WO2021100340A1 - Stratifié composite et corps assemblé - Google Patents

Stratifié composite et corps assemblé Download PDF

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Publication number
WO2021100340A1
WO2021100340A1 PCT/JP2020/037803 JP2020037803W WO2021100340A1 WO 2021100340 A1 WO2021100340 A1 WO 2021100340A1 JP 2020037803 W JP2020037803 W JP 2020037803W WO 2021100340 A1 WO2021100340 A1 WO 2021100340A1
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Prior art keywords
group
resin
treatment
layer
polyphenylene ether
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PCT/JP2020/037803
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English (en)
Japanese (ja)
Inventor
大谷　和男
臣二 沼尾
高橋　信行
良太 新林
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昭和電工株式会社
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Priority to JP2020559567A priority Critical patent/JP6923762B1/ja
Publication of WO2021100340A1 publication Critical patent/WO2021100340A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/04—Dielectric heating, e.g. high-frequency welding, i.e. radio frequency welding of plastic materials having dielectric properties, e.g. PVC
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/06—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using friction, e.g. spin welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/08—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using ultrasonic vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • B29C65/20—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools with direct contact, e.g. using "mirror"
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • B29C65/24—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools characterised by the means for heating the tool
    • B29C65/30—Electrical means
    • B29C65/32—Induction
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins

Definitions

  • the present invention provides a composite laminate capable of bonding at least one material selected from the group consisting of fiber reinforced plastics, glass and ceramics with modified polyphenylene ether with high strength, a method for producing the same, and the material and modified polyphenylene ether.
  • the present invention relates to a joined body formed by joining and a method for manufacturing the same.
  • a multi-material structure in which different materials (hereinafter, different materials) are arranged in the right place is indispensable.
  • the multi-material structure is formed by joining dissimilar materials, and various joining techniques such as melt welding and bonding are being studied as the joining means.
  • the entire surface is vitrified, and a technique for joining glass and a highly transparent resin such as polycarbonate by insert molding or the like is required.
  • Patent Document 1 As a method for joining glass and resin, the engineering plastic is melt-bonded to the glass by applying an adhesive force improving agent to the glass to the pellet-shaped engineering plastic and then heating and melting the engineering plastic in contact with the glass.
  • Patent Document 1 In automobiles, there are scenes where FRP (fiber reinforced plastic) and resin are joined, and a technique for firmly joining FRP and resin is required.
  • insulators such as insulating containers made of ceramic as an insert material and molded with resin are often used, and a technique for firmly joining ceramic and resin is required.
  • Non-Patent Document 1 a technique for preventing the occurrence of cracks at the internal interface of the resin mold structure by applying a silane coupling agent between the ceramic and the resin to perform interfacial treatment has been developed. It is disclosed (Non-Patent Document 1).
  • Non-Patent Document 1 paying attention to the above points, the adhesive strength of the internal interface of the resin mold structure is improved by the interface treatment with a silane coupling agent.
  • Patent Document 1 In the prior art, there is a problem that sufficient bonding strength cannot be realized between glass and resin in applications such as automobile parts and OA equipment. Further, in the technique of Patent Document 1, it is necessary to reduce the upper limit of the injection pressure to about 60 MPa at the maximum as a measure against glass breakage during insert molding, and the problem that the injection pressure cannot be sufficiently increased and the demand for improvement of durability are met. There is a problem that it is difficult to respond. Further, the technique of Non-Patent Document 1 cannot solve the problem that stress is concentrated on the resin end of the interface due to the difference in heat shrinkage between the materials, and it is difficult to further improve the joint strength and durability.
  • the present invention has been made in view of such technical background, and is used for bonding modified polyphenylene ether with at least one material selected from the group consisting of fiber reinforced plastics, glass and ceramics with high strength.
  • An object of the present invention is to provide a suitable composite laminate and related techniques thereof.
  • the related technology means a method for producing the composite laminate, a bonded body formed by bonding the material and a modified polyphenylene ether, and a method for producing the same.
  • joining means connecting objects to each other, and adhesion and welding are subordinate concepts thereof.
  • Adhesion means that two adherends (those to be bonded) are put into a bonded state via an organic material (thermosetting resin, thermoplastic resin, etc.) such as tape or adhesive.
  • welding means that the surface of a thermoplastic resin or the like, which is an adherend, is melted by heat and entangled by molecular diffusion and crystallized by contact pressurization and cooling to form a bonded state.
  • Composite lamination having a material layer composed of at least one selected from the group consisting of fiber reinforced plastic, glass and ceramic, and a resin coating layer composed of one or a plurality of resin layers laminated on the material layer.
  • at least one layer of the resin layer is a re-modified-modified polyphenylene ether layer formed of a resin composition containing a re-modified-modified polyphenylene ether, and the re-modified-modified polyphenylene ether layer is a body.
  • a composite which is at least one selected from a layer containing a mixture 1 which is a mixture of a modified polyphenylene ether and a thermoplastic epoxy resin, and a layer containing a mixture 2 which is a mixture of a modified polyphenylene ether and a (meth) acrylic resin.
  • Laminated body [2] The composite laminate according to [1], wherein the mixture 1 is formed by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in a solution containing a modified polyphenylene ether. [3] The composite laminate according to [1], wherein the mixture 1 is a mixture of a modified polyphenylene ether and a thermoplastic epoxy resin.
  • thermosetting resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin and unsaturated polyester resin.
  • a functional group-containing layer laminated in contact with the material layer and the resin coating layer is provided between the material layer and the resin coating layer, and the functional group-containing layer is described in (1) to (1) to the following.
  • a functional group derived from a silane coupling agent A functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound (3)
  • a mercapto group derived from a silane coupling agent has an epoxy compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and an epoxy group.
  • a thiol compound is reacted with a (meth) acryloyl group derived from a silane coupling agent.
  • An epoxy group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound.
  • Functional group (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound [9]
  • the surface of the material layer is subjected to at least one pretreatment selected from the group consisting of degreasing treatment, UV ozone treatment, blast treatment, polishing treatment, plasma treatment and corona discharge treatment. [1] ] To [8].
  • the composite laminate according to any one of.
  • Treatment to add a thiol compound after treatment (5') After treatment with a silane coupling agent having an epoxy group, it is selected from the group consisting of compounds having amino groups and (meth) acryloyl groups, amino compounds, and thiol compounds. Treatment to add at least one (6') Treatment with isocyanate compound (7') Treatment with thiol compound [11] Before forming the functional group-containing layer, at least one pretreatment selected from the group consisting of degreasing treatment, UV ozone treatment, blast treatment, polishing treatment, plasma treatment and corona discharge treatment is performed on the material layer. The method for producing a composite laminate according to [10].
  • the present invention provides a composite laminate suitable for high-strength bonding of at least one material selected from the group consisting of fiber reinforced plastics, glass and ceramics and a modified polyphenylene ether, and related techniques thereof. be able to.
  • (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
  • (meth) acrylic means acrylic and / or methacrylic
  • (meth) acrylate means acrylate and / or methacrylate.
  • the composite laminate 1 of the present embodiment is laminated on the material layer 2 composed of at least one selected from the group consisting of fiber reinforced plastic (FRP), glass, and ceramic. It is a composite laminate having a resin coating layer 3 composed of one or a plurality of resin layers. At least one layer of the resin coating layer 3 is a re-denatured-modified polyphenylene ether layer 31 formed from a resin composition containing a re-modified-modified polyphenylene ether.
  • FRP fiber reinforced plastic
  • the form of the material layer 2 is not particularly limited, and may be in the form of a lump or a film.
  • the fiber reinforced plastic (FRP), glass, and ceramic constituting the material layer 2 are not particularly limited.
  • FRP fiber reinforced plastic
  • a glass fiber reinforced plastic in which various fibers are compounded with a heat-curable resin such as urethane resin, epoxy resin, vinyl ester resin, unsaturated polyester, polyamide resin, and phenol resin to improve strength.
  • GFRP carbon fiber reinforced plastic
  • BFRP boron fiber reinforced plastic
  • AFRP aramid fiber reinforced plastic
  • the glass examples include soda-lime glass, lead glass, borosilicate glass, quartz glass, and the like.
  • the ceramic include oxide-based ceramics such as alumina, zirconia and barium titanate, hydroxide-based ceramics such as hydroxyapatite, carbide-based ceramics such as silicon carbide, and nitride-based ceramics such as silicon nitride.
  • the thickness of the glass in the material layer 2 is preferably 0.3 mm or more, more preferably 0.5 mm or more, from the viewpoint of strength.
  • the upper limit of the thickness of the glass is not particularly limited, but is preferably 30 mm or less, more preferably 10 mm or less.
  • the thickness of the FRP and the ceramic in the material layer 2 is preferably 1.0 mm or more, more preferably 2.0 mm or more, respectively, from the viewpoint of strength.
  • the upper limit of the thickness of the FRP and the ceramic is not particularly limited, but is preferably 20 mm or less, more preferably 15 mm or less.
  • the surface of the material layer 2 Before laminating the resin coating layer 3 on the material layer 2, it is preferable to pretreat the surface of the material layer 2 for the purpose of removing contaminants on the surface and / or an anchor effect.
  • fine irregularities 21 can be formed on the surface of the material layer 2 to roughen the surface.
  • the adhesiveness between the surface of the material layer 2 and the resin coating layer 3 can be improved.
  • Examples of the pretreatment include degreasing treatment, UV ozone treatment, blast treatment, polishing treatment, plasma treatment, corona discharge treatment, laser treatment, etching treatment, frame treatment and the like.
  • a pretreatment for cleaning the surface of the material layer 2 or a pretreatment for making the surface uneven is preferable, and specifically, a degreasing treatment, a UV ozone treatment, a blast treatment, a polishing treatment, a plasma treatment and a corona discharge treatment. At least one selected from the group consisting of is preferable.
  • the pretreatment may be performed with only one type or two or more types. As a specific method of these pretreatments, a known method can be used.
  • hydroxyl groups derived from resin or reinforcing material are present on the surface of FRP, and it is considered that hydroxyl groups are originally present on the surface of glass or ceramic. However, new hydroxyl groups are generated by the above pretreatment, and the material layer 2 The number of hydroxyl groups on the surface can be increased.
  • the degreasing treatment is a method of removing stains such as oils and fats on the surface of the material layer by dissolving them with an organic solvent such as acetone or toluene.
  • the UV and ozone treatment with a force of ozone (O 3) generated energy and thereby having a short wavelength ultraviolet ray emitted from a low-pressure mercury lamp, a process for modifying or cleaning the surface.
  • O 3 ozone
  • a cleaning surface modifier using a low-pressure mercury lamp is called a "UV ozone cleaner", a “UV cleaning apparatus”, an “ultraviolet surface modifier” or the like.
  • blasting treatment examples include wet blasting treatment, shot blasting treatment, sandblasting treatment, and the like. Above all, the wet blast treatment is preferable because a finer surface can be obtained as compared with the drive last treatment.
  • polishing treatment examples include buffing using a polishing cloth, roll polishing using polishing paper (sandpaper), electrolytic polishing, and the like.
  • the plasma treatment is to create a plasma beam with a high-voltage power supply and a rod and hit it against the surface of the material to excite molecules to make it in a functional state.
  • Examples thereof include an atmospheric pressure plasma treatment method capable of imparting hydroxyl groups and polar groups to the surface of the material. Be done.
  • the corona discharge treatment includes a method applied to surface modification of a polymer film, and starts from a radical generated by cutting a polymer main chain or a side chain of a polymer surface layer by electrons emitted from an electrode. This is a method of generating a hydroxyl group or a polar group on the surface.
  • the laser treatment is a technique for improving surface characteristics by rapidly heating and cooling only the surface layer by laser irradiation, and is an effective method for roughening the surface.
  • Known laser processing techniques can be used.
  • the etching treatment includes, for example, a chemical etching treatment such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and a salt iron method, and an electrochemical etching treatment such as an electrolytic etching method.
  • a chemical etching treatment such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and a salt iron method
  • an electrochemical etching treatment such as an electrolytic etching method.
  • the frame treatment is a method of converting oxygen in the air into plasma by burning a mixed gas of combustion gas and air, and applying oxygen plasma to the object to be treated to make the surface hydrophilic.
  • Known frame processing techniques can be used.
  • the resin coating layer is laminated on the surface of the material layer.
  • the resin coating layer may be laminated on the surface of the material layer that has not been subjected to the pretreatment, or may be laminated on the surface of the material layer that has been subjected to the pretreatment. Alternatively, it may be laminated on the surface of the functional group-containing layer described later.
  • a re-denatured-modified polyphenylene ether layer 31 formed from a resin composition containing a re-modified-modified polyphenylene ether.
  • a re-modified-modified polyphenylene ether means a mixture of a modified polyphenylene ether and a thermoplastic epoxy resin described later, and / or a mixture of a modified polyphenylene ether and a (meth) acrylic resin.
  • the composite laminate of the present embodiment can exhibit excellent adhesiveness to the modified polyphenylene ether.
  • the resin coating layer is composed of a plurality of layers including the re-modified-modified polyphenylene ether layer 31 and a layer other than the re-modified-modified polyphenylene ether layer, and the layer other than the re-modified-modified polyphenylene ether layer is a thermoplastic epoxy. It may be at least one selected from the thermoplastic epoxy resin layer 32 formed of the resin composition containing the resin and the thermosetting resin layer 33 formed of the resin composition containing the thermosetting resin.
  • the resin coating layer is composed of a plurality of layers, it is preferable that the essential re-denatured-modified polyphenylene ether layer 31 is laminated so as to be the outermost surface on the opposite side of the material layer.
  • the re-modified-modified polyphenylene ether layer 31 is at least one selected from a layer containing a mixture 1 of a modified polyphenylene ether and a thermoplastic epoxy resin and a layer containing a mixture 2 of a modified polyphenylene ether and a (meth) acrylic resin. It is composed.
  • the re-modified-modified polyphenylene ether layer 31 preferably contains 50 to 95% by mass of the modified polyphenylene ether, and more preferably 70 to 90% by mass.
  • modified polyphenylene ether is a polymer alloy of polyphenylene ether (PPE), which is a polymer of 2,6-dimethylphenylene oxide, and polystyrene (PS), polyamide (PA), polyphenylene sulfide (PPS), polypropylene (PP), etc. is there.
  • PPE polyphenylene ether
  • PS polystyrene
  • PA polyamide
  • PPS polyphenylene sulfide
  • PP polypropylene
  • SABIC NORYL series PPE / PS: 731, 7310, 731F, 7310F, Asahi Kasei Chemicals Co., Ltd.
  • PPE / PS Zylon series
  • PP / PPE PP / PPE
  • PA / PPE PA / PPE
  • PPS / PPE PPA / PPE
  • Epiace series manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • Remalloy series PPE / PS, PPE / PA
  • a polymer alloy of PPE and PS is preferable.
  • Mixture 1 is a mixture of the modified polyphenylene ether and a thermoplastic epoxy resin.
  • the thermoplastic epoxy resin that can be used in the mixture 1 is a resin that is also called a field-polymerized phenoxy resin, a field-curable phenoxy resin, a field-curable epoxy resin, or the like, and a bifunctional epoxy resin and a bifunctional phenol compound are present as catalysts.
  • a thermoplastic structure that is, a linear polymer structure is formed.
  • Thermoplastic epoxy resins have thermoplasticity, unlike thermosetting resins that form a three-dimensional network with a crosslinked structure.
  • bifunctional epoxy resin examples include bisphenol type epoxy resin and biphenyl type epoxy resin. Of these, one type may be used alone, or two or more types may be used in combination. Specifically, “jER (registered trademark) 828", “jER (registered trademark) 834", “jER (registered trademark) 1001", “jER (registered trademark) 1004", and the same, manufactured by Mitsubishi Chemical Corporation. Examples thereof include “jER (registered trademark) 1007" and "jER (registered trademark) YX-4000".
  • bifunctional phenol compound examples include bisphenol and biphenol. Of these, one type may be used alone, or two or more types may be used in combination. Examples of these combinations include bisphenol A type epoxy resin and bisphenol A, bisphenol A type epoxy resin and bisphenol F, biphenyl type epoxy resin and 4,4'-biphenol and the like. Further, for example, a combination of "WPE190" and "EX-991L” manufactured by Nagase ChemteX Corporation can be mentioned.
  • Mixture 1 can be obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of a catalyst in a solution containing a modified polyphenylene ether.
  • the modified polyphenylene ether may be mixed after the bifunctional epoxy resin and the bifunctional phenol compound are subjected to a double addition reaction in the presence of a catalyst in the solution.
  • tertiary amines such as triethylamine and 2,4,6-tris (dimethylaminomethyl) phenol
  • phosphorus compounds such as triphenylphosphine are preferably used. Used.
  • the total amount of the bifunctional epoxy resin and the bifunctional phenol compound used in producing the mixture 1 is preferably 5 to 100 parts by mass and 5 to 60 parts by mass when the modified polyphenylene ether is 100 parts by mass. It is more preferably parts, and even more preferably 20 to 40 parts by mass.
  • Mixture 2 is a mixture of modified polyphenylene ether and (meth) acrylic resin.
  • the (meth) acrylic resin used in the mixture 2 is a resin containing 25% by mass or more of units derived from the (meth) acrylate monomer.
  • a monomer other than the (meth) acrylate monomer may be copolymerized. Examples of the other monomer include styrene, (meth) acrylic acid, (meth) acrylamide, and the like, and styrene and methacrylic acid are preferable. Further, some polyfunctional monomers may be copolymerized in order to increase the strength.
  • the modified polyphenylene ether used for the mixture 2 can be the same as that used for producing the mixture 1.
  • ((Meta) acrylate monomer) As the (meth) acrylate monomer, a known monofunctional (meth) acrylic acid ester is used. Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, 3-chloro-2-hydroxyprop
  • Mixture 2 can be obtained by radical polymerization of a (meth) acrylate monomer in a solution containing a modified polyphenylene ether.
  • the mixture 2 can also be obtained by mixing the modified polyphenylene ether and the (meth) acrylic resin by a conventional method.
  • the total amount of the (meth) acrylic resin used in producing the mixture 2 is preferably 5 to 100 parts by mass and 5 to 60 parts by mass when the modified polyphenylene ether is 100 parts by mass. Is more preferable, and 20 to 40 parts by mass is further preferable.
  • the resin coating layer 3 is composed of a plurality of resin layers of the remodified-modified polyphenylene ether layer and other layers, and at least one of the resin layers other than the remodified-modified polyphenylene ether layer is heated. It can be composed of a thermoplastic epoxy resin layer 32 formed of a resin composition containing a plastic epoxy resin.
  • the resin composition containing the thermoplastic epoxy resin preferably contains 40% by mass or more of the thermoplastic epoxy resin, and more preferably 70% by mass or more.
  • thermoplastic epoxy resin Similar to the thermoplastic epoxy resin used for producing the mixture 1, the thermoplastic epoxy resin has a thermoplastic structure, that is, a bifunctional epoxy resin and a bifunctional phenol compound undergoing a crosslink reaction in the presence of a catalyst. , A resin that forms a linear polymer structure, and has thermoplasticity, unlike thermosetting resins that form a three-dimensional network with a crosslinked structure. Due to these characteristics, the thermoplastic epoxy resin has excellent adhesiveness to the material layer due to in-situ polymerization, and also has excellent adhesiveness to the remodified-modified polyphenylene ether layer 31. The epoxy resin layer 32 can be formed.
  • thermoplastic epoxy resin layer 32 in the layer below the re-modified-modified polyphenylene ether layer 31 (on the material layer 2 side).
  • the thermoplastic epoxy resin layer 32 can be formed by subjecting a composition containing a monomer of the thermoplastic epoxy resin to a heavy addition reaction. The heavy addition reaction is preferably carried out on the surface of the functional group-containing layer 4 described later.
  • the resin coating layer 3 including the thermoplastic epoxy resin layer 32 formed in such an embodiment is excellent in adhesiveness to the material layer 2 and also excellent in adhesiveness to the object to be bonded, which will be described later.
  • the coating method for forming the thermoplastic epoxy resin layer 32 with the composition containing the monomer of the thermoplastic epoxy resin is not particularly limited, and examples thereof include a spray coating method and a dipping method.
  • the composition containing the monomer of the thermoplastic epoxy resin a solvent and, if necessary, a colorant and the like are added in order to sufficiently proceed the polyaddition reaction of the thermoplastic epoxy resin and form a desired resin coating layer. It may contain an agent.
  • the monomer of the thermoplastic epoxy resin is the main component among the components other than the solvent of the composition.
  • the main component means that the content of the thermoplastic epoxy resin is 50 to 100% by mass. The content is preferably 60% by mass or more, more preferably 80% by mass or more.
  • the monomer for obtaining the thermoplastic epoxy resin is preferably a combination of a bifunctional epoxy resin and a bifunctional phenolic compound.
  • the heavy addition reaction is preferably carried out by heating at 120 to 200 ° C. for 5 to 90 minutes, although it depends on the type of reaction compound and the like.
  • the thermoplastic epoxy resin layer 32 can be formed by coating the resin composition, volatilizing a solvent as appropriate, and then heating to carry out a double addition reaction.
  • the resin coating layer 3 is composed of a plurality of resin layers of the re-modified-modified polyphenylene ether layer and other layers, and at least one of the resin layers other than the re-modified-modified polyphenylene ether layer is heated. It can also be composed of a thermosetting resin layer 33 formed of a cured product of a resin composition containing a curable resin.
  • thermosetting resin In the resin composition containing the thermosetting resin, a solvent and, if necessary, a colorant and the like are added in order to sufficiently proceed the curing reaction of the thermosetting resin and form a desired resin coating layer. It may contain an agent.
  • the thermosetting resin is the main component among the components other than the solvent of the resin composition.
  • the main component means that the content of the thermosetting resin is 40 to 100% by mass.
  • the content is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.
  • thermosetting resin examples include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin.
  • thermosetting resin layer 33 may be formed by one of these resins alone, or may be formed by mixing two or more of them.
  • the thermosetting resin layer 33 may be composed of a plurality of layers, and each layer may be formed of a resin composition containing a different type of thermosetting resin.
  • the coating method for forming the thermosetting resin layer 33 with the composition containing the monomer of the thermosetting resin is not particularly limited, and examples thereof include a spray coating method and a dipping method.
  • the thermosetting resin referred to in the present embodiment broadly means a resin that is cross-linked and cured, and is not limited to the heat-curing type, but also includes a room temperature curing type and a photocuring type.
  • the normal temperature refers to 5 to 35 ° C, preferably 15 to 25 ° C.
  • the photocurable type can be cured in a short time by irradiating with visible light or ultraviolet rays.
  • the photo-curing type may be used in combination with a heat-curing type and / or a room temperature curing type.
  • Examples of the photocurable type include vinyl ester resins such as "Lipoxy (registered trademark) LC-760" and "Lipoxy (registered trademark) LC-720" manufactured by Showa Denko KK.
  • the urethane resin is usually a resin obtained by reacting an isocyanato group of an isocyanate compound with a hydroxyl group of a polyol compound, and is defined in ASTM D16 as "a coating material containing a polyisocyanate having a vehicle non-volatile component of 10% by mass or more".
  • the urethane resin corresponding to the above is preferable.
  • the urethane resin may be a one-component type or a two-component type.
  • the one-component urethane resin examples include an oil-modified type (which cures by oxidative polymerization of unsaturated fatty acid groups), a moisture-curing type (which cures by the reaction of isocyanato groups with water in the air), and a block type (which cures by the reaction of isocyanato groups with water in the air).
  • examples thereof include a lacquer type (which cures when the solvent volatilizes and dries), a lacquer type (which cures when the isocyanato group dissociated and regenerated by heating reacts with a hydroxyl group).
  • a moisture-curable one-component urethane resin is preferably used from the viewpoint of ease of handling and the like. Specific examples thereof include "UM-50P" manufactured by Showa Denko KK.
  • Examples of the two-component urethane resin include a catalyst-curable type (a catalyst-curable type in which an isocyanato group reacts with water in the air to cure in the presence of a catalyst) and a polyol-curable type (a reaction between an isocyanato group and a hydroxyl group of a polyol compound). (Those that are cured by) and the like.
  • polyol compound in the polyol curing type examples include polyester polyols, polyether polyols, and phenol resins.
  • isocyanate compound having an isocyanato group in the polyol-curable type examples include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and diimalate diisocyanate; 2,4- or 2,6-tolylene diisocyanate.
  • HDI hexamethylene diisocyanate
  • tetramethylene diisocyanate tetramethylene diisocyanate
  • diimalate diisocyanate 2,4- or 2,6-tolylene diisocyanate.
  • TDI p-phenylenediocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) and aromatic isocyanates such as polypeptide MDI which is a polynuclear mixture thereof; alicyclic isocyanates such as isophorone diisocyanate (IPDI) and the like.
  • the compounding ratio of the polyol compound and the isocyanate compound in the polyol-curable two-component urethane resin is preferably in the range of 0.7 to 1.5 in the molar equivalent ratio of the hydroxyl group / isocyanato group.
  • urethanization catalyst used in the two-component urethane resin examples include triethylenediamine, tetramethylguanidine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethyletheramine, N, N, N', N'', N''-pentamethyldipropylene-triamine, N-methylmorpholin, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine and other amine-based catalysts; dibutyltindi Examples thereof include organotin catalysts such as acetate, dibutyltin dilaurate, dibutyltin thiocarboxylate and dibutyltin dimalate. In the polyol curing type, it is generally preferable that 0.01 to 10 parts by mass of the urethanization catalyst is blended with respect to 100 parts by mass of the polyol compound.
  • the epoxy resin is a resin having at least two epoxy groups in one molecule.
  • the prepolymer before curing of the epoxy resin include ether-based bisphenol-type epoxy resin, novolac-type epoxy resin, polyphenol-type epoxy resin, aliphatic-type epoxy resin, ester-based aromatic epoxy resin, and cyclic aliphatic epoxy resin. , Ether-ester type epoxy resin and the like, and among these, bisphenol A type epoxy resin is preferably used. Of these, one type may be used alone, or two or more types may be used in combination.
  • Specific examples of the bisphenol A type epoxy resin include "jER (registered trademark) 828" and "jER (registered trademark) 1001" manufactured by Mitsubishi Chemical Corporation.
  • Specific examples of the novolak type epoxy resin include "DEN (registered trademark) 438 (registered trademark)” manufactured by The Dow Chemical Company.
  • Examples of the curing agent used for the epoxy resin include known curing agents such as aliphatic amines, aromatic amines, acid anhydrides, phenol resins, thiols, imidazoles, and cationic catalysts.
  • the curing agent is used in combination with a long-chain aliphatic amine and / or a thiol, the effect of having a large elongation rate and excellent impact resistance can be obtained.
  • Specific examples of the thiols include the same compounds as those exemplified as the thiol compounds for forming the functional group-containing layer described later.
  • pentaerythritol tetrakis (3-mercaptobutyrate) for example, "Carens MT (registered trademark) PE1” manufactured by Showa Denko KK
  • Carens MT registered trademark
  • PE1 manufactured by Showa Denko KK
  • the vinyl ester resin is obtained by dissolving a vinyl ester compound in a polymerizable monomer (for example, styrene). Although it is also called an epoxy (meth) acrylate resin, the vinyl ester resin also includes a urethane (meth) acrylate resin.
  • a polymerizable monomer for example, styrene
  • the vinyl ester resin also includes a urethane (meth) acrylate resin.
  • the vinyl ester resin for example, those described in "Polyester Resin Handbook” (Nikkan Kogyo Shimbun, published in 1988), "Paint Glossary” (Japan Society of Color Material, published in 1993), etc. shall also be used.
  • Lipoxy (registered trademark) R-802 "Lipoxy (registered trademark) R-804", “Lipoxy (registered trademark) R-806", etc. manufactured by Showa Denko KK, etc. Can be mentioned.
  • the urethane (meth) acrylate resin is obtained by, for example, reacting an isocyanate compound with a polyol compound and then reacting with a hydroxyl group-containing (meth) acrylic monomer (and, if necessary, a hydroxyl group-containing allyl ether monomer).
  • a hydroxyl group-containing (meth) acrylic monomer and, if necessary, a hydroxyl group-containing allyl ether monomer.
  • examples thereof include radically polymerizable unsaturated group-containing oligomers. Specific examples thereof include "Lipoxy (registered trademark) R-6545" manufactured by Showa Denko KK.
  • the vinyl ester resin can be cured by radical polymerization by heating in the presence of a catalyst such as an organic peroxide.
  • a catalyst such as an organic peroxide.
  • the organic peroxide is not particularly limited, but for example, ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxides. Oxide carbonates and the like can be mentioned. By combining these with a cobalt metal salt or the like, curing at room temperature is also possible.
  • the cobalt metal salt is not particularly limited, and examples thereof include cobalt naphthenate, cobalt octylate, and cobalt hydroxide. Of these, cobalt naphthenate and / and cobalt octylate are preferred.
  • the unsaturated polyester resin is a monomer (eg, styrene, etc.) in which a condensation product (unsaturated polyester) obtained by an esterification reaction of a polyol compound and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) is polymerized. ) Is dissolved.
  • a condensation product unsaturated polyester obtained by an esterification reaction of a polyol compound and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) is polymerized.
  • unsaturated polyester resin those described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Paint Glossary” (Japan Society of Color Material, published in 1993), etc. can also be used. Yes, and more specifically, "Rigolac (registered trademark)" manufactured by Showa Denko KK can be mentioned.
  • the unsaturated polyester resin can be cured by radical polymerization by heating in the presence of a catalyst similar to the vinyl ester resin.
  • the resin coating layer 3 is formed on the surface of the material layer 2 with excellent adhesiveness, and exhibits excellent adhesiveness with the modified polyphenylene ether to be bonded. Further, the surface of the material layer 2 is protected by the resin coating layer 3, and the adhesion of dirt to the surface of the material layer can be suppressed.
  • the resin coating layer can impart excellent bondability to the modified polyphenylene ether to be bonded to the material layer. Further, it is possible to obtain a composite laminate capable of maintaining a state in which excellent adhesiveness can be obtained for a long period of several months while the surface of the material layer is protected as described above.
  • the resin coating layer has an effect of imparting excellent bonding properties to the modified polyphenylene ether to be bonded to the material layer
  • the resin coating layer can be a primer layer of the composite laminate.
  • the primer layer referred to here is a material that is interposed between the material layer and the bonding target when the material layer is bonded and integrated with a bonding target such as a resin material, for example, as in the case of a bonded body described later. It shall mean a layer that improves the adhesiveness of the layer to the object to be joined.
  • the functional group-containing layer 4 When the functional group-containing layer 4 is provided, the functional group formed by the functional group-containing layer reacts with the hydroxyl group on the surface of the material layer and the functional group of the resin constituting the resin coating layer to form a chemical bond. As a result, the effect of improving the adhesiveness between the surface of the material layer and the resin coating layer can be obtained. In addition, the effect of improving the bondability with the bonding target can also be obtained.
  • the functional group-containing layer 4 at least a part of the functional groups on the surface of the silane coupling agent-treated layer spread in two dimensions is one or more compounds selected from the group consisting of isocyanate compounds, thiol compounds, epoxy compounds, and amino compounds. It is possible to form a functional group-containing structure in which a functional group capable of chemically bonding with a functional group of an organic material is extended in a three-dimensional direction by reacting.
  • One or more compounds selected from the group consisting of the isocyanate compound, the thiol compound, the epoxy compound, and the amino compound are groups capable of reacting with functional groups on the surface of the silane coupling agent layer and functionalities of the resin constituting the resin coating layer. It is preferably a compound having a group capable of reacting with the group.
  • the functional group-containing layer 4 is preferably formed by subjecting the surface of the material layer 2 to at least one treatment selected from the group consisting of the following (1') to (7').
  • Treatment to add a thiol compound after treatment (5') After treatment with a silane coupling agent having an epoxy group, it is selected from the group consisting of compounds having amino groups and (meth) acryloyl groups, amino compounds, and thiol compounds. Treatment to add at least one (6') Treatment with isocyanate compound (7') Treatment with thiol compound
  • the functional group-containing layer 4 preferably contains the functional group introduced by the above treatment, and specifically, preferably contains at least one functional group selected from the group consisting of the following (1) to (7). .. (1) At least one functional group derived from a silane coupling agent and selected from the group consisting of an epoxy group, an amino group, a (meth) acryloyl group and a mercapto group. (2) An amino group derived from a silane coupling agent.
  • a functional group obtained by reacting at least one selected from an epoxy compound and a thiol compound (3)
  • a mercapto group derived from a silane coupling agent has an epoxy compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and an epoxy group.
  • a thiol compound is reacted with a (meth) acryloyl group derived from a silane coupling agent.
  • An epoxy group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound.
  • Functional group (6) Isocyanato group derived from isocyanate compound (7) Mercapto group derived from thiol compound
  • the above pretreatment can also be applied to the surface of the material layer before forming the functional group-containing layer 4 in the material layer.
  • the pretreatment at least one selected from the group consisting of degreasing treatment, UV ozone treatment, blast treatment, polishing treatment, plasma treatment and corona discharge treatment is preferable.
  • the method for forming the functional group-containing layer with the silane coupling agent, the isocyanate compound, the thiol compound and the like is not particularly limited, and examples thereof include a spray coating method and a dipping method. Specifically, the material layer is immersed in a solution of a silane coupling agent having a concentration of 5 to 50% by mass at room temperature to 100 ° C. for 1 minute to 5 days, and then dried at room temperature to 100 ° C. for 1 minute to 5 hours. It can be done by a method such as making it.
  • silane coupling agent for example, known ones used for surface treatment of glass fibers and the like can be used.
  • a silanol group generated by hydrolyzing a silane coupling agent or a silanol group obtained by oligomerizing the silanol group reacts with a hydroxyl group existing on the surface of the material layer 2 and bonds to the resin coating layer 3 to be chemically bonded.
  • a functional group based on the structure of the silane coupling agent can be imparted (introduced) to the material layer.
  • the silane coupling agent is not particularly limited, but a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, a silane coupling agent having a (meth) acryloyl group, and the like. Can be used.
  • the silane coupling agent having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like.
  • Examples thereof include 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane.
  • Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2-(. Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like can be mentioned.
  • silane coupling agent having a mercapto group examples include 3-mercaptopropylmethyldimethoxysilane and dithioltriazinepropyltriethoxysilane.
  • silane coupling agent having a (meth) acryloyl group examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. , 3-Acryloxypropyltrimethoxysilane and the like.
  • silane coupling agents having a vinyl group such as 3-isocyanatopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3- Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminopropyltrimethoxysilane hydrochloride, tris- (Trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, and the like. These may be used alone or in combination of two or more.
  • Epoxy compound As the epoxy compound, a known epoxy compound or the like can be used. A polyvalent epoxy compound or a compound having an alkenyl group other than the epoxy group is preferable.
  • the epoxy compound is not particularly limited, but for example, glycidyl (meth) acrylate, allyl glycidyl ether, which can have a (meth) acryloyl group or an allyl group whose terminal group is a radical reactive group, and allyl glycidyl ether, and the like. Examples thereof include 1,6-hexanediol diglycidyl ether having an epoxy group as the terminal group, and an epoxy resin having two or more epoxy groups in the molecule.
  • the thiol compound is based on the structure of the thiol compound which can be chemically bonded to a resin coating layer or a bonding target by reacting and bonding a mercapto group in the thiol compound with a hydroxyl group existing on the surface of the material layer 2. Functional groups can be imparted (introduced) to the material layer.
  • the thiol compound is not particularly limited, but for example, pentaerythritol tetrakis (3-mercaptopropionate) having a mercapto group as a terminal group (for example, "QX40" manufactured by Mitsubishi Chemical Corporation, Toray. Fine Chemicals Co., Ltd. "QE-340M”), ether-based first-class thiols (for example, "Cup Cure 3-800” manufactured by Cognis), 1,4-bis (3-mercaptobutylyloxy) butane (for example, Showa Denko Co., Ltd.
  • pentaerythritol tetrakis (3-mercaptopropionate) having a mercapto group as a terminal group for example, "QX40" manufactured by Mitsubishi Chemical Corporation, Toray. Fine Chemicals Co., Ltd. "QE-340M”
  • ether-based first-class thiols for example, "Cup Cure 3-800” manufactured by Cognis
  • Kevron MT registered trademark
  • Pentaerythritol tetrakis (3-mercaptobutylate)
  • Karenzu MT registered trademark
  • PE1 1, 3, 5 -Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione
  • Karens MT registered trademark
  • NR1 manufactured by Showa Denko KK
  • amino compound As the amino compound, a known amino compound or the like can be used. Polyfunctional amino compounds and compounds having an alkenyl group in addition to the amino group (including amide) are preferable.
  • the amino compound is not particularly limited, but for example, ethylenediamine having an amino group at the terminal, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, hexamethylenediamine, and the like.
  • the isocyanate compound is a functional group based on the structure of the isocyanate compound, which can be chemically bonded to the resin coating layer 3 by reacting and bonding an isocyanato group in the isocyanate compound with a hydroxyl group existing on the surface of the material layer 2. Can be imparted (introduced) to the material layer.
  • the isocyanate compound is not particularly limited, but is, for example, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), isophorone diisocyanate, which are polyfunctional isocyanates having an isocyanato terminal group.
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • TDI tolylene diisocyanate
  • isophorone diisocyanate which are polyfunctional isocyanates having an isocyanato terminal group.
  • 2-Isocyanatoethyl methacrylate for example, "Karens MOI (registered trademark)" manufactured by Showa Denko Co., Ltd., which is an isocyanate compound whose terminal group can be a (meth) acryloyl group which is a radical reactive group in addition to (IPDI) and the like.
  • 2-Isocyanate ethyl acrylate for example,“ Karens AOI® ”,“ AOI-VM® ”), 1,1- (bisacryloyloxyethyl) ethyl isocyanate manufactured by Showa Denko Co., Ltd. (For example, "Karens BEI (registered trademark)” manufactured by Showa Denko Co., Ltd.) and the like.
  • the resin coating layer 3 of the composite laminate 1 is a primer layer as described above, and the surface on the primer layer side and the modified polyphenylene ether 6 are used. Is joined and integrated.
  • the thickness of the primer layer depends on the material of the bonding target and the contact area of the bonding portion, but when the bonding target is not a film, a viewpoint of obtaining excellent bonding strength with the bonding target.
  • the thickness is preferably 1 ⁇ m to 10 mm from the viewpoint of suppressing stress concentration at the resin end of the interface due to the difference in heat shrinkage between the materials. It is more preferably 20 ⁇ m to 3 mm, and even more preferably 40 ⁇ m to 1 mm.
  • the thickness of the primer layer is the total thickness of each layer.
  • the thickness of the primer layer (thickness after drying) is preferably 0.1 ⁇ m to 1 mm, more preferably 0.1 ⁇ m to 100 ⁇ m.
  • the modified polyphenylene ether in the conjugate is not particularly limited, and the above-mentioned ones can be used.
  • a composite laminate and a molded body of modified polyphenylene ether separately produced can be bonded and integrated.
  • the molded body of the modified polyphenylene ether is molded by a method such as injection molding, press molding, or transfer molding, and at the same time, the surface of the composite laminate on the primer layer side and the modified polyphenylene ether are joined and integrated.
  • a method of welding the modified polyphenylene ether and a method of injection welding the modified polyphenylene ether onto the surface of the composite laminate on the primer layer side can be mentioned.
  • a modified polyphenylene ether (NOLYL731 manufactured by SABIC): 3.77 g and xylene: 95 g were charged in a flask, and the temperature was raised to 125 ° C. with stirring to dissolve.
  • a bifunctional epoxy resin jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Co., Ltd.): 1.0 g, bisphenol A: 0.22 g, 2,4,6-tris (dimethylaminomethyl) phenol: 0.005 g.
  • jER registered trademark
  • bisphenol A 0.22 g
  • 2,4,6-tris dimethylaminomethyl
  • a modified polyphenylene ether (NOLYL731 manufactured by SABIC): 3.75 g and xylene: 95 g were placed in a flask and dissolved by raising the temperature to 125 ° C. with stirring.
  • a bifunctional epoxy resin (jER (registered trademark) 1007 manufactured by Mitsubishi Chemical Co., Ltd.): 1.18 g, bisphenol A: 0.065 g, 2,4,6-tris (dimethylaminomethyl) phenol: 0.004 g.
  • jER registered trademark
  • bisphenol A 0.065 g
  • 2,4,6-tris dimethylaminomethyl
  • a modified polyphenylene ether (NOLYL731 manufactured by SABIC): 7.0 g and xylene: 95 g were charged in a flask, and the temperature was raised to 125 ° C. with stirring to dissolve.
  • an organic peroxide catalyst Perbutyl (registered trademark) O manufactured by Nichiyu Co., Ltd.): 0.1 g in a monomer mixture in which methacrylic acid: 1.0 g, methyl methacrylate: 1.0 g, and styrene: 1.0 g were mixed.
  • ⁇ Manufacturing example 4> In a flask, a bifunctional epoxy resin (jER® 1007 manufactured by Mitsubishi Chemical Co., Ltd.): 1.18 g, bisphenol A: 0.065 g, 2,4,6-tris (dimethylaminomethyl) phenol: 0.004 g, Xylene: 95 g was charged, the temperature was raised to 140 ° C., and the reaction was carried out with stirring for 1 hour to obtain a thermoplastic epoxy resin.
  • jER® 1007 manufactured by Mitsubishi Chemical Co., Ltd. a bifunctional epoxy resin (jER® 1007 manufactured by Mitsubishi Chemical Co., Ltd.): 1.18 g, bisphenol A: 0.065 g, 2,4,6-tris (dimethylaminomethyl) phenol: 0.004 g, Xylene: 95 g was charged, the temperature was raised to 140 ° C., and the reaction was carried out with stirring for 1 hour to obtain a thermoplastic epoxy resin.
  • modified polyphenylene ether (NOLYL731 manufactured by SABIC) was added, and the mixture was stirred and mixed for 10 minutes to obtain a re-modified-modified polyphenylene ether modified with a thermoplastic epoxy resin: re-modified m-PPE-4. It was.
  • polyphenylene ether (NOLYL731 manufactured by SABIC) was added, and the mixture was stirred and mixed for 10 minutes to obtain a re-modified polyphenylene ether modified with a methacrylic resin: re-modified m-PPE-5.
  • Example 1-1 (Preprocessing) The surface of a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) having a thickness of 18 mm ⁇ 45 mm and a thickness of 1.2 mm was degreased with acetone.
  • a glass substrate manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass
  • Example 1-2 A modified polyphenylene ether resin (NOLYL731 manufactured by SABIC) to be bonded was placed on the surface of the composite laminate produced in Example 1-1 on the resin coating layer side, and an injection molding machine (SE100V manufactured by Sumitomo Heavy Industries, Ltd .; cylinder).
  • SE100V manufactured by Sumitomo Heavy Industries, Ltd .; cylinder.
  • 10 mm ⁇ 45 mm ⁇ 3 mm, overlapping length of joint portion 5 mm, width 10 mm) (glass-modified polyphenylene ether junction) was prepared.
  • the tensile test test piece prepared in Example 1-2 was left at room temperature (temperature 23 ° C., 50% RH) for 1 day, and then subjected to a tensile tester (manufactured by Shimadzu Corporation) in accordance with ISO19095 1-4.
  • the tensile shear joint strength test was performed on the autograph "AG-IS"; load cell 10 kN, tensile speed 10 mm / min, temperature 23 ° C., 50% RH), and the joint strength was measured. The measurement results are shown in Table 1 below.
  • Example 2-1> (Preprocessing) The same operation as in Example 1-1 was carried out, and the surface of a glass substrate (18 mm ⁇ 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.
  • thermoplastic epoxy resin composition (jER® 1001 manufactured by Mitsubishi Chemical Corporation): 100 g, bisphenol A: 24 g, and triethylamine: 0.4 g are dissolved in 250 g of acetone on the surface of the functional group-containing layer.
  • the thermoplastic epoxy resin composition was applied by a spray method so that the thickness after drying was 30 ⁇ m. After volatilizing the solvent by leaving it in the air at room temperature (23 ° C) for 30 minutes, leave it in a furnace at 150 ° C for 30 minutes to perform a heavy addition reaction, and allow it to cool to room temperature (23 ° C).
  • the first resin coating layer (thermoplastic epoxy resin layer) was formed.
  • Example 2-2 A test piece for a tensile test was prepared by performing the same operation as in Example 1-2 on the surface of the composite laminate prepared in Example 2-1 on the resin coating layer side of the second layer. The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.
  • Example 3-1 (Preprocessing) The same operation as in Example 1-1 was carried out, and the surface of a glass substrate (18 mm ⁇ 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.
  • the pretreated glass base material was prepared by dissolving 0.5 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shinetsu Silicone Co., Ltd .; a silane coupling agent) in 100 g of industrial ethanol at 70 ° C. After immersing in the silane coupling agent solution of silane for 5 minutes, the glass substrate was taken out and dried, and a functional group (methacryloyloxy group) derived from the silane coupling agent was introduced on the surface of the glass substrate.
  • KBM-503 manufactured by Shinetsu Silicone Co., Ltd .
  • silane coupling agent a silane coupling agent
  • a bifunctional thiol compound 1,4 bis (3-mercaptobutyryloxy) butane Showa Denko KK Karens MT (registered trademark) BD1: 0.6 g, 2,4,6-tris (dimethylaminomethyl) Phenol (DMP-30): 0.05 g was immersed in a solution dissolved in 150 g of toluene at 70 ° C. for 10 minutes, and then lifted and dried. In this way, a functional group (mercapto group) -containing layer having a chemically bondable functional group was formed.
  • Example 3-2 A test piece for a tensile test was prepared by performing the same operation as in Example 1-2 on the surface of the composite laminate prepared in Example 3-1 on the resin coating layer side. The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.
  • Example 4-1 (Preprocessing) A glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) having a thickness of 18 mm ⁇ 45 mm and a thickness of 1.2 mm was subjected to a wet blast treatment to form fine irregularities on the surface of the glass substrate.
  • a glass substrate manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass having a thickness of 18 mm ⁇ 45 mm and a thickness of 1.2 mm was subjected to a wet blast treatment to form fine irregularities on the surface of the glass substrate.
  • Example 4-2 A test piece for a tensile test was prepared by performing the same operation as in Example 1-2 on the surface of the composite laminate prepared in Example 4-1 on the resin coating layer side. The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.
  • Example 5-1 (Preprocessing) A glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) having a thickness of 18 mm ⁇ 45 mm and a thickness of 1.2 mm was subjected to a wet blast treatment to form fine irregularities on the surface of the glass substrate.
  • a glass substrate manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass having a thickness of 18 mm ⁇ 45 mm and a thickness of 1.2 mm was subjected to a wet blast treatment to form fine irregularities on the surface of the glass substrate.
  • Example 5-2> A test piece for a tensile test was prepared by performing the same operation as in Example 1-2 on the surface of the composite laminate prepared in Example 5-1 on the resin coating layer side. The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.
  • Example 6-1 (Preprocessing) A glass substrate (manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) having a thickness of 18 mm ⁇ 45 mm and a thickness of 1.2 mm was subjected to a wet blast treatment to form fine irregularities on the surface of the glass substrate.
  • a glass substrate manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass having a thickness of 18 mm ⁇ 45 mm and a thickness of 1.2 mm was subjected to a wet blast treatment to form fine irregularities on the surface of the glass substrate.
  • pentaerythritol tetrakis (3-mercaptobutyrate) Showa Denko KK "Karensu MT (registered trademark) PE1": 1.2 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30)
  • DMP-30 2,4,6-tris (dimethylaminomethyl) phenol
  • thermosetting resin layer first layer of the resin coating layer.
  • the re-denatured m-PPE-5 obtained in Production Example 5 was applied to the surface of the thermosetting resin layer of the glass substrate, xylene was volatilized and held at 150 ° C. for 30 minutes to contain the functional group.
  • a composite laminate in which a resin-coated layer (thickness 30 ⁇ m) of re-modified m-PPE-5 was formed on the surface of the layer was prepared.
  • Example 6-2 A test piece for a tensile test was prepared by performing the same operation as in Example 1-2 on the surface of the composite laminate prepared in Example 6-1 on the resin coating layer side. The joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.
  • Example 1-1 (Pretreatment process) The same operation as in Example 1-1 was carried out, and the surface of a glass substrate (18 mm ⁇ 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.
  • Example 1-2 The same injection molding operation as in Example 1-2 was performed on the surface of the glass substrate after the acetone degreasing treatment produced in Comparative Example 1-1, but the m-PPE resin was adhered to the surface of the glass substrate. Therefore, it was not possible to prepare a glass-modified polyphenylene ether conjugate.
  • Example 2-1> (Pretreatment process) The same operation as in Example 1-1 was carried out, and the surface of a glass substrate (18 mm ⁇ 45 mm, 1.2 mm thick, manufactured by Nippon Electric Glass Co., Ltd., chemically strengthened glass) was degreased with acetone.
  • Example 1-1 (Functional group-containing layer forming step) Next, the same operation as in Example 1-1 was carried out to form a functional group (amino group) -containing layer on the surface of the glass substrate after the acetone degreasing treatment.
  • Example 2-2 The same operation as in Example 1-2 was carried out on the surface of the functional group-containing layer of Comparative Example 2-1 to prepare a test piece for a tensile test.
  • the joint strength of the test piece was measured by the same method as in Example 1-2. The measurement results are shown in Table 1 below.
  • test piece [Material for test piece] The following materials were prepared as test piece materials.
  • CFRP CF-SMC Rigolac RCS-1000BK (CF: 50% by mass) manufactured by Showa Denko KK using a 1500 kN press and pressure-molded at 140 ° C. for 5 minutes. Dimensions: 18 mm x 45 mm x 1.5 mm.
  • Ceramic Substrate for thick film (alumina) manufactured by Kyocera Corporation. Dimensions: 18 mm x 45 mm x 1.5 mm.
  • Modified polyphenylene ether (m-PPE) plate An m-PPE plate of 10 mm ⁇ 45 mm ⁇ 3 mm for preparing a test piece for a tensile test conforming to ISO19095 was molded by the molding method of Example 1-2.
  • Example 7-1> (Pretreatment Wet blast treatment) A CFRP having a size of 18 mm ⁇ 45 mm and a thickness of 1.5 mm was subjected to a wet blast treatment in the same manner as in Example 4-1 to form fine irregularities on the CFRP surface.
  • Example 7-2 CFRP-modified polyphenylene ether conjugate>
  • Example 8-1> (Pretreatment Wet blast treatment) A CFRP having a size of 18 mm ⁇ 45 mm and a thickness of 1.5 mm was subjected to a wet blast treatment in the same manner as in Example 4-1 to form fine irregularities on the CFRP surface.
  • Example 7-1 Formation of functional group-containing layer Treatment with silane coupling agent
  • Example 8-2 CFRP-modified polyphenylene ether conjugate>
  • Example 7-2 the same operation as in Example 7-2 was performed, and the surface of the composite laminate prepared in Example 8-1 on the resin coating layer side and the m-PPE plate were ultrasonically welded to prepare a test piece. ..
  • the joint strength of the test piece was measured by the same method as in Example 7-2. The measurement results are shown in Table 2 below.
  • Example 9-1 (Pretreatment Wet blast treatment) A ceramic having a size of 18 mm ⁇ 45 mm and a thickness of 1.5 mm was subjected to a wet blast treatment in the same manner as in Example 4-1 to form fine irregularities on the ceramic surface.
  • Example 7-1 Formation of functional group-containing layer Treatment with silane coupling agent
  • Example 9-2 Ceramic-modified polyphenylene ether conjugate> Next, the same operation as in Example 7-2 was performed, and the surface of the composite laminate prepared in Example 9-1 on the resin coating layer side and the m-PPE plate were ultrasonically welded to prepare a test piece. .. The joint strength of the test piece was measured by the same method as in Example 7-2. The measurement results are shown in Table 2 below.
  • Example 10-1 (Pretreatment Wet blast treatment) A ceramic having a size of 18 mm ⁇ 45 mm and a thickness of 1.5 mm was subjected to a wet blast treatment in the same manner as in Example 4-1 to form fine irregularities on the ceramic surface.
  • Example 7-1 Formation of functional group-containing layer Treatment with silane coupling agent
  • Example 10-2 Ceramic-modified polyphenylene ether conjugate> Next, the same operation as in Example 7-2 was performed, and the surface of the composite laminate prepared in Example 10-1 on the resin coating layer side and the m-PPE plate were ultrasonically welded to prepare a test piece. .. The joint strength of the test piece was measured by the same method as in Example 7-2. The measurement results are shown in Table 2 below.
  • Example 7-1 the composite lamination was carried out in the same manner as in Example 7-1, except that the thermoplastic epoxy resin composition for comparative resin coating was used instead of the re-modified m-PPE-1.
  • the body was made.
  • Example 3-2 The same operation as in Example 7-2 was carried out, and the surface of the composite laminate prepared in Comparative Example 3-1 on the resin coating layer side and the m-PPE plate were ultrasonically welded to prepare a test piece.
  • the joint strength of the test piece was measured by the same method as in Example 7-2. The measurement results are shown in Table 2 below.
  • thermoplastic epoxy resin composition for comparative resin coating prepared in Comparative Example 3-1 was used instead of the re-modified m-PPE-3 in Example 9-1.
  • thermoplastic epoxy resin composition for comparative resin coating prepared in Comparative Example 3-1 was used instead of the re-modified m-PPE-3 in Example 9-1.
  • Example 4-2 The same operation as in Example 7-2 was carried out, and the surface of the composite laminate prepared in Comparative Example 4-1 on the resin coating layer side and the m-PPE plate were ultrasonically welded to prepare a test piece.
  • the joint strength of the test piece was measured by the same method as in Example 7-2. The measurement results are shown in Table 2 below.
  • Examples (1-2) to (10-2) of Table 1 by using a composite laminate having a resin coating layer containing a re-modified-modified polyphenylene ether layer, a material layer and modified polyphenylene are used. It can be bonded to ether with high strength.
  • the composite laminate according to the present invention is joined and integrated with a modified polyphenylene ether, for example, a door side panel, a bonnet roof, a tailgate, a steering hanger, an A pillar, a B pillar, a C pillar, a D pillar, a crash box, and a power.
  • Automobiles such as control unit (PCU) housings, electric compressor members (inner wall, suction port, exhaust control valve (ECV) insertion, mount boss, etc.), lithium-ion battery (LIB) spacers, battery cases, LED headlamps, etc. It is used as a component for parts, a smartphone, a notebook computer, a tablet computer, a smart watch, a large LCD TV (LCD-TV), a structure for outdoor LED lighting, and the like, but the application is not particularly limited to these examples.
  • PCU control unit
  • ECV exhaust control valve
  • LIB lithium-ion battery

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • Toxicology (AREA)
  • Manufacturing & Machinery (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un stratifié composite et une technique associée à celui-ci, le stratifié composite étant approprié pour une application dans l'assemblage, avec une résistance élevée, d'un poly(phénylène éther) modifié et d'un matériau comprenant au moins un élément choisi dans le groupe constitué par un plastique renforcé par des fibres, du verre et de la céramique.　Le stratifié composite comportant une couche de matériau comprenant au moins un élément choisi dans le groupe constitué par un plastique renforcé par des fibres, du verre et de la céramique, et une couche de revêtement de résine comprenant une ou plusieurs couches de résine stratifiées sur la couche de matériau, au moins une des couches de résines étant une couche de poly(phénylène éther) modifié/remodifié formée à partir d'une composition de résine comprenant le poly(phénylène éther) modifié/remodifié, la couche de poly(phénylène éther) modifié/remodifié étant au moins une couche choisie parmi une couche comprenant un mélange 1, qui est un mélange d'un poly(phénylène éther) modifié et d'une résine époxydique thermoplastique, et une couche comprenant un mélange 2, qui est un mélange d'un poly(phénylène éther) modifié et d'une résine (méth)acrylique.
PCT/JP2020/037803 2019-11-22 2020-10-06 Stratifié composite et corps assemblé WO2021100340A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2017170736A1 (fr) * 2016-03-29 2017-10-05 株式会社クラレ Feuille stratifiée ionomère, son procédé de production et corps stratifié
WO2018124215A1 (fr) * 2016-12-28 2018-07-05 新日鉄住金化学株式会社 Corps composite de matériau de métal/résine renforcée par des fibres, son procédé de production et feuille de liaison
JP2019151106A (ja) * 2018-02-28 2019-09-12 日本製鉄株式会社 金属−繊維強化樹脂材料複合体及び金属−繊維強化樹脂材料複合体の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017170736A1 (fr) * 2016-03-29 2017-10-05 株式会社クラレ Feuille stratifiée ionomère, son procédé de production et corps stratifié
WO2018124215A1 (fr) * 2016-12-28 2018-07-05 新日鉄住金化学株式会社 Corps composite de matériau de métal/résine renforcée par des fibres, son procédé de production et feuille de liaison
JP2019151106A (ja) * 2018-02-28 2019-09-12 日本製鉄株式会社 金属−繊維強化樹脂材料複合体及び金属−繊維強化樹脂材料複合体の製造方法

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