JP2001062921A - Heat-curable resin composition for pipe lining material, pipe lining material and pipe lining construction method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make both high impregnation operating efficiency and thioxotropy compatible with each other by using an unsaturated polyester resin, a polymerizable monomer and a thioxotropy imparting agent as main components and making the blending contents of the unsaturated polyester resin and the polymerizable monomer satisfy a specific formula and further setting the viscosity and the thioxotropy of the resin and the monomer within a specific range. SOLUTION: When the blend content of an unsaturated polyester resin (a) is given as (a) pts.wt. and the blend content of a polymerizable monomer (b) is given as (b) pts.wt., both unsaturated polyester resin (a) and polymerizable monomer (b) are blended in such a content ratio as to meet the formula (1). Besides, the viscosity of the blend falls within the range of 0.5-8.0 Pa.s and the thioxotropy within the range of 1.2-4.4. In case a/(a+b) exceeds 0.70, the viscosity of a heat-curable resin composition tends to be excessively high, so that the composition shows the deterioration of the impregnation operating efficiency. On the other hand, in case the a/(a+b) is 0.50 or below, the thioxotropy imparting effects are hardly obtainable sufficiently and at the same time, the mechanical strength tends to be significantly undermined. Thus it is possible to achieve the high impregnation operating efficiency and the good thioxotropy which prevents the heat-curable resin composition from sagging.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting method in which a tubular pipe lining material is reversely inserted into a pipe by fluid pressure, and the pipe lining material is impregnated into the pipe while being pressed against the inner wall surface of the pipe. In a pipe lining method of heating and curing a thermosetting resin composition to line a lining pipe inside a pipe, a thermosetting resin composition used for a pipe lining material and a thermosetting resin composition are obtained. The present invention relates to a pipe lining material and a pipe lining method performed using the pipe lining material.

[0002]

2. Description of the Related Art In recent years, pipes mainly buried underground, such as gas pipes, water pipes, and sewer pipes, have been used for the purpose of reinforcing the strength of existing pipes, taking measures to prevent corrosion, preventing leakage and flooding, or improving flow rates. With the existing pipe inner surface impregnated with the liquid thermosetting resin composition being pressed against the inner peripheral wall of the pipe by fluid pressure or the like, the inside of the pipe lining material becomes the pipe wall side, while The inside of the pipe lining material is advanced so that the inside and outside surfaces of the pipe lining are reversed so that the outside of the lining material is on the inside surface side of the pipe, and the inverted pipe lining material is pressed against the existing pipe inside surface by fluid pressure and thermoset Tube lining method, which forms a synthetic resin tube on the inner surface of an existing tube by curing a conductive resin, has been spotlighted.

[0003] The outline of the steps of the reversing pipe lining method will be described in order. First, a flexible film layer is provided on the outside corresponding to the entire inner diameter of the existing pipe, and a felt, woven or non-woven fabric is provided on the inside. Make a tubular body. Next, the inside of this tubular body is depressurized for the purpose of easily uniformly impregnating the felt or the woven or nonwoven fabric with the curable resin composition mainly composed of the liquid curable resin and the curing agent and, if necessary, the curing accelerator. To remove air and gradually impregnate the curable resin composition over the entire length of the tubular body from one end of the tubular body to obtain a pipe lining material. Next, the pipe lining material is transported to the insertion port of the existing pipe while being kept in a frozen state or a refrigerated state, and is inverted while being in close contact with the existing pipe by a fluid pressure such as air or water pressure, and thereafter, hot air, hot steam, It is cured while being in close contact with the existing pipe using warm water or the like. Finally, the excess pipe lining material of the installed state-of-the-art pipe lining material stopper and insertion portion is cut, and the lined pipe is spliced to complete.

[0004] In this reversing method, when a pipe lining material is first produced, a curable resin composition is impregnated into a tubular fiber reinforced material. It is desirable that the viscosity of the curable resin composition be as low as possible. Next, the pipe lining material obtained by impregnating the curable resin composition is inverted by fluid pressure while being in close contact with the existing pipe, and is cured as it is using hot air, hot steam, hot water, or the like. If the curable resin composition impregnated in the fiber reinforced material in the pipe lining material that adheres to the inside of the pipe sags from the top or the side to the bottom,
The lining tube obtained after curing cannot obtain a predetermined thickness. For this reason, in order to prevent sagging, the curable resin composition is required to have high thixotropy. Further, the lining pipe formed inside the existing pipe obtained by curing the curable resin composition is at least a lining pipe formed on the existing pipe in consideration of breakage and erosion of the existing pipe, water leakage and flooding. It is desirable that the tube itself functions as a self-standing tube. Therefore, high mechanical properties are required for the lining pipe.

In addition, since the reversing method is mainly used for repairing sewer pipes and agricultural water pipes, the curable resin composition used for the pipes is required to be inexpensive. The above-mentioned required characteristics are preferably achieved by using an inexpensive curable resin composition.

[0006] In this inverted pipe lining method, UKW
ater Industry Engineering
and Operations Committee
Under the supervision of WRc plc, "Specific
station For Renovation Of
Gravity Sewers By Lining
With Cure-in place pipe
s (Guidelines for sewerage repair by lining using hardened pipes in-situ)), the specification describes the required quality of the material used for the reversing pipe lining material and the required performance of the pipe lining material. I have. However, in this specification, the quality control items and control width of mainly used materials,
It only describes the test methods for mechanical properties and chemical durability of pipe lining materials and the structural thickness design determined by the test results, and specifically mentions the properties and required values of the curable resin composition. Absent.

On the other hand, JP-A-2-188227 discloses a tubular pipe lining material in which a fiber layer impregnated with a photocurable resin composition is used as an innermost layer, and a light-impermeable film is used as an outermost layer. Manufacturing methods have been proposed. However, this method is not a solution to the above problem, but is aimed at shortening the construction time, and is different from the present invention.

Further, Japanese Patent Application Laid-Open Nos. Hei 3-281223, Hei 3-281224 and Hei 4-44830 are disclosed.
In the publication, for the purpose of extending the storable period of the pipe lining material and achieving quick curing at the same time, a main component mainly composed of an epoxy resin obtained by reacting a specific component and a curing agent having a specific chemical structure. An epoxy resin composition containing an agent has been proposed. However, the epoxy resin is expensive, and the epoxy resin composition in which a curing agent is mixed with the epoxy resin is difficult to handle. In addition, the use of a pipe lining material composed of an epoxy resin composition is generally limited to internal pressure pipes and water pipes, and an unsaturated polyester resin is used for sewer pipes and agricultural water pipes where the reverse pipe lining method is most often used. Compositions and vinyl ester resin compositions are the mainstream.

Japanese Patent Application Laid-Open No. 4-147834 proposes a resin composition comprising an unsaturated polyester resin or vinyl ester resin, a polymerizable monomer and an isocyanate compound. This was proposed in order to solve both the prevention of the exudation of the impregnated thermosetting resin composition when the pipe lining material is inverted in the existing pipe, and the reduction of the working time when impregnating the fiber layer. However, in practice, a method of controlling the viscosity of the thermosetting resin composition by adjusting the compounding amounts of the polymerizable monomer and the thixotropic agent has been adopted. There is no.

Further, Japanese Patent Application Laid-Open No. 6-297574 discloses an inner / outer double tube structure in which an inner layer and an outer layer are formed of a nonwoven fabric composed of yarns having specific thicknesses different from each other. A repair method using a pipe lining material impregnated with a curable resin mixed with a filler and having a high degree of viscosity and thixotropicity, and a non-woven fabric forming the outer layer impregnated with a curable resin mixed with a filler having a large particle size. Has been proposed. However, this proposal prevents the poor curing of the curable resin impregnated in the pipe lining material due to infiltration of groundwater when the pipe lining material is inverted and cured, and can be integrated with the branch pipe lining material. The purpose is to provide a tube lining material, which is different from the purpose of the present invention.

As described above, a tubular pipe lining material impregnated with a thermosetting resin composition is invertedly inserted into a pipe by fluid pressure, and the pipe lining material is pressed against the inner wall surface of the pipe. In the pipe lining method in which the thermosetting resin composition impregnated in the pipe is heated and cured to line the lining pipe inside the pipe, the thermosetting resin composition used for the pipe lining material is required. At present, little has been done on the performance and / or performance required of the pipe lining material.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art, and to provide good workability of impregnation of a curable resin composition when producing a pipe lining material, and to insert the pipe in an existing pipe by inversion. Thereafter, since the lining tube obtained by curing has a predetermined thickness, it is possible to provide a thermosetting resin composition for a pipe lining material which can achieve both good thixotropicity preventing sagging of the curable resin composition. It is in.

Another object of the present invention is to provide a thermosetting resin composition for a pipe lining material which has both good impregnation workability and thixotropic properties, is inexpensive and has excellent mechanical properties. is there.

Another object of the present invention is to provide a tube lining material having good thixotropic property for preventing sagging of a thermosetting resin composition and excellent mechanical properties.

Another object of the present invention is to provide a pipe lining material which can function as a self-supporting pipe and which becomes a lining pipe having excellent mechanical properties.

Another object of the present invention is to provide a pipe lining method capable of manufacturing the above-mentioned lining pipe.

[0017]

The present invention comprises an unsaturated polyester resin (a), a polymerizable monomer (b) and a thixotropic agent (c) as essential components. When the compounding amount is a part by weight and the compounding amount of the polymerizable monomer (b) is b part by weight, the unsaturated polyester resin (a) and the polymerizable monomer (b) are represented by the following formula (1). It is blended in a satisfactory ratio and has a viscosity of 0.5 to 8.0.
Pa · s, and the degree of fluctuation is 1.2 to 4.4.
And a thermosetting resin composition for a pipe lining material. 0.50 ≦ a / (a + b) ≦ 0.70 (1) The unsaturated polyester resin (a), which is an essential component of the thermosetting resin composition for a pipe lining material of the present invention, comprises α, β- Ethylenically unsaturated dibasic acid (I) and terephthalic acid (I
An unsaturated polyester resin obtained by reacting a polybasic acid component containing I) as an essential component with a polyhydric alcohol component containing neopentyl glycol (III) and ethylene glycol (IV) as essential components, wherein α, The molar amount of β-ethylenically unsaturated dibasic acid (I) is I, the molar amount of terephthalic acid (II) is II, and neopentyl glycol (I
II) molar amount of III, ethylene glycol (IV)
Is preferably obtained by reacting at a ratio satisfying all of the following formulas (2) to (4), where IV is the molar amount of IV. 0.30 ≦ II / (I + II) ≦ 0.60 (2) 0.10 ≦ III ≦ 0.80 (3) 0.30 ≦ IV ≦ 0.60 (4) In the thermosetting resin composition for a pipe lining material of the present invention, the cured product preferably has a tensile elongation in the range of 3.0 to 6.0%.

Further, the thermosetting resin composition for a pipe lining material of the present invention preferably contains calcium carbonate and / or aluminum hydroxide as a filler.

The present invention also relates to a pipe lining material obtained by impregnating a thermosetting resin composition into a tubular body having a fiber reinforced material made of a fibrous woven or nonwoven fabric or a mixture of both.

Further, the present invention relates to a pipe lining material characterized in that the cured product has a tensile elongation of 0.8% or more and a flexural modulus of 2.0 to 4.5 GPa.

Then, the pipe lining material is reversely inserted into the pipe by fluid pressure, and the thermosetting resin composition impregnated therein is cured by heating while pressing the pipe lining material against the inner wall surface of the pipe. The present invention relates to a pipe lining method characterized by lining a lining pipe inside a pipe.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermosetting resin composition used in the present invention contains an unsaturated polyester resin (a), a polymerizable monomer (b) and a thixotropic agent (c) as essential components. I do.

The unsaturated polyester resin (a), which is one of the essential components of the thermosetting resin composition, contains α, β-ethylenically unsaturated dibasic acid (I) and terephthalic acid (I) as polybasic acid components. An unsaturated polyester resin obtained by reacting a polybasic acid component containing II) as an essential component with a polyhydric alcohol component containing neopentyl glycol (III) and ethylene glycol (IV) as essential components, wherein α, The molar amount of β-ethylenically unsaturated dibasic acid (I) is I, the molar amount of terephthalic acid (II) is II, the molar amount of neopentyl glycol (III) is III, and the molar amount of ethylene glycol (IV) is When IV is used, a compound obtained by reacting at a ratio satisfying any of the following formulas (2) to (4) is preferable. 0.30 ≦ II / (I + II) ≦ 0.60 (2) 0.10 ≦ III ≦ 0.80 (3) 0.30 ≦ IV ≦ 0.60 (4) α Examples of the .alpha.,. Beta.-ethylenically unsaturated dibasic acid (I) include maleic acid, fumaric acid, and chlormaleic acid, and it is preferable to use maleic acid or fumaric acid. These can use the acid anhydride. As the polybasic acid component, a saturated dibasic acid other than terephthalic acid (II) can be used. Examples of saturated dibasic acids other than terephthalic acid (II) include isophthalic acid, phthalic acid, phthalic anhydride, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, oxalic acid, and malonic acid. Succinic acid, adipic acid, sebacic acid and the like and acid anhydrides thereof.
These are used in combination with terephthalic acid as necessary, but it is preferable to use isophthalic acid in combination with the pipe lining method because it aims at reinforcing the strength of existing pipes, countermeasures against corrosion, measures against water leakage and flooding, etc. .

As the polyhydric alcohol component, neopentyl glycol (III) and ethylene glycol (IV) are essential components, and other polyhydric alcohols can be used. Other polyhydric alcohols include diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, hydrogenated bisphenol A, and the like. . The polyhydric alcohol component is used in an amount of 1.0 mol per mol of the polybasic acid component.
It is desirable to use in the range of ~ 1.2 mol.

The unsaturated polyester resin (a), which is one of the essential components of the thermosetting resin composition of the present invention, comprises a saturated dibasic acid component, terephthalic acid (II), and a polyhydric alcohol component, ethylene glycol ( IV) can also be obtained from waste PET collected from a polyethylene terephthalate (hereinafter abbreviated as PET) bottle or the like. Specifically, the collected PET bottles are crushed into rice grains, washed,
The main component is a mixture of dried transparent pellets and pellets of each color.However, the remainder of the punching of floppy disks, the broken end of video or audio tape, packaging containers for foods and beverages such as confectionery, candy, chocolate, etc. Defective products generated in the inspection process are exemplified. These are used in such a manner that the repeating unit (I) represented by the following formula (I) of the waste PET is 1 mol and is blended at a ratio satisfying the above formula (2).

[0026]

Embedded image In practice, a predetermined amount of waste PET having the repeating unit (I) represented by the formula (I) is set at 200 ° C. based on a known technique.
The melted state is maintained at ２270 ° C., and the above-mentioned polyvalent glycol is added thereto successively to carry out the glycol decomposition of the waste PET. In this glycol decomposition, terephthalic acid and ethylene glycol which are essential components of the unsaturated polyester resin (a) can be obtained at the same time, and can be used as it is when producing the unsaturated polyester resin (a).

The unsaturated polyester resin has a weight average molecular weight (determined in terms of standard polystyrene using gel permeation chromatography, hereinafter the same) of 8,000 to
It is preferably in the range of 50,000,
More preferably, it is in the range of 00 to 45,000. Further, the acid value is preferably in the range of 5 to 35 KOH mg / g, and more preferably in the range of 7 to 30 KOH mg / g.

The unsaturated polyester resin is used by dissolving it in the polymerizable monomer (b). Polymerizable monomer (b)
Examples thereof include aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, and t-butylstyrene; methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Alkyl acrylates such as alkyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, etc .; polyhydric alcohols such as neopentyl glycol dimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate Methacrylate, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipenta Multivalent methacrylic acid ester of an alcohol, such as Risuri hexaacrylate, diallyl phthalate, triallyl cyanurate, but and acrylonitrile, to use easy styrene available at low cost are common.

In the thermosetting resin composition for a pipe lining material of the present invention, the compounding amount of the unsaturated polyester resin (a) is a
When the amount of the polymerizable monomer (b) is set to b parts by weight, the unsaturated polyester resin (a) and the polymerizable monomer (b) satisfy the following formula (1). The viscosity is in the range of 0.5 to 8.0 Pa · s, and the thixotropic degree is in the range of 1.2 to 4.4. 0.50 ≦ a / (a + b) ≦ 0.70 (1) When a / (a + b) exceeds 0.70, the viscosity of the thermosetting resin composition becomes too high and the impregnation workability is poor. On the other hand, if it is less than 0.50, the effect of imparting thixotropic properties is not sufficiently obtained, and the mechanical properties are significantly reduced.

The thixotropic agent (c) is used as an essential component in the thermosetting resin composition for a pipe lining material of the present invention. As the thixotropic agent (c), known thixotropic agents such as silica powder, asbestos powder, hydrogenated castor oil and fatty acid amide can be used as they are, but silica powder is easily available and inexpensive. Most preferred. Specifically, Aerosil # 200 (trade name, manufactured by Nippon Aerosil Co., Ltd.)
And the like. The mixing ratio of the component (c) is 0.01 to 100 parts by weight of the total amount of the components (a) and (b).
It is preferred to be blended in a range of from 5 to 5 parts by weight,
More preferably, it is blended in the range of 3 to 3 parts by weight. When the amount is less than the above range, the effect of imparting thixotropic properties is not sufficiently obtained, and after the pipe lining material is invertedly inserted in the existing pipe, the thermosetting resin for curing the lining pipe having a predetermined thickness is obtained. The sagging of the composition cannot be sufficiently prevented. on the other hand,
If it is more than the range, the viscosity of the thermosetting resin composition becomes too high, and the impregnation workability becomes poor.

In the thermosetting resin composition for a pipe lining material of the present invention, if the viscosity and the thixotropic degree of the thermosetting resin composition are smaller than the above ranges, the impregnation workability is good, but the thixotropic property is not increased. The effect is not sufficiently obtained, and after the pipe lining material is invertedly inserted in the existing pipe, the lining pipe obtained by curing has a predetermined thickness, so that the sagging of the thermosetting resin composition cannot be sufficiently prevented. On the other hand, if the viscosity and thixotropic degree are larger than the above ranges, the impregnating workability becomes remarkably poor. A more preferable range of the viscosity is 1.0 to 6.0 Pa · s, and a more preferable range of the thixotropic degree is 1.2 to 4.0.

The cured product of the thermosetting resin composition of the present invention comprises
It preferably has a tensile elongation in the range of 3.0 to 6.0%. The cured product can be obtained, for example, as follows. A resin composition was prepared by adding 4.0 g of benzoyl peroxide as a curing catalyst to 400 g of the thermosetting resin composition of the present invention, and a 3 mm-thick spacer was placed between two metal plates coated with a 35 cm square polyester film. Inject into the sandwiched mold. This is put into a drier and post-cured at 80 ° C. for 2 hours and further at 120 ° C. for 2 hours to produce a cured product.

The tensile elongation of the cured product can be determined, for example, by cutting the cured product of the thermosetting resin composition into predetermined shapes and dimensions.
It is measured at 23 ° C. according to JIS K7113 “Plastic tensile test method” or JIS K7162 “Tensile property test method”. If the tensile elongation of the cured product is less than the above range, cracks are likely to occur in the lining pipe formed inside the existing pipe after curing the thermosetting resin composition impregnated in the pipe lining material,
On the other hand, if the tensile elongation is larger than the above range, the mechanical properties are reduced, and it is difficult to obtain a lining pipe having excellent functions as a self-standing pipe.

[0034] The thermosetting resin composition of the present invention may further contain calcium carbonate and / or aluminum hydroxide as a filler. Commercial products of calcium carbonate include Super S, Super SS, Super SSS, Super 4S, Super # 1500, Super # 1700, Super # 2000 (manufactured by Maruo Calcium Co., Ltd., trade name), NS # 100, NS # 200, N
S # 400, NS # 600, NS # 1000, NS # 3
000, S-Lite1200, SS # 30, SS # 5
0, SS # 80 (trade name, manufactured by Nitto Powder Chemical Co., Ltd.),
Escalon # 100, Escalon # 200, Escalon # 400, Escalon # 1500, Escalon # 200
0, Escalon # 2200 (trade name, manufactured by Sankyo Seiko KK). Commercially available aluminum hydroxides include A-30, A-30F, A-325, and A-325.
315, A-308, A-305, C-31, C-3
3, C-331, C-333 (Alcoa Chemical Co., Ltd.
(Product name), B103, B153, B303, B703,
BW53, BW153, BW103 (trade name, manufactured by Nippon Light Metal Co., Ltd.), H-31, H-32, H-42, H-
43, H-100, H-210, H-310, H-32
0 (made by Showa Denko KK). These can be used alone or in combination. These compounding ratios are determined according to the unsaturated polyester resin (a) of the present invention,
5-5 parts per 100 parts by weight of the total amount of the thermosetting resin composition comprising the polymerizable monomer (b) and the thixotropic agent (c).
It is preferred that the compounding be carried out within a range of 0 parts by weight,
More preferably, it is blended within the range of 0 parts by weight. When the mixing ratio is larger than the above range, the mechanical properties are good, but the impregnating workability is remarkably reduced. On the other hand, when the mixing ratio is smaller than the above range, the mechanical properties due to the inclusion of the filler are included. It is difficult to obtain the effect of improvement.

In curing the thermosetting resin composition of the present invention, a curing catalyst or a curing catalyst and a curing accelerator are used.

As the curing catalyst, a heat curing agent which starts a curing reaction at a specific temperature, a curing accelerator which starts a redox reaction with a combination of a curing accelerator containing an organometallic compound or metal or a tertiary amine, and Is mentioned. As a thermosetting agent which initiates a curing reaction at a specific temperature, in particular, 80
A thermosetting agent which initiates a curing reaction even at a temperature lower than 0 ° C. is preferable. For percarbonates, Bis- (4-t-butylcyclohexyl) peroxydicarbonate, di-2-methoxyethylperoxydicarbonate, di-3-methoxy Butyl peroxy dicarbonate, di-2-methylhexyl peroxy dicarbonate, di-isopropyl peroxy dicarbonate, and alkyl peresters include 1,1,3,3-tetramethylbutyl peroxy neodecane, α- Cumene peroxy neodecaneate,
t-butyl peroxyneodecanate, t-hexylperoxyneodecanate, t-butylperoxypivalate, t-hexylperoxypivalate, 1,1,
3,3-tetramethylbutyl peroxydi-2-ethyl hexanate, t-hexyl peroxy-2-ethyl hexanate, t-butyl peroxy-2-ethyl hexanate, t-butyl peroxy isobutyrate, 2,5
-Dimethyl-2,5-Bis- (2-ethylhexanoylperoxy) hexane, t-amylperoxy-2-
In ethyl hexanate and diacyl peroxides,
Isobutyroyl peroxide, Bis-3,5,5
-Organic peroxides such as trimethylhexanoyl peroxide and lauroyl peroxide. Examples of the curing agent that initiates a redox reaction in combination with an organometallic compound or a metal-containing curing accelerator or a tertiary amine include methyl ethyl ketone peroxide, acetylacetone peroxide, cumene hydroperoxide, and t-butyl peroxide. −3,5,5-
Organic peroxides such as trimethylhexanate, t-butylperoxydiisopropyl carbonate, t-butylperoxybenzoate, and benzoyl peroxide are exemplified. In the present invention, a thermosetting agent that initiates a curing reaction even at a temperature of less than 80 ° C. and a curing accelerator that initiates a redox reaction with a combination of an organometallic compound or a metal-containing curing accelerator or a tertiary amine are selected from each. If necessary, two or more kinds of thermosetting agents that initiate a curing reaction at a temperature lower than 80 ° C. may be selected and used, but Bis- (4-t-butylcyclohexyl) peroxy may be used. Dicarbonate and t-butylperoxy-2-ethylhexanate are preferred. If necessary, two or more curing agents that initiate a redox reaction in combination with an organometallic compound or a curing accelerator containing a metal may be selected and used, but cumene hydroperoxide may be used. Is most preferred. The amount of the curing agent used is preferably 0.1 to 5 parts by weight, and more preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the total amount of the unsaturated polyester resin (a) and the polymerizable monomer (b). More preferably, it is used within the range.

The most commonly used curing accelerators are organometallic compounds, for example, metal soaps (fatty acids such as acetic acid, octenoic acid and stearic acid or Mg, Ca and Z of naphthenic acid).
n, Al, V, Cr, Mn, Fe, Co, Ni, Pb,
Metal salts of metals such as Cu and Zr, particularly preferably cobalt salts and manganese salts, organic metal complexes (such as acetylacetone complexes of transition elements such as cobalt acetylacetonate and manganese acetylacetonate), tertiary amines ( N, N
-Dimethylaniline and the like). These curing accelerators are used in combination with a curing accelerator that initiates a redox reaction in combination with a curing accelerator containing an organometallic compound or metal or a tertiary amine. These may be used alone or in combination. The amount of the curing accelerator used is preferably 0.01 to 3 parts by weight, and more preferably 0.05 to 2 parts by weight based on 100 parts by weight of the total amount of the unsaturated polyester resin (a) and the polymerizable monomer (b). It is more preferable to use within the range.

The thermosetting resin composition for a pipe lining material of the present invention is used by adding a curing retarder or a thickening agent for adjusting the curing time, if necessary, such as molding conditions and required characteristics. be able to.

Examples of the curing retarder include hydroquinone, 2,6-di-t-butyl-methylphenol, methylhydroquinone, etc., and include those of the unsaturated polyester resin (a) and the polymerizable monomer (b). It is preferably 0.1 part by weight or less based on 100 parts by weight in total,
When used, it is preferable to use 0.001 part by weight or more.

As the thickener, a metal compound composed of a divalent metal oxide or hydroxide is used, and examples thereof include magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide. These are used alone or in combination. The amount of the thickener used is preferably 3 parts by weight or less based on 100 parts by weight of the total amount of the unsaturated polyester resin (a) and the polymerizable monomer (b). It is preferable to use more than one part.

The thermosetting resin composition for a pipe lining material of the present invention can be produced by impregnating a tubular body having a fiber reinforced material composed of a fibrous woven or nonwoven fabric or a mixture of both.

As the fiber reinforcing material, polyester fiber is the most common, but felt, cloth, nonwoven fabric, etc. of fibers such as acrylic fiber, vinylon fiber, carbon fiber, polyamide fiber, glass fiber and the like can be used. These types, the amount used, etc. can be selected according to the required properties and the like, the amount used is a thermosetting resin composition and, if necessary, a curing retarder, a filler, a thickener, Total amount 10
The amount is preferably 5 to 100 parts by weight with respect to 0 parts by weight.

A tubular pipe lining material impregnated with the thermosetting resin composition is reversely inserted into the pipe by fluid pressure, and the pipe lining material is impregnated into the pipe while being pressed against the inner wall surface of the pipe. In a pipe lining method in which the thermosetting resin composition thus obtained is heated and cured to line a lining pipe inside a pipe, a cured product of the pipe lining material has a tensile elongation of 0.8% or more, and 2. It preferably has a flexural modulus of 0 to 4.5 GPa, and the cured product of the pipe lining material has a tensile elongation of 1.0% or more and 2.5
More preferably, it has a flexural modulus of ~ 4.5 GPa. The cured product of the pipe lining material can be obtained, for example, as follows. 0.92 g of 6% cobalt octenoate as a curing accelerator and Bis- (4-t-) as a thermosetting agent were added to 920 g of the thermosetting resin composition for a pipe lining material of the present invention.
Butylcyclohexyl) peroxydicarbonate (9.2 g) and t-butylperoxy-2-ethylhexanate (4.6 g) as a curing agent for initiating a redox reaction in combination with an organometallic compound or a curing accelerator containing a metal. To prepare a thermosetting resin composition for a pipe lining material. Next, in a polyethylene film bag having a thickness of 100 μm, a size of 22 cm × 28 cm having a thickness of 9 mm and a weight per unit area of 0.2 g / cm ^2.
Polyester felt is put, and the thermosetting resin composition for the pipe lining material immediately after preparation is injected, and the inside of the polyethylene film bag is evacuated and defoamed using a vacuum pump, and the pipe lining is made on the polyester felt. A tube lining material is obtained by impregnating the thermosetting resin composition for a material and sealing the polyethylene film. The obtained tube lining material is sandwiched between two metal plates covered with a 35 cm square polyester film and fixed with a clamp. This is put into a drier, heated from room temperature to 60 ° C. at a rate of 20 ° C./hour, kept at 60 ° C. for 60 minutes, and then from 60 ° C. to 85 ° C. for 75 minutes (heating rate: 20 ° C.) / Hour), and finally hold at 85 ° C. for 60 minutes to produce a cured pipe lining material.

The tensile elongation of the cured product of the pipe lining material is determined, for example, by cutting the cured product of the thermosetting resin composition into a predetermined shape and dimensions, and JIS K7113 at 23 ° C.
"Plastic tensile test method" or JIS K7
162 "Test method for tensile properties". If the tensile elongation is less than the above range, cracks are likely to occur in the lining tube formed inside the existing tube after the thermosetting resin composition impregnated in the tube lining material is cured. The flexural modulus of the cured product of the pipe lining material can be determined, for example, by cutting the cured product of the thermosetting resin composition into a predetermined shape and dimensions, and applying JIS K71 at 23 ° C.
71 "Testing methods for plastic bending properties" or JI
It is measured according to SK7203 “Bending test method of hard plastic”. If the flexural modulus is smaller than the above range, the mechanical properties will be reduced, and it will be difficult to obtain a lining tube having an excellent function as a self-standing tube, while the flexural modulus is larger than the above range. Although the mechanical properties are good, cracks are likely to occur in the lining pipe formed inside the existing pipe after curing the thermosetting resin composition impregnated in the pipe lining material.

A pipe lining method for lining a pipe lining inside a pipe using a tubular pipe lining material having a fiber reinforcement obtained by impregnating the thermosetting resin composition for a pipe lining material of the present invention. The conditions such as the type and pressure of the fluid when the pipe lining material is inserted into the pipe by inversion in the pipe and pressed against the inner wall face of the pipe can be appropriately selected, and further, the pipe lining material is pressed against the inner wall face of the pipe. Molding conditions such as heating temperature and heating time when the thermosetting resin composition impregnated with the pipe lining material is heat-cured are determined by the above-described thermosetting agent and / or a curing accelerator containing an organometallic compound or a metal. It can be appropriately selected in consideration of the combination and amount of a curing agent that initiates a redox reaction in combination with a tertiary amine.

[0046]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 (Production of unsaturated polyester resin composition (UP-1)) 1322 g (0.35 mol) of terephthalic acid, 378 g (0.10 mol) of isophthalic acid, 1227 maleic anhydride
g (0.55 mol), 473 g neopentyl glycol
(0.20 mol), 965 g of diethylene glycol
(0.40 mol), 635 g of ethylene glycol (0.
45 mol) and 0.25 g of hydroquinone were charged into a 5,000 ml four-necked flask equipped with a thermometer, a stirring blade, an inert gas inlet tube, and a condenser, and heated to 225 ° C. under a nitrogen stream. Then, a dehydration-condensation reaction was performed by a usual method. When the acid value reached 26 KOH mg / g, the reaction temperature was lowered to 215 ° C., and the reaction was continued. The reaction was stopped when the acid value reached 22 KOHmg / g. To this, 0.25 g of hydroquinone was added to obtain an unsaturated polyester resin. The molecular weight of this product was determined in terms of standard polystyrene using gel permeation chromatography.
00.

Synthesis Example 2 (Production of unsaturated polyester resin composition (UP-2)) Using the same apparatus as in Synthesis Example 1, terephthalic acid 2125
g (0.60 mol), 354 g of isophthalic acid (0.10 mol
Mol), 627 g (0.30 mol) of maleic anhydride, 666 g (0.30 mol) of neopentyl glycol, 566 g (0.25 mol) of diethylene glycol, 662 g (0.50 mol) of ethylene glycol and 0.25 g of hydroquinone The mixture was charged in the same apparatus as in Synthesis Example 1, heated to 225 ° C. under a nitrogen stream, and subjected to a dehydration condensation reaction by a usual method. Acid value is 25KOHmg /
g, the reaction temperature was lowered to 215 ° C., and the reaction was continued. The reaction was stopped when the acid value reached 21 KOHmg / g. Hydroquinone 0.2
5 g was added to obtain an unsaturated polyester resin. Its weight average molecular weight was 21,500.

Synthesis Example 3 (Production of unsaturated polyester resin composition (UP-3)) In the same manner as in Synthesis Example 1, 778 g of terephthalic acid (0.
20 mol), 1838 g (0.80 mol) of maleic anhydride, 975 g (0.40 mol) of neopentyl glycol, 1118 g (0.45 mol) of diethylene glycol, 291 g (0.20 mol) of ethylene glycol and 0.25 g of hydroquinone The resulting mixture was charged into the same apparatus as in Synthesis Example 1, heated to 225 ° C. under a nitrogen stream, and subjected to a dehydration condensation reaction by a usual method. Acid value is 2
At 0 KOHmg / g, the reaction temperature was increased to 215
C., and the reaction was continued as it was. Acid value is 16KOHm
The reaction was stopped when g / g was reached. To this, 0.25 g of hydroquinone was added to obtain an unsaturated polyester resin. Its weight average molecular weight was 38,400.

Synthesis Example 4 (Production of unsaturated polyester resin composition (UP-4)) 1307 g (0.35 mol) of terephthalic acid, 374 g (0.10 mol) of isophthalic acid, 1213 of maleic anhydride
g (0.55 mol), 117 g of neopentyl glycol
(0.05 mol), 1431 g of diethylene glycol
(0.60 mol), 558 g of ethylene glycol (0.
40 mol) and 0.25 g of hydroquinone were charged into an apparatus similar to that of Synthesis Example 1 and mixed under a nitrogen stream.
The temperature was raised to 25 ° C., and a dehydration condensation reaction was performed by a usual method. When the acid value reached 28 KOH mg / g, the reaction temperature was lowered to 215 ° C., and the reaction was continued. The reaction was stopped when the acid value reached 20 KOHmg / g. To this, 0.25 g of hydroquinone was added to obtain an unsaturated polyester resin. Its weight average molecular weight is 2
It was 2,400.

Synthesis Example 5 (Production of unsaturated polyester resin composition (UP-5)) In the same manner as in Synthesis Example 1, 1,783 g of terephthalic acid
(0.50 mol), 1053 g of maleic anhydride (0.5
0 mol), 1898 g of neopentyl glycol (0.8
5 mol), 266 g (0.20 mol) of ethylene glycol and 0.25 g of hydroquinone
Charged in the same apparatus as in Synthesis Example 1, 225 ° C. under a nitrogen stream
, And a dehydration-condensation reaction was performed in a usual manner. When the acid value reached 27 KOH mg / g, the reaction temperature was lowered to 215 ° C., and the reaction was continued. Acid value is 20K
The reaction was stopped when OH mg / g was reached. to this,
By adding 0.25 g of hydroquinone, an unsaturated polyester resin was obtained. Its weight average molecular weight is 18,2
00.

Synthesis Example 6 (Production of unsaturated polyester resin composition (UP-6)) Terephthalic acid 1600 g (0.40 mol), maleic anhydride 1417 g (0.60 mol), neopentyl glycol 501 g (0.20 mol) Mol), 511 g (0.20 mol) of diethylene glycol, 971 ethylene glycol
g (0.65 mol) and 0.25 g of hydroquinone were charged into the same apparatus as in Synthesis Example 1, heated to 225 ° C. under a nitrogen stream, and subjected to a dehydration condensation reaction by a usual method. . When the acid value reached 25 KOHmg / g, the reaction temperature was lowered to 215 ° C, and the reaction was continued. The reaction was stopped when the acid value reached 20 KOHmg / g. To this, 0.25 g of hydroquinone was added to obtain an unsaturated polyester resin. Its weight average molecular weight was 14,000.

Synthesis Example 7 (Production of Unsaturated Polyester Resin Composition (UP-7)) A composition comprising 1412 g (0.40 mol) of isophthalic acid, 1548 g (0.70 mol) of neopentyl glycol and 0.25 g of hydroquinone Was placed in the same apparatus as in Synthesis Example 1, the temperature was increased to 235 ° C. under a nitrogen stream, and a dehydration condensation reaction was performed by a usual method. Acid value is 5KOHmg
/ G when the reaction was stopped.

To this, 1251 g of maleic anhydride (0.
60 mol), 789 g of diethylenelene glycol (0.
35 mol), and the temperature was raised again to 225 ° C. to carry out a dehydration condensation reaction. When the acid value reached 24 KOHmg / g, the reaction temperature was lowered to 215 ° C, and the reaction was continued. The reaction was stopped when the acid value reached 16 KOHmg / g. To this, 0.25 g of hydroquinone was added to obtain an unsaturated polyester resin. Its molecular weight was determined by gel permeation chromatography in terms of standard polystyrene and found to be 18,400 in weight average molecular weight.

Production Example 1 (Production of thermosetting resin composition (1)) The unsaturated polyester resin obtained in Synthesis Example 1 (UP-
1) 65 parts by weight were dissolved in 35 parts by weight of a styrene monomer, and 0.003 g of 2,6-di-t-butyl-4-methylphenol and 1.2 g of aerosil were added.
A thermosetting resin composition (1) was prepared. At this time, JI
The viscosity and thixotropic degree measured in accordance with SK6901 are as follows:
It was 3.6 Pa · s and 2.2.

Production Example 2 (Production of thermosetting resin composition (2)) In the same manner as in Production Example 1, 60 parts by weight of the unsaturated polyester resin (UP-1) obtained in Synthesis Example 1 was replaced with styrene monomer 40 The mixture was dissolved in parts by weight, and 0.003 g of 2,6-di-t-butyl-4-methylphenol and 0.6 g of Aerosil were further added to prepare a thermosetting resin composition (2). The viscosity and thixotropic degree at this time were 1.0 Pa · s and 1.2.

Production Example 3 (Production of thermosetting resin composition (3)) In the same manner as in Production Example 2, 60 parts by weight of the unsaturated polyester resin (UP-1) obtained in Synthesis Example 1 was replaced with styrene monomer 40 The mixture was dissolved in parts by weight, and 0.003 g of 2,6-di-t-butyl-4-methylphenol and 1.8 g of Aerosil were further added to prepare a thermosetting resin composition (3). The viscosity and thixotropic degree at this time were 5.0 Pa · s and 4.0.

Production Example 4 (Production of thermosetting resin composition (4)) In the same manner as in Production Example 1, 65 parts by weight of the unsaturated polyester resin (UP-1) obtained in Synthesis Example 1 was replaced with styrene monomer 35. The mixture was dissolved in parts by weight, and 0.003 g of 2,6-di-t-butyl-4-methylphenol was further added to prepare a thermosetting resin composition (4). The viscosity and thixotropic degree at this time were 1.8 Pa · s and 1.0.

Production Example 5 (Production of thermosetting resin composition (5)) In the same manner as in Production Example 1, 65 parts by weight of the unsaturated polyester resin (UP-1) obtained in Synthesis Example 1 was replaced with styrene monomer 35. The mixture was dissolved in parts by weight, and 0.003 g of 2,6-di-t-butyl-4-methylphenol and 1.8 g of Aerosil were added to prepare a thermosetting resin composition (5). The viscosity and thixotropic degree at this time were 10.2 Pa · s and 5.1.

Production Example 6 (Production of thermosetting resin composition (6)) In the same manner as in Production Example 1, 45 parts by weight of the unsaturated polyester resin (UP-1) obtained in Synthesis Example 1 was replaced with styrene monomer 55. The resulting mixture was dissolved in parts by weight, and 0.003 g of 2,6-di-t-butyl-4-methylphenol and 1.2 g of aerosil were added to prepare a thermosetting resin composition (6). At this time, the viscosity and the thixotropic degree were 0.4 Pa · s and 1.0.

Production Example 7 (Production of thermosetting resin composition (7)) In the same manner as in Production Example 1, 75 parts by weight of the unsaturated polyester resin (UP-1) obtained in Synthesis Example 1 was replaced with styrene monomer 25. The mixture was dissolved in parts by weight, and 0.003 g of 2,6-di-t-butyl-4-methylphenol and 1.2 g of aerosil were added to prepare a thermosetting resin composition (7). At this time, the viscosity and the degree of thixotropicity were 8.2 Pa · s and 1.2.

Production Example 8 (Production of thermosetting resin composition (8)) In the same manner as in Production Example 1, 65 parts by weight of the unsaturated polyester resin (UP-2) obtained in Synthesis Example 2 was replaced with styrene monomer 35. The mixture was dissolved in parts by weight, and 0.003 g of 2,6-di-t-butyl-4-methylphenol and 0.6 g of Aerosil were added to prepare a thermosetting resin composition (8). However, it was crystalline at room temperature and was solid.

Production Example 9 (Production of thermosetting resin composition (9)) In the same manner as in Production Example 1, 65 parts by weight of the unsaturated polyester resin (UP-3) obtained in Synthesis Example 3 was replaced with styrene monomer 35. The mixture was dissolved in parts by weight, and 0.003 g of 2,6-di-t-butyl-4-methylphenol and 1.2 g of aerosil were added to prepare a thermosetting resin composition (9). The viscosity and thixotropic degree at this time were 4.5 Pa · s and 1.6.

Production Example 10 (Thermosetting resin composition (10)
In the same manner as in Production Example 1, 65 parts by weight of the unsaturated polyester resin (UP-4) obtained in Synthesis Example 4 was dissolved in 35 parts by weight of styrene monomer, and 2,6-di-t-butyl was further dissolved. 0.003 g of -4-methylphenol and 1.2 g of aerosil were added to prepare a thermosetting resin composition (10). The viscosity and thixotropic degree at this time were 3.8 Pa · s and 1.3.

Production Example 11 (Thermosetting resin composition (11)
In the same manner as in Production Example 1, 65 parts by weight of the unsaturated polyester resin (UP-5) obtained in Synthesis Example 5 was dissolved in 35 parts by weight of styrene monomer, and 2,6-di-t-butyl was further dissolved. 0.003 g of -4-methylphenol and 1.2 g of aerosil were added to prepare a thermosetting resin composition (11). However, it was crystalline at room temperature and was solid.

Production Example 12 (Thermosetting resin composition (12)
In the same manner as in Production Example 1, 65 parts by weight of the unsaturated polyester resin (UP-6) obtained in Synthesis Example 6 was dissolved in 35 parts by weight of styrene monomer, and 2,6-di-t-butyl was further dissolved. 0.003 g of -4-methylphenol and 1.2 g of aerosil were added to prepare a thermosetting resin composition (12). The viscosity and thixotropic degree at this time were 3.0 Pa · s and 1.2.

Production Example 13 (Thermosetting resin composition (13)
In the same manner as in Production Example 1, 65 parts by weight of the unsaturated polyester resin (UP-7) obtained in Synthesis Example 7 was dissolved in 35 parts by weight of a styrene monomer, and 2,6-di-t-butyl was further dissolved. 0.003 g of -4-methylphenol and 1.2 g of aerosil were added to prepare a thermosetting resin composition (13). At this time, the viscosity and thixotropicity measured in accordance with JIS K6901 were 3.4 Pa · s and 2.0.

Example 1 (Production of Cured Resin A1, Tube Lining Material Resin Composition B1 and Tube Lining Material C1) 400 g of the thermosetting resin composition (1) obtained in Production Example 1
Then, 4.0 g of benzoyl peroxide was added as a curing agent to prepare a resin composition, and the mixture was poured into a mold in which a 3 mm-thick spacer was sandwiched between two metal plates covered with a 35 cm square polyester film. This is put into the dryer, 8
It was post-cured at 0 ° C. for 2 hours and further at 120 ° C. for 2 hours to produce a cured resin (A1).

Further, 0.92 g of 6% cobalt octenoate as a curing accelerator was added to 920 g of the thermosetting resin composition (1) obtained in Production Example 1, and a curing agent Parloyl TCP (trade name, manufactured by NOF Corporation) 9.2 g and Kayaester O-50
4.6 g (manufactured by Kayaku Akzo Co., Ltd.) was added to prepare a resin composition (B1) for a pipe lining material.

Next, a polyester felt having a thickness of 9 mm, a weight per unit area of 0.2 g / cm ^{2 and} a size of 22 cm × 28 cm was put into a 100 μm-thick polyethylene film bag. (B1) was injected. Next, using a vacuum pump, the resin composition for a pipe lining material (B1) is impregnated into a polyester felt while decompressing and defoaming the inside of a polyethylene film bag, and the polyethylene film is sealed. A lining material (C1) was obtained.

This pipe lining material (C1) was
A 9 mm-thick spacer was sandwiched between two metal plates covered with a corner polyester film and fixed with a clamp.
The fixed pipe lining material (C1) is put into a dryer so as to be vertical, and the temperature is raised from 15 ° C to 60 ° C for 135 minutes (heating rate: 20 ° C / hour) and maintained at 60 ° C for 60 minutes. Then, from 60 ° C. to 85 ° C. for 75 minutes (heating rate: 20
° C / hour) and finally hold at 85 ° C for 60 minutes,
The pipe lining material (C1) was cured to obtain a cured pipe lining material (D1). The thickness of the cured pipe lining material (D1) obtained at this time was 9 mm, and the thickness of the resin composition for a pipe lining material (B1) decreased due to sagging, and the resin pool at the bottom of the cured pipe lining material (D1) was reduced. I couldn't see it.

Example 2 (Production of cured resin A2, resin composition of pipe lining material B2, and pipe lining material C2) Except for using the thermosetting resin composition (2) obtained in Production Example 2, all procedures were performed. In the same manner as in Example 1, the cured resin (A
2) was produced.

A resin composition (B2) for a pipe lining material was prepared in the same manner as in Example 1 except that the thermosetting resin composition (2) obtained in Production Example 2 was used. And a pipe lining material (C2). Further, the pipe lining material (C2) was cured to obtain a cured pipe lining material (D2). The thickness of the cured pipe lining material (D2) obtained at this time was 9 mm, and the thickness of the resin composition for a pipe lining material (B2) was reduced by sagging, and the resin pool at the bottom of the cured pipe lining material (D2) was reduced. I couldn't see it.

Example 3 (Production of Cured Resin A3, Resin Composition B3 of Tube Lining Material and Tube Lining Material C3) Except for using the thermosetting resin composition (3) obtained in Production Example 3, all procedures were carried out. In the same manner as in Example 1, the cured resin (A
3) was produced.

A resin composition (B3) for a pipe lining material was prepared in the same manner as in Example 1 except that the thermosetting resin composition (3) obtained in Production Example 3 was used. And a pipe lining material (C3). Further, this pipe lining material (C3) was cured to obtain a cured pipe lining material (D3). The thickness of the cured pipe lining material (D3) obtained at this time was 9 mm, and the thickness of the resin composition for a pipe lining material (B3) decreased due to sagging, and the resin pool at the bottom of the cured pipe lining material (D3) was reduced. I couldn't see it.

Comparative Example 1 (Production of cured resin A4, resin composition of pipe lining material B4 and pipe lining material C4) Except for using the thermosetting resin composition (4) obtained in Production Example 4, all procedures were carried out. In the same manner as in Example 1, the cured resin (A
4) was produced.

A resin composition (B4) for a pipe lining material was prepared in the same manner as in Example 1 except that the thermosetting resin composition (4) obtained in Production Example 4 was used. And a pipe lining material (C4). Further, this pipe lining material (C4) was cured to obtain a cured pipe lining material (D4). The thickness of the cured pipe lining material (D4) obtained at this time was 7 mm, the thickness of the resin composition for a pipe lining material (B4) decreased due to sagging, and the resin accumulation at the bottom of the cured pipe lining material (D4). Was seen.

Comparative Example 2 (Production of Cured Resin A5, Pipe Lining Material Resin Composition B5, and Pipe Lining Material C5) Except for using the thermosetting resin composition (5) obtained in Production Example 5, all procedures were performed. In the same manner as in Example 1, the cured resin (A
5) was produced. Further, a resin composition for a pipe lining material (B5) was prepared in the same manner as in Example 1 except that the thermosetting resin composition (5) obtained in Production Example was used.
Next, a pipe lining material (C5) was obtained. Further, the pipe lining material (C5) was cured to obtain a cured pipe lining material (D5). The thickness of the cured pipe lining material (D5) obtained at this time was 9 mm, and the thickness of the resin composition for a pipe lining material (B5) was reduced due to sagging, and the resin pool at the bottom of the cured pipe lining material (D5) was reduced. I couldn't see it.

Comparative Example 3 (Production of cured resin A6, resin composition of pipe lining material B6 and pipe lining material C6) Except for using the thermosetting resin composition (6) obtained in Production Example 6, all procedures were carried out. In the same manner as in Example 1, the cured resin (A
6) was produced.

A resin composition (B6) for a pipe lining material was prepared in the same manner as in Example 1 except that the thermosetting resin composition (6) obtained in Production Example 6 was used. And a pipe lining material (C6). Further, the pipe lining material (C6) was cured to obtain a cured pipe lining material (D6). The thickness of the cured pipe lining material (D6) obtained at this time was 7 mm, and the thickness of the resin composition for a pipe lining material (B6) decreased due to sagging, and the resin accumulation at the bottom of the cured pipe lining material (D6). Was seen.

Comparative Example 4 (Production of Cured Resin A7, Resin Composition B7 of Tube Lining Material and Tube Lining Material C7) Except for using the thermosetting resin composition (7) obtained in Production Example 7, all procedures were carried out. In the same manner as in Example 1, the cured resin (A
7) was produced. Further, a resin composition for a pipe lining material (B7) was prepared in the same manner as in Example 1 except that the thermosetting resin composition (7) obtained in Production Example was used.
Next, a pipe lining material (C7) was obtained. Further, the pipe lining material (C7) was cured to obtain a cured pipe lining material (D7). The thickness of the cured pipe lining material (D7) obtained at this time was 7 mm, and the thickness of the resin composition for a pipe lining material (B7) was reduced by sagging, and the resin pool at the bottom of the cured pipe lining material (D) was reduced. I couldn't see it.

Comparative Example 5 (Production of cured resin A8, resin composition of pipe lining material B8 and pipe lining material C8) Except for using the thermosetting resin composition (8) obtained in Production Example 8, all procedures were carried out. In the same manner as in Example 1, the cured resin (A
8) was attempted, but could not be produced because the thermosetting resin composition (8) was solid at room temperature.

Further, the resin composition for a pipe lining material (B
Preparation of 8) and preparation of the pipe lining material (C8) and the cured product of the pipe lining material (D8) also failed.

Example 4 (Production of cured resin A9, resin composition of pipe lining material B9 and pipe lining material C9) Except for using the thermosetting resin composition (9) obtained in Production Example 9, all procedures were carried out. In the same manner as in Example 1, the cured resin (A
9) was produced.

A resin composition (B9) for a pipe lining material was prepared in the same manner as in Example 1 except that the thermosetting resin composition (9) obtained in the Production Example was used. A pipe lining material (C9) was obtained. Further, this pipe lining material (C9) was cured to obtain a cured pipe lining material (D9). The thickness of the cured pipe lining material (D9) obtained at this time was 9 mm, and the thickness of the resin composition for a pipe lining material (B9) decreased due to sagging, and the resin pool at the bottom of the cured pipe lining material (D9) was reduced. I couldn't see it.

Example 5 (Production of cured resin A10, resin composition of pipe lining material B10 and pipe lining material C10) Except for using the thermosetting resin composition (10) obtained in Production Example 10, In the same manner as in Example 1, a cured resin (A10) was produced.

A resin composition (B10) for a pipe lining material was prepared in the same manner as in Example 1 except that the thermosetting resin composition (10) obtained in the production example was used.
Next, a pipe lining material (C10) was obtained. Further, the pipe lining material (C10) was cured to obtain a cured pipe lining material (D10). The thickness of the cured pipe lining material (D10) obtained at this time was 9 mm, and the thickness of the resin composition for a pipe lining material (B10) decreased due to sagging, and the resin pool at the bottom of the cured pipe lining material (D10) was reduced. I couldn't see it.

Comparative Example 6 (Production of cured resin A11, resin composition of pipe lining material B11 and pipe lining material C11) Except for using the thermosetting resin composition (11) obtained in Production Example 11, all procedures were carried out. An attempt was made to produce a cured resin (A11) in the same manner as in Example 1, but the production was not possible because the thermosetting resin composition (11) was solid at room temperature.

Further, the resin composition for a pipe lining material (B1
The preparation of 1) and the production of the pipe lining material (C11) and the cured product of the pipe lining material (D11) also failed.

Example 6 (Production of cured resin A12, resin composition of pipe lining material B12 and pipe lining material C12) Except for using the thermosetting resin composition (12) obtained in Production Example 12, all procedures were carried out. In the same manner as in Example 1, a cured resin (A12) was produced.

A resin composition (B12) for a pipe lining material was prepared in the same manner as in Example 1 except that the thermosetting resin composition (12) obtained in Production Example 12 was used. And a pipe lining material (C12). Further, the pipe lining material (C12) was cured to obtain a cured pipe lining material (D12). The thickness of the cured pipe lining material (D12) obtained at this time was 9 mm, and the thickness of the resin composition for a pipe lining material (B12) decreased due to sagging, and the resin pool at the bottom of the cured pipe lining material (D12) was reduced. I couldn't see it.

Example 7 (Production of cured resin A10, resin composition of pipe lining material B10 and pipe lining material C10) Except for using the thermosetting resin composition (13) obtained in Production Example 13, all procedures were carried out. In the same manner as in Example 1, a cured resin (A13) was produced.

A resin composition (B13) for a pipe lining material was prepared in the same manner as in Example 1 except that the thermosetting resin composition (13) obtained in Production Example 13 was used. And a pipe lining material (C13). Further, this pipe lining material (C13) was cured to obtain a cured pipe lining material (D13). The thickness of the cured pipe lining material (D13) obtained at this time was 9 mm, and the thickness of the resin composition for a pipe lining material (B13) decreased due to sagging, and the resin pool at the bottom of the cured pipe lining material (D13) was reduced. I couldn't see it.

Table 1 shows the mixing ratio of the raw material compounds of the unsaturated polyester resin.

The tensile properties of the obtained cured resin products A1 to A13 except for the cured resin products A8 and A11 were examined. In addition, bending properties and tensile properties of the obtained cured pipe lining materials D1 to D13 excluding D8 and D11 were examined. Table 2 shows the results together with the a / b ratio.
Shown in The test method was as shown below.

Bending characteristics: According to JIS K7203,
A strength test of the cured product was performed using the heat-cured tube lining material.

Tensile properties: According to JIS K7113, a cured product was subjected to a strength test using a cured resin product after heating and a tube lining material.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

The thermosetting resin composition for a pipe lining material of the present invention has good workability of impregnating the curable resin composition at the time of manufacturing the pipe lining material, and hardens after inverted insertion in an existing pipe. Since the obtained lining tube has a predetermined thickness, it is possible to achieve both good thixotropicity that prevents sagging of the curable resin composition.

Further, the thermosetting resin composition for a pipe lining material of the present invention has both good impregnating workability and thixotropic properties, and is inexpensive and has excellent mechanical properties.

Further, the tube lining material and the thermosetting resin composition of the present invention have good thixotropic properties for preventing sagging and excellent mechanical properties.

Further, the pipe lining material of the present invention can provide a lining pipe having excellent mechanical properties capable of functioning as a self-standing pipe.

Further, the pipe lining method of the present invention can produce a lining pipe having excellent mechanical properties that can function as a self-standing pipe.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // B29K 67:00 105: 08 B29L 9:00 23:00 F term (reference) 2D063 EA07 4F211 AA24 AA24A AB07 AD16 AG03 AG08 SA14 SC03 SD04 SD23 SP12 4J002 AE052 CF221 DE148 DE238 DJ017 DJ027 EA046 EB126 EH076 EH146 EP017 ET006 EU186 FD010 FD018 FD140 FD150 FD156 FD202 FD207 FD330 FD332 FD337 GH00 GL00 4J038 BA202 FA191 FA041 FA061 FA041 FA041 FA041 FA04 JB12 KA07 KA08 MA15 NA11 NA23 PA19 PB06

Claims (7)

[Claims] 1. An unsaturated polyester resin (a), a polymerizable monomer (b) and a thixotropic agent (c) are essential components, and the compounding amount of the unsaturated polyester resin (a) is a part by weight. When the amount of the polymerizable monomer (b) is b parts by weight, the unsaturated polyester resin (a) and the polymerizable monomer (b) are compounded in such a ratio as to satisfy the following formula (1). A thermosetting resin for a pipe lining material, wherein the viscosity is in the range of 0.5 to 8.0 Pa · s and the degree of thixotropicity is in the range of 1.2 to 4.4. Composition. 0.50 ≦ a / (a + b) ≦ 0.70 (1) 2. An unsaturated polyester resin (a) comprising α,
a polybasic acid component having β-ethylenically unsaturated dibasic acid (I) and terephthalic acid (II) as essential components, neopentyl glycol (III) and ethylene glycol (I
An unsaturated polyester resin obtained by reacting a polyhydric alcohol component containing V) as an essential component, wherein the molar amount of α, β-ethylenically unsaturated dibasic acid (I) is I, terephthalic acid (II) Is II, the molar amount of neopentyl glycol (III) is III, and the ethylene glycol (I
When the molar amount of V) is IV, the following formulas (2) to (4)
2. The thermosetting resin composition for a pipe lining material according to claim 1, wherein the thermosetting resin composition is obtained by reacting at a ratio satisfying any one of the following. 0.30 ≦ II / (I + II) ≦ 0.60 (2) 0.10 ≦ III ≦ 0.80 (3) 0.30 ≦ IV ≦ 0.60 (4) 3. The thermosetting resin composition for a pipe lining material according to claim 1, wherein the cured product has a tensile elongation of 3.0 to 6.0%. 4. The composition according to claim 1, further comprising calcium carbonate and / or aluminum hydroxide as a filler.
The thermosetting resin composition for a pipe lining material according to any one of the above. 5. A tubular body having a fiber reinforcement comprising a fibrous woven or nonwoven fabric or a mixture of both.
4. A pipe lining material impregnated with the thermosetting resin composition for a pipe lining material according to any one of 4. 6. The pipe lining material according to claim 5, wherein the cured product has a tensile elongation of 0.8% or more and a flexural modulus of 2.0 to 4.5 GPa. 7. The pipe lining material according to claim 5, which is reversely inserted into the pipe by fluid pressure, and while the pipe lining material is pressed against the inner wall surface of the pipe, the pipe lining material is impregnated with the heat. A pipe lining method, wherein a curable resin composition is heated and cured to line a lining pipe inside a pipe.