Laminated Products

Abstract

This layered article comprises, in the given order towards one side in the thickness direction, the following: reinforcing fibers; a molded layer comprising a cured product of a first resin composition; an inorganic non-woven fabric; and a heat insulation layer comprising a cured product of a second resin composition. The first resin composition contains a first thermosetting resin and aluminum hydroxide. The second resin composition contains a second thermosetting resin. The first resin composition and the second resin composition are the same as, or different from, each other.

Description

Technical Field

[0001] The present invention relates to a laminated product.

Background Art

[0002] Conventionally, molded products made of a molding material containing a resin (especially, sheet molding compound (SMC)) are excellent in appearance, mechanical properties, water resistance, and corrosion resistance, and are used in a wide range of fields.

[0003] As such a molding material, for example, a thermosetting resin composition containing an unsaturated polyester, aluminum hydroxide, and a fiber reinforcing material has been proposed (see, for example, Patent Document 1 below). Aluminum hydroxide is blended in this molding material from the viewpoint of improving flame retardancy.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, further improvement in flame retardancy has been required for molded products made of such molding materials.

[0006] The present invention provides a laminated product excellent in flame retardancy.

Means for Solving the Problems

[0007] The present invention [1] is a laminate comprising, in order toward one side in a thickness direction, a molding layer consisting of reinforcing fibers and a cured product of a first resin composition, and an insulating layer consisting of an inorganic nonwoven fabric and a cured product of a second resin composition, wherein the first resin composition contains a first thermosetting resin and aluminum hydroxide, and the second resin composition contains a second thermosetting resin, and the first resin composition and the second resin composition are the same or different.

[0008] The present invention [2] includes the laminate according to the above [1], in which the second resin composition contains aluminum hydroxide.

[0009] The present invention [3] includes the laminate according to the above [1] or [2], in which the second resin composition contains expanded graphite.

[0010] The present invention [4] includes the laminate according to any one of the above [1] to [3], in which the first resin composition contains expanded graphite.

[0011] The present invention [5] includes a laminate described in any one of [1] to [4] above, which has a second insulation layer on the other side in the thickness direction of the molded layer, and the second insulation layer includes an inorganic fiber fabric. Effect of the Invention

[0012] The laminate of the present invention has a molding layer containing aluminum hydroxide and a heat insulating layer containing an inorganic nonwoven fabric, which are arranged in this order toward one side in the thickness direction, and therefore has excellent flame retardancy. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic diagram showing a first embodiment of the laminate of the present invention. [Diagram 2] 2A to 2C are schematic diagrams showing one embodiment of a method for producing a laminate in the first embodiment. Fig. 2A shows a first step of preparing a molding material and a prepreg. Fig. 2B shows a second step of molding the molding material together with the prepreg. Fig. 2C shows the obtained laminate. [Diagram 3] FIG. 3 is a schematic diagram showing a second embodiment of the laminate of the present invention. [Figure 4] 4A to 4C are schematic diagrams showing one embodiment of a method for producing a laminate in the second embodiment. Fig. 4A shows a third step of preparing a molding material and an inorganic nonwoven fabric. Fig. 4B shows a fourth step of molding the molding material and the inorganic nonwoven fabric. Fig. 4C shows the obtained laminate. [Diagram 5] 5A to 5C are schematic diagrams showing one embodiment of a method for producing a laminate having a second insulation layer in the first embodiment. Fig. 5A shows a first step of preparing a prepreg for the second insulation layer together with a molding material and a prepreg. Fig. 5B shows a second step of molding the molding material together with the prepreg and the prepreg for the second insulation layer. Fig. 5C shows the obtained laminate. [Figure 6] 6A to 6C are schematic diagrams showing an embodiment of a method for producing a laminate having a second heat insulating layer in the second embodiment. Fig. 6A shows a third step of preparing a molding material, an inorganic nonwoven fabric, and an inorganic fiber fabric. Fig. 6B shows a fourth step of molding the molding material, the inorganic nonwoven fabric, and the inorganic fiber fabric. Fig. 6C shows the obtained laminate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] In the laminate of the present invention, the molding layer contains a cured product of a first resin composition, and the heat insulating layer contains a cured product of a second resin composition, the first resin composition and the second resin composition being the same or different.

[0015] Hereinafter, a first embodiment in which the first resin composition and the second resin composition are different from each other and a second embodiment in which the first resin composition and the second resin composition are the same will be described. Embodiment This section will explain in detail.

[0016] <<First embodiment>> A first embodiment of the laminate of the present invention will be described with reference to FIG.

[0017] In Fig. 1, the up-down direction of the paper surface is the thickness direction, the upper side of the paper surface is one side in the thickness direction, and the lower side of the paper surface is the other side in the thickness direction. The left-right direction and the depth direction of the paper surface are surface directions perpendicular to the thickness direction. Specifically, they correspond to the directional arrows in each figure.

[0018] <Laminated products> 1, the laminate 1 includes a molded layer 2 and a heat insulating layer 3 in this order toward one side in the thickness direction. Specifically, the laminate 1 includes the molded layer 2 and the heat insulating layer 3 disposed directly on one surface of the molded layer 2 in the thickness direction.

[0019] In FIG. 1, the laminate 1 is shaped into a plate, but the shape of the laminate 1 is not particularly limited, and various shapes can be selected.

[0020] <Molding layer> The molding layer 2 is disposed over the entire other surface of the heat insulating layer 3 in the thickness direction so as to be in contact with the other surface of the heat insulating layer 3 in the thickness direction.

[0021] In FIG. 1, the molded layer 2 is shaped into a plate shape, but the shape of the molded layer 2 is not particularly limited, and various shapes can be selected.

[0022] The molded layer 2 includes reinforcing fibers and a cured product of a first resin composition. More specifically, the molded layer 2 includes a cured product of a molding material including reinforcing fibers and the first resin composition.

[0023] The molding material includes reinforcing fibers and a first resin composition.

[0024] [Reinforced fiber] 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-based fibers, polyester-based fibers, polyamide-based fibers, fluororesin-based fibers, and phenol-based fibers. Natural fibers include, for example, hemp and kenaf.

[0025] The reinforcing fibers are preferably inorganic fibers, and more preferably glass fibers.

[0026] The shape of these reinforcing fibers may be, for example, a cloth, a mat, a strand, a roving, a nonwoven fabric, or a paper. An example of the cloth may be a roving cloth. An example of the mat may be a chopped strand mat, a preformable mat, a continuous strand mat, or a surfacing mat. An example of the strand may be a chopped strand.

[0027] The shape of the reinforcing fibers is preferably a mat shape, more preferably chopped strands, and even more preferably chopped strands dispersed in a non-directional manner in a sheet shape.

[0028] Moreover, the reinforcing fibers preferably do not include inorganic nonwoven fabrics (nonwoven inorganic fibers) described below and inorganic fiber woven fabrics (cloth-like inorganic fibers) described below.

[0029] The length of the reinforcing fibers is not particularly limited. The length of the reinforcing fibers is, for example, 0.1 mm or more, preferably 1.5 mm or more, more preferably 5 mm or more, and further preferably 15 mm or more, and is, for example, 80 mm or less, preferably 40 mm or less.

[0030] The blending ratio of reinforcing fibers (for example, when the reinforcing fibers are glass fibers, hereinafter, glass fibers) fiber The content (%) of the first resin composition and the reinforcing fibers is, for example, 5 mass% or more, preferably 10 mass% or more, more preferably 20 mass% or more, and for example, 50 mass% or less, preferably 40 mass% or less, based on the total amount of the first resin composition and the reinforcing fibers.

[0031] [First resin composition] The first resin composition includes a first resin component and aluminum hydroxide.

[0032] The first resin component includes a first thermosetting resin.

[0033] The first thermosetting resin may, for example, be an unsaturated polyester resin, a vinyl ester resin, or an acrylic syrup, and preferably, an unsaturated polyester resin or a vinyl ester resin.

[0034] The unsaturated polyester resin comprises an unsaturated polyester and a polymerizable monomer.

[0035] Unsaturated polyesters are the polymerization products of polybasic acids and polyhydric alcohols.

[0036] 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).

[0037] Examples of the ethylenically unsaturated bond-containing polybasic acid include ethylenically unsaturated aliphatic dibasic acids, halides of ethylenically unsaturated aliphatic dibasic acids, and alkyl esters of ethylenically unsaturated aliphatic dibasic acids.

[0038] Examples of ethylenically unsaturated aliphatic dibasic acids include maleic acid, fumaric acid, itaconic acid, and dihydromuconic acid. Examples of ethylenically unsaturated bond-containing polybasic acids include acid anhydrides derived from the above ethylenically unsaturated aliphatic dibasic acids. Examples of ethylenically unsaturated bond-containing polybasic acids include maleic anhydride. Examples of ethylenically unsaturated bond-containing polybasic acids include maleic anhydride and fumaric acid.

[0039] Examples of polybasic acids not containing ethylenically unsaturated bonds include saturated aliphatic polybasic acids, saturated alicyclic polybasic acids, aromatic polybasic acids, halides of these acids, and alkyl esters of these acids.

[0040] Examples of the saturated aliphatic polybasic acid include saturated aliphatic dibasic acids.

[0041] Examples of saturated aliphatic dibasic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylsuccinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Examples of saturated aliphatic polybasic acids include acid anhydrides derived from the above-mentioned saturated aliphatic dibasic acids. Examples of acid anhydrides derived from saturated aliphatic dibasic acids include oxalic anhydride and succinic anhydride.

[0042] Examples of the saturated alicyclic polybasic acid include saturated alicyclic dibasic acids.

[0043] Examples of saturated alicyclic dibasic acids include HET acid, 1,2-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid (cis- or trans-1,4-cyclohexanedicarboxylic acid or mixture thereof), and dimer acid. Examples of saturated alicyclic polybasic acids include acid anhydrides derived from the above-mentioned saturated alicyclic dibasic acids. Examples of acid anhydrides derived from saturated alicyclic dibasic acids include HET acid anhydride.

[0044] Examples of aromatic polybasic acids include aromatic dibasic acids.

[0045] 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.

[0046] As the polybasic acid not containing an ethylenically unsaturated bond, preferably, an aromatic polybasic acid is used, more preferably, an aromatic dibasic acid is used, further preferably, phthalic acid is used, and particularly preferably, isophthalic acid is used.

[0047] The polybasic acids can be used alone or in combination of two or more kinds.

[0048] When the polybasic acid includes an ethylenically unsaturated bond-containing polybasic acid and an ethylenically unsaturated bond-free polybasic acid, the mixing ratio of the ethylenically unsaturated bond-containing polybasic acid to the polybasic acid is, for example, 50 mol % or more, preferably 60 mol % or more, and for example, 99 mol % or less, preferably 80 mol % or less.

[0049] Polyhydric alcohols include, for example, dihydric and trihydric alcohols.

[0050] Examples of dihydric alcohols include aliphatic diols, alicyclic diols, and aromatic diols. Examples of aliphatic diols include alkane diols and ether diols. Examples of alkane diols include ethylene glycol, propylene glycol (1,2- or 1,3-propane diol or a mixture thereof), butylene glycol (1,2- or 1,3- or 1,4-butylene glycol or a mixture thereof), 1,5-pentane diol, 1,6-hexane diol, neopentyl glycol, 2-methyl-1,3-propane diol, 2-butyl-2-ethyl-1,3-propane diol, 3-methyl-1,5-pentane diol, 2,2,2-trimethylpentane diol, and 3,3-dimethylol heptane. Examples of ether diols include diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of alicyclic diols include cyclohexanediol (1,2- or 1,3- or 1,4-cyclohexanediol or a mixture thereof), cyclohexanedimethanol (1,2- or 1,3- or 1,4-cyclohexanedimethanol or a mixture thereof), cyclohexanediethanol (1,2- or 1,3- or 1,4-cyclohexanediethanol or a mixture thereof), and hydrogenated bisphenol A. Examples of aromatic diols include bisphenol A, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A.

[0051] Examples of trihydric alcohols include glycerin, trimethylolpropane, and triisopropanolamine.

[0052] The polyhydric alcohol is preferably a dihydric alcohol, more preferably an aliphatic diol, further preferably an alkane diol, particularly preferably propylene glycol and neopentyl glycol.

[0053] The polyhydric alcohols can be used alone or in combination of two or more.Preferably, the polyhydric alcohols include propylene glycol and neopentyl glycol.

[0054] The unsaturated polyester can be obtained by polycondensation of a polybasic acid and a polyhydric alcohol.

[0055] To polycondense a polybasic acid with a polyhydric alcohol, the polybasic acid and the polyhydric alcohol are first mixed in the following equivalent ratio.

[0056] 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 or more, preferably 0.95 or more, and for example, 1.2 or less, preferably 1.1 or less.

[0057] After mixing the polybasic acid and the polyhydric alcohol, the polybasic acid and the polyhydric alcohol are reacted with each other while stirring under normal pressure and in a nitrogen atmosphere. The reaction temperature is, for example, 150° C. or higher, preferably 190° C. or higher, and, for example, 250° C. or lower, preferably 230° C. or lower.

[0058] In the above reaction, a known solvent and a known catalyst can be added, if necessary.

[0059] This gives an unsaturated polyester.

[0060] The acid value of the unsaturated polyester (measurement method: in accordance with JIS K6901 (2008)) is, for example, 20 mgKOH / g or more, preferably 25 mgKOH / g or more, and for example, less than 40 mgKOH / g, preferably 30 mgKOH / g or less.

[0061] The weight average molecular weight of the unsaturated polyester is, for example, 4,000 or more, preferably 6,000 or more, and for example, 25,000 or less, preferably 20,000 or less.

[0062] The weight average molecular weight is a weight average molecular weight calculated in terms of polystyrene by gel permeation chromatography (GPC), and can be determined by measuring the unsaturated polyester by GPC.

[0063] Examples of the polymerizable monomer include styrene-based monomers and (meth)acrylic acid ester-based monomers.

[0064] Styrenic monomers include, for example, styrene, vinyltoluene, t-butylstyrene, and chlorostyrene.

[0065] 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, and isobutyl (meth)acrylate. Ru,Examples of the (meth)acrylic acid allyl ester include allyl (meth)acrylate. Examples of the ring-containing (meth)acrylic acid ester 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 the (meth)acrylic acid hydroxyalkyl ester include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Examples of the (meth)acrylic acid alkoxyalkyl ester include 2-methoxyethyl (meth)acrylate and 2-ethoxyethyl (meth)acrylate. Examples of (meth)acrylic acid aminoalkyl esters include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and chloride salts thereof. Examples of (meth)acrylic acid fluoroalkyl esters 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.

[0066] As the polymerizable monomer, preferably, a styrene-based monomer is used, and more preferably, styrene is used.

[0067] The polymerizable monomers can be used alone or in combination of two or more kinds.

[0068] The unsaturated polyester resin is prepared by dissolving the unsaturated polyester in the polymerizable monomer. In preparing the unsaturated polyester resin, the blending ratio of the polymerizable monomer is, for example, 50 parts by mass or more, preferably 60 parts by mass or more, and, for example, 80 parts by mass or less, based on 100 parts by mass of the unsaturated polyester.

[0069] In addition, after preparing the unsaturated polyester resin, when this unsaturated polyester resin is mixed with other components (vinyl ester resin, acrylic syrup, low shrinkage agent (described later), aluminum hydroxide, and additives (described later)), a polymerizable monomer can also be further blended.

[0070] The vinyl ester resin comprises a vinyl ester and a polymerizable monomer.

[0071] Vinyl esters are the reaction products of epoxy resins and unsaturated monobasic acids.

[0072] Examples of epoxy resins include bisphenol type epoxy resins and novolac type epoxy resins.

[0073] The bisphenol type epoxy resin is, for example, a reaction product of a phenol component and an epoxy component. The phenol component includes, for example, a bisphenol compound (e.g., bisphenol A). The epoxy component includes, for example, a bisphenol A type epoxy compound.

[0074] To obtain a bisphenol-type epoxy resin, a phenol component and an epoxy component are reacted with each other. Specifically, the phenol component and the epoxy component are mixed together and reacted with each other.

[0075] In the above reaction, the mixing ratio of the epoxy component relative to 1 equivalent of the phenol component is, for example, 1.5 equivalents or more, preferably 2.0 equivalents or more, more preferably 3.0 equivalents or more, and for example, 5.0 equivalents or less, preferably 4.0 equivalents or less.

[0076] In the above reaction, a catalyst can be added, if necessary.

[0077] Examples of catalysts include amines, quaternary ammonium salts, imidazoles, and phosphines. Examples of amines include triethylamine and benzyldimethylamine. Examples of quaternary ammonium salts include tetramethylammonium chloride and triethylbenzylammonium chloride. Examples of imidazoles include 2-ethyl-4-imidazole. Examples of phosphines include triphenylphosphine.

[0078] The catalyst is preferably a quaternary ammonium salt, more preferably triethylbenzylammonium chloride.

[0079] These catalysts can be used alone or in combination of two or more kinds.

[0080] The mixing ratio of the catalyst is, for example, 0.01 part by mass or more and, for example, 1.0 part by mass or less, preferably 0.1 part by mass or less, relative to 100 parts by mass in total of the phenol component and the epoxy component.

[0081] In the above reaction, the reaction temperature is, for example, 100°C or higher, preferably 130°C or higher, and, for example, 180°C or lower.

[0082] This results in a bisphenol type epoxy resin.

[0083] The epoxy equivalent of the bisphenol type epoxy resin is, for example, 150 g / eq or more, preferably 250 g / eq or more, and for example, 800 g / eq or less, preferably 400 g / eq or less, more preferably 350 g / eq or less.

[0084] In addition, when two kinds of bisphenol-type epoxy resins are used in combination, the above-mentioned epoxy equivalent is the epoxy equivalent of all bisphenol-type epoxy resins obtained by multiplying the epoxy equivalent of each bisphenol-type epoxy resin by the mass ratio of each bisphenol-type epoxy resin to the total amount of bisphenol-type epoxy resins and adding them together.

[0085] Novolac-type epoxy resins are, for example, reaction products of novolac and epichlorohydrin.

[0086] Moreover, commercially available epoxy resins can also be used.

[0087] Examples of unsaturated monobasic acids include monocarboxylic acids and reaction products of dibasic acid anhydrides with alcohols having at least one unsaturated group in the molecule.

[0088] Examples of monocarboxylic acids include (meth)acrylic acid, crotonic acid, cinnamic acid, and sorbic acid. Note that (meth)acrylic is synonymous with methacrylic and / or acrylic.

[0089] Examples of dibasic acid anhydrides include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Examples of alcohols having an unsaturated group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and glycerin di(meth)acrylate.

[0090] As the unsaturated monobasic acid, preferably, a monocarboxylic acid is used, more preferably, (meth)acrylic acid is used, and further preferably, methacrylic acid is used.

[0091] The unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0092] In the reaction between the epoxy resin and the unsaturated monobasic acid, an addition reaction occurs between the epoxy group of the epoxy resin and the unsaturated monobasic acid.

[0093] In the above reaction, the equivalent of the carboxyl group of the unsaturated monobasic acid to the epoxy group of the epoxy resin is, for example, 0.8 or more, preferably 1.0 or more, and for example, 1.5 or less, preferably 1.2 or less.

[0094] In the above reaction, a catalyst can be added, if necessary.

[0095] The catalyst may be the same as the catalyst used in the reaction between the phenol component and the epoxy component described above. The catalyst may preferably be a quaternary ammonium salt, more preferably triethylbenzylammonium chloride.

[0096] The mixing ratio of the catalyst is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, and for example, 1.0 part by mass or less, preferably 0.6 part by mass or less, relative to 100 parts by mass of the epoxy resin.

[0097] In the above reaction, a polymerization inhibitor (described below) (preferably hydroquinone) can be added, if necessary.

[0098] The mixing ratio of the polymerization inhibitor relative to 100 parts by mass of the epoxy resin is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, and for example, 0.5 part by mass or less, preferably 0.1 part by mass or less.

[0099] In the above reaction, the reaction temperature is, for example, 80° C. or more, preferably 100° C. or more, and for example, 150° C. or less, preferably 130° C. or less.

[0100] The above reaction can also be carried out following the above reaction between the phenol component and the epoxy component.

[0101] This gives a vinyl ester.

[0102] The acid value of the vinyl ester (measurement method: in accordance with JIS K6901 (2008)) can be determined from the charging ratio of the epoxy resin and the unsaturated monobasic acid, and is, for example, 1 mgKOH / g or more and, for example, 20 mgKOH / g or less, preferably 10 mgKOH / g or less.

[0103] Examples of the polymerizable monomer include the polymerizable monomers exemplified for the unsaturated polyester resin, and preferably, styrene-based monomers, more preferably, styrene.

[0104] The vinyl ester resin is prepared by dissolving the vinyl ester in the polymerizable monomer. In preparing the vinyl ester resin, the blending ratio of the polymerizable monomer is, for example, 50 parts by mass or more, preferably 60 parts by mass or more, and for example, 80 parts by mass or less, based on 100 parts by mass of the unsaturated polyester.

[0105] The first thermosetting resin can be used alone or in combination of two or more kinds, and preferably, an unsaturated polyester resin and a vinyl ester resin are used in combination. When an unsaturated polyester resin and a vinyl ester resin are used in combination, the blending ratio of the unsaturated polyester is, for example, 70 parts by mass or more, preferably 80 parts by mass or more, and, for example, 90 parts by mass or less, based on 100 parts by mass of the total amount of the unsaturated polyester and the vinyl ester. The blending ratio of the vinyl ester is, for example, 10 parts by mass or more, and, for example, 30 parts by mass or less, and, preferably, 20 parts by mass or less.

[0106] The first resin component preferably contains a low shrinkage agent.

[0107] The low shrinkage agent is blended in order to suppress cure shrinkage and heat shrinkage of the molded layer 2 obtained by using the first resin composition.

[0108] Examples of low shrinkage agents include polyethylene, polystyrene, styrene-based thermoplastic elastomers, crosslinked polystyrene, polyvinyl acetate-polystyrene block copolymers, polyvinyl acetate, polymethyl methacrylate, and saturated polyester resins, including polyethylene and polystyrene.

[0109] The low shrinkage agents can be used alone or in combination of two or more kinds, and preferably polyethylene and polystyrene are used in combination.

[0110] The mixing ratio of the low shrinkage agent relative to 100 parts by mass of the first resin component is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 20 parts by mass or less, preferably 15 parts by mass or less.

[0111] Aluminum hydroxide is blended in order to impart flame retardancy to the molded layer 2 obtained using the first resin composition, as well as to impart transparency and depth.

[0112] The mixing ratio of aluminum hydroxide is 30 parts by mass or more, preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and 300 parts by mass or less, preferably 200 parts by mass or less, per 100 parts by mass of the first resin component.

[0113] 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.

[0114] The average particle size of aluminum hydroxide can be determined by creating a particle size distribution curve using a laser diffraction / scattering type particle size distribution measurement device and calculating the 50% by mass equivalent particle size.

[0115] The first resin composition is obtained by blending the first resin component and aluminum hydroxide in the above-mentioned blending ratio.

[0116] If necessary, additives may be added to the first resin composition within the range that does not impair the effects of the present invention.

[0117] Examples of additives include expandable graphite, polymerization inhibitors, curing agents, release agents, colorants, wetting and dispersing agents, thickeners, flame retardants, fillers, pattern materials, antibacterial agents, hydrophilic agents, photocatalysts, UV absorbers, UV stabilizers, separation inhibitors, 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.

[0118] Expandable graphite is a graphite intercalation compound in which sulfuric acid or other substances are inserted between the layers of flake-like natural graphite, and the spaces between the layers expand at temperatures of about 150 to 300°C. Expandable graphite is this graphite intercalation compound before heating.

[0119] The blending ratio of the expanded graphite is 3 parts by mass or more, preferably 5 parts by mass or more, and 10 parts by mass or less, preferably 8 parts by mass or less, based on 100 parts by mass of the first resin component.

[0120] When the blending ratio of the expandable graphite is equal to or more than the above lower limit, the molded layer 2 obtained by using the unsaturated polyester resin composition has excellent flame retardancy.

[0121] 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.

[0122] The average particle size of the expanded graphite can be determined by observing with an optical microscope, measuring the maximum diameter (long diameter) and the particle diameter (short diameter) in the direction perpendicular to the maximum diameter for 50 randomly selected particles of expanded graphite, and calculating the average value of the long diameter and the short diameter.

[0123] As the expanded graphite, commercially available products can be used, specifically, 9510045 from Ito Graphite Industries Co., Ltd.

[0124] The polymerization inhibitor is added to adjust the pot life and the curing reaction.

[0125] Examples of the polymerization inhibitor include hydroquinone compounds, benzoquinone compounds, catechol compounds, phenol compounds, and N-oxyl compounds. Examples of the hydroquinone compounds include hydroquinone, methylhydroquinone, and t-butylhydroquinone. Examples of the benzoquinone compounds include p-benzoquinone and methyl-p-benzoquinone. Examples of the catechol compounds include t-butylcatechol. Examples of the phenol compounds include 2,6-di-t-butyl-4-methylphenol and 4-methoxyphenol.Examples of N-oxyl compounds include 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 4-hydroxy-2,2,6,6-tetrapiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate, and 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoate. 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-4-t-butylbenzoate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-oxyl-2,2 ,6,6-tetramethylpiperidin-4-yl) n-butyl malonate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N,N'-bis(1-oxyl-2 ,2,6,6-tetramethylpiperidin-4-yl)adipamide, N-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)caprolactam, N-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)dodecylsuccinimide, 2,4,6-tris-[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-s-triazine, and 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one.

[0126] As the polymerization inhibitor, preferably, a benzoquinone compound is used, more preferably, p-benzoquinone is used.

[0127] The polymerization inhibitors can be used alone or in combination of two or more kinds.

[0128] The mixing ratio of the polymerization inhibitor relative to 100 parts by mass of the first resin component is, for example, 0.01 part by mass or more and, for example, 0.1 part by mass or less.

[0129] The curing agent may be, for example, a peroxide. Examples of the peroxide include benzoyl peroxide, t-butylperoxyisopropyl monocarbonate, t-amylperoxyisopropyl monocarbonate, 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, and preferably t-butylperoxyisopropyl monocarbonate.

[0130] The curing agents can be used alone or in combination of two or more kinds.

[0131] The mixing ratio of the curing agent relative to 100 parts by mass of the resin component is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 5 parts by mass or less, preferably 2 parts by mass or less.

[0132] Examples of the release agent include fatty acids, fatty acid metal salts, paraffin, 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.

[0133] The release agent is preferably a fatty acid metal salt, more preferably zinc stearate.

[0134] The release agents can be used alone or in combination of two or more kinds.

[0135] The mixing ratio of the release agent relative to 100 parts by mass of the resin component is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and for example, 10 parts by mass or less.

[0136] The colorant is not particularly limited, and examples of the colorant include polyester toners mixed with known pigments such as titanium oxide, carbon black, red iron oxide, and phthalocyanine blue.

[0137] As the colorant, preferably, a polyester toner is used.

[0138] The colorants can be used alone or in combination of two or more kinds.

[0139] The mixing ratio of the colorant relative to 100 parts by mass of the resin component is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 20 parts by mass or less.

[0140] The wetting and dispersing agent is added to optimize the viscosity of the first resin composition.

[0141] Wetting and dispersing agents include, for example, copolymers having acid groups, phosphate polyesters, and alkyl ammonium salts.

[0142] Specifically, examples of copolymers having an acid group that can be used include BYK-W995, BYK-W996, and BYK-W9010 (all manufactured by BYK-CHEMIE).

[0143] The alkyl ammonium salt may be, for example, an alkyl ammonium salt of a polymer copolymer, such as BYK-9076 manufactured by BYK-CHEMIE, which has an amine value of 44 mg / KOH / g and an acid value of 38 mg / KOH / g.

[0144] The wetting and dispersing agent may be used alone or in combination of two or more kinds. As the wetting and dispersing agent, a copolymer having an acid group and an alkyl ammonium salt are preferably used in combination.

[0145] The mixing ratio of the wetting dispersant per 100 parts by mass of the first resin component is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, and for example, 5 parts by mass or less, preferably 2 parts by mass or less.

[0146] The thickener is blended to thicken the first resin composition to a viscosity suitable for heat compression molding. The thickener is preferably blended before (preferably immediately before) impregnating the first resin composition into reinforcing fibers (described later).

[0147] Examples of the thickener include alkaline earth metal oxides and alkaline earth metal hydroxides. Examples of the alkaline earth metal oxides include magnesium oxide. Examples of the alkaline earth metal hydroxides include magnesium hydroxide and calcium hydroxide.

[0148] The thickener preferably includes an alkaline earth metal oxide, more preferably magnesium oxide.

[0149] The thickeners can be used alone or in combination of two or more kinds.

[0150] The mixing ratio of the thickener relative to 100 parts by mass of the first resin component is, for example, 0.5 parts by mass or more, and for example, 10 parts by mass or less, preferably 3 parts by mass or less.

[0151] The flame retardant is blended in order to impart flame retardancy to the molded layer 2 obtained by using the first resin composition.

[0152] Examples of the flame retardant include halogen-based flame retardants and non-halogen-based flame retardants. Examples of the halogen-based flame retardants include bromine-based flame retardants. Examples of the non-halogen-based flame retardants include phosphorus-based flame retardants, inorganic flame retardants, and nitrogen compound-based flame retardants.

[0153] The blending ratio of the flame retardant is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and, for example, 50 parts by mass or less, preferably 20 parts by mass or less with respect to 100 parts by mass of the first resin component.

[0154] Examples of the filler include inorganic fillers (excluding aluminum hydroxide).

[0155] Examples of the inorganic fillers include oxides, hydroxides (excluding aluminum hydroxide), carbonates, sulfates, silica, glass powder, hollow fillers, silicates, fluorides, phosphates, and clay minerals. Examples of the oxides include alumina and titania. Examples of the hydroxides include magnesium hydroxide. Examples of the carbonates include calcium carbonate. Examples of the sulfates include barium sulfate. Examples of the silica include crystalline silica, fused silica, fumed silica, and dry silica (aerosil). Examples of the hollow fillers include glass balloons, silica balloons, and alumina balloons. Examples of the silicates include silica sand, diatomaceous earth, mica, clay, kaolin, and talc. Examples of the fluorides include fluorspar. Examples of the phosphates include calcium phosphate. Examples of the clay minerals include smectite.

[0156] The filler can be used alone or in combination of two or more.

[0157] The blending ratio of the filler is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and, for example, 50 parts by mass or less, preferably 30 parts by mass or less with respect to 100 parts by mass of the first resin component.

[0158] Furthermore, when the first thermosetting resin is mixed with other components (the low shrinkage agent, aluminum hydroxide, and additives) to obtain the first resin composition, a polymerizable monomer can also be further blended therein.

[0159] The molding material is obtained by impregnating reinforcing fibers with the first resin composition.

[0160] The thickness of the molded layer 2 is, for example, 1 mm or more, preferably 1.5 mm or more, and for example, 5 mm or less, preferably 2.5 mm or less.

[0161] <Thermal insulation layer> The heat insulating layer 3 has a sheet shape and is disposed over the entire one surface of the molded layer 2 in the thickness direction so as to be in contact with the one surface of the molded layer 2 in the thickness direction.

[0162] The heat insulating layer 3 includes an inorganic nonwoven fabric and a cured product of the second resin composition. More specifically, the heat insulating layer 3 includes an inorganic nonwoven fabric and a cured product of a prepreg including the second resin composition.

[0163] The prepreg includes an inorganic nonwoven fabric and a second resin composition.

[0164] [Inorganic nonwoven fabric] The inorganic nonwoven fabric is, for example, inorganic fibers in the form of a nonwoven fabric.

[0165] Inorganic nonwoven fabrics are formed into a mat shape by depositing and / or entangling inorganic fibers. More specifically, in inorganic nonwoven fabrics, inorganic fibers are not woven with each other, but are deposited and / or entangled with each other randomly in the in-plane direction and / or thickness direction of the inorganic nonwoven fabric. In other words, inorganic nonwoven fabrics are distinguished from inorganic fiber woven fabrics in which inorganic fibers are woven with each other, as will be described in detail later.

[0166] Examples of inorganic nonwoven fabrics include fiber paper and fiber felt. In particular, fiber felt manufactured by combining mechanical action such as needle punching and bonding is superior in flame retardancy to chemical bonding methods such as binders.

[0167] Examples of the inorganic fibers in the inorganic nonwoven fabric include glass fibers, ceramic fibers, carbon fibers, silicon carbide fibers, and boron fibers, and preferably include glass fibers and carbon fibers.

[0168] The basis weight of the inorganic nonwoven fabric is, for example, 50 g / m 2 More than 80 g / m 2 or more, for example, 1000 g / m 2 The following is the result.

[0169] [Second resin composition] The second resin composition includes a second resin component.

[0170] The second resin component contains a second thermosetting resin and, if necessary, the above-mentioned low shrinkage agent.

[0171] The second thermosetting resin may, for example, be an unsaturated polyester resin, a vinyl ester resin, or an acrylic syrup, and preferably, an unsaturated polyester resin or a vinyl ester resin.

[0172] The second resin composition preferably contains aluminum hydroxide. When the second resin composition contains aluminum hydroxide, the flame retardancy is excellent.

[0173] The second resin composition preferably contains expandable graphite. When the second resin composition contains expandable graphite, the second resin composition has excellent flame retardancy.

[0174] The second resin composition may also contain the additives exemplified for the first resin composition (except for expanded graphite).

[0175] In the first embodiment, the first resin composition is different from the second resin composition. Specifically, the first thermosetting resin and the second thermosetting resin are different in type and / or mixing ratio, and / or components other than the first thermosetting resin (aluminum hydroxide and additives) and components other than the second thermosetting resin (aluminum hydroxide and additives) are different.

[0176] More specifically, the mixing ratio of aluminum hydroxide per 100 parts by mass of the second resin component is lower than the mixing ratio of aluminum hydroxide per 100 parts by mass of the first resin component, and specifically, for example, 20 parts by mass or more and, for example, 130 parts by mass or less, preferably 90 parts by mass or less. In addition, when the first resin composition does not contain expandable graphite, the second resin composition preferably contains expandable graphite from the viewpoint of improving flame retardancy.

[0177] The second resin composition can be prepared in the same manner as the first resin composition.

[0178] The prepreg is obtained by impregnating an inorganic nonwoven fabric with the second resin composition.

[0179] The heat insulating layer 3 has a thickness of, for example, 0.1 mm or more, preferably 0.5 mm or more, and for example, 2 mm or less, preferably 1 mm or less.

[0180] <Manufacturing method of laminated products> A method for producing the laminate 1 will be described with reference to FIGS. 2A to 2C.

[0181] The manufacturing method of the laminate 1 (sometimes referred to as the first method) includes a first step of preparing the molding material 10 and the prepreg 11, and a second step of molding the molding material 10 together with the prepreg 11.

[0182] In the first step, as shown in FIG. 2A, a molding material 10 and a prepreg 11 are prepared. In FIG. 2A, the molding material 10 is maintained in a sheet shape.

[0183] The molding material 10 is prepared by blending the reinforcing fibers with the first resin composition. More specifically, the reinforcing fibers are impregnated with the first resin composition.

[0184] The molding material 10 may be a molding material obtained by a known manufacturing method, such as a sheet molding compound (SMC), a thick molding compound (TMC), and a bulk molding compound (BMC).

[0185] As a result, a molding material 10 containing the reinforcing fibers and the first resin composition is obtained.

[0186] With respect to the molding material 10, the total amount (volume content) of the components excluding the filler is, for example, 40 vol% or more, preferably 45 vol% or more, and for example, 70 vol% or less, preferably 60 vol% or less.

[0187] The component excluding the filler is the total amount of the components of the first resin composition excluding aluminum hydroxide, expandable graphite, and the filler that is added as needed. In other words, the component excluding the filler is the total amount of the first resin component and additives other than the filler that is added as needed.

[0188] The volume content of aluminum hydroxide in the molding material 10 is, for example, 10 vol% or more, preferably 20 vol% or more, and for example, 40 vol% or less.

[0189] In addition, the volume content of expanded graphite (calculated assuming a density of 1.8 g / ml) in the molding material 10 is, for example, 1 volume % or more, and, for example, 5 volume % or less, preferably 3 volume % or less (in terms of weight %, it is 1 weight % or more, and, for example, 5 weight % or less, preferably 3 weight % or less).

[0190] The volume content of the reinforcing fibers in the molding material 10 is, for example, 15 vol% or more, preferably 20 vol% or more, and for example, 40 vol% or less, preferably 35 vol% or less.

[0191] Next, such molding material 10 is aged to thicken it so that it can be subjected to heat compression molding (described later).

[0192] In the aging, the aging temperature is, for example, 20°C or higher and, for example, 50°C or lower. The aging time is, for example, 8 hours or more and, for example, 120 hours or less.

[0193] In this way, the molding material 10 is maintained in, for example, a sheet shape. That is, the molding material 10 has a sheet shape. In this way, the molding material 10 is prepared.

[0194] Separately, a prepreg 11 is prepared.

[0195] To prepare the prepreg 11, the inorganic nonwoven fabric is mixed with the second resin composition. Specifically, the inorganic nonwoven fabric is impregnated with the second resin composition. After impregnation, the mixture is aged at, for example, 20° C. or higher and, for example, 50° C. or lower, for example, 8 hours or longer and, for example, 120 hours or shorter, to thicken the mixture so that it can be subjected to heat compression molding (described later).

[0196] In this way, the prepreg 11 is prepared.

[0197] In the second step, the molding material 10 is molded together with the prepreg 11. Specifically, the prepreg 11 is placed on the bottom of the mold 20, and then the molding material 10 is placed on one surface of the prepreg 11 in the thickness direction.

[0198] Then, the molding material 10 and the prepreg 11 are heated and compressed and molded by a known method.

[0199] The conditions of the heat compression molding are appropriately set according to the purpose and use. In the heat compression molding, the molding temperature is, for example, 100° C. or more, and, for example, 200° C. or less. The molding pressure is, for example, 0.1 MPa or more, preferably 1 MPa or more, more preferably 5 MPa or more, and, for example, 20 MPa or less, preferably 15 MPa or less.

[0200] As described above, in the second step, the molding material 10 and the prepreg 11 are cured. As a result, the molding layer 2 and the heat insulating layer 3 are obtained at the same time, and the laminate 1 is obtained as shown in FIG. 2C.

[0201] According to the first method, since an inorganic nonwoven fabric having a large unit weight can be integrally molded, the fire resistance is excellent.

[0202] <<Second embodiment>> In the second embodiment, the same reference numerals are used for the same members and steps as in the first embodiment, and detailed descriptions thereof will be omitted. In addition, the second embodiment can achieve the same effects as the first embodiment, except as otherwise specified. Furthermore, the first embodiment, the second embodiment, and their modified examples can be appropriately combined.

[0203] A second embodiment of the laminate of the present invention will now be described with reference to FIG.

[0204] The laminate 1 includes a molding layer 2 and a heat insulating layer 3 in this order toward one side in the thickness direction.

[0205] The molded layer 2 includes reinforcing fibers and a cured product of a first resin composition. More specifically, the molded layer 2 includes a cured product of a molding material including reinforcing fibers and the first resin composition.

[0206] The heat insulating layer 3 includes an inorganic nonwoven fabric and a cured product of the second resin composition. More specifically, the heat insulating layer 3 includes an inorganic nonwoven fabric and a cured product of a prepreg including the second resin composition.

[0207] On the other hand, in the second embodiment, the first resin composition and the second resin composition are the same.

[0208] Although details will be described later, the second resin composition in the second embodiment is a composition in which a part of the first resin composition contained in the molding material is impregnated into the inorganic nonwoven fabric in the fourth step described later.

[0209] <Manufacturing method of laminated products> The manufacturing method of the laminate 1 (sometimes referred to as the second method) includes a third step of preparing the molding material 10 and the inorganic nonwoven fabric 12, and a fourth step of molding the molding material 10 and the inorganic nonwoven fabric 12.

[0210] In the third step, as shown in Fig. 4A, a molding material 10 and an inorganic nonwoven fabric 12 are prepared. In Fig. 4A, the molding material 10 and the inorganic nonwoven fabric 12 are maintained in a sheet-like shape.

[0211] The molding material 10 can be prepared in a manner similar to the first method described above.

[0212] In the fourth step, the molding material 10 is molded. Specifically, the inorganic nonwoven fabric 12 is placed on the bottom of the mold 20, and then the molding material 10 is placed on one surface of the inorganic nonwoven fabric 12 in the thickness direction.

[0213] Then, the molding material 10 is heated and compressed and molded by a known method.

[0214] The conditions for the heat compression molding are the same as those exemplified in the second step.

[0215] At this time, a part of the first resin composition contained in the molding material 10 impregnates the inorganic nonwoven fabric 12. Then, the first resin composition is cured. As a result, the inorganic nonwoven fabric and the first resin composition are hardened. 2 A heat insulating layer 3 containing a cured product of the resin composition (first resin composition) is formed.

[0216] As a result, a laminate 1 is obtained as shown in FIG. 4C.

[0217] According to the second method, the step of preparing the prepreg 11 can be omitted.

[0218] <Action and effect> The laminate 1 includes, in order toward one side in the thickness direction, a molded layer 2 containing aluminum hydroxide and a heat insulating layer 3 containing an inorganic nonwoven fabric, and therefore has excellent flame retardancy.

[0219] In detail, since the molding layer 2 contains aluminum hydroxide, the flame retardancy is improved, and since the insulating layer 3 containing inorganic nonwoven fabric contains inorganic fibers in a compressed form, it is possible to suppress combustion from the insulating layer 3 side without increasing the plate thickness. Lamination The flame retardancy of product 1 is improved.

[0220] As described above, the heat insulating layer 3 contains inorganic nonwoven fabric. The inorganic fibers are randomly deposited and / or entangled. When the heat insulating layer 3 containing such inorganic nonwoven fabric is exposed to flames, the inorganic fibers that were compressed during molding expand (for example, the inorganic fibers are transformed into a cotton-like shape and expand). This allows the heat insulating layer 3 to exhibit heat insulating properties. As a result, combustion from the heat insulating layer 3 side can be suppressed.

[0221] Such a laminate 1 can be widely used in, for example, building materials, housings, casting materials, machine parts (for example, battery cases for electric vehicles), electronic and electrical parts, and various members for vehicles, ships, and aircraft.

[0222] In particular, battery cases for electric vehicles may be required to have excellent flame retardancy to retard the spread of fire in the event of a vehicle fire.

[0223] On the other hand, the laminate 1 has excellent flame retardancy and can therefore be suitably used for battery cases of electric vehicles.

[0224] <Modification> In the modified example, the same components and steps as those in the first and second embodiments are given the same reference numerals, and detailed descriptions thereof are omitted. In addition, the modified example can achieve the same effects as those in the first and second embodiments, unless otherwise specified. Furthermore, the first and second embodiments and the modified examples thereof can be appropriately combined.

[0225] A second heat insulating layer 4 (shown by imaginary lines in Figs. 1 and 3) may also be provided on the other side of the molding layer 2 in the thickness direction.

[0226] The second heat insulating layer 4 has a sheet shape. The heat insulating layer 3 is disposed on the other side in the thickness direction of the molded layer 2 so as to contact the other side in the thickness direction of the molded layer 2.

[0227] The second insulation layer 4 includes an inorganic fiber fabric and a cured product of the third resin composition. More specifically, the second insulation layer 4 includes an inorganic fiber fabric and a cured product of a prepreg for the second insulation layer that includes the third resin composition.

[0228] The inorganic fiber fabric is a cloth-shaped inorganic fiber. More specifically, the inorganic fiber fabric is a fabric in which inorganic fibers are woven together. More specifically, the inorganic fiber fabric is a fabric in which, for example, carbon fiber, glass strand, glass yarn, or roving is woven in a plain weave, twill weave, satin weave, or other folding method. In other words, it is distinguished from inorganic nonwoven fabrics in which inorganic fibers are randomly stacked and / or entangled with each other.

[0229] As the inorganic fibers, the same inorganic fibers as those exemplified for the heat insulating layer 3 can be used.

[0230] The third resin composition may be the same as the first resin composition, and is preferably the same as the first resin composition.

[0231] The third resin composition can be prepared in the same manner as the first resin composition.

[0232] In the first method, the laminated body having the second heat insulating layer 4 ProductTo manufacture 1, in the first step, a molding material 10, a prepreg 11, and a prepreg 13 for the second heat insulation layer are prepared as shown in FIG. 5A.

[0233] The prepreg 13 for the second heat insulating layer is obtained by blending an inorganic fiber fabric with a third resin composition. More specifically, the inorganic fiber fabric is impregnated with the third resin composition. After impregnation, the mixture is aged, for example, at 20° C. or higher and 50° C. or lower, for example, for 8 hours or longer and 120 hours or shorter, to thicken the mixture so that it can be subjected to heat compression molding. In this way, the prepreg 13 for the second heat insulating layer is prepared.

[0234] 5B, in the second step, the molding material 10 is molded together with the prepreg 11 and the second insulation layer prepreg 13. Specifically, the prepreg 11 is placed on the bottom of the mold 20, then the molding material 10 is placed on one surface in the thickness direction of the prepreg 11, and then the second insulation layer prepreg 13 is placed on one surface in the thickness direction of the molding material 10.

[0235] Then, the molding material 10, the prepreg 11 and the prepreg 13 for the second heat insulating layer are heated and compressed and molded under the above-mentioned conditions by a known method.

[0236] This causes the molding material 10, the prepreg 11, and the second insulation layer prepreg 13 to harden. This simultaneously produces the molding layer 2, the insulation layer 3, and the second insulation layer 4, and produces the laminate 1 as shown in Fig. 5C.

[0237] In the first method, the laminated body having the second heat insulating layer 4 Product When manufacturing the molded article 1, in the first step, an inorganic fiber fabric 14 can be prepared together with the molding material 10 and the prepreg 11.

[0238] In such a case, in the second step, prepreg 11 is placed on the bottom of mold 20, then molding material 10 is placed on one surface in the thickness direction of prepreg 11, and then inorganic fiber fabric 14 is placed on one surface in the thickness direction of molding material 10, and then heated and compressed to be molded.

[0239] At this time, a portion of the first resin composition contained in the molding material 10 impregnates the inorganic fiber fabric 14. Then, this first resin composition is cured. As a result, a second insulation layer 4 containing the inorganic fiber fabric 14 and a cured product of the third resin composition (first resin composition) is formed together with the insulation layer 3.

[0240] In the second method, the laminated body having the second heat insulating layer 4 is Product To manufacture the molded article 1, in the third step, an inorganic fiber fabric 14 is prepared together with a molding material 10 and an inorganic nonwoven fabric 12, as shown in FIG. 6A.

[0241] 6B, in the fourth step, the molding material 10 is molded. Specifically, an inorganic nonwoven fabric 12 is placed on the bottom of a mold 20, then the molding material 10 is placed on one surface in the thickness direction of the inorganic nonwoven fabric 12, and then an inorganic fiber fabric 14 is placed on one surface in the thickness direction of the molding material 10.

[0242] Then, the molding material 10 is heated and compressed under the above-mentioned conditions by a known method.

[0243] At this time, a portion of the first resin composition contained in the molding material 10 impregnates the inorganic nonwoven fabric 12 and also the inorganic fiber woven fabric 14. The first resin composition then hardens. As a result, a second insulation layer 4 containing the inorganic fiber woven fabric 14 and a hardened product of the third resin composition (first resin composition) is formed together with the insulation layer 3.

[0244] As a result, a laminate 1 is obtained as shown in FIG. 6C.

[0245] In the second method, the laminated body having the second heat insulating layer 4 is ProductWhen manufacturing the laminated laminate 1, in the third step, a prepreg 13 for the second heat insulating layer can also be prepared together with the molding material 10 and the inorganic nonwoven fabric 12.

[0246] Even in such a case, the molding material 10 and the prepreg 13 for the second heat insulating layer are cured in the same manner as described above.

[0247] If the laminate 1 is provided with the second heat insulating layer 4, the heat insulating properties of the laminate 1 after combustion are improved, and the strength is also improved.

[0248] The thickness of the second heat insulating layer 4 is, for example, 0.03 mm or more and, for example, 5 mm or less.

[0249] In the above explanation, the laminate 1 of the second embodiment is produced by the first method, but it can also be produced by the second method in which the second resin composition is changed to the first resin composition. EXAMPLES

[0250] Specific numerical values ​​of the blending ratio (content ratio), 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 ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention." In addition, unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0251] 1.Details of ingredients Expanded graphite (average particle size 70 μm): Trade name "9510045" manufactured by Ito Graphite Industries Co., Ltd. was used as is (this product was 100 mesh on 25%). OP1230: Flame retardant, metal phosphinate, product name "Exolit OP1230", manufactured by Clariant Chemicals MC-4000: Flame retardant (nitrogen compound flame retardant), manufactured by Nissan Chemical Co., Ltd. SB-140: Glass fiber paper, basis weight 140g / m2 Manufactured by Olivest Co., Ltd. CFZ-100RD: Carbon fiber paper, basis weight 100g / m 2 , manufactured by Japan Polymer Industries Co., Ltd. CFZ-500SD: Carbon fiber felt, basis weight 500g / m 2 , manufactured by Japan Polymer Industries Co., Ltd. MNA-600-1000: Glass fiber felt (heat-resistant glass felt), glass needle mat MNA-600-1000-30m, basis weight 600g / m 2 , manufactured by Japan Glass Fiber Industrial Co., Ltd. M100K 104H: Glass cloth, weight 105g / m 2 , manufactured by Unitika Ltd. M205K 104H: Glass cloth, weight 200g / m 2 , manufactured by Unitika Ltd.

[0252] 2. Preparation of Unsaturated Polyester Resin Synthesis Example 1 In a flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a stirrer, 10.0 mol of maleic anhydride, 6.5 mol of propylene glycol, and 4.0 mol of neopentyl glycol were charged. Then, the mixture was subjected to a polycondensation reaction at 200°C to 210°C while stirring under a nitrogen gas atmosphere. This resulted in an unsaturated polyester having an acid value of 26.5 mgKOH / g. The acid value was measured according to JIS K6901 (2008). Next, 0.01 parts by mass of hydroquinone and 66.7 parts by mass of styrene were added as polymerization inhibitors to 100 parts by mass of this unsaturated polyester, and these were mixed uniformly. This resulted in an unsaturated polyester resin (styrene content 40% by mass).

[0253] 3. Preparation of Vinyl Ester Resin Synthesis Example 2 In a flask equipped with a stirrer, a reflux condenser, and a gas inlet tube, 1850 parts by mass (10.0 equivalents) of a bisphenol A type epoxy compound (epoxy equivalent 185 g / eq), 317 parts by mass (2.78 equivalents) of bisphenol A, and 1.0 parts by mass of triethylbenzylammonium chloride as a catalyst were charged. Then, while blowing in nitrogen, the reaction was carried out at 170°C for 5 hours. As a result, an epoxy resin with an epoxy equivalent of 298 g / eq was obtained. Then, the mixture was cooled to 120°C, and 1.0 part by mass of hydroquinone as a polymerization inhibitor, 5.0 parts by mass of triethylbenzylammonium chloride as a catalyst, and 636 parts by mass (7.40 equivalents) of methacrylic acid were added. Then, while blowing in air, the reaction was carried out at 110°C for 8 hours. As a result, a vinyl ester with an acid value of 8.0 mgKOH / g was obtained. Next, 1869 parts by mass of styrene (66.7 parts by mass relative to 100 parts by mass of vinyl ester) was added to this vinyl ester, thereby obtaining a vinyl ester resin (styrene content: 40% by mass).

[0254] 4. Manufacturing of laminated products Example 1 (First Method) <1st process> The following components were added in order while being mixed, thereby obtaining a first resin composition.

[0255] Unsaturated polyester resin: 60 parts by mass of the unsaturated polyester resin of Synthesis Example 1 (36 parts by mass of unsaturated polyester, 24 parts by mass of styrene) Vinyl ester resin: 10 parts by mass of the vinyl ester resin of Synthesis Example 2 (6 parts by mass of vinyl ester, 4 parts by mass of styrene) Polymerizable monomer: 10 parts by mass of styrene Shrinkage reducing agent: 15 parts by mass of polystyrene solution (styrene solution of polystyrene (weight average molecular weight approximately 200,000) (styrene content 65%)) and 5 parts by mass of polyethylene powder Aluminum hydroxide: 150 parts by weight of aluminum hydroxide (average particle size 8 μm) Polymerization inhibitor: p-benzoquinone 0.05 parts by mass Hardener: 1 part by mass of t-butyl peroxy isopropyl carbonate Release agent: zinc stearate 5 parts by weight Colorant: Black polyester toner (carbon black dispersed in polyester resin) 10 parts by weight Wetting and dispersing agent: 1.0 part by weight of copolymer having an acid group and 0.5 part by weight of alkyl ammonium salt of high molecular weight polymer Thickener: Magnesium oxide 0.8 parts by weight

[0256] Next, using a known sheet molding compound (SMC) impregnation machine, chopped strands obtained by continuously cutting glass rovings into 25 mm pieces were added (dispersed in a sheet shape in a non-directional manner) to the first resin composition applied to a carrier film using a doctor blade so that the glass fiber content was 35% by mass (25.5% by volume), and a molding material (sheet molding compound (SMC)) was obtained through an impregnation process. Next, this molding material was aged at 40°C for 48 hours to thicken the molding material until it became capable of being heated and compressed for molding, and a molding material was obtained.

[0257] Separately, the following components were added in order while being mixed, thereby obtaining a second resin composition.

[0258] Unsaturated polyester resin: 60 parts by mass of the unsaturated polyester resin of Synthesis Example 1 (36 parts by mass of unsaturated polyester, 24 parts by mass of styrene) Vinyl ester resin: 10 parts by mass of the vinyl ester resin of Synthesis Example 2 (6 parts by mass of vinyl ester, 4 parts by mass of styrene) Polymerizable monomer: 10 parts by mass of styrene Shrinkage reducing agent: 15 parts by mass of polystyrene solution (styrene solution of polystyrene (weight average molecular weight approximately 200,000) (styrene content 65%)) and 5 parts by mass of polyethylene powder Aluminum hydroxide: 40 parts by weight of aluminum hydroxide (average particle size 8 μm) Polymerization inhibitor: p-benzoquinone 0.05 parts by mass Hardener: 1 part by mass of t-butyl peroxy isopropyl carbonate Release agent: zinc stearate 5 parts by weight Colorant: Black polyester toner (carbon black dispersed in polyester resin) 10 parts by weight Wetting and dispersing agent: 1.0 part by weight of copolymer having an acid group and 0.5 part by weight of alkyl ammonium salt of high molecular weight polymer Thickener: Magnesium oxide 0.8 parts by weight

[0259] Next, using a known sheet molding compound (SMC) impregnation machine, CFZ-500SD was added onto the second resin composition that had been applied onto a carrier film using a doctor blade, and a prepreg (sheet molding compound (SMC)) was obtained through an impregnation process. Next, this prepreg was aged at 40°C for 48 hours to thicken the molding material until it became capable of being heated and compressed for molding, thereby obtaining a prepreg.

[0260] <Second process> The molding material with the adjusted weight and the prepreg were simultaneously heated and compressed into a 300 mm x 300 mm flat metal plate to obtain a flat laminate with a thickness of 2.5 mm.

[0261] The molding was performed under the following conditions: mold temperature was 140°C on both the product side and the back side, molding pressure was 10 MPa, and retention time in the mold was 300 seconds. The prepreg was placed on the bottom surface of the mold.

[0262] After being removed from the mold, the laminate was immediately sandwiched between iron plates and cooled.

[0263] Examples 2 to 6 (First Method) The same treatment as in Example 1 was carried out to obtain a laminate.

[0264] However, the formulation was changed according to the descriptions in Tables 1 to 4.

[0265] Example 7 and Example 8 (Second Method) <3rd process> A molding material was obtained in the same manner as in Example 1. However, the compounding recipe was changed according to the descriptions in Tables 2 and 4. In addition, an inorganic nonwoven fabric was prepared separately.

[0266] <4th process> The molding material with the adjusted weight and the inorganic nonwoven fabric were simultaneously heated, compressed and molded using a 300 mm×300 mm flat metal plate to obtain a flat laminate with a thickness of 2.5 mm to 3 mm.

[0267] The molding was performed under the following conditions: mold temperature was 140°C on both the product side and the back side, molding pressure was 10 MPa, and retention time in the mold was 300 seconds. The inorganic nonwoven fabric was placed on the bottom surface of the mold.

[0268] After being removed from the mold, the laminate was immediately sandwiched between iron plates and cooled.

[0269] Examples 9 and 10 A laminate was obtained in the same manner as in Example 1, except that the compounding recipe was changed according to the descriptions in Tables 2 and 4.

[0270] In Example 9, in the third step, an inorganic fiber fabric was prepared together with the molding material and prepreg. In the fourth step, the prepreg was placed on the bottom of the mold, the molding material was placed on one side of the prepreg in the thickness direction, and the inorganic fiber fabric was placed on one side of the molding material in the thickness direction, and the molding material was then cured according to the same procedure as in Example 1. This produced a laminate having a second heat insulating layer. Product was manufactured.

[0271] In addition, in Example 10, in the first step, a third resin composition was prepared together with the molding material and prepreg according to the formulation shown in Table 5, and a prepreg for the second insulation layer was prepared from the third resin composition in the same manner as in Example 1.

[0272] In the second step, a molding material was molded together with the prepreg and the prepreg for the second heat insulating layer.

[0273] Specifically, a prepreg was placed on the bottom of a mold, then a molding material was placed on one surface in the thickness direction of the prepreg, and then a prepreg for a second insulation layer was placed on one surface in the thickness direction of the molding material.

[0274] The molding material, the prepreg, and the prepreg for the second heat insulating layer were then subjected to heat compression molding in the same manner as in Example 1. As a result, a laminate having a second heat insulating layer was obtained. Product was manufactured.

[0275] Comparative Example 1 to Comparative Example 3 A molding material was obtained in the same manner as in Example 1. However, the compounding recipe was changed according to the descriptions in Tables 1 to 4.

[0276] Next, the molding material with the adjusted weight was simultaneously heated and compressed and molded using a 300 mm×300 mm flat metal plate to obtain a flat laminated product with a thickness of 2 to 3 mm.

[0277] Molding was carried out under the following conditions: mold temperature was 140°C on both the product side and the back side, molding pressure was 10 MPa, and retention time in the mold was 300 seconds.

[0278] After being removed from the mold, the laminate was immediately sandwiched between iron plates and cooled.

[0279] 5. Evaluation <Flame retardancy test> (Maximum temperature on the back of the test piece during flame radiation) Test pieces (150 mm x 150 mm) were cut from the laminates of each Example and Comparative Example. Next, using a commercially available cooking burner (Iwatani Corporation's cassette gas cooking burner CJ2), the length of the inner flame of the burner was adjusted to about 50 mm and the temperature of the inner flame tip was adjusted to about 1000°C. Furthermore, the center of the 150 mm x 150 mm test piece was fixed in a vertical position 40 mm from the tip of the burner. Furthermore, the test piece was fixed so that the center of the back side could be measured with an infrared thermometer. The burner was ignited, and a flame was emitted while measuring the temperature of the test piece, and the flame was stopped after 5 minutes. The maximum temperature of the back side of the test piece when the flame was emitted is shown in Tables 2 and 4.

[0280] (Strength after extinguishing) After the fire was extinguished, the specimens were cooled to room temperature and the strength was evaluated based on the following criteria by pressing them with a finger. The results are shown in Tables 2 and 4. [Evaluation Criteria] ○: The test piece did not crumble. ×: The test piece crumbled.

[0281] (Expansion of the insulation layer) The heat insulating layer was observed to see if it expanded, and the results are shown in Tables 2 and 4. [Evaluation Criteria] ○: A rise of about 1 mm was observed compared to the test piece before the flame radiation. ×: No swelling was observed.

[0282] (Bending strength after burning) After the fire was extinguished, the laminates of Examples 9 and 10 were cooled to room temperature and cut into test pieces with a width of 25 mm. The bending strength was measured according to JIS K7074 (1988). The results are shown in Table 4.

[0283] [Table 1]

[0284] [Table 2]

[0285] [Table 3]

[0286] [Table 4]

[0287] [Table 5]

[0288] 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 being limited. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims. [Industrial Applicability]

[0289] The laminate of the present invention Product The above-mentioned battery case can be particularly suitably used in a battery case of an electric vehicle. [Explanation of symbols]

[0290] 1 Laminated product 2 molding layer 3. Insulation layer 4 Second insulation layer

Claims

1. A molding layer including reinforcing fibers and a cured product of a first resin composition; a heat insulating layer made of an inorganic nonwoven fabric and a cured product of a second resin composition; are provided in order toward one side in the thickness direction, the first resin composition includes a first thermosetting resin and aluminum hydroxide; The second resin composition includes a second thermosetting resin, The first resin composition and the second resin composition are the same or different, The first thermosetting resin is at least one selected from the group consisting of an unsaturated polyester resin, a vinyl ester resin, and an acrylic syrup; the second thermosetting resin is at least one selected from the group consisting of an unsaturated polyester resin, a vinyl ester resin, and an acrylic syrup; The reinforcing fibers are in the form of strands, A laminate in which one surface in the thickness direction of the heat insulating layer is exposed.

2. The laminate according to claim 1 , wherein the second resin composition comprises aluminum hydroxide.

3. The laminate of claim 1 , wherein the second resin composition comprises expanded graphite.

4. The laminate of claim 1 , wherein the first resin composition comprises expanded graphite.

5. A second insulating layer is provided on the other side in the thickness direction of the molding layer, The laminate of claim 1 , wherein the second insulating layer comprises a woven inorganic fiber fabric.

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