WO2024075339A1 - Stratifié ainsi que procédé de fabrication de celui-ci, et boîtier de batterie - Google Patents

Stratifié ainsi que procédé de fabrication de celui-ci, et boîtier de batterie Download PDF

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Publication number
WO2024075339A1
WO2024075339A1 PCT/JP2023/022187 JP2023022187W WO2024075339A1 WO 2024075339 A1 WO2024075339 A1 WO 2024075339A1 JP 2023022187 W JP2023022187 W JP 2023022187W WO 2024075339 A1 WO2024075339 A1 WO 2024075339A1
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meth
laminate
acrylate
resin
core layer
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PCT/JP2023/022187
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English (en)
Japanese (ja)
Inventor
智昭 新地
秀樹 鳥井
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Dic株式会社
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Publication of WO2024075339A1 publication Critical patent/WO2024075339A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
    • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
    • H01M50/231—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks having a layered structure

Definitions

  • the present invention relates to a laminate that is lightweight and thin, yet has excellent flame resistance and strength, and can be used effectively in a variety of molded product applications, and a battery case that uses the laminate.
  • a so-called FRP sandwich molding which uses a resin foam as the core material and sandwiches it between fiber-reinforced plastic, is known as a lightweight, high-strength molding material (see, for example, Patent Document 1).
  • the resin foam that is the core material of this sandwich molding is generally flammable, and in order to impart a certain degree of flame resistance, it is necessary to use a resin foam that is sufficiently thick, so it cannot be used for applications such as battery cases that require both high flame resistance and fire resistance, as well as light weight and space saving.
  • the problem that the present invention aims to solve is to provide a molding material that is lightweight and thin, yet has excellent flame resistance and strength, and that can be suitably used for molded products such as battery cases, and a battery case using the same.
  • a laminate including a core layer (A) formed by compressing a foam in the thickness direction and an outer layer (B) made of fiber-reinforced plastic is lightweight and thin, yet has excellent flame resistance and strength, and can be used in a variety of molded product applications, including battery cases, and thus completed the present invention.
  • the present invention relates to (I) a laminate comprising a core layer (A) formed by compressing a foam in the thickness direction and an outer layer (B) made of a fiber-reinforced plastic.
  • the present invention further relates to (II) the laminate described in (I) above, in which the compression ratio of the core layer (A) is 40% or more in terms of thickness.
  • the present invention further relates to (III) the laminate described in (I) or (II) above, in which the aspect ratio of the foam cells of the core layer (A) is 2 or more.
  • the present invention further relates to (IV) a laminate according to any one of (I) to (III) above, in which the outer layer (B) is obtained by hot molding a prepreg containing reinforcing fibers (f) and a matrix resin (r), and the matrix resin is a resin composition (1) containing a polyisocyanate compound (r1) and a polyhydroxy(meth)acrylate compound (r2), or a resin composition (2) containing a polyisocyanate compound (r1), a monohydroxy(meth)acrylate compound (r3), and a polyhydroxy compound (r4).
  • the matrix resin is a resin composition (1) containing a polyisocyanate compound (r1) and a polyhydroxy(meth)acrylate compound (r2), or a resin composition (2) containing a polyisocyanate compound (r1), a monohydroxy(meth)acrylate compound (r3), and a polyhydroxy compound (r4).
  • the present invention further relates to (V) a method for producing a laminate according to any one of (I) to (IV) above, in which a precursor is formed by laminating a core layer (a) made of a foam and an outer layer (b) made of a prepreg containing reinforcing fibers (f) and a matrix resin (r) under conditions in which the core layer (a) is compressed.
  • the present invention further relates to (VI) a method for producing a laminate described in any one of (I) to (IV) above, in which the core layer (A) and the outer layer (B) made of fiber-reinforced plastic are bonded together using an adhesive.
  • the present invention further relates to (VII) a method for producing a laminate according to any one of (I) to (IV) above, in which a precursor obtained by laminating the core layer (A) and an outer layer (b) made of a prepreg containing reinforcing fibers (f) and a matrix resin (r) is heated and molded.
  • the present invention further relates to (VIII) a battery case using the laminate described in any one of (I) to (IV).
  • the present invention provides a laminate that is lightweight and thin, yet has excellent flame resistance and strength, and is suitable for use in molded products such as battery cases, and a battery case using the laminate.
  • the laminate of the present invention is characterized by including a core layer (A) made of foam compressed in the thickness direction and an outer layer (B) made of fiber-reinforced plastic.
  • foams made of various resin materials can be used without any particular restrictions.
  • the resin materials include polyurethane resin, phenol resin, melamine resin, acrylic resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polystyrene resin, styrene acrylic resin, ABS resin, polyphenylene ether resin, polyetherimide resin, polymethyl methacrylate resin, polymethacrylimide resin, etc.
  • the foaming method and foaming agent used for these resin materials are not particularly limited, and foams made by publicly known and commonly used foaming agents and foaming methods can be used. Among them, bead foams are preferred because the resulting laminate has better flame resistance, and bead foams of polystyrene resin are more preferred.
  • the bead foam can be produced, for example, by injecting a foaming gas into particles made of the various resin materials, heating the particles to pre-expand, and then foaming the resulting foam beads under heat and pressure.
  • the average particle size of the foam beads is preferably in the range of 0.5 to 5 mm, since the resulting laminate has better flame resistance and strength.
  • the foaming gas include propane, butane, and pentane, and the amount of gas injected is preferably 5 to 7 mass% of the foam beads.
  • the expansion ratio is preferably 40 to 70 times, since the resulting laminate has better flame resistance and strength.
  • the density of the foam is preferably in the range of 0.01 to 0.07 g/cm 3 , since the laminate has a good balance of light weight, flame resistance, and strength.
  • a functional coating agent can be applied to the surface of the foamable beads, which are the raw material, to impart desired performance to the resulting foam.
  • functional coating agents include flame-retardant coating agents and heat-resistant coating agents.
  • resin bead foams with a flame-retardant coating agent applied to the surface are preferred, since the resulting laminate has better flame resistance.
  • the flame-retardant coating agent include those containing phosphorus atom-containing compounds, halogen atom-containing compounds, nitrogen atom-containing compounds, hydrated metal compounds, borates, metal oxides, silicone compounds, etc. as flame retardants.
  • the core layer (A) of the present invention is obtained by compressing the foam in the thickness direction.
  • the compression ratio of the core layer (A) is preferably 40% or more, more preferably 60% or more, and particularly preferably 85% or more, in terms of thickness, since the resulting laminate is thin but has sufficient flame resistance. Also, it is preferably 97% or less, and more preferably 95% or less.
  • the aspect ratio of the foam cells of the core layer (A) is preferably 1.7 or more, more preferably 2.5 or more, and particularly preferably 6.7 or more, since the resulting laminate is thin but has sufficient flame resistance. Also, it is preferably 30 or less, and more preferably 20 or less.
  • the thickness of the core layer (A) is preferably in the range of 0.5 to 5 mm, and more preferably in the range of 1 to 3 mm, since the resulting laminate has an excellent balance of flame resistance, strength, and light weight.
  • the core layer (A) may be formed of only one layer, or may be multi-layered. When the core layer (A) is multi-layered, each layer may be formed of the same type of foam, or each layer may be formed of a different type of foam. Even when the core layer (A) is multi-layered, the total thickness of the core layer (A) is preferably in the range of 0.5 to 5 mm, and more preferably in the range of 1 to 3 mm.
  • the outer layer (B) made of the fiber-reinforced plastic is specifically obtained by hot molding a prepreg containing reinforcing fibers (f) and a matrix resin (r).
  • the reinforcing fibers (f) include, for example, carbon fibers, glass fibers, silicon carbide fibers, alumina fibers, boron fibers, metal fibers, and organic fibers such as aramid fibers, vinylon fibers, and tetron fibers. These may be used alone or in combination of two or more types. Among these, carbon fibers and glass fibers are preferred because they provide a laminate with higher strength.
  • carbon fiber such as polyacrylonitrile, pitch, and rayon, but among these, polyacrylonitrile is preferred because it produces carbon fiber with higher strength.
  • the shape of the reinforcing fiber (f) is not particularly limited, and examples thereof include reinforcing fiber tows in which reinforcing fiber filaments are bundled, unidirectional materials in which reinforcing fiber tows are aligned in one direction, woven fabrics, short cut reinforcing fibers, and nonwoven fabrics or papers made of short cut reinforcing fibers.
  • the reinforcing fiber (f) is a fabric
  • examples thereof include a plain weave, twill weave, satin weave, or non-crimped fabric, which is a sheet in which fiber bundles are aligned in one direction, or a sheet in which the fibers are stacked at different angles, stitched to prevent unraveling.
  • reinforcing fiber (f) When short cut reinforcing fibers are used as the reinforcing fiber (f), it is preferable to use fibers cut to a length of 2.5 to 50 mm, since this improves the fluidity in the mold during molding and the appearance of the molded product. Among these, it is preferable to use unidirectional materials or woven fabrics as the reinforcing fibers, since this results in a stronger outer layer (B).
  • prepregs that use unidirectional reinforcing fibers multiple sheets can be stacked in a quasi-isotropic manner, for example with the fiber directions alternating between 0° and 90°, to obtain an outer layer (B) with higher strength.
  • the length of the short cut reinforcing fibers is more preferably 8 to 50 mm, and particularly preferably 10 to 30 mm.
  • the basis weight (weight per 1 m2 of fiber) of the reinforcing fiber (f) can be of various types without any particular limitation. The optimum value also differs depending on the reinforcing fiber (f). In general, the basis weight is preferably in the range of 30 to 650 g/ m2 , since it is excellent in balance between the uniformity of the fiber width of the reinforcing fiber (f) and the impregnation of the matrix resin (r).
  • the basis weight is preferably 50 g/ m2 or more, and more preferably 100 g/ m2 or more. Also, it is preferably 600 g/ m2 or less, and more preferably 350 g/ m2 or less.
  • the reinforcing fiber (f) is a carbon fiber
  • it is preferably 50 g/ m2 or more, and more preferably 80 g/ m2 or more. Also, it is preferably 300 g/ m2 or less, and more preferably 200 g/ m2 or less.
  • the basis weight of the short cut reinforcing fibers is preferably 250 to 1500 g/m 2 , more preferably 300 to 1400 g/m 2 , and particularly preferably 400 to 1300 g/m 2 , from the viewpoint of achieving both favorable impregnation properties and high strength.
  • the content of the reinforcing fibers (f) in the prepreg is preferably 40% by mass or more, and more preferably 50% by mass or more, since this results in a stronger outer layer (B).
  • the content of the reinforcing fibers (f) in the prepreg is preferably 90% by mass or less, and more preferably 80% by mass or less.
  • the matrix resin (r) can be impregnated into the reinforcing fiber (f) and can be molded by heating or the like, and a wide variety of resins can be used without particular restrictions. Among them, a thermosetting resin composition is preferable because of ease of handling. Furthermore, since the outer layer (B) obtained is a prepreg that is high in strength, easy to handle, and has excellent moldability into various shapes, it is preferable that the resin composition contains a urethane reaction component formed by an isocyanate group and a hydroxyl group, and that a polymerizable unsaturated group is present in the resin composition.
  • resin compositions include a resin composition (1) containing a polyisocyanate compound (r1) and a polyhydroxy(meth)acrylate compound (r2), and a resin composition (2) containing a polyisocyanate compound (r1), a monohydroxy(meth)acrylate compound (r3), and a polyhydroxy compound (r4).
  • a (meth)acrylate compound refers to a compound having either or both of an acryloyl group and a methacryloyl group
  • a (meth)acryloyl group refers to either or both of an acryloyl group and a methacryloyl group
  • a (meth)acrylic acid refers to either or both of an acrylic acid and a methacrylic acid.
  • the polyisocyanate compound (r1) may be, for example, an aliphatic diisocyanate compound such as butane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, or dimer acid diisocyanate; an alicyclic diisocyanate compound such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, or hydrogenated diphenylmethane diisocyanate; or tolylene diisocyanate.
  • an aliphatic diisocyanate compound such as butane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, or dimer acid
  • xylylene diisocyanate tetramethyl xylylene diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and other aromatic diisocyanate compounds; and modified products of these isocyanate compounds, such as isocyanurate modified products, biuret modified products, allophanate modified products, carbodiimide modified products, urethane imine modified products, and polyol modified products modified with polyols such as diethylene glycol and dipropylene glycol. These may be used alone or in combination of two or more kinds.
  • aromatic diisocyanate compounds and various modified products thereof are preferred because they provide an outer layer (B) with excellent heat resistance.
  • the proportion of aromatic diisocyanate compounds and their various modified products relative to the total mass of polyisocyanate compounds (r) is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the polyhydroxy(meth)acrylate compound (r2) may be, for example, a (meth)acrylate compound made from epoxy resin and (meth)acrylic acid as reaction raw materials.
  • the epoxy resin may be, for example, diglycidyloxybenzene, diglycidyloxynaphthalene, aliphatic epoxy resin, biphenol type epoxy resin, bisphenol type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, heterocyclic type epoxy resin, glycidyl ester type epoxy resin, triphenolmethane type epoxy resin, phenol or naphthol aralkyl type epoxy resin, phenylene or naphthylene ether type epoxy resin, oxodoridone modified epoxy resin, or brominated epoxy resins thereof.
  • the epoxy resin may be an epoxy resin obtained by extending the specific examples described above with an extender.
  • the aliphatic epoxy resins include, for example, various aliphatic polyol compounds and one or more of these alkylene oxide adducts that have been polyglycidyl etherified with epihalohydrin.
  • the aliphatic polyol compound include aliphatic diol compounds such as ethylene glycol, propylene glycol, 1,3-propanediol, 2-methylpropanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4
  • the biphenol-type epoxy resins include, for example, biphenol compounds such as biphenol and tetramethylbiphenol, and polyglycidyl ethers of one or more of these alkylene oxide adducts with epihalohydrin.
  • the bisphenol type epoxy resins include, for example, bisphenol compounds such as bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, and biscresol fluorene, and polyglycidyl ethers of one or more of these alkylene oxide adducts with epihalohydrin.
  • the novolac type epoxy resin may be, for example, a novolac resin made of one or more of various phenolic compounds such as phenol, dihydroxybenzene, cresol, xylenol, naphthol, dihydroxynaphthalene, bisphenol, biphenol, etc., which is polyglycidyl etherified with epihalohydrin.
  • Alicyclic epoxy resins include, for example, those obtained by hydrogenating the biphenol compounds or bisphenol compounds, and those obtained by polyglycidyl etherifying one or more of these alkylene oxide adducts with epihalohydrin, as well as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, etc.
  • Examples of the glycidylamine type epoxy resin include N,N-diglycidylaniline, triglycidylaminophenol, tetraglycidylxylenediamine, 4,4'-methylenebis[N,N-diglycidylaniline], etc.
  • heterocyclic epoxy resin examples include 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate.
  • Examples of the glycidyl ester type epoxy resin include diglycidyl ester of phthalic acid, diglycidyl ester of tetrahydrophthalic acid, diglycidyl-p-oxybenzoic acid, and glycidyl ester of dimer acid.
  • extenders for epoxy resins include the various biphenol compounds and their hydrogenated products, the various bisphenol compounds and their hydrogenated products, dibasic acid compounds, and acid group-containing polyester resins.
  • the bisphenol type epoxy resin is preferred because it has excellent impregnation properties into the reinforcing fiber (f) and the strength of the resulting outer layer (B).
  • the epoxy equivalent of the epoxy resin is preferably in the range of 150 to 600 g/equivalent, and more preferably in the range of 200 to 450 g/equivalent.
  • the reaction between epoxy resin and (meth)acrylic acid can be carried out in the presence of any esterification catalyst by heating at a temperature of about 60 to 140°C. If necessary, a reaction solvent or a polymerization inhibitor may be added.
  • the reaction ratio between epoxy resin and (meth)acrylic acid is preferably such that the molar ratio of the functional groups of both [carboxy group/epoxy group] is in the range of 0.6 to 1.1.
  • the hydroxyl value of the resulting (meth)acrylate compound is preferably 50 to 200 mg/KOH.
  • the (meth)acryloyl group equivalent is preferably in the range of 300 to 600 g/equivalent.
  • the polyhydroxy(meth)acrylate compound (r2) may be used alone or in combination of two or more kinds.
  • the ratio of the bisphenol type epoxy resin (meth)acrylate compound to the total mass of the polyhydroxy(meth)acrylate compound (r2) is preferably 50 mass% or more, more preferably 70 mass% or more, and particularly preferably 80 mass% or more.
  • Examples of the monohydroxy(meth)acrylate compound (r3) include hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (poly)oxyalkylene (meth)acrylate compounds having (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains introduced into the molecular structures of these compounds, and lactone-modified (meth)acrylate compounds having (poly)lactone structures introduced into the molecular structures of these compounds. These compounds may be used alone or in combination.
  • the proportion of hydroxyethyl(meth)acrylate to the total mass of the monohydroxy(meth)acrylate compounds (r3) is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • polyhydroxy compound (r4) examples include dihydroxybenzene, dihydroxynaphthalene, the various aliphatic polyols mentioned above, biphenol compounds, bisphenol compounds, their alkylene oxide adducts, and lactone-modified compounds. These may be used alone or in combination. Among these, alkylene oxide adducts of bisphenol compounds are preferred because they provide an excellent balance between the impregnation of the reinforcing fibers (f) and the strength of the resulting outer layer (B). The average number of moles of alkylene oxide added is preferably in the range of 2 to 10 moles.
  • the ratio of the alkylene oxide adduct of the bisphenol compound to the total mass of the polyhydroxy compounds (r4) is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the molar ratio (NCO/OH) of the isocyanate groups contained in the polyisocyanate compound (r1) to the hydroxyl groups contained in the polyhydroxy(meth)acrylate compound (r2) is preferably in the range of 0.3 to 1.2, more preferably in the range of 0.4 to 1.1, and particularly preferably in the range of 0.5 to 1.0, in order to provide excellent ease of handling and moldability of the prepreg.
  • the molar ratio (NCO/OH) of the isocyanate group contained in the polyisocyanate compound (r1) to the sum of the hydroxyl group contained in the monohydroxy(meth)acrylate compound (r3) and the hydroxyl group contained in the polyhydroxy compound (r4) is preferably in the range of 0.7 to 1.3, more preferably in the range of 0.8 to 1.1, and particularly preferably in the range of 0.8 to 1.0, because this provides excellent ease of handling and moldability of the prepreg.
  • the molar ratio (r3/r4) of the monohydroxy(meth)acrylate compound (r3) to the polyhydroxy compound (r4) is preferably in the range of 40/60 to 80/20, and more preferably in the range of 50/50 to 70/30, because this further improves heat resistance and curability.
  • the resin compositions (1) and (2) may contain other polymerizable unsaturated group-containing compounds other than the polyhydroxy(meth)acrylate compound (r2) and the monohydroxy(meth)acrylate compound (r3).
  • Specific examples thereof include, for example, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate, isotridecyl(meth)acrylate, n-stearyl(meth)acrylate, ethylene glycol(meth)acrylate alkyl ether, propylene glycol(meth)acrylate ...
  • Aliphatic mono(meth)acrylate compounds such as ricolin (meth)acrylate alkyl ether; alicyclic mono(meth)acrylate compounds such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl mono(meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentanyl methacrylate; heterocycle-containing mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, and the like.
  • aromatic ring-containing mono(meth)acrylate compounds such as phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzyl benzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a propylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glyco
  • Such compounds include aliphatic poly(meth)acrylate compounds having 4 or more functional groups, such as tetrafunctional (poly)oxyalkylene-modified poly(meth)acrylate compounds having 4 or more functional groups, in which a (poly)oxyalkylene chain, such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain, has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; and lactone-modified poly(meth)acrylate compounds having 4 or more functional groups, in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound.
  • These compounds may be used alone or in combination.
  • bifunctional or higher (meth)acrylate compounds having a molecular weight in the range of 150 to 600 are preferred, as they provide an excellent balance between the impregnation of the reinforcing fibers (f) and the strength of the resulting outer layer (B).
  • the ratio of bifunctional or higher (meth)acrylate compounds having a molecular weight in the range of 150 to 600 to the total mass of other polymerizable unsaturated group-containing compounds is preferably 50 mass% or more, more preferably 80 mass% or more, and particularly preferably 90 mass% or more.
  • the amount of the compounds is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the polyisocyanate compound (r1) and the polyhydroxy(meth)acrylate compound (r2), because this provides an excellent balance between the impregnation of the reinforcing fiber (f) and the strength of the resulting outer layer (B).
  • the amount of the compounds is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the polyisocyanate compound (r1), the monohydroxy(meth)acrylate compound (r3), and the polyhydroxy compound (r4).
  • the resin compositions (1) and (2) may contain a polymerization initiator. Any common polymerization initiator may be used without any particular restrictions, but organic peroxides are particularly preferred. Examples of organic peroxides include diacyl peroxide compounds, peroxyester compounds, hydroperoxide compounds, ketone peroxide compounds, alkyl perester compounds, percarbonate compounds, and peroxyketals. These may be used alone or in combination. Among them, those having a temperature of 60°C or higher for obtaining a 10-hour half-life are preferred because they shorten the molding time.
  • the core layer (a) or the core layer (A) is a polystyrene foam
  • those having a 10-hour half-life temperature of 90°C or lower are preferred, those having a temperature of 80°C or lower are more preferred, and those having a temperature of 70°C or lower are particularly preferred.
  • polymerization initiators examples include 1,6-bis(t-butylperoxycarbonyloxy)hexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, t-butylperoxydiethyl acetate, t-butylperoxyisopropyl carbonate, t-butylperoxy2-ethylhexyl carbonate, t-amylperoxyisopropyl carbonate, and t-amylperoxy2-ethylhexyl.
  • polymerization initiator examples include butyl peroxy isopropyl carbonate, di-tert-butyl peroxy hexahydroterephthalate, t-amyl peroxy trimethyl hexanoate, t-amyl peroxy isononaate, t-hexyl peroxy 2-ethyl hexanoate, n-butyl 4,4-di(t-butylperoxy)valerate, 1,1,3,3-tetramethyl butyl peroxy 2-ethyl hexanoate, t-butyl peroxy 2-ethyl hexanoate, and t-butyl peroxy pivalate.
  • the amount of the polymerization initiator added is preferably in the range of 0.5 to 3% by mass based on the total mass of the polymerizable unsaturated group-containing compound in the resin composition.
  • the resin compositions (1) and (2) may contain other components in addition to the various compounds described above.
  • other components include thermoplastic resins, polymerization inhibitors, curing accelerators, fillers, shrinkage reducing agents, release agents, thickeners, viscosity reducers, pigments, antioxidants, plasticizers, flame retardants, antibacterial agents, UV stabilizers, reinforcing materials, and photocuring agents.
  • thermoplastic resins include, for example, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, urethane resin, polypropylene resin, polyethylene resin, polystyrene resin, acrylic resin, polybutadiene resin, polyisoprene resin, and resins modified by copolymerization or the like. These may be used alone or in combination of two or more types.
  • polymerization inhibitor examples include hydroquinone, trimethylhydroquinone, p-t-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, copper chloride, etc. These may be used alone or in combination of two or more types.
  • curing accelerator examples include metal soaps such as cobalt naphthenate, cobalt octenate, vanadyl octenate, copper naphthenate, and barium naphthenate, and metal chelate compounds such as vanadyl acetylacetate, cobalt acetylacetate, and iron acetylacetonate.
  • metal soaps such as cobalt naphthenate, cobalt octenate, vanadyl octenate, copper naphthenate, and barium naphthenate
  • metal chelate compounds such as vanadyl acetylacetate, cobalt acetylacetate, and iron acetylacetonate.
  • amines examples include N,N-dimethylamino-p-benzaldehyde, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, and diethanolaniline. These may be used alone or in combination of two or more.
  • the fillers are broadly divided into inorganic compounds and organic compounds. Fillers are components added primarily to adjust the physical properties of molded products, such as strength, elastic modulus, impact strength, and fatigue durability.
  • the inorganic compounds include, for example, calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barite, baryta, silica, silica sand, dolomitic limestone, gypsum, aluminum fine powder, hollow balloons, alumina, glass powder, aluminum hydroxide, kansui stone, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder, etc.
  • the organic compounds include natural polysaccharide powders such as cellulose and chitin, and synthetic resin powders.
  • the synthetic resin powders include organic powders composed of hard resins, soft rubbers, elastomers, polymers (copolymers), etc., and particles having a multilayer structure such as a core-shell type.
  • Specific examples of synthetic resin powders include particles composed of butadiene rubber, acrylic rubber, urethane rubber, silicone rubber, etc., polyimide resin powder, fluororesin powder, and phenolic resin powder. These may be used alone or in combination of two or more types.
  • release agent examples include zinc stearate, calcium stearate, paraffin wax, polyethylene wax, carnauba wax, etc. Preferred are paraffin wax, polyethylene wax, carnauba wax, etc. These may be used alone or in combination of two or more.
  • the thickener may be, for example, a metal oxide or hydroxide such as magnesium oxide, magnesium hydroxide, calcium oxide, or calcium hydroxide, or an acrylic resin-based fine particle. These thickeners may be used alone or in combination of two or more kinds.
  • Examples of the flame retardant include phosphorus atom-containing compounds, halogen atom-containing compounds, nitrogen atom-containing compounds, hydrated metal compounds, borates, metal oxides, silicone compounds, etc. These flame retardants can be used alone or in combination of two or more kinds.
  • the method for producing the prepreg is not particularly limited, but examples include a method in which the components of the matrix resin (r) are mixed using a known mixer such as a static mixer, power mixer, planetary mixer, or kneader, and then the matrix resin is impregnated into the reinforcing fibers (f), which are then sandwiched between release films and rolled using a rolling machine.
  • a known mixer such as a static mixer, power mixer, planetary mixer, or kneader
  • the matrix resin is impregnated into the reinforcing fibers (f)
  • it may be heated as appropriate.
  • the sheet after rolling can be left at room temperature to 50°C to cause a urethane reaction between the isocyanate groups and hydroxyl groups in the resin composition, thereby making it possible to produce a prepreg with excellent storage stability and ease of handling.
  • the resin composition may be one in which the urethane reaction has progressed partially during the preparation process.
  • the thickness of the prepreg is preferably 0.02 mm or more, and more preferably 0.05 mm or more, because this is easy to handle and has excellent moldability. It is also preferable that the thickness is 1.0 mm or less, and more preferably 0.5 mm or less.
  • the outer layer (B) can be obtained by hot molding the prepreg.
  • One example of the hot molding method is, for example, a method in which a plurality of prepregs are laminated and placed in a mold preheated to 110°C to 160°C, clamped and molded with a compression molding machine, and cured while maintaining a molding pressure of 0.1 to 10 MPa.
  • a manufacturing method is preferred in which a mold having a shear edge is used, a molding pressure of 1 to 8 MPa is maintained at a mold temperature of 130°C to 160°C, and hot compression molding is performed for 1 to 3 minutes per 1 mm thickness of the molded product.
  • the number of prepregs can be set arbitrarily based on the balance between moldability and the strength of the obtained outer layer (B), but it is preferable that it is in the range of 1 to 20 sheets because it is lightweight.
  • the orientation of the prepregs when stacking the prepregs can be set arbitrarily based on the desired strength, but it is preferable to stack them so that they are quasi-isotropic. For example, it is preferable to stack them in order so that the fiber directions are alternated between 0° and 90°.
  • the thickness of the outer layer (B) is preferably 0.1 mm or more, more preferably 0.4 mm or more, and particularly preferably 0.6 mm or more, in order to balance the strength and lightness of the resulting laminate. It is also preferably 2.0 mm or less, and more preferably 1.5 mm or less.
  • the laminate of the present invention may include the core layer (A) and the outer layer (B), and as described above, the core layer (A) may be multi-layered, or the outer layer (B) may be multi-layered.
  • the laminate of the present invention may also have other layers in addition to these.
  • the other layers may be arranged on both sides of the core layer (A) or only on one side. It is preferable that the other layers are located between the core layer (A) and the outer layer (B).
  • Examples of the other layers include a metal layer, a resin layer, and an adhesive layer.
  • the ratio of the thickness of the core layer (A) and the outer layer (B) to the total thickness of the laminate is preferably 80% or more, and more preferably 85% or more.
  • the method for producing the laminate of the present invention is not particularly limited, and the laminate can be produced by a wide variety of methods depending on the application and desired shape of the laminate. As some specific examples, the following three production methods can be mentioned. These production methods will be described below.
  • Manufacturing method 1 A method for manufacturing a laminate, in which a precursor, in which a core layer (a) made of a foam and an outer layer (b) made of a prepreg containing reinforcing fibers (f) and a matrix resin (r) are laminated, is heated and molded under conditions in which the core layer (a) is compressed.
  • (Manufacturing method 2) A method for manufacturing a laminate, in which the core layer (A) and the outer layer (B) made of the fiber-reinforced plastic are bonded together using an adhesive.
  • (Manufacturing method 3) A method for manufacturing a laminate, in which a precursor, in which the core layer (A) and the outer layer (b) made of a prepreg containing reinforcing fibers (f) and a matrix resin (r) are laminated, is heated and molded.
  • the manufacturing method 1 is a method of heat-molding a precursor obtained by laminating a core layer (a) made of a foam and an outer layer (b) made of a prepreg containing reinforcing fibers (f) and a matrix resin (r) under conditions in which the core layer (a) is compressed.
  • the outer layer (b) is preferably a laminate of a plurality of prepregs, specifically, 1 to 20 prepregs.
  • the lamination direction when laminating the prepregs can be set arbitrarily in consideration of the desired strength, but it is preferable to laminate them so as to be quasi-isotropic. For example, it is preferable to laminate them in order so that the fiber directions are alternated between 0° and 90°.
  • the core layer (a) and the outer layer (b) may be directly laminated, or another layer such as an adhesive layer may be provided between them.
  • the moldable temperature of the prepreg constituting the outer layer (b) is preferably 140°C or less, and more preferably 110°C or less.
  • the molding conditions are not particularly limited, but examples include a method in which molding is performed for several minutes to several tens of minutes at a temperature of 80 to 140°C and a pressure of 0.1 to 6 MPa. If necessary, a release agent may be applied to the mold, and the precursor is preferably filled in the center of the mold. In addition, the thickness of the laminate may be adjusted using a spacer or the like so that it has a predetermined thickness.
  • the manufacturing method 2 is a method of bonding the core layer (A) and the outer layer (B) made of the fiber-reinforced plastic with an adhesive.
  • the core layer (A) and outer layer (B) used in manufacturing method 2 are as described above.
  • the adhesive used in manufacturing method 2 is not particularly limited and is selected according to the application and desired shape of the laminate, and examples include acrylic resin-based, urethane resin-based, rubber-based, polyester resin-based, epoxy resin-based, cyanoacrylate resin-based, silicone resin-based, and modified silicone resin-based adhesives.
  • the adhesive may be in any form, such as one-component liquid, two-component liquid, sheet, or double-sided tape.
  • the manufacturing method 3 is a method of hot-molding a precursor obtained by laminating the core layer (A) and the outer layer (b) made of a prepreg containing reinforcing fibers (f) and a matrix resin (r).
  • the core layer (A) used in manufacturing method 3 is as described above.
  • the outer layer (b) is preferably a laminate of multiple prepregs, specifically, 1 to 20 prepregs.
  • the direction in which the prepregs are laminated can be set arbitrarily taking into account the desired strength, but it is preferable to laminate them so that they are quasi-isotropic. For example, it is preferable to laminate them in order so that the fiber directions are staggered between 0° and 90°.
  • the core layer (A) and the outer layer (b) may be laminated directly, or other layers such as an adhesive layer may be provided between them. Furthermore, when manufacturing a laminate using manufacturing method 3, in order to prevent the foam that forms the core layer (A) from further foaming during the heat forming process, the moldable temperature of the prepreg that forms the outer layer (b) is preferably 140°C or lower, and more preferably 110°C or lower.
  • the molding conditions are not particularly limited, but examples include a method in which molding is performed for several minutes to several tens of minutes at a temperature of 80 to 140°C and a pressure of 0.1 to 6 MPa. If necessary, a release agent may be applied to the mold, and it is preferable to fill the precursor in the center of the mold. In addition, the thickness of the laminate may be adjusted using a spacer or the like so that it has a predetermined thickness.
  • the laminate of the present invention is lightweight yet has excellent flame resistance and strength, making it suitable for use in a variety of applications, including battery cases, aerospace aircraft components, railway vehicle components, housing equipment components, electronic equipment components, medical equipment components, home appliance components, and automotive components.
  • Diphenylmethane diisocyanate (BASFINOAC Polyurethanes, "Lupranate MI") 13 parts by mass, epoxy (meth)acrylate resin (1) obtained above 80 parts by mass, ethylenically unsaturated monomer (butanediol dimethacrylate) 20 parts by mass, and polymerization initiator (Kayaku Akzo Co., Ltd. "Trigonox 122-C80", organic peroxide, 10-hour half-life temperature 87°C) 11.3 parts by mass were mixed to obtain matrix resin (1).
  • glass fiber Nippon Electric Glass Co., Ltd. "ER1620F”, glass fiber basis weight 162 g/m 2
  • matrix resin (1) was impregnated with matrix resin (1) so that the resin mass content was 35%, and a prepreg (1) having a thickness of 0.13 mm was obtained.
  • Production Example 2 Production of prepreg (2) 13 parts by mass of diphenylmethane diisocyanate ("Lupranate MI” manufactured by BASFINOAC Polyurethanes Co., Ltd.), 80 parts by mass of the epoxy (meth)acrylate resin (1) obtained in Production Example 1, 20 parts by mass of an ethylenically unsaturated monomer (butanediol dimethacrylate), and 18.1 parts by mass of a polymerization initiator ("Trigonox 421-70” manufactured by Kayaku Akzo Co., Ltd., organic peroxide, 10-hour half-life temperature 65°C) were mixed to obtain a matrix resin (2).
  • diphenylmethane diisocyanate (“Lupranate MI” manufactured by BASFINOAC Polyurethanes Co., Ltd.)
  • the epoxy (meth)acrylate resin (1) obtained in Production Example 1 20 parts by mass of an ethylenically unsaturated monomer (butanediol dimethacrylate)
  • glass fibers (“ER1620F” manufactured by Nippon Electric Glass Co., Ltd., glass fiber basis weight 162 g/m 2 ) were impregnated with the matrix resin (2) so that the resin mass content was 35%, and a prepreg (2) having a thickness of 0.13 mm was obtained.
  • Prepreg (3) 100 parts by mass of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate ("Millionate MR-200" manufactured by Tosoh Corporation, polymethylene polyphenyl polyisocyanate content of 55 to 65 mass), 59 parts by mass of hydroxyethyl methacrylate, 24 parts by mass of an ethylene oxide adduct of bisphenol A ("Newpol BPE-20" manufactured by Sanyo Chemical Industries, Ltd., hydroxyl group equivalent of 164 g/equivalent), 31 parts by mass of an ethylene oxide adduct of bisphenol A (“Newpol BPE-40” manufactured by Sanyo Chemical Industries, Ltd., hydroxyl group equivalent of 204 g/equivalent), and 2.1 parts by mass of a polymerization initiator ("Trigonox 122-C80" manufactured by Kayaku Akzo Co., Ltd., organic peroxide) were mixed to obtain a matrix resin (2).
  • glass fibers (“ER1620F” manufactured by Nippon Electric Glass Co., Ltd., glass fiber basis weight 162 g/ m2 ) were impregnated with matrix resin (3) so that the resin mass content was 35%, and a prepreg (3) with a thickness of 0.13 mm was obtained.
  • Prepreg (4) 100 parts by mass of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate ("Millionate MR-200" manufactured by Tosoh Corporation, polymethylene polyphenyl polyisocyanate content of 55 to 65% by mass), 59 parts by mass of hydroxyethyl methacrylate, 24 parts by mass of an ethylene oxide adduct of bisphenol A ("Newpol BPE-20" manufactured by Sanyo Chemical Industries, Ltd., hydroxyl group equivalent of 164 g/equivalent), 31 parts by mass of an ethylene oxide adduct of bisphenol A (“Newpol BPE-40” manufactured by Sanyo Chemical Industries, Ltd., hydroxyl group equivalent of 204 g/equivalent), and 2.1 parts by mass of a polymerization initiator ("Trigonox 122-C80" manufactured by Kayaku Akzo Co., Ltd., organic peroxide) were mixed to obtain a matrix resin (3).
  • Examples 1 to 4 and Comparative Example 1 The laminates (1) to (9) and the laminate (1') were produced as follows, and various evaluation tests were carried out. The evaluation results of each laminate are shown in Tables 1 and 2.
  • Example 1 Production of laminate (1)
  • the prepreg (1) obtained in Production Example 1 was cut into sizes of 298 mm x 218 mm and 298 mm x 218 mm, and eight sheets were laminated in order so that the fiber directions of the prepreg were alternated between the 0° direction and the 90° direction. This was filled into the center of a flat plate mold coated with a mold release agent, and compression molded under conditions of a pressure of 4 MPa, an upper mold temperature of 140°C, a lower mold temperature of 135°C, and a molding time of 3 minutes to obtain an outer layer (B1) of 300 mm x 220 mm x 1 mm.
  • the flexural modulus of the outer layer (B1) measured in accordance with JIS K 7017 was 24.6 GPa.
  • a 4 mm thick polystyrene foam plate ("Varishield” manufactured by Ushiomatex Co., Ltd., a foam of styrene beads with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times) was cut to a size of 298 mm x 218 mm, and then filled into the center of a flat plate mold and compression molded under conditions of upper mold temperature 30°C, lower mold temperature 30°C, and molding time 5 minutes to obtain a core layer (A1) of 300 mm x 220 mm x 2 mm.
  • the compression ratio in the thickness direction of the core layer (A1) was 50%, the specific gravity was 0.08 g/ m3 , and the aspect ratio of the foam cells calculated from the compression ratio was 2.
  • a flame-retardant double-sided tape No. 5011N, manufactured by Nitto Denko Corporation, thickness 0.15 mm
  • one sheet of the outer layer (B1) was attached to each side of the core layer (A1) to obtain a laminate (1).
  • Example 2 Production of laminate (2)
  • the thermosetting prepreg (1) obtained in Production Example 1 was cut into sizes of 298 mm x 218 mm and 298 mm x 218 mm, and four sheets were laminated in order so that the fiber directions of the prepreg were alternated between the 0° direction and the 90° direction. This was filled into the center of a flat plate mold coated with a release agent, and compression molded under conditions of a pressure of 4 MPa, an upper mold temperature of 140°C, a lower mold temperature of 135°C, and a molding time of 3 minutes to obtain an outer layer (B2) of 300 mm x 220 mm x 0.5 mm.
  • the flexural modulus of the outer layer (B2) measured in accordance with JIS K 7017 was 24.6 GPa.
  • a 10 mm thick polystyrene foam plate (“Varishield” manufactured by Ushiomatex Co., Ltd., a foam of styrene beads with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times) was cut to a size of 298 mm x 218 mm, and then filled into the center of a flat plate mold and compression molded under conditions of upper mold temperature 30°C, lower mold temperature 30°C, and molding time 5 minutes to obtain a core layer (A2) of 300 mm x 220 mm x 2 mm.
  • the compression ratio in the thickness direction of the core layer (A2) was 80%, the specific gravity was 0.20 g/ m3 , and the aspect ratio of the foam cells calculated from the compression ratio was 5.
  • a flame-retardant double-sided tape No. 5011N, manufactured by Nitto Denko, thickness 0.15 mm
  • one sheet of the outer layer (B2) was attached to each side of the core layer (A2) to obtain a laminate (2).
  • Example 3 Production of laminate (3)
  • the thermosetting prepreg (1) obtained in Production Example 1 was cut into sizes of 298 mm x 218 mm and 298 mm x 218 mm, and three sheets were laminated in order so that the fiber directions of the prepreg were alternated between the 0° direction and the 90° direction.
  • the pieces were filled into the center of a flat plate mold coated with a release agent, and compression molded in a compression molding machine under conditions of a pressure of 4 MPa, an upper mold temperature of 140°C, a lower mold temperature of 135°C, and a molding time of 3 minutes to obtain an outer layer (B3) having a width of 300 mm x 220 mm x 0.35 mm.
  • the flexural modulus of the outer layer (B3) measured in accordance with JIS K 7017 was 24.6 GPa.
  • a 20 mm thick polystyrene foam plate ("Varishield” manufactured by Ushiomatex Co., Ltd., a foam of styrene beads with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times) was cut to a size of 298 mm x 218 mm, filled into the center of a flat plate mold, and compression molded under conditions of upper mold temperature 30°C, lower mold temperature 30°C, and molding time 5 minutes to obtain a core layer (A3) of 300 mm x 220 mm x 2 mm.
  • the compression ratio in the thickness direction of the core layer (A3) was 90%, the specific gravity was 0.40 g/ m3 , and the aspect ratio of the foam cells calculated from the compression ratio was 10.
  • a flame-retardant double-sided tape No. 5011N, manufactured by Nitto Denko, thickness 0.15 mm
  • one sheet of the outer layer (B3) was attached to each side of the core layer (A3) to obtain a laminate (3).
  • Example 4 Production of Laminate (4)
  • a 20 mm thick polystyrene foam plate (“Varishield” manufactured by Ushiomatex Co., Ltd., a styrene bead foam with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times) was cut into a size of 298 mm x 218 mm, and then filled into the center of a flat plate mold and compression molded under the conditions of upper mold temperature 30°C, lower mold temperature 30°C, and molding time 5 minutes to obtain a core layer (A4) of 300 mm x 220 mm x 1.5 mm.
  • Varishield manufactured by Ushiomatex Co., Ltd., a styrene bead foam with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times
  • the compression ratio of the core layer (A4) in the thickness direction was 92.5%, the specific gravity was 0.53 g/ m3 , and the aspect ratio of the foam cell calculated from the compression ratio was 13.3.
  • a flame-retardant double-sided tape (Nitto Denko Corporation's "No. 5011N", thickness 0.15 mm)
  • one outer layer (B2) obtained in Example 2 was attached to each side of the core layer (A4) to obtain a laminate (4).
  • Example 5 Production of Laminate (5)
  • the prepreg (2) obtained in Production Example 2 was cut into sizes of 298 mm x 218 mm and 298 mm x 218 mm, and eight sheets were laminated in order so that the fiber directions of the prepregs were alternated between the 0° direction and the 90° direction.
  • Example 6 Production of Laminate (6)
  • a 20 mm thick polystyrene foam plate (“Varishield” manufactured by Ushiomatex Co., Ltd., a styrene bead foam with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times) was cut into a size of 298 mm x 218 mm, and then packed into the center of a flat plate mold and compression molded under the conditions of an upper mold temperature of 30°C, a lower mold temperature of 30°C, and a molding time of 5 minutes to obtain a core layer (A4) of 300 mm x 220 mm x 4 mm.
  • Varishield manufactured by Ushiomatex Co., Ltd., a styrene bead foam with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times
  • the prepreg (2) obtained in Production Example 2 was cut to sizes of 298 mm x 218 mm and 298 mm x 218 mm, and eight prepregs were laminated in order so that the fiber directions of the prepregs were alternately in the 0° direction and the 90° direction, and then the prepregs were loaded into the center of a flat plate mold coated with a release agent, a 4 mm spacer was placed, and compression molded under conditions of a pressure of 4 MPa, an upper mold temperature of 105°C, a lower mold temperature of 100°C, and a molding time of 5 minutes, to obtain a laminate (6) of 300 mm x 220 mm x 4 mm.
  • the flexural modulus of the outer layer measured in accordance with JIS K 7017 was 24.6 GPa.
  • Example 7 Production of laminate (7)
  • the prepreg (3) obtained in Production Example 3 was cut into sizes of 298 mm x 218 mm and 298 mm x 218 mm, and eight sheets were laminated in order so that the fiber directions of the prepreg were alternated between the 0° direction and the 90° direction. This was filled into the center of a flat plate mold coated with a mold release agent, and compression molded under conditions of a pressure of 4 MPa, an upper mold temperature of 140°C, a lower mold temperature of 135°C, and a molding time of 3 minutes to obtain an outer layer (B4) of 300 mm x 220 mm x 1 mm.
  • the flexural modulus of the outer layer (B4) measured in accordance with JIS K 7017 was 23.2 GPa.
  • a 20 mm thick polystyrene foam plate (“Varishield” manufactured by Ushiomatex Co., Ltd., a foam of styrene beads with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times) was cut to a size of 298 mm x 218 mm, filled into the center of a flat plate mold, and compression molded under conditions of upper mold temperature 30°C, lower mold temperature 30°C, and molding time 5 minutes to obtain a core layer (A3) of 300 mm x 220 mm x 2 mm.
  • the compression ratio in the thickness direction of the core layer (A3) was 90%, the specific gravity was 0.40 g/ m3 , and the aspect ratio of the foam cells calculated from the compression ratio was 10.
  • a flame-retardant double-sided tape No. 5011N, manufactured by Nitto Denko Corporation
  • one sheet of the outer layer (B4) was attached to each side of the core layer (A3) to obtain a laminate (7).
  • Example 8 Production of laminate (8)
  • the prepreg (4) obtained in Production Example 4 was cut into sizes of 298 mm x 218 mm and 298 mm x 218 mm, and eight sheets were laminated in order so that the fiber directions of the prepreg were alternated between the 0° direction and the 90° direction. This was filled into the center of a flat plate mold coated with a mold release agent, and compression molded under conditions of a pressure of 4 MPa, an upper mold temperature of 140°C, a lower mold temperature of 135°C, and a molding time of 3 minutes to obtain an outer layer (B5) of 300 mm x 220 mm x 1 mm.
  • the flexural modulus of the outer layer (B5) measured in accordance with JIS K 7017 was 61.5 GPa.
  • a 20 mm thick polystyrene foam plate ("Varishield” manufactured by Ushiomatex Co., Ltd., a foam of styrene beads with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times) was cut to a size of 298 mm x 218 mm, filled into the center of a flat plate mold, and compression molded under conditions of upper mold temperature 30°C, lower mold temperature 30°C, and molding time 5 minutes to obtain a core layer (A3) of 300 mm x 220 mm x 2 mm.
  • the compression ratio in the thickness direction of the core layer (A3) was 90%, the specific gravity was 0.40 g/ m3 , and the aspect ratio of the foam cells calculated from the compression ratio was 10.
  • a flame-retardant double-sided tape No. 5011N, manufactured by Nitto Denko Corporation
  • one sheet of the outer layer (B5) was attached to each side of the core layer (A3) to obtain a laminate (8).
  • Example 9 Production of laminate (9)
  • the prepreg (5) obtained in Production Example 5 was cut to a size of 290 mm x 212 mm.
  • One of these sheets was placed in the center of a flat plate mold coated with a release agent, and compression molded under conditions of a pressure of 10 MPa, an upper mold temperature of 145°C, a lower mold temperature of 145°C, and a molding time of 3 minutes to obtain an outer layer (B5) of 300 mm x 220 mm x 1.5 mm.
  • the flexural modulus of the outer layer (B5) measured in accordance with JIS K 7017 was 29 GPa.
  • a 20 mm thick polystyrene foam plate (“Varishield” manufactured by Ushiomatex Co., Ltd., a foam of styrene beads with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times) was cut to a size of 298 mm x 218 mm, and then filled into the center of a flat plate mold and compression molded under conditions of upper mold temperature 30°C, lower mold temperature 30°C, and molding time 5 minutes to obtain a core layer (A3) of 300 mm x 220 mm x 2 mm.
  • Varishield manufactured by Ushiomatex Co., Ltd., a foam of styrene beads with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times
  • the compression ratio in the thickness direction of the core layer (A3) was 80%, the specific gravity was 0.20 g/ m3 , and the aspect ratio of the foam cells calculated from the compression ratio was 5.
  • a flame-retardant double-sided tape No. 5011N, manufactured by Nitto Denko Corporation
  • one sheet of the outer layer (B5) was attached to each side of the core layer (A3) to obtain a laminate (9).
  • Comparative Example 1 Production of Laminate (1') A polystyrene foam plate having a thickness of 2 mm ("Varishield” manufactured by Ushiomatex Co., Ltd., a foam of styrene beads with a flame retardant coating on the surface, density 0.04 g/ cm3 , expansion ratio 60 times) was cut into a size of 300 mm x 220 mm to form a core layer (A1').
  • the outer layers (B1) obtained in Example 1 were attached to both sides of the core layer (A1') one by one using a flame-retardant double-sided tape (No. 5011N, manufactured by Nitto Denko, thickness 0.15 mm) to obtain a laminate (1').
  • the total thickness of the core layer (A) and the outer layer (B) (two layers) was evaluated as the thickness of the laminate. In this evaluation, the thickness of the double-sided tape used in the manufacturing process of the laminate was not included in the thickness of the laminate.
  • the bending stiffness (D) was calculated as an index showing the strength of the laminate and evaluated.
  • the bending stiffness (D) was calculated from the following formula.
  • D ((E1 x t1) x (E2 x t2) x (T + tc) 2 ) / 4 ⁇ (E1 x t1 + E2 x t2)
  • E is the flexural modulus of the outer layer (B) [kN/ mm2 ] (upper layer E1, lower layer E2)
  • t is the thickness [mm] of the outer layer (B) (upper layer t1, lower layer t2)
  • tc is the thickness [mm] of the core layer (A)
  • T is the thickness [mm] of the laminate.
  • ⁇ is calculated as 1-(Poisson's ratio) 2 , with 0.99 used as the coefficient for anisotropic materials.

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Abstract

L'invention fournit un matériau de moulage qui malgré sa légèreté et la finesse de sa paroi, présente d'excellentes caractéristiques en termes de propriétés ignifuges et de résistance, et qui peut être mis en œuvre de manière adéquate dans une application pour article moulé telle qu'un boîtier de batterie, ou similaire. Plus précisément, l'invention concerne un stratifié qui est caractéristique en ce qu'il contient une couche centrale (A) dans laquelle une mousse est comprimée dans une direction épaisseur, et une couche externe (B) constituée d'un plastique renforcé par des fibres. Le stratifié de l'invention présente d'excellentes caractéristiques en termes de propriétés ignifuges et de résistance malgré sa légèreté et la finesse de sa paroi, et se révèle avantageux en tant que matériau de moulage pouvant être mis en œuvre de manière adéquate dans diverses applications pour article moulé dont un boîtier de batterie.
PCT/JP2023/022187 2022-10-04 2023-06-15 Stratifié ainsi que procédé de fabrication de celui-ci, et boîtier de batterie WO2024075339A1 (fr)

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JP2014208418A (ja) * 2013-03-29 2014-11-06 積水化成品工業株式会社 繊維強化複合体及びその製造方法
JP2015085678A (ja) * 2013-09-27 2015-05-07 積水化成品工業株式会社 繊維強化複合体、輸送機器構成用部材及び繊維強化複合体の製造方法
JP2015523254A (ja) * 2012-07-24 2015-08-13 エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ Ｐｍｉ発泡材料のための新規の成形法、またはこの方法により製造された複合構造部材
JP2018144462A (ja) * 2017-03-09 2018-09-20 旭化成株式会社 繊維複合体及びその製造方法
WO2021131564A1 (fr) * 2019-12-25 2021-07-01 Dic株式会社 Préimprégné et article moulé
WO2022009671A1 (fr) * 2020-07-06 2022-01-13 株式会社イノアックコーポレーション Corps moulé en résine renforcée par des fibres et son procédé de fabrication, préimprégné pour moulage en résine renforcée par des fibres, corps moulé renforcé par des fibres et procédé de fabrication de corps moulé renforcé par des fibres, et feuille de résine, composite sandwich renforcé par des fibres, et procédé de fabrication de corps moulé renforcé par des fibres

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015523254A (ja) * 2012-07-24 2015-08-13 エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ Ｐｍｉ発泡材料のための新規の成形法、またはこの方法により製造された複合構造部材
JP2014208418A (ja) * 2013-03-29 2014-11-06 積水化成品工業株式会社 繊維強化複合体及びその製造方法
JP2015085678A (ja) * 2013-09-27 2015-05-07 積水化成品工業株式会社 繊維強化複合体、輸送機器構成用部材及び繊維強化複合体の製造方法
JP2018144462A (ja) * 2017-03-09 2018-09-20 旭化成株式会社 繊維複合体及びその製造方法
WO2021131564A1 (fr) * 2019-12-25 2021-07-01 Dic株式会社 Préimprégné et article moulé
WO2022009671A1 (fr) * 2020-07-06 2022-01-13 株式会社イノアックコーポレーション Corps moulé en résine renforcée par des fibres et son procédé de fabrication, préimprégné pour moulage en résine renforcée par des fibres, corps moulé renforcé par des fibres et procédé de fabrication de corps moulé renforcé par des fibres, et feuille de résine, composite sandwich renforcé par des fibres, et procédé de fabrication de corps moulé renforcé par des fibres

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