Curable resin composition, resin molded article, and method for producing resin molded article

Abstract

To provide a curable resin composition that can reduce fluctuations in curing reactivity caused by differences in the production source of fly ash.SOLUTION: A curable resin composition comprises a polyol compound, an isocyanate compound, reinforcing long fibers having a fiber length of 50 mm or more, and a combustion product of fly ash, wherein the combustion product of fly ash either comprises no unburned carbon or comprises unburned carbon, and when the combustion product of fly ash comprises unburned carbon, the unburned carbon content in 100 wt.% of the combustion product of fly ash is 0.15 wt.% or less.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a curable resin composition containing a polyol compound and an isocyanate compound. The present invention also relates to a resin molded article using the curable resin composition and a method for producing a resin molded article using the curable resin composition. [Background technology]

[0002] In recent years, resin molded bodies are sometimes used as structural materials such as building materials instead of wood, etc. For example, as railroad ties, resin molded body sleepers are sometimes used instead of wooden sleepers and concrete sleepers.

[0003] As an example of such a resin molded product, the following Patent Document 1 discloses a resin molded product molded from a resin composition containing 1% by weight to 15% by weight of glass fiber and 30% by weight to 85% by weight of fly ash having a diameter distribution of 5 μm to 200 μm. In the examples of Patent Document 1, a polyol compound, an isocyanate compound, a filler, glass fiber, and a catalyst are mixed in an extruder to prepare a resin composition, which is then extruded under pressure into a mold through the extruder head to produce a resin molded product. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2007 / 014332A2 Summary of the Invention [Problem to be solved by the invention]

[0005] As described in Patent Document 1, a resin molded body may be produced by curing a curable resin composition containing a polyol compound, an isocyanate compound, and fly ash. The present inventors have found that the curing reactivity of the curable resin composition varies depending on the production area of ​​the fly ash. If the curing reactivity of the curable resin composition varies, a resin molded body may not be obtained satisfactorily.

[0006] An object of the present invention is to provide a curable resin composition capable of suppressing variation in curing reactivity due to differences in the origin of fly ash. Another object of the present invention is to provide a resin molded product using the curable resin composition and a method for producing a resin molded product using the curable resin composition. [Means for solving the problem]

[0007] This specification discloses the following curable resin composition, resin molded article, and method for producing a resin molded article.

[0008] Item 1. A curable resin composition comprising a polyol compound, an isocyanate compound, reinforcing long fibers having a fiber length of 50 mm or more, and a combusted product of fly ash, wherein the combusted product of fly ash does not contain unburned carbon or contains unburned carbon, and when the combusted product of fly ash contains unburned carbon, the content of unburned carbon is 0.15% by weight or less in 100% by weight of the combusted product of fly ash.

[0009] Item 2. The curable resin composition according to item 1, wherein the content of the fly ash combustion product is 40 parts by weight or more and 240 parts by weight or less relative to 100 parts by weight of the total of the polyol compound and the isocyanate compound.

[0010] Item 3. The curable resin composition according to item 1 or 2, wherein the content of the reinforcing long fiber is 40 parts by weight or more and 380 parts by weight or less per 100 parts by weight of the total of the polyol compound and the isocyanate compound.

[0011] Item 4. The curable resin composition according to any one of Items 1 to 3, wherein the reinforcing long fibers are long glass fibers.

[0012] Item 5. The curable resin composition according to any one of Items 1 to 4, further comprising a foaming agent.

[0013] Item 6. A resin molded product comprising a urethane resin, reinforcing long fibers having a fiber length of 50 mm or more, and a combustion product of fly ash, the resin molded product being a cured product of the curable resin composition according to any one of items 1 to 5.

[0014] Item 7. The resin molded article according to item 6, which is a foamed resin molded article.

[0015] Item 8. The resin molded article according to item 7, wherein the expansion ratio of the urethane resin is 1.1 times or more and 5 times or less.

[0016] Item 9. The resin molded article according to any one of items 6 to 8, which is a sleeper.

[0017] Item 10. A method for producing a resin molded product according to any one of items 6 to 9, comprising: a step of obtaining a first composition containing a polyol compound, an isocyanate compound, and a combusted product of fly ash; an impregnation step of impregnating a space between reinforcing long fibers with the first composition to obtain a curable resin composition; and a curing step of curing the curable resin composition in a mold.

[0018] Item 11. The method for producing a resin molded product according to Item 10, further comprising a combustion step of combusting fly ash to obtain a fly ash combustion product prior to the step of obtaining the first composition.

[0019] Item 12. The method for producing a resin molded product according to Item 11, wherein in the combustion step, the fly ash is burned at 500° C. or more and 1000° C. or less for one hour or more.

[0020] Item 13. The method for producing a resin molded product according to any one of items 10 to 12, wherein the step of obtaining the first composition includes a step of obtaining a composition A containing a polyol compound and a combustion product of fly ash, and a step of mixing the composition A with an isocyanate compound to obtain the first composition.

[0021] Item 14. The method for producing a resin molded product according to Item 13, wherein the pH of the composition A is 11.8 or more.

[0022] Item 15. The method for producing a resin molded body according to any one of Items 10 to 14, wherein the content of the fly ash combustion product in the first composition is 40 parts by weight or more and 240 parts by weight or less relative to 100 parts by weight of the total of the polyol compound and the isocyanate compound in the first composition.

[0023] Item 16. The method for producing a resin molded product according to any one of Items 10 to 15, wherein the first composition contains a foaming agent, and in the curing step, the curable resin composition is foamed and cured in a mold. Effect of the Invention

[0024] The curable resin composition according to the present invention includes a polyol compound, an isocyanate compound, reinforcing long fibers having a fiber length of 50 mm or more, and a fly ash combustion product, and the fly ash combustion product does not contain or contains unburned carbon. In the curable resin composition according to the present invention, when the fly ash combustion product contains unburned carbon, the content of unburned carbon is 0.15% by weight or less in 100% by weight of the fly ash combustion product. Since the curable resin composition according to the present invention has the above-mentioned configuration, it is possible to suppress variation in curing reactivity due to differences in the production area of ​​the fly ash. [Brief description of the drawings]

[0025] [Figure 1] FIG. 1 is a cross-sectional view that illustrates a resin molded product according to one embodiment of the present invention. [Diagram 2]FIG. 2 is a diagram for explaining a method for producing a resin molded product according to one embodiment of the present invention. [Diagram 3] FIG. 3 is a graph in which the horizontal axis represents the test items of the cup test and the vertical axis represents the measurement results in Experimental Examples 1 to 8. [Figure 4] FIG. 4 is a graph in which the horizontal axis represents the test items of the cup test and the vertical axis represents the measurement results in Experimental Examples 6A to 7A. [Diagram 5] FIG. 5 is a graph in which the horizontal axis represents the test items of the cup test and the vertical axis represents the measurement results in Experimental Examples 2B to 7B. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] The present invention will be described in detail below.

[0027] (Curable resin composition) The curable resin composition according to the present invention includes a polyol compound, an isocyanate compound, reinforcing long fibers having a fiber length of 50 mm or more, and a fly ash combustion product, and the fly ash combustion product does not contain unburned carbon or contains unburned carbon. In the curable resin composition according to the present invention, when the fly ash combustion product contains unburned carbon, the content of unburned carbon is 0.15% by weight or less in 100% by weight of the fly ash combustion product.

[0028] Since the curable resin composition according to the present invention has the above-mentioned configuration, it is possible to suppress variations in curing reactivity due to differences in the production area of ​​fly ash.

[0029] Fly ash generally contains unburned carbon. The content of unburned carbon contained in fly ash varies depending on the origin of the fly ash. For example, fly ash contains about 1 to 5% by weight of unburned carbon. The present inventors have found that the unburned carbon contained in fly ash affects the curing reactivity of the curable resin composition. This is presumably because a highly polar component (e.g., a catalyst) in the curable resin composition is adsorbed to the unburned carbon, and the function of the component is reduced or lost. The present inventors have found that the variation in the curing reactivity of the curable resin composition can be suppressed by burning the fly ash to reduce the amount of unburned carbon.

[0030] Hereinafter, the components contained in the curable resin composition according to the present invention will be described in detail.

[0031] [Polyol compounds] A polyol compound is a compound having two or more hydroxyl groups (-OH groups).

[0032] The polyol compound contained in the curable resin composition includes polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polyether polyol, etc. The polyol compound may be a polymer polyol. The polyol compound may be used alone or in combination of two or more kinds.

[0033] Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.

[0034] The polycarbonate polyol may be a dealcoholization reaction product of a hydroxyl group-containing compound and a carbonate compound. The hydroxyl group-containing compound may be ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, nonanediol, etc. The carbonate compound may be diethylene carbonate, dipropylene carbonate, etc.

[0035] Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, and cresol novolac.

[0036] Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.

[0037] Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

[0038] Examples of the polyester polyol include dehydration condensates of polybasic acids and polyhydric alcohols, ring-opening polymerization products of lactones, and condensates of hydroxycarboxylic acids and polyhydric alcohols. Examples of the polybasic acids include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. Examples of the polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. Examples of the lactones include ε-caprolactone and α-methyl-ε-caprolactone. Examples of the hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0039] The polyether polyol may be a ring-opening polymer of an active hydrogen compound having two or more active hydrogen atoms and an alkylene oxide. The alkylene oxide may be ethylene oxide, propylene oxide, tetrahydrofuran, or the like. The molecular weight of the active hydrogen compound is preferably small. The active hydrogen compound may be a diol compound such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, or 1,6-hexanediol; a triol compound such as glycerin or trimethylolpropane; or an amine compound such as ethylenediamine or butylenediamine.

[0040] Examples of the polymer polyol include graft polymers in which an unsaturated organic compound is graft polymerized onto a polyol compound, polybutadiene polyol, modified polyol of a polyhydric alcohol, and hydrogenated products thereof.

[0041] Examples of the polyol compound in the graft polymer include aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polyether polyol, etc. Examples of the unsaturated organic compound in the graft polymer include acrylonitrile, styrene, methyl acrylate, methacrylate, etc.

[0042] The modified polyol of the polyhydric alcohol may be a reaction modified product of a polyhydric alcohol with an alkylene oxide. Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof; phenolic compounds such as phenol, phloroglucine, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, anthrol, 1,4,5,8-tetrahydroxyanthracene, and 1-hydroxypyrene; polybutadiene polyols; castor oil polyols; (co)polymers of hydroxyalkyl (meth)acrylates; polyfunctional polyols (e.g., having 2 to 100 functional groups) such as polyvinyl alcohol; and condensates (novolacs) of phenol and formaldehyde. The alkylene oxide may be an alkylene oxide having 2 to 6 carbon atoms. Specific examples of the alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, and 1,4-butylene oxide. From the viewpoint of improving properties and reactivity, the alkylene oxide is preferably 1,2-propylene oxide, ethylene oxide, or 1,2-butylene oxide, and more preferably 1,2-propylene oxide or ethylene oxide. The alkylene oxide may be used alone or in combination of two or more kinds.

[0043] When two or more kinds of the alkylene oxides are used, the addition form may be block addition, random addition, or both block addition and random addition.

[0044] From the viewpoint of enhancing the dispersibility of the fly ash combustion product, the polyol compound is preferably a polyester polyol or a polyether polyol.

[0045] The viscosity of the polyol compound at 12° C. is preferably 200 cps or more, more preferably 300 cps or more, preferably 1000 cps or less, more preferably 800 cps or less. When the viscosity is equal to or more than the lower limit and equal to or less than the upper limit, the combustion products of the fly ash are more likely to impregnate between the reinforcing long fibers in the curable resin composition, and the abrasion resistance and flexural modulus of the resin molded product can be increased.

[0046] The viscosity at 12° C. can be measured, for example, using a Brookfield viscometer.

[0047] [Isocyanate compounds] An isocyanate compound is a compound having one or more isocyanate groups (-NCO groups).

[0048] Examples of the isocyanate compound contained in the curable resin composition include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. From the viewpoint of efficiently proceeding with the curing reaction, the isocyanate compound is preferably a polyisocyanate compound. The isocyanate compound may be used alone or in combination of two or more kinds.

[0049] Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

[0050] Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0051] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0052] The isocyanate compound is preferably diphenylmethane diisocyanate, since it is easily available and has excellent convenience.

[0053] The polyol compound and the isocyanate compound can be used in an appropriate amount so as to efficiently form a urethane bond. From the viewpoint of increasing the reaction efficiency, the content of the isocyanate compound is preferably 100 parts by weight or more, more preferably 120 parts by weight or more, even more preferably 130 parts by weight or more, preferably 180 parts by weight or less, more preferably 160 parts by weight or less, and even more preferably 150 parts by weight or less, relative to 100 parts by weight of the polyol compound. When the content of the isocyanate compound is the lower limit or more and the upper limit or less, the amount of unreacted polyol compound or unreacted isocyanate compound is reduced, and a resin molded product having a better bending elastic modulus is easily formed.

[0054] [Reinforced long fibers with fiber length of 50 mm or more] The reinforcing long fiber is a reinforcing fiber and a long fiber. The reinforcing fiber is a fibrous material having a certain strength. For example, carbon fiber, glass fiber, aramid fiber, etc. are known as reinforcing fibers. The reinforcing long fiber may be a reinforcing long fiber sheet.

[0055] Examples of the reinforcing long fibers contained in the curable resin composition include long carbon fibers, long glass fibers, long aramid fibers, long reinforcing fibers, etc. The reinforcing long fibers may be used alone or in combination of two or more kinds.

[0056] From the viewpoint of further increasing the flexural modulus of the resin molded article, the reinforcing long fibers are preferably long glass fibers. The long glass fibers are fibrous materials obtained by melting and drawing glass to form fibers.

[0057] From the viewpoint of increasing the flexural modulus of the resin molded body, the fiber length of the reinforcing long fiber is 50 mm or more, preferably 70 mm or more. The reinforcing long fiber can be cut to a desired size after pultrusion molding, and the fiber length of the reinforcing long fiber can be appropriately changed depending on the cutting length, so that the upper limit of the fiber length of the reinforcing long fiber is not particularly limited. Even if the fiber length of the reinforcing long fiber is long, the reinforcing long fiber can be made less likely to be cut or entangled by impregnating the reinforcing long fiber with a composition containing components other than the reinforcing long fiber. In addition, by pultrusion molding, molding is possible even if the blending ratio of the reinforcing long fiber is increased.

[0058] The reinforcing long fibers are preferably fibers obtained by roving monofilaments. The fiber diameter of the monofilaments is preferably 1 μm or more, more preferably 2 μm or more, and is preferably 50 μm or less, more preferably 40 μm or less.

[0059] The content of the reinforcing long fiber is preferably 40 parts by weight or more, more preferably 50 parts by weight or more, preferably 380 parts by weight or less, more preferably 300 parts by weight or less, and even more preferably 200 parts by weight or less, based on 100 parts by weight of the total of the polyol compound and the isocyanate compound. When the content of the reinforcing long fiber is equal to or more than the lower limit, the bending modulus of the resin molded product can be further increased. When the content of the reinforcing long fiber is equal to or less than the upper limit, the composition (first composition) containing the polyol compound, the isocyanate compound, and the combusted fly ash is easily impregnated between the reinforcing long fibers. In addition, the wear resistance and bending modulus of the resin molded product can be increased.

[0060] [Fly ash combustion products] The fly ash combustion product is a filler that is dispersed and filled in the resin part of the resin molded product to reinforce the strength. The fly ash combustion product can be obtained by burning fly ash.

[0061] The fly ash combustion product does not contain unburned carbon or contains unburned carbon. When the fly ash combustion product contains unburned carbon, the content of unburned carbon is 0.15% by weight or less in 100% by weight of the fly ash combustion product.

[0062] When the fly ash combustion product contains unburned carbon, the content of unburned carbon in 100% by weight of the fly ash combustion product is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, and even more preferably 0.01% by weight or less. When the content of unburned carbon is equal to or less than the upper limit, the effect of the present invention can be more effectively exhibited. Note that the content of unburned carbon in 100% by weight of the fly ash combustion product may be 0.01% by weight or more, or may be 0.05% by weight or more.

[0063] The content of unburned carbon in the fly ash combustion product can be measured, for example, as follows.

[0064] The weight of the fly ash combustion product is measured and designated as weight (A). The fly ash combustion product whose weight has been measured is placed in a crucible and ignited at 750±50°C for one hour, after which the fly ash combustion product is allowed to cool to room temperature (25°C) for ignition treatment. The weight of the fly ash combustion product after ignition treatment is measured and the weight change rate of the fly ash combustion product before and after one ignition treatment is determined. The above ignition treatment is repeated until the weight change rate of the fly ash combustion product is 0.1% by weight or less. The weight of the fly ash combustion product after the above ignition treatment when the weight change rate of the fly ash combustion product is 0.1% by weight or less is designated as weight (B). The content of unburned carbon in the fly ash combustion product is calculated from weight (A) and weight (B) using the following formula:

[0065] Unburned carbon content (wt%) = [AB] / A x 100 A: Weight (A) B: Weight (B)

[0066] An example of a method for reducing the content of unburned carbon in the fly ash combustion product to the above upper limit is a method in which the fly ash is burned at 500° C. or higher for one hour or more.

[0067] Examples of the fly ash in the fly ash combustion product include fly ash type I, fly ash type II, and fly ash type IV. The fly ash may be used alone or in combination of two or more. The fly ash combustion product may be used alone or in combination of two or more.

[0068] The above-mentioned fly ash type I is defined as a material with a silicon dioxide content of 45% or more, a 45μm sieve residue of 10% or less, and a specific surface area of ​​5000cm 2 / g or more.

[0069] The above-mentioned fly ash type II is defined as a material having a silicon dioxide content of 45% or more, a 45μm sieve residue of 40% or less, and a specific surface area of ​​2500cm. 2 / g or more.

[0070] The above-mentioned fly ash type IV is a type of ash with a silicon dioxide content of 45% or more, a 45μm sieve residue of 70% or less, and a specific surface area of ​​1500cm 2 / g or more.

[0071] From the viewpoint of improving the wear resistance and flexural modulus of the resin molded body, the specific gravity of the fly ash combustion product is preferably 2 or more, preferably 4 or less, more preferably less than 4, and even more preferably 3 or less. When the specific gravity of the fly ash combustion product is equal to or more than the lower limit and equal to or less than the upper limit (or less than the upper limit), the fly ash combustion product is less likely to settle and is easily uniformly dispersed in the curable resin composition. As a result, a resin molded body in which the fly ash combustion product is uniformly dispersed can be obtained satisfactorily.

[0072] The content of the fly ash combustion product is preferably 40 parts by weight or more, more preferably 60 parts by weight or more, and preferably 240 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the total of the polyol compound and the isocyanate compound. When the content of the fly ash combustion product is equal to or more than the lower limit, the wear resistance and flexural modulus of the resin molded product can be further improved.

[0073] [Foaming agent] A blowing agent is a substance that produces a gas upon decomposition or that is itself a gas.

[0074] From the viewpoint of obtaining a foamed resin molded product, the curable resin composition preferably contains a foaming agent. The foamed resin molded product can be obtained by foaming the curable resin composition with the foaming agent. The foamed resin molded product has an advantage of being lighter than a non-foamed resin molded product.

[0075] The foaming agent includes water and organic halogen compounds. The foaming agent is preferably water because it is easily available and has excellent convenience. Water acts as a foaming agent by reacting with an isocyanate compound to generate CO2. The foaming agent may be used alone or in combination of two or more kinds.

[0076] The organic halogen compound includes an organic chlorine compound, an organic fluorine compound, an organic bromine compound, and an organic iodine compound. The organic halogen compound may be an organic halogen compound in which all hydrogen atoms are replaced with halogen atoms, or an organic halogen compound in which some hydrogen atoms are replaced with halogen atoms. From the viewpoint of improving the foamability during the formation of the resin molded body and maintaining the thermal conductivity of the resin molded body low for a longer period of time, the organic halogen compound is preferably an organic chlorine compound or an organic fluorine compound.

[0077] The organic chlorine compounds include saturated organic chlorine compounds and unsaturated organic chlorine compounds. The saturated organic chlorine compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. From the viewpoint of improving the foamability during the formation of the resin molded body and maintaining the thermal conductivity of the resin molded body low for a longer period of time, the organic chlorine compounds are preferably saturated organic chlorine compounds, and more preferably saturated organic chlorine compounds having 2 to 5 carbon atoms.

[0078] The organic fluorine compound includes saturated organic fluorine compounds and unsaturated organic fluorine compounds.

[0079] The saturated organic fluorine compound may, for example, be a hydrofluorocarbon. Examples of the hydrofluorocarbon include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1,2,2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee).

[0080] The unsaturated organic fluorine compound may include hydrofluoroolefins, such as 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze) (E and Z isomers), and 1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz) (E and Z isomers).

[0081] Furthermore, the organic fluorine compound may also include a compound having a chlorine atom, a fluorine atom, and a double bond. Examples of the compound having a chlorine atom, a fluorine atom, and a double bond include 1,2-dichloro-1,2-difluoroethene (E and Z isomers) and hydrochlorofluoroolefins. The hydrochlorofluoroolefins include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) (E and Z isomers), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd) (E and Z isomers), 1-(4)chloro-1,3,3-trifluoropropene (HCFO-1233zb) (E and Z isomers), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xe) (E and Z isomers), 2-chloro-2,2,3-trifluoropropene (HCFO-1233xc), 2-chloro-3,3,3-trifluoropropene (HCFO-1233x ...2-chloro-3,3,3-trifluoropropene (HCFO-1233xc) (E and Z isomers), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xd) (E and Z isomers), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xc) (E and Z isomers), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xd) (E and Z isomers), 2-chloro HCFO-1233xf), 3-chloro-1,2,3-trifluoropropene (HCFO-1233ye) (E and Z isomers), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc), 3,3-dichloro-3-fluoropropene, 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd) (E and Z isomers), 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E and Z isomers), and 2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene (E and Z isomers).

[0082] From the viewpoint of improving the foaming properties during the formation of the resin molded body and maintaining the thermal conductivity of the resin molded body at a low level for an even longer period of time, the above-mentioned organic halogen compound is preferably a hydrochlorofluoroolefin, a hydrofluorocarbon, or a hydrofluoroolefin.

[0083] Considering the foaming property, the foaming agent can be used at an appropriate content. The content of the foaming agent is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 1.0 parts by weight or less, more preferably 0.8 parts by weight or less, based on 100 parts by weight of the polyol compound. When the content of the foaming agent is equal to or more than the lower limit, foaming is promoted, the resin molded body is well formed, and the resin molded body is less likely to have dimensional defects. When the content of the foaming agent is equal to or less than the upper limit, the curable resin composition can be prevented from overflowing from the mold due to excessive foaming.

[0084] [catalyst] A catalyst is a substance that accelerates a chemical reaction.

[0085] The curable resin composition preferably contains a catalyst. Examples of the catalyst include a urethanization catalyst and a trimerization catalyst. The catalyst may be used alone or in combination of two or more.

[0086] The curable resin composition preferably contains a urethanization catalyst, which promotes the reaction between the hydroxyl group of the polyol compound and the isocyanate group of the isocyanate compound to promote the formation of a urethane bond.

[0087] Examples of the urethanization catalyst include organic tin compounds such as dibutyltin dimaleate, dibutyltin diuralate, and dibutylbis(oleoyloxy)stannane; tertiary amine compounds such as triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl)ether, and N,N,N',N'',N''-pentamethyldiethylenetriamine; N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N-methyl,N'-dimethylaminoethylpiperazine, and imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group. The urethanization catalyst may be used alone or in combination of two or more.

[0088] The urethane catalyst can be used in an appropriate content so that the polyol compound and the isocyanate compound react well. The content of the urethane catalyst is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, preferably 1.0 parts by weight or less, more preferably 0.8 parts by weight or less, based on 100 parts by weight of the polyol compound. When the content of the urethane catalyst is above the lower limit, the urethane reaction proceeds effectively. When the content of the urethane catalyst is below the upper limit, the trimerization of the isocyanate group of the isocyanate compound is less likely to be inhibited.

[0089] The trimerization catalyst promotes the trimerization reaction of the isocyanate group of the isocyanate compound, promotes the formation of an isocyanurate ring, and further suppresses the expansion of the resin molded article during combustion.

[0090] Examples of the trimerization catalyst include aromatic compounds, alkali metal salts of carboxylic acids, quaternary ammonium salts of carboxylic acids, and quaternary ammonium salt / ethylene glycol mixtures. Examples of the aromatic compounds include tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine. Examples of the alkali metal salts of carboxylic acids include potassium acetate and potassium 2-ethylhexanoate. The trimerization catalyst may be used alone or in combination of two or more.

[0091] The trimerization catalyst can be used in an appropriate content so as to promote the trimerization reaction well. The content of the trimerization catalyst is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, preferably 1.0 parts by weight or less, and preferably 0.8 parts by weight or less, relative to 100 parts by weight of the polyol compound. When the content of the trimerization catalyst is equal to or more than the lower limit, the expansion of the resin molded body during the formation of the resin molded body is easily suppressed. When the content of the trimerization catalyst is equal to or less than the upper limit, the formation of the urethane bond is less likely to be inhibited.

[0092] [Other ingredients] The curable resin composition may contain other components such as a flame retardant, a foam stabilizer, a thixotropic agent, and a filler other than fly ash, within the scope of the present invention. The other components may be used alone or in combination of two or more.

[0093] The flame retardant is a substance that, when added to a flammable material such as plastic, wood, or fiber, can impart flame retardancy to the material.

[0094] Examples of the flame retardant include nitrogen-containing non-halogen flame retardants, red phosphorus, phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, metal hydroxides, etc. The flame retardants may be used alone or in combination of two or more.

[0095] The foam stabilizer is a substance that prevents the bubbles from becoming coarse and uneven, and enables the bubbles to be formed stably and satisfactorily.

[0096] Examples of the foam stabilizer include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, silicone foam stabilizers such as organopolysiloxanes, etc. The foam stabilizers may be used alone or in combination of two or more.

[0097] The foam stabilizer can be used in an appropriate content so as to stably and satisfactorily form bubbles. From the viewpoint of stably and satisfactorily forming bubbles, the content of the foam stabilizer is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, even more preferably 0.2 parts by weight or more, preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and even more preferably 1 part by weight or less, relative to 100 parts by weight of the polyol compound.

[0098] Examples of the filler other than the fly ash include carbonate compounds, minerals, sulfate compounds, silicate compounds, clay, nitrides, carbon compounds, titanium compounds, metal borate compounds, sulfides, carbides, sand, and pyroclastic materials. Only one type of the filler other than the fly ash may be used, or two or more types may be used in combination.

[0099] (Other details of the curable resin composition) The curable resin composition can be prepared by mixing the polyol compound, the isocyanate compound, the reinforcing long fiber, the fly ash combustion product, and other components as necessary. The method of mixing each component is not particularly limited. A curable resin composition may be obtained by preparing a plurality of liquids containing one or a plurality of components and mixing the plurality of liquids. The mixing of the plurality of liquids may be performed when forming a resin molded body. The liquid containing the polyol compound may be mixed with the fly ash combustion product and the isocyanate compound, and then the reinforcing long fiber may be impregnated with this liquid. The liquid containing the polyol compound may be mixed with the fly ash combustion product, and then the isocyanate compound may be mixed, and then the reinforcing long fiber may be impregnated with this liquid.

[0100] (Resin molding) A resin molded body can be obtained by molding and curing the curable resin composition according to the present invention. The resin molded body is a cured product of the above-mentioned curable resin composition. The resin molded body is a molded and cured product of the above-mentioned curable resin composition. The resin molded body includes a urethane resin, a reinforcing long fiber having a fiber length of 50 mm or more, and a combusted fly ash. The resin molded body may be a foamed resin molded body. The resin molded body may be a foamed and cured product of the above-mentioned curable resin composition.

[0101] For example, the curable resin composition according to the present invention can be heated at 40° C. to 80° C., molded and cured to obtain a resin molded product.

[0102] FIG. 1 is a cross-sectional view that illustrates a resin molded product according to one embodiment of the present invention.

[0103] A resin molded body 91 shown in Fig. 1 contains a urethane resin 92, a reinforcing long fiber 93, and a fly ash combustion product 94. Fig. 1 shows a cross section of a fiber diameter portion of the reinforcing long fiber 93. The fiber length of the reinforcing long fiber 93 is 50 mm or more.

[0104] The expansion ratio of the urethane resin in the resin molded product is preferably 1.1 times or more, more preferably 1.5 times or more, and preferably 5 times or less, more preferably 3 times or less. When the expansion ratio is equal to or more than the lower limit, a lightweight foamed resin molded product is easily obtained. When the expansion ratio is equal to or less than the upper limit, a foamed resin molded product having a good bending elastic modulus is easily obtained.

[0105] The expansion ratio of the urethane resin is calculated by dividing the volume content of the resin in the resin molded body by the volume fraction V urethane , the volume content of the filler determined by the firing method of JIS K7052 V filler , and the volume fraction V of the reinforcing long fibers fiber It can be calculated by the following formula. When the resin molding contains only the above fly ash combustion material as a filler, V filler is the volume fraction of fly ash in the combustion product.

[0106] Urethane resin foaming ratio = (1-V filler -V fiber ) / V urethane

[0107] V urethane : Volume content of resin (volume %) V filler : Volume content of filler (volume %) V fiber : Volume content of reinforcing long fibers (volume%)

[0108] The content of the fly ash combustion product relative to 100 parts by weight of the urethane resin is preferably 40 parts by weight or more, more preferably 60 parts by weight or more, and preferably 240 parts by weight or less, more preferably 200 parts by weight or less. When the content of the fly ash combustion product is equal to or more than the lower limit, the abrasion resistance and flexural modulus of elasticity of the resin molded product can be further improved.

[0109] In 100% by volume of the resin molded body, the volume content of the fly ash combustion product is preferably 6% by volume or more, more preferably 10% by volume or more, preferably 30% by volume or less, more preferably 25% by volume or less. When the volume content of the fly ash combustion product is equal to or more than the lower limit and equal to or less than the upper limit, the abrasion resistance and the bending modulus can be further improved. When the volume content of the fly ash combustion product is equal to or more than the lower limit, the abrasion resistance can be further improved compared to when it is less than the lower limit.

[0110] The volume content of the fly ash combustion product can be determined in accordance with the calcination method described in JIS K7052.

[0111] The volume content of the reinforcing long fibers in 100 volume% of the resin molded body is preferably 6 volume% or more, more preferably 8 volume% or more, and preferably 25 volume% or less, more preferably 20 volume% or less. When the volume content of the reinforcing long fibers is equal to or more than the lower limit and equal to or less than the upper limit, the bending modulus of the resin molded body can be further increased.

[0112] The volume content of the reinforcing long fibers can be determined in accordance with the sintering method described in JIS K7052.

[0113] The reinforcing long fibers are preferably uniformly dispersed in the resin molded product. In the curable resin composition according to the present invention, the composition (first composition) containing a polyol compound, an isocyanate compound, and a fly ash combustion product is easily impregnated between the reinforcing long fibers, and the first composition is easily held between the reinforcing long fibers. As a result, the reinforcing long fibers are easily dispersed uniformly in the resin molded product.

[0114] The resin molded article is preferably used as a sleeper. The resin molded article is preferably a sleeper. The curable resin composition is preferably used to obtain a sleeper.

[0115] When the resin molding is used as a sleeper or the like, the size of the resin molding is preferably 140 mm×240 mm×2600 mm (height (h)×width (w)×length (l)).

[0116] The height (h) is preferably 50 mm or more, more preferably 70 mm or more, even more preferably 90 mm or more, and is preferably 300 mm or less, more preferably 280 mm or less, even more preferably 260 mm or less.

[0117] The width (w) is preferably 50 mm or more, more preferably 100 mm or more, even more preferably 150 mm or more, and is preferably 300 mm or less, more preferably 280 mm or less, even more preferably 260 mm or less.

[0118] The length (l) is preferably 300 mm or more, more preferably 800 mm or more, even more preferably 1200 mm or more, and preferably 5000 mm or less, more preferably 3800 mm or less, even more preferably 3500 mm or less.

[0119] When the size of the resin molded body is equal to or larger than the above lower limit and equal to or smaller than the above upper limit, the resin molded body has a satisfactory bending elastic modulus as a sleeper.

[0120] The shape of the sleeper is not particularly limited. For example, the sleeper may be a rectangular parallelepiped sleeper, or may be a sleeper having a rectangular parallelepiped main body and a protrusion protruding outward from the main body.

[0121] The sleeper (resin molded product) may have a length direction and a width direction. From the viewpoint of further improving the bending elastic modulus of the sleeper, it is preferable that the reinforcing long fibers are arranged along the length direction of the sleeper (resin molded product).

[0122] (Manufacturing method of resin molded body (sleeper)) The method for producing a resin molded product according to the present invention preferably includes a step of obtaining a first composition containing a polyol compound, an isocyanate compound, and a combustion product of fly ash, an impregnation step of impregnating spaces between reinforcing long fibers with the first composition to obtain a curable resin composition, and a curing step of curing the curable resin composition in a mold.

[0123] In the method for producing a resin molded product according to the present invention, it is preferable to further include a combustion step of combusting fly ash to obtain a fly ash combustion product prior to the step of obtaining the first composition.

[0124] In the method for producing a resin molded product according to the present invention, it is preferable that the step of obtaining the first composition includes a step of obtaining a composition A containing a polyol compound and a combustion product of fly ash, and a step of mixing the composition A with an isocyanate compound to obtain the first composition.

[0125] Fig. 2 is a diagram for explaining a method for producing a resin molded article according to one embodiment of the present invention, Fig. 2 is a diagram for explaining a method for producing a resin molded article used as a sleeper.

[0126] The manufacturing apparatus 100 includes a hopper 11, a belt feeder 12, an extruder 4 with a built-in screw, a pump 43, a first raw material tank 21, a pump 22, a second raw material tank 31, a pump 51, a mixing and spraying device 5, a kneading plate 61, an impregnation plate 62, and a mold 63 with a heating section.

[0127] <Combustion process> Fly ash is prepared. The fly ash is combusted to obtain a fly ash combustion product.

[0128] In the combustion step, the fly ash is preferably burned at 500°C or higher and 1000°C or lower for 1 hour or longer. In this case, a fly ash combustion product with a low content of unburned carbon is efficiently obtained. The combustion temperature of the fly ash is more preferably 550°C or higher, and more preferably 900°C or lower. The combustion time of the fly ash is preferably 3 hours or shorter, and more preferably 2 hours or shorter.

[0129] <Step of Obtaining First Composition> The fly ash combustion product 1 is charged into a hopper 11, and then the fly ash combustion product 1 is transported by a belt feeder 12 and supplied to an extruder 4. Also, a first raw material 2 is charged into a first raw material tank 21 and mixed. The first raw material 2 is a liquid containing a polyol compound and a foaming agent. The first raw material 2 is supplied to the extruder 4 by a pump 22. In the extruder 4, the fly ash combustion product 1 and the first raw material 2 are mixed by the rotation of the screw of the extruder 4, and a composition A, which is a mixed liquid of the fly ash combustion product 1 and the first raw material 2, is obtained. Therefore, the composition A contains a polyol compound, a fly ash combustion product, and a foaming agent. The first raw material may not contain a foaming agent. Also, the first raw material may contain a catalyst, may contain a foam stabilizer, or may contain a catalyst and a foam stabilizer.

[0130] The pH of composition A is preferably 11.7 or more, more preferably 11.8 or more, and preferably 12.0 or less. Fly ash contains sulfuric anhydride (SO3) derived from FeS2 in the raw coal, and the content of sulfuric anhydride also varies depending on the origin of the fly ash. When fly ash is used, the pH of composition A varies depending on the origin of the fly ash, so the curing reactivity of the curable resin composition is likely to vary. In contrast, in the present invention, since the combusted material of fly ash is used, sulfuric anhydride is effectively removed during the combustion of the fly ash, and the content of sulfuric anhydride in the combusted material of the fly ash can be reduced. Therefore, the variation in the pH of composition A can be suppressed. As a result, the variation in the pH of the curable resin composition can be suppressed, and the variation in the curing reactivity due to the difference in the origin of the fly ash can be suppressed. In addition, since the curing reaction of the urethane resin proceeds better at a higher pH, the curing reactivity can be increased by having the pH of composition A be equal to or higher than the above lower limit.

[0131] The second raw material 3 is charged into the second raw material tank 31. The second raw material 3 is an isocyanate compound.

[0132] Composition A is supplied to the mixing and spraying device 5 by a pump 43. The second raw material 3 is supplied to the mixing and spraying device 5 by a pump 51. In the mixing and spraying device 5, composition A and the second raw material 3 are uniformly mixed to obtain a first composition 7 (a mixed liquid of a polyol compound, an isocyanate compound, a fly ash combustion product 1, and a blowing agent).

[0133] The content of the fly ash combustion product 1 in the first composition 7 is preferably 40 parts by weight or more, more preferably 60 parts by weight or more, even more preferably 100 parts by weight or more, preferably 240 parts by weight or less, more preferably 200 parts by weight or less, and even more preferably 170 parts by weight or less, relative to 100 parts by weight of the total of the polyol compound and the isocyanate compound in the first composition 7. That is, in the step of obtaining the first composition 7, it is preferable to mix the polyol compound, the isocyanate compound, and the fly ash combustion product 1 so that the content of the fly ash combustion product 1 satisfies the above-mentioned preferable lower limit or upper limit relative to 100 parts by weight of the total of the polyol compound and the isocyanate compound.

[0134] <Impregnation process> The first composition 7 is sprayed onto the reinforcing long fiber bundle 8, which is a fiber bundle of reinforcing long fibers, from the discharge port of the mixing and spraying device 5. It is preferable that the first composition 7 is sprayed onto the reinforcing long fiber bundle 8 while the reinforcing long fiber bundle 8 is moved in one direction. The reinforcing long fiber is a long glass fiber, and the reinforcing long fiber bundle 8 is a long glass fiber bundle.

[0135] The first composition 7 and the reinforcing long fiber bundles 8 are kneaded between the kneading plate 61 and the impregnation plate 62, and the first composition 7 is uniformly impregnated between the reinforcing long fibers constituting the reinforcing long fiber bundles 8. In this manner, a curable resin composition 81 is obtained.

[0136] In the impregnation step, it is preferable that the first composition is impregnated between the reinforcing long fibers so that the content of the reinforcing long fibers is 20 parts by weight or more and 150 parts by weight or less per 100 parts by weight of the first composition.

[0137] <Curing process> A foamed resin molded article can be produced by foaming and curing the curable resin composition 81 in the mold 63. More specifically, the curable resin composition 81 is transferred to the mold 63, and the curable resin composition 81 is foamed and cured in the mold 63 to produce a foamed resin molded article corresponding to the shape of the mold 63. By sequentially transferring the curable resin composition 81 to the mold 63, the foamed resin molded articles can be produced continuously.

[0138] In addition, when the curable resin composition 81 does not contain a foaming agent, the curable resin composition 81 can be cured in the mold 63 to produce a resin molded body corresponding to the shape of the mold 63.

[0139] An experimental example is shown below.

[0140] The following materials were prepared:

[0141] (Polyol Compound) Polyether polyol ("V883" manufactured by Sumika Covestro Urethane Co., Ltd.)

[0142] (Isocyanate compounds) Diphenylmethane diisocyanate ("DESMODUR" manufactured by Sumika Covestro Urethane Co., Ltd.)

[0143] (Fly ash) Fly ash 1 (EP ENERGO MINERAL "Fly Ash in June") Fly Ash 2 (EP ENERGO MINERAL "Fly Ash in July") Fly ash 3 ("Takehara Fly Ash Type II" manufactured by Tokyo Power Technology Co., Ltd.) Fly ash 4 (Tokyo Power Technology's "Hekinan Fly Ash Type II") Fly ash 5 ("Fly ash type II" manufactured by Shiden Business Co., Ltd.) Fly ash 6 (Kansai Electric Power Co.'s "Fly ash type II") Fly ash 7 (Zero Techno's "High quality fly ash type II") Fly ash 8 (Chugoku Electric Power "Fly ash type II")

[0144] (foaming agent) water

[0145] (catalyst) Amine catalyst A (Evonik Japan "POLYCAT SA1 / 10") Amine catalyst B (Evonik Japan "DABCO 33LV")

[0146] (Foam stabilizer) Silicone oil (Evonik Japan "TEGOSTAB B 8404")

[0147] (Preparation of fly ash combustion products) <Combustion conditions: 550℃ and 1 hour> The fly ash 6 was burned in an oven at 550°C for 1 hour to obtain a fly ash combustion product 6A. Similarly, the fly ash 7 was burned in an oven at 550°C for 1 hour to obtain a fly ash combustion product 7A.

[0148] <Combustion conditions: 900℃ and 1 hour> The fly ash 2 was burned in an oven at 900° C. for 1 hour to obtain the fly ash combustion product 2B. Similarly, the fly ash 3 to 7 were each burned in an oven at 900° C. for 1 hour to obtain the fly ash combustion products 3B to 7B.

[0149] (Experimental Examples 1 to 8) The polyol compound, fly ash, foaming agent, catalyst, and foam stabilizer were placed in a 500 mL disposable cup and stirred at 2000 rpm for 60 seconds using a Homo Disper 2.5 (manufactured by Primix Corporation) to obtain composition A. The amounts of each component and the type of fly ash are shown in the table below.

[0150] A composition B was prepared by placing 104.0 parts by weight of the isocyanate compound in a 300 mL disposable cup.

[0151] (Experimental Examples 6A to 7A and 2B to 7B) Compositions A and B were obtained in the same manner as in Experimental Examples 1 to 8, except that fly ash was replaced with a fly ash combustion product. The amounts of each component and the types of fly ash combustion product are shown in the table below.

[0152] (evaluation) (1) Unburned carbon content The content of unburned carbon in the fly ash combustion products 6A to 7A and 2B to 7B was determined by the above-mentioned method. Also, the content of unburned carbon in the fly ash 1 to 8 was determined by the above-mentioned method (except that fly ash was used instead of the fly ash combustion product).

[0153] (2) pH of Composition A The pH of Composition A was measured.

[0154] (3) Hardening reactivity (cup test) Composition A and composition B were left to stand at 20° C. for 3 hours, and the temperatures of composition A and composition B were adjusted to 20±0.5° C. Then, the entire amount of composition A and the entire amount of composition B were mixed to obtain a first composition. The obtained first composition was stirred at 20±0.5° C. at 2000 rpm for 30 seconds using a Homo Disper 2.5 type (manufactured by Primix Corporation) to allow the curing reaction to proceed.

[0155] (3-1) Cream Time (CT) The liquid level of the first composition before stirring with Homo Disper 2.5 type was set as the reference level. The time from the start of stirring with Homo Disper 2.5 type until the liquid level of the reactant reached a position 4 mm higher than the reference level was measured, and this time was set as the cream time (CT).

[0156] (3-2) Full-fill time The time required for the volume of the reactant to reach the volume of the expansion ratio was measured, and this time was regarded as the full-fill time.

[0157] (3-3) Gel Time (GT) The time from the start of stirring with a Homo Disper 2.5 type to the time when the reactant's surface became threadlike when touched was measured, and this time was taken as the gel time (GT).

[0158] (3-4) Tag Free Time (TFT) The time from the start of stirring with the Homo Disper 2.5 type to the time when the reactant no longer adhered to the finger even when the surface of the reactant was touched was measured, and this time was defined as the tag-free time (TFT).

[0159] (3-5) Rise Time (RT) The time from the start of stirring with Homo Disper 2.5 type to the end of the foaming reaction and the end of the rise in the surface height of the reactants was measured, and this time was defined as the rise time (RT).

[0160] Details and results are shown in Tables 1 to 3 and Figures 3 to 5 below.

[0161] [Table 1]

[0162] [Table 2]

[0163] [Table 3]

[0164] Fig. 3 is a graph in which the horizontal axis indicates the test items in the cup test and the vertical axis indicates the measurement results in Experimental Examples 1 to 8. Fig. 4 is a graph in which the horizontal axis indicates the test items in the cup test and the vertical axis indicates the measurement results in Experimental Examples 6A to 7A. Fig. 5 is a graph in which the horizontal axis indicates the test items in the cup test and the vertical axis indicates the measurement results in Experimental Examples 2B to 7B. In Figs. 4 and 5, "combustion products of fly ash" is abbreviated to "fly ash".

[0165] As shown in Figure 3, it can be seen that the hardening reactivity varies depending on the origin of the fly ash. On the other hand, as shown in Figures 4 and 5, it can be seen that the variation in hardening reactivity due to the origin of the fly ash can be suppressed by reducing the content of unburned carbon.

[0166] Although no reinforcing long fibers were used in this experiment, similar results to those of this experiment can be obtained when reinforcing long fibers are used. [Explanation of symbols]

[0167] 1. Fly ash combustion products 2...First raw material 3...Second raw material 4…Extruder 5…Mixing spraying device 7...First composition 8…Reinforced long fiber bundle 11. Hopper 12…Belt feeder 21…First raw material tank 22…Pump 31…Second raw material tank 43…Pump 51…Pump 61...Kneading board 62...Impregnated board 63...Mold 81...Curable resin composition 91...Resin molding 92...Urethane resin 93...Reinforced long fiber 94...Fly ash combustion products 100...Manufacturing equipment

Claims

1. The present invention relates to a method for making a composite material for a fly ash composite material, the method comprising: forming a composite material for a fly ash composite material; The fly ash combustion product does not contain or contains unburned carbon, A curable resin composition, wherein when the fly ash combustion product contains unburned carbon, the content of unburned carbon is 0.15% by weight or less based on 100% by weight of the fly ash combustion product.

2. The curable resin composition according to claim 1, wherein the content of the fly ash combustion product is 40 parts by weight or more and 240 parts by weight or less per 100 parts by weight of the total of the polyol compound and the isocyanate compound.

3. 3. The curable resin composition according to claim 1, wherein the content of the reinforcing long fiber is 40 parts by weight or more and 380 parts by weight or less per 100 parts by weight of the total of the polyol compound and the isocyanate compound.

4. The curable resin composition according to claim 1 or 2, wherein the reinforcing long fibers are long glass fibers.

5. The curable resin composition according to claim 1 or 2, further comprising a foaming agent.

6. The present invention includes a urethane resin, a reinforcing long fiber having a fiber length of 50 mm or more, and a combusted fly ash, A resin molded article which is a cured product of the curable resin composition according to claim 1 or 2.

7. The resin molded article according to claim 6, which is a foamed resin molded article.

8. The resin molded article according to claim 7, wherein the expansion ratio of the urethane resin is 1.1 times or more and 5 times or less.

9. The resin molded article according to claim 6, which is a railroad tie.

10. A method for producing the resin molded article according to claim 6, comprising the steps of: Obtaining a first composition comprising a polyol compound, an isocyanate compound, and a fly ash combustion product; an impregnation step of impregnating the first composition between reinforcing long fibers to obtain a curable resin composition; and a curing step of curing the curable resin composition in a mold.

11. The method for producing a resin molded article according to claim 10, further comprising a combustion step of combusting fly ash to obtain a fly ash combustion product, prior to the step of obtaining the first composition.

12. The method for producing a resin molded product according to claim 11, wherein in the combustion step, the fly ash is burned at 500°C or higher and 1000°C or lower for one hour or longer.

13. The step of obtaining the first composition comprises: Obtaining a composition A containing a polyol compound and a fly ash combustion product; The method for producing a resin molded article according to claim 10, further comprising: a step of mixing the composition A with an isocyanate compound to obtain a first composition.

14. The method for producing a resin molded article according to claim 13, wherein the pH of the composition A is 11.8 or more.

15. 11. The method for producing a resin molded body according to claim 10, wherein the content of the fly ash combustion product in the first composition is 40 parts by weight or more and 240 parts by weight or less per 100 parts by weight of the total of the polyol compound and the isocyanate compound in the first composition.

16. the first composition comprises a blowing agent; The method for producing a resin molded article according to claim 10 , wherein in the curing step, the curable resin composition is foamed and cured in a mold.

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