CN117794719A

CN117794719A - Lining material

Info

Publication number: CN117794719A
Application number: CN202280055543.6A
Authority: CN
Inventors: 冈田尚人; 小林健一; 后藤直树; 井上悟志; 丸茂和将
Original assignee: Lishennoco Co ltd
Current assignee: Lishennoco Co ltd
Priority date: 2021-08-13
Filing date: 2022-08-12
Publication date: 2024-03-29

Abstract

A lining material comprising a fibrous base material comprising a resin composition comprising a vinyl ester resin (A) having an acid value of 1 to 35KOHmg/g, a monomer (B) containing an ethylenically unsaturated group, at least 1 compound (C) selected from oxides and hydroxides of group IIA elements, and a photopolymerization initiator (D).

Description

Lining material

Technical Field

The present invention relates to lining materials.

Background

In recent years, the deterioration of paved pipelines buried in the ground, such as tap water pipes, sewage pipes, and power pipes, has become serious, and various methods for repairing them have been proposed.

For example, patent document 1 discloses a method for repairing a paved pipe, which includes the following curing steps: a tubular lining material is brought into close contact with the inner wall surface of a laid pipe buried underground, compressed air is supplied into the lining material, and light is irradiated onto the inner surface of the lining material by a movable light irradiation device introduced into the lining material, thereby curing the lining material. In addition, as a material for a lining material, a material obtained by impregnating a photocurable resin composition into an impregnated base material made of fibers or the like is described, and a composition obtained by dissolving a polymerizable resin such as an unsaturated polyester resin or a vinyl ester resin in a solvent such as styrene is also described as the photocurable resin composition.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2020-82408

Disclosure of Invention

Problems to be solved by the invention

In recent years, demands for a thinner and higher strength lining material for repairing a paved pipeline have been increasing, and accordingly, a fiber base material constituting the lining material tends to be thinner and higher in density. The fiber base material is usually impregnated with a resin composition or the like in advance, and the lining material is produced in a state in which the resin composition is contained in the fiber base material. Accordingly, with the trend toward higher density of the fiber base material, there is a trend toward a resin composition having a lower viscosity so as to be easily impregnated into the fiber base material.

In addition, when the lining material is disposed on the inner surface of a laid pipe for construction, it is required that the resin composition in the fiber base material is not unevenly distributed and has a viscosity which can be maintained in a state of being uniformly distributed. That is, it is desirable that the resin composition has a low viscosity when the fiber base material is impregnated with the resin composition and is thickened with time so that the resin composition is maintained in a state of being high in viscosity when repairing a pipe which has been laid. However, the conventional lining material does not sufficiently control the viscosity of the resin composition in each step, and has problems such as poor impregnation of the resin composition into the fiber base material and uneven distribution of the resin composition during construction. In particular, in the case of thinning the lining material, in order to impart sufficient strength to the pipe, it is necessary to reduce the allowable range of uneven distribution of the resin composition at the time of repairing the already laid pipe, and it is necessary to make the uneven distribution less likely, that is, to make the resin composition more capable of maintaining the retained state.

In addition, if the amount of the resin composition in the lining material is relatively reduced due to the thinning, the curability of the lining material tends to be reduced. That is, the curing speed tends to be low. Therefore, a lining material having more excellent curability is demanded.

In addition, in repairing a damaged pipe, there are cases where, when a lining material is placed on the inner surface of a laid pipe, a bending portion is generated in the lining material and the thickness becomes locally thick, such as a joint portion between a branch pipe and a main pipe, a joint portion between a longitudinal hole connected to a manhole, and a portion where a part of the height is uneven due to breakage of the pipe. The resin composition in the part where the thickness is locally increased is likely to be defective in curing, and there is a problem in that the tube cannot be properly repaired.

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a lining material which suppresses uneven distribution of a resin composition after curing, is excellent in curability, and suppresses curing failure.

Means for solving the problems

Namely, the present invention provides the following means.

[1] A lining material comprising a fibrous base material comprising a resin composition,

The resin composition comprises:

vinyl ester resin (A),

An ethylenically unsaturated group-containing monomer (B),

At least 1 compound (C) selected from oxides and hydroxides of group IIA elements, and

a photopolymerization initiator (D),

the acid value of the vinyl ester resin (A) is 1-35 KOHmg/g.

[2] The lining material according to the above [1], wherein the vinyl ester resin (A) is a reaction product of a resin precursor (P1) and an unsaturated monoacid (a-3), and the resin precursor (P1) is a reaction product of an epoxy compound (a-1) having 2 epoxy groups in 1 molecule and a bisphenol compound (a-2).

[3] The lining material according to the above [1], wherein the vinyl ester resin (A) is a reaction product of a resin precursor (P2) and an unsaturated polybasic acid (a-4), the resin precursor (P2) is a reaction product of a resin precursor (P1) and an unsaturated monobasic acid (a-3), and the resin precursor (P1) is a reaction product of an epoxy compound (a-1) having 2 epoxy groups in 1 molecule and a bisphenol compound (a-2).

[4] The lining material according to any one of [1] to [3], wherein the weight average molecular weight (Mw) of the vinyl ester resin (A) is 2000 to 5000.

[5] The lining material according to any one of [1] to [4], wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the vinyl ester resin (A) is 1.5 or more.

[6] The lining material according to any one of the above [1] to [5], wherein the vinyl ester resin (A) has a hydroxyl value of 10 to 120KOHmg/g.

[7] The lining material according to any one of [1] to [6], wherein the content of the component (C) is 0.3 to 3 parts by mass based on 100 parts by mass of the total of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B).

[8] The lining material according to any one of [1] to [7], wherein the resin composition further comprises a compound (E) which is at least 1 selected from water and hydroxyl-containing compounds.

[9] The lining material according to any one of [1] to [8], wherein the photocurable resin composition further contains a carboxyl group-containing compound (F).

[10] The lining material according to any one of the above [1] to [9], wherein the lining material comprises, based on 100 parts by mass of the total of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B),

contains 30 to 90 parts by mass of the vinyl ester resin (A),

containing 10 to 70 parts by mass of the ethylenically unsaturated group-containing monomer (B),

contains 0.05 to 10 parts by mass of the photopolymerization initiator (D).

[11] The lining material according to any one of [1] to [10], wherein the photocurable resin composition further contains a thixotropic agent.

[12] The lining material according to any one of [1] to [11], which comprises an inner film provided on one surface of the fibrous base material and an outer film provided on the other surface.

[13] A cured product of the lining material according to any one of the above [1] to [12 ].

Effects of the invention

According to the present invention, it is possible to provide a lining material which suppresses uneven distribution of a resin composition after curing, is excellent in curability, and suppresses curing failure.

Drawings

FIG. 1 is a schematic view for explaining a method of evaluating the curability of a bent portion of a lining material.

Detailed Description

First, definitions and meanings of terms and expressions in the present specification are shown below.

(meth) acrylic acid is a generic term for acrylic acid and methacrylic acid. Similarly, the term "(meth) acrylate" refers to the general term of acrylate and methacrylate, and the term "(meth) acryl" refers to the general term of acryl and methacryl.

The "weight average molecular weight Mw" (hereinafter, also simply referred to as "Mw") and the "number average molecular weight Mn" (hereinafter, also simply referred to as "Mn") are molecular weights calculated as standard polystyrene by Gel Permeation Chromatography (GPC) measurement. Specifically, the measurement was performed by the method described in examples described below.

The "viscosity" of the vinyl ester resin is expressed by the viscosity of the mixture of the vinyl ester resin and the ethylenically unsaturated group-containing monomer (B). Is a value measured at a temperature of 25℃using an E-type viscometer. Specifically, the measurement was performed by the method described in examples described below.

The "viscosity" of the resin composition is a value measured at a temperature of 23℃using a B-type viscometer. Specifically, the measurement was performed by the method described in examples described below. The "initial viscosity" means a viscosity measured within 1 hour immediately after the production of the resin composition.

[ Lining Material ]

The lining material of the present embodiment contains a fibrous base material containing a resin composition. The resin composition comprises a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), at least 1 compound (C) selected from oxides and hydroxides of group IIA elements, and a photopolymerization initiator (D), wherein the vinyl ester resin (A) has an acid value of 1 to 35KOHmg/g.

The lining material of the present embodiment suppresses uneven distribution of the resin composition after curing, is excellent in curability, and suppresses curing failure.

The lining material of the present embodiment is tubular and can be used for repairing a paved pipeline or the like (also referred to as a pipe repair). Tube repair is typically performed as follows: the resin composition contained in the lining material is cured by disposing the lining material along the inner periphery of the inner surface of the tube, pressing the lining material against the inner surface of the tube, and then irradiating the tube with light such as ultraviolet rays or visible rays. In the present specification, an operation of disposing a lining material along the inner periphery of the pipe inner surface, pressing the lining material against the pipe inner surface, and then irradiating ultraviolet rays or visible rays or the like to cure the resin composition contained in the lining material is also called a repair pipe.

From the viewpoint of easiness in the construction of the pipe repair, the lining material preferably contains an inner film in the innermost layer of the inner face, an outer film in the outermost layer of the outer face, a fibrous base material containing a resin composition between the inner film and the outer film, or a fibrous base material containing a resin composition between the inner film and the outer film, an outer film in the innermost layer of the inner face, an inner film in the outermost layer of the outer face.

The lining material preferably has a diameter that is approximately the same as the inner diameter of the pipe being repaired. Thereby, the strength of the repaired pipe is improved.

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

When the inner diameter of the lining material is 100mm or more, the photo-curing is easy to perform, and when the inner diameter of the lining material is 1500mm or less, the workability in the pipe repair is good.

[ resin composition ]

The resin composition of the present embodiment contains a vinyl ester resin (a), an ethylenically unsaturated group-containing monomer (B), at least 1 compound (C) selected from oxides and hydroxides of group iia elements, and a photopolymerization initiator (D).

The resin composition used for the lining material for pipe repair is required to have a low viscosity so as to be easily impregnated into a fibrous base material to be described later. On the other hand, in the case of performing pipe repair, it is required that the resin composition contained in the lining material has a viscosity which is maintained in a state of being uniformly distributed in the fiber base material without maldistribution.

From the viewpoint of efficiently and sufficiently impregnating the fiber substrate with the resin composition in a homogeneous state, the viscosity at 25 ℃ after 1 hour of preparation of the resin composition is preferably 0.1 to 3.0pa·s, more preferably 0.2 to 2.8pa·s, still more preferably 0.3 to 2.5pa·s, still more preferably 0.3 to 2.3pa·s.

Here, the viscosity at 25 ℃ after 1 hour after the preparation of the resin composition means the viscosity at 25 ℃ after 1 hour from the time when the resin composition is prepared by mixing all the components constituting the resin composition.

The viscosity of at least one of 2 days and 5 days after the preparation of the resin composition is preferably 400pa·s or more, more preferably 450pa·s or more, still more preferably 500pa·s or more, from the viewpoint of suppressing the flow of the resin composition contained in the fiber base material in the lining material at the time of pipe repair and suppressing the uneven distribution of the resin composition after curing, the viscosity of at least one of 2 days and 5 days after the preparation of the resin composition is preferably 3,500pa·s or less, more preferably 2,500pa·s or less, and even more preferably 2,000pa·s, from the viewpoint of obtaining the lining material having flexibility such that the workability at the time of pipe repair is good.

Here, the viscosity at 25 ℃ at least one of 2 days and 5 days after the preparation of the resin composition means the viscosity at 25 ℃ at least one of 2 days and 5 days after the preparation of the resin composition, from the time when the resin (a), the ethylenically unsaturated group-containing monomer (B), the compound (C), and the photopolymerization initiator (D) are all mixed, that is, when the resin composition containing all the above components is prepared.

< vinyl ester resin (A) >)

The vinyl ester resin (a) is not particularly limited as long as it has an ethylenically unsaturated group, but preferably contains at least 1 selected from the group consisting of a vinyl ester resin (A1), a vinyl ester resin (A2) and a vinyl ester resin (A3) described later. These resins may be used alone or in combination of 1 or 2 or more. Further, vinyl ester resins other than the vinyl ester resins (A1) to (A3) may be contained.

The vinyl ester resin (A) has an acid value of 1 to 35KOHmg/g. By setting the acid value to 1 to 35KOHmg/g, the resin composition can be efficiently tackified and the tackification rate of the resin composition can be controlled.

The acid value of the vinyl ester resin (A) is preferably 5KOHmg/g or more, more preferably 8KOHmg/g or more, and still more preferably 10KOHmg/g or more, from the viewpoint of more efficiently thickening the resin composition. In addition, from the viewpoint of further controlling the tackifying rate of the resin composition, the acid value of the vinyl ester resin (A) is preferably 30KOHmg/g or less, more preferably 25KOHmg/g or less, and still more preferably 20KOHmg/g or less.

The hydroxyl value of the vinyl ester resin (A) is preferably 10KOHmg/g or more, more preferably 15KOHmg/g or more, and still more preferably 20KOHmg/g or more, from the viewpoint of controlling the tackifying rate of the resin composition. In order to efficiently thicken the resin composition, the hydroxyl value of the vinyl ester resin (A) is preferably 120KOHmg/g or less, more preferably 110KOHmg/g or less, and still more preferably 100KOHmg/g or less.

The vinyl ester resin (a) is preferably used by adjusting the viscosity with a solvent, a reactive diluent or the like from the viewpoints of proper control of the initial viscosity of the resin composition, ease of mixing and the like. The viscosity to be adjusted is preferably 0.05 to 100pa·s, more preferably 0.1 to 50pa·s, and still more preferably 0.2 to 15pa·s.

Vinyl ester resin (A1)

The vinyl ester resin (A1) is a reaction product of a resin precursor (P1) and an unsaturated monobasic acid (a-3), and the resin precursor (P1) is a reaction product of an epoxy compound (a-1) having 2 epoxy groups in the molecule and a bisphenol compound (a-2).

The vinyl ester resin (A1) tackifies the resin composition by the interaction of the compound (C) with the hydroxyl group generated by the ring opening of the epoxy group of the epoxy compound (a-1).

If the resin composition contains the vinyl ester resin (A1), the tackifying rate of the resin composition can be easily controlled, and the physical properties of the cured product of the resin composition can be easily adjusted.

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

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

The Mw/Mn of the vinyl ester resin (A1) is preferably 1.05 or more, more preferably 1.1 or more, further preferably 1.3 or more from the viewpoint of easiness in controlling the synthesis conditions, and is preferably 3.0 or less, more preferably 2.5 or less, further preferably 2.3 or less from the viewpoint of suppressing variation in physical properties of the resin composition and controlling the thickening speed.

The Mw/Mn is an index of molecular weight distribution, and when Mw/Mn is 1, the polymer is represented as a monodisperse polymer, and the larger the ratio, the wider the molecular weight distribution.

The amount of bisphenol compound (a-2) in vinyl ester resin (A1) is preferably such that the total amount of hydroxyl groups of bisphenol compound (a-2) is 10 mol or more, more preferably 20 mol or more, still more preferably 25 mol or more, preferably 70 mol or less, still more preferably 60 mol or less, still more preferably 50 mol or less, based on 100 mol of the total amount of epoxy groups of epoxy compound (a-1).

When the total amount of hydroxyl groups of the bisphenol compound (a-2) is 10 mol or more relative to 100 mol of the total amount of epoxy groups of the epoxy compound (a-1), the molecular weight distribution of the vinyl ester resin (a) becomes broad, whereby the viscosity achieved by the resin composition can be easily controlled. In addition, when the total amount of hydroxyl groups of the bisphenol compound (a-2) is 70 mol or less based on 100 mol of the total amount of epoxy groups of the epoxy compound (a-1), the tackifying rate of the resin composition can be easily controlled.

The amount of the unsaturated monoacid (a-3) in the vinyl ester resin (A1) is preferably an amount such that the total amount of acid groups of the unsaturated monoacid (a-3) is 30 moles or more, more preferably 40 moles or more, still more preferably 50 moles or more, preferably 120 moles or less, more preferably 100 moles or less, and still more preferably 80 moles or less, based on 100 moles of the total amount of epoxy groups of the epoxy compound (a-1).

When the total amount of the acid groups of the unsaturated monoacid (a-3) is 30 mol or more relative to 100 mol of the total amount of the epoxy groups of the epoxy compound (a-1), a sufficient amount of the ethylenically unsaturated groups can be introduced into the vinyl ester resin (A1), and therefore the resin composition is liable to exhibit good curability. In addition, from the viewpoint of controlling the tackifying rate and suppressing uneven distribution of the resin composition after curing and from the viewpoint of manufacturing stability, the total amount of the acid groups of the unsaturated monoacid (a-3) is preferably 120 mol or less relative to 100 mol of the total amount of the epoxy groups of the epoxy compound (a-1).

Vinyl ester resin (A2)

The vinyl ester resin (A2) is a reaction product of a resin precursor (P2) and an unsaturated polybasic acid (a-4), the resin precursor (P2) is a reaction product of a resin precursor (P1) and an unsaturated monobasic acid (a-3), and the resin precursor (P1) is a reaction product of an epoxy compound (a-1) having 2 epoxy groups in 1 molecule and a bisphenol compound (a-2).

The vinyl ester resin (A2) tackifies the resin composition by the interaction of the compound (C) with the hydroxyl group generated by the ring opening of the epoxy group of the epoxy compound (a-1).

If the resin composition contains the vinyl ester resin (A2), the tackifying rate of the resin composition can be easily controlled, and the physical properties of the cured product of the resin composition can be easily adjusted.

The weight average molecular weight Mw of the vinyl ester resin (A2) is preferably 500 or more, more preferably 600 or more, further preferably 800 or more from the viewpoint of more efficiently thickening the resin, and is preferably 6,000 or less, more preferably 5,000 or less, further preferably 4,500 or less from the viewpoint of controlling the thickening speed of the resin composition.

The number average molecular weight Mn of the vinyl ester resin (A2) is preferably 400 or more, more preferably 500 or more, further preferably 600 or more from the viewpoint of efficiently thickening the resin composition, and the number average molecular weight Mn of the vinyl ester resin (A2) is preferably 2,000 or less, more preferably 1,500 or less, further preferably 1,300 or less from the viewpoint of controlling the thickening speed of the resin composition.

The Mw/Mn of the vinyl ester resin (A2) is preferably 1.05 or more, more preferably 1.1 or more, still more preferably 1.3 or more from the viewpoint of easiness in controlling the synthesis conditions, and is preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.3 or less from the viewpoint of suppressing variation in physical properties of the resin composition and controlling the thickening speed.

The amount of bisphenol compound (a-2) in vinyl ester resin (A2) is preferably such that the total amount of hydroxyl groups of bisphenol compound (a-2) is 10 moles or more, more preferably 15 moles or more, still more preferably 20 moles or more, still more preferably 70 moles or less, still more preferably 60 moles or less, still more preferably 50 moles or less, based on 100 moles of the total amount of epoxy groups of epoxy compound (a-1).

The amount of the unsaturated monoacid (a-3) in the vinyl ester resin (A2) is preferably an amount such that the total amount of acid groups of the unsaturated monoacid (a-3) is 30 moles or more, more preferably 40 moles or more, still more preferably 50 moles or more, preferably 120 moles or less, more preferably 100 moles or less, still more preferably 80 moles or less, based on 100 moles of the total amount of epoxy groups of the epoxy compound (a-1).

When the total amount of the acid groups of the unsaturated monoacid (a-3) is 30 mol or more relative to 100 mol of the total amount of the epoxy groups of the epoxy compound (a-1), a sufficient amount of the ethylenically unsaturated groups can be introduced into the vinyl ester resin (A2), and therefore the resin composition is liable to exhibit good curability. In addition, from the viewpoints of controlling the thickening speed, suppressing uneven distribution of the resin composition after curing, and repairing the pipe uniformly, and from the viewpoint of manufacturing stability, the total amount of the acid groups of the unsaturated monoacid (a-3) is preferably 120 mol or less relative to 100 mol of the total amount of the epoxy groups of the epoxy compound (a-1).

The amount of the unsaturated polybasic acid (a-4) in the vinyl ester resin (A2) is preferably an amount of 0.5 mol or more, more preferably an amount of 1 mol or more, still more preferably an amount of 3 mol or more, preferably an amount of 15 mol or less, still more preferably an amount of 10 mol or less, and still more preferably an amount of 8 mol or less, based on 100 mol of the total amount of epoxy groups of the epoxy compound (a-1).

When the amount of the unsaturated polybasic acid (a-4) is 0.5 mol or more based on 100 mol of the total amount of epoxy groups in the epoxy compound (a-1), a sufficient amount of the ethylenically unsaturated groups can be introduced into the vinyl ester resin (A2), and therefore the resin composition tends to exhibit good curability. From the viewpoint of controlling the thickening rate, the unsaturated polybasic acid (a-4) is preferably 15 mol or less based on 100 mol of the total amount of epoxy groups of the epoxy compound (a-1).

Vinyl ester resin (A3)

The vinyl ester resin (A3) is a reaction product of an epoxy compound (a-1) having 2 epoxy groups in the molecule and an unsaturated monoacid (a-3).

The vinyl ester resin (A3) tackifies the resin composition by the interaction of the compound (C) with the hydroxyl group generated by the ring opening of the epoxy group of the epoxy compound (a 1-1).

The weight average molecular weight Mw of the vinyl ester resin (A3) is preferably 500 or more, more preferably 600 or more, further preferably 700 or more from the viewpoint of more effectively thickening the resin composition, and is preferably 6,000 or less, more preferably 5,000 or less, further preferably 4,500 or less from the viewpoint of controlling the thickening speed of the resin composition.

The number average molecular weight Mn of the vinyl ester resin (A3) is preferably 300 or more, more preferably 400 or more, further preferably 500 or more from the viewpoint of efficiently thickening the resin composition, and the number average molecular weight Mn of the vinyl ester resin (A3) is preferably 2,000 or less, more preferably 1,500 or less, further preferably 1,300 or less from the viewpoint of controlling the thickening speed of the resin composition.

The Mw/Mn of the vinyl ester resin (A3) is preferably 1.05 or more, more preferably 1.1 or more, still more preferably 1.3 or more from the viewpoint of easiness in controlling the synthesis conditions, and the Mw/Mn of the vinyl ester resin (A3) is preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.3 or less from the viewpoint of suppressing variation in physical properties of the resin composition and controlling the thickening speed.

The amount of the unsaturated monoacid (a-3) in the vinyl ester resin (A3) is preferably an amount such that the total amount of acid groups of the unsaturated monoacid (a-3) is 30 moles or more, more preferably 50 moles or more, still more preferably 70 moles or more, preferably 140 moles or less, more preferably 120 moles or less, still more preferably 110 moles or less, based on 100 moles of the total amount of epoxy groups of the epoxy compound (a-1).

When the total amount of the acid groups of the unsaturated monoacid (a-3) is 30 mol or more relative to 100 mol of the total amount of the epoxy groups of the epoxy compound (a-1), a sufficient amount of the ethylenically unsaturated groups can be introduced into the vinyl ester resin (A3), and therefore the resin composition is liable to exhibit good curability. Further, from the viewpoints of controlling the tackifying rate and suppressing uneven distribution of the resin composition after curing and from the viewpoint of production stability, it is more preferable that unreacted epoxy groups remain in the vinyl ester resin (A3), and the total amount of acid groups of the unsaturated monoacid (a-3) is preferably 100 moles with respect to 100 moles of the total amount of epoxy groups of the epoxy compound (a-1).

(epoxy Compound (a-1))

The epoxy compound (a-1) is a compound having 2 epoxy groups in 1 molecule, and all of monomers, oligomers and polymers can be used, and the molecular weight and molecular structure thereof are not particularly limited. The number of the epoxy compounds (a-1) may be 1 alone, or 2 or more may be used in combination.

Examples of the epoxy compound (a-1) include bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and bisphenol AF epoxy resin; tertiary butyl catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic type epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, phenol novolac type epoxy resin, and the like. Among them, bisphenol type epoxy resins and phenol novolac type epoxy resins are preferable, more preferable are one or more selected from bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins and bisphenol AF type epoxy resins, and still more preferable are bisphenol a type epoxy resins, from the viewpoint of suppressing excessive increase in viscosity of the resin composition and controlling the thickening rate.

The epoxy equivalent of the epoxy compound (a-1) is preferably 100 to 1,000, more preferably 120 to 500, even more preferably 140 to 400, even more preferably 150 to 300, from the viewpoints of obtaining the vinyl ester resins (A1) to (A3) without gelation, controlling the tackifying rate, and suppressing uneven distribution of the resin composition after curing.

From the viewpoint of easiness and efficiency of synthesis of the vinyl ester resins (A1) to (A3), the epoxy compound (a-1) is preferably an epoxy compound which is liquid at 25 ℃.

(bisphenol Compound (a-2))

The molecular weight and molecular structure of bisphenol compound (a-2) are not particularly limited. The bisphenol compound (a-2) may be used singly or in combination of 2 or more.

Examples of bisphenol compounds (a-2) include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, and the like. Among them, from the viewpoint of suppressing excessive increase in viscosity and controlling the thickening speed achieved by the resin composition, at least 1 or more selected from bisphenol a, bisphenol E, bisphenol F and bisphenol S is preferable, bisphenol a, bisphenol E and bisphenol F are more preferable, and bisphenol a is further preferable from the viewpoints of corrosion resistance, versatility and cost.

(unsaturated monoacid (a-3))

The molecular weight and molecular structure of the unsaturated monoacid (a-3) are not particularly limited, but monocarboxylic acids having an ethylenically unsaturated group are preferable. The number of unsaturated monobasic acids (a-3) may be 1 alone or 2 or more.

Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, and cinnamic acid. Among them, from the viewpoints of versatility, reactivity in the synthesis of the vinyl ester resins (A1) to (A3), and obtaining a resin composition having good curability, at least 1 selected from (meth) acrylic acid and crotonic acid is preferable, (meth) acrylic acid is more preferable, and methacrylic acid is even more preferable.

(unsaturated polybasic acid (a-4))

The unsaturated polybasic acid (a-4) is a compound having 2 or more carboxyl groups and 1 or more unsaturated groups in 1 molecule, and the molecular weight and molecular structure thereof are not particularly limited. The number of unsaturated polybasic acids (a-4) may be 1 alone or 2 or more.

Examples of the unsaturated polybasic acid (a-4) include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and the like. Among them, 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 from the viewpoint of production cost.

< ethylenically unsaturated group-containing monomer (B) >)

The ethylenically unsaturated group-containing monomer (B) is not particularly limited as long as it has no carboxyl group but has an ethylenically unsaturated group, but is preferably a monomer having a (meth) acryloyl group or a vinyl group. The ethylenically unsaturated group-containing monomer (B) may be 1 kind alone or 2 or more kinds may be used in combination.

There is a tendency to: the higher the content of the ethylenically unsaturated group-containing monomer (B), the more the viscosity and the thickening speed of the resin composition in step 1 of impregnating the resin composition in the production of the lining material and the increase in the viscosity of the resin composition in the case of disposing the lining material in a pipe during the repair of the pipe can be suppressed. In addition, the hardness, strength, chemical resistance, water resistance, and the like of the lining material after photocuring can be improved.

Among the ethylenically unsaturated group-containing monomers (B), examples of the monomer having a (meth) acryloyl group include (meth) acrylic acid esters and the like. The (meth) acrylate may be monofunctional or multifunctional.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentadienyloxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono 2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono 2-ethylhexyl ether (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentadienyloxyethyl (meth) acrylate, and (meth) amino acid, and (meth) decyl (meth) acrylate Caprolactone-modified hydroxyethyl (meth) acrylate, allyl (meth) acrylate, and the like.

Examples of the polyfunctional (meth) acrylate include polyoxyalkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, 1, 2-propylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate, alkane diol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate, and trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol diacrylate mono-stearate, 1, 3-bis (meth) oxy) -2-hydroxypropoxy-a (meth) acrylate, bisphenol A (meth) acrylate, tris- (2- (meth) acryloyloxyethyl) isocyanurate, and the like.

Among the ethylenically unsaturated group-containing monomers (B), other than the (meth) acrylic acid ester, examples of the monomer having a (meth) acryloyl group include acryloylmorpholine, 2-hydroxyethyl (meth) acrylamide, 2-hydroxyethyl-N-methyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, and the like. Examples of the monomer having a vinyl group other than the monomer having a (meth) acryloyl group include a vinyl benzyl compound such as styrene, p-chlorostyrene, vinyl toluene, α -methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diallyl fumarate, diallyl phthalate, triallyl isocyanurate, and vinylbenzyl butyl ether, vinylbenzyl hexyl ether, and divinylbenzene.

Among them, the ethylenically unsaturated group-containing monomer (B) is preferably at least one selected from 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, neopentyl glycol (meth) acrylate, and phenoxyethyl methacrylate, more preferably from the viewpoints of proper control of the tackifying rate of the resin composition, curability, manufacturing cost, mechanical strength, heat resistance, chemical resistance, and the like of the lining material after photocuring.

< Compound (C) >

The compound (C) is at least 1 selected from oxides and hydroxides of group IIA elements. The compound (C) has an effect of thickening the resin composition with time by interaction with the carboxyl group and the hydroxyl group of the vinyl ester resin (a) and the carboxyl group and the hydroxyl group of the compound of other components.

The number of the compounds (C) may be 1 alone, or 2 or more compounds may be used in combination.

Examples of the oxides of group IIA elements include magnesium oxide, calcium oxide, and barium oxide.

Examples of the group IIA element hydroxide include magnesium hydroxide, calcium hydroxide, and barium hydroxide.

Among them, magnesium oxide is preferable from the viewpoints of thickening effect, versatility, cost, and the like.

< photopolymerization initiator (D) >)

The photopolymerization initiator (D) is not particularly limited as long as it is a photopolymerization initiator that generates radicals by irradiation with light. Examples thereof include benzoin and alkyl ethers thereof, such as benzoin, benzoin methyl ether and benzoin ethyl ether; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 1-dichloroacetophenone, and 4- (1-tert-butyldioxy-1-methylethyl) acetophenone; alpha-hydroxyalkylphenones such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropane-1-one; anthraquinones such as 2-methylanthraquinone, 2-pentylalnthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthones 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' -tetra (t-butyldioxycarbonyl) benzophenone; morpholines such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; acyl phosphine oxides such as phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide; xanthones, and the like. These may be used alone or in combination of 2 or more.

From the viewpoint of reactivity, the photopolymerization initiator (D) is preferably an intramolecular cleavage type photopolymerization initiator that does not require a hydrogen donor. Further, 2-dimethoxy-2-phenylacetophenone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, and 1-hydroxycyclohexyl phenyl ketone, which efficiently produce active species in the above wavelength range, are preferable from the viewpoint of absorbing light having a wavelength of 315 to 460nm to produce active species.

< Compound (E) >)

The resin composition of the present embodiment may contain a compound (E) which is at least 1 selected from water and hydroxyl-containing compounds. By including the compound (E) in the resin composition, the tackifying speed can be controlled more easily. Examples of the hydroxyl group-containing compound include alcohols having a boiling point of 50℃or higher such as benzyl alcohol, stearyl alcohol and isostearyl alcohol. Examples of the other compounds include hydroxycarboxylic acids such as lactic acid, glycerin, polyhydric alcohols, and (meth) acrylic esters containing hydroxyl groups. These may be used alone or in combination of 2 or more. Among them, water and alcohol are preferable, and water is more preferable from the viewpoints of availability, cost, and the like.

< carboxyl group-containing Compound (F) >)

The resin composition of the present embodiment may contain a carboxyl group-containing compound (F), which is a compound having at least 1 carboxyl group.

Examples of the carboxyl group-containing compound (F) include maleic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, fumaric acid, endomethylene tetrahydrophthalic 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, 6-endomethylene-1, 2,3, 6-tetrahydrophthalic acid, trimellitic acid, 3-dodecenyl succinic acid, and (meth) acrylic acid. Among them, 3-dodecenylsuccinic acid, methacrylic acid, and acrylic acid are preferable, and 3-dodecenylsuccinic acid is more preferable, from the viewpoints of controlling the tackifying rate, suppressing excessive tackifying of the resin composition immediately after the production of the resin composition (within 5 hours after the production), and further suppressing excessive increase in the viscosity achieved by the resin composition.

The number of the carboxyl group-containing compounds (F) may be 1 alone or 2 or more.

< other ingredients >

The resin composition of the present embodiment may contain, for example, other resins, polymerization inhibitors, thixotropic agents, curing accelerators, catalysts, adhesion promoters, curing retarders, surfactants, interface regulators, wetting dispersants, defoamers, leveling agents, coupling agents, light stabilizers, waxes, flame retardants, plasticizers, and other additives as other components. The content of the additive is not particularly limited as long as it is within a range that does not hinder the effects of the present invention.

(polymerization inhibitor)

The polymerization inhibitor may be used to inhibit the progress of polymerization of the resin composition. The resin composition of the present embodiment preferably contains a polymerization inhibitor.

As the polymerization inhibitor, known polymerization inhibitors can be used, and examples thereof include hydroquinone, methyl hydroquinone, trimethyl hydroquinone, phenothiazine, catechol, 4-t-butyl catechol, copper naphthenate, and the like. The number of these may be 1 alone or 2 or more.

(thixotropic agent)

The resin composition in this embodiment preferably contains a thixotropic agent. Thixotropic agents are used to adjust the miscibility and flowability of the resin composition. Examples of the thixotropic agent include organic thixotropic agents and inorganic thixotropic agents. They may be used singly or in combination of 2 or more.

When the thixotropic agent is contained in the resin composition of the present embodiment, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total of the resin (a) and the ethylenically unsaturated group-containing monomer (B).

Examples of the organic thixotropic agent include hydrogenated castor oil, amide, oxidized polyethylene, vegetable oil polymer oil, and surfactant, and a combination thereof. Specifically, "fvs (registered trademark) SP-1000AF" (manufactured by co-Rong chemical Co., ltd.), and "dubian (registered trademark) 6900-20X" (manufactured by phoenix chemical Co., ltd.) are cited.

Examples of the inorganic thixotropic agent include hydrophobic-treated or hydrophilic-treated silica, bentonite, and the like. As the hydrophobic inorganic thixotropic agent, specifically, examples thereof include "wire (registered trademark) PM-20L" (manufactured by tikuku corporation), "a-super (registered trademark) R-106" (manufactured by japanese a-super corporation), and "CAB-O-SIL (registered trademark)" (manufactured by tiku corporation). Specific examples of the hydrophilic inorganic thixotropic agent include "a-d (registered trademark) -200" (manufactured by a-d-c corporation). In the case of using the hydrophilic fumed silica, the thixotropic modifiers "BYK (registered trademark) -R605" and "BYK (registered trademark) -R606" (both manufactured by BYK corporation) are effective in combination for proper control of the thickening rate.

< content of each component in resin composition >

The content of each component constituting the resin composition of the present embodiment is not limited, but preferred are embodiments 1 and 2 described below.

[ the resin composition according to embodiment 1 ]

The content of the vinyl ester resin (a) in the resin composition according to embodiment 1 is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass, and even more preferably 50 to 70 parts by mass, based on 100 parts by mass of the total of the vinyl ester (a) and the ethylenically unsaturated group-containing monomer (B).

When the content of the resin (a) is 30 parts by mass or more, it is easy to appropriately increase the tackifying rate of the resin composition by the vinyl ester resin (a). When the vinyl ester resin (a) is 90 parts by mass or less, the fiber base material is easily impregnated with the resin.

The content of the vinyl ester resin (a) in the resin composition according to embodiment 1 is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass, and even more preferably 50 to 70 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to embodiment 1 is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and even more preferably 30 to 50 parts by mass, based on 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

When the amount of the ethylenically unsaturated group-containing monomer (B) is 10 parts by mass or more, the viscosity of the resin composition after 1 hour is easily reduced, and the resin composition is easily impregnated into the fiber base material. When the amount of the ethylenically unsaturated group-containing monomer (B) is 70 parts by mass or less, a resin composition having a more excellent tackiness is obtained.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to embodiment 1 is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and even more preferably 30 to 50 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.

The content of the compound (C) in the resin composition according to embodiment 1 is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 3 parts by mass, and even more preferably 0.5 to 1.5 parts by mass, based on 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

When the amount of the compound (C) is 0.1 part by mass or more, the tackiness of the resin composition becomes more favorable. When the amount of the compound (C) is 10 parts by mass or less, excessive tackiness of the resin composition is easily suppressed, and coloring of the resin composition and curing failure are suppressed.

The content of the compound (C) in the resin composition according to embodiment 1 is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 3 parts by mass, and even more preferably 0.5 to 1.5 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.

The content of the photopolymerization initiator (D) in the resin composition according to embodiment 1 is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

When the content of the photopolymerization initiator (D) is 0.05 parts by mass or more, a resin composition having more excellent 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 less likely to occur during curing of the resin composition, cracking is likely to be suppressed, and a lining material having more excellent balance of physical properties such as strength, toughness, heat resistance, and chemical resistance is likely to be obtained.

The content of the photopolymerization initiator (D) in the resin composition according to embodiment 1 is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.

When the resin composition according to embodiment 1 contains the compound (E) which is at least 1 selected from water and a hydroxyl group-containing compound, the content of the compound (E) in the resin composition is preferably 0.01 to 3 parts by mass, more preferably 0.02 to 2 parts by mass, and even more preferably 0.03 to 1 part by mass, relative to 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

If the compound (E) is 0.01 parts by mass or more, it is easy to control the tackifying rate of the resin composition and to suppress excessive tackifying. When the amount of the compound (E) is 3 parts by mass or less, a lining material having more excellent balance of physical properties such as strength, toughness, heat resistance and chemical resistance can be easily obtained.

When the resin composition according to embodiment 1 contains the compound (E) as at least 1 selected from water and a hydroxyl group-containing compound, the content of the compound (E) in the resin composition is preferably 0.01 to 3 parts by mass, more preferably 0.02 to 2 parts by mass, and even more preferably 0.03 to 1 part by mass, relative to 100 parts by mass of the total amount of the resin composition.

In one embodiment of the present invention, the resin composition preferably contains 30 to 90 parts by mass of the vinyl ester resin (a), 10 to 70 parts by mass of the ethylenically unsaturated group-containing monomer (B), and 0.05 to 10 parts by mass of the photopolymerization initiator (D) per 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

In one embodiment of the present invention, the resin composition preferably contains 30 to 90 parts by mass of the vinyl ester resin (a), 10 to 70 parts by mass of the ethylenically unsaturated group-containing monomer (B), and 0.05 to 10 parts by mass of the photopolymerization initiator (D) per 100 parts by mass of the total amount of the resin composition.

The resin composition according to embodiment 1 of the present embodiment preferably has a viscosity of 400 to 3,500pa·s at 25 ℃ after 2 days of preparation of the resin composition.

[ resin composition according to embodiment 2 ]

The content of the vinyl ester resin (a) in the resin composition according to embodiment 2 is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass, and even more preferably 50 to 70 parts by mass, based on 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

When the vinyl ester resin (a) is 30 parts by mass or more, it is easy to appropriately increase the tackifying rate of the resin composition by the vinyl ester resin (a). When the vinyl ester resin (a) is 90 parts by mass or less, the fiber base material is easily impregnated with the resin.

The content of the vinyl ester resin (a) in the resin composition according to embodiment 2 is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass, and even more preferably 50 to 70 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to embodiment 2 is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and even more preferably 30 to 50 parts by mass, based on 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

When the amount of the ethylenically unsaturated group-containing monomer (B) is 10 parts by mass or more, the fiber base material is easily impregnated with the monomer. When the amount of the ethylenically unsaturated group-containing monomer (B) is 70 parts by mass or less, a resin composition having a more excellent tackiness is obtained.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition according to embodiment 2 is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and even more preferably 30 to 50 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.

The content of the compound (C) in the resin composition according to embodiment 2 is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 3 parts by mass, and even more preferably 0.5 to 1.5 parts by mass, based on 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

The content of the compound (C) in the resin composition according to embodiment 2 is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 3 parts by mass, and even more preferably 0.5 to 1.5 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.

The content of the photopolymerization initiator (D) in the resin composition according to embodiment 2 is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

The content of the photopolymerization initiator (D) in the resin composition according to embodiment 2 is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.

The resin composition according to embodiment 2 of the present embodiment preferably has a viscosity of 400 to 3,500pa·s at 25 ℃ after 5 days from preparation of the resin composition.

When the resin composition according to embodiment 2 contains the compound (E) which is at least 1 selected from water and a hydroxyl group-containing compound, the content of the compound (E) in the resin composition is preferably 0.01 to 3 parts by mass, more preferably 0.02 to 2 parts by mass, and even more preferably 0.03 to 1 part by mass, relative to 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

In another aspect of the present embodiment, the resin composition preferably contains 30 to 90 parts by mass of the vinyl ester resin (a), 10 to 70 parts by mass of the ethylenically unsaturated group-containing monomer (B), and 0.05 to 10 parts by mass of the photopolymerization initiator (D) per 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

[ fibrous substrate ]

The lining material according to the present embodiment contains a fibrous base material containing a resin composition.

The fibers constituting the fiber base material include, for example, synthetic fibers such as amide, nylon, aramid, vinylon, polyester and phenolic resin, so-called reinforcing fibers such as carbon fibers, glass fibers, metal fibers and ceramic fibers, and composite fibers thereof, from the viewpoint of mechanical strength and the like. These may be used alone or in combination of 2 or more. Among them, aramid fibers, carbon fibers and glass fibers are preferable, and glass fibers are more preferable from the viewpoints of strength, hardness, availability, price and the like. In particular, glass fibers and polyester fibers having light transmittance are preferable from the viewpoint of photocuring the resin composition contained in the fiber base material.

Examples of the form of the fibrous base material include a sheet, a chopped strand, chopped strands, and milled fibers. Examples of the sheet include a sheet formed by doubling a plurality of reinforcing fibers in one direction, a bi-directional fabric such as a plain weave or a twill weave, a multiaxial fabric, a non-hemmed fabric, a nonwoven fabric, a felt, a knitted fabric (knit), a braid, and a paper obtained by papermaking reinforcing fibers. The fibrous base material may be used alone or in combination of 1 or more than 2 kinds, and may be a single layer or may be laminated in a plurality of layers.

The thickness of the sheet is preferably 0.01 to 5mm in the case of a single layer, for example, and is preferably 1 to 20mm, more preferably 1 to 15mm in the case of a multilayer stack, from the viewpoint of the impregnation property of the resin composition.

Examples of the shape of the fibrous base material include a cylindrical shape, a sheet shape, and a belt shape.

[ fibrous substrate comprising a resin composition ]

The fiber base material containing the resin composition can be obtained, for example, by impregnating the fiber base material with the above resin composition.

The content of the resin composition in the fiber base material containing the resin composition is preferably 20 to 95% by mass, more preferably 25 to 85% by mass, and still more preferably 25 to 75% by mass. When the content of the resin composition is 20 mass% or more, appropriate flexibility can be imparted to the lining material, and workability at the time of pipe repair becomes good. When the content of the resin composition is 85 mass% or less, sufficient strength can be imparted to the liner material after photocuring.

The content of the fiber base material in the fiber base material containing the resin composition is preferably 5 to 80% by mass, more preferably 15 to 75% by mass, and even more preferably 25 to 75% by mass. When the content of the fiber base material is 5 mass% or more, sufficient strength can be imparted to the liner material after photocuring. When the content of the fiber base material is 80 mass% or less, appropriate flexibility can be imparted to the lining material, and workability in repairing the pipe is improved.

The pipe can be repaired by curing the resin composition in the lining material, that is, the resin composition in the fiber base material by irradiation of ultraviolet rays or visible rays or the like to the lining material. Therefore, the liner material cured with the resin composition needs to have mechanical strength to such an extent that it can repair a pipe.

For example, in the case of using glass fibers as the fiber base material, the flexural strength of the cured product (FRP) of the fiber base material containing the resin composition is preferably 100 to 1000MPa, more preferably 120 to 900MPa, and still more preferably 150 to 800MPa. The flexural modulus of the FRP is preferably 5 to 40GPa, more preferably 7 to 35GPa, and even more preferably 8 to 30GPa.

The values of the flexural strength and flexural modulus are values according to JIS K7171: 2016.

[ internal film ]

As the internal film, for example, a resin film such as a polyethylene film, a polypropylene film, or a polyethylene terephthalate film can be used. The inner film needs to have permeability to light irradiated by the light irradiation device at the time of tube repair construction. This can efficiently cure the lining material, and can appropriately perform pipe repair. The inner film may be peeled off after the inner liner material is cured.

The thickness of the internal film is not particularly limited, but is preferably 50 to 200. Mu.m, more preferably 80 to 170. Mu.m. When the thickness of the inner film is 50 μm or more, the inner film is not broken and is not wrinkled at the time of or before the pipe repair work, and a sufficient strength can be imparted to the pipe. When the thickness of the inner film is 200 μm or less, the production of the lining material becomes easy, and workability in the pipe repair work is good.

[ external film ]

As the outer film, a resin film can be used in the same manner as the inner film. The outer film preferably has light-shielding properties. This can prevent the lining material from being cured by light from the outside before the pipe repair is performed.

In addition, at the time of pipe repair, the irradiated light can be suppressed from penetrating the lining material, and the lining material can be efficiently photocured. As the external film having light-shielding properties, for example, a laminate film having a colored film layer of yellow or the like between 2 transparent polyethylene films can be used.

The thickness of the outer film is not particularly limited, but is preferably 5 to 100. Mu.m, more preferably 10 to 90. Mu.m. When the thickness of the outer film is 5 μm or more, the outer film is not broken and wrinkles are not generated before light irradiation at the time of pipe repair work, and sufficient strength can be imparted to the pipe. When the thickness of the outer film is 100 μm or less, the production of the lining material becomes easy, and workability in the pipe repair work is good.

[ method for producing vinyl ester (A) ]

< method for producing vinyl ester resin (A1)

The method for producing the vinyl ester resin (A1) comprises the following steps: a step of reacting an epoxy compound (a-1) having 2 epoxy groups in 1 molecule with a bisphenol compound (a-2) to obtain a resin precursor (P1); and a step of reacting the resin precursor (P1) with an unsaturated monoacid (a-3) to obtain a vinyl ester resin (A1).

The step of obtaining the resin precursor (P1) is a step of obtaining the resin precursor (P1) by reacting an epoxy compound (a-1) having 2 epoxy groups in 1 molecule with a bisphenol compound (a-2).

In the step of obtaining the resin precursor (P1), from the viewpoint of widening the molecular weight distribution of the vinyl ester resin (a) and controlling the viscosity of the resin composition, it is preferable to react the epoxy compound (a-1) having 2 epoxy groups in 1 molecule with the bisphenol compound (a-2) so that the total amount of hydroxyl groups of the bisphenol compound (a-2) is preferably 10 to 70 moles, more preferably 20 to 60 moles, and even more preferably 25 to 50 moles, relative to 100 moles of the total amount of epoxy groups of the epoxy compound (a-1).

In the step of obtaining the resin precursor (P1), for example, the resin precursor (P1) can be obtained by mixing at least one of the solvent and the reactive diluent with the epoxy compound (a-1) and the bisphenol compound (a-2) in a reaction vessel capable of being heated and stirred, if necessary, and heating the mixture in the presence of the esterification catalyst at a temperature of preferably 70 to 160 ℃, more preferably 80 to 155 ℃, still more preferably 90 to 150 ℃ for 1 to 3 hours.

Examples of the esterification catalyst include tertiary amines such as triethylamine, triethylenediamine, N-dimethylbenzylamine, N-dimethylaniline, 2,4, 6-tris (dimethylaminomethyl) phenol and diazabicyclooctane, phosphorus compounds such as triphenylphosphine and benzyltriphenyl phosphonium chloride, diethylamine hydrochloride, trimethylbenzyl ammonium chloride and lithium chloride. They may be used singly or in combination of 2 or more. Among them, catalysts such as phosphorus-based catalysts and ammonium salts are preferable, and ammonium salts are more preferable, from the viewpoints of preventing gelation of the resin by slowing down the reaction rate and facilitating control of the molecular weight distribution.

The amount of the esterification catalyst used 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, based on 100 parts by mass of the total of the epoxy compound (a-1), bisphenol compound (a-2) and unsaturated monoacid (a-3), from the viewpoint of promoting the reaction and suppressing the thickening of the vinyl ester resin (A1).

From the viewpoint of easy uniform mixing of the epoxy compound (a-1), bisphenol compound (a-2) and unsaturated monoacid (a-3), a solvent and a reactive diluent may be used as needed. The mixing method is not particularly limited, and may be performed by a known method.

The solvent is not particularly limited as long as it is a solvent inactive to the epoxy compound (a-1), bisphenol compound (a-2) and unsaturated monoacid (a-3). Examples thereof include known solvents having a boiling point of 70 to 150℃under 1 atmosphere such as methyl isobutyl ketone. The solvent may be used alone or in combination of 2 or more.

As the reactive diluent, an ethylenically unsaturated group-containing monomer (B) which is inactive with respect to the epoxy compound (a-1), bisphenol compound (a-2) and unsaturated monoacid (a-3) is preferable.

From the viewpoint of suppressing the progress of the polymerization reaction of the resin precursor (P1), a polymerization inhibitor may be added. The polymerization inhibitor is suitably used as described in the above item < other component >. The amount of the polymerization inhibitor to be added may be, for example, 0.0001 to 10 parts by mass, preferably 0.001 to 1 part by mass, based on 100 parts by mass of the total of the epoxy compound (a-1), bisphenol compound (a-2) and unsaturated monoacid (a-3).

The step of obtaining the vinyl ester resin (A1) is a step of obtaining the vinyl ester resin (A1) by reacting the resin precursor (P1) with the unsaturated monoacid (a-3).

In the step of obtaining the vinyl ester resin (A1), the total amount of the acid groups of the unsaturated monoacid (a-3) is preferably 30 to 120 moles, more preferably 40 to 100 moles, still more preferably 50 to 80 moles, based on 100 moles of the total amount of the epoxy groups of the epoxy compound (a-1), from the viewpoints of controlling the tackifying rate, suppressing uneven distribution of the resin composition after curing, and manufacturing stability.

In the step of obtaining the vinyl ester resin (A1), for example, the unsaturated monoacid (A1-3) is added in the presence of the esterification catalyst in a reaction vessel in which the resin precursor (P1) is synthesized, and the mixture is heated at a temperature of 70 to 150 ℃, preferably 80 to 140 ℃, more preferably 90 to 130 ℃ for 30 minutes to 4 hours while mixing, whereby the vinyl ester resin (A1) can be produced.

The esterification catalyst used in the step of obtaining the vinyl ester resin (A1) may be the same as that used in the step of obtaining the resin precursor (P1). The esterification catalyst used in the production of the resin precursor (P1) may be the same or different from the esterification catalyst used in the production of the vinyl ester resin (A1) from the resin precursor (P1).

In the step of obtaining the vinyl ester resin (A1), at least one of a solvent, a reactive diluent, and a polymerization inhibitor may be added as needed, as in the step of obtaining the resin precursor (P1). The mixing method can be performed by a known method in the same manner as the step of obtaining the resin precursor (P1). The same applies to the preferred embodiment.

< method for producing vinyl ester resin (A2)

The method for producing the vinyl ester resin (A2) comprises the following steps: a step of reacting an epoxy compound (a-1) having 2 epoxy groups in 1 molecule with a bisphenol compound (a-2) to obtain a resin precursor (P1); a step of reacting the resin precursor (P1) with an unsaturated monobasic acid (a-3) to obtain a resin precursor (P2); and a step of reacting the resin precursor (P2) with an unsaturated polybasic acid (a-4) to obtain a vinyl ester resin (A2).

In the step of obtaining the resin precursor (P1), from the viewpoint of controlling the tackifying rate of the resin composition, the epoxy compound (a-1) having 2 epoxy groups in 1 molecule and the bisphenol compound (a-2) are preferably reacted so that the total amount of hydroxyl groups of the bisphenol compound (a-2) is preferably 10 to 70 moles, more preferably 15 to 60 moles, and even more preferably 20 to 50 moles, relative to 100 moles of the total amount of epoxy groups of the epoxy compound (a-1).

The step of obtaining the resin precursor (P1) in the production of the vinyl ester resin (A2) may be the same method as the step of obtaining the resin precursor (P1) in the production method of the vinyl ester resin (A1), and the preferred embodiment is the same.

The step of obtaining the resin precursor (P2) is a step of reacting the resin precursor (P1) with the unsaturated monobasic acid (a-3) to obtain the resin precursor (P2).

In the step of obtaining the resin precursor (P2), the total amount of the acid groups of the unsaturated monoacid (a-3) is preferably 40 to 120 moles, more preferably 50 to 100 moles, and even more preferably 60 to 80 moles, relative to 100 moles of the total amount of the epoxy groups of the epoxy compound (a-1), from the viewpoints of controlling the tackifying rate, suppressing uneven distribution of the resin composition after curing, and manufacturing stability.

The step of obtaining the resin precursor (P2) may be carried out by the same method as the step of obtaining the vinyl ester resin (A1) in the above-mentioned method of producing the vinyl ester resin (A1), and the preferable mode is the same.

The step of obtaining the vinyl ester resin (A2) is a step of reacting the resin precursor (P2) with the unsaturated polybasic acid (a-4) to obtain the vinyl ester resin (A2).

In the step of obtaining the vinyl ester resin (A2), the unsaturated polybasic acid (a-4) is preferably reacted so as to be 0.5 to 15 moles, more preferably 1 to 10 moles, and even more preferably 3 to 8 moles, based on 100 moles of the total amount of epoxy groups of the epoxy compound (a-1), from the viewpoint of controlling the tackifying rate.

In the step of obtaining the vinyl ester resin (A2), for example, the unsaturated polybasic acid (a-4) is added in the presence of the esterification catalyst in a reaction vessel in which the resin precursor (P2) is synthesized, and the mixture is heated at a temperature of 70 to 150 ℃, preferably 80 to 140 ℃, more preferably 90 to 130 ℃ for 30 minutes to 4 hours while mixing, whereby the vinyl ester resin (A2) can be produced.

The esterification catalyst used in the step of obtaining the vinyl ester resin (A2) may be the same as that used in the step of obtaining the resin precursor (P1) of the vinyl ester resin (A1). The esterification catalyst used in the production of the resin precursors (P1) and (P2) may be the same or different from the esterification catalyst used in the production of the vinyl ester resin (A2) from the resin precursor (P2).

In the step of obtaining the vinyl ester resin (A2), at least one of a solvent, a reactive diluent, and a polymerization inhibitor may be added as needed, as in the step of obtaining the resin precursors (P1) and (P2). The mixing method can be performed by a known method in the same manner as the step of obtaining the resin precursor (P1). The same applies to the preferred embodiment.

< method for producing vinyl ester resin (A3) >)

The method for producing the vinyl ester resin (A3) comprises the following steps: the vinyl ester resin (A3) is obtained by reacting an epoxy compound (a-1) having 2 epoxy groups in 1 molecule with an unsaturated monoacid (a-3).

The step of obtaining the vinyl ester resin (A3) is a step of obtaining the vinyl ester resin (A3) by reacting an epoxy compound (a-1) having 2 epoxy groups in 1 molecule with an unsaturated monoacid (a-3).

In the step of obtaining the vinyl ester resin (A3), from the viewpoints of controlling the tackifying rate, suppressing uneven distribution of the resin composition after curing, and manufacturing stability, it is preferable to react the epoxy compound (a-1) having 2 epoxy groups in 1 molecule with the unsaturated monoacid (a-3) so that the total amount of the acid groups of the unsaturated monoacid (a-3) is preferably 30 to 140 moles, more preferably 50 to 120 moles, and still more preferably 70 to 110 moles, relative to 100 moles of the total amount of the epoxy groups of the epoxy compound (a-1).

The step of obtaining the vinyl ester resin (A3) may be carried out by the same method as the step of obtaining the resin precursor (P1) in the above-mentioned method of producing the vinyl ester resin (A1), and the same preferable embodiment is also adopted.

When the reactive diluent is added to the vinyl ester resin (a) for the purpose of lowering the viscosity of the vinyl ester resin (a), it is preferable to add the reactive diluent and mix it after the vinyl ester resin (a) is synthesized, and when the reactive diluent is added for the purpose of facilitating the synthesis of the vinyl ester resin (a), it is preferable to add the reactive diluent at the time of synthesizing the vinyl ester resin (a), and further add the reactive diluent and other components and mix them after the vinyl ester resin (a) is synthesized.

[ method for producing resin composition ]

The method for preparing the resin composition of the present embodiment is not particularly limited, and the resin composition can be produced by mixing the vinyl ester resin (a), the ethylenically unsaturated group-containing monomer (B), the compound (C), and the photopolymerization initiator (D). In addition, in addition to the vinyl ester resin (a), the ethylenically unsaturated group-containing monomer (B), the compound (C), and the photopolymerization initiator (D), any component such as the compound (E), the carboxyl group-containing compound (F), and the other components described above may be mixed.

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

The mixing method is not particularly limited, and may be performed using, for example, a disperser, a planetary mixer, a kneader, or the like. The mixing temperature is preferably 10 to 50 ℃, more preferably 15 to 40 ℃, and even more preferably 20 to 30 ℃ from the viewpoint of ease of mixing and the like.

In addition, from the viewpoint of easy uniform mixing of the vinyl ester resin (a), the ethylenically unsaturated group-containing monomer (B), the compound (C), and the photopolymerization initiator (D), and adjustment of the viscosity, the vinyl ester resin (a) may be diluted in advance with at least one of a solvent and a reactive diluent.

[ method for producing lining Material ]

The method for producing the lining material may be a conventionally known method.

In the case of producing the lining material using the resin composition according to embodiment 1, the following steps 1 and 2 are preferably included.

In the case of producing the lining material using the resin composition according to embodiment 2, the following steps 1 to 3 are preferably included.

[ procedure 1 ]

Step 1 is a step of impregnating a fiber base material with a resin composition to obtain a fiber base material containing the resin composition.

In step 1, the resin composition may be impregnated into the fiber base material on which the inner film and the outer film are not laminated, or the fiber base material on which the inner film and the outer film are laminated on the surface thereof may be used.

In the case of using a fiber base material having an inner film and an outer film laminated on the surface, the resin composition is impregnated into the fiber base material through the inner film and the outer film.

The fibrous base material used in step 1 may be cylindrical, sheet-like or belt-like.

In the case of using the resin composition according to embodiment 1, the fibrous base material is preferably cylindrical, and in the case of using the resin composition according to embodiment 2, the fibrous base material is preferably sheet-like or belt-like.

In step 1, the viscosity of the resin composition at 25℃when the resin composition is impregnated into the fiber base material is preferably 0.1 to 3.0 Pa.s, and the viscosity at 25℃after 1 hour of preparation of the resin composition is preferably in the above range. By setting the viscosity of the resin composition to the above range, the impregnation failure of the resin composition into the fiber base material is reduced, and it is easy to obtain a fiber base material uniformly impregnated with the resin composition, that is, a fiber base material containing the resin composition in a state of being uniformly distributed. From the viewpoint of further reducing the impregnation failure and allowing the resin composition to be impregnated more uniformly, the viscosity of the resin composition at 25 ℃ when the resin composition is impregnated into the fiber base material is more preferably 0.2 to 2.8pa·s, still more preferably 0.25 to 2.5pa·s, still more preferably 0.3 to 2.3pa·s.

From the viewpoint of reducing the impregnation failure and uniformly impregnating the resin composition, the time for impregnating the resin composition in the fiber base material is preferably 0.5 to 24 hours, more preferably 1 to 10 hours, and even more preferably 1.5 to 5 hours.

The time from the preparation of the resin composition, that is, from the completion of the impregnation of the resin composition, to the completion of the production of the resin composition is preferably 1 to 30 hours, more preferably 2 to 24 hours, and even more preferably 5 to 10 hours.

[ procedure 2 ]

Step 2 is a step of laminating an inner film and an outer film on a fibrous base material.

The method for laminating the inner film and the outer film is not particularly limited, and examples thereof include a method in which a liquid film composition is applied to a fibrous base material and cured to laminate the film composition; a method of laminating a film on a fibrous base material or a fibrous base material containing a resin composition via an adhesive layer; a method of directly laminating a film to a fibrous substrate or a fibrous substrate comprising a resin composition, and the like. The inner film and the outer film may be laminated by different methods, or may be laminated by the same method.

The inner film and the outer film may be laminated independently of each other before the resin composition is impregnated into the fiber base material, or may be laminated after the resin composition is impregnated into the fiber base material. The process may be performed before the step 3 described below, or may be performed after the step 3 described below.

[ procedure 3 ]

Step 3 is a step of processing into a cylindrical shape. When a fiber base material having a cylindrical shape is used, step 3 is not required, and when a fiber base material having a sheet or tape shape is used, step 3 is performed.

In step 3, the fiber base material is wound around a mandrel having a diameter substantially equal to the diameter of the inner surface of the tube, and the fiber base material is connected and fixed with a resin composition contained in the fiber base material, thereby being processed into a cylindrical shape.

Specifically, when the fiber base material is sheet-shaped, two sides in the longitudinal direction are overlapped by about 1 to 10cm after being wound around the mandrel, and the fiber base material is connected and fixed by the resin composition contained in the fiber base material. When the fiber base material is in a belt shape, the fiber base material is wound in a spiral shape while being overlapped by about 1 to 10cm, and the overlapped portions are connected and fixed by the resin composition contained in the fiber base material.

In step 3, when the fiber base material containing the resin composition is wound with the inner film disposed on the mandrel in advance, it is not necessary to laminate the inner film on the fiber base material or the fiber base material containing the resin composition, and the mandrel after winding the fiber base material containing the resin composition is preferably removed easily.

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

In step 3, the overlapping portions of the fiber base material are connected and fixed by the resin composition contained in the fiber base material. Therefore, the viscosity of the resin composition contained in the fibrous base material at this time is preferably a viscosity having moderate tackiness, preferably 30 to 1,500pa·s, more preferably 40 to 1,300pa·s, and still more preferably 250 to 1,300pa·s.

When the viscosity of the resin composition contained in the fiber base material is 30pa·s or more, the resin composition has moderate adhesiveness, and the resin composition is not unevenly distributed in the fiber base material, and can be maintained in a uniformly contained state. In addition, when the viscosity of the resin composition is 1,500pa·s or less, it is easy to process into a cylindrical shape.

The method for producing the lining material may further include a curing step in addition to the steps 1 to 3.

The curing step is a step for suitably thickening the resin composition until a viscosity suitable for each step is reached. Preferably, the resin composition is provided after impregnating the fiber substrate with the resin composition or before repairing the tube.

The curing temperature in the curing step is preferably 10 to 40 ℃, more preferably 15 to 30 ℃, and even more preferably 20 to 30 ℃. The curing temperature may be appropriately adjusted according to the target viscosity of the resin composition, curing time, and the like.

In the case of producing the lining material using the resin composition according to embodiment 1, it is preferable to provide a curing step in a period from the step 1 to the pipe repair. The curing time is preferably 6 hours to 3.5 days, more preferably 12 hours to 3 days, and still more preferably 1 to 2 days.

In the case of producing the lining material using the resin composition according to embodiment 2, it is preferable to provide a curing step immediately after step 1, and it is preferable to provide a curing step during a period from the time of step 3 to the time of pipe repair.

The curing time for curing immediately after the step 1 is preferably 12 hours to 3 days, more preferably 1 day to 2.5 days, and still more preferably 1.5 to 2 days. When the curing time is within the above range, the resin composition exhibits moderate adhesion, and the overlapping portions of the base material impregnated with the resin composition can be joined and fixed with sufficient strength.

The curing time from the step 3 to the pipe repair is preferably 6 hours to 3.5 days, more preferably 12 hours to 3 days, and still more preferably 1 to 2 days.

The storage period of the lining material is preferably 1 to 6 months, more preferably 2 to 5 months, from the viewpoint of quality stability.

< tube repair >

The lining material may be directly introduced from a manhole or the like in the work of introducing the lining material into the laid pipe, but a roll-over construction method in which the lining material is pressed into the laid pipe while being rolled over from the front end is suitably used. The lining material comprising an outer film in the innermost layer of the inner surface, an inner film in the outermost layer of the outer surface, and a fibrous base material comprising a resin composition between the inner film and the outer film is preferably used in the inversion method.

Since the expansion operation of the lining material is performed by blowing air into the inner cavity of the lining material, both end portions of the lining material are provided with caps for sealing the lining material. By blowing air from the end cap side of one end, the pressure in the inner cavity of the lining material increases, and the diameter of the lining material is enlarged so as to be in close contact with the inner peripheral surface of the laid pipe. In this case, in view of the fact that the resin composition in the lining material does not leak and fall or is unevenly distributed in the lining material, and the lining material preferably has a moderate flexibility, the viscosity of the resin composition at 25 ℃ when the lining material is disposed in a pipe, that is, the viscosity of the resin composition at 25 ℃ in a base material impregnated with the resin composition contained in the lining material is 400 to 3,500pa·s, preferably 450 to 2,500pa·s, more preferably 500 to 2,000pa·s, and preferably the same as the viscosity at 25 ℃ at least one of 2 days and 5 days after the resin composition is prepared.

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

If the radiation intensity is 0.0008W/mm ² As described above, the working efficiency is good, and sufficient strength can be imparted to the pipe. In addition, if the radiation intensity is 0.03W/mm ² In the following, the inner surface layer of the lining material can be prevented from being partially excessively irradiated, and deterioration and strength decrease of the lining material can be prevented.

As the light irradiation device, a light source that emits light in the ultraviolet to visible light region (generally, wavelength of 200 to 800 nm) can be used as the light source. Examples of the light source include metal halide lamps such as gallium lamps, mercury lamps, chemical lamps, xenon lamps, halogen lamps, mercury halogen lamps, carbon arc lamps, incandescent lamps, lasers, and LEDs.

The ultraviolet or visible light irradiation device having a peak wavelength in the wavelength region of 350 to 450nm is preferable from the viewpoint of workability in the tube repair work, and the gallium lamp and the LED are more preferable from the viewpoint of curing the resin composition efficiently, and the gallium lamp is further preferable.

The light irradiation device is not particularly limited as long as it has 1 or more irradiation units, but preferably has a lamp connector formed by connecting a plurality of irradiation lamps in series. By having a lamp connector, tube repair can be efficiently performed.

In the case of producing a lining material using the resin composition according to embodiment 1 of the present embodiment, the number of days elapsed from the preparation of the resin composition (after the production of the resin composition) until the pipe repair is performed is preferably 1 to 4 days, more preferably 1 to 3 days, and even more preferably 1 to 2 days.

In the case of producing the lining material using the resin composition according to embodiment 2 of the present embodiment, the number of days elapsed from the preparation of the resin composition (after the production of the resin composition) until the pipe repair is performed is preferably 2 to 7 days, more preferably 3 to 6 days, and even more preferably 4 to 5 days.

Examples

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

[ Synthesis of vinyl ester resin ]

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

The following is a description of the details of the epoxy compounds used for synthesizing vinyl ester resins in the following synthesis examples and comparative synthesis examples.

Epoxy compound (1): bisphenol a type epoxy resin; "Epoder" R140P (registered trademark), manufactured by Sanjingku chemical Co., ltd., has an epoxy equivalent of 188

Epoxy compound (2): bisphenol a type epoxy resin; "jER (registered trademark) 834", mitsubishi chemical corporation, having an epoxy equivalent of 245

Epoxy compound (3): phenol novolac type epoxy resin; "EPICLON (registered trademark) N-740", manufactured by DIC Co., ltd., epoxy equivalent is 172

The epoxy equivalent is according to JIS K7236: 2001.

Synthesis example 1

In a 5L four-necked separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, 1512g of an epoxy compound (1) and 429g of bisphenol A (47 moles of the total amount of hydroxyl groups of bisphenol A based on 100 moles of the total amount of epoxy groups of the epoxy compound (1)) were charged and heated to 80 ℃. Then, 3.9g of triethylamine (manufactured by dow cell corporation) (0.2 parts by mass based on 100 parts by mass of the total of the epoxy compound (a-1) and bisphenol (a-2)) was charged as a catalyst, and the mixture was heated to 145℃to perform a reaction for 1 hour to synthesize a resin precursor (P1). Then, after cooling to 110℃the mixture was charged with 429g of styrene (10% by mass based on the total mass of the components) as a reactive diluent, 0.04g of 5% copper naphthenate as a polymerization inhibitor (0.0019 parts by mass based on 100 parts by mass of the epoxy compound (a-1), bisphenol (a-2) and unsaturated monoacid (a-3), 1.3g of trimethylhydroquinone (0.056 parts by mass based on 100 parts by mass of the epoxy compound (a-1), bisphenol (a-2) and unsaturated monoacid (a-3)) and 2,4, 6-tris (dimethylaminomethyl) phenol ("smart TDMP", manufactured by Seku Chemicals Co., ltd.) with a purity of more than 95% and heated to 110℃were 6.9g (0.3 parts by mass based on 100 parts by mass of the epoxy compound (a-1), bisphenol (a-2) and unsaturated monoacid (a-3)). Then, 365g of methacrylic acid (based on 100 moles of the total amount of the epoxy groups of the epoxy compound (1) as the unsaturated monobasic acid (a-3)) was added dropwise over about 30 minutes, and then heated to 130℃to react for about 2 hours, thereby obtaining a vinyl ester resin (A1-1).

The reaction product was cooled to 90℃and 0.13g (0.003 parts by mass based on 100 parts by mass of the total of all components) of hydroquinone as a polymerization inhibitor and 1546g (36% by mass based on 36% by mass of the total of the components) of styrene as a reactive diluent (ethylenically unsaturated group-containing monomer (B)) were added to obtain a mixture of 54% by mass (based on the total mass of the components) of vinyl ester resin and 46% by mass of styrene.

Synthesis example 2

Into a 5L four-necked separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, 1795g of an epoxy compound (1) and 271g of bisphenol A (the total amount of hydroxyl groups of bisphenol A was 25 moles based on 100 moles of the total amount of epoxy groups of the epoxy compound (1)) were charged and heated to 80 ℃. Then, 3.1g of triethylamine (manufactured by dow cell corporation) (0.15 parts by mass based on 100 parts by mass of the total of the epoxy compound (a-1) and bisphenol (a-2)) was charged as a catalyst, and the mixture was heated to 145℃to perform a reaction for 1 hour to synthesize a resin precursor (P1). Then, after cooling to 110℃to add 496g of styrene as a reactive diluent (10 parts by mass based on the total mass of the components) and 0.05g of 5% copper naphthenate as a polymerization inhibitor (0.0019 parts by mass based on the total 100 parts by mass of the epoxy compound (a-1), bisphenol (a-2) and unsaturated monoacid (a-3)), 1.0g of methyl hydroquinone (0.04 parts by mass based on the total 100 parts by mass of the epoxy compound (a-1), bisphenol (a-2) and unsaturated monoacid (a-3)), 1.5g of trimethyl hydroquinone (0.057 parts by mass based on the total 100 parts by mass of the epoxy compound (a-1), 2,4, 6-tris (dimethylaminomethyl) phenol ("TDMP", manufactured by Sea chemical engineering chemical Co., ltd.) as an esterification catalyst, purity of more than 95.0 g (95% by mass) and (0.564 minutes) of acrylic acid were added dropwise to the total 100 parts by mass of the epoxy compound (a-3) and the total 100 parts by mass of the epoxy compound (a-3) at about 0.564 minutes after heating to about the total of the epoxy compound (a-3) to about 30 minutes, the resin precursor (P2) was synthesized. Then, 33g of fumaric acid (6 moles of fumaric acid based on 100 moles of the total amount of epoxy groups of the epoxy compound (1)) was added as the unsaturated polybasic acid (a-4), and the reaction was carried out for about 1 hour to obtain a vinyl ester resin (A2-1).

The reaction product was cooled to 90℃and 1784g (36 mass% based on the total mass of the components) of styrene as a reactive diluent (ethylenically unsaturated group-containing monomer (B)) was added to obtain a mixture of 54 mass% of vinyl ester resin (based on the total mass of the components) and 46 mass% of styrene.

[ Synthesis example 3 ]

In a 5L four-necked separable flask equipped with a stirrer, a reflux condenser, a gas introduction tube, and a thermometer, 1950g of an epoxy compound (1) was heated to 80℃and 407g (10 parts by mass based on the total mass of the components) of styrene as a reactive diluent, 0.04g (0.0014 parts by mass based on the total 100 parts by mass of an epoxy compound (a-1) and an unsaturated monoacid (a-3) of copper naphthenate as a polymerization inhibitor, 0.9g (0.03 parts by mass based on the total 100 parts by mass of an epoxy compound (a-1) and an unsaturated monoacid (a-3)) of methyl hydroquinone, 1.6g (0.057 parts by mass based on the total 100 parts by mass of an epoxy compound (a-1) and an unsaturated monoacid (a-3)) and 2,4, 6-tris (dimethylaminomethyl) phenol as an esterification catalyst ("high-temperature TDMP"), a finishing chemical society, a higher than 8 g (0.95 mol%) of an acrylic acid (a-3) were added dropwise to the total 100 parts by mass of an epoxy compound (a-3) at about 0.3) of a total of 3 mol, and the total of an unsaturated monoacid (a-3) was heated to about 100 mol% of an acrylic acid (1) at about 0.3 mol% when the total amount of the epoxy compound (a-3) was heated, the vinyl ester resin (A3-1) was obtained.

The reaction product was cooled to 90℃and 815g (20 mass% based on the total mass of the components) of styrene as a reactive diluent (ethylenically unsaturated group-containing monomer (B)) was added to obtain a mixture of 70 mass% of vinyl ester resin (based on the total mass of the components) and 30 mass% of styrene.

[ Synthesis example 4 and 5 ]

The synthesis was performed in the same manner as in Synthesis example 3 except that the compounding compositions shown in Table 2 were set, and vinyl ester resins (A3-2) and (A3-3) were obtained. In synthesis example 5, "cartridge" (registered trademark) M was used as a catalyst ₂ 100R "(purity: more than 90 mass%) of (manufactured by Nikko Co., ltd.).

With respect to the vinyl ester resin (A3-2), after cooling to 90 ℃, 1222g of styrene as a reactive diluent (ethylenically unsaturated group-containing monomer (B)) was added to obtain a mixture of 70 mass% of the vinyl ester resin (based on the total mass of the compounding ingredients) and 30 mass% of styrene.

As to the vinyl ester resin (A3-3), after cooling to 90℃1543g of phenoxyethyl methacrylate as a reactive diluent (ethylenically unsaturated group-containing monomer (B)) was added to obtain a mixture of 65% by mass of the vinyl ester resin (based on the total mass of the components) and 35% by mass of styrene.

Comparative Synthesis example 1

In a 5L four-necked separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, 1960g of an epoxy compound (2), 1.0g of methyl hydroquinone as a polymerization inhibitor (0.04 parts by mass per 100 parts by mass of the total of the epoxy compound (a-1) and the unsaturated monoacid (a-3)), and tetradecyldimethylbenzyl ammonium chloride ("Populin (registered trademark)) M as a catalyst were added ₂ 100R "(manufactured by Nikko Co., ltd.) 8.0g (0.3 parts by mass based on 100 parts by mass of the total of the epoxy compound (a-1), the unsaturated monoacid (a-3) and the maleic anhydride), 688g of methacrylic acid (100 mol based on the total amount of epoxy groups of the epoxy compound (1), the total amount of acid groups of methacrylic acid being 100 mol) and 157g of maleic anhydride (20 mol based on the total amount of epoxy groups of the epoxy compound (1)) were heated to 110℃and dropwise added as the unsaturated monoacid (a-3) over about 30 minutes, followed by a reaction for about 4 hours to obtain the vinyl ester resin (A' -1).

The reaction product was cooled to 90℃and 1512g of phenoxyethyl methacrylate as a reactive diluent (ethylenically unsaturated group-containing monomer (B)) was added to obtain a mixture of 65 mass% of a vinyl ester resin (based on the total mass of the components) and 35 mass% of phenoxyethyl methacrylate.

Comparative Synthesis example 2

The synthesis was performed in the same manner as in comparative synthesis example 1 except that the raw materials and the mixing ratios shown in table 2 were set, and a vinyl ester resin (a' -2) was obtained.

[ evaluation of vinyl ester resin measurement ]

The vinyl ester resins (A1-1), (A2-1), (A3-1) to (A3-3), (A '-1) and (A' -2) obtained in the above synthesis examples were evaluated for measurement in the following items. The measurement and evaluation results are summarized in table 2 below.

Details of the mixture (measurement sample) containing the vinyl ester resin (a) obtained in each synthesis example are shown in table 3.

< acid value >

For the acid value of the vinyl ester resin, the acid value was measured in accordance with JIS K6901:2008 "partial acid value (indicator titration method)", the mass of potassium hydroxide required for neutralizing the acid component contained in the vinyl ester resin is measured, and the acid value of the vinyl ester resin is obtained.

The measurement sample was a mixture of the vinyl ester resin obtained in the above synthesis example and comparative synthesis example and a reactive diluent, and the mass of potassium hydroxide required for neutralizing the acid component contained in the mixture was measured, and then the acid value of the vinyl ester resin was calculated based on the measurement value. As the titration apparatus, a seal UCB-2000 (manufactured by mithen industry corporation) was used, and as the indicator, a mixed indicator of bromothymol blue and phenol red was used.

< hydroxyl value >

For the hydroxyl value of the resin (a), the hydroxyl value was measured in accordance with JIS K6901:2008 "hydroxyl value (neutralization titration)", the mass of potassium hydroxide required for neutralizing acetic acid produced by acetylation of 1g of vinyl ester resin was measured, and the hydroxyl value was determined.

In the vinyl ester resin (A1), a mixture (65 mass% of the vinyl ester resin (A1)) obtained by diluting the vinyl ester resin (A1) with phenoxyethyl methacrylate (manufactured by makrote corporation of sho and B) as the ethylenically unsaturated group-containing monomer (B), and 2 mixtures (70 mass% and 54 mass% of the vinyl ester resin (A1)) obtained by diluting the vinyl ester resin (A1) with styrene were used as measurement samples. The hydroxyl value of the resin (A) was obtained from the measured value of the measurement sample. Neutralization titration was performed manually, using 1% phenolphthalein (ethanol solution) as an indicator.

< weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw/Mn >

The weight average molecular weight Mw and the number average molecular weight Mn of the vinyl ester resin were measured by Gel Permeation Chromatography (GPC) under the following conditions, and were obtained as molecular weights in terms of standard polystyrene. Mw/Mn is calculated from the values of Mn and Mw.

Device: "Populus (registered trademark) GPC-101" (manufactured by Zhaowa electric Co., ltd.)

Column: "UO-UO (registered trademark) LF-804" (manufactured by Zhao electric Co., ltd.)

Detector: differential refractometer "Pop' S Uster (registered trademark) RI-71S" (manufactured by Zhaowa electric Co., ltd.)

Column temperature: 40 DEG C

Sample: 0.2% by mass of a tetrahydrofuran solution of the vinyl ester resin (A)

Developing solvent: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

< viscosity >

The viscosities of the mixtures of the vinyl ester resins obtained in the above synthesis examples and comparative synthesis examples and the reactive diluents were measured at a temperature of 25℃using an E-type viscometer ("RE-85U" (manufactured by Toku Kagaku Co., ltd.) and a conical rotor of 1℃34'. Times.R 24 at a rotation speed of 50rpm to 0.5 rpm).

When the viscosity of the mixture is greater than 0 Pa.s and less than 1.0 Pa.s, the mixture is measured at a rotation speed of 50 rpm.

When the viscosity of the mixture is more than 1.0 Pa.s and less than 2.0 Pa.s, the rotation speed is measured at 20 rpm.

When the viscosity of the mixture is greater than 2.0 Pa.s and less than 4.0 Pa.s, the mixture is measured at a rotation speed of 10 rpm.

When the viscosity of the mixture is greater than 4.0 Pa.s and less than 8.0 Pa.s, the mixture is measured at a rotation speed of 5 rpm.

When the viscosity of the mixture is more than 8.0 Pa.s and 18.0 Pa.s or less, the rotation speed is measured at 2.5 rpm.

When the viscosity of the mixture is greater than 18.0 Pa.s and 45.0 Pa.s or less, the mixture is measured at a rotation speed of 1.0 rpm.

When the viscosity of the mixture is more than 45.0 Pa.s and 100.0 Pa.s or less, the rotation speed is measured at 0.5 rpm.

The rotational speed of the conical rotor corresponding to the measured viscosity is shown in table 1 below.

TABLE 1

Viscosity [ Pa.s ]]	Rotational speed [ rpm ]]
		Greater than 0 and less than 1.0	50
Greater than 1.0 and less than 2.0	20
		Greater than 2.0 and less than 4.0	10
Greater than 4.0 and less than 8.0	5
		Greater than 8.0 and less than 18.0	2.5
Greater than 18.0 and less than 45.0	1.0
		Greater than 45.0 and less than 100.0	0.5

< depth of cure >

A mixture (i) obtained by adding 1.2 parts by mass of magnesium oxide as the compound (C) ("Makeup chemical Co., ltd., magnesium oxide content: 30% by mass (estimation)" manufactured by Yuanzhiki Seisakusho) to a mixture (A1-1) of 54% by mass of vinyl ester resin (A1-1) and 46% by mass of styrene, a mixture (ii) obtained by adding 1.5 parts by mass of the above-mentioned magnesium oxide to the mixture (A1-1), and a mixture (iii) obtained by adding 2 parts by mass of magnesium oxide to the mixture (A1-1) were prepared. For the prepared mixtures (i) to (iii), about 100g of the mixtures (i) to (iii) were then put into a 100ml plastic container having side surfaces and bottom surfaces shielded from light by aluminum foil, and the mixture was left standing in a sealed state at 25℃for 120 hours and 216 hours, and after curing, a 3kW gallium lamp (peak wavelength: 420 nm) was used to irradiate the plastic container with an illuminance of 20mW/cm from the upper part thereof ² The light of (illuminometer "IL1400A" (made by nano corporation, optical receiver model SEL005, measurement wavelength range: 380 to 450nm, center value: 415 nm)) was for 20 minutes, and a cylindrical cured product having a height of about 65mm and a width of about 50mm was obtained. After the irradiation, a product obtained by removing the uncured resin-like portion and gel-like portion from the back surface of the irradiated surface by a cutter was used as a completely cured portion, and the height from the irradiated surface to the back surface of the irradiated surface was measured by a vernier caliper and used as the curing depth. The curing depth was evaluated according to the following evaluation criteria.

And (3) the following materials: the depth of solidification is more than 25mm

And (2) the following steps: a curing depth of 20mm or more and less than 25mm

Delta: the depth of solidification is 15-19 mm

X: the depth of solidification is less than 15mm

When the curing depth is 25mm or more, it is considered that the curability is extremely excellent.

The depth of cure was also evaluated in the same manner for a mixture (A3-3) of 65 mass% of the vinyl ester resin (A3-3) and 35 mass% of phenoxyethyl methacrylate.

TABLE 2

/>

TABLE 3

TABLE 3 Table 3

[ production of resin composition ]

Using the vinyl ester resin (mixture of vinyl ester resin and reaction diluent) obtained in the above synthesis example and comparative synthesis example, a resin composition was produced.

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

Thixotropic agent (1): an organic thixotropic agent; "Fanflow SP-1000AF", manufactured by Zoo Chemie Co., ltd

Thixotropic agent (2): hydrophobic silica; "one-touch PM-20L", available from corporation

[ production example 1 ]

To a mixture of 54 parts by mass of a vinyl ester resin (A1-1) and 46 parts by mass of styrene as an ethylenically unsaturated group-containing monomer (B), 0.2 part by mass of 2, 2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator (D), 0.2 parts by mass of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 0.1 part by mass of water as a compound (E), 1.0 parts by mass of a thixotropic agent (1), and a dispersion medium (Kagaku Kogyo Co., ltd.) was added, and the mixture was mixed at 2000 to 3000rpm for 20 minutes using a disperser (high speed disperser "Du Ji Shu 2.5" Du Ku Shu Co., ltd.). To this, 1.2 parts by mass (0.36 parts by mass of magnesium oxide) was added as the compound (C) (the magnesium oxide content was 30% by mass (presumed to be the same) and the mixture was further mixed for about 1 minute to prepare a resin composition (X-1).

[ production examples 2, 3, 5 to 11, 13, 14, 17 to 22, comparative production examples 1 and 2 ]

Resin compositions (X-2), (X-3), (X-5) to (X-11), (X-13), (X-14), (X-17) to (X-22) and (X '-1) to (X' -3) were obtained by preparing the same in preparation example 1 with the exception of setting the raw materials and the blending ratios as described in tables 6 to 8.

[ production examples 4, 12, 15 and 16 ]

In production example 1, resin compositions (X-4), (X-12), (X-15) and (X-16) were obtained by preparing a mixture of a vinyl ester resin (A1-1) and styrene as an ethylenically unsaturated group-containing monomer (B) in the same manner except that 3-dodecenylsuccinic acid as the carboxyl group-containing compound (F) was further added in the mixture ratio shown in tables 6 and 7 and the other raw materials and mixture ratios shown in tables 6 and 7 were set.

Comparative production example 3

In production example 1, a resin composition (X' -3) was prepared in the same manner except that 10 parts by mass of isophorone diisocyanate was added instead of the compound (C), and the raw materials and the mixing ratio were set as described in table 8.

[ evaluation of measurement of resin composition ]

The resin compositions (X-1) to (X-22) and (X '-1) to (X' -3) obtained in the above production examples and comparative production examples were subjected to measurement and evaluation of viscosity and tackiness. The results are shown in tables 6 to 8 below.

< viscosity >

Immediately after the preparation, 280g of the resin composition was filled into 300ml containers, and the containers were kept in a sealed state at 25℃for storage.

The viscosity at 25℃after 1 hour of preparation of the resin composition and the viscosity at 25℃after 2 days of preparation of the resin composition were measured for the resin compositions (X-1) to (X-11).

The viscosity at 25℃after 1 hour of preparation of the resin composition, the viscosity at 25℃after 2 days of preparation of the resin composition, and the viscosity at 25℃after 5 days of preparation of the resin composition were measured for the resin compositions (X-12) to (X-22), (X '-1) and (X' -2). The following 2 devices are suitably selected according to the viscosity range, and measured at a temperature of 25 ℃. Since the resin composition (X' -3) gelled, the viscosity could not be measured.

( 1) "RB80 viscometer" (manufactured by DONGMACHINE CORPORATION; rotor No. 3-4 )

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

When the viscosity of the resin composition is more than 1.0 Pa.s and 5.0 Pa.s or less, the rotation speed of the rotor No.4 is measured at 60 rpm.

When the viscosity of the resin composition is more than 5.0 Pa.s and 25.0 Pa.s or less, the rotation speed of the rotor No.4 is measured at 12 rpm.

When the viscosity of the resin composition is greater than 25.0 Pa.s and 50.0 Pa.s or less, the rotation speed of the rotor No.4 is measured at 6 rpm.

When the viscosity of the resin composition is more than 50.0 Pa.s and 100.0 Pa.s or less, the rotation speed of the rotor No.4 is measured at 3 rpm.

The rotor used and the rotational speed corresponding to the measured viscosity are shown in table 4 below.

TABLE 4

TABLE 4 Table 4

Viscosity [ Pa.s ]]	Rotor No.	Rotational speed [ rpm ]]
			Greater than 0 and less than 1.0	3	60
Greater than 1.0 and less than 5.0	4	60
			More than 5.0 and less than 25.0	4	12
Greater than 25.0 and less than 50.0	4	6
			Greater than 50.0 and less than 100.0	4	3

( 2) "HBDVE viscometer" (made by Ying Hongjing Co., ltd.; t-type rotors T-A to T-D, rotating speed: 1rpm )

When the viscosity of the resin composition is more than 100.0 Pa.s and 800.0 Pa.s or less, a T-rotor T-A is used.

When the viscosity of the resin composition is more than 800.0 Pa.s and 1600.0 Pa.s or less, a T-rotor T-B is used.

When the viscosity of the resin composition is more than 1600.0 Pa.s and not more than 4000.0 Pa.s, a T-type rotor T-C is used.

When the viscosity of the resin composition is more than 4000.0 Pa.s and 10000.0 Pa.s or less, a T-type rotor T-D is used.

The type of T-rotor used in accordance with the measured viscosity is shown in table 4 below.

TABLE 5

Viscosity [ Pa.s ]]	T-shaped rotor
		Greater than 100 and less than 800	T-A
Greater than 800 and less than 1600	T-B
		More than 1600 and less than 4000	T-C
More than 4000 and less than 10000	T-D

< thickening Property >

The resin compositions (X-1) to (X-11) were evaluated for tackiness according to the following evaluation criteria.

And (3) the following materials: the viscosity of the resin composition after 2 days was 1,000 Pa.s or more (the thickening property was very good)

O: the viscosity of the resin composition after 2 days of preparation is 400 Pa.s or more and less than 1,000 Pa.s

X: the viscosity of the resin composition after 2 days of preparation is less than 400 Pa.s

The resin compositions (X-12) to (X-22) and (X '-1) to (X' -3) were evaluated for tackiness according to the following evaluation criteria.

And (3) the following materials: the viscosity of the resin composition after 5 days was 1,000 Pa.s or more (the thickening property was very good)

O: the viscosity of the resin composition after 5 days of preparation is 400 Pa.s or more and less than 1,000 Pa.s

X: the viscosity of the resin composition after 5 days of preparation is less than 400 Pa.s

TABLE 6

TABLE 7

TABLE 8

[ production of lining Material ]

[ example 1 ]

< Lining Material for evaluation of simulated tube workability >

A polyethylene film (manufactured by i-chemical industry Co., ltd.) having a length of 1400mm and a thickness of 100 μm was wound around an aluminum plate having a width of 220mm, a length of 1000mm, and a thickness of 4mm, and the end portion thereof was curved with R2, and the coated portion was heat-sealed with a styrene resin (manufactured by white light Co., ltd.). Next, a glass fiber chopped strand mat (450 g/m) ² "MC 450A", manufactured by Nito Kabushiki Kaisha Co., ltd.) was impregnated with the resin composition (X-1) obtained in the production example by using a deaeration roll while winding, to obtain a fibrous base material (design thickness 3.0mm:4 layers, 40% glass content). The amount of the resin composition contained in the fiber base material was 60 mass%.

Further, a polyethylene film having a length of 1400mm×a thickness of 100 μm was coated as an outer film over a fibrous base material containing the resin composition, and the wrapping portion was fixed by a masking tape (3M commercial). Next, the aluminum plate was pulled out, and cured at 25℃for 2 days to obtain a lining material (x 1-1).

< lining Material for evaluation of Curve curability >

As shown in fig. 1, a base was formed using a concrete block and a glass plate so that the bending angle became 20 °. A PET film was laid on the base, and a glass fiber chopped strand mat (450 g/m) ² "MC 450A", manufactured by Nitto Kabushiki Kaisha). The resin composition (X-1) obtained in the production example was impregnated into the fiber base material using a defoaming roller to obtain a fiber base material containing the resin composition (design thickness 5.0mm:6 layers, glass content 40%). The amount of the resin composition contained in the fiber base material was 60 mass%.

Then, after laminating a PET film on the surface of the fibrous base material containing the resin composition opposite to the susceptor, the entire fibrous base material containing the resin composition was light-shielded by an aluminum sheet, and cured for 120 hours at 23±2 ℃ to obtain a lining material (x 2-1).

[ examples 2 to 22, comparative examples 1 to 3 ]

Lining materials (x 1-2) to (x 1-22) and (x 2-2) to (x 2-22) were obtained in the same manner as in example 1 except that the resin compositions described in tables 6 and 7 were used.

In the case of using the resin compositions (X '-1) to (X' -3), the viscosity of the resin composition is low, and therefore, the resin composition cannot be held on the fiber base material, and the lining material cannot be produced.

[ evaluation of measurement of lining Material ]

The lining materials obtained in the examples and comparative examples were subjected to simulated pipe construction evaluation and bend curability evaluation. The measurement and evaluation results are shown in table 9 below.

< simulation tube workability >

After the lining material was introduced into a acrylic tube having an inner diameter of 150mm×a length of 1000mm, both ends of the lining material were bundled with a tie and sealed, air was injected from one end at a rate of 4L/sec, and the lining material was expanded in diameter and pressure-bonded to the inner surface of an acrylic tube as a dummy tube. Then, both ends of the lining material were fixed to a sub-gram force pipe, one end was provided with a cover having an air injection hole, and the other end was provided with a cover having a nano-ceramic コ, ultraviolet LED fluorescent lamp NS365-FTL-C30 as a light source. While injecting air at 4L/sec from a cap with an air injection hole, the illuminance was 10mW/cm ² The lining material was photo-cured under conditions of a light meter, a light-off UIT-201, a sensitive wavelength range of 330 to 490nm, and an irradiation time of 60 minutes, whereby tube repair of the pseudo tube was performed.

When the diameter of the lining material can be enlarged without any problem, it is determined that the diameter can be enlarged.

After the lining material was cured, the inner film was removed, and the thickness of the cured lining material layer was confirmed. The cured layer of the lining material means the thickness of the fibrous base material containing the resin composition.

The thickness of the cured layer of the lining material was measured at 4 points up, down, left, right, and a total of 12 points on the cross section of the dummy tube at 3 points 200mm apart from both ends of the center portion of the dummy tube.

Based on the above results, the simulated pipe workability was evaluated according to the following evaluation criteria.

And (2) the following steps: satisfying the following (1) to (3)

X: at least 1 of the following (1) to (3) is not satisfied

(1): the lining material can expand the diameter

(2): the lower limit value of the thickness of the cured layer of the lining material is more than 3.0mm

(3): the upper limit of the thickness of the cured layer of the lining material is 3.6mm or less

The lining material was evaluated as a lining material suitable for pipe repair, which suppresses uneven distribution of the resin composition in the lining material and has a good appearance.

< Curve curability >

With the lining material set on the base, the illumination was 10mW/cm using a gallium lamp (Tsuk-300I) (made by Toyun-Tongyi Co., ltd.) ² (illuminometer: light-curing the resin composition in the lining material under conditions of light-curing over UIT-201, sensitive wavelength region 330-490 nm) and irradiation time of 1 minute.

After leaving for 5 minutes, the bending portion of the lining material was touched with a finger, and the bending portion curability was evaluated according to the following evaluation criteria.

And (3) the following materials: non-adhesive

And (2) the following steps: slightly tacky or fingerprint attached to fibrous substrate Δ comprising resin composition: adhesive (resin composition of fibrous substrate surface can be peeled off by nail) ×: having tackiness (uncured)

TABLE 9

As is clear from the evaluation results of the simulated tube workability in table 9, the lining material of the present embodiment suppresses maldistribution of the resin composition after curing. Further, as is clear from the evaluation result of the curability of the bent portion, the lining material of the present embodiment can suppress curing failure even when the pipe is bent.

Claims

1. A lining material comprising a fibrous base material comprising a resin composition,

the resin composition comprises:

Vinyl ester resin (A),

An ethylenically unsaturated group-containing monomer (B),

a photopolymerization initiator (D),

the acid value of the vinyl ester resin (A) is 1-35 KOHmg/g.

2. The lining material according to claim 1, wherein the vinyl ester resin (a) is a reaction product of a resin precursor (P1) and an unsaturated monoacid (a-3), and the resin precursor (P1) is a reaction product of an epoxy compound (a-1) having 2 epoxy groups in 1 molecule and a bisphenol compound (a-2).

3. The lining material according to claim 1, wherein the vinyl ester resin (a) is a reaction product of a resin precursor (P2) and an unsaturated polybasic acid (a-4), the resin precursor (P2) is a reaction product of a resin precursor (P1) and an unsaturated monobasic acid (a-3), and the resin precursor (P1) is a reaction product of an epoxy compound (a-1) having 2 epoxy groups in 1 molecule and a bisphenol compound (a-2).

4. The lining material according to claim 1 or 2, wherein the weight average molecular weight Mw of the vinyl ester resin (a) is 2000 to 5000.

5. The lining material according to claim 1 or 2, wherein the ratio of the weight average molecular weight Mw to the number average molecular weight Mn of the vinyl ester resin (a), i.e., mw/Mn, is 1.5 or more.

6. The lining material according to claim 1 or 2, wherein the vinyl ester resin (a) has a hydroxyl value of 10 to 120KOHmg/g.

7. The lining material according to claim 1 or 2, wherein the content of the component (C) is 0.3 to 3 parts by mass based on 100 parts by mass of the total of the vinyl ester resin (a) and the ethylenically unsaturated group-containing monomer (B).

8. The lining material according to claim 1 or 2, wherein the resin composition further contains a compound (E) which is at least 1 selected from water and a hydroxyl group-containing compound.

9. The lining material according to claim 1 or 2, wherein the photocurable resin composition further contains a carboxyl group-containing compound (F).

10. The lining material according to claim 1 or 2, wherein the lining material comprises, relative to 100 parts by mass of the total of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B),

contains 30 to 90 parts by mass of the vinyl ester resin (A),

contains 0.05 to 10 parts by mass of the photopolymerization initiator (D).

11. The lining material according to claim 1 or 2, wherein the photocurable resin composition further contains a thixotropic agent.

12. The lining material according to claim 1 or 2, which has an inner film provided on one side of the fibrous base material and an outer film provided on the other side.

13. A cured product of the lining material according to claim 1 or 2.