KR20240054353A - Resin compositions and lining materials for pipe rehabilitation - Google Patents

Abstract

An unsaturated polyester resin (A), an ethylenically unsaturated group-containing monomer (B), at least one compound selected from oxides and hydroxides of Group 2 elements (C), and water and a hydroxyl group-containing compound. A resin composition containing at least one compound (D) and a dicarboxylic acid (E), wherein the unsaturated polyester resin (A) is a reaction product of a diol (a1) and a dibasic acid (a2), and the diol ( a1) contains 43 to 85 mol% of diol (a1-1), which is an alkanediol with a molecular weight of 90 to 500, based on 100 mol% of diol (a1), and the dibasic acid (a2) is a dibasic acid containing an ethylenically unsaturated group. (a2-1) and a dibasic acid (a2-2) not containing an ethylenically unsaturated group, and the content of the compound (D) is such that the content of the unsaturated polyester resin (A), the monomer (B) containing an ethylenically unsaturated group, and the compound (D) and dicarboxylic acid (E) in an amount of 0.1 to 1% by mass based on a total of 100% by mass.

Description

Resin compositions and lining materials for pipe rehabilitation

The present invention relates to a resin composition containing an unsaturated polyester resin, a composite material, and a lining material for pipe rehabilitation.

Recently, the deterioration of existing pipes buried in the ground, such as water pipes, sewer pipes, and power pipes, is becoming more serious, and various methods for repairing them have been proposed.

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

Japanese Patent Publication No. 2020-82408

Recently, there has been an increasing demand for lining materials for repairing existing pipes to be thinner and higher in strength, and accordingly, the base materials that make up the lining materials also tend to be thinner and higher in strength. For this reason, the resin composition used as a material for the lining material preferably has a low viscosity that is easily impregnated into the base material. On the other hand, when constructing a lining material by placing it on the inner surface of an existing pipe, it is required to have a viscosity sufficient to maintain a uniformly distributed state in the impregnated base material so that the resin composition is not unevenly distributed. That is, a resin composition that has a low viscosity when impregnating the impregnated base material with the resin composition, but thickens over time and has a high viscosity enough to maintain the resin composition when repairing an existing pipe is desirable.

However, there are cases where the viscosity of the resin composition becomes unstable, such as when the lining material is stored, the resin composition absorbs moisture from the outside air, and the viscosity gradually decreases after the resin composition reaches the target viscosity.

The present invention was made to solve the problems described above, and its purpose is to provide a resin composition with a controlled thickening rate and excellent viscosity stability after thickening. Additionally, the object is to provide a composite material containing the resin composition and a lining material containing the composite material.

That is, the present invention provides the following means.

[1] Unsaturated polyester resin (A),

A monomer (B) containing an ethylenically unsaturated group,

Compound (C) which is at least one type selected from oxides and hydroxides of Group 2 elements,

Compound (D) which is at least one type selected from water and hydroxyl group-containing compounds,

A resin composition containing dicarboxylic acid (E),

The unsaturated polyester resin (A) is a reaction product of diol (a1) and dibasic acid (a2),

The diol (a1) contains 43 to 85 mol% of diol (a1-1), which is an alkanediol with a molecular weight of 90 to 500, based on 100 mol% of the diol (a1),

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

The content of the compound (D) is based on a total of 100% by mass of the unsaturated polyester resin (A), the ethylenically unsaturated group-containing monomer (B), the compound (D), and the dicarboxylic acid (E). A resin composition of 0.1 to 1% by mass.

[2] The alkanediol (a1-1) is at least selected from 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, and hydrogenated bisphenol A. One type of resin composition according to [1] above.

[3] The resin composition according to [1] or [2], wherein the unsaturated polyester resin (A) has a weight average molecular weight of 5,000 to 20,000.

[4] The dibasic acid (a2) is 20 to 80 mol% of the dibasic acid (a2-1) containing an ethylenically unsaturated group, based on 100 mol% of the dibasic acid (a2), and the dibasic acid without an ethylenically unsaturated group. The resin composition according to any one of [1] to [3] above, containing 20 to 80 mol% of (a2-2).

[5] The resin composition according to any one of [1] to [4], wherein the compound (C) is at least one selected from magnesium oxide and magnesium hydroxide.

[6] The resin composition according to any one of [1] to [5] above, further comprising a photopolymerization initiator (F).

[7] For a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated group-containing monomer (B),

20 to 80 parts by mass of the unsaturated polyester resin (A),

20 to 80 parts by mass of the ethylenically unsaturated group-containing monomer (B),

0.01 to 6 parts by mass of the compound (C),

The resin composition according to any one of [1] to [6] above, comprising 0.01 to 5 parts by mass of the dicarboxylic acid (E).

[8] A composite material comprising the resin composition according to any one of [1] to [7] above and a fiber base.

[9] A lining material for pipe rehabilitation, comprising the composite material described in [8] above, an inner film, and an outer film.

According to the present invention, a resin composition with a controlled thickening rate and excellent viscosity stability after thickening, a composite material containing the resin composition, and a lining material containing the composite material are provided.

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

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

“Weight average molecular weight (Mw)” (hereinafter also referred to simply as “Mw”) and “Number average molecular weight (Mn)” (hereinafter referred to simply as “Mn”) are measured by gel permeation chromatography (GPC). This is the standard polystyrene conversion molecular weight obtained by . Specifically, it is measured by the method described in the Examples described later.

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

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

“Immediately after adjustment” refers to within 1 hour after preparation of the resin composition.

The “initial viscosity” of the resin composition refers to the viscosity measured within 5 hours after preparation of the resin composition. “Middle-term viscosity” of a resin composition refers to the viscosity measured within 24 to 48 hours (1 to 2 days) after preparation of the resin composition. “Late-term viscosity” of the resin composition refers to the viscosity measured within 168 to 840 hours (1 to 2 days) after preparation of the resin composition. This refers to the viscosity measured within 1 to 5 weeks.

“And/or” means “A and B” and “A or B” when A and/or B are written.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below.

[Resin composition]

The resin composition of the present embodiment includes an unsaturated polyester resin (A), an ethylenically unsaturated group-containing monomer (B), at least one compound (C) selected from oxides and hydroxides of Group 2 elements, water, and hydroxide. It contains at least one compound (D) selected from roxyl group-containing compounds and dicarboxylic acid (E). In addition, the unsaturated polyester resin (A) is a reaction product of diol (a1) and dibasic acid (a2), and the diol (a1) is 43 to 85 moles of alkanediol (a1-1) with a molecular weight of 90 to 500. %, and the dibasic acid (a2) includes a dibasic acid (a2-1) containing an ethylenically unsaturated group and a dibasic acid (a2-2) without an ethylenically unsaturated group, and the content of the compound (D) is as follows. It is 0.1 to 1% by mass based on a total of 100% by mass of the unsaturated polyester resin (A), the ethylenically unsaturated group-containing monomer (B), the compound (D), and the dicarboxylic acid (E).

The resin composition of this embodiment has a controlled thickening rate and is excellent in viscosity stability after thickening.

For example, the resin composition used in the lining material is required to have a low viscosity so that it can be easily impregnated into the base material constituting the lining material. On the other hand, when performing pipe rehabilitation, the resin composition is required to have a viscosity that maintains a uniformly distributed state in the fiber substrate without being unevenly distributed.

The resin composition of the present embodiment has a low viscosity when impregnated into a substrate, and thickens at an appropriate rate over time, and when performing pipe rehabilitation, the viscosity is high enough to maintain a uniformly distributed state in the fiber substrate. Since is controlled, it can be suitably used as a lining material.

[Unsaturated polyester resin (A)]

Unsaturated polyester resin (A) is a reaction product of diol (a1) and dibasic acid (a2).

The acid value of the unsaturated polyester resin (A) is preferably 3 KOH mg/g or more, more preferably 5 KOH mg/g or more, from the viewpoint of making the latter viscosity high enough to maintain a uniformly distributed state in the fiber base material. More preferably, it is 8KOHmg/g or more, and from the viewpoint of promoting thickening of the resin composition, it is preferably 25KOHmg/g or less, more preferably 20KOHmg/g or less, and even more preferably 16KOHmg/g or less.

The weight average molecular weight (Mw) of the unsaturated polyester resin (A) is preferably from the viewpoint of promoting the thickening rate of the resin composition and making the later viscosity high enough to maintain a uniformly distributed state in the fiber base. It is 5,000 or more, more preferably 7,000 or more, even more preferably 9,000 or more, and from the viewpoint of suppressing the decrease in viscosity due to moisture absorption of the resin composition and obtaining a resin composition with excellent viscosity stability after thickening, preferably 20,000 or less. Preferably it is 17,000 or less, more preferably 15,000 or less.

The number average molecular weight (Mn) of the unsaturated polyester resin (A) is preferably from the viewpoint of promoting the thickening rate of the resin composition and making the later viscosity high enough to maintain a uniformly distributed state in the fiber substrate. It is 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more. From the viewpoint of suppressing the decrease in viscosity of the resin composition due to moisture absorption and obtaining a resin composition with excellent viscosity stability after thickening, preferably 7,000 or less. Preferably it is 5,000 or less, more preferably 4,000 or less.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the unsaturated polyester resin (A) is not particularly limited, but it promotes the thickening rate and distributes the late viscosity uniformly in the fiber substrate. From the viewpoint of making the viscosity high enough to maintain the viscosity, it is preferably 15 or less, more preferably 10 or less, even more preferably 5 or less, and from the viewpoint of productivity, preferably 1 or more, more preferably It is 1.5 or more, more preferably 2 or more.

The content ratio (molar ratio) of the structural unit derived from diol (a1) and the structural unit derived from dibasic acid (a2) contained in the unsaturated polyester resin (A) is determined by dehydration condensation polymerization to form an unsaturated polyester resin of the desired molecular weight. From the viewpoint of controlling the thickening rate by obtaining ester, the ratio is preferably 40:60 to 60:40, more preferably 45:55 to 55:45, and even more preferably 50:50.

The content of the unsaturated polyester resin (A) in the resin composition is preferably 20 to 80 parts by mass, based on a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated group-containing monomer (B). Preferably it is 30 to 70 parts by mass, more preferably 40 to 65 parts by mass.

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

The content of the unsaturated polyester resin (A) in the resin composition is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 40 to 65 parts by mass, based on 100 parts by mass of the total amount of the resin composition. It is wealth.

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

<Dior (a1)>

Diol (a1) is a compound having two hydroxyl groups in one molecule. And diol (a1) contains 43 to 85 mol% of alkanediol (a1-1) with a molecular weight of 90 to 500.

In addition to alkanediol (a1-1), diol (a1) is alkanediol (a1-2), which is different from alkanediol (a1-1), but is different from alkanediol (a1-1) and alkanediol (a1-2). Other different diols may be included.

(alkanediol(a1-1))

Alkanediol (a1-1) is an alkanediol with a molecular weight of 90 to 500, and is a compound in which one hydrogen atom bonded to two carbon atoms of a hydrocarbon is replaced with a hydroxyl group. Alkanediol (a1-1) may be used alone or in combination of two or more types.

Since alkanediol (a1-1) does not contain polar groups or highly electronegative atoms other than the hydroxyl group in the molecule, its interaction with water molecules is small compared to polyoxyalkylene polyols, etc., which have ether bonds. . Therefore, by the resin composition containing the unsaturated polyester resin (A), which is a reaction product of alkanediol (a1-1) and dibasic acid (a2), the hygroscopicity of the resin composition is reduced, the viscosity change after thickening of the resin composition is suppressed, and the viscosity is increased. It has excellent stability.

When the molecular weight of alkanediol (a1-1) is 90 or more, the hygroscopicity of the resin composition can be reduced, and when it is 500 or less, ease of manufacture and productivity improve. The molecular weight of the alkanediol (a1-1) is preferably 95 or more, more preferably 100 or more, from the viewpoint of lowering the hygroscopicity of the resin composition, suppressing the viscosity change after thickening of the resin composition, and obtaining a resin composition with excellent viscosity stability. , more preferably 103 or more, and from the viewpoint of ease of manufacture and manufacturing cost, preferably 400 or less, more preferably 300 or less, even more preferably 250 or less.

Examples of alkanediol (a1-1) include 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-Butanediol, 2,3-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentane Diol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 1,2-nonanediol, 1,4 -Cyclohexanediol, 1,8-octanediol, 1,9-nonanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2- di(4-hydroxycyclohexyl)propane, and hydrides of bisphenol A, bisphenol F, and bisphenol S, etc.

Among these, from the viewpoint of obtaining a resin composition with excellent viscosity stability after thickening, alkanediols having 4 to 8 carbon atoms are preferable, such as 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol. , the hydride of bisphenol A is more preferable, and 2,2-dimethyl-1,3-propanediol is preferable from the viewpoint of availability and production cost.

The content of alkanediol (a1-1) in diol (a1) lowers the hygroscopicity of the resin composition relative to 100 mol% of diol (a1), suppresses the viscosity change after thickening of the resin composition, and provides a resin composition with excellent viscosity stability after thickening. From the viewpoint of obtaining, it is 43 mol% or more, preferably 45 mol% or more, and more preferably 48 mol% or more. In addition, from the viewpoint of suppressing the precipitation of crystals such as low molecular weight substances and unreacted raw materials when synthesizing the unsaturated polyester resin (A) and further improving the impregnation of the resin composition into the fiber base material, 85 mol% Below, preferably 80 mol% or less, more preferably 75 mol% or less.

The total content of alkanediol (a1-1) and alkanediol (a1-2) described later in diol (a1) lowers the hygroscopicity of the resin composition relative to the total amount of 100 mol% of diol (a1), and the amount of alkanediol (a1-2) after thickening of the resin composition decreases. From the viewpoint of suppressing viscosity change and obtaining a resin composition with excellent viscosity stability after thickening, the content is preferably 70 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more, and even more preferably 100 mol% or more. It is mol%.

(alkanediol(a1-2))

Alkanediol (a1-2) is an alkanediol different from alkanediol (a1-1), and does not include alkanediols with a molecular weight of 90 to 500.

The molecular weight of the alkanediol (a1-2) is preferably 60 or more, more preferably 65 or more, and still more preferably 70 or more from the viewpoint of viscosity stability after thickening of the resin composition, and from the viewpoint of ease of manufacture and manufacturing cost. , Preferably it is 85 or less, more preferably 80 or less, and even more preferably 78 or less.

Examples of alkanediol (a1-2) include ethylene glycol and propylene glycol.

Among these, propylene glycol is more preferable from the viewpoint of viscosity stability after thickening of the resin composition.

The content of alkanediol (a1-2) in diol (a1) is based on 100 mol% of diol (a1), based on the precipitation of crystals such as low molecular weight substances and unreacted raw materials when synthesizing the unsaturated polyester resin (A). From the viewpoint of suppressing this and further improving the impregnability of the resin composition into the fiber base, it is 15 mol% or more, preferably 20 mol% or more, and more preferably 25 mol% or more. In addition, from the viewpoint of further lowering the hygroscopicity of the resin composition, suppressing the viscosity change after thickening of the resin composition, and obtaining a resin composition with excellent viscosity stability after thickening, it is 57 mol% or less, preferably 55 mol% or less, more preferably 52 mol%. It is less than mol%.

(Other Dior)

Other diols are diols different from alkanediol (a1-1) and alkanediol (a1-2).

The molecular weight of other diols is preferably 70 or more, more preferably 85 or more, and even more preferably 100 or more from the viewpoint of manufacturing cost and good toughness of the cured product, and from the viewpoint of ease of manufacture and manufacturing cost, it is preferably is 500 or less, more preferably 300 or less, and even more preferably 150 or less.

Examples of other diols include polyoxyalkylene polyols such as diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol.

Among these, diethylene glycol and dipropylene glycol are more preferable from the viewpoint of manufacturing cost and improving the toughness of the cured product.

<Dibasic acid (a2)>

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

The dibasic acid (a2) may be used alone or in combination of two or more types.

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

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

The content of dibasic acid (a2-1) containing an ethylenically unsaturated group in dibasic acid (a2) is preferably 20 mol% or more from the viewpoint of mechanical strength of the cured product of the resin composition, based on 100 mol% of dibasic acid (a2). , more preferably 30 mol% or more, further preferably 40 mol% or more, even more preferably 45 mol% or more, preferably 80 mol% or less, more preferably 75 mol% or less, even more preferably is 70 mol% or less, and even more preferably 65 mol% or less.

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

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

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

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

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

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

[Monomer (B) containing ethylenically unsaturated group]

The ethylenically unsaturated group-containing monomer (B) is not particularly limited as long as it is a monomer having an ethylenically unsaturated group, but it is preferable to have a vinyl group, an allyl group, a (meth)acryloyl group, etc., and a vinyl group, a (meth)acryloyl group, etc. It is more desirable to have. The ethylenically unsaturated group-containing monomer (B) may be used alone or in combination of two or more types.

As the content of the ethylenically unsaturated group-containing monomer (B) increases, the increase in the initial viscosity of the resin composition tends to be suppressed, and the increase in the thickening rate and the ultimate viscosity after thickening tends to be suppressed. Additionally, the hardness, mechanical strength, chemical resistance, water resistance, etc. of the cured resin composition can be improved.

Examples of the ethylenically unsaturated group-containing monomer (B) having a (meth)acryloyl group include (meth)acrylic acid and (meth)acrylate. (Meta)acrylate may be monofunctional or polyfunctional.

Monofunctional (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, and t-butyl (meth)acrylate. Acrylate, 2-ethylhexyl, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate , Ethylene glycol monohexyl ether (meth)acrylate, Ethylene glycol mono2-ethylhexyl ether (meth)acrylate, Diethylene glycol monomethyl ether (meth)acrylate, Diethylene glycol monoethyl ether (meth)acrylate, Diethylene glycol monobutyl ether (meth)acrylate, Diethylene glycol monohexyl ether (meth)acrylate, Diethylene glycol mono2-ethylhexyl ether (meth)acrylate, dicyclopentenyl (meth)acrylate, DC Clopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, caprolactone-modified hydroxyethyl (meth)acrylate, allyl (meth)acrylate, etc. I can hear it.

Examples of polyfunctional (meth)acrylate include ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1, Alkanediol di(meth)acrylates such as 4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate; 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 poly Polyoxyalkylene glycol di(meth)acrylate such as tetramethylene glycol di(meth)acrylate, also trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, and pentaerythritol di(meth)acrylate. , trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol di. Acrylate monostearate, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethoxylated bisphenol A di(meth)acrylate, tris-(2-(meth)acryloxyethyl) Isocyanurate, etc. can be mentioned.

Among the ethylenically unsaturated group-containing monomers (B), those having a (meth)acryloyl group in addition to (meth)acrylate include acryloylmorpholine, 2-hydroxyethyl (meth)acrylamide, and 2-hydroxyethyl-N. -Methyl (meth)acrylamide, 3-hydroxypropyl (meth)acrylamide, etc. are mentioned. In addition to having a (meth)acryloyl group, examples of those having an ethylenically unsaturated group include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, Styrene compounds such as vinyl benzyl butyl ether, vinyl benzyl hexyl ether, and divinyl benzyl ether, vinyl acetate, diallyl fumarate, diallyl phthalate, and triallyl isocyanurate are included.

Among these, the ethylenically unsaturated group-containing monomer (B) is a styrene compound and (meta) from the viewpoints of control of the thickening rate of the resin composition, curability, production cost, and mechanical strength, heat resistance, chemical resistance, etc. of the cured product of the resin composition. Acrylates are preferred. More specifically, styrene, methyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate. At least one selected from the group consisting of polyethylene glycol, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate is preferable, and more preferably, it is styrene.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 20 parts by mass or more, more preferably 20 parts by mass or more, based on a total of 100 parts by mass of the unsaturated polyester resin (A) and the monomer (B) containing an ethylenically unsaturated group. Preferably it is 30 parts by mass or more, more preferably 35 parts by mass or more, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less.

If the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the initial viscosity of the resin composition can be easily reduced and workability becomes good. If the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, a resin composition with better thickening properties will be obtained.

The content of the ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more, based on 100 parts by mass of the total amount of the resin composition. and is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less.

If the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the initial viscosity of the resin composition can be easily reduced and workability becomes good. If the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, a resin composition with better thickening properties will be obtained.

[Compound (C)]

Compound (C) is at least one type selected from oxides and hydroxides of Group 2 elements, and may be used alone or in combination of two or more types. Compound (C) has the effect of thickening the resin composition over time by interacting with the carboxyl group or hydroxyl group of the unsaturated polyester resin (A).

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

Examples of hydroxides of Group 2 elements include magnesium hydroxide, calcium hydroxide, and barium hydroxide. Among them, from the viewpoint of thickening effect, versatility, cost, etc., one or more types are preferably selected from magnesium oxide and magnesium hydroxide.

The content of compound (C) in the resin composition is determined by mixing the unsaturated polyester resin (A) and the ethylenically unsaturated group-containing monomer from the viewpoint of making the late-stage viscosity of the resin composition high enough to maintain a uniformly distributed state in the fiber base. With respect to a total of 100 parts by mass of (B), the amount is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and still more preferably 0.1 part by mass or more, to suppress excessive thickening of the resin composition and to increase the thickening rate. From the viewpoint of further control, it is preferably 6 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less.

The content of compound (C) in the resin composition is preferably 0.01 with respect to 100 parts by mass of the total amount of the resin composition from the viewpoint of making the late-stage viscosity of the resin composition high enough to maintain a uniformly distributed state in the fiber base material. Parts by mass or more, more preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and from the viewpoint of suppressing excessive thickening of the resin composition and better controlling the thickening rate, preferably 6 parts by mass or less. Preferably it is 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less.

[Compound (D)]

Compound (D) is at least one selected from water and hydroxyl group-containing compounds. In addition, the content of compound (D) immediately after preparation of the resin composition (within 1 hour after adjustment) is as follows: unsaturated polyester resin (A), ethylenically unsaturated group-containing monomer (B), compound (D), and dicarboxylic acid ( It is 0.1 to 1 mass% with respect to the total of 100 mass% of E). Compound (D) is used for the purpose of controlling the thickening rate in response to changes in the thickening rate over time.

Examples of the hydroxyl group-containing compound include alcohols with a boiling point of 50°C or higher, such as benzyl alcohol, stearyl alcohol, and isostearyl alcohol. In addition, hydroxycarboxylic acids such as lactic acid, glycerin, polyols, (meth)acrylates containing a hydroxyl group, etc. can be mentioned. These may be used individually, or two or more types may be used together. Among these, from the viewpoint of availability, production cost, etc., water and alcohol are preferred, and water is more preferred.

The content of compound (D) in the resin composition is the sum of the unsaturated polyester resin (A), the ethylenically unsaturated group-containing monomer (B), the compound (D), and the dicarboxylic acid (E) immediately after preparation of the resin composition. With respect to 100 mass%, it is preferably 0.15 mass% or more, more preferably 0.2 mass% or more, preferably 0.7 mass% or less, and more preferably 0.4 mass% or less.

When the compound (D) is 0.1% by mass or more, it becomes easier to control the thickening rate of the resin composition and suppress excessive thickening. If the compound (D) is 1% by mass or less, the cured product of the resin composition will have better physical properties such as mechanical strength, toughness, heat resistance, and chemical resistance.

The content of compound (D) in the resin composition is preferably 0.15% by mass or more, more preferably 0.2% by mass or more, based on 100% by mass of the total amount of the resin composition immediately after preparation of the resin composition, and preferably 0.7% by mass. It is mass % or less, more preferably 0.4 mass % or less.

When the compound (D) is 0.1% by mass or more, it becomes easier to control the thickening rate of the resin composition and suppress excessive thickening. If the compound (D) is 1% by mass or less, the cured product of the resin composition will have better physical properties such as mechanical strength, toughness, heat resistance, and chemical resistance.

[Dicarboxylic acid (E)]

Dicarboxylic acid (E) is a compound that has two carboxyl groups in one molecule.

Since the dicarboxylic acid (E) has a lower molecular weight than the unsaturated polyester molecule, an interaction occurs between the carboxyl group or hydroxyl group of the unsaturated polyester resin (A) and the compound (C), and the resin composition deteriorates over time. Before thickening, an interaction occurs between the dicarboxylic acid (E) and the compound (C), which can suppress the increase in initial viscosity (within 5 hours after preparation of the resin composition).

Additionally, water is generated by interaction between the dicarboxylic acid (E) and the compound (C). This generated water promotes the thickening of the resin composition 24 to 48 hours after preparation, allowing the target viscosity to be reached quickly. In addition, when dicarboxylic acid (E) is included in the resin composition, the apparent molecular weight formed by the interaction of the unsaturated polyester resin (A), dicarboxylic acid (E), and compound (C) is lowered, It is possible to suppress the attained viscosity of the resin composition from becoming excessively high.

The dicarboxylic acid (E) may be used alone or in combination of two or more types.

The molecular weight and molecular structure of the dicarboxylic acid (E) are not particularly limited, but from the viewpoint of appropriate interaction between the unsaturated polyester resin (A) and the compound (C), the molecular weight is preferably 90 or more, From the viewpoint of controlling viscosity, it is preferably 500 or less, more preferably 400 or less, and even more preferably 300 or less.

If the molecular weight of the dicarboxylic acid (E) is 90 or more, a decrease in the achieved viscosity due to the inclusion of a low molecular weight compound is suppressed, and since the molecular mobility is not excessively high, it quickly interacts with the compound (C) and immediately Consumption is suppressed, and an increase in initial viscosity can be suppressed. In addition, if the molecular weight of the dicarboxylic acid (E) is 500 or less, the molecular mobility is significantly greater than that of the unsaturated polyester resin (A), so excessive thickening of the resin composition within 5 hours after adjustment can be further suppressed. Therefore, it is possible to further suppress the attained viscosity of the resin composition from becoming excessively high.

Examples of dicarboxylic acid (E) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 3-dodecenylsuccinic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. Commercially available products include HARIDIMER 250 (manufactured by Harima Chemicals Group). Among these, from the viewpoint of controlling the thickening rate, suppressing excessive thickening of the resin composition immediately after preparation of the resin composition (within 5 hours after adjustment), and further suppressing the ultimate viscosity of the resin composition from excessively increasing, oxalic acid , malonic acid, succinic acid, glutaric acid, adipic acid, 3-dodecenylsuccinic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and HARIDIMER 250 are preferred, and 3-dodecenylsuccinic acid and HARIDIMER 250 are more preferred.

The content of dicarboxylic acid (E) in the resin composition can further suppress excessive thickening of the resin composition immediately after preparation of the resin composition (within 5 hours after adjustment) and prevent the ultimate viscosity of the resin composition from becoming excessively high. From the viewpoint of further suppression, the amount is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and even more preferably 0.1 part by mass or more, relative to the total amount of 100 parts by mass of the resin composition. Additionally, as the content of dicarboxylic acid (E) in the resin composition increases, the hygroscopicity of the resin composition increases. Therefore, from the viewpoint of suppressing the hygroscopicity of the resin composition, it is preferably 5 parts by mass or less, more preferably 3.5 parts by mass or less. It is 2 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less.

[Light polymerization initiator (F)]

The resin composition of this embodiment may further contain a photopolymerization initiator (F).

As the photopolymerization initiator (F), known intramolecular cleavage type photopolymerization initiators can be used, and one or two or more types can be appropriately selected and used depending on the wavelength of the irradiated light from the light source used when curing the resin composition. .

The resin composition containing the photopolymerization initiator (F) is copolymerized with the unsaturated polyester resin (A) and the monomer (B) containing an ethylenically unsaturated group by irradiating a light source with an emission wavelength corresponding to the absorption wavelength of the photopolymerization initiator (F). It becomes a hardened product.

The photopolymerization initiator is not particularly limited as long as it generates radicals upon light irradiation, and examples include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; α-hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; Thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone. ; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone- Morpholines such as 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; Acylphosphine oxides such as phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide; Xanthons, etc. can be mentioned.

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

The content of the photopolymerization initiator (F) is not particularly limited, but is preferably 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated group-containing monomer (B) from the viewpoint of the mechanical strength of the cured product. 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.1 parts by mass or more, and from the viewpoint of manufacturing cost, preferably 15 parts by mass or less, more preferably 5 parts by mass or less, even more preferably It is 1.0 parts by mass or less.

The content of the photopolymerization initiator (F) is not particularly limited, but from the viewpoint of the mechanical strength of the cured product, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, with respect to 100 parts by mass of the total amount of the resin composition. It is preferably 0.1 parts by mass or more, and from the viewpoint of manufacturing cost, preferably 15 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1.0 parts by mass or less.

[Other ingredients]

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

[Viscosity of resin composition]

The initial viscosity of the resin composition at 25°C (viscosity within 5 hours after preparation of the resin composition) makes it easy to maintain the resin composition in the fiber base, from the viewpoint of obtaining a composite material in which the resin composition is uniformly impregnated into the fiber base. , preferably 0.1 Pa·s or more, more preferably 0.2 Pa·s or more, and still more preferably 0.5 Pa·s or more, to reduce impregnation defects of the resin composition into the fiber base material and to reduce the impregnation of the resin composition into the fiber base material. From the viewpoint of obtaining a uniformly impregnated composite material, preferably 30 Pa·s or less, more preferably 20 Pa·s or less, further preferably 15 Pa·s or less, even more preferably 10 Pa·s or less, particularly preferably is less than 5Pa·s.

The mid-term viscosity at 25°C (viscosity within 24 to 48 hours after preparation of the resin composition) is determined by dripping of the resin composition or shape of the composite material in the process of processing the composite material into a cylindrical shape, which will be described later. From the viewpoint of having adequate adhesion to prevent collapse and maintaining a uniformly contained state in which the resin composition is not distributed in the composite material, it is preferably 40 Pa·s or more, more preferably 50 Pa·s or more. Preferably it is 60 Pa·s or more, more preferably 70 Pa·s or more, and from the viewpoint of ease of processing the composite material into a cylindrical shape, preferably 1,200 Pa·s or less, more preferably 1,100 Pa·s or less, More preferably, it is 1,000 Pa·s or less, and even more preferably, it is 500 Pa·s or less.

The late-stage viscosity at 25°C of the resin composition (viscosity within 1 to 5 weeks from preparation of the resin composition) is sufficient for pipe rehabilitation in a state in which the resin composition is uniformly impregnated into the fiber base, and pipe rehabilitation is performed. From the viewpoint of providing strength, it is preferably 300 Pa·s or more, more preferably 400 Pa·s or more, even more preferably 450 Pa·s or more, and even more preferably 500 Pa·s or more, and the From the viewpoint of ease of operation, it is preferably 4,000 Pa·s or less, more preferably 3,000 Pa·s or less, further preferably 2,500 Pa·s or less, and even more preferably 2,000 Pa·s or less.

According to the resin composition of the present embodiment, since the stability of the viscosity in the later stage after thickening is excellent, it is possible to perform pipe rehabilitation construction by storing it for a certain period of time after manufacturing the lining material. Therefore, it becomes possible to secure inventory of the lining material, and it becomes possible to supply the lining material stably.

In one embodiment of the present invention, the resin composition of the present embodiment includes an unsaturated polyester resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C), a compound (D), and a dicarboxylic It contains an acid (E) and may contain other components in addition to these components, but from the viewpoint of obtaining the effect of the present invention, the unsaturated polyester resin (A) and the ethylenically unsaturated group-containing monomer (B) For a total of 100 parts by mass,

The unsaturated polyester resin (A) is preferably used in an amount of 20 to 80 parts by mass, more preferably in an amount of 30 to 70 parts by mass, and even more preferably in an amount of 40 to 65 parts by mass,

The ethylenically unsaturated group-containing monomer (B) is preferably used in an amount of 20 to 80 parts by mass, more preferably in an amount of 30 to 70 parts by mass, and even more preferably in an amount of 35 to 60 parts by mass,

The compound (C) is preferably used in an amount of 0.01 to 6 parts by mass, more preferably in an amount of 0.05 to 5 parts by mass, and even more preferably in an amount of 0.1 to 4 parts by mass,

The dicarboxylic acid (E) is preferably contained in an amount of 0.01 to 5 parts by mass, more preferably in an amount of 0.05 to 4 parts by mass, and even more preferably in an amount of 0.1 to 3.5 parts by mass.

[Method for producing unsaturated polyester resin (A)]

The unsaturated polyester resin (A) of the present embodiment is obtained by dehydration condensation polymerization of diol (a1), dibasic acid (a2-1) containing an ethylenically unsaturated group, and dibasic acid (a2-2) without an ethylenically unsaturated group. It can be manufactured.

For example, in a reaction vessel capable of heating and stirring, diol (a1), dibasic acid (a2-1) containing an ethylenically unsaturated group, and dibasic acid (a2-2) without an ethylenically unsaturated group are heated at 150 to 250°C, preferably. Can be prepared by reacting at 170 to 240°C, more preferably at 180 to 230°C for 8 to 15 hours.

In this embodiment, from the viewpoint of the mechanical strength of the cured product of the resin composition, the molar ratio of diol (a1) and dibasic acid (a2-2) not containing an ethylenically unsaturated group (diol (a1): dibasic acid not containing an ethylenically unsaturated group It is preferable to react so that the base acid (a2-2)) is 50:50 to 85:15, more preferably 55:45 to 80:20, and even more preferably 60:40 to 75:25.

The timing of mixing the diol (a1), the dibasic acid (a2-1) containing an ethylenically unsaturated group, and the dibasic acid (a2-2) without an ethylenically unsaturated group is not particularly limited and can be carried out by a known method. .

[Method for producing resin composition]

The resin composition in this embodiment is a mixture of an unsaturated polyester resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C), a compound (D), and a dicarboxylic acid (E). It can be manufactured by doing this.

In the production of a resin composition, in addition to the unsaturated polyester resin (A), the ethylenically unsaturated group-containing monomer (B), the compound (C), the compound (D), and the dicarboxylic acid (E), a photopolymerization initiator (D) and the above You may mix arbitrary components such as other components.

The mixing order is not particularly limited, but for example, vinyl ester resin (A) is mixed and dissolved in ethylenically unsaturated group-containing monomer (B), compound (C), compound (D), dicarboxylic acid (E) and A resin composition is obtained by adding and mixing the above optional components. From the viewpoint of facilitating control of the thickening rate, it is preferable to add compound (C) last.

There is no particular limitation on the mixing method, and for example, it can be performed using a disper, planetary mixer, kneader, etc. The kneading temperature is preferably 10 to 40°C, more preferably 15 to 30°C, and more preferably 20 to 30°C from the viewpoint of ease of mixing.

[composite material]

The composite material in this embodiment includes the above-described resin composition and a fiber base material.

As a composite material, for example, it is preferable to impregnate a fiber base with a resin composition and store it (cure) for a certain period of time to thicken it. This composite material has good shape retention, and a cured product (molded product) with excellent mechanical strength is obtained.

[Fiber base material]

From the viewpoint of mechanical strength, etc., fiber base materials include, for example, organic fibers such as amide, aranide, vinylon, polyester, and phenol, so-called reinforcing fibers such as carbon fiber, glass fiber, metal fiber, and ceramic fiber, and composites thereof. Fibers can be mentioned. Among these, aramid fiber, carbon fiber, and glass fiber are preferable, and glass fiber is more preferable from the viewpoints of strength, availability, price, etc. In particular, when photocuring a resin composition impregnated in a fiber substrate, glass fibers or polyester fibers having light transparency are preferable.

It is possible to use one type of fiber base material alone or in combination of two or more types.

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

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

From the viewpoint of the impregnability of the resin composition, the thickness of the fiber base is preferably 0.01 to 5 mm when it is a single layer, and when it is laminated in multiple layers, the total thickness is preferably 1 to 20 mm, more preferably 1 to 15 mm. . These fiber base materials may contain a known sizing agent in a known content.

The mechanical strength required for the cured product of composite material (fiber reinforced plastic: FRP) varies depending on the intended use, but for example, for composite materials using a glass fiber base material, the bending strength of FRP is generally preferably 100. ~1000MPa, more preferably 150~800MPa. Additionally, the bending elastic modulus of FRP is preferably 5 to 40 GPa, more preferably 7 to 35 GPa, and still more preferably 8 to 30 GPa.

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

The content of the resin composition in the composite material is not particularly limited, but is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 40 to 60% by mass from the viewpoint of mechanical strength. If the content of the resin composition is 20% by mass or more, appropriate flexibility can be provided to the lining material described later. If the content of the resin composition is 80% by mass or less, sufficient strength can be provided to the composite material containing the cured resin composition.

The content of the fiber base material in the composite material is preferably 5 to 80 mass%, more preferably 15 to 75 mass%, and even more preferably 25 to 75 mass%. If the content of the fiber base is 5% by mass or more, sufficient strength can be provided to the composite material containing the cured resin composition. If the content of the fiber base material is 80% by mass or less, appropriate flexibility can be provided to the lining material described later.

[Method for manufacturing composite materials]

The manufacturing method of the composite material may be appropriately selected depending on the purpose, and is not particularly limited.

A method of producing a composite material includes impregnating a fiber base with a resin composition and curing the resin composition at a certain temperature until it reaches the target viscosity to thicken the resin composition. Storage methods include bellows folding or winding the sheet-shaped composite material for storage.

When impregnating a fiber substrate with a resin composition, the resin composition may be impregnated into a fiber substrate on which an inner film and an outer film, which will be described later, are laminated on the surface, or a fiber substrate on which an inner film and an outer film are not laminated may be used. .

Additionally, when a fiber base material having an inner film and an outer film laminated on the surface is used, the resin composition is impregnated into the fiber base material through at least one of the inner film or the outer film.

There are no particular restrictions on the method of laminating the inner film and outer film, for example, a method of applying a liquid film composition to a fiber substrate and curing it to laminate, a method of laminating a film to a fiber substrate through an adhesive layer, or a method of laminating a film to a fiber substrate through an adhesive layer. A laminating method, etc. can be mentioned. The inner film and the outer film may be laminated using different methods, or may be laminated using the same method.

The inner film and the outer film may each independently be laminated before or after impregnating the fiber substrate with the resin composition. In addition, it may be performed before or after step 3 described later.

The fiber base material may be cylindrical, sheet-shaped, or tape-shaped.

When impregnating a fiber base material with the resin composition, the viscosity of the resin composition at 25°C is preferably 0.1 to 30 Pa·s. When the viscosity of the resin composition is within the above range, poor impregnation of the resin composition into the fiber base is reduced and it becomes easy to obtain a composite material in which the resin composition is uniformly impregnated into the fiber base. The viscosity of the resin composition at 25°C when impregnating the fiber substrate with the resin composition is more preferably 0.2 to 20 Pa·s, more preferably from the viewpoint of reducing impregnation defects and impregnating the resin composition more uniformly. Preferably it is 0.5 to 15 Pa·s, more preferably 0.5 to 10 Pa·s, and particularly preferably 0.5 to 5 Pa·s.

The time for impregnating the fiber base with the resin composition is preferably 0.5 to 24 hours, more preferably 1 to 10 hours, and even more preferably from the viewpoint of reducing impregnation defects and uniformly impregnating the resin composition into the fiber base. It is 1.5 to 5 hours.

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

[Lining material]

Lining material is used for repairing pipes such as existing pipes. Pipe repair is performed by arranging a lining material along the inner circumference of the inner surface of the pipe, pressing the lining material to the inner surface of the pipe, and then curing the resin composition contained in the lining material by irradiating light such as ultraviolet rays or visible light. In addition, in this specification, a lining material is disposed along the inner circumference of the inner surface of the pipe, the lining material is pressed against the inner surface of the pipe, and then the resin composition contained in the lining material is cured by irradiating ultraviolet rays or visible light, etc. They also say that they are constructing pipe rehabilitation.

The lining material is usually cylindrical and includes a composite material in which a fiber base material is impregnated with a resin composition.

From the viewpoint of ease of pipe rehabilitation construction, the lining material has an inner film as the innermost layer on the inner surface, an outer film as the outermost layer on the outer surface, and a composite material between the inner film and the outer film, or an outer film as the innermost layer on the inner surface, It is desirable to have an inner film as the outermost layer of the outer surface and a composite material between the inner film and the outer film. In addition, a lining material having an outer film as the innermost layer on the inner surface, an inner film as the outermost layer on the outer surface, and a composite material between the inner film and the outer film is preferably used in an inversion method in which the lining material is inverted and introduced into the inner surface of the pipe.

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

The lining material is preferably in a cylindrical shape with a diameter approximately equal to the diameter of the inner surface of the pipe. This improves the strength of the pipe after repair.

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

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

[Inner film]

As the inner film, for example, resin films such as polyethylene film, polypropylene film, and polyethylene terephthalate film can be used. The inner film needs to have transparency to the light irradiated from the light irradiation device during pipe rehabilitation construction. As a result, the lining material can be efficiently hardened, and pipe rehabilitation can be performed appropriately. Additionally, the inner film may be peeled off after curing the lining material.

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

[Outer Film]

As an outer film, a resin film can be used like the inner film. The outer film preferably has light-shielding properties. As a result, it is possible to suppress the curing of the resin composition in the lining material by light from the outside before construction of pipe rehabilitation.

In addition, during construction of pipe rehabilitation, the irradiated light can be suppressed from penetrating the lining material, and the lining material can be photocured efficiently. Examples of the outer film having light-shielding properties include a laminated film having a colored coating layer, such as yellow, between two transparent polyethylene films.

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

[Method for manufacturing lining material]

The manufacturing method of the lining material can be a conventionally known manufacturing method.

When using a composite material obtained by impregnating a resin composition into a fiber base material on which an inner film and an outer film are not laminated on the surface, it is preferable to include the following steps I and II.

When using a composite material obtained by impregnating a resin composition into a fiber base with an inner film and an outer film laminated on the surface, it is preferable to include the following process II.

(Process I)

Process I is a process of laminating the inner film and outer film on the surface of the fiber substrate.

There are no particular restrictions on the method of laminating the inner film and outer film, for example, a method of applying a liquid film composition to a composite material and curing it to laminate, a method of laminating a film to a composite material through an adhesive layer, or a method of laminating a film to a composite material. A laminating method, etc. can be mentioned. The inner film and the outer film may be laminated using different methods, or may be laminated using the same method.

The inner film and outer film may be performed before Process II, which will be described later, or may be performed after Process II.

(Process II)

Process II is a process of processing the composite material into a cylindrical shape. In addition, when a fiber base material already in a cylindrical shape is used, there is no need to perform step II, and it is carried out when a sheet-shaped or tape-shaped fiber base material is used.

In step II, the composite material is wound on a mandrel with a diameter approximately equal to the inner diameter of the pipe, and processed into a cylindrical shape by fixing it with a resin composition contained in the composite material.

Specifically, when the composite material is in the form of a sheet, after winding it on a mandrel, the two longitudinal sides are overlapped by about 1 to 10 cm and fixed with a resin composition contained in the composite material. Additionally, when the composite material is in the form of a tape, the composite material is wound in a spiral shape while overlapping about 1 to 10 cm, and the overlapping portion is fixed with a resin composition contained in the composite material.

In step II, if the resin composition-impregnated base material is wound with the inner film already placed on the mandrel, there is no need to laminate the inner film on the fiber base or composite material, and the mandrel can be easily removed after winding the composite material. It is desirable because it loses.

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

In process II, the overlapping portion of the composite material is fixed with a resin composition. Therefore, the viscosity of the resin composition contained in the composite material at this time is preferably one with appropriate adhesiveness, preferably 40 to 1,200 Pa·s, more preferably 50 to 1,100 Pa·s, even more preferably It is 60 to 1,000 Pa·s, more preferably 70 to 500 Pa·s.

If the viscosity of the resin composition contained in the composite material is 40 Pa·s or more, the resin composition has appropriate adhesiveness and can maintain a uniformly contained state without dripping or uneven distribution in the composite material. Additionally, if the viscosity of the resin composition is 1,200 Pa·s or less, it is easy to process it into a cylindrical shape.

When manufacturing composite materials and lining materials, a curing process may be included.

The curing process is a process for appropriately thickening the resin composition until it reaches a viscosity suitable for each process.

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

In one form of the present invention, it is preferable to provide a curing process for 6 hours to 3.5 days between impregnating the resin composition into the fiber base and performing pipe rehabilitation, more preferably 12 hours to 3.5 days. daily, more preferably 1 to 2 days.

In another form of the present invention, it is preferable to perform a curing process for 12 hours to 3 days immediately after impregnating the resin composition into the fiber base, more preferably 1 day to 2.5 days, and still more preferably 1.5 to 2 days. am.

In another form of the present invention, it is preferable to perform a curing process for 6 hours to 3.5 days between the production of the lining material and the construction of pipe rehabilitation, more preferably 12 hours to 3 days. Usually it is 1 to 2 days.

In another form of the present invention, it is possible to stabilize the supply of the lining material during construction by storing it for a certain period of time after manufacturing the lining material and securing a certain amount of inventory. The storage period at this time is, for example, within 3 months, preferably within 5 weeks.

[Gwan Rehabilitation]

The lining material obtained by using the resin composition according to this embodiment can be suitably used for pipe rehabilitation purposes.

Pipe rehabilitation is performed, for example, by placing a lining material along the inner circumference of the inner surface of the pipe, pressing the lining material to the inner surface of the pipe, and then photocuring the lining material by irradiating ultraviolet rays or visible light.

In order to facilitate transportation, the lining material is generally transported in a folded state to the pipe rehabilitation site, and during pipe rehabilitation construction, the folded lining material is introduced into the existing pipe and expanded. At this time, it is preferable that the resin composition in the lining material does not leak and hang or is unevenly distributed in the lining material, and that the lining material has appropriate flexibility. From that viewpoint, the viscosity of the resin composition in the lining material at the time of pipe rehabilitation construction at a temperature of 25°C is preferably 300 to 4,000 Pa·s, more preferably 400 to 3,000 Pa·s, even more preferably is 450 to 2,500 Pa·s, more preferably 500 to 2,000 Pa·s. Additionally, it is preferable that the viscosity at 25°C on the 2nd and/or 5th day after adjusting the resin composition is within the above range.

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

Since the diameter expansion operation of the lining material is performed by blowing air into the lumen of the lining material, end packers are provided at both ends of the lining material to seal the lining material. By blowing air from the end packer side of one end, the pressure in the lumen of the lining material increases and the diameter of the lining material is expanded so that it is in close contact with the inner peripheral surface of the existing pipe.

The enlarged lining material is irradiated with ultraviolet rays or visible light, etc., to the inner surface of the lining material by a mobile light irradiation device, so that the resin composition contained in the lining material is hardened, and the inner surface of the existing pipe is covered with the lining material in which the resin composition has been cured. . The radiation intensity by the light irradiation device is not particularly limited, but is preferably 0.0008 to 0.0046 W/mm2.

If the radiation intensity is 0.0008 W/mm2, the work efficiency is good and sufficient strength can be provided to the pipe. Additionally, if the radiation intensity is 0.0046 W/mm2 or less, excessive local irradiation of the inner surface layer of the lining material can be suppressed, and deterioration of the lining material and a decrease in strength can be suppressed.

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

From the viewpoint of work efficiency during pipe rehabilitation construction, at least one of ultraviolet and visible light irradiation devices having a peak wavelength in the wavelength range of 350 to 450 nm is preferable, and from the viewpoint of efficiently curing the resin composition, a gallium lamp is more preferable. desirable.

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

In one form of the present invention, the number of days elapsed from preparation of the resin composition to construction of pipe rehabilitation is preferably 1 to 4 days, more preferably 1 to 3 days, and still more preferably 1 to 2 days.

In another form of the present invention, the number of days elapsed from preparation of the resin composition to construction of pipe rehabilitation is preferably 2 to 7 days, more preferably 3 to 6 days, and even more preferably 4 to 5 days.

In another form of the present invention, it is also possible to store the lining material for a certain period of time after manufacturing it and secure a certain amount of inventory before performing pipe rehabilitation.

Example

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

[Synthesis of unsaturated polyester resin (A)]

Unsaturated polyester resin (A) was synthesized according to the following synthesis examples and comparative synthesis examples.

[Synthesis Example 1]

224.6 g of propylene glycol as diol (a1) (27.5 mol% relative to 100 mol% of diol (a1)), 2, in a 3L four-neck separable flask equipped with a thermometer, stirrer, inert gas inlet pipe, and reflux condenser. 810.5 g of 2-dimethyl-1,3-propanediol (neopentyl glycol) (72.5 mol% based on 100 mol% of diol (a1)), 472.6 isophthalic acid as dibasic acid (a2-2) not containing an ethylenically unsaturated group. g (26.5 mol% based on 100 mol% of diol (a1)), 356.6 g of terephthalic acid (20.0 mol% based on 100 mol% of diol (a1)), anhydrous dibasic acid (a2-1) containing an ethylenically unsaturated group 563.1 g of maleic acid (53.5 mol% based on 100 mol% of diol (a1)) was added, and a condensation reaction was performed at 215°C for 10 hours to obtain an unsaturated polyester resin (A1).

Table 1 shows the mixing amount of each component.

[Synthesis Examples 2 to 9, Comparative Synthesis Examples 1 to 6]

In Synthesis Example 1, Synthesis Examples 2 to 9 were synthesized using the raw materials and mixing ratios shown in Table 1, and Comparative Synthesis Examples 1 to 6 were synthesized in the same manner except that the raw materials and mixing ratios shown in Table 2 were used. In Synthesis Examples 2 to 9 and Comparative Synthesis Examples 1 to 5, unsaturated polyester resins (A2 to A9, AX1 to AX5) were obtained, but in Comparative Synthesis Example 6, precipitates precipitated and turbidity occurred, resulting in unsaturated polyester resins (A2 to A9, AX1 to AX5). Resin was not obtained.

[Measurement evaluation of unsaturated polyester resin]

The unsaturated polyester resins (A1 to A9, AX1 to AX5) obtained in the above synthesis examples and comparative synthesis examples were measured and evaluated for the items shown below. These measurement and evaluation results are summarized in Tables 1 and 2 below.

Table 3 shows details of the mixture (measurement sample) containing the unsaturated polyester resin (A) obtained in each synthesis example.

<Sanga>

The acid value of the unsaturated polyester resin is based on JIS K6901:2008 “Partial acid value (indicator titration method)” and is the mass of potassium hydroxide required to neutralize the acid component contained in the unsaturated polyester resin (A1 to 9, AX1 to 5). was measured to determine the acid value of the unsaturated polyester resin (A1 to 9, AX1 to 5). In addition, the measurement sample used was a mixture (57% to 65% by mass of unsaturated polyester resin) obtained by diluting an unsaturated polyester resin with styrene, which is an ethylenically unsaturated group-containing monomer (B). The acid value of the unsaturated polyester resin was determined from the measured value of the measurement sample. “Auto Burette UCB-2000” (produced by Hiranuma Sangyo Co., Ltd.) was used as a titrator, and a mixed indicator of bromothymol blue and phenol red was used as an indicator.

<Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn)>

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the unsaturated polyester resin were measured under the following conditions by gel permeation chromatography (GPC) and obtained as standard polystyrene equivalent molecular weight.

·Device: “SHODEX (registered trademark) GPC-101” (Product of Showa Denko K.K.)

Column: “SHODEX (registered trademark) LF-804” (Product of Showa Denko K.K.)

・Detector: Difference refractometer “SHODEX (registered trademark) RI-71S” (Product of Showa Denko K.K.)

·Column temperature: 40℃

Sample: 0.2% by mass tetrahydrofuran solution of unsaturated polyester resin

·Developing solvent: tetrahydrofuran

·Flow rate: 1.0mL/min

The molecular weight distribution (Mw/Mn) was calculated from the values of number average molecular weight (Mn) and weight average molecular weight (Mw).

<Equilibrium water content (hygroscopicity)>

A mixture of unsaturated polyester resins (A1 to 9, AX1 to 5) diluted with styrene, an ethylenically unsaturated group-containing monomer (B), was placed in a bag of 20 × 20 cm polyethylene film (film thickness: 145 μm) (unsaturated polyester 145 g (60% by mass of resin, 40% by mass of styrene) was added, heat-compressed, and sealed. This was left standing in an environment of 25°C and 50% RH or in an environment of 25°C and 80% RH. Then, after 3 weeks, the equilibrium water content of the mixture was measured using a volumetric titration method using a Karl Fischer moisture meter shown below.

·Device: 「701 KF Titrino」 (Metrohm Japan Ltd. product)

·Karl Fischer reagent: “AQUAMICRON (registered trademark) titrant SS 3mg” (Mitsubishi Chemical Corp. product)

Dehydration solvent: chloroform/methanol = 3 volume%/1 volume%

[Manufacture of resin composition]

In the above synthesis examples and comparative synthesis examples, a resin composition was prepared using an unsaturated polyester resin.

[Example 1]

Mixture (1) was prepared by dissolving 54.74 parts by mass of unsaturated polyester resin (A1) in 44.63 parts by mass of styrene as an ethylenically unsaturated group-containing monomer (B). Additionally, 0.63 parts by mass of 3-dodecenylsuccinic acid as dicarboxylic acid (E) was dissolved in 0.63 parts by mass of styrene to prepare mixture (2).

Subsequently, 99.37 parts by mass of the mixture (1), 1.26 parts by mass of the mixture (2), 0.2 parts by mass of water as the compound (D), and phenyl bis (2,4,6-trimethylbenzoyl) as the photopolymerization initiator (F). Add 0.11 parts by mass of phosphine oxide and 0.11 parts by mass of 2,2-dimethoxy-2-phenylacetophenone, and mix for about 10 minutes at 2000 to 3000 rpm using a disper (high-speed disperser “HOMODISPER 2.5 type” manufactured by Primix Corporation). did. Additionally, as compound (C), 0.96 parts by mass (0.29 parts by mass in terms of magnesium oxide) of magnesium oxide (Magmicron MD-4AM-2, manufactured by MIKUNI COLOR LTD., estimated magnesium oxide content of 30% by mass) was added, and disper was added. and mixed at 2000 to 3000 rpm for about 1 minute to obtain a resin composition (X-1).

[Examples 2 to 16, Comparative Examples 1 to 10]

Resin compositions (X-2 to

In addition, details of the components used as compound (C) and compound (D) are shown below.

<Compound (C)>

· Magnesium hydroxide: “Magnesium hydroxide (deer grade 1)”, KANTO CHEMICAL CO., INC. Product, magnesium hydroxide content 100% by mass

<Compound (D)>

· 「HARIDIMER 250」: Harima Chemicals Group, Inc. product

[Measurement evaluation of resin composition]

The resin compositions (X-1 to X-16, Y-1 to Y-10) obtained in the above examples and comparative examples were measured and evaluated for the items shown below. The results of these measurement evaluations are summarized in Tables 6 and 7 below.

[Amount of moisture in resin composition containing compound (C)]

In the production of the resin composition, an unsaturated polyester resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C), a compound (D), a dicarboxylic acid (E), and photopolymerization. 1.5 g of the resin composition mixed with the initiator (F) was collected, and the moisture content in the resin composition was measured using the volumetric titration method using the same Karl Fischer moisture meter as the device that measured the moisture content in the unsaturated polyester resin.

[viscosity]

Immediately after adjustment, 500 g of the resin compositions (X-1 to . This was placed in a bag (410 mm × 280 mm, material: polyethylene, film thickness: 30 μm), sealed by heat compression, and left to stand in an environment of 25°C and 50% RH or in an environment of 25°C and 80% RH. Thereafter, the viscosity of the resin composition was measured 0 (immediately after adjustment), 3, 5, 24, 48, 168, 336, 504, and 840 hours after manufacture.

Regarding the resin compositions (Y-6 to Y-8), immediately after adjustment, they were placed in 500 mL metal cylindrical cans, covered with metal lids, and left to stand in an environment of 23°C and 50% RH. Thereafter, the viscosity of the resin composition was measured 0 (immediately after adjustment), 3, 5, 24, 48, 168, 336, 504, and 840 hours after manufacture. Depending on the viscosity range, the following two types of equipment were appropriately selected and measured at a temperature of 25°C.

(1) “RB 80 type viscometer” (Toki Sangyo Co., Ltd. product; Rotor No. 3 to 4)

According to the measured viscosity, the rotor used and the rotation speed were set as shown in Table 4 below.

(2) “HBDVE type viscometer” (EKO INSTRUMENTS Co., Ltd. product; T-bar spindle: T-A to T-D, rotation speed: 1 rpm)

According to the measured viscosity, the T-bar spindle shown in Table 5 below was used.

[Thickening properties, viscosity stability]

Regarding the viscosity of the resin composition, if the viscosity (initial viscosity) up to 5 hours after preparation of the resin composition is 0.1 to 30 Pa·s, the viscosity (mid-term viscosity) 24 to 48 hours after preparation of the resin composition is 40 to 1,200 Pa·s. In this case, the case where the viscosity (late viscosity) 168 to 840 hours after preparation of the resin composition is 300 to 4,000 Pa·s is set to “○” as the thickening property is good and the thickening speed is appropriate at the above time, and other than the above In the case of , “×” was set, and if there was no measurement data, it was set to “-”.

In addition, in the late viscosity (viscosity 168 to 840 hours after preparing the resin composition), after reaching the maximum viscosity, when the viscosity exceeds 50% from the maximum achieved viscosity and does not decrease (viscosity reduction rate of 50% or less), viscosity stability It is set as “○” because it is said to be excellent, and when the viscosity decreases by more than 50% from the maximum achieved viscosity, or when the thickening rate exceeds 50% and the thickening does not stop between 168 and 840 hours, the viscosity stability is said to be deteriorated. ×” was set. In addition, when the viscosity 168 hours after preparation of the resin composition was the maximum viscosity of the late viscosity, the viscosity was referred to as the maximum viscosity.

In addition, if all of the above evaluations are ○, it is assumed that it is a resin composition with good thickening properties, controlled thickening speed, and excellent viscosity stability after thickening, and the overall evaluation is set to “○”, and at least one × in the above evaluation is assumed to be If there was one, the overall evaluation was set to “×”.

As shown in Table 6, the resin compositions of Examples 1 to 16 had a controlled thickening rate and were excellent in viscosity stability after thickening. On the other hand, the resin compositions of Comparative Examples 1 to 10 did not have a controlled thickening rate and were not excellent in viscosity stability after thickening.

According to this embodiment, a resin composition with a controlled thickening rate and excellent viscosity stability after thickening is provided. Additionally, a composite material obtained by impregnating a fiber substrate with the resin composition, and a lining material containing the composite material are provided.

Claims (9)

An unsaturated polyester resin (A),
A monomer (B) containing an ethylenically unsaturated group,
Compound (C) which is at least one type selected from oxides and hydroxides of group 2 elements,
Compound (D) which is at least one type selected from water and hydroxyl group-containing compounds,
A resin composition containing dicarboxylic acid (E),
The unsaturated polyester resin (A) is a reaction product of diol (a1) and dibasic acid (a2),
The diol (a1) contains 43 to 85 mol% of diol (a1-1), which is an alkanediol with a molecular weight of 90 to 500, based on 100 mol% of the diol (a1),
The dibasic acid (a2) includes a dibasic acid (a2-1) containing an ethylenically unsaturated group and a dibasic acid (a2-2) without an ethylenically unsaturated group,
The content of the compound (D) is based on a total of 100% by mass of the unsaturated polyester resin (A), the ethylenically unsaturated group-containing monomer (B), the compound (D), and the dicarboxylic acid (E). A resin composition of 0.1 to 1% by mass. According to claim 1,
The alkanediol (a1-1) is at least one resin selected from 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, and hydrogenated bisphenol A. Composition. The method of claim 1 or 2,
A resin composition wherein the unsaturated polyester resin (A) has a weight average molecular weight of 5,000 to 20,000. The method of claim 1 or 2,
The dibasic acid (a2) is composed of 20 to 80 mol% of the dibasic acid (a2-1) containing an ethylenically unsaturated group, based on 100 mol% of the dibasic acid (a2), and the dibasic acid (a2-) without an ethylenically unsaturated group. 2) A resin composition containing 20 to 80 mol%. The method of claim 1 or 2,
A resin composition wherein the compound (C) is at least one selected from magnesium oxide and magnesium hydroxide. The method of claim 1 or 2,
A resin composition further comprising a photopolymerization initiator (F). The method of claim 1 or 2,
For a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated group-containing monomer (B),
20 to 80 parts by mass of the unsaturated polyester resin (A),
20 to 80 parts by mass of the ethylenically unsaturated group-containing monomer (B),
0.01 to 6 parts by mass of the compound (C),
A resin composition containing 0.01 to 5 parts by mass of the dicarboxylic acid (E). A composite material comprising the resin composition according to claim 1 or 2 and a fiber base. A lining material for pipe rehabilitation comprising the composite material according to claim 8, an inner film, and an outer film.