Curable resin composition for lining material, lining material, and pipeline repair method using the same

Abstract

To provide a non-styrene curable resin composition for a lining material, with high strength and excellent flexibility.SOLUTION: A curable resin composition for a lining material, being the curable resin composition contained in the lining material for covering an inner wall surface of a pipeline, contains (A) an unsaturated polyester resin or a vinyl ester resin, (B) a tri- or higher functional (meth)acrylate monomer, and (C) a polymerization initiator.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable resin composition for a lining material for coating the inner wall surface of a pipeline, a lining material, and a pipeline repair method using the same.

Background Art

[0002] Pipelines such as sewer pipes are corroded and cracked due to long-term use, so it is necessary to repair them at a predetermined time. There are various repair methods, but as a general method, a method of coating the inner wall surface of a pipeline with a resin lining material is used from the viewpoints of repair effect and work efficiency. In this method, the inner surface of the structure is coated with the lining material before curing, and in this state, the curable resin composition contained in the lining material is cured by light irradiation or heating, thereby forming a resin rehabilitation pipe inside the existing pipeline.

[0003] Conventionally, as such a curable resin composition for a lining material, a curable resin composition containing a polymerizable resin such as an unsaturated polyester resin or a vinyl ester resin, styrene, and a polymerization initiator has been used.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Styrene has problems with odor and toxicity. In recent years, the demand for curable resin compositions for so-called non-styrene lining materials that do not contain styrene has been increasing, and they have actually been developed. However, when styrene is not included, there is a problem that the crosslink density (strength) after curing decreases. In addition, although the conventional curable resin composition for lining materials using styrene is excellent in strength, its flexibility is insufficient, and its performance against shaking caused by earthquakes and the like is insufficient.

[0006] Therefore, an object of the present invention is to provide a curable resin composition for a non-styrene lining agent that has high strength and excellent flexibility. Another object of the present invention is to provide a lining material containing this curable resin composition and a method for repairing a pipeline using the lining material.

Means for Solving the Problems

[0007] The above object is achieved by a curable resin composition for a non-styrene lining material contained in a lining material for covering the inner wall surface of a pipeline, (A) Unsaturated polyester resin or vinyl ester resin, (B) (Meth)acrylate monomer, (C) Polymerization initiator, and (D) which contains cellulose nanofibers having a number average fiber diameter of 1 to 1000 nm and an aspect ratio of 100 to 500, the content of the (B) (meth)acrylate monomer is 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) unsaturated polyester resin or vinyl ester resin , the (D) content of the cellulose nanofibers is 0.01 to 5% by mass based on the total weight of the curable resin composition for the non-styrene lining material.

[0011] Also, the above object is achieved by a lining material containing the curable resin composition for a lining material of the present invention. non-styrene

[0012] ​Furthermore, the above object is achieved by a pipeline repair method including a step of coating the inner wall surface of a pipeline with the lining material of the present invention and curing the curable resin composition in that state.

Effect of the Invention

[0013] According to the present invention, a curable resin composition for a non-styrene lining agent having a high crosslink density and excellent flexibility can be provided. Therefore, a pipeline repair method with good working efficiency and high reliability can be provided.

Embodiments for Carrying Out the Invention

[0014] Hereinafter, the present invention will be described in detail. The curable resin composition for a lining material of the present invention includes, as described above, (A) an unsaturated polyester resin or a vinyl ester resin, (B) a trifunctional or higher (meth)acrylate monomer, and (C) a polymerization initiator, and further includes, if necessary, (D) cellulose nanofibers and other additives. Hereinafter, each component will be described in detail.

[0015] [(A) Unsaturated Polyester Resin] Any unsaturated polyester can be used as the unsaturated polyester. For example, the unsaturated polyester is obtained by an esterification reaction of an α,β-unsaturated carboxylic acid and a polyhydric alcohol, followed by a glycol elimination reaction. In addition to the α,β-unsaturated carboxylic acid, a saturated carboxylic acid may also be included.

[0016] Generally, the ortho type can be subjected to a one-step reaction, the iso type can be subjected to a two-step reaction, and the tere type can be esterified after a transesterification reaction. The reaction temperature during esterification is preferably in the range of 190 to 220°C. In order to obtain a highly reactive ester, it is preferably 200°C or lower. Esterification can be advanced by a conventional method while flowing nitrogen gas.

[0017] The acid value of the resulting unsaturated polyester is not particularly limited, but for example, it is 5 to 30 mgKOH / g, and particularly preferably 15 to 30 mgKOH / g. Since the acid value is low, thickening with the thermoplastic resin powder is particularly effective. Also, the hydroxyl value of the resulting unsaturated polyester is not particularly limited, but for example, it is 10 to 200 mgKOH / g, more preferably 15 to 170 mgKOH / g, and particularly preferably 15 to 30 mgKOH / g.

[0018] Examples of α,β-unsaturated carboxylic acids include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, chloromaleic acid, or dimethyl esters thereof, etc. These α,β-unsaturated carboxylic acids may be used alone or in combination of two or more. Also, as saturated carboxylic acids, for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, het acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, adipic acid, sebacic acid, etc. can be used. These saturated carboxylic acids may be used alone or in combination of two or more.

[0019] On the other hand, examples of polyhydric alcohols include diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, alkylene oxide adducts of hydrogenated bisphenol A, etc., triols such as trimethylolpropane, and tetraols such as pentaerythritol, etc. These polyhydric alcohols may be used alone or in combination of two or more.

[0020] In addition, dicyclopentadiene can also be used, which is obtained by adding dicyclopentadiene and reacting it with the above α,β-unsaturated carboxylic acid, saturated carboxylic acid and polyhydric alcohol.

[0021] Moreover, a glycol decomposition product obtained by reacting recycled polyethylene terephthalate (hereinafter abbreviated as PET) and polyhydric alcohol at a high temperature can be used as a main raw material, and a PET-based unsaturated polyester obtained by reacting it with the above α,β-unsaturated carboxylic acid and polyhydric alcohol can also be used as the unsaturated polyester of the present invention.

[0022] (A) The number average molecular weight (Mn) of the unsaturated polyester is not particularly limited, but from the viewpoint of good handling viscosity, for example, it is in the range of 500 to 4000, and preferably in the range of 500 to 3000.

[0023] (A) The amount of the unsaturated polyester used is 30 to 70% by mass, preferably 35 to 65% by mass, based on the total weight of the curable resin composition of the present invention.

[0024] [(B) 3-functional or higher (meth)acrylate monomer] Any (B) 3-functional or higher (meth)acrylate monomer can be used in the present invention. Specifically, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol polyacrylate, ethoxylated polyglycerin polyacrylate, ethoxylated sorbitol polyacrylate, etc. can be mentioned. The (B) component preferably has 4 to 7 functional groups, more preferably 5 to 7 functional groups, and particularly preferably 5 to 6 functional groups.

[0025] (B) The content of the (meth)acrylate monomer having 3 or more functional groups is generally 0.1 to 25% by mass, preferably 5 to 15% by mass, based on the total weight of the curable resin composition of the present invention.

[0026] [(C) Polymerization initiator] The polymerization initiator may be a conventionally used one, and a photopolymerization initiator or an organic peroxide is used. As the photopolymerization initiator, a known ultraviolet polymerization initiator and / or a visible light polymerization initiator capable of curing a curable composite material even in a thick film can be used. Examples of the ultraviolet polymerization initiator include benzoin ether-based isopropyl benzoin ether, isobutyl benzoin ether, benzoin ethyl ether, benzoin methyl ether, benzyl ketal-based hydrocyclohexyl phenyl ketone, benzyldimethyl ketal, ketone benzophenone-based benzyl, methyl-O-benzoin benzoate, 2-chlorothioxanthone, methylthioxanthone, benzophenone-based benzophenone / tertiary amine, 2,2-diethoxyacetophenone, α-hydroxyisobutyl phenyl ketone, acylphosphine oxide, bisacylphosphine oxide, camphorquinone, etc. can be cited as representative examples. In the case of the photocurable tubular lining material used in the present invention, a coating method is adopted in which ultraviolet rays are inserted into the pipe interior and irradiated with ultraviolet rays for rapid curing. A photopolymerization initiator having absorption in the ultraviolet wavelength region from 250 nm to the visible wavelength region of 450 nm is preferred. 2,4,6-Trimethylbenzoyldiphenylphosphine oxide and benzyl methyl ketal are preferred and may be used alone or in combination.

[0027] In addition, as the visible light polymerization initiator, an acylphosphine oxide compound is effective. Examples thereof include bis(2,6-dichlorobenzoyl)-phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-ethoxyphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like. They may be used alone or in combination.

[0028] The amount of the photopolymerization initiator used is, for example, in the range of 0.01 to 5% by mass based on the total weight of the curable resin composition of the present invention.

[0029] Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; peroxy esters such as t-butyl peroxy octoate and t-butyl peroxy benzoate; dialkyl peroxides such as dicumyl peroxide; and diacyl peroxides such as lauroyl peroxide and benzoyl peroxide.

[0030] The amount of the organic peroxide used is, for example, in the range of 0.01 to 5% by mass based on the total weight of the curable resin composition of the present invention.

[0031] [(D) Cellulose nanofiber] Cellulose nanofiber refers to a biomass material obtained by refining wood fibers obtained from wood or the like to a nano-order size. The number average fiber diameter of the cellulose nanofiber is, for example, 1 to 1000 nm, preferably 5 to 500 nm, particularly 10 to 100 nm, and the aspect ratio is , for example 、1It is from 0 to 500. The cellulose nanofibers may be chemically modified or unmodified.

[0032] (D) The content of the cellulose nanofibers is generally 0.01 to 5% by mass, preferably 0.1 to 2% by mass, more preferably 0.1 to 1% by mass, and particularly preferably 0.1 to 0.5% by mass based on the total weight of the curable resin composition of the present invention.

[0033] [Other components] The resin composition used in the present invention can be used alone, but in consideration of the sick house problem and the regulation of styrene emission concentration by the Chemical Substances Release and Transfer Registration Law (PRTR Law), etc., it can also be used as a resin composition in which the following crosslinkable polymerizable vinyl monomers are used in combination to significantly reduce the crosslinkable polymerizable monomer with a high vapor pressure.

[0034] Examples of the crosslinkable polymerizable vinyl monomers include aromatic vinyl monomers such as styrene, vinyltoluene, and α-methylstyrene; and methacrylate-based monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate. These crosslinkable polymerizable monomers may be used alone or in combination of two or more. Generally, styrene is used. The blending amount of the crosslinkable polymerizable monomer is preferably 30% by mass (crosslinkable polymerizable monomer content rate of 23% or less) or less based on the total weight of the curable resin composition of the present invention.

[0035] The resin composition of the present invention is characterized by excellent drying property with only the components of the resin composition, but paraffin and / or waxes may be used in combination for the purpose of further improving the drying property.

[0036] Examples of the paraffin and / or waxes used in the curable resin composition of the present invention include paraffins such as paraffin wax and polyethylene wax; higher fatty acids such as stearic acid and 1,2-hydroxystearic acid. Paraffin wax is preferred. This paraffin and / or waxes are added for the purpose of air-blocking action during the curing reaction on the coating film surface and improvement of stain resistance. The addition rate is 0.1 to 5% by mass, preferably 0.2 to 2% by mass, based on the total weight of the curable resin composition of the present invention.

[0037] Examples of the inert particulate and / or granular inorganic aggregate materials used in the present invention include sand, silica powder, crushed rock, calcium carbonate, alumina powder, clay, silica flour, talc, glass powder, silica powder, aluminum hydroxide, silica sand, aluminum silicate, magnesium silicate, cement, and the like.

[0038] When using the inert particulate and / or granular inorganic aggregate materials, in the case of the tubular lining material obtained by impregnating the thermosetting resin composition into the fibrous cylindrical body, the amount used is preferably 30% by mass or less based on the total weight of the curable resin composition of the present invention. This is because when mixed in a large amount, the impregnation property decreases while the thermal conductivity increases, and the curing time with hot air or hot water from the heating heat source becomes longer. In addition, in the tubular lining material using the photocurable resin composition mixed with the inorganic aggregate material, since ultraviolet rays are less likely to penetrate, only a small amount of a specific filler can be mixed. In this case, the blending amount is preferably 10% by mass or less based on the total weight of the curable resin composition of the present invention.

[0039] Furthermore, glass flakes, mica flakes, etc. can be used as the scaly inorganic filler in the curable resin composition of the present invention. The average particle size of the scaly inorganic filler is generally in the range of 10 to 4000 μm. However, in order to maintain the impregnability of the resin composition into the fibrous cylindrical body and the anticorrosion durability, the average particle size is preferably 100 to 3000 μm, and the blending amount is preferably 10% by mass or less based on the total weight of the curable resin composition of the present invention. Note that it is preferable to use glass flakes as the scaly inorganic filler in terms of water absorption weight stability.

[0040] In addition, pigments, antioxidants, flow control agents, thixotropic agents, plasticizers, shrinkage inhibitors, defoaming agents, colorants, polymerization inhibitors, etc. can also be added to these thermosetting resin compositions or photocurable resin compositions as necessary.

[0041] [Lining material] The lining material containing the curable resin composition may have any configuration, but generally, a configuration in which these are laminated in the order of an inner protective film / fibrous reinforcing material such as glass fiber, etc. contained in the curable resin composition / outer protective film can be used. The shape of the lining material is appropriately formed into a sheet shape, a tubular shape, etc. according to the shape of the pipeline to be repaired. The weight ratio of the fibrous reinforcing material to the curable resin composition is preferably in the ratio of 4:6 to 6:4.

[0042] [Pipeline repair method] The method of repairing a pipeline using the lining material of the present invention can be carried out by a conventionally used method. For example, after introducing the lining material formed into a tubular shape of the present invention into the pipeline, air is introduced into the inside of the lining material, and the outer surface of the lining material and the inner surface of the pipeline are brought into close contact, and then the curable resin composition contained in the lining material is cured by irradiating electromagnetic waves such as heating or light including ultraviolet rays. Thereafter, post-treatment such as end treatment is performed to repair the pipeline. Examples of the pipeline to be repaired include main sewer pipes, attachment pipes, manholes, etc., and it is applicable not only to sewers but also to any aged pipeline.

[0043] According to the present invention, as described above, it is possible to provide a curable resin composition for a non-styrene lining agent having a high crosslinking density and excellent flexibility. Therefore, it is possible to provide a pipeline repair method with good working efficiency and high reliability.

Claims

1. A non-styrene curable resin composition for a lining material contained in a lining material for covering an inner wall surface of a pipeline, (A) an unsaturated polyester resin or a vinyl ester resin, (B) a (meth)acrylate monomer, (C) a polymerization initiator, and (D) cellulose nanofibers having a number average fiber diameter of 1 to 1000 nm and an aspect ratio of 100 to 500; the content of the (B) (meth)acrylate monomer is 0.1 to 25 parts by mass relative to 100 parts by mass of the (A) unsaturated polyester resin or vinyl ester resin, The content of the (D) cellulose nanofiber is 0.01 to 5 mass% based on the total weight of the non-styrene curable resin composition for lining material. A non-styrene curable resin composition for lining materials.

2. A lining material comprising the non-styrene curable resin composition for lining materials according to claim 1.

3. A method for repairing a pipeline, comprising the steps of covering an inner wall surface of a pipeline with the lining material according to claim 2 and curing the curable resin composition in that state.