Resin composition, molding material, and refractory material

Abstract

This resin composition contains a resin component containing a thermosetting resin containing an unsaturated polyester and a polymerizable monomer, and aluminum hydroxide. The glass transition temperature when the mixture of the thermosetting resin and the polymerizable monomer is cured is 0°C to 60°C inclusive. The content of the polymerizable monomer relative to the total amount of the polymerizable monomer and the thermosetting resin is 40 mass% or less. The content of aluminum hydroxide relative to 100 parts by mass of the resin component is 120 parts by mass or more. The mass ratio of aluminum hydroxide relative to the polymerizable monomer is 15.0 or less.

Description

Resin composition, molding material and fire-resistant material

[0001] The present invention relates to a resin composition, a molding material, and a fire-resistant material, and more particularly to a resin composition, a molding material containing the resin composition, and a fire-resistant material containing a cured product of the molding material.

[0002] Conventionally, molded articles made of molding materials containing resin compositions (particularly, sheet molding compounds (SMC), bulk molding compounds (BMC), and thick molding compounds (TMC)) have been used in a wide range of fields due to their excellent mechanical properties, water resistance, electrical insulation, and corrosion resistance.

[0003] As such a molding material, a molding material containing an unsaturated polyester resin, a polyvinyl acetate resin, aluminum hydroxide particles, and chopped glass fiber has been proposed (see, for example, Example 1 of Patent Document 1 below).

[0004] Japanese Patent Application Laid-Open No. 2004-161813

[0005] On the other hand, molding materials are sometimes used as fire-resistant materials. Such fire-resistant materials are required to have flexibility depending on the purpose and application. Furthermore, fire-resistant materials are required to be thin in order to save space and reduce weight, and even thin plates are required to have excellent flame retardancy.

[0006] The present invention provides a resin composition for producing a fire-resistant material that has excellent flexibility and excellent flame retardancy even in the form of a thin plate, a molding material containing the resin composition, and a fire-resistant material containing a cured product of the molding material.

[0007] The present invention [1] is a resin composition comprising a thermosetting resin containing an unsaturated polyester, a resin component containing a polymerizable monomer, and aluminum hydroxide, wherein the glass transition temperature when the mixture of the thermosetting resin and the polymerizable monomer is cured is 0°C or higher and 60°C or lower, the content of the polymerizable monomer is 40 mass% or lower with respect to the total amount of the polymerizable monomer and the thermosetting resin, the content of the aluminum hydroxide is 120 mass parts or higher with respect to 100 mass parts of the resin component, and the mass ratio of the aluminum hydroxide to the polymerizable monomer is 15.0 or lower.

[0008] The present invention [2] includes the resin composition according to the above [1], in which the unsaturated polyester is a reaction product of a polybasic acid and a polyhydric alcohol, and the polybasic acid includes a linear saturated aliphatic dibasic acid having 8 or more carbon atoms.

[0009] The present invention [3] includes the resin composition according to the above [1] or [2], in which the resin component does not contain a thermoplastic resin, or, if the resin component contains a thermoplastic resin, the content of the thermoplastic resin is 5 mass% or less relative to the resin component.

[0010] The present invention [4] includes a molding material containing the resin composition according to any one of the above [1] to [3] and reinforcing fibers.

[0011] The present invention [5] includes a fire-resistant material characterized by containing a cured product of the molding material described in the above [4].

[0012] In the resin composition of the present invention, the glass transition temperature when the mixture of the thermosetting resin and the polymerizable monomer is cured is 0° C. or higher and 60° C. or lower, and the content of the polymerizable monomer is 40 mass % or lower based on the total amount of the polymerizable monomer and the thermosetting resin. Therefore, a fire-resistant material obtained using this resin composition has excellent flexibility.

[0013] In addition, the resin composition contains 120 parts by mass or more of aluminum hydroxide per 100 parts by mass of the resin component, and the mass ratio of aluminum hydroxide to the polymerizable monomer is 15.0 or less. Therefore, a fire-resistant material obtained using this resin composition has excellent flame retardancy even in the form of a thin plate.

[0014] The molding material of the present invention contains the resin composition of the present invention. Therefore, a fire-resistant material obtained using this molding material has excellent flexibility and excellent flame retardancy even in the form of a thin plate.

[0015] The fire-resistant material of the present invention contains a cured product of the molding material of the present invention, and therefore has excellent flexibility and excellent flame retardancy even in the form of a thin plate.

[0016] 1. Resin Composition The resin composition contains a resin component and aluminum hydroxide.

[0017] <Resin Component> The resin component contains a thermosetting resin and a polymerizable monomer.

[0018] [Thermosetting Resin] The thermosetting resin contains an unsaturated polyester resin as an essential component. The unsaturated polyester resin contains an unsaturated polyester and a polymerizable monomer (described later). That is, the thermosetting resin contains an unsaturated polyester. In other words, the unsaturated polyester resin is an unsaturated polyester resin composition containing an unsaturated polyester and a polymerizable monomer (described later).

[0019] Unsaturated polyesters are obtained by reacting polybasic acids with polyhydric alcohols.

[0020] The polybasic acid includes a polybasic acid having an ethylenically unsaturated double bond as an essential component (hereinafter referred to as an ethylenically unsaturated bond-containing polybasic acid) and a polybasic acid not having an ethylenically unsaturated double bond as an optional component (hereinafter referred to as an ethylenically unsaturated bond-free polybasic acid).

[0021] Examples of ethylenically unsaturated bond-containing polybasic acids include ethylenically unsaturated aliphatic dibasic acids and anhydrides thereof, halides of ethylenically unsaturated aliphatic dibasic acids, and alkyl esters of ethylenically unsaturated aliphatic dibasic acids.

[0022] Examples of ethylenically unsaturated aliphatic dibasic acids include maleic acid, fumaric acid, itaconic acid, and dihydromuconic acid. Furthermore, examples of ethylenically unsaturated bond-containing polybasic acids include acid anhydrides derived from the above-mentioned ethylenically unsaturated aliphatic dibasic acids. Examples of acid anhydrides derived from ethylenically unsaturated aliphatic dibasic acids include maleic anhydride.

[0023] As the ethylenically unsaturated bond-containing polybasic acid, preferred are maleic acid and fumaric acid, and more preferred is fumaric acid.

[0024] Examples of polybasic acids not containing ethylenically unsaturated bonds include saturated aliphatic polybasic acids, saturated alicyclic polybasic acids, aromatic polybasic acids, anhydrides of these acids, halides of these acids, and alkyl esters of these acids.

[0025] Examples of saturated aliphatic polybasic acids include saturated aliphatic dibasic acids.

[0026] Examples of saturated aliphatic dibasic acids include saturated aliphatic dibasic acids having 2 to 7 carbon atoms and saturated aliphatic dibasic acids having 8 or more carbon atoms.

[0027] Examples of saturated aliphatic dibasic acids having 2 to 7 carbon atoms include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 3,3-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, adipic acid, and pimelic acid.

[0028] Examples of saturated aliphatic dibasic acids having 8 or more carbon atoms include linear saturated aliphatic dibasic acids having 8 or more carbon atoms. Examples of linear saturated aliphatic dibasic acids having 8 or more carbon atoms include suberic acid, azelaic acid, and sebacic acid. A preferred example of a linear saturated aliphatic dibasic acid having 8 or more carbon atoms is sebacic acid.

[0029] The saturated aliphatic polybasic acids also include acid anhydrides derived from the above-mentioned saturated aliphatic dibasic acids, such as oxalic anhydride and succinic anhydride.

[0030] Examples of saturated alicyclic polybasic acids include saturated alicyclic dibasic acids.

[0031] Examples of saturated alicyclic dibasic acids include HET acid, 1,2-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid (cis- or trans-1,4-cyclohexanedicarboxylic acid or a mixture thereof). Examples of saturated alicyclic polybasic acids include acid anhydrides derived from the above saturated alicyclic dibasic acids. Examples of acid anhydrides derived from saturated alicyclic dibasic acids include HET acid anhydride.

[0032] Examples of aromatic polybasic acids include aromatic dibasic acids.

[0033] Examples of aromatic dibasic acids include phthalic acid (orthophthalic acid, isophthalic acid, terephthalic acid), trimellitic acid, and pyromellitic acid. Examples of aromatic polybasic acids include acid anhydrides derived from the above aromatic dibasic acids. Examples of acid anhydrides derived from aromatic dibasic acids include phthalic anhydride. A preferred example of an aromatic dibasic acid is isophthalic acid.

[0034] As the polybasic acid not containing an ethylenically unsaturated bond, preferably, a saturated aliphatic polybasic acid and an aromatic dibasic acid are used.

[0035] The polybasic acids can be used alone or in combination of two or more kinds.

[0036] When the polybasic acid contains an ethylenically unsaturated bond-containing polybasic acid and an ethylenically unsaturated bond-free polybasic acid, from the viewpoint of flexibility, the content of the ethylenically unsaturated bond-containing polybasic acid is, for example, 10 mol% to 30 mol%, or preferably 15 mol% to 20 mol%, relative to 100 mol of all polybasic acids. The content of the ethylenically unsaturated bond-free polybasic acid is, for example, 70 mol% to 90 mol%, or preferably, for example, 80 mol% to 85 mol%.

[0037] The polybasic acid preferably contains a saturated aliphatic dibasic acid having 8 or more carbon atoms (preferably a linear saturated aliphatic dibasic acid having 8 or more carbon atoms). When the polybasic acid contains a saturated aliphatic dibasic acid having 8 or more carbon atoms (preferably a linear saturated aliphatic dibasic acid having 8 or more carbon atoms), water resistance can be improved.

[0038] The content of saturated aliphatic dibasic acids having 8 or more carbon atoms is 40 mol % to 70 mol %, preferably 50 mol % to 65 mol %, based on 100 mol of the total polybasic acids, from the viewpoint of water resistance.

[0039] The polybasic acid preferably comprises an ethylenically unsaturated bond-containing polybasic acid and an ethylenically unsaturated bond-free polybasic acid.

[0040] Polyhydric alcohols include, for example, dihydric alcohols and trihydric alcohols.

[0041] Examples of dihydric alcohols include aliphatic diols, alicyclic diols, and aromatic diols.

[0042] Examples of the aliphatic diol include alkane diols and ether diols.

[0043] Examples of the alkanediol include alkanediols having 2 to 10 carbon atoms. Examples of the alkanediols having 2 to 10 carbon atoms include ethylene glycol, propylene glycol (1,2- or 1,3-propanediol or a mixture thereof), butylene glycol (1,2-, 1,3-, or 1,4-butylene glycol or a mixture thereof), 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, and 3,3-dimethylolheptane. Preferred examples of the alkanediol include ethylene glycol and propylene glycol. More preferred examples of the alkanediol include propylene glycol.

[0044] Examples of the ether diol include diethylene glycol, triethylene glycol, and dipropylene glycol. Of the ether diols, diethylene glycol is preferred.

[0045] Examples of alicyclic diols include cyclohexanediol (1,2-, 1,3-, or 1,4-cyclohexanediol or a mixture thereof), cyclohexanedimethanol (1,2-, 1,3-, or 1,4-cyclohexanedimethanol or a mixture thereof), cyclohexanediethanol (1,2-, 1,3-, or 1,4-cyclohexanediethanol or a mixture thereof), and hydrogenated bisphenol A.

[0046] Examples of aromatic diols include ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A.

[0047] Examples of trihydric alcohols include glycerin, trimethylolpropane, and triisopropanolamine.

[0048] As the polyhydric alcohol, preferably, a dihydric alcohol is used, and more preferably, an aliphatic diol is used.

[0049] The polyhydric alcohols can be used alone or in combination of two or more kinds.

[0050] The unsaturated polyester is prepared by reacting a polybasic acid with a polyhydric alcohol.

[0051] The equivalent ratio of the polyhydric alcohol to the polybasic acid (hydroxyl groups of the polyhydric alcohol / carboxyl groups of the polybasic acid) is, for example, 0.9 to 1.2, or preferably 0.95 to 1.1.

[0052] The reaction temperature is, for example, 150°C to 250°C, preferably 190°C to 230°C.

[0053] In the above reaction, a known solvent and a known reaction catalyst may be added as needed.

[0054] This prepares an unsaturated polyester.

[0055] The acid value of the unsaturated polyester (measurement method: in accordance with JIS K6901 (2008)) is, for example, 5 mgKOH / g to 40 mgKOH / g, preferably 10 mgKOH / g to 30 mgKOH / g, and more preferably 20 mgKOH / g to 30 mgKOH / g.

[0056] The weight average molecular weight of the unsaturated polyester is, for example, 2,000 to 25,000, or preferably 4,000 to 20,000.

[0057] The weight average molecular weight is a weight average molecular weight calculated in terms of polystyrene by GPC (gel permeation chromatography).

[0058] The unsaturated polyesters can be used alone or in combination of two or more kinds.

[0059] The thermosetting resin contains a vinyl ester resin as an optional component. The vinyl ester resin contains a vinyl ester and a polymerizable monomer (described later). That is, the thermosetting resin contains a vinyl ester. In other words, the vinyl ester resin is a vinyl ester resin composition containing a vinyl ester and a polymerizable monomer (described later).

[0060] Vinyl esters are the addition reaction products of epoxy resins and unsaturated monocarboxylic acids.

[0061] The epoxy resin contains at least one epoxy group. Examples of the epoxy resin include bisphenol-type epoxy resins (e.g., bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, brominated bisphenol A-type epoxy resins, etc.), novolac-type epoxy resins (e.g., phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, brominated novolac-type epoxy resins, etc.), aliphatic-type epoxy resins, alicyclic-type epoxy resins, hydrogenated bisphenol-type epoxy resins, and amine-type epoxy resins. The epoxy resin is preferably a bisphenol-type epoxy resin. The epoxy resin is more preferably a bisphenol A-type epoxy resin.

[0062] The epoxy resins can be used alone or in combination of two or more kinds.

[0063] The epoxy equivalent of the epoxy resin is, for example, 100 g / eq to 700 g / eq, or preferably 150 g / eq to 300 g / eq. The epoxy equivalent can be measured in accordance with JIS K 7236.

[0064] The unsaturated monocarboxylic acid contains at least one unsaturated double bond and at least one carboxy group. Examples of the unsaturated monocarboxylic acid include unsaturated monofatty acids (e.g., (meth)acrylic acid, crotonic acid, sorbic acid, etc.), aromatic unsaturated monocarboxylic acids (e.g., cinnamic acid, etc.), and ester bond-containing unsaturated monocarboxylic acids (e.g., reaction products of acid anhydrides and unsaturated alcohols, etc.). Note that (meth)acrylic is synonymous with methacrylic and / or acrylic. A preferred example of the unsaturated monocarboxylic acid is methacrylic acid.

[0065] The unsaturated monocarboxylic acids can be used alone or in combination of two or more kinds.

[0066] The vinyl ester is prepared by subjecting the epoxy group of the epoxy resin described above to a ring-opening addition reaction with the carboxy group of the unsaturated monobasic acid described above.

[0067] The thermosetting resins can be used alone or in combination of two or more. When an unsaturated polyester resin and a vinyl ester resin are used in combination, the content of the unsaturated polyester is, for example, 55 to 99 parts by mass, preferably 90 to 99 parts by mass, per 100 parts by mass of the total of the unsaturated polyester and the vinyl ester. The content of the vinyl ester is, for example, 1 to 45 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the total of the unsaturated polyester and the vinyl ester.

[0068] The content of the unsaturated polyester relative to the resin component is, for example, 55% by mass to 90% by mass, preferably 60% by mass to 85% by mass, more preferably 65% ​​by mass to 80% by mass, and even more preferably 70% by mass to 78% by mass.

[0069] The content of the vinyl ester is 1% by mass to 10% by mass relative to the resin component.

[0070] The thermosetting resin preferably does not contain vinyl ester resin and is composed of unsaturated polyester resin.

[0071] [Polymerizable Monomer] Examples of the polymerizable monomer include styrene-based monomers and (meth)acrylic acid ester-based monomers.

[0072] Examples of styrene-based monomers include styrene, vinyltoluene, t-butylstyrene, and chlorostyrene.

[0073] Examples of (meth)acrylic acid ester monomers include (meth)acrylic acid alkyl esters, (meth)acrylic acid allyl esters, ring-containing (meth)acrylic acid esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid alkoxyalkyl esters, (meth)acrylic acid aminoalkyl esters, (meth)acrylic acid fluoroalkyl esters, and polyfunctional (meth)acrylic acid esters. Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate. Examples of (meth)acrylic acid allyl esters include allyl (meth)acrylate. Examples of ring-containing (meth)acrylate esters include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate. Examples of hydroxyalkyl (meth)acrylate esters include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Examples of alkoxyalkyl (meth)acrylate esters include 2-methoxyethyl (meth)acrylate and 2-ethoxyethyl (meth)acrylate. Examples of aminoalkyl (meth)acrylate esters include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and chloride salts thereof. Examples of the fluoroalkyl (meth)acrylate include trifluoroethyl (meth)acrylate and heptadecafluorodecyl (meth)acrylate.Examples of polyfunctional (meth)acrylic acid esters include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0074] As the polymerizable monomer, preferably, a styrene-based monomer is used, and more preferably, styrene is used.

[0075] The polymerizable monomers can be used alone or in combination of two or more kinds.

[0076] The content of the polymerizable monomer relative to the resin component is, for example, 15% by mass to 40% by mass, preferably 20% by mass to 35% by mass, and more preferably 20% by mass to 30% by mass.

[0077] The content of the polymerizable monomer relative to the total amount of the polymerizable monomer and the thermosetting resin is 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 28% by mass or less, and for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and from the viewpoint of water resistance, even more preferably 18% by mass or more, particularly preferably 20% by mass or more.

[0078] When the content ratio of the polymerizable monomer to the total amount of the polymerizable monomer and the thermosetting resin is equal to or less than the above upper limit, flexibility can be improved.

[0079] On the other hand, if the content ratio of the polymerizable monomer to the total amount of the polymerizable monomer and the thermosetting resin exceeds the upper limit, the flexibility and appearance of the fireproof material will be deteriorated, and the amount of residual polymerizable monomer will increase, increasing the environmental load.

[0080] [Thermoplastic Resin] Examples of the thermoplastic resin include polyethylene, polystyrene, styrene-based thermoplastic elastomer, cross-linked polystyrene, polyvinyl acetate-polystyrene block copolymer, polyvinyl acetate, polymethyl methacrylate, and saturated polyester resin. Preferably, the thermoplastic resin is polystyrene.

[0081] The thermoplastic resins can be used alone or in combination of two or more kinds.

[0082] Alternatively, the thermoplastic resin can be dissolved in the polymerizable monomer to prepare a polymerizable monomer solution of the thermoplastic resin.

[0083] In the polymerizable monomer solution of the thermoplastic resin, the solid content concentration of the thermoplastic resin is, for example, 10% by mass to 70% by mass, or preferably 20% by mass to 40% by mass.

[0084] The thermoplastic resins can be used alone or in combination of two or more kinds.

[0085] The content of the thermoplastic resin relative to the resin component is, for example, 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 0% by mass. That is, more preferably, the resin component does not contain a thermoplastic resin.

[0086] When the content of the thermoplastic resin is equal to or less than the upper limit, the flame retardancy can be improved.

[0087] <Aluminum Hydroxide> Aluminum hydroxide imparts flame retardancy.

[0088] The average particle size of the aluminum hydroxide is, for example, 1 μm or more, and for example, 50 μm or less, preferably 25 μm or less.

[0089] The average particle size of aluminum hydroxide can be determined by creating a particle size distribution curve using a laser diffraction / scattering particle size distribution analyzer and calculating the 50% by mass equivalent particle size.

[0090] The content of aluminum hydroxide is, relative to 100 parts by mass of the resin component, 120 parts by mass or more, preferably 140 parts by mass or more, more preferably 160 parts by mass or more, even more preferably 200 parts by mass or more, particularly preferably 250 parts by mass or more, most preferably 300 parts by mass or more, or even 340 parts by mass or more, and for example, 450 parts by mass or less, preferably 400 parts by mass or less.

[0091] When the content of aluminum hydroxide is equal to or greater than the above lower limit, the flame retardancy can be improved.

[0092] On the other hand, if the content of aluminum hydroxide is less than the lower limit, the flame retardancy decreases.

[0093] Furthermore, if the content of aluminum hydroxide is equal to or less than the above upper limit, the viscosity of the resin composition can be prevented from increasing excessively.

[0094] The mass ratio of aluminum hydroxide to the polymerizable monomer (aluminum hydroxide / polymerizable monomer) is 15.0 or less, and, for example, 3.0 or more, preferably 5.0 or more, more preferably 7.0 or more, even more preferably 9.0 or more, particularly preferably 11.0 or more, most preferably 13.0 or more, or even 14.0 or more.

[0095] When the mass ratio is equal to or less than the upper limit, the flame retardancy of a fire-resistant material obtained using this resin composition can be improved even in the case of a thin plate.

[0096] On the other hand, if the mass ratio exceeds the upper limit, the viscosity of the resin composition increases excessively, and it may become impossible to produce a fire-resistant material.

[0097] Furthermore, if the mass ratio is equal to or greater than the lower limit, the flame retardancy can be improved.

[0098] <Additives> Additives can be blended into the resin composition as needed, within the range that does not impair the effects of the present invention.

[0099] Examples of additives include release agents, curing agents, polymerization inhibitors, flame retardants, thickeners, fillers, colorants, wetting and dispersing agents, pattern materials, antibacterial agents, hydrophilic agents, photocatalysts, ultraviolet absorbers, ultraviolet stabilizers, separation prevention agents, silane coupling agents, antistatic agents, thixotropic agents, thixotropic stabilizers, and polymerization accelerators. The additives can be used alone or in combination of two or more.

[0100] [Release Agent] Examples of the release agent include fatty acids, fatty acid metal salts, liquid wax, fluoropolymers, and silicon-based polymers. Examples of the fatty acids include stearic acid and lauric acid. Examples of the fatty acid metal salts include zinc stearate and calcium stearate.

[0101] The release agent is preferably a fatty acid metal salt, more preferably zinc stearate.

[0102] The release agents can be used alone or in combination of two or more.

[0103] The content ratio of the release agent relative to 100 parts by mass of the resin component is, for example, 1 to 10 parts by mass, or preferably 3 to 8 parts by mass.

[0104] [Curing Agent] Examples of the curing agent include peroxides. Examples of peroxides include benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxyisopropyl carbonate, t-hexylperoxyisopropyl monocarbonate, 1,1-bis(t-butylperoxy)cyclohexane, t-butylperoxy-2-ethylhexanoate, amylperoxy-2-ethylhexanoate, 2-ethylhexylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, t-hexylperoxybenzoate, and t-hexylperoxyacetate. A preferred curing agent is t-butylperoxyisopropyl carbonate.

[0105] The curing agents can be used alone or in combination of two or more.

[0106] The content ratio of the curing agent relative to 100 parts by mass of the resin component is, for example, 0.1 to 5 parts by mass, or preferably 1 to 3 parts by mass.

[0107] [Polymerization Inhibitor] The polymerization inhibitor adjusts the pot life and the curing reaction.

[0108] Examples of the polymerization inhibitor include hydroquinone compounds, benzoquinone compounds, catechol compounds, phenol compounds, and N-oxyl compounds.

[0109] As the polymerization inhibitor, preferably, a benzoquinone compound, a hydroquinone compound, or an N-oxyl compound is used.

[0110] An example of the benzoquinone compound is p-benzoquinone.

[0111] Examples of the hydroquinone compound include hydroquinone, methylhydroquinone, and t-butylhydroquinone. A preferred example of the hydroquinone compound is t-butylhydroquinone.

[0112] As the polymerization inhibitor, a benzoquinone compound is more preferred.

[0113] The polymerization inhibitors can be used alone or in combination of two or more kinds.

[0114] The content ratio of the polymerization inhibitor relative to 100 parts by mass of the resin component is, for example, 0.01 to 2 parts by mass, or preferably 0.02 to 1 part by mass.

[0115] [Flame Retardant] Examples of the flame retardant (excluding aluminum hydroxide) include phosphorus-containing flame retardants, nitrogen-containing flame retardants, expandable graphite, halogen-based flame retardants, diantimony trioxide, zinc stannate, and zinc borate. Preferred flame retardants include phosphorus-containing flame retardants, nitrogen-containing flame retardants, phosphorus- and nitrogen-containing flame retardants, and expandable graphite.

[0116] Phosphorus-containing flame retardants contain phosphorus but no nitrogen, and include, for example, red phosphorus, phosphate esters, polyphosphates, and metal phosphinates.

[0117] Phosphate esters include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tricresyl phosphate.

[0118] An example of the polyphosphate is aluminum polyphosphate.

[0119] Examples of the metal phosphinate include aluminum trisdiethylphosphinate and aluminum trismethylethylphosphinate.

[0120] Commercially available phosphorus-containing flame retardants can be used, specifically, the OP series (specifically, Exolit OP1230 (aluminum trisdiethylphosphinate), manufactured by Clariant Chemicals).

[0121] As the phosphorus-containing flame retardant, preferably, a metal phosphinate is used, and more preferably, aluminum trisdiethylphosphinate is used.

[0122] The nitrogen-containing flame retardant contains nitrogen and does not contain phosphorus. Examples of the nitrogen-containing flame retardant include triazine compounds.

[0123] The triazine compound is a compound having a triazine skeleton, and examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, triguanamine, and melamine cyanurate.

[0124] The nitrogen-containing flame retardant may be a commercially available product, such as MC-4000 (melamine cyanurate, manufactured by Nissan Chemical Industries, Ltd.).

[0125] As the nitrogen-containing flame retardant, preferably, a triazine compound is used, and more preferably, melamine cyanurate is used.

[0126] Examples of phosphorus and nitrogen combined flame retardants include ammonium polyphosphate and melamine polyphosphate.

[0127] Expanded graphite is a graphite intercalation compound in which sulfuric acid or the like is inserted between the layers of flake-like natural graphite. Expanded graphite expands at temperatures of around 150 to 300°C.

[0128] The average particle size of the expanded graphite is 150 μm or less, preferably 100 μm or less, and for example, 10 μm or more, preferably 50 μm or more.

[0129] The average particle size of the expanded graphite can be determined by observing with an optical microscope, measuring the maximum diameter (major diameter) and the particle diameter (minor diameter) in the direction perpendicular to the maximum diameter for 50 randomly selected particles of expanded graphite, and calculating the average value of the major diameter and the minor diameter.

[0130] As the expanded graphite, commercially available products can also be used, specifically, 9510045 manufactured by Ito Graphite Industries Co., Ltd.

[0131] The flame retardants can be used alone or in combination of two or more.

[0132] The content of the flame retardant is, for example, 1 to 30 parts by mass with respect to 100 parts by mass of the resin component.

[0133] [Thickener] The thickener is blended to thicken the resin composition to a viscosity suitable for heat compression molding. The thickener is preferably blended before (preferably immediately before) impregnating the resin composition into reinforcing fibers (described below).

[0134] Examples of thickeners include alkaline earth metal oxides and alkaline earth metal hydroxides. Examples of alkaline earth metal oxides include magnesium oxide. Examples of alkaline earth metal hydroxides include magnesium hydroxide and calcium hydroxide. Furthermore, examples of thickeners that can be used include isocyanate monomers (e.g., toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI)) and prepolymers thereof.

[0135] As the thickener, preferably, an alkaline earth metal oxide is used, and more preferably, magnesium oxide is used.

[0136] The thickeners can be used alone or in combination of two or more.

[0137] The content of the thickener is, for example, 0.1 to 20 parts by mass relative to 100 parts by mass of the resin component. In particular, when the thickener is an alkaline earth metal oxide or an alkaline earth metal hydroxide, the content of the thickener is, for example, 0.1 to 1 part by mass relative to 100 parts by mass of the resin component. Furthermore, when the thickener is an isocyanate monomer or a prepolymer thereof, the content of the thickener is, for example, 0.1 to 20 parts by mass relative to 100 parts by mass of the resin component.

[0138] [Filler] The filler is a filler other than aluminum hydroxide, and examples thereof include inorganic fillers. Examples of inorganic fillers include oxides (e.g., alumina, titanium oxide), hydroxides (e.g., magnesium hydroxide, excluding aluminum hydroxide), carbonates (e.g., calcium carbonate), sulfates (e.g., barium sulfate), silica (e.g., crystalline silica, fused silica, fumed silica, dry silica (Aerosil)), hollow fillers, silicates (e.g., silica sand, diatomaceous earth, glass powder, glass balloons, mica, clay, kaolin, talc), fluorides (e.g., fluorite), phosphates (e.g., calcium phosphate), metal powders, ceramics, milled fibers, and clay minerals (e.g., smectite).

[0139] The fillers can be used alone or in combination of two or more.

[0140] The content ratio of the filler relative to 100 parts by mass of the resin component is, for example, 30 to 200 parts by mass, or preferably 50 to 150 parts by mass.

[0141] [Colorant] The colorant is not particularly limited, and examples of the colorant include polyester toners containing known pigments such as titanium oxide, carbon black, red iron oxide, and phthalocyanine blue.

[0142] The colorants can be used alone or in combination of two or more.

[0143] The content of the colorant is, for example, 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

[0144] <Preparation of Resin Composition> The resin composition is prepared by mixing a resin component, aluminum hydroxide, and additives that are blended as needed.

[0145] In the above preparation, the unsaturated polyester resin can also be prepared by dissolving the unsaturated polyester in a polymerizable monomer (preferably styrene) in advance and then blending the above additives as necessary.

[0146] In preparing the unsaturated polyester resin, the content of the polymerizable monomer is, for example, 10 to 40 parts by mass, or preferably 20 to 35 parts by mass, relative to 100 parts by mass of the unsaturated polyester.

[0147] In the above preparation, the vinyl ester resin can also be prepared by dissolving the vinyl ester in a polymerizable monomer (preferably styrene) in advance and then blending the above additives as necessary.

[0148] In preparing the vinyl ester resin, the content of the polymerizable monomer relative to 100 parts by mass of the vinyl ester is, for example, 50 to 80 parts by mass, or preferably 60 to 70 parts by mass.

[0149] Furthermore, after preparing the unsaturated polyester resin and / or vinyl ester resin, when this unsaturated polyester resin and / or vinyl ester resin is mixed with other components (aluminum hydroxide and additives added as needed), a polymerizable monomer can also be added.

[0150] In this way, a resin composition is prepared.

[0151] In such a resin composition, the glass transition temperature when the mixture of the thermosetting resin and the polymerizable monomer is cured is 0°C to 60°C, preferably 10°C to 50°C, more preferably 20°C to 40°C, and even more preferably 30°C to 35°C.

[0152] Specifically, the glass transition temperature is 0°C or higher, preferably 10°C or higher, more preferably 20°C or higher, even more preferably 30°C or higher, and 60°C or lower, preferably 50°C or lower, more preferably 40°C or lower, even more preferably 35°C or lower.

[0153] If the glass transition temperature is equal to or higher than the lower limit, the moldability can be improved, whereas if the glass transition temperature is lower than the lower limit, the moldability will be reduced.

[0154] Furthermore, if the glass transition temperature is equal to or higher than the lower limit, the water resistance can be improved.

[0155] Furthermore, when the glass transition temperature is equal to or lower than the upper limit, flexibility is improved.

[0156] On the other hand, if the glass transition temperature exceeds the upper limit, flexibility decreases.

[0157] The method for measuring the glass transition temperature will be described in detail in the Examples below.

[0158] A molding material can be prepared by blending reinforcing fibers into such a resin composition, and a fire-resistant material can be obtained from such a molding material by a known method.

[0159] 2. Molding Material The molding material contains a resin composition and reinforcing fibers.

[0160] <Reinforcing Fibers> Examples of reinforcing fibers include inorganic fibers, organic fibers, and natural fibers. Examples of inorganic fibers include glass fibers, carbon fibers, metal fibers, and ceramic fibers. Examples of organic fibers include polyvinyl alcohol fibers, polyester fibers, polyamide fibers, fluororesin fibers, and phenolic fibers. Examples of natural fibers include hemp and kenaf.

[0161] As the reinforcing fiber, preferably, inorganic fiber is used, and more preferably, glass fiber is used.

[0162] Examples of the shape of the reinforcing fibers include cloth (e.g., roving cloth), mat (e.g., chopped strand mat, preformable mat, continuous strand mat, and surfacing mat), strand, roving, nonwoven fabric, and paper.

[0163] The length of the reinforcing fibers is not particularly limited and is, for example, 1.5 mm or more, and from the viewpoint of improving strength, is preferably 5 mm or more, more preferably 20 mm or more, and is, for example, 80 mm or less, preferably 40 mm or less.

[0164] <Preparation of molding material> To prepare the molding material, reinforcing fibers are blended with a resin composition. Specifically, the reinforcing fibers are impregnated with the resin composition.

[0165] The resin composition can be prepared by a known method. Specific examples include sheet molding compound (SMC), thick molding compound (TMC), and bulk molding compound (BMC). SMC and BMC are preferred.

[0166] The content of the reinforcing fibers relative to the molding material is, for example, 10% by mass to 50% by mass, or preferably 10% by mass to 30% by mass.

[0167] This gives a molding material (preferably a sheet-like molding material) containing the resin composition and the reinforcing fibers.

[0168] The molding material contains the resin composition, and therefore the fire-resistant material obtained using the molding material has excellent flexibility and excellent flame retardancy even in the form of a thin plate.

[0169] 3. Fire-resistant material The fire-resistant material includes a cured product of the above molding material.

[0170] To harden the molding material, the molding material is first aged to increase its viscosity so that it can be subjected to heat compression molding (described later).

[0171] In the aging, the aging temperature is, for example, 20° C. or higher and, for example, 50° C. or lower, and the aging time is, for example, 8 hours or higher and, for example, 120 hours or lower.

[0172] This allows the molding material to maintain its shape.

[0173] Next, the molding material is subjected to heat compression molding by a known method.

[0174] The conditions for the heat compression molding are appropriately set depending on the purpose and application. In the heat compression molding, the molding temperature is, for example, 100°C to 200°C. The molding pressure is, for example, 0.1 MPa to 20 MPa, preferably 1 MPa to 15 MPa, and more preferably 5 MPa to 12 MPa.

[0175] This allows the molding material to be shaped and hardened to obtain a fire-resistant material.

[0176] In addition, examples of molding methods using extrusion hardening include press molding, injection molding, transfer molding, calendar molding, pultrusion molding, resin transfer molding, preform matched die molding, double belt press molding, and extrusion molding.Preferably, examples of molding methods using extrusion hardening include press molding, injection molding, double press molding, and calendar molding.More preferably, examples of molding methods using extrusion hardening include press molding and injection molding.More preferably, examples of molding methods using extrusion hardening include press molding.

[0177] The thickness of the fire-resistant material is, for example, 4.0 mm or less, preferably 3.5 mm or less, more preferably 3.0 mm or less, even more preferably 2.5 mm or less, particularly preferably 2.0 mm or less, most preferably 1.5 mm or less, even more preferably 1.0 mm or less, even more preferably 0.8 mm or less, even more preferably 0.6 mm or less, or, for example, 0.2 mm or more.

[0178] Furthermore, from the viewpoint of attaching various components to the fire-resistant material, the fire-resistant material may have, in addition to the above-described thickness, a thick portion having a relatively large thickness and a thin portion having a relatively small thickness. Such a thick portion and a thin portion are formed, for example, to form a rib or a boss for attaching various components.

[0179] The fire-resistant material contains the cured product of the molding material, and therefore has excellent flexibility and excellent flame retardancy even in the form of a thin plate.

[0180] Such fire-resistant materials are suitably used, for example, as fire-resistant sheets, connector covers for electrical components, gaskets (sealing materials for fixing), brackets (supporting parts), bus bars, connector parts for harnesses (electric wires in which the ends of multiple wires are treated with terminals or connectors so that they can be connected to other devices), supporting parts, insulation (insulating, blocking materials), filters, plugs, clips, and sealing materials. The fire-resistant material is preferably used as a fire-resistant sheet (a fire-resistant sheet having a sheet shape, preferably a fire-resistant sheet having a uniform thickness and a sheet shape).

[0181] 4. Effects and Effects When the mixture of the thermosetting resin and the polymerizable monomer in the resin composition is cured, the glass transition temperature is from 0° C. to 60° C. Therefore, the cured product of the resin composition can be softened and has excellent flexibility.

[0182] In addition, the content of the polymerizable monomer in the resin composition is 40 mass % or less based on the total amount of the polymerizable monomer and the thermosetting resin, and therefore, a fire-resistant material obtained using this resin composition has excellent flexibility.

[0183] In detail, the molding material of Patent Document 1 contains an unsaturated polyester resin (an unsaturated polyester resin containing an unsaturated polyester and a polymerizable monomer), a polyvinyl acetate resin (a polyvinyl acetate resin containing polyvinyl acetate and a polymerizable monomer), aluminum hydroxide particles, and chopped glass fibers, and the content of the polymerizable monomer is 57.9 mass% relative to the total amount of the polymerizable monomer and the thermosetting resin.

[0184] The polymerizable monomer is a solvent for dissolving the unsaturated polyester, and is also a crosslinkable monomer (reactive diluent) that can crosslink with the unsaturated polyester when the unsaturated polyester resin is cured.

[0185] In Patent Document 1, an excess amount of polymerizable monomer is blended with respect to the unsaturated polyester. The excess polymerizable monomer does not react with the unsaturated polyester, but polymerizes with itself to form a cured product of the polymerizable monomer. This cured product reduces flexibility.

[0186] In contrast, in the resin composition, the content of the polymerizable monomer is 40 mass% or less relative to the total amount of the polymerizable monomer and the thermosetting resin, which reduces the amount of the cured product of the polymerizable monomer, thereby improving flexibility.

[0187] In addition, the resin composition contains 120 parts by mass or more of aluminum hydroxide per 100 parts by mass of the resin component, and the mass ratio of aluminum hydroxide to the polymerizable monomer is 15.0 or less. Therefore, a fire-resistant material obtained using this resin composition has excellent flame retardancy even in the form of a thin plate.

[0188] Specifically, increasing the content of aluminum hydroxide improves the flame retardancy and the mechanical strength of the fire-resistant material, and therefore, by increasing the content of aluminum hydroxide, it is possible to produce a fire-resistant material with excellent flame retardancy even in the form of a thin plate.

[0189] On the other hand, if the content of aluminum hydroxide is too high, the viscosity of the resin composition increases excessively, making it impossible to produce a fire-resistant material.

[0190] In contrast, in the resin composition, the content of aluminum hydroxide is adjusted to a predetermined range, so that a fire-resistant material with excellent flame retardancy can be produced even in the form of a thin plate.

[0191] The molding material contains the resin composition, and therefore, the fire-resistant material obtained using this molding material has excellent flexibility and excellent flame retardancy even in the form of a thin plate.

[0192] The fire-resistant material contains the cured product of the molding material, and therefore has excellent flexibility and excellent flame retardancy even in the form of a thin plate.

[0193] The present invention will be described in more detail below with reference to examples. However, the following description is of one embodiment of the present invention, and the present invention is not limited to these descriptions.

[0194] Specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values ​​(numerical values ​​defined as "not more than" or "less than") or lower limit values ​​(numerical values ​​defined as "not less than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Modes for Carrying Out the Invention." Furthermore, unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0195] <Details of Components> The trade names and abbreviations of the components used in each example and each comparative example are described in detail below. Polystyrene powder: polystyrene (number average molecular weight of approximately 110,000) Polyvinyl acetate solution: styrene solution of polyvinyl acetate (styrene content 64%) Aluminum hydroxide: average particle size 8 μm Expanded graphite: trade name "9510045", manufactured by Ito Graphite Industries Co., Ltd. Phosphorus-based flame retardant: metal phosphinate, trade name "Exolit OP1230", manufactured by Clariant Chemicals Nitrogen-containing flame retardant, melamine cyanurate, nitrogen content 49% by mass, trade name "MC-4000", manufactured by Nissan Chemical Industries, Ltd.

[0196] Synthesis of Unsaturated Polyester Resin Synthesis Example 1 An unsaturated polyester was prepared by reacting 2,400 parts by mass of propylene glycol, 620 parts by mass of fumaric acid, 3,830 parts by mass of sebacic acid, and 1,200 parts by mass of isophthalic acid at a reaction temperature of 200° C. until the acid value reached 27 mgKOH / g. Next, 18 parts by mass of styrene was mixed with 100 parts by mass of the unsaturated polyester to obtain an unsaturated polyester resin (styrene 15% by mass).

[0197] Synthesis Examples 2 to 5 Unsaturated polyester resins were synthesized according to the same procedure as in Synthesis Example 1. However, the formulation of each component was changed based on Table 1.

[0198] Synthesis Example 6: 9,366 parts by mass of diethylene glycol and 8,500 parts by mass of isophthalic acid were reacted at a reaction temperature of 200°C until the acid value reached 15 mgKOH / g. Next, 3,345 parts by mass of maleic anhydride was added, and the reaction was continued at a reaction temperature of 200°C until the acid value reached 20 mgKOH / g. This resulted in an unsaturated polyester. Next, 67 parts by mass of styrene was mixed with 100 parts by mass of the unsaturated polyester to obtain an unsaturated polyester resin (styrene 40% by mass).

[0199] Synthesis of Vinyl Ester Resin Synthesis Example 7 A flask equipped with a stirrer, reflux condenser, and gas inlet tube was charged with 1,850 parts by mass (10.0 equivalents) of a bisphenol A epoxy compound (epoxy equivalent: 185 g / eq), 317 parts by mass (2.78 equivalents) of bisphenol A, and 1.0 part by mass of triethylbenzylammonium chloride as a catalyst. Next, while blowing in nitrogen, the mixture was reacted at 170°C for 5 hours. This resulted in an epoxy resin with an epoxy equivalent of 298 g / eq. The mixture was then cooled to 120°C, and 1.0 part by mass of hydroquinone as a polymerization inhibitor, 4.0 parts by mass of triethylbenzylammonium chloride as a catalyst, and 636 parts by mass (7.40 equivalents) of methacrylic acid were added. Next, while blowing in air, the mixture was reacted at 110°C for 8 hours. This resulted in a vinyl ester with an acid value of 8.0 mgKOH / g. Next, 1,869 parts by mass of styrene (66.7 parts by mass per 100 parts by mass of vinyl ester) was added to this vinyl ester, thereby obtaining a vinyl ester resin (styrene content: 40% by mass).

[0200] <Production of resin compositions, molding materials, and fire-resistant materials> Examples 1 to 3, Comparative Example 2, Examples 13 to 15, Comparative Example 5, Example 17, Comparative Example 6, Example 22, Example 23, and Comparative Example 7 [Production of resin compositions] According to the formulations shown in Tables 2 to 7, the components except for the thickener were mixed using a kneader. This gave resin compositions.

[0201] [Production of molding material] A thickener was added to the resin composition according to the formulation shown in Tables 2 to 7, and then reinforcing fibers were added and mixed, thereby obtaining a molding material (BMC).

[0202] [Production of Fire-Resistant Material] The molding material was subjected to heat compression molding using a 300 mm x 300 mm flat metal plate to produce a fire-resistant material of a predetermined thickness.

[0203] Specifically, molding was performed under the following conditions: mold temperature on both the product surface and the back surface was 140°C, molding pressure was 10 MPa, and retention time in the mold was 300 seconds. After that, the molded product was removed from the mold and immediately sandwiched between iron plates to cool.

[0204] Examples 4 to 12, Comparative Example 1, Example 16, Examples 18 to 21 [Production of Resin Compositions] Each component, except for the thickener, was added in order and mixed according to the formulations shown in Tables 2 to 7. In this way, resin compositions were prepared.

[0205] [Production of molding material] According to the formulations shown in Tables 2 to 7, magnesium oxide was added as a thickener to the resin composition, and then reinforcing fibers were added, and molding materials (SMC) were prepared using a known SMC impregnation machine.

[0206] [Production of Fireproof Material] A fireproof material was produced according to the same procedure as in Example 1.

[0207] <Evaluation> (Glass Transition Temperature) 0.5 parts by mass of 8% by mass cobalt octenoate and 1 part by mass of 55% by mass methyl ethyl ketone peroxide were added to 100 parts by mass of a mixture of thermosetting resin and polymerizable monomer, and the mixture was stirred and left to cure at room temperature for 15 hours. The cured product was then post-cured at 140°C for 2 hours, and the peak temperature of the loss tangent measured by the DMA method at a heating rate of 5°C / min and a frequency of 1 Hz was taken as the glass transition temperature. The results are shown in Tables 2 to 7.

[0208] (Flexibility) The fireproof materials of each Example and Comparative Example were cut into pieces measuring 300 mm lengthwise and 100 mm widthwise. Force was applied by hand in the lengthwise direction and the pieces were bent. Flexibility was evaluated based on the following criteria. The results are shown in Tables 2 to 7. {Criteria} ◯: Able to bend until the distance between both ends was 100 mm. △: Able to bend until the distance between both ends was 100 mm, but cracks occurred when held in this state for 30 seconds. ×: Cracks or cracks occurred before the distance between both ends was 100 mm.

[0209] (Appearance) The fireproof materials of each Example and Comparative Example were left at 25°C for 24 hours and then their appearances were observed. The appearances were evaluated based on the following criteria. The results are shown in Tables 2 to 7. {Criteria} ◯: No blistering or unevenness was observed. Δ: No blistering was observed, but no unevenness was observed. ×: Blisters and unevenness were observed.

[0210] (Shrinkage Rate) The fire-resistant materials of each Example and Comparative Example were left to stand at 25°C for 24 hours. Thereafter, the dimensions of the four sides of the molded article at 25°C were measured, and the shrinkage rate was calculated based on the ratio to the dimensions of the flat mold. The shrinkage rate was evaluated based on the following criteria. The results are shown in Tables 2 to 7. {Criteria} ◯: The shrinkage rate was less than 0.1%. ×: The shrinkage rate was 0.1% or more.

[0211] (Residual Styrene Amount) The fire-resistant materials of each Example and Comparative Example were left to stand at 25°C for one week. A sample solution was prepared in accordance with JIS K6904:2016, and the amount of residual styrene was quantified. The amount of residual styrene was evaluated based on the following criteria. The results are shown in Tables 2 to 7. {Criteria} ◯: The amount of residual styrene was less than 0.5% by mass when the fire-resistant material was taken as 100% by mass. ×: The amount of residual styrene was 0.5% by mass or more when the fire-resistant material was taken as 100% by mass.

[0212] (Flame retardancy) The fire-resistant materials of each example and each comparative example were evaluated for flame retardancy in accordance with fire resistance tests: JIS C 60695-11-3: 2014, JIS C 60695-11-4: 2014 (UL94 V0 / 5V). V0 conformance was evaluated as ◯. The results are shown in Tables 2 to 7.

[0213] (Water Resistance) The fireproof materials of each Example and Comparative Example were boiled at 100°C for 100 hours. The ratio of volume resistivity (after boiling / before boiling) of the fireproof material after boiling to that before boiling was measured in accordance with JIS K6911:1995, and was calculated. The water resistance was evaluated based on the following criteria. The results are shown in Tables 2 to 7. {Criteria} ◯: The volume resistivity ratio was 1 / 1000 or more. Δ: The volume resistivity ratio was 1 / 10000 or more and less than 1 / 1000. ×: The volume resistivity ratio was less than 1 / 10000.

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[0221] The above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted as limiting. Modifications of the present invention that are obvious to those skilled in the art are intended to be included in the scope of the following claims.

[0222] The resin composition, molding material and fire-resistant material of the present invention are suitably used, for example, in the production of fire-resistant sheets.

Claims

1. A resin composition comprising a thermosetting resin containing an unsaturated polyester and a polymerizable monomer, aluminum hydroxide, wherein the glass transition temperature when the mixture of the thermosetting resin and the polymerizable monomer is cured is 0°C or higher and 60°C or lower, the content ratio of the polymerizable monomer is 40% by mass or less based on the total amount of the polymerizable monomer and the thermosetting resin, the content ratio of the aluminum hydroxide is 120 parts by mass or more based on 100 parts by mass of the resin component, and the mass ratio of the aluminum hydroxide to the polymerizable monomer is 15.0 or less.

2. The resin composition according to claim 1, wherein the unsaturated polyester is a reaction product of a polybasic acid and a polyhydric alcohol, and the polybasic acid contains a linear saturated aliphatic dibasic acid having 8 or more carbon atoms.

3. The resin composition according to claim 1, wherein the resin component does not contain a thermoplastic resin, or when the resin component contains a thermoplastic resin, the content ratio of the thermoplastic resin is 5% by mass or less based on the resin component.

4. A molding material comprising the resin composition according to any one of claims 1 to 3 and a reinforcing fiber.

5. A refractory characterized by comprising a cured product of the molding material according to claim 4.