WO2018038220A1 - Composition durcissable, produit durci et stratifié - Google Patents

Composition durcissable, produit durci et stratifié Download PDF

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WO2018038220A1
WO2018038220A1 PCT/JP2017/030381 JP2017030381W WO2018038220A1 WO 2018038220 A1 WO2018038220 A1 WO 2018038220A1 JP 2017030381 W JP2017030381 W JP 2017030381W WO 2018038220 A1 WO2018038220 A1 WO 2018038220A1
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curable composition
sulfonic acid
group
furan resin
mass
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PCT/JP2017/030381
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English (en)
Japanese (ja)
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剛 ▲高▼比良
江口　勇司
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積水化学工業株式会社
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Publication of WO2018038220A1 publication Critical patent/WO2018038220A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/14—Furfuryl alcohol polymers

Definitions

  • the present invention relates to a curable composition containing a furan resin, a cured product thereof, and a resin composite containing the cured product.
  • curable compositions containing various thermosetting resins are often cured by a curing catalyst blended in the curable composition.
  • a curing catalyst for example, when the thermosetting resin is an addition condensation type, aromatic sulfonic acid such as para-toluenesulfonic acid is widely used.
  • aromatic sulfonic acid primary ester such as ethyl paratoluenesulfonate may be used to suppress the curability of the curable composition.
  • furan resin is widely used because it can be produced from biomass and the cured product is excellent in heat resistance, solvent resistance, chemical resistance, and the like. It is coming.
  • Furan resin is used for matrix resin of composite materials such as steel pipe lining, joint cement, and fiber reinforced plastic (FRP).
  • FRP fiber reinforced plastic
  • Examples of furan resins include those obtained by polycondensation of furan compounds such as furfuryl alcohol and furfural, or those obtained by cocondensation of furan compounds with aldehydes such as formaldehyde, phenols, and the like. .
  • Patent Document 2 a compound having two furan rings such as 1,5-difuranyl-3-pentanol obtained by condensing 2 equivalents of furfural with acetone and then hydrogenating; Co-condensation with aldehydes has also been studied.
  • a curable composition containing a furan resin is cured using a curing catalyst such as p-toluenesulfonic acid, which is generally used for addition condensation type thermosetting resins
  • the curable composition is cured. May be too high. Therefore, the pot life is shortened.
  • the curable composition is impregnated into a fibrous base material or the like and cured, the curable composition is cured before the impregnation.
  • the curability is not good. May be sufficient. Therefore, various physical properties of the cured product are lowered, and problems such as difficulty in lowering the curing temperature are likely to occur.
  • the present invention has been made in view of the above circumstances, and has an appropriate curability, for example, lengthens the pot life, enables appropriate curing at a moderate temperature, and various physical properties of the cured product. It is an object of the present invention to provide a curable composition containing a furan resin capable of improving the viscosity.
  • the present inventors have found that the above problems can be solved by using a curable composition in which a specific curing catalyst is blended with a furan resin, and have completed the following present invention. That is, the present invention provides the following [1] to [16].
  • a curable composition comprising a furan resin and a sulfonic acid secondary ester.
  • the curable composition according to the above [1], wherein the furan resin is represented by the following formula (1).
  • each A is independently a hydrogen atom or a group represented by * —CR 3 R 4 OH. * Indicates the bonding position with the furan ring.
  • R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 8 carbon atoms which may contain a hetero atom.
  • R 1 and R 2 , and R 3 and R 4 may be linked to form a ring structure.
  • n is an integer of 0 to 100.
  • a method for producing a cured product wherein a cured product is obtained by curing the curable composition according to any one of [1] to [10] by heating.
  • a furan resin that has an appropriate curability, for example, lengthens the pot life, enables appropriate curing at a moderate temperature, and improves various physical properties of the cured product.
  • a curable composition is provided.
  • FIG. 2 is a diagram showing a 1 H-NMR spectrum of a furan resin obtained in Synthesis Example 1.
  • the curable composition of the present invention contains a furan resin and a sulfonic acid secondary ester.
  • a furan resin contains a furan resin and a sulfonic acid secondary ester.
  • each component contained in the curable composition will be described in detail.
  • the furan resin is a condensate having two or more furan rings and includes a structural unit derived from a furan compound such as furfuryl alcohol and furfural. Moreover, you may have a structural unit derived from aldehydes, ketones, phenols, melamine, urea etc. as needed. Specifically, furfuryl alcohol and a condensate of furan compounds selected from furfural, these furan compounds and at least one compound selected from aldehydes, ketones, phenols, melamine, urea, etc. Examples include condensates.
  • aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, glyoxal, glutaraldehyde, and terephthalaldehyde.
  • ketones include acetone and methyl ethyl ketone.
  • phenols include phenol, cresol, resorcin, bisphenol A, bisphenol C, bisphenol E, and bisphenol F.
  • the furan resin is preferably a furan resin represented by the following formula (1).
  • the curability of the curable composition and various physical properties such as the mechanical strength and elongation characteristics of the cured product can be improved. Furthermore, it becomes easy to improve the adhesiveness of the hardened
  • each A is independently a hydrogen atom or a group represented by * —CR 3 R 4 OH. * Indicates the bonding position with the furan ring.
  • R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 8 carbon atoms which may contain a hetero atom.
  • R 1 and R 2 , and R 3 and R 4 may be linked to form a ring structure.
  • n is an integer of 0 to 100.
  • the organic group used for R 1 , R 2 , R 3 and R 4 is preferably an alkyl group.
  • the alkyl group may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. Note that “various” means that it includes linear and all branched chains, and the same applies hereinafter.
  • the ring structure is preferably one having a cycloalkyl structure such as cyclopentane or cyclohexane.
  • a hetero atom a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a halogen atom are mentioned, for example.
  • R 1 , R 2 , R 3 and R 4 are each independently one or more selected from a hydrogen atom, a methyl group, and an ethyl group from the viewpoint of ease of production. Are preferred, and it is more preferred that all of R 1 , R 2 , R 3 and R 4 are hydrogen atoms.
  • N is an integer from 0 to 100, and is a number corresponding to the weight average molecular weight described later.
  • a plurality of R 1 in one molecule may be the same as or different from each other. The same applies to R 2 , R 3 and R 4 .
  • furan resin may be used individually by 1 type and may use 2 or more types together.
  • the weight average molecular weight (Mw) of the furan resin is, for example, 220 to 25000, but the weight average molecular weight should be relatively low. By reducing the weight average molecular weight of the furan resin, it becomes easy to increase the curability of the furan resin. For example, when the curable composition is cured with a sulfonic acid secondary ester at a moderate temperature, a cured product having various physical properties can be obtained. From such a viewpoint, the weight average molecular weight of the furan resin is preferably 250 to 2000, more preferably 280 to 1000, and particularly preferably less than 1000.
  • the molecular weight distribution (Mw / Mn) of the furan resin is preferably 1 to 5, more preferably 1.1 to 4, and further preferably 1.1 to 2 from the viewpoint of obtaining a homogeneous furan resin.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the furan resin are the number average molecular weight and the weight average molecular weight in terms of polystyrene determined from the measurement of gel permeation chromatography (GPC). .
  • Furan resin can enhance its curability by a hydroxyl group at the molecular end. Therefore, when the furan resin is a compound represented by the above formula (1), it is better to have a hydroxyl group at the molecular end (A in the above formula (1)). That is, the furan resin represented by formula (1) preferably contains a furan resin in which at least one of A is —CR 3 R 4 OH, and a furan resin in which both A are —CR 3 R 4 OH. It is more preferable to contain a resin. In the furan resin represented by the formula (1), the ratio of the molecular terminal having a hydroxyl group is preferably 50% or more, more preferably 55% or more, and further preferably 60% or more.
  • the ratio which has a hydroxyl group in a molecular terminal is high, the curability of furan resin will become high. And when a curable composition is hardened by sulfonic acid secondary ester, for example under moderate temperature, it will become possible to obtain the hardened
  • the upper limit of the proportion of the hydroxyl group is not particularly limited and may be 100% or less, but may be 80% or less in consideration of easiness of production.
  • the ratio of the molecular terminal having a hydroxyl group is calculated from a 1 H-NMR spectrum.
  • the terminal structure of the furan resin represented by the above formula (1) has a structure in which a hydrogen atom is bonded to the 5-position of the furan ring, or —CR 3 R 4 OH is bonded to the 5-position of the furan ring. Either having a structure.
  • R 3 and R 4 are hydrogen atoms in the furan resin represented by the formula (1), the molecular ends are The proportion having a hydroxyl group is also referred to as a methylolation rate because it indicates the proportion of molecular ends converted to methylol.
  • the compound represented by the above formula (1) may be used alone, or a compound represented by the above formula (1) and a furan resin other than the compound represented by the above formula (1) may be used in combination. May be.
  • the compound represented by the above formula (1) is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more with respect to the total furan resin.
  • the furan resin includes a furan resin represented by the above formula (1), and in the formula (1), n is 0 and A is a hydrogen atom. .
  • a furan resin has a low weight average molecular weight (preferably 250 to 2000, more preferably 250 or more and less than 1000, particularly preferably 280 or more and less than 1000), and various physical properties of the obtained cured product are improved.
  • the furan resin is represented by the formula (1) with respect to the total furan resin, and the ratio of the furan resin in which n is 0 and A is a hydrogen atom is 5% by mass or more. Is preferable, and it is more preferable that it is 10 mass% or more.
  • a furan resin represented by the above formula (1) and used together with a furan resin in which n is 0 and A is a hydrogen atom in the formula (1) is a condensate of furfuryl alcohol; Condensates; and one or more selected from furan resins other than furan resins represented by the above formula (1), where n is 0 and A is a hydrogen atom.
  • the condensate of furfuryl alcohol, the condensate of furfuryl alcohol and formaldehyde, and these mixtures are preferable.
  • the content of the furan resin is preferably 20 to 99.9% by mass, more preferably 40 to 99% by mass, and more preferably 50 to 99% by mass with respect to the total amount of the curable composition. Further preferred.
  • content of furan resin By making content of furan resin into these ranges, it becomes easy to improve sclerosis
  • the furan resin may be obtained by polycondensation reaction of the above furan compounds, or a furan compound and at least one selected from aldehydes, ketones, phenols, melamine, urea, and the like. May be obtained by condensation reaction or polycondensation reaction, or selected from at least one selected from these reaction products and furan compounds, aldehydes, ketones, phenols, melamine, urea, etc. It may be obtained by further performing condensation or polycondensation reaction with at least one of the above.
  • the furan resin represented by the above formula (1) is obtained by reacting a furan compound represented by the following formula (1-1) and a carbonyl compound represented by the following formula (1-2) in the presence of an acid catalyst. It is preferable to obtain. According to this method, the furan resin represented by the above formula (1) can be efficiently produced.
  • R 1, R 2, R 3 and R 4 have the same meaning as R 1, R 2, R 3 and R 4 in the formula (1) .
  • the furan compound represented by the above formula (1-1) is obtained by appropriately reacting, for example, furfural with ketones according to the following reaction formulas (1-3), (1-4), and (1-5). Obtainable.
  • (Formula (1-3), (1-4), and (R 1 and R 2 in 1-5) has the same meaning as R 1 and R 2 in the formula (1).)
  • a condensate of furfuryl alcohol a condensate of furfuryl alcohol and formaldehyde
  • a furan resin obtained by mixing the selected furan resin with a furan compound represented by the formula (1-1) may be used.
  • furan resin one or more compounds selected from the above formula (1-1), formula (a), and formula (b) are copolymerized with the above-mentioned other furan compounds, and the like.
  • a furan resin having a structural unit derived from one or more compounds selected from the formula (1-1), the formula (a), and the formula (b) may be used.
  • Examples of the carbonyl compound represented by the formula (1-2) include formaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone. From the viewpoint of reactivity, formaldehyde is preferable.
  • the furan compound represented by the formula (1) as described above, it is more preferable that all of R 1 , R 2 , R 3 and R 4 are hydrogen atoms. Therefore, the furan resin represented by the formula (1) is more preferably obtained by reacting 1,5-difuranyl-3-pentanol and formaldehyde.
  • paraformaldehyde which is the polymer.
  • formaldehyde is generated by depolymerization that occurs in the reaction system, and this formaldehyde reacts with the furan compound represented by formula (1-1). Similar furan resins can be obtained.
  • paraformaldehyde is used in the reaction between the furan compound and the carbonyl compound, the ratio of the molecular terminal having a hydroxyl group can be easily increased.
  • an excess amount of the carbonyl compound represented by the formula (1-2) is mixed with the furan compound represented by the formula (1-1) to obtain the compound represented by the formula (1). preferable.
  • the carbonyl compound represented by the formula (1-2) is, for example, 1.5 to 10 mol, preferably 2 to 6 mol, relative to 1 mol of the furan compound represented by the formula (1-1). More preferably, a 3 to 5 molar reaction system may be charged.
  • "mol” here means formaldehyde conversion amount, when using paraformaldehyde.
  • acid catalysts examples include inorganic acids such as sulfuric acid and phosphoric acid, sulfonic acids such as benzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, and methanesulfonic acid, tartaric acid, citric acid, and malic acid.
  • organic carboxylic acids such as glycolic acid, lactic acid, benzoic acid, formic acid, and acetic acid.
  • An acid catalyst may be used individually by 1 type, and may use 2 or more types together. Of these, organic carboxylic acids are preferable, and lactic acid is more preferable.
  • the amount of the acid catalyst used is preferably 0.01 to 20 parts by mass and more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the raw material monomer from the viewpoint of shortening the production time.
  • the mass part of the raw material monomer means the total amount of the furan compound represented by the formula (1-1) and the carbonyl compound represented by the formula (1-2).
  • a catalyst other than the acid catalyst may be added to perform a preliminary reaction.
  • the catalyst other than the acid catalyst include an alkali catalyst.
  • the catalyst other than the acid catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, and barium hydroxide.
  • Alkaline earth metal oxides such as magnesium oxide, calcium oxide and barium oxide, metal salts of organic acids such as magnesium acetate, zinc acetate and zinc formate, amines such as aqueous ammonia and triethylamine, sodium carbonate, potassium carbonate, etc.
  • Catalysts other than these acid catalysts may be used alone or in combination of two or more.
  • the amount of the catalyst other than the acid catalyst used is preferably 0.01 to 10 parts by mass and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the raw material monomer.
  • Solvents include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol and other alcohol solvents, dibutyl ether, tetrahydrofuran, dioxane and other ether solvents, pentane, hexane and other fats.
  • aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as methylene chloride, and the like. These may be used alone or in combination of two or more.
  • water and alcohol solvents having 1 to 4 carbon atoms are preferable from the viewpoint of availability.
  • the reaction temperature in this production method is preferably 40 to 150 ° C., more preferably 50 to 90 ° C., and still more preferably 55 to 70 ° C.
  • the reaction time is preferably 1 to 20 hours, and more preferably 1 to 8 hours.
  • a furan compound, a carbonyl compound, and an acid catalyst may be added to the reaction system and further reacted.
  • the reaction can be stopped by adding an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous sodium hydrogen carbonate solution to neutralize the reaction system, whereby the desired furan resin can be obtained.
  • the catalyst residue and the like may be removed by a purification operation after neutralization.
  • the sulfonic acid secondary ester contained in the curable composition is an organic sulfonic acid ester, and the carbon atom directly bonded to oxygen of the sulfo group (SO 3 group) of the organic sulfonic acid is a secondary carbon.
  • the sulfonic acid secondary ester is a latent curing catalyst whose catalytic action is activated by heating.
  • the curable composition of the present invention is blended with a sulfonic acid secondary ester as a curing catalyst, so that the curing is difficult to proceed under a low temperature environment, and the pot life of the curable composition can be extended.
  • the sulfonic acid secondary ester exhibits such curing characteristics is not clear, but the carbon atom directly bonded to the oxygen atom of the sulfo group is a secondary carbon. It is presumed that the organic group containing the secondary carbon is dissociated to generate a small amount of free sulfonic acid, and the small amount of the free sulfonic acid gradually cures the curable composition.
  • the sulfonic acid used in the sulfonic acid secondary ester may have one sulfo group in the molecule or two or more.
  • bonded with oxygen of a sulfo group may be secondary carbon, However, At least 1 carbon atom should just be a secondary carbon.
  • the sulfonic acid is preferably an aromatic sulfonic acid, and the specific sulfonic acid secondary ester is preferably a compound represented by the following formula (2).
  • Ar represents an aromatic ring which may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and a halogen group.
  • the aromatic ring specifically represents a benzene ring or a naphthalene ring, but a benzene ring is preferred.
  • the alkyl group used as a substituent in Ar preferably has 1 to 2 carbon atoms, and more preferably a methyl group.
  • n is an integer of 1 to 4.
  • R is an organic group in which at least one of the carbon atoms directly bonded to the oxygen atom of the sulfo group (SO 3 group) is a secondary carbon, and R has 3 to 80 carbon atoms.
  • R may be composed of a hydrocarbon, but may have a hetero atom.
  • the hetero atom include a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a halogen atom.
  • R is preferably a hydrocarbon group that may have a hydroxyl group, and more preferably an alkyl group that may have a hydroxyl group.
  • the hydrocarbon group and alkyl group referred to here may have not only a branched or straight chain but also a cyclic structure such as a cycloalkyl group.
  • R has 1 to 4 binding sites, and the number of binding sites varies depending on the number of n. When n is 1, the binding site is 1, and similarly when n is 2 to 4. , There are 2 to 4 binding sites.
  • n is 1 and is preferably a compound represented by the following formula (2-1).
  • Ar is the same as described above.
  • R is an organic group in which the carbon atom directly bonded to the oxygen atom of the sulfo group (SO 3 group) is a secondary carbon, and R has 3 to 24 carbon atoms.
  • R may be composed of a hydrocarbon, but may have a hetero atom. Examples of the hetero atom include a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a halogen atom.
  • R is preferably a hydrocarbon group that may have a hydroxyl group, and more preferably an alkyl group that may have a hydroxyl group.
  • the hydrocarbon group and alkyl group referred to here may have not only a branched or straight chain but also a cyclic structure such as a cycloalkyl group.
  • the carbon number of R is preferably 3 to 12, more preferably 3 to 8.
  • R is preferably a substituent represented by the following formula (2-2).
  • R 5 to R 9 each independently represents an organic group, a hydrogen atom, a hydroxyl group, or a halogen group, which may have a hetero atom.
  • the hetero atom is as described above. * Is the bonding position of the sulfo group (SO 3 group) with the oxygen atom.
  • the total carbon number of R 5 to R 9 is 0 to 21, preferably 0 to 9, and more preferably 0 to 5.
  • R 5 to R 9 are each independently preferably selected from a hydrogen atom, a hydroxyl group and a hydrocarbon group, and the hydrocarbon group in R 5 to R 9 is preferably a saturated hydrocarbon group.
  • One organic group (for example, a hydrocarbon group) of R 5 and R 6 and one organic group (for example, a hydrocarbon group) of R 7 to R 9 are connected to form a ring structure. It may be formed.
  • R is a substituent represented by the formula (2-2)
  • the reason for this is that when the substituent represented by formula (2-2) is heated, the secondary carbon atom bonded to the oxygen atom of the sulfo group and the carbon atom adjacent to the secondary carbon atom are unsaturated bonds. This is presumed to be easier to form.
  • R 5 is a hydroxyl group, a hydrogen atom or a hydrocarbon group
  • R 6 to R 9 are each independently a hydrogen atom or a hydrocarbon group.
  • the sulfonic acid secondary ester having such a structure can be easily synthesized by reacting an epoxy compound or an alcohol compound with sulfonic acid or a derivative thereof.
  • R 6 and R 7 are preferably hydrocarbon groups, and R 6 and R 7 are preferably linked to form a ring structure.
  • the ring structure is preferably a cycloalkane structure such as cyclopentane, cyclohexane, cycloheptane, or cyclooctane structure, and more preferably a cyclohexane structure. More preferably, R 5 is a hydroxyl group.
  • Ar examples include phenyl group, tolyl group, xylyl group, naphthyl group, hydroxyphenyl group, dihydroxyphenyl group, hydroxymethylphenyl group, hydroxynaphthyl group, Examples include halogen-substituted phenyl groups such as chlorophenyl group, dichlorophenyl group, tetrachlorophenyl group, bromophenyl group, dibromophenyl group, tetrabromophenyl group, among which phenyl group, tolyl group, xylyl group, chlorophenyl group are more preferable, and paratolyl group Is more preferable.
  • halogen-substituted phenyl groups such as chlorophenyl group, dichlorophenyl group, tetrachlorophenyl group, bromophenyl group, dibromophenyl group, tetrabromophenyl group, among which
  • R examples include cyclohexyl, cyclopentyl, isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl and 3-hexyl.
  • a cyclohexyl group and a 2-hydroxycyclohexyl group are more preferable, and a cyclohexyl group is most preferable.
  • addition reaction product of a sulfonic acid and an epoxy compound as a sulfonic acid secondary ester.
  • the addition reaction product is obtained by adding a sulfonic acid to an epoxy compound and opening an epoxy ring. Therefore, the addition reaction product has a hydroxyl group, and the hydroxyl group is bonded to the carbon atom at the 2-position.
  • the carbon atom at the 2nd position means a carbon atom adjacent to the carbon atom with the carbon atom to which the sulfo group is bonded as the 1st position.
  • R is an organic group having a hydroxyl group, and the hydroxyl group is bonded to the carbon atom at the 2-position. To do.
  • R 5 or R 9 is a hydroxyl group.
  • the sulfonic acid used in the addition reaction product is an organic sulfonic acid as described above, and an aromatic sulfonic acid is preferable as described above.
  • the aromatic sulfonic acid include sulfonic acids represented by the following formula (2-3).
  • Ar is the same as described above.
  • Preferable specific examples of the sulfonic acid include benzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, chlorobenzenesulfonic acid, dichlorobenzenesulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, and the like.
  • Acid paratoluenesulfonic acid, xylenesulfonic acid, and parachlorobenzenesulfonic acid are more preferable, and paratoluenesulfonic acid is particularly preferable.
  • a sulfonic acid may be used individually by 1 type, you may use it in combination of 2 or more type.
  • Examples of the epoxy compound include an epoxy compound having one or more epoxy groups and 3 to 80 carbon atoms.
  • Specific examples of the epoxy compound include alicyclic epoxy compounds, alkyloxiranes, glycidyl ether compounds, epoxidized vegetable oils, and terpene epoxidized products.
  • An alicyclic epoxy compound is a compound having a structure in which carbon atoms constituting an epoxy group directly constitute an alicyclic ring.
  • Specific examples of the alicyclic epoxy compound include 1,2-epoxycyclobutane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycycloheptane, and 1,2-epoxycyclooctane.
  • 1,2-epoxycyclononane and epoxycycloalkanes such as 1,2-epoxycyclodecane.
  • it may be a polyfunctional alicyclic epoxy compound having two or more epoxycycloalkane structures in one molecule, such as an epoxycyclohexane structure, and specifically, 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxy.
  • Cyclohexanecarboxylate 3 ′, 4′-epoxy-6′-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy -6-methylcyclohexyl) adipate, ethylenebis (3,4-epoxycyclohexanecarboxylate), ethylenebis (3,4-epoxy-6-methylcyclohexanecarboxylate), 2,2-bis (3,4-epoxycyclohexyl) ) Propane and the like.
  • Alkyloxiranes include 1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2, -Epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxy-4-methylpentane and the like.
  • glycidyl ether compounds include alkyl glycidyl ether compounds such as methyl glycidyl ether, ethyl glycidyl ether, and butyl glycidyl ether; aryl glycidyl ether compounds such as phenyl glycidyl ether and methylphenyl glycidyl ether; neopentyl glycol diglycidyl ether; Examples thereof include polyfunctional glycidyl ether type epoxy compounds such as glycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, and among these, neopentyl glycol diglycidyl ether is preferable.
  • examples of the epoxidized vegetable oil include epoxy compounds of vegetable oils such as soybean oil, linseed oil, and cottonseed oil.
  • examples of the terpene epoxidized compound include compounds obtained by epoxidizing terpenes such as pinene and limonene, and specific compounds include pinene oxide and limonene oxide. These are also alicyclic epoxy compounds.
  • epoxy compounds having 3 to 24 carbon atoms are preferable, and the carbon number thereof is more preferably 3 to 12, and further preferably 5 to 8.
  • alicyclic epoxy compounds are preferable, epoxy cycloalkanes having one epoxy group are more preferable, and 1,2-epoxycyclohexane is most preferable.
  • impurities such as a sulfonic acid primary ester are not generated in the addition reaction, and a sulfonic acid secondary ester can be obtained at a high production rate.
  • an epoxy compound in order to obtain a sulfonic acid secondary ester with a high production rate, in the alicyclic epoxy compound, it is preferable that one hydrogen atom is bonded to each of two carbon atoms constituting the epoxy ring.
  • the addition reaction product of an epoxy compound and sulfonic acid include 2-hydroxycyclohexyl benzenesulfonate, 2-hydroxycyclohexyl paratoluenesulfonate, 2-hydroxycyclohexyl xylenesulfonate, and 2-chlorocyclohexylsulfonate. Examples include hydroxycyclohexyl.
  • an epoxy compound may be used individually by 1 type, but may be used in combination of 2 or more type.
  • the addition reaction product of the epoxy compound and the sulfonic acid may be obtained by addition reaction of the sulfonic acid to the epoxy compound.
  • it can be obtained by mixing the epoxy compound and the sulfonic acid in the presence of a solvent.
  • a solvent an organic solvent or a mixed solvent of water and an organic solvent may be used. Examples of the organic solvent include dichloromethane and THF.
  • a catalyst such as a phase transfer catalyst may be appropriately added to the reaction system.
  • the addition reaction product is added to a sulfonic acid secondary ester other than a sulfonic acid secondary ester such as a sulfonic acid primary ester or a sulfonic acid tertiary ester. May contain product.
  • the obtained addition reaction product may be purified to remove a product other than the sulfonic acid secondary ester, or cured while containing a product other than the sulfonic acid secondary ester. You may mix
  • Sulfonic acid primary esters and sulfonic acid tertiary esters are less active as curing catalysts than sulfonic acid secondary esters. Therefore, if these are used as they are as a curing catalyst without removing them, the curing rate can be reduced.
  • the addition reaction between an epoxy compound such as an alkyloxirane or glycidyl ether compound and a sulfonic acid typically produces a sulfonic acid primary ester in addition to the sulfonic acid secondary ester.
  • the formation rate of the sulfonic acid secondary ester can be increased by making the SN1-type regioselectivity dominant, and the sulfonic acid primary ester by making the SN2-type regioselectivity dominant.
  • the production rate of can be increased.
  • the production rate can be adjusted by adjusting the acid concentration in the solvent.
  • the addition reaction product blended in the curable composition contains a sulfonic acid ester other than a sulfonic acid secondary ester such as a sulfonic acid primary ester or a sulfonic acid tertiary ester in addition to the sulfonic acid secondary ester.
  • the acid secondary ester is preferably the main component.
  • the content of the sulfonic acid secondary ester in the addition reaction product is preferably 50% by mass or more, more preferably 70 to 100% by mass, still more preferably 90 to 100% by mass, based on the total sulfonic acid ester. Most preferably, it is 100 mass%.
  • an addition reaction product obtained by addition reaction of an epoxy compound and a sulfonic acid may contain an unreacted sulfonic acid or an epoxy compound.
  • One or both of the acid and the epoxy compound may be removed by purification or the like, or may be blended in the curable composition as a curing catalyst while being contained. Since the unreacted sulfonic acid functions as a curing catalyst, the curability of the curable composition is easily increased by keeping the sulfonic acid contained. Therefore, the curability of the curable composition can be adjusted by whether or not the unreacted sulfonic acid is removed and by adjusting the residual amount of the sulfonic acid in the addition reaction product.
  • the epoxy compound is a curable compound, it can be incorporated into the molecular chain of the cured product together with the furan resin by remaining.
  • the solvent used in the addition reaction may remain in the addition reaction product.
  • the addition reaction product of the epoxy compound and the sulfonic acid contains a compound other than the sulfonic acid secondary ester (unreacted organic sulfonic acid, sulfonic acid primary ester, etc.)
  • the blending amount of the sulfonic acid secondary ester is preferably in the range of 0.5 to 10 parts by mass, more preferably 0.5 to 6 parts by mass, and further preferably 0.8 to 4 parts by mass with respect to 100 parts by mass of the furan resin.
  • blend with a curable composition.
  • the amount of sulfonic acid in the curable composition is preferably 0.01 to 1.0 parts by mass as described later. It is preferable to adjust appropriately so that it is preferably in the range of 0.05 to 0.8 parts by mass, more preferably in the range of 0.1 to 0.5 parts by mass.
  • Preferred specific examples of the sulfonic acid secondary ester include cyclohexyl benzene sulfonate, isopropyl benzene sulfonate, cyclohexyl para-toluene sulfonate, isopropyl para-toluene sulfonate, cyclohexyl xylene sulfonate, isopropyl xylene sulfonate, and as described above.
  • Examples thereof include 2-hydroxycyclohexyl benzenesulfonate, 2-hydroxycyclohexyl paratoluenesulfonate, 2-hydroxycyclohexyl xylenesulfonate, and 2-hydroxycyclohexyl parachlorobenzenesulfonate.
  • cyclohexyl paratoluenesulfonate, paratoluene More preferred are isopropyl sulfonate and 2-hydroxycyclohexyl p-toluenesulfonate.
  • cyclohexyl paratoluenesulfonate is more preferable from the viewpoint of reactivity. From the viewpoint of reactivity and ease of production, 2-hydroxycyclohexyl paratoluenesulfonate is more preferable.
  • the sulfonic acid secondary ester may be used alone or in combination of two or more.
  • the blending amount of the sulfonic acid secondary ester in the curable composition is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the furan resin.
  • the blending amount of the sulfonic acid secondary ester is 0.5 parts by mass or more, it is possible to sufficiently cure the curable composition.
  • hardenability corresponding to a compounding quantity can be provided to a curable composition, and it also prevents that the sclerosis
  • the blending amount of the sulfonic acid secondary ester is more preferably 0.5 to 6 parts by mass, and further preferably 0.8 to 4 parts by mass.
  • dissolving in a dilution solvent examples include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, and isobutanol.
  • the dilution concentration is not particularly limited, but is, for example, 10 to 70% by mass, preferably 30 to 55% by mass.
  • the curable composition may contain a curing catalyst other than the sulfonic acid secondary ester. What is necessary is just to use what is conventionally used as a curing catalyst of furan resin as curing catalysts other than sulfonic acid secondary ester. Specifically, inorganic acids such as sulfuric acid, phosphoric acid and hydrochloric acid, organic sulfonic acids, sulfonic acid esters other than sulfonic acid secondary esters, organic acids such as organic carboxylic acids, and the like can also be used.
  • inorganic acids such as sulfuric acid, phosphoric acid and hydrochloric acid, organic sulfonic acids, sulfonic acid esters other than sulfonic acid secondary esters, organic acids such as organic carboxylic acids, and the like can also be used.
  • Examples of the organic sulfonic acid include p-toluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, and the like.
  • Examples of the sulfonic acid esters other than the sulfonic acid secondary ester include, in the above general formulas (2) and (2-1), a carbon atom in which R is directly bonded to an oxygen atom of a sulfo group (SO 3 group) is a primary carbon, Examples thereof include an organic group which is a tertiary carbon and in which R has 3 to 80 carbon atoms, preferably 3 to 24 carbon atoms.
  • organic carboxylic acid examples include malonic acid, succinic acid, maleic acid, oxalic acid, acetic acid, lactic acid, malic acid, tartaric acid, benzoic acid, citric acid and the like.
  • organic sulfonic acid is preferable and paratoluenesulfonic acid is more preferable.
  • the curing catalyst other than the sulfonic acid secondary ester may be used alone or in combination of two or more.
  • the curing catalyst other than the sulfonic acid secondary ester may be added to the curable composition in an amount that does not promote the curing of the curable composition more than necessary in a low temperature environment.
  • the amount of the organic sulfonic acid is 0.01 to 1.0 part by mass relative to 100 parts by mass of the furan resin.
  • 0.05 to 0.8 parts by mass is more preferable, and 0.1 to 0.5 parts by mass is still more preferable.
  • the curable composition contains other optional components such as a reactive diluent, filler, inorganic salt, plasticizer, antifoaming agent, and curing agent in addition to the above-mentioned furan resin, sulfonic acid secondary ester, and curing catalyst. You may do it. These arbitrary components may contain 1 type in these, and may contain 2 or more types.
  • the reactive diluent has a low viscosity, is compatible with a furan resin, and further reacts and solidifies when the curable composition is cured, such as furfuryl alcohol, furfural, or furfuryl alcohol. A mixture with furfural is preferred.
  • the reactive diluent can adjust the viscosity and reactivity of the curable composition.
  • the content thereof is preferably 0.5 to 100 parts by mass and more preferably 1 to 80 parts by mass with respect to 100 parts by mass of the furan resin.
  • Examples of the filler include organic fillers such as an inorganic filler, carbon powder, and wood powder.
  • Examples of the inorganic filler include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, titanium oxide, and antimony oxide, metal powder such as zinc, and carbon powder such as carbonic acid.
  • Examples thereof include metal carbonates such as calcium, magnesium carbonate, barium carbonate, and zinc carbonate, calcium sulfate, barium sulfate, calcium silicate, mica, talc, bentonite, zeolite, silica gel, aluminum oxide, and glass powder. These fillers may be used alone or in combination of two or more.
  • the inorganic filler is preferably one that has been subjected to a surface treatment with a surface treatment agent.
  • a surface treatment agent an organosilane surface treatment agent is preferable, and specifically, an aminosilane surface treatment agent, an epoxysilane surface treatment agent, and an acrylic silane surface treatment agent are more preferable.
  • the content thereof is preferably 0.5 to 300 parts by mass and more preferably 1 to 250 parts by mass with respect to 100 parts by mass of the furan resin.
  • the inorganic salt include one or more selected from sodium chloride, lithium chloride, sodium bromide, and lithium bromide.
  • lithium chloride is more preferable from the viewpoint of reducing the dimensional change of the cured product and the solubility in the furan resin at room temperature.
  • the content thereof is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the furan resin.
  • the plasticizer include phthalic acid esters such as diethyl phthalate and dibutyl phthalate, phosphoric acid esters, fatty acid esters, and epoxy plasticizers.
  • the content of the plasticizer is not particularly limited, but is preferably 0.01 to 20 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the furan resin.
  • Antifoaming agents include oil-type silicone antifoaming agents, emulsion-type silicone antifoaming agents, antifoaming polymer-type antifoaming agents such as nonionic polyethers, special nonionic surfactants, and polyether-modified methylalkylpolysiloxanes. Examples include copolymers, polyethylene glycol type nonionic surfactants, vegetable oil-based antifoaming agents, and the like.
  • the content of the antifoaming agent is not particularly limited, but is preferably 0.01 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the furan resin.
  • curing agent is a compound which forms the network by bridge
  • a bismaleimide type compound and a polyfunctional (meth) acrylic-type compound are mentioned.
  • the bismaleimide compounds include N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1 , 3- (2-Methylphenylene)] bismaleimide, N, N ′-[1,3- (4-methylphenylene)] bismaleimide, N, N ′-(1,4-phenylene) bismaleimide, bis ( 4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis (4-maleimidopheny
  • polyfunctional (meth) acrylic compound examples include bifunctional (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate compounds such as (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. It is done.
  • (meth) acrylate means “acrylate or methacrylate”.
  • the content thereof is preferably 0.01 to 100 parts by mass and more preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the furan resin.
  • the curable composition preferably contains water.
  • the temperature of the curable composition at the time of curing is easily suppressed to about the boiling point of water, and the curing temperature is prevented from becoming higher than necessary.
  • hardening temperature becomes low because curable composition contains water, it can prevent that sclerosis
  • the water content is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and even more preferably 3 to 9% by mass based on the total amount of water and furan resin (100% by mass).
  • the curable composition can have good processability by reducing the viscosity.
  • the viscosity of the curable composition is preferably 10,000 mPa ⁇ s or less, and more preferably 8000 mPa ⁇ s or less.
  • the curable composition may be impregnated into a fibrous base material such as glass fiber by vacuum impregnation or the like. In such a case, in order to appropriately penetrate the curable composition into the fibrous fiber.
  • the viscosity of the curable composition should be even lower.
  • the viscosity of the curable composition is more preferably 4000 mPa ⁇ s or less, and further preferably 3000 mPa ⁇ s or less.
  • the minimum of the viscosity of a curable composition is not specifically limited, It is preferable that it is 100 mPa * s or more, and 400 mPa * s or more is more preferable.
  • the viscosity of a curable composition means the viscosity in 25 degreeC, and is specifically measured by the method as described in the Example mentioned later.
  • the curable composition of the present invention can be produced by mixing the furan resin and the sulfonic acid secondary ester using a homodisper or the like.
  • a curing catalyst other than the sulfonic acid secondary ester other components, water, and the like may be mixed.
  • the cured product of the present invention is obtained by curing the above-described curable composition.
  • the cured product may be formed into a predetermined shape such as a film shape, or may be combined with another material such as a fibrous base material by adhesion, lamination, penetration, or the like.
  • the curable composition may be used to form a resin composite including a cured product and a material other than the cured product such as a fibrous base material to be combined with the cured product.
  • cured material for a resin composite it is preferable that the curable composition impregnated at the fibrous base material was hardened
  • the fibrous base material used in the resin composite examples include glass fiber, carbon fiber, metal fiber, woven fabric made of paper, cotton, hemp, non-woven fabric, chopped strand mat, roving cloth, and the like.
  • the material for the nonwoven fabric for example, polyester, high density polyethylene (HDPE), polypropylene and the like are preferable.
  • a flexible, porous felt, mat, spunbond, web or the like with continuous filaments or staple fibers can be used.
  • a chopped strand mat for example, strands such as glass fibers are cut into a certain length and dispersed in a mat shape, and then an adhesive such as a thermoplastic resin and a pressure-sensitive adhesive are uniformly applied and thermally melted.
  • the roving cloth is preferably made of glass fiber, carbon fiber, aramid fiber, inorganic fiber, organic fiber, whisker or other reinforcing fiber.
  • the reinforcing fiber preferably has a fiber diameter of 3 to 25 ⁇ m, and more preferably has a fiber diameter of 5 to 20 ⁇ m from the viewpoint of strength and price.
  • glass fibers that have good adhesion to the cured product of the present invention and are excellent in balance between strength and price are preferable.
  • the fibrous base material may have a single layer or multilayer structure using a single material, or may have a single layer or multilayer structure using two or more materials.
  • the liquid-permeable impermeable film may be formed in the one or both surfaces of a fibrous base material.
  • the water-impermeable film can be formed of, for example, a synthetic resin material such as polyethylene, polypropylene, nylon, polyester, polyvinyl chloride, elastomer, and synthetic rubber. If only one side has a water-impermeable film, the fibrous base material can be impregnated with a brush or impregnation roller. If it is formed on both sides, it is cured by vacuum impregnation. The composition can be impregnated.
  • the cured product is obtained by curing the curable composition by heating.
  • the temperature (heating temperature) of the curable composition at the time of heat curing is preferably controlled so as not to exceed 110 ° C., more preferably 105 ° C., and still more preferably 100 ° C. By making the heating temperature relatively low as described above, it is possible to prevent the curing reaction from proceeding rapidly and causing side reactions.
  • the specific heating temperature is preferably 50 to 110 ° C, more preferably 55 to 105 ° C, and further preferably 60 to 100 ° C.
  • the heating time is, for example, about 30 minutes to 10 hours, preferably 1 to 8 hours.
  • Heat curing is preferably performed in two stages. Specifically, the first stage heating is performed at 50 to 70 ° C., preferably 55 to 65 ° C., and then the second stage is performed at 75 to 110 ° C., preferably 80 to 105 ° C., more preferably 85 to 100 ° C. Heat your eyes.
  • the heating time for the first stage and the second stage is, for example, 15 minutes to 3 hours, preferably 30 minutes to 2 hours, and the second stage is, for example, 30 minutes to 9 hours, preferably 1 Time to 8 hours.
  • the curing catalyst other than the sulfonic acid secondary ester is a sulfonic acid secondary ester such as an organic sulfonic acid.
  • a catalyst having a higher activity than that of the secondary ester may be used.
  • the curable composition may be cured by, for example, filling a curable composition into a container or mold having a predetermined shape and then heating. At this time, the curable composition may be heated by placing the container or the mold in a thermostatic bath adjusted to a predetermined temperature and a thermostatic water bath, or hot air or heat circulated in the container or the mold. The curable composition may be heated with a heating medium such as water. Alternatively, the curable composition may be cast on a film of polyethylene terephthalate, polyimide, or the like and cured by heating in an oven or the like.
  • the curable composition may be cured after impregnating the fibrous base material.
  • the method for impregnating the fibrous base material with the curable composition is not particularly limited, and examples thereof include vacuum impregnation.
  • Vacuum impregnation is a method in which a fibrous base material is placed in a vacuum or reduced pressure space, and the curable composition is filled into the space.
  • a fibrous base material may be impregnated with a curable composition by an impregnation roll, a brush, or the like.
  • the amount of impregnation of the curable composition is not particularly limited.
  • the curing method of the curable composition impregnated in the fibrous base material is not particularly limited.
  • the fibrous base material impregnated with the curable composition is placed in a mold and heated with hot air or on a hot plate.
  • a method of sandwiching and curing by heating can be used.
  • the curable composition of the present invention has a long pot life and hardly cures under a low temperature environment. Therefore, by controlling the temperature of the curable composition when impregnating into the fibrous base material, the curable composition can be impregnated into the fibrous base material in a state where the curing does not progress much, It becomes easy to permeate the curable composition into the fibrous base material.
  • the temperature at which the fibrous base material is impregnated with the curable composition is, for example, less than 60 ° C., and preferably 10 to 45 ° C.
  • the cured product of the present invention may be cured in a closed space such as the inside of a mold, but may be cured in an open space.
  • a sealed space such as the inside of the mold, water does not volatilize, so that the heating temperature is easily maintained at a relatively low temperature.
  • cured products ie, resin composites
  • fibrous base materials are used for tubular lining materials that are coated on the inner surfaces of pipes such as water and sewage pipes, agricultural water pipes, and industrial water pipes embedded in the ground.
  • the tubular lining material may be composed of a single resin composite in which a cured product is combined with a fibrous base material, or a laminate of a plurality of these, and further, glass fiber, carbon fiber, aramid fiber, It may be a reinforcing fiber substrate formed from inorganic fibers, organic fibers, whiskers, or the like, or one provided with the above-described water-impermeable film.
  • the tubular lining material for example, one or more fibrous base materials and one or more members such as a reinforcing fiber base material and an impermeable film are laminated in an appropriate order, and the curable composition is formed on the fibrous base material.
  • the impregnated laminate is formed by curing the curable composition while being pressed against the inner surface of the pipe. Since the curable composition of the present invention has a long pot life, the curable composition can be cured at a desired timing even when used in a tubular lining material.
  • the 1 H-NMR spectrum of the obtained furan resin in DMSO-d6 is shown in FIG. In the 1 H-NMR spectrum, from the integrated value of the peak (5.09 ppm) based on the 5-position hydrogen atom of the terminal furan ring and the integrated value of the peak (4.31 ppm) based on the hydrogen atom of the hydroxyl group of —CH 2 OH The calculated methylolation rate was 66%.
  • m represents the degree of polymerization.
  • a 1 is either a hydrogen atom or a methylol group (—CH 2 OH))
  • Example 1 Ion exchange water was added to the furan resin obtained in Synthesis Example 1 to prepare a furan resin containing 7% by mass of water. 100 parts by mass of this hydrofuran resin was diluted with 5.3 parts by mass of furfuryl alcohol, and 2.1 parts by mass of a 50% ethanol solution of cyclohexyl paratoluenesulfonate (1.13 parts by mass with respect to 100 parts by mass of furan resin). ) And stirred to obtain a uniform curable composition. The initial viscosity of this composition was 1700 mPa ⁇ s. This composition was allowed to stand at room temperature and the change in viscosity over time was measured.
  • the viscosity after 6 hours was 7200 mPa ⁇ s, and it was confirmed that the composition had a sufficient pot life.
  • a part of the curable composition was impregnated into a glass fiber cloth placed in a SUS frame, laminated with a PET film, sandwiched between SUS plates, heated at 60 ° C. for 1 hour, and then 90 ° C. And cured for 1 hour to obtain a composite cured film having a thickness of 0.2 mm.
  • the elongation at break was 2.7%
  • the strength at break was 173 MPa
  • the elastic modulus was 6.0 GPa.
  • Example 2 Instead of 2.1 parts by mass of a 50% by mass ethanol solution of cyclohexyl paratoluenesulfonate, 2.5 parts by mass of a 40% by mass tetrahydrofuran solution of the addition reaction product obtained in Catalyst Synthesis Example 1 (into 100 parts by mass of furan resin) On the other hand, the same procedure as in Example 1 was carried out except that 1 part by mass of 2-hydroxycyclohexyl paratoluenesulfonate was used.
  • the initial viscosity of the curable composition in Example 2 was 2570 mPa ⁇ s. The composition was allowed to stand at room temperature, and the change in viscosity over time was measured.
  • the viscosity after 6 hours was 5830 mPa ⁇ s, and it was confirmed that the composition had a sufficient pot life.
  • a composite cured film having a thickness of 0.2 mm was obtained in the same manner as in Example 1 using the curable composition after 6 hours.
  • the elongation at break was 2.9%
  • the breaking strength was 200.3 MPa
  • the elastic modulus was 6.4 GPa.
  • Comparative Example 2 The same procedure as in Example 1 was performed except that a 50% by mass ethanol solution of ethyl paratoluenesulfonate was used instead of the 50% by mass ethanol solution of cyclohexyl paratoluenesulfonate.
  • the initial viscosity of the curable composition in Comparative Example 2 was 2280 mPa ⁇ s. This composition was allowed to stand at room temperature and the change in viscosity over time was measured. As a result, the viscosity after 6 hours was 2250 mPa ⁇ s, and it was confirmed that the composition had a sufficient pot life.
  • a composite cured film having a thickness of 0.2 mm was obtained in the same manner as in Example 1 using the curable composition after 6 hours.
  • the elongation at break was 6.3%
  • the breaking strength was 71.5 MPa
  • the elastic modulus was 1.1 GPa
  • the elastic modulus was B
  • the overall judgment was also B, indicating no sufficient characteristics.
  • Comparative Example 3 The same procedure as in Example 1 was performed except that a 50% by mass ethanol solution of cyclohexyl paratoluenesulfonate was used instead of the 50% by mass ethanol solution of cyclohexyl paratoluenesulfonate.
  • the initial viscosity of the curable composition in Comparative Example 3 was 2340 mPa ⁇ s. This composition was allowed to stand at room temperature and the change in viscosity over time was measured. As a result, the viscosity after 6 hours was 2230 mPa ⁇ s, and it was confirmed that the composition had a sufficient pot life. However, when a composite cured film was prepared using the curable composition after the lapse of 6 hours in the same manner as in Example 1, the curing was insufficient and an appropriate cured product could not be obtained.

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Abstract

La présente invention se rapporte au problème de la fourniture d'une composition durcissable comprenant une résine furannique qui est capable d'allonger la durée de vie en pot en tant que composition ayant une aptitude au durcissement appropriée ainsi qu'un durcissement approprié à des températures modérées et d'améliorer diverses propriétés physiques du produit durci. Cette composition durcissable comprend une résine furannique et un ester secondaire d'acide sulfonique.
PCT/JP2017/030381 2016-08-25 2017-08-24 Composition durcissable, produit durci et stratifié WO2018038220A1 (fr)

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JPH02258862A (ja) * 1989-01-24 1990-10-19 Monsanto Co ハイブリッドアミノ樹脂組成物
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JP2007510543A (ja) * 2003-11-07 2007-04-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー カルバメート透明塗装上のフロントガラス用プライマーレス・シーラントの接着性を達成する方法
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WO2014171305A1 (fr) * 2013-04-16 2014-10-23 住友ベークライト株式会社 Composition de résine, agent d'injection et procédé de remplissage
WO2016031988A1 (fr) * 2014-08-29 2016-03-03 積水化学工業株式会社 Résine furannique, son procédé de production, composition de résine furannique thermodurcissable, produit durci, et composite de résine furannique

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