pipe rehabilitation method comprising 0.01 to 5 parts by mass of the carboxyl group-containing compound. The method of claim 1 or 2,
A pipe rehabilitation method wherein the resin composition in step (III) has a viscosity of 30 to 1,500 Pa·s at 25°C. According to claim 10,
A pipe rehabilitation method in which the number of days from the completion of the above process (I) to the completion of the process (III) or curing process is 3 or more days and less than 6 days. According to claim 10,
The resin (A) includes the vinyl ester resin (A1),
The resin composition contains 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 vinyl ester resin (A1),
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),
A pipe rehabilitation method comprising 0.01 to 10 parts by mass of the photopolymerization initiator (D). According to claim 10,
The resin (A) includes the unsaturated polyester resin (A2),
For a total of 100 parts by mass of the unsaturated polyester resin (A2) and the ethylenically unsaturated group-containing monomer (B),
20 to 80 parts by mass of the unsaturated polyester resin (A2),
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)
A pipe rehabilitation method comprising 0.01 to 5 parts by mass of the carboxyl group-containing compound. The method of claim 1 or 2,
A pipe rehabilitation method wherein the thickener (C) is at least one selected from oxides and hydroxides of Group 2 elements. The method of claim 1 or 2,
A pipe rehabilitation method wherein the resin composition further contains at least one compound (E) selected from water and a hydroxy group-containing compound. The method of claim 1 or 2,
A pipe rehabilitation method wherein the resin composition further contains a thixotropic agent. According to claim 2,
A method for rehabilitating pipes wherein the vinyl ester resin (A1) has a hydroxyl value of 10 to 120 KOHmg/g.