Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G

Definitions

• the present invention relates to a thermosetting resin composition for pipe lining materials and its cured product.
• thermosetting rehabilitation method using lining materials made from styrene-based unsaturated polyester resin compositions and vinyl ester resin compositions is often used to repair deteriorated pipes in sewer systems, etc.
• the problem that the present invention aims to solve is to provide a resin composition for pipe lining materials that can produce a cured pipe lining material that has a long pot life, excellent fast curing properties, excellent workability (thixotropy), and excellent bending strength, tensile elongation, and heat resistance.
• thermosetting resin composition for pipe lining materials containing a resin component essentially consisting of a specific maleic acid-modified epoxy (meth)acrylate and an unsaturated monomer, a thixotropic agent, a thermally decomposable curing agent, and a curing accelerator can solve the above problems, and thus completed the present invention.
• the present invention relates to a thermosetting resin composition for pipe lining material, which contains a resin component (A) having as essential components a maleic acid-modified epoxy (meth)acrylate (A1) and an unsaturated monomer (A2), a thermally decomposable curing agent (B), and a curing accelerator (C), and is characterized in that the maleic acid-modified epoxy (meth)acrylate (A1) is a reaction product of a hydroxyl group of the epoxy (meth)acrylate (a1) and a carboxyl group of maleic acid (anhydride).
• the pipe lining material obtained from the thermosetting resin composition for pipe lining of the present invention has a long pot life, excellent fast curing properties, excellent thixotropy, and excellent bending strength, tensile elongation, and heat resistance, and can be used favorably for pipe rehabilitation of sewer pipes, water pipes, gas pipes, electric power pipes, etc.
• thermosetting resin composition for pipe lining of the present invention is a thermosetting resin composition for pipe lining containing a resin component (A) having as essential components a maleic acid modified epoxy (meth)acrylate (A1) and an unsaturated monomer (A2), a thermally decomposable curing agent (B), and a curing accelerator (C), and the maleic acid modified epoxy (meth)acrylate (A1) is a reaction product of a hydroxyl group of the epoxy (meth)acrylate (a1) and a carboxyl group of maleic acid (anhydride).
• a resin component (A) having as essential components a maleic acid modified epoxy (meth)acrylate (A1) and an unsaturated monomer (A2), a thermally decomposable curing agent (B), and a curing accelerator (C)
• the maleic acid modified epoxy (meth)acrylate (A1) is a reaction product of a hydroxyl group of the epoxy (meth)acrylate (a1) and a carboxyl group of
• (meth)acrylate refers to either or both of acrylate and methacrylate
• (meth)acrylic acid refers to either or both of acrylic acid and methacrylic acid
• (anhydride)maleic acid refers to either or both of maleic acid and maleic anhydride
• the epoxy (meth)acrylate (a1) is obtained, for example, by reacting an epoxy resin with (meth)acrylic acid, and has no epoxy groups but has (meth)acryloyl groups and hydroxyl groups.
• the epoxy resins include, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol fluorene type epoxy resins, and biscresol fluorene type epoxy resins, novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins, oxazolidone modified epoxy resins, and brominated epoxy resins of these resins, glycidyl ethers of phenols such as dipropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl ether of alkylene oxide adduct of bisphenol A, and glycidyl ether of polyhydric alcohols such as diglycidyl ether of hydrogenated bisphenol A, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-ethylenediaminetetraacetate
• epoxy resins include alicyclic epoxy resins such as 3,4-epoxycyclohexane, glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl-p-oxybenzoate, and dimer acid glycidyl ester, glycidyl amines such as tetraglycidyldiaminodiphenylmethane, tetraglycidyl-m-xylenediamine, triglycidyl-p-aminophenol, and N,N-diglycidylaniline, and heterocyclic epoxy resins such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate.
• alicyclic epoxy resins such as 3,4-epoxycyclohexane
• glycidyl esters such as diglycidyl phthalate, diglycidy
• bifunctional aromatic epoxy resins are preferred because they are superior in rehabilitating pipe strength and handling of the lining material, and in fluidity during the manufacture of the lining material, and bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferred. These epoxy resins can be used alone or in combination of two or more types.
• the epoxy equivalent of the epoxy resin is preferably 180 to 420 g/eq, more preferably 180 to 250 g/eq, because this improves the strength of the rehabilitated pipe, the ease of handling the lining material, and the fluidity during the manufacture of the lining material.
• the reaction between the epoxy resin and (meth)acrylic acid is preferably carried out at 60 to 140°C using an esterification catalyst.
• a polymerization inhibitor, etc. may also be used.
• the maleic acid modified epoxy (meth)acrylate (A1) is obtained by an ester reaction between the hydroxyl group of the epoxy (meth)acrylate (a1) and the carboxyl group of the maleic acid (anhydride). Since this improves the balance between the pot life and fast curing required for rehabilitating pipes, the molar ratio (OH/COOH) of the hydroxyl group (OH) of the epoxy (meth)acrylate (a1) to the carboxyl group (COOH) of the maleic acid (anhydride) is preferably 100/5 to 100/75, more preferably 100/10 to 100/50.
• the maleic acid-modified epoxy (meth)acrylate (A1) is preferably one in which 5 to 75% of the hydroxyl groups of the epoxy (meth)acrylate (a1) are esterified, and more preferably one in which 10 to 50% are esterified.
• the acid value of the maleic acid-modified epoxy (meth)acrylate (A1) is preferably 10 to 70 mgKOH/g, more preferably 20 to 60 mgKOH/g, since this improves the balance between the usable time and fast curing properties required for rehabilitating pipes.
• Examples of the unsaturated monomer (A2) include monofunctional (meth)acrylate compounds such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate alkyl ether, polypropylene glycol (meth)acrylate alkyl ether, 2-ethylhexyl methacrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isotridecyl (meth)acrylate, n-stearyl (meth)acrylate, tetrahydrofurfuryl methacrylate, isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl methacrylate, and methacrylic (meth)acrylate; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and
• di(meth)acrylate compounds examples include 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol di(meth)acrylate, and 1,4-cyclohexanedimethanol di(meth)acrylate; tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; polyfunctional (meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate; styrene, ⁇ -methylstyrene, vinyltoluene, diallyl phthalate, and divinylbenzene; among these, aromatic unsaturated monomers are preferred because they provide molded products with higher strength, and styrene
• the mass ratio (A1/A2) of the maleic acid modified epoxy (meth)acrylate (A1) to the unsaturated monomer (A2) is preferably 25/75 to 75/25, more preferably 30/70 to 70/30, since this improves the strength of the rehabilitated pipe, the handleability of the lining material, and the fluidity during the production of the lining material.
• the resin component (A) contains the maleic acid-modified epoxy (meth)acrylate (A1) and the unsaturated monomer (A2) as essential components, but may contain other resin components.
• the thermally decomposable curing agent (B) is not particularly limited, but is preferably an organic peroxide.
• organic peroxide for example, ketone peroxides such as methyl ethyl ketone peroxide and acetyl lactone peroxide; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; diacyl peroxides such as dilauryl peroxide and dibenzyl peroxide; dialkyl peroxides such as dicumyl peroxide and dibutyl peroxide; peroxyketals such as 1,1-di(t-butylperoxy)cyclohexane and 2,2-di(t-amylperoxy)butane; alkyl peresters such as cumyl peroxy neodecanate and t-butylperoxy 2-ethylhexanate; and percarbonates such as di(4-t-butylcyclohexyl)per
• thermally decomposable hardeners with a temperature of 40°C or higher and 130°C or lower to obtain a 10-hour half-life are preferred, as they have a better balance between pot life and fast curing.
• the content of the thermally decomposable curing agent (B) is preferably 0.3 to 3 mass% relative to the resin component (A) because this provides a better balance between pot life and fast curing.
• the curing accelerator (C) is a substance that decomposes the thermally decomposable curing agent (C) by a redox reaction and facilitates the generation of active radicals
• examples of such substances include organic acid salts of cobalt such as cobalt naphthenate and cobalt octylate, metal soaps such as zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate, metal chelates such as vanadium acetylacetate, cobalt acetylacetate, and iron acetylacetonate; aniline, N,N-dimethylaniline, N,N-diethylaniline, p-toluidine, N,N-dimethyl-p-toluidine, ethylene oxide adduct of N,N-dimethyl-p-toluidine, and N,N-bis(2-hydroxyethyl)-p-toluidine.
• Examples of the curing accelerator include N,N-substituted anilines such as ruidine, 4-(N,N-dimethylamino)benzaldehyde, 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, 4-(N-methyl-N-hydroxyethylamino)benzaldehyde, N,N-bis(2-hydroxypropyl)-p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N,N-bis(hydroxyethyl)aniline, and diethanolaniline; amine compounds such as N,N-substituted-p-toluidine and 4-(N,N-substituted amino)benzaldehyde; however, cobalt organic acid salts are preferred.
• These curing accelerators can be used alone or in combination of two or more
• the content of the curing accelerator (C) is preferably 0.1 to 3 mass% relative to the resin component (A) since this provides a better balance between pot life and rapid curing.
• thermosetting resin composition for pipe lining materials of the present invention contains a resin component (A), a thermally decomposable curing agent (B), and a curing accelerator (C), and may contain other additives as necessary.
• the other additives include, for example, thixotropic agents, polymerization inhibitors, antioxidants, light stabilizers, solvents, defoamers, leveling agents, tackifiers, antistatic agents, flame retardants, pigments, fillers, reinforcing materials, aggregates, etc.
• the thermosetting resin composition for pipe lining material of the present invention preferably contains a thixotropic agent, since this improves the thixotropic properties.
• the thixotropic agent is not particularly limited as long as it can impart thixotropy to the resin composition, but examples include silica powder such as fumed silica, asbestos, smectite, and calcium sulfate whiskers.
• Commercially available fumed silica products include the Reolosil QS series (manufactured by Tokuyama Corporation), the Aerosil series (manufactured by Nippon Aerosil Co., Ltd.), the CABOSIL series (manufactured by CABOT), and the HDK series (manufactured by WACKER).
• thixotropic agents can be used alone or in combination of two or more types.
• compounds having polar groups such as water, glycol, and polyethylene glycol can also be used as thixotropic assistants that further strengthen the hydrogen bonds of the thixotropic agent.
• the amount of the thixotropic agent used is preferably 0.1 to 5 parts by mass per 100 parts by mass of the resin component (A) from the viewpoint of the balance between thixotropy and moldability.
• thermosetting resin composition for pipe lining materials of the present invention can be easily obtained by mixing the resin component (A), the thermally decomposable curing agent (B), the curing accelerator (C), and other additives as necessary.
• thermosetting resin composition for pipe lining materials of the present invention is, for example, to pre-cure by heating at 50 to 100°C for 0.5 to 4 hours, and then post-cure by heating at 80 to 130°C for 0.5 to 4 hours.
• thermosetting resin composition for pipe lining materials of the present invention has a long pot life, excellent fast curing properties, and excellent workability, and the resulting cured product has excellent bending strength, tensile elongation, and heat resistance, making it suitable for use as a pipe lining material.
• thermosetting resin composition for pipe lining material of the present invention can be exemplified as follows. First, a tubular body is prepared with a flexible film layer on the outside that matches the entire inner diameter of the existing pipe and a fiber reinforcement material on the inside. Next, the inside of the tubular body is depressurized to remove the air, and the thermosetting resin composition of the present invention is gradually impregnated from one end of the tubular body over the entire length of the tubular body to obtain a pipe lining material.
• This pipe lining material is transported to the insertion port of the existing pipe while being kept in a frozen or refrigerated state, and is turned over while being adhered to the existing pipe by fluid pressure such as air or water pressure, and then hardened while being adhered to the existing pipe using hot air, hot steam, hot water, etc. Finally, the excess pipe lining material at the stop part and the insertion part of the most advanced pipe lining material that has been applied is cut off, and the lined pipe is joined to complete the process.
• maleic acid-modified epoxy (meth)acrylate (A1-1) 0.11 parts by mass of methylhydroquinone, 0.11 parts by mass of tertiary butylcatechol, and 383 parts by mass of styrene were added and dissolved, and cooled to around 40°C, to obtain a resin solution of maleic acid-modified epoxy (meth)acrylate (A1-1).
• the molar ratio (OH/COOH) was 100/25, and 25% of the hydroxyl groups of the epoxy (meth)acrylate (a1-1) were esterified.
• the acid value of the maleic acid-modified epoxy (meth)acrylate (A1-1) was 31.1 mgKOH/g.
• maleic acid-modified epoxy (meth)acrylate (A1-2) 0.12 parts by mass of methylhydroquinone, 0.12 parts by mass of tertiary butylcatechol, and 414 parts by mass of styrene were added and dissolved, and the mixture was cooled to about 40°C to obtain a resin solution of maleic acid-modified epoxy (meth)acrylate (A1-2).
• the molar ratio (OH/COOH) was 100/50, and 50% of the hydroxyl groups of the epoxy (meth)acrylate (a1-2) were esterified.
• the acid value of the maleic acid-modified epoxy (meth)acrylate (A1-2) was 54.2 mgKOH/g.
• thermosetting resin composition (1) for pipe lining material 100 parts by mass of the resin solution of maleic acid modified epoxy (meth)acrylate obtained in Synthesis Example 1, 1.0 part by mass of fumed silica ("Aerogel #200” manufactured by Nippon Aerosil Co., Ltd.), and 0.2 parts by mass of polyethylene glycol (“PEG #400” manufactured by NOF Corporation) were mixed and stirred with a dispersing stirrer.
• thermosetting resin composition (1) for pipe lining materials.
• Examples 2 and 3 Production of thermosetting resin compositions (2) and (3) for pipe lining materials
• Thermosetting resin compositions (2) and (3) for pipe lining materials were obtained in the same manner as in Example 1, except that the resin solution of the maleic acid-modified epoxy (meth)acrylate (A1-1) used in Example 1 was changed to the resin solution of the maleic acid-modified epoxy (meth)acrylate (A1-2) or (A1-3) obtained in Synthesis Example 2 or 3.
• thermosetting resin composition for pipe lining material (R1) was obtained in the same manner as in Example 1, except that the resin solution of the maleic acid-modified epoxy (meth)acrylate (A1-1) used in Example 1 was changed to the resin solution of the epoxy (meth)acrylate (a1-4) obtained in Synthesis Example 4.
• thermosetting resin composition for pipe lining material obtained above was measured at 25°C using a Brookfield viscometer (BF rotational viscometer, manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K 6901, the thixotropy (6 rpm viscosity/60 rpm viscosity) was determined, and the workability was evaluated according to the following criteria.
• thixotropy is less than 2.0
• thermosetting resin composition for pipe lining material obtained above 70 g was placed in a 70 ml bottle and stored at 20° C. The time until gelation occurred was measured and the pot life was evaluated according to the following criteria. ⁇ : Time until gelling occurs is 90 hours or more. ⁇ : Time until gelling occurs is less than 90 hours.
• thermosetting resin composition for pipe lining material obtained above, the gel time at 80° C. was measured in accordance with JIS K 6901, and the rapid curing property was evaluated according to the following criteria. ⁇ : gelation time is less than 3 minutes ⁇ : gelation time is 3 minutes or more
• thermosetting resin composition for pipe lining material obtained above was subjected to vacuum degassing, and then cast into a mold using a gap formed by sealing the entire area except for the upper edge of two glass plates whose inner surfaces had been subjected to a release treatment with a 3 mm thick silicone rubber packing.
• the molded plate was then cured for 4 hours in a dryer at 50°C, and then after-cured for 2 hours in a dryer at 120°C. A cast plate was produced and various physical properties were measured.
• thermosetting resin compositions (1) to (3) and (R1) for pipe lining materials obtained above are shown in Table 1.
• thermosetting resin compositions for pipe lining materials of the present invention in Examples 1 to 3 were confirmed to have a long pot life, excellent fast curing properties, and excellent workability, and the resulting cured products were confirmed to have excellent bending strength, tensile elongation, and heat resistance.
• Comparative Example 1 is an example in which a non-maleic acid modified epoxy (meth)acrylate was used instead of the maleic acid modified epoxy (meth)acrylate (A1), but it was confirmed that the fast curing property, workability, and pot life were insufficient.

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