JP2020015785A - Foam molded body - Google Patents

Abstract

To provide a foam molded body capable of enhancing compression strength and flexure elastic modulus, suppressing abrasion of processing tools when processed by using the processing tools, and maintaining processing tolerance high.SOLUTION: The foam molded body is a foam molded body containing a cured article of a heat curable compound, a filler, and a fiber, and having content of the filler of 15 wt.% to 50 wt.%, content of the fiber of 15 wt.% to 50 wt.%, and compression fracture strength of the filler of less than 200 mN.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a foamed molded article containing a cured product of a thermosetting compound, a filler, and fibers.

  Conventionally, wood has been used as a sleeper for supporting rails, a board for supporting a hull during shipbuilding, a linker for placing building materials, and a lightweight and easy-to-process building material. However, when wood is used for such purposes, the wood may corrode or absorb water, and the strength of the wood may decrease.

  On the other hand, synthetic wood is known as a material that is hardly corroded and hardly absorbs water. By using a foamed molded article including a plurality of cells as synthetic wood, the weight of the synthetic wood can be reduced. Further, in order to increase the compressive strength of the foamed molded article, a filler may be blended in the foamed molded article.

  As an example of a foamed molded article containing a filler, Patent Literature 1 below contains a large number of long fibers aligned in one direction and a filler, and the content of the filler is 15% by weight or less. A long fiber reinforced curable resin foam molded article is disclosed. In addition, according to Patent Document 1, when the content of the filler exceeds 15% by weight, the viscosity of the foaming curable resin liquid impregnated into the bundle of long fibers significantly increases, and the filler is uniformly dispersed in the bundle of long fibers. It is described that it is difficult to impregnate the foamed molded article, and as a result, the long fibers are not uniformly dispersed in the foamed molded article, and the physical properties such as the mechanical strength of the foamed molded article are reduced.

  Patent Literature 2 below discloses a technique for improving the strength of a foamed molded article by reducing the content of fibers and increasing the content of a filler. Specifically, Patent Document 2 contains a thermosetting component, a filler, and a short fiber, the content of the filler is 30 to 85% by weight, and the content of the short fiber is 1 to 15% by weight. % Or less.

JP 2000-80191 A WO2007 / 014332A2

  A conventional foam molded article as described in Patent Document 1 may have low compressive strength in some cases. For this reason, when pressure is applied to the foamed molded product, for example, by placing a member or the like on the foamed molded product, the foamed molded product may be deformed, or the foamed molded product may be cracked or cracked. Further, in the foam molded article described in Patent Document 1, although the content of the fiber can be increased, the content of the filler cannot be increased, so that the apparent density increases and the weight of the foam molded article decreases. Heavier.

  In the foam molded article described in Patent Literature 2, since the content of the filler can be increased, the compressive strength can be increased to some extent. However, in the foam molded article described in Patent Literature 2, since the content of the fiber amount is small and short fibers are used as the fibers, when a load is applied to the foam molded article, bending deformation may occur. It is difficult to maintain the initial shape. Therefore, when the foam molded article described in Patent Document 2 is used as, for example, a sleeper, the possibility that the train will derail from the track cannot be denied.

  There is a trade-off between the amount of filler and the amount of fiber that can be blended in the foamed molded article, and it is difficult to increase the amount of filler and the amount of fiber.

  In addition, when a conventional foam molded article containing a filler is cut using a cutting tool or drilled using a drill, a processing tool such as a cutting tool or a drill comes into contact with the filling material and the processing tool. May be worn or damaged. For this reason, if the processed foam is continuously processed using the worn processing tool, the processing accuracy may be reduced.

  An object of the present invention is to provide a foam molded article that can increase compressive strength and flexural modulus, suppress wear of a processing tool when processing using the processing tool, and maintain high processing accuracy. That is.

  According to a wide aspect of the present invention, there is provided a foamed molded article containing a cured product of a thermosetting compound, a filler, and fibers, wherein the content of the filler is 15% by weight or more and 50% by weight or less. In addition, the present invention provides a foam molded article, wherein the content of the fiber is 15% by weight or more and 50% by weight or less, and the compressive breaking strength of the filler is less than 200 mN.

  In a specific aspect of the foam molded article according to the present invention, the cured product of the thermosetting compound contains a urethane resin.

  In a specific aspect of the foam molded article according to the present invention, the filler is fly ash I type or fly ash II type.

  In a specific aspect of the foam molded article according to the present invention, the fiber is a reinforced long fiber.

  The foam molded article according to the present invention is preferably made of synthetic wood.

  The foam molded article according to the present invention is a foam molded article containing a cured product of a thermosetting compound, a filler, and fibers. In the foamed molded article according to the present invention, the content of the filler is 15% by weight or more and 50% by weight or less, the content of the fiber is 15% by weight or more and 50% by weight or less, and the compression fracture of the filler is performed. The strength is less than 200 mN. In the foam molded article according to the present invention, since the above-described configuration is provided, the compressive strength and the bending elastic modulus can be increased, and when processing using the processing tool, the wear of the processing tool is suppressed, and the processing accuracy is improved. Can be kept high.

FIG. 1 is a cross-sectional view schematically showing a foam molded article according to the first embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

  The foam molded article according to the present invention is a foam molded article containing a cured product of a thermosetting compound, a filler, and fibers. In the foamed molded article according to the present invention, the content of the filler is 15% by weight or more and 50% by weight or less, the content of the fiber is 15% by weight or more and 50% by weight or less, and the compression fracture of the filler is performed. The strength is less than 200 mN.

  In the foam molded article according to the present invention, since the above-described configuration is provided, the compressive strength and the bending elastic modulus can be increased, and when processing using the processing tool, the wear of the processing tool is suppressed, and the processing accuracy is improved. Can be kept high.

  Since the foamed molded article according to the present invention has the above-described configuration, it is lightweight and excellent in handleability.

  FIG. 1 is a cross-sectional view schematically showing a foam molded article according to the first embodiment of the present invention.

  The foam molded article 1 shown in FIG. 1 includes a cured product 11 of a thermosetting compound, a fiber 12, and a filler 13. FIG. 1 shows a cross section of a fiber diameter portion of the fiber 12.

  The foam molded article can be obtained by foaming a curable composition containing a thermosetting component, a filler, a fiber, and a foaming agent. In the curable composition, the content of the filler is 15% by weight or more and 50% by weight or less, and the content of the fiber is 15% by weight or less in 100% by weight of the component in the curable composition excluding the blowing agent. % By weight or more and 50% by weight or less. In the curable composition, the filler has a compressive breaking strength of less than 200 mN.

  The curable composition can be favorably foamed. By foaming the curable composition, it is possible to increase the compressive strength and the flexural modulus, and to suppress the wear of the processing tool when processing with the processing tool, and to maintain the processing accuracy high. A molded article can be obtained.

  Hereinafter, details of the components contained in the curable composition and the components constituting the foamed molded article according to the present invention will be described.

(Thermosetting component and cured product of thermosetting compound)
The curable composition contains a thermosetting component. The foam molded article according to the present invention contains a cured product of a thermosetting compound. As the cured product of the thermosetting component and the thermosetting compound, only one type may be used, or two or more types may be used in combination.

  By thermosetting the thermosetting component, a cured product of the thermosetting compound can be obtained. The thermosetting component preferably includes a first compound and a second compound that reacts with the first compound. A cured product of the thermosetting compound can be obtained by reacting the first compound with the second compound and thermosetting the same. As the first compound and the second compound, only one kind may be used, or two or more kinds may be used in combination.

  Examples of the cured product of the thermosetting compound include a urethane resin, a phenol resin, and a polyester resin.

  Examples of the first compound used for obtaining the urethane resin include a polyol compound. Examples of the second compound used for obtaining the urethane resin include an isocyanate compound. A urethane resin can be obtained by reacting the polyol compound and the isocyanate compound in the presence of a urethane-forming catalyst.

  Examples of the first compound used for obtaining the phenol resin include phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcinol, and modified products thereof. Examples of the second compound used to obtain the phenol resin include formaldehyde, paraformaldehyde, furfural, and acetaldehyde.

  Examples of the first compound used to obtain the polyester resin include terephthalic acid and dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid. Examples of the second compound used to obtain the polyester resin include polyhydric alcohols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. Can be

  The thermosetting component preferably contains a polyol compound and an isocyanate compound from the viewpoint of maintaining the flexural modulus of the foamed molded product higher. From the viewpoint of maintaining the flexural modulus of the foamed molded product higher, the cured product of the thermosetting compound preferably contains a urethane resin.

<Polyol compound>
The polyol compound is a compound having two or more hydroxyl groups (-OH groups).

  Examples of the polyol compound include a polylactone polyol, a polycarbonate polyol, an aromatic polyol, an alicyclic polyol, an aliphatic polyol, a polyester polyol, and a polyether polyol. The polyol compound may be a polymer polyol. As the polyol compound, only one kind may be used, or two or more kinds may be used in combination.

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

  Examples of the polycarbonate polyol include a dealcoholation reaction product of a hydroxyl group-containing compound and a carbonate compound. Examples of the hydroxyl group-containing compound include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol. Examples of the carbonate compound include diethylene carbonate and dipropylene carbonate.

  Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolak, and cresol novolak.

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

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

  Examples of the polyester polyol include a dehydration condensate of a polybasic acid and a polyhydric alcohol, a ring-opening polymer of lactone, and a condensate of a hydroxycarboxylic acid and a polyhydric alcohol. Examples of the polybasic acids include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. Examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. Examples of the lactone include ε-caprolactone and α-methyl-ε-caprolactone. Examples of the hydroxycarboxylic acid include castor oil and a reaction product of castor oil with ethylene glycol.

  Examples of the polyether polyol include a ring-opened polymer of an active hydrogen compound having two or more active hydrogen atoms and an alkylene oxide. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and tetrahydrofuran. The molecular weight of the active hydrogen compound is preferably small. Examples of the active hydrogen compound include diol compounds such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol; triol compounds such as glycerin and trimethylolpropane; amines such as ethylenediamine and butylenediamine. And the like.

  Examples of the polymer polyol include a graft polymer in which an unsaturated organic compound is graft-polymerized on a polyol compound, polybutadiene polyol, a modified polyol of a polyhydric alcohol, and a hydrogenated product thereof.

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

  Examples of the polyhydric alcohol modified polyol include a reaction modified product of a polyhydric alcohol and an alkylene oxide. Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methylglucoside, and derivatives thereof. Phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, anthrol Phenol compounds such as 1,4,5,8-tetrahydroxyanthracene and 1-hydroxypyrene; polybutadiene polyol; castor oil polyol; Kill (meth) acrylate (co) polymers; polyfunctional (e.g. two functional groups to 100) polyol such as polyvinyl alcohol; condensates of phenol and formaldehyde (novolac), and the like. Examples of the alkylene oxide include alkylene oxides 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 is 1,2-propylene oxide or ethylene oxide. Is more preferable. As the alkylene oxide, only one kind may be used, or two or more kinds may be used in combination.

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

  The polyol compound is preferably a polyester polyol or a polyether polyol, because it is easily available and excellent in convenience.

<Isocyanate compound>
An isocyanate compound is a compound having one or more isocyanate groups (-NCO groups).

  Examples of the isocyanate compound include aromatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate. From the viewpoint of allowing the curing reaction to proceed efficiently, the isocyanate compound is preferably a polyisocyanate compound. One of the above isocyanate compounds may be used alone, or two or more thereof may be used in combination.

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

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

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

  The isocyanate compound is preferably diphenylmethane diisocyanate because it is easily available and excellent in convenience.

  The polyol compound and the isocyanate compound can be used in appropriate amounts so that a urethane bond is efficiently formed. 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, still more preferably 130 parts by weight or more, based on 100 parts by weight of the polyol compound. Is 180 parts by weight or less, more preferably 160 parts by weight or less, still more preferably 150 parts by weight or less. When the content of the isocyanate compound is equal to or more than the lower limit and equal to or less than the upper limit, the amount of the unreacted polyol compound or the unreacted isocyanate compound is reduced, and a foam molded article having more favorable compressive strength is easily formed. .

(Filling material)
A filler is a substance that can reduce the amount of resin used while maintaining the function of the resin when compounded, and is an inert substance that does not normally react with the resin.

  Examples of the filler contained in the curable composition and the foamed molded article include a powdery filler. From the viewpoint of satisfactorily impregnating the filler between the fibers, the filler is preferably a powdery filler. As the filler, only one kind may be used, or two or more kinds may be used in combination.

  Examples of the filler include inorganic powder.

  As the filler of the inorganic powder, carbonate compounds, minerals, sulfate compounds, silicate compounds, clays, nitrides, carbon compounds, titanium compounds, metal borate compounds, sulfides, carbides, ash, sand, And volcaniclastics.

  Examples of the above-mentioned carbide compound include calcium carbonate, magnesium carbonate, zinc carbonate, and barium carbonate. Examples of the mineral include dawsonite, hydrotalcite, mica, imogolite, sericite, and gypsum fiber. Examples of the sulfate compound include calcium sulfate, barium sulfate, and magnesium sulfate. Examples of the silicate compound include calcium silicate. Examples of the clay include talc, clay, montmorillonite, bentonite, activated clay, sepiolite, and the like. Examples of the nitride include aluminum nitride, boron nitride, and silicon nitride. Examples of the carbon compound include carbon black, graphite, carbon balloon, and charcoal powder. Examples of the titanium compound include potassium titanate and lead zirconate titanate. Examples of the metal borate compound include aluminum borate. Examples of the sulfide include molybdenum sulfide and the like. Examples of the carbide include silicon carbide. Examples of the ash include fly ash, coal ash, and shirasu balloon. Examples of the sand include silica sand. Pumice etc. are mentioned as said volcaniclastic material.

  From the viewpoint of further increasing the compressive strength of the foamed molded article, suppressing the wear of the processing tool, and maintaining the processing accuracy even higher, the filler is preferably fly ash, and fly ash I or fly ash is preferred. More preferably, it is Ash II.

  By using Fly Ash I or Fly Ash II as the filler, even if the content of the filler in the curable composition is 100% by weight, excluding the blowing agent, the content of the filler is 15% by weight or more. The viscosity of the curable composition impregnated in the bundle of long fibers can be kept low. Therefore, in the obtained foamed molded article, the fibers and the filler can be uniformly dispersed. As a result, the compressive strength and flexural modulus of the foamed molded article can be further increased, and the processing accuracy of the foamed molded article can be maintained at a higher level.

  The fly ash class I and the fly ash class II are preferably fly ash conforming to the quality standard of JIS A6201.

The fly ash class I is ash having a silicon dioxide content of 45% or more, a 45 μm sieve residue (%) of 10% or less, and a specific surface area of 5000 cm ² / g or more.

The fly ash II is ash having a silicon dioxide content of 45% or more, a 45 μm sieve residue (%) of 40% or less, and a specific surface area of 2500 cm ² / g or more.

  The compression fracture strength of the filler is less than 200 mN from the viewpoint of suppressing abrasion of the processing tool when processing the foam molded article using the processing tool and maintaining high processing accuracy. When the compressive breaking strength of the filler is 200 mN or more, the processing tool is worn when the processing tool comes into contact with the filler, and as a result, the processing accuracy may be reduced.

  From the viewpoint of further increasing the compression strength of the foamed molded article and maintaining high processing accuracy, the compression fracture strength of the filler is preferably 5 mN or more, more preferably 10 mN or more, preferably 190 mN or less, more preferably 150 mN or less. Hereinafter, it is more preferably 100 mN or less, particularly preferably 90 mN or less.

  The compressive breaking strength is the strength at which the filler is broken when the filler is compressed using a plane indenter. The compressive breaking strength of the filler can be measured as follows.

  Using a micro-compression tester, one filler is compressed, and the strength at which the filler is broken is measured. The above measurement is performed on five or more fillers arbitrarily selected from fillers having an equivalent circle diameter of ± 10% of the average particle diameter. The average value of the strength at which each filler is broken is defined as the compressive breaking strength.

  The equivalent circle diameter means the diameter of a circle having the same area as the projected area of the filler. The circle equivalent diameter can be calculated by, for example, taking an electron micrograph of the filler or the filler contained in the foamed molded article, and analyzing the electron micrograph using commercially available image analysis software. . Further, the average particle diameter means an average particle diameter described later.

  The filler used in the measurement of the compressive breaking strength may be a filler before being mixed with the curable composition, or may be a filler isolated from the curable composition or the foamed molded article. You may. The above-mentioned isolated filler is preferably washed with a solvent or the like.

  From the viewpoint of further increasing the compressive strength and the flexural modulus of the foamed molded article, and from the viewpoint of maintaining the processing accuracy even higher, the average particle diameter of the filler is preferably more than 1 μm, more preferably 2 μm or more, furthermore Preferably it is 3 μm or more, preferably less than 250 μm, more preferably 200 μm or less, even more preferably 150 μm or less. When the average particle diameter of the filler is less than the upper limit (or less than the upper limit), the filler does not easily settle, and the filler is easily dispersed uniformly in the curable composition. As a result, a foam molded article in which the filler is uniformly dispersed can be favorably obtained.

  The average particle diameter of the above-mentioned filler means a volume average particle diameter. The volume average particle diameter of the filler is an average diameter measured on a volume basis, and is a value of a median diameter (D50) which is 50%. The volume average particle diameter (D50) can be measured by a laser diffraction / scattering method, an image analysis method, a Coulter method, a centrifugal sedimentation method, or the like. The volume average particle diameter (D50) of the filler is preferably determined by measurement by a laser diffraction / scattering method.

  From the viewpoint of increasing the compressive strength and the flexural modulus, the content of the filler in the curable composition is 15% by weight in 100% by weight of the components excluding the blowing agent or in 100% by weight of the foamed molded article. Not less than 50% by weight.

  The content of the filler is preferably 20% by weight or more, and more preferably 45% by weight or less in 100% by weight of the curable composition excluding the blowing agent or in 100% by weight of the foamed molded article. It is. When the content of the filler is not less than the lower limit, the compressive strength and the flexural modulus of the foam molded article can be further increased. When the content of the filler is equal to or less than the upper limit, the viscosity of the curable composition can be suppressed to be low, so that the filler can be favorably impregnated between the fibers. As a result, a foam molded article in which the filler is uniformly dispersed can be favorably obtained.

(fiber)
Examples of the fibers contained in the curable composition and the foamed molded article include inorganic fibers and organic fibers. The fiber may be a reinforcing fiber or a reinforced long fiber. Only one type of the above fibers may be used, or two or more types may be used in combination.

  The fibers are preferably reinforced fibers, and more preferably reinforced long fibers.

  Examples of the inorganic fibers include glass fibers, asbestos fibers, mineral fibers, stainless fibers, slag fibers, silica alumina fibers, alumina fibers, silica fibers, zirconia fibers, and carbon fibers.

  Examples of the organic fibers include natural fibers (wood fibers) such as cotton and hemp, regenerated fibers such as rayon, and synthetic fibers such as polyamide, polyester, and polyolefin.

  From the viewpoint of further increasing the flexural modulus, the fiber is preferably a long fiber, and preferably has a length of 50 mm or more.

  The fiber is preferably glass fiber from the viewpoint of effectively achieving a balance between suppressing bending deflection and increasing economic efficiency.

  From the viewpoint of further increasing the productivity of the foam molded article, the fiber is preferably a continuous fiber because it is formed by pultrusion molding.

  From the viewpoint of satisfactorily impregnating a filler or the like between the fibers during molding, the fiber diameter of the fibers is preferably 1 μm or more, more preferably 5 μm or more, preferably 50 μm or less, and more preferably 25 μm or less.

  From the viewpoint of increasing the compressive strength and the flexural modulus and effectively suppressing the bending deflection of the foamed molded article, 100% by weight or 100 wt% of the foamed molded article in the curable composition excluding the foaming agent. %, The content of the fiber is 15% by weight or more and 50% by weight or less.

  In 100% by weight of the components excluding the blowing agent in the curable composition, or in 100% by weight of the foamed molded article, the content of the fiber is preferably 20% by weight or more, and preferably 45% by weight or less. is there. When the content of the fiber is equal to or more than the lower limit, the bending deflection of the foam molded article can be more effectively suppressed. When the content of the fiber is equal to or less than the upper limit, a lightweight foam molded article in which the filler is uniformly impregnated can be obtained.

(Foaming agent)
A blowing agent is a substance that generates a gas by decomposition or a substance that itself becomes a gas.

  From the viewpoint of obtaining a foam molded article, the curable composition contains a foaming agent. By foaming the curable composition with a foaming agent, a foam molded article can be obtained. The foam molded article has an advantage that it is lighter in weight than a non-foamed molded article.

Examples of the foaming agent include water and an organic halogen compound. The foaming agent is preferably water because it is easily available and excellent in convenience. When an isocyanate compound is contained as the thermosetting component, water acts as a foaming agent by reacting with the isocyanate compound to generate CO ₂ . One of the above foaming agents may be used alone, or two or more thereof may be used in combination.

  Examples of the organic halogen compound include 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 of the hydrogen atoms have been replaced with halogen atoms, or may be an organic halogen compound in which some of the hydrogen atoms have been replaced with halogen atoms. From the viewpoint of improving the foamability during the formation of the foamed molded article and keeping the thermal conductivity of the foamed molded article low for a longer period of time, the organic halogen compound may be an organic chlorine compound or an organic fluorine compound. preferable.

  Examples of the organic chlorine compound include a saturated organic chlorine compound and an unsaturated organic chlorine compound. Examples of the saturated organic chlorine compound 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 foamed molded article and keeping the thermal conductivity of the foamed molded article low for a longer period of time, the organic chlorine compound is preferably a saturated organic chlorine compound, Is more preferably 2 to 5 saturated organic chlorine compounds.

  Examples of the organic fluorine compound include a saturated organic fluorine compound and an unsaturated organic fluorine compound.

  Examples of the saturated organic fluorine compounds include hydrofluorocarbons. 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) and the like.

  Examples of the unsaturated organic fluorine compound include hydrofluoroolefins. Examples of the hydrofluoroolefin include 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) and the like.

  Further, examples of the organic fluorine compound 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 hydrochlorofluoroolefin. Examples of the hydrochlorofluoroolefin include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) (E and Z isomers) and 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-trimer Fluoropropene (HCFO-1233xe) (E and Z isomers), 2-chloro-2,2,3-trifluoropropene (HCFO-1233xc), 2-chloro-3,3,3-trifluoropropene (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) and the like.

  The foaming agent can be used in an appropriate content in consideration of foamability. When a urethane resin is obtained as a cured product of the thermosetting compound, the content of the foaming agent (when a plurality of foaming agents are used, the total content) is preferably based on 100 parts by weight of the polyol compound. It is at least 0.01 part by weight, more preferably at least 0.05 part by weight, preferably at most 5 parts by weight, more preferably at most 2 parts by weight. When the content of the foaming agent is equal to or more than the lower limit and equal to or less than the upper limit, foaming is promoted, and a lightweight foamed molded article can be favorably obtained.

(catalyst)
A catalyst is a substance that promotes a chemical reaction.

  The curable composition preferably contains a catalyst. One of the above catalysts may be used alone, or two or more thereof may be used in combination.

  Examples of the catalyst in the case of obtaining a urethane resin as a cured product of the thermosetting compound include a urethane-forming catalyst and a trimerization catalyst. When a urethane resin is obtained as a cured product of the thermosetting compound, the curable composition preferably contains a urethane-forming catalyst. The urethane-forming catalyst promotes a reaction between a hydroxyl group of the polyol compound and an isocyanate group of the isocyanate compound, and promotes formation of a urethane bond.

  Examples of the urethanization catalyst include organotin compounds such as dibutyltin dimaleate, dibutyltin diurarate and dibutylbis (oleoyloxy) stannane; triethylamine, N-methylmorpholinebis (2-dimethylaminoethyl) ether and N, N, N ' Tertiary amine compounds such as N, N ", N" -pentamethyldiethylenetriamine; N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N ' -Dimethylaminoethylpiperazine, and imidazole compounds in which a secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group. As the urethane-forming catalyst, only one kind may be used, or two or more kinds may be used in combination.

  The urethane-forming catalyst can be used at an appropriate content so that the polyol compound and the isocyanate compound react well. The content of the urethanization catalyst is preferably at least 0.01 part by weight, more preferably at least 0.02 part by weight, preferably at most 1.0 part by weight, more preferably at most 1.0 part by weight, based on 100 parts by weight of the polyol compound. 0.8 parts by weight or less. When the content of the urethanization catalyst is at least the above lower limit, the urethanization reaction effectively proceeds. When the content of the urethanization catalyst is equal to or less than the upper limit, trimerization of the isocyanate group of the isocyanate compound is not easily inhibited.

  The trimerization catalyst promotes a trimerization reaction of an isocyanate group of the isocyanate compound, and promotes formation of an isocyanurate ring. Furthermore, the trimerization catalyst suppresses expansion of the foam molded article during combustion.

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

  The trimerization catalyst can be used at an appropriate content so that the trimerization reaction is favorably promoted. The content of the trimerization catalyst is preferably at least 0.01 part by weight, more preferably at least 0.05 part by weight, preferably at most 1.0 part by weight, preferably at most 1.0 part by weight, based on 100 parts by weight of the polyol compound. 0.8 parts by weight or less. When the content of the trimerization catalyst is equal to or more than the above lower limit, expansion of the foam molded article during the formation of the foam molded article is easily suppressed. When the content of the trimerization catalyst is equal to or less than the upper limit, generation of urethane bonds is not easily inhibited.

  Examples of the catalyst for obtaining a phenol resin as a cured product of the thermosetting compound include an acid catalyst. When a phenol resin is obtained as a cured product of the thermosetting compound, the curable composition preferably contains an acid catalyst.

  The acid catalyst can be used in an appropriate amount.

  When the polyester resin is obtained as a cured product of the thermosetting compound, examples of the catalyst include organic peroxides. When a polyester resin is obtained as a cured product of the thermosetting compound, the curable composition preferably contains an organic peroxide.

  The organic peroxide can be used in an appropriate amount.

[Other components]
The curable composition and the foamed molded article may contain other components such as a coloring agent, a flame retardant, a foam stabilizer, and an ultraviolet absorber as long as the object of the present invention is not impaired. As the other components such as the coloring agent, the flame retardant, the foam stabilizer, and the ultraviolet absorber, one kind may be used alone, or two or more kinds may be used in combination.

  The colorant is a substance capable of coloring the foamed molded article.

  Examples of the colorant include a pigment.

  The flame retardant is, for example, a substance capable of imparting flame retardancy to a combustible substance such as plastic, wood, or fiber when added to the substance.

  Examples of the flame retardant include nitrogen-containing non-halogen flame retardant, red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide. Can be

  The foam stabilizer is a substance that can prevent the bubbles from becoming coarse and non-uniform, and can form bubbles stably and favorably.

  Examples of the foam stabilizer include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ether, and silicone foam stabilizers such as organopolysiloxane.

  The foam stabilizer can be used in an appropriate content so that bubbles are formed stably and well. When a urethane resin is obtained as a cured product of the thermosetting compound, the content of the foam stabilizer is preferably at least 0.01 part by weight, more preferably 0.1 part by weight, based on 100 parts by weight of the polyol compound. Parts by weight, more preferably 0.2 parts by weight or more, preferably 5 parts by weight or less, more preferably 3 parts by weight or less, further preferably 1 part by weight or less. When the content of the foam stabilizer is equal to or greater than the lower limit and equal to or less than the upper limit, bubbles can be formed stably and favorably.

  The ultraviolet absorber is a substance that absorbs ultraviolet energy and suppresses deterioration of the foam molded article.

(Other details of the curable composition)
The curable composition can be prepared by mixing the thermosetting component, the filler, the fiber, the foaming agent, and if necessary, other components. The mixing method of each component is not particularly limited. A plurality of liquids containing one or more components may be prepared, and the plurality of liquids may be mixed to obtain a curable composition. The mixing of the plurality of liquids may be performed at the time of forming the foam molded article. Alternatively, the curable composition may be obtained by spraying a component other than the fiber over the fibers aligned in one direction to impregnate the fiber with the component other than the fiber.

(Foam molding)
By molding the curable composition according to the present invention, a lightweight foam molded article can be obtained. The foam molded article has high compressive strength and flexural modulus. In the foam molded article, when the foam molded article is processed using the processing tool, wear of the processing tool can be suppressed. As a result, high processing accuracy can be maintained.

  For example, a foam molded article can be obtained by heating the curable composition at 40 to 80 ° C. to foam, mold, and cure.

From the viewpoint of further reducing the weight of the foamed molded article, the apparent density of the foamed molded article is preferably less than 1100 kg / m ³ .

  The apparent density is determined in accordance with JIS K7222.

  Synthetic wood is processed into a desired shape using a processing tool. Synthetic wood may be used in an environment in which a large pressure is applied to the synthetic wood, such as a member being installed on the synthetic wood. Since the foam molded article has high compressive strength and flexural modulus, and suppresses abrasion of the processing tool when processing the foam molded article using the processing tool, it is possible to maintain high processing accuracy. For example, it is suitably used as synthetic wood. The curable composition is suitably used for obtaining synthetic wood.

  Also, a molded product such as synthetic wood may be used as a sleeper. The sleeper is, for example, cut to length and drilled for screwing. Since the foam molded article has high compressive strength and flexural modulus, and suppresses abrasion of the processing tool when processing the foam molded article using the processing tool, it is possible to maintain high processing accuracy. For example, it is suitably used as a sleeper. The curable composition is suitably used for obtaining a sleeper.

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

  The sleeper (foam molded body) may have a length direction and a width direction. From the viewpoint of further improving the compressive strength of the sleeper and further reducing the variation in the compressive strength of the sleeper, it is preferable that the fibers are arranged along the length direction of the sleeper (foam molded body).

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

  The following materials were prepared.

(Thermosetting component)
Polyol compound:
Polyether polyol (“MULTRANOL 9158” manufactured by Sumika Covest Low Urethane Co., Ltd.)
Isocyanate compound:
Diphenylmethane diisocyanate (“Sumidur 44V20L” manufactured by Sumika Covest Low Urethane Co., Ltd.)

(Filling material)
Fly ash class I (“Fineash” manufactured by Shiden Business Co., Ltd., average particle size 9.5 μm)
Fly Ash II Class (“Shiden Fly Ash” manufactured by Shiden Business Co., Ltd., average particle diameter 11 μm)
Silica sand No. 7 (“Silicon sand No. 7” manufactured by Mikawa Keiseki Co., Ltd., average particle size 212 μm)

  The average particle size (volume average particle size (D50)) of the filler was determined by measuring the particle size distribution using a laser diffraction type particle size distribution measuring device (“SALD-3100” manufactured by Shimadzu Corporation). Specifically, in the obtained particle diameter distribution, the particle diameter at which the cumulative volume calculated from the smaller diameter side becomes 50% was defined as the volume average particle diameter (D50) of the filler.

(fiber)
Glass long fiber with a fiber diameter of 12 μm (Reinforced long fiber manufactured by UZY BASE)

(Foaming agent)
water

(catalyst)
Dioctyl tin ("SCAT31A" manufactured by Nitto Kasei)
Tertiary amine catalyst ("TOYOCAT-DB30" manufactured by Tosoh Corporation)

(Foam stabilizer)
Silicone foam stabilizer ("SZ-1729" manufactured by Dow Corning Toray)

(Example 1)
(Preparation of curable resin composition)
The fibers were aligned in a first direction. A first composition containing a polyol compound, a filler, a foaming agent, a catalyst, and a foam stabilizer was obtained. In addition, a second composition containing an isocyanate compound was obtained. The obtained first composition and the obtained second composition were mixed to obtain a third composition. The obtained third composition is sprayed over the aligned fibers, rubbed and crushed between a rubbing plate and an impregnated plate, and the third composition is impregnated into the fibers to form a curable composition. I got The fillers and fibers were used in the amounts shown in Tables 2 and 3 below (contents in 100% by weight of the components excluding the foaming agent in the curable composition).

(Preparation of foam molded article)
The obtained curable composition was conveyed to a molding passage. By heating the curable composition at 60 ° C. for 180 minutes in the molding passage, it was foam-cured to obtain a foam molded article in which fibers were arranged along the length direction of the foam molded article. The obtained foamed molded article contains a urethane resin as a cured product of a thermosetting compound. The size of the obtained foamed molded article was 50 mm long × 50 mm wide × 390 mm deep.

(Examples 2 to 5, Comparative Examples 1 to 7)
A curable composition and a foamed molded article were obtained in the same manner as in Example 1 except that the types and amounts (parts by weight) of the used components were changed as shown in Tables 2 and 3 below. In Comparative Examples 1 and 5, the viscosity of the obtained third composition was high, the fibers could not be impregnated with the third composition, and a foam molded article could not be obtained.

(Evaluation)
The following evaluations (1) to (5) were performed. In Comparative Examples 1 and 5, the following (2) to (5) were not evaluated because a foam molded article could not be obtained.

(1) Compressive fracture strength of filler Five fillers having an equivalent circle diameter of ± 10% of the average particle diameter were arbitrarily selected. Using a micro compression tester (“MCT-510” manufactured by Shimadzu Corporation), one filler was compressed under the following measurement conditions, and the strength when the filler was broken was measured. The above measurements were performed on five fillers. The average value of the strength when each filler was broken was calculated, and the compressive breaking strength was obtained. In addition, appropriate test force, load speed, and indenter size were set according to the equivalent circle diameter of the filler and the destructive test force. Specifically, the compressive breaking strength was measured under the conditions shown in Table 1.

  In addition, the compressive breaking strength of the filler isolated from the obtained foam molded article was determined in the same manner as described above, and it was confirmed that equivalent results were obtained.

[Judgment criteria for compressive fracture strength of filler]
：: Compressive breaking strength is less than 200 mN ×: Compressive breaking strength is 200 mN or more

(2) Apparent density According to JIS K7222, the dimensions and weight of the obtained foamed molded article were measured, and the apparent density was measured.

[Criteria for apparent density]
：: Apparent density is less than 1100 kg / m ³ ×: Apparent density is 1100 kg / m ³ or more

(3) Abrasion amount of processing tool An electric drill for drilling was prepared by attaching a woodworking drill (Φ8 mm in diameter, material S55C) to an electric drill (“D13SB” manufactured by Hitachi Koki Co., Ltd.). Using the above-mentioned electric drill for drilling, 50 holes having a depth of 40 mm were formed in the obtained foamed molded product. The weight of the woodworking drill before and after drilling is measured, and the difference between the weight of the woodworking drill after drilling and the weight of the woodworking drill before drilling (weight of the woodworking drill before drilling-after drilling) Weight of wood drill).

[Criteria for determining the amount of wear of processing tools]
：: Weight difference of less than 0.06 g Δ: Weight difference of 0.06 g or more and 0.1 g or less ×: Weight difference of more than 0.1 g

(4) Partial compression proportional limit stress (non-fiber direction)
The obtained foam molded body was cut into a size of 20 mm long × 20 mm wide × 40 mm high to obtain a test material. According to JIS Z2101, the obtained test material was compressed with an iron plate having a width of 13 mm, a length of 30 mm, and a thickness of 5 mm, and a partial compression proportional limit stress was measured.

[Criteria for Partial Compression Proportional Limit Stress (non-fiber direction)]
：: Partial compression proportional limit stress is 8 MPa or more ×: Partial compression proportional limit stress is less than 8 MPa

(5) Flexural Modulus The obtained foam molded article was cut into a size of 21 mm long × 36 mm wide × 390 mm long to obtain a test material. In accordance with JIS Z2101, the obtained test material was compressed with an iron plate having a width of 13 mm, a length of 30 mm and a thickness of 5 mm, and the flexural modulus (three-point flexural modulus) was measured.

[Criteria for flexural modulus]
：: Flexural modulus of 4000 MPa or more ×: Flexural modulus of less than 4000 MPa

(6) Comprehensive evaluation From the evaluation results of the above (1) to (5), comprehensive judgment was made based on the following criteria.

[Comprehensive evaluation criteria]
：: All the evaluation results of the above (1) to (5) are ○
Δ: The evaluation result of the above (1) to (5) has a Δ, and there is no X. X: The evaluation result of the above (1) to (5) has a X.

  The compositions and results are shown in Tables 2 and 3 below.

DESCRIPTION OF SYMBOLS 1 ... Foam molding 11 ... Cured product of thermosetting compound 12 ... Fiber 13 ... Filler

Claims (5)

A cured product of a thermosetting compound, a filler, and a foamed molded article containing fibers,
The content of the filler is 15% by weight or more and 50% by weight or less,
The content of the fiber is 15% by weight or more and 50% by weight or less,
A foam molded article, wherein the compression fracture strength of the filler is less than 200 mN.   The foamed molded article according to claim 1, wherein the cured product of the thermosetting compound contains a urethane resin.   The foam molded article according to claim 1, wherein the filler is fly ash I or fly ash II.   The foam molded article according to any one of claims 1 to 3, wherein the fiber is a reinforced long fiber. The foam molded article according to any one of claims 1 to 4, which is a synthetic wood.

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