WO2022181754A1 - Stratifié composite et corps assemblé - Google Patents

Stratifié composite et corps assemblé Download PDF

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Publication number
WO2022181754A1
WO2022181754A1 PCT/JP2022/007818 JP2022007818W WO2022181754A1 WO 2022181754 A1 WO2022181754 A1 WO 2022181754A1 JP 2022007818 W JP2022007818 W JP 2022007818W WO 2022181754 A1 WO2022181754 A1 WO 2022181754A1
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Prior art keywords
resin
resin composition
thermoplastic resin
type epoxy
epoxy resin
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PCT/JP2022/007818
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English (en)
Japanese (ja)
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和男 大谷
信行 高橋
良太 新林
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昭和電工株式会社
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Priority to JP2023502530A priority Critical patent/JPWO2022181754A1/ja
Publication of WO2022181754A1 publication Critical patent/WO2022181754A1/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
    • 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
    • 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
    • B29C65/56—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using mechanical means or mechanical connections, e.g. form-fits
    • B29C65/64—Joining a non-plastics element to a plastics element, e.g. by force
    • 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 containing a base material made of metal or resin, wherein the base materials can be welded and joined together at a low temperature, a method for producing the same, and each base material using the composite laminate.
  • the present invention relates to a bonded body and a method for manufacturing the same.
  • metal substrates and resin substrates, metal substrates and metal substrates, and resin substrates and resin substrates are collectively referred to as "
  • adhesive bonding using an adhesive is often used as a method for bonding substrates.
  • vinyl chloride resin pipes are widely used due to their excellent hydraulic characteristics, chemical resistance, and ease of handling. in use.
  • the adhesive used for joining vinyl chloride resin pipes is usually a solution-type adhesive dissolved in a solvent such as tetrahydrofuran or methyl ethyl ketone. These solution-type adhesives are applied to the adhesive surfaces of pipes and joints, the applied surfaces are swollen, and the swollen surfaces are pressed together to entangle the vinyl chloride resin molecules of both, and the solvent evaporates to achieve bonding. It is something to do.
  • the adhesive used for adhesive bonding it is suitable for bonding hard-to-bond and flexible resin adherends such as polyvinyl chloride sheets to hard base materials such as steel plates and concrete, and is suitable for initial bonding.
  • a first liquid containing an isocyanato group-terminated urethane polymer A multi-liquid type adhesive composition consisting of a second liquid containing an active hydrogen-containing compound having two or more active hydrogens has been proposed (Patent Document 1).
  • Patent Document 2 As a resin adhesive that can efficiently and firmly bond an article made of vinyl chloride resin and other articles, a moisture-curable urethane prepolymer having an isocyanato group at the end and an active hydrogen A resin adhesive made of an organic solvent that does not dissolve is proposed (Patent Document 2).
  • JP 2020-105460 Composite material with low friction slidability and excellent safety Composite material with low friction slidability and excellent safety
  • the present invention has been made under such circumstances, and joins base materials with high joint strength in a short time even under low temperature conditions without requiring time for evaporation of the solvent at the site of the joint work.
  • An object of the present invention is to provide a composite laminate and a method for manufacturing the same, and to provide a joined body using the composite laminate and a method for manufacturing the same.
  • the “low temperature condition” in the present invention is a temperature condition that does not affect the resin such as vinyl chloride resin having low heat resistance such as deformation. means a temperature condition of 70°C or less.
  • the present invention by providing a resin primer layer formed of a specific material on the surface of a base material, it is possible to easily weld and bond on site, and to develop high bonding strength in a short time even under the above-mentioned low temperature conditions. This is based on the discovery of
  • the present invention provides the following [1] to [20].
  • a composite laminate having a substrate made of metal or resin and one or more resin primer layers laminated on the surface of the substrate, At least one layer of the resin primer layer is a polymer layer made of a polymer of an in-situ polymerizable thermoplastic resin composition containing the following (A), and a polymer of an in-situ polymerizable thermoplastic resin composition containing the following (B).
  • the resin primer layer is laminated on the surface-treated surface of the base material,
  • the substrate is made of a metal selected from the group consisting of aluminum, iron and stainless steel.
  • the substrate comprises a resin selected from the group consisting of polyvinyl chloride, polyethylene and polypropylene.
  • A a combination of a bifunctional thiol compound and a phenol novolak-type epoxy resin and/or a cresol novolac-type epoxy resin
  • B a combination of a bifunctional amino compound and a phenol novolak-type epoxy resin and/or a cresol novolac-type epoxy resin
  • C a combination of a bifunctional carboxy compound and a phenol novolak type epoxy resin and/or a cresol novolak type epoxy resin
  • D a combination of a difunctional isocyanate compound and a phenol novolak resin and/or a cresol novolak resin
  • E maleic anhydride-modified polyolefins and/or chlorinated polyolefins
  • the substrate is treated with at least one selected from the group consisting of a silane coupling agent, an isocyanate compound and a thiol compound to form a functional group-introduced layer on the substrate.
  • the method for manufacturing a composite laminate according to any one of [6] to [8].
  • a method for manufacturing a joined body At least one method selected from the group consisting of high-frequency induction welding, high-frequency dielectric welding, ultrasonic welding, laser welding, thermal welding, injection welding, and press welding is applied to the surface of the composite laminate on the primer layer side and the thermoplastic resin.
  • a method for manufacturing a joined body in which the material is welded and joined together.
  • a method for manufacturing a joined body The surfaces on the primer layer side of the composite laminate are welded together by at least one method selected from the group consisting of high-frequency induction welding, high-frequency dielectric welding, ultrasonic welding, laser welding, heat welding, injection welding, and press welding.
  • a method for manufacturing a bonded body, in which the bonded body is integrated by [15] The method for producing a joined body according to [13] or [14], wherein the welding is performed at a temperature of 80° C. or lower.
  • ⁇ Resin composition for heat welding, film for primer> [16] An in-situ polymerization type thermoplastic resin composition containing the following (A), an in-situ polymerization type thermoplastic resin composition containing the following (B), an in-situ polymerization type thermoplastic resin composition containing the following (C), and the following (D) At least one selected from the group consisting of an in-situ polymerization type thermoplastic resin composition containing, and an in-situ polymerization type thermoplastic resin composition containing any of the following (A) to (D) and the following (E) , a resin composition for heat welding.
  • A a combination of a bifunctional thiol compound and a phenol novolak-type epoxy resin and/or a cresol novolac-type epoxy resin
  • B a combination of a bifunctional amino compound and a phenol novolak-type epoxy resin and/or a cresol novolac-type epoxy resin
  • C a combination of a bifunctional carboxy compound and a phenol novolak type epoxy resin and/or a cresol novolak type epoxy resin
  • D a combination of a difunctional isocyanate compound and a phenol novolak resin and/or a cresol novolak resin
  • E maleic anhydride-modified polyolefins and/or chlorinated polyolefins [17]
  • a primer film obtained by subjecting the heat-welding resin composition of [16] to a polyaddition reaction to form a film.
  • a film for a primer in which the heat-welding resin composition according to [16] is applied onto the surface of a release mold or a release film, subjected to a polyaddition reaction, and then released to obtain a film-like polymer.
  • Production method. ⁇ Method for manufacturing joined body using primer film> [19] a base material made of metal or resin; A method for manufacturing a joined body, wherein a primer film is sandwiched between a base material A made of metal or resin and a base material B made of metal or resin, and the base material A and the base material B are joined and integrated.
  • the primer film is a polymer of an in situ polymerization type thermoplastic resin composition containing (A) below, a polymer of an in situ polymerization type thermoplastic resin composition containing (B) below, and an in situ polymerization containing (C) below.
  • a polymer of a type thermoplastic resin composition, a polymer of an in-situ polymerization type thermoplastic resin composition containing the following (D), and an in-situ polymerization type containing any of the following (A) to (D) and the following (E) A method for producing a joined body comprising at least one selected from the group consisting of a polymer of a thermoplastic resin composition.
  • the base material A and the base material B are welded by at least one method selected from the group consisting of high-frequency induction welding, high-frequency dielectric welding, ultrasonic welding, laser welding, heat welding, injection welding, and press welding.
  • the base materials can be bonded together in a short time with high bonding strength.
  • FIG. 3 is a cross-sectional view schematically showing another embodiment of the composite laminate of the present invention.
  • 1 is a cross-sectional view schematically showing an embodiment of a joined body of the present invention;
  • FIG. 3 is a cross-sectional view schematically showing another embodiment of the composite laminate of the present invention.
  • “Welding” means heating the joint surfaces of joint materials such as resins and metals to a temperature exceeding the softening point or melting point of the component present on at least one joint surface, and It means to form a bonding state by entanglement by diffusion or crystallization.
  • adhesive means bonding of adherends via an organic material (thermosetting resin, thermoplastic resin, etc.) such as a tape or adhesive.
  • FIG. 1 shows one embodiment of the composite laminate of the present invention.
  • the composite laminate 1 shown in FIG. 1 is a composite laminate comprising a substrate 2 made of metal or resin and one or more resin primer layers 3 laminated on the surface of the substrate 2 .
  • At least one layer of the resin primer layer 3 is a polymer layer made of a polymer of an in-situ polymerizable thermoplastic resin composition containing the following (A), and a polymer of an in-situ polymerizable thermoplastic resin composition containing the following (B).
  • the composite laminate has the polymer layer on the outermost surface.
  • each polymer layer may be formed of the same in-situ polymerizable thermoplastic resin composition, or may be formed of a different in-situ polymerizable thermoplastic resin composition.
  • may (A) a combination of a bifunctional thiol compound and a phenol novolak-type epoxy resin and/or a cresol novolac-type epoxy resin; (B) a combination of a bifunctional amino compound and a phenol novolak-type epoxy resin and/or a cresol novolac-type epoxy resin; (C) a combination of a bifunctional carboxy compound and a phenol novolak type epoxy resin and/or a cresol novolak type epoxy resin; (D) a combination of a difunctional isocyanate compound and a phenol novolak resin and/or a cresol novolak resin; (E) maleic anhydride-modified polyolefin and/or chlorinated polyolefin
  • the term "comprising" in the expression "in-situ polymerization type thermoplastic resin composition containing (A)” means that the combination of (A) is blended as a composition raw material of the in-situ polymerization type thermoplastic resin composition.
  • thermoplastic resin composition containing (B) means that "In-situ polymerization type thermoplastic resin composition containing (B)", “In-situ polymerization type thermoplastic resin composition containing (C)”, “In-situ polymerization type thermoplastic resin composition containing (D)", "( Similarly, the expression “in-situ polymerization type thermoplastic resin composition containing any of A) to (D) and (E)” also means that the combination of (B) is blended as a composition raw material, and The combination of (C) is blended, the combination of (D) is blended as a composition raw material, the combination of (A) to (D) as a composition raw material, and further (E ) is blended.
  • Metal base material The type of metal base material applied to the composite laminate of the present invention is not particularly limited.
  • the types of metal substrates include aluminum materials, iron materials, titanium materials, magnesium materials, stainless steel materials, and copper materials. These metal substrates may be single metals or alloys. Among these, aluminum is preferably used from the viewpoint of light weight and ease of processing.
  • the type of resin constituting the resin base material applied to the composite laminate of the present invention is not particularly limited, but examples thereof include polyvinyl chloride, polyethylene, polypropylene and the like, which are used particularly for infrastructure piping and the like.
  • Polyvinyl chloride includes resins called rigid vinyl chloride and soft vinyl chloride
  • polyethylene includes high-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene, ultra-high-molecular-weight polyethylene, etc.
  • Polypropylene is a homopolymer. , random copolymers, block copolymers, etc.
  • a resin primer layer is laminated on the surface of the substrate.
  • the resin primer layer may be composed of one layer, or may be composed of two or more layers.
  • the substrate can be bonded to another substrate with high bonding strength.
  • the resin primer layer is firmly adhered to the surface of the base material, and can protect the surface of the base material from deterioration such as dirt and oxidation.
  • the polymer layer constituting at least one layer of the resin primer layer can be formed by heating under low temperature conditions that do not affect the resin having low heat resistance such as deformation.
  • the base material in the composite laminate having the polymer layer on the outermost surface, can be joined to the polymer layer by welding under low temperature conditions that do not affect the resin with low heat resistance such as deformation, A high bonding strength can be expressed.
  • the "phenol novolak type epoxy resin” and “cresol novolak type epoxy resin”, which are the raw materials for the composition of the polymer layer, are resins having an epoxy group having a plurality of nuclei.
  • "Resin” is a resin having a phenolic hydroxyl group with a plurality of nuclear bodies.
  • "Phenol novolak type epoxy resin”, “cresol novolak type epoxy resin”, “phenol novolak resin” and “cresol novolak resin” have a distribution in the number of nuclei of the novolacs used as raw materials.
  • the binuclear bisphenol F portion is a portion having the following linear polymer structure.
  • the linear polymer means a one-dimensional linear polymer that does not contain a crosslinked structure in the polymer molecule.
  • the polymer of the in-situ polymerizable thermoplastic resin composition containing (A) has a thermoplastic structure, that is, a linear polymer structure resulting from a polyaddition reaction of a bifunctional thiol compound and a bifunctional epoxy resin in the presence of a catalyst.
  • the polymer of the in-situ polymerizable thermoplastic resin composition containing (B) has a thermoplastic structure, that is, a linear polymer structure resulting from a polyaddition reaction of a bifunctional amino compound and a bifunctional epoxy resin in the presence of a catalyst. .
  • the polymer of the in-situ polymerizable thermoplastic resin composition containing (C) has a thermoplastic structure, that is, a linear polymer structure resulting from a polyaddition reaction of a bifunctional carboxy compound and a bifunctional epoxy resin in the presence of a catalyst.
  • the polymer of the in-situ polymerizable thermoplastic resin composition containing (D) is a polyaddition reaction of a bifunctional isocyanate compound and a bifunctional phenol in the presence of a catalyst, and/or a bifunctional isocyanate compound and a bifunctional cresol. It has a thermoplastic structure, that is, a linear polymer structure due to a polyaddition reaction in the presence of a catalyst.
  • a portion of the novolak having three or more nuclear bodies has a complicated structure including a ladder structure and a partial cross-linking structure, so that a structure that can maintain a relatively high heat resistance can be derived.
  • a polymer layer made of the polymer of the in-situ polymerization type thermoplastic resin composition containing the above (A), a polymer layer made of the polymer of the in-situ polymerization type thermoplastic resin composition containing the above (B), the above A polymer layer comprising a polymer of the in-situ polymerizable thermoplastic resin composition containing (C), a polymer layer comprising a polymer of the in-situ polymerizable thermoplastic resin composition containing (D), the (A) to A polymer layer composed of a polymer of an in-situ polymerizable thermoplastic resin composition containing any of (D) and the above (E) differs from a thermosetting resin that is entirely composed of a three-dimensional network with a crosslinked structure.
  • the composite laminate of the present invention comprises an in-situ polymerizable thermoplastic resin composition containing (A), an in-situ polymerizable thermoplastic resin composition containing (B), and an in-situ polymerizable thermoplastic resin composition containing (C) on the surface of the base material.
  • the resin primer layer is produced through a step of forming one or more layers of the resin primer layer by subjecting at least one of the in-situ polymerization type thermoplastic resin compositions to a polyaddition reaction.
  • the method of coating the surface of the substrate with the in-situ polymerizable thermoplastic resin composition is not particularly limited, but examples thereof include a spray coating method and an immersion method.
  • the heating temperature for forming a resin primer layer by polyaddition reaction of the coated in-situ polymerizable thermoplastic resin composition depends on the type of the compound to be reacted, but it is important for ease of operation in in-situ polymerization and composite lamination. From the viewpoint of production efficiency of the body, the temperature is preferably normal temperature to 80°C, more preferably 50 to 80°C, and still more preferably 60 to 80°C. From the same point of view, the heating time is preferably 5 to 90 minutes, more preferably 10 to 80 minutes, even more preferably 15 to 60 minutes.
  • the in-situ polymerization type thermoplastic resin composition contains a solvent
  • after coating the in-situ polymerization type thermoplastic resin composition it is appropriately dried for volatilization of the solvent, and then heated to initiate the polyaddition reaction. preferably.
  • the bifunctional thiol compound in (A) a combination of a bifunctional thiol compound and a phenol novolac epoxy resin and/or a cresol novolak epoxy resin is a compound having two mercapto groups in the molecule, for example, a bifunctional difunctional Class thiol compound 1,4-bis(3-mercaptobutyryloxy)butane (for example, "Karenzu MT (registered trademark) BD1" manufactured by Showa Denko KK) can be mentioned.
  • a tetrafunctional thiol compound may also be used in combination from the viewpoint of increasing the number of crosslinking points.
  • pentaerythritol tetrakis (3-mercaptobutyrate) for example, Showa Denko Co., Ltd. "Karenzu MT (registered trademark) PE1
  • a well-known thing can be used as a phenol novolak-type epoxy resin.
  • Specific examples include YDPN-638 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.) and N-740 (manufactured by DIC Corporation).
  • a known cresol novolac type epoxy resin can also be used.
  • o-cresol novolak type epoxy resins YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704L (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), N-680 (DIC Corporation (manufactured by Changchun Group) and CNE-202 (manufactured by Changchun Group).
  • the bifunctional amino compound in (B) a combination of a bifunctional amino compound and a phenol novolac type epoxy resin and/or a cresol novolac type epoxy resin is a compound having two amino groups, such as a secondary amine amino group.
  • a secondary amine amino group such as piperazine and the like having two are preferred, compounds having two amino groups, which are secondary amines, can also be used. Or it may be an amine having one primary amine with two active hydrogens.
  • Compounds having two amino groups, which are primary amines include bifunctional aliphatic diamines and aromatic diamines.
  • Aliphatic diamines include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine, 2,5-dimethyl-2,5-hexane Diamine, 2,2,4-trimethylhexamethylenediamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminocyclohexane, N-aminoethylpiperazine and the like, and aromatic diamines include includes diaminodiphenylmethane, diaminodiphenylpropane and the like.
  • 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine and the like are preferable from the viewpoint of primer toughness.
  • a well-known thing can be used as a phenol novolak-type epoxy resin. Specific examples include YDPN-638 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.) and N-740 (manufactured by DIC Corporation). A known cresol novolac type epoxy resin can also be used.
  • o-cresol novolak type epoxy resins YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704L (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), N-680 (DIC Corporation (manufactured by Changchun Group) and CNE-202 (manufactured by Changchun Group).
  • the bifunctional carboxy compound in (C) a combination of a bifunctional carboxy compound and a phenol novolac type epoxy resin and/or a cresol novolak type epoxy resin is a compound having two carboxy groups, such as oxalic acid, malonic acid, and succinic acid. , glutaric acid, adipic acid, maleic acid, fumaric acid, isophthalic acid, terephthalic acid, and the like. Among them, isophthalic acid, terephthalic acid, adipic acid, and the like are preferable from the viewpoint of primer strength and toughness.
  • a well-known thing can be used as a phenol novolak-type epoxy resin.
  • Specific examples include YDPN-638 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.) and N-740 (manufactured by DIC Corporation).
  • a known cresol novolac type epoxy resin can also be used.
  • o-cresol novolak type epoxy resins YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704L manufactured by Nippon Steel Chemical & Materials Co., Ltd.
  • N-680 DIC Corporation
  • CNE-202 manufactured by Changchun Group
  • the bifunctional isocyanate compound in (D) a combination of a bifunctional isocyanate compound and a phenol novolac resin and/or a cresol novolac resin is a compound having two isocyanato groups, such as hexamethylene diisocyanate, tetramethylene diisocyanate, dimer acid diisocyanate, Diisocyanate compounds such as 2,4- or 2,6-tolylene diisocyanate (TDI) or mixtures thereof, p-phenylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate (MDI) can be mentioned.
  • TDI 2,4- or 2,6-tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • TDI, MDI, and the like are preferable from the viewpoint of primer strength.
  • phenol novolak resins include BRG-555, BRG-556, BRG-557, BRG-558, and CRG-951 (manufactured by Aica Kogyo Co., Ltd.).
  • Cresol novolac resins include ortho-, meta-, and para-cresol novolacs. Specifically, for example, meta-para-cresol novolak: LF-100, LF-110, LF-120, ortho-cresol novolak: LF-200, para-cresol novolac: LF-400 (manufactured by Lignite Co., Ltd.), and the like. .
  • the compounding ratio of the bifunctional thiol compound and the phenol novolak epoxy resin and/or the cresol novolac epoxy resin in the in situ polymerizable thermoplastic resin composition containing (A) is determined by considering the reactivity of both.
  • the molar equivalent ratio of thiol to epoxy groups is preferably set to 0.7 to 1.5, more preferably 0.8 to 1.4, and still more preferably 0.9 to 1.3. do.
  • the compounding ratio of the bifunctional amino group to the phenol novolak epoxy resin and/or the cresol novolac epoxy resin is determined by considering the reactivity of both.
  • the molar equivalent ratio of amino groups to epoxy groups is preferably set to 0.7 to 1.5, more preferably 0.8 to 1.4, still more preferably 0.9 to 1.3. and
  • the compounding ratio of the bifunctional carboxyl group to the phenol novolak type epoxy resin and/or cresol novolak type epoxy resin is determined in consideration of the reactivity of both.
  • the molar equivalent ratio of carboxy groups to epoxy groups is preferably set to 0.7 to 1.5, more preferably 0.8 to 1.4, and still more preferably 0.9 to 1.3.
  • the compounding ratio of the bifunctional osocyanate and the phenol novolak resin and/or cresol novolak resin is determined by taking into consideration the reactivity of both isocyanato groups relative to the epoxy groups. is preferably set to be 0.7 to 1.5, more preferably 0.8 to 1.4, and still more preferably 0.9 to 1.3.
  • At least one polymer layer of the resin primer layer 3 is selected from the group consisting of the combination of (A), the combination of (B), the combination of (C) and the combination of (D). It consists of a polymer of an in-situ polymerization type thermoplastic resin composition containing any one of them, and the in-situ polymerization type thermoplastic resin composition may contain a mixture of two or more selected from the above group. Here, the mixing ratio is not particularly limited.
  • a known catalyst can be used for the polyaddition reaction.
  • tertiary amines such as triethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; phosphorus compounds such as triphenylphosphine; and the like are preferably used.
  • the amount of the catalyst used is preferably 0.01 with respect to a total of 100 parts by mass of the raw material compounds forming the in-situ polymerization type thermoplastic resin, from the viewpoint of moderate acceleration of the polyaddition reaction. to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass.
  • the in-situ polymerization type thermoplastic resin composition containing at least one selected from the group consisting of the combination of (A), the combination of (B), the combination of (C) and the combination of (D) may contain a solvent from the viewpoint of ease of mixing of composition raw materials and ease of coating of the in-situ polymerization type thermoplastic resin composition.
  • the solvent is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, Cyclohexane, n-hexane, ethanol, methanol and the like are preferably used, but methyl ethyl ketone and tetrahydrofuran are preferably used for improving adhesion to polyvinyl chloride.
  • the in-situ polymerization type thermoplastic resin composition may contain additives such as colorants as necessary in order to form a desired resin coating layer.
  • additives such as colorants as necessary in order to form a desired resin coating layer.
  • 100% by mass of the in-situ polymerization type thermoplastic resin composition (excluding the solvent) 0.1 to It is preferably 5% by mass, more preferably 0.5 to 3% by mass.
  • thermoplastic resin composition containing any of (A) to (D) and (E)
  • the maleic anhydride-modified polyolefin is obtained by grafting maleic anhydride to polyolefin, and includes maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, and the like.
  • maleic anhydride-modified polyethylene maleic anhydride-modified polypropylene, and the like.
  • Kayabrid 002PP, 002PP-NW, 003PP, 003PP-NW manufactured by Kayaku Akzo Co., Ltd. and Modic series manufactured by Mitsubishi Chemical.
  • SCONA TPPP2112GA, TPPP8112GA, and TPPP9212GA manufactured by BYK may also be used together as polypropylene additives functionalized with maleic anhydride.
  • Toyobo Hardren registered trademark
  • 13-LP As chlorinated polyolefins, Toyobo Hardren (registered trademark) 13-LP, 13-LLP, 15-LP, Nippon Paper Industries Co., Ltd.
  • Superchron registered trademark 814HS, 390S, 803LT (toluene solution), 803L (toluene solution ), 1026 (toluene solution), and the like.
  • the amount of (E) added to (A) to (D) is the total of (A) to (D) (E) is preferably 5 to 200 parts by mass (solid content), more preferably 20 to 100 parts by mass (solid content), with respect to 100 parts by mass (solid content). If the amount added is less than 5 parts by mass, bonding with polyolefin will not be possible, and if the amount exceeds 200 parts by mass, sufficient bonding strength with polyvinyl chloride will not be exhibited. Further, when the maleic anhydride-modified polyolefin is added, the reaction may proceed at room temperature to 150°C.
  • thermosetting resin When the resin primer layer consists of a plurality of layers, at least one of the layers is a layer formed from a cured product of a resin composition containing a thermosetting resin (hereinafter also referred to as a "thermosetting resin layer"). It is also preferable that examples of the thermosetting resin include allyl-modified maleimide resin, urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin. Each layer of the thermosetting resin layer may be formed of one of these resins alone, or may be formed of a mixture of two or more. Alternatively, two or more layers may be thermosetting resin layers of different types.
  • the surface of the substrate preferably has a surface-treated surface. Since the resin primer layer is formed on the surface-treated surface of the base material, it can be easily and firmly adhered to the base material.
  • Examples of the surface treatment include cleaning with a solvent or the like, degreasing treatment, blasting treatment, polishing treatment, etching treatment, chemical conversion treatment, and the like. These treatments may be used alone or in combination of two or more. Among these, it is preferable that the surface be subjected to at least one surface treatment selected from the group consisting of plasma treatment, corona discharge treatment, UV ozone treatment, blasting treatment, polishing treatment, etching treatment and chemical conversion treatment.
  • the surface treatment is performed by cleaning the surface of the base material, generating hydroxyl groups on the surface, or by the anchor effect of forming fine unevenness (roughening) on the surface. This is done for the purpose of improving the adhesion of the primer layer.
  • the properties of the surface of the base material surface-treated by the above-described method may change from that immediately after the surface treatment due to the formation of a resin primer layer or the like on the surface-treated surface. . For this reason, it is considered impossible or impractical to specify and express the properties of the surface of the surface-treated substrate in the composite laminate. Therefore, in the present invention, the surface of the substrate that has undergone surface treatment is specified by the surface treatment method.
  • Various treatments of the surface treatment can be performed by known methods. As a specific treatment method, for example, the following method can be used.
  • the cleaning or degreasing treatment with a solvent or the like includes, for example, a method of cleaning the surface of the base material with an organic solvent such as acetone or toluene or wiping the surface for degreasing.
  • blasting examples include shot blasting and sandblasting.
  • polishing treatment examples include buffing using an abrasive cloth, roll polishing using abrasive paper (sandpaper), electropolishing, and the like.
  • Examples of the etching treatment when the substrate is aluminum include chemical etching treatments such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, an iron salt method, and an electrolytic etching method. and other electrochemical etching treatments.
  • the etching treatment is preferably an alkali method using an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and particularly preferably a caustic soda method using an aqueous sodium hydroxide solution.
  • the alkali method for example, the aluminum substrate can be immersed in an aqueous solution of sodium hydroxide or potassium hydroxide having a concentration of 3 to 20% by mass at 20 to 70° C. for 1 to 15 minutes.
  • a chelating agent, an oxidizing agent, a phosphate, or the like may be added. After the immersion, it is preferable to neutralize (desmut) with a 5 to 20% by mass nitric acid aqueous solution or the like, wash with water, and dry.
  • the chemical conversion treatment is to form a chemical conversion film mainly on the surface of the substrate.
  • Examples of the chemical conversion treatment applied when the substrate is made of an aluminum material include boehmite treatment and zirconium treatment, with boehmite treatment being particularly preferred. It is also preferable that the chemical conversion treatment be performed after the etching treatment.
  • the boehmite treatment is carried out, for example, by treating an aluminum substrate with hot water of about 90 to 100° C. to form a boehmite (aluminum hydrated oxide) film on the surface of the substrate.
  • a reaction accelerator ammonia, triethanolamine, or the like may be added to water.
  • boehmite treatment can be performed by immersing an aluminum substrate in hot water of 90 to 100° C. containing triethanolamine at a concentration of 0.1 to 5.0% by mass for 3 seconds to 5 minutes.
  • baking is preferably performed after the treatment with hot water or the like, in order to form a good boehmite film.
  • the zirconium treatment is carried out, for example, by immersing an aluminum base material in a zirconium salt-containing liquid such as zirconium phosphate to form a zirconium compound film on the surface of the base material.
  • a zirconium salt-containing liquid such as zirconium phosphate
  • an aluminum substrate is immersed in a solution of a chemical conversion agent for zirconium treatment such as "Palcoat 3762" or "Palcoat 3796" (manufactured by Nihon Parkerizing Co., Ltd.) at 45 to 70°C for 0.5 to 3 minutes.
  • a chemical conversion agent for zirconium treatment such as "Palcoat 3762" or "Palcoat 3796" (manufactured by Nihon Parkerizing Co., Ltd.) at 45 to 70°C for 0.5 to 3 minutes.
  • zirconium treatment can also be performed.
  • the surface treatment When surface treatment is applied to a substrate made of an aluminum material, the surface treatment preferably includes one or more selected from the group consisting of etching treatment and boehmite treatment.
  • FIG. 2 shows another preferred embodiment of the composite laminate of the present invention.
  • the composite laminate 1 shown in FIG. 2 has a functional group-introduced layer 4 laminated between a substrate 2 made of metal (hereinafter referred to as a metal substrate) and a resin coating layer 3 in contact with both.
  • the functional group-introduced layer has a structure derived from one or more functional groups selected from the group consisting of (C1) to (C7) below.
  • the structure derived from the functional group in the functional group-introduced layer chemically bonds with each of the metal substrate and the resin coating layer laminated in contact with the functional group-introduced layer, whereby the metal substrate and the resin It becomes easier to adhere firmly to the coating layer.
  • the functional group-introduced layer can also contribute to improving the bonding strength between the surface of the composite laminate on the resin coating layer side and the resin material.
  • the functional group-introduced layer has a structure derived from the functional groups (C1) to (C7) is confirmed by analysis immediately after the functional group-introduced layer is formed on the surface of the metal substrate. In some cases, it is possible, but in the obtained composite laminate, the structure derived from these functional groups is changed by chemically bonding with the resin coating layer, and the presence of the group or structure in the functional group-introduced layer It is impossible or impractical to ascertain Therefore, in the present invention, the functional group-introduced layer is formed on the basis of the functional groups possessed by the silane coupling agent and/or other compounds capable of generating structures derived from the functional groups (C1) to (C7). We will specify the configuration.
  • the functional group-introduced layer is preferably laminated on the surface of the metal substrate that has undergone the surface treatment described above. That is, it is preferable that the metal substrate be subjected to the surface treatment before forming the functional group-introduced layer.
  • the synergistic effect of the surface treatment and the chemical bond provided by the functional group-introduced layer facilitates strong adhesion between the metal substrate and the resin coating layer. Also, the bonding strength between the surface of the composite laminate on the resin coating layer side and the resin material can be improved.
  • the functional group-introduced layer is formed by treating the surface of the substrate with one or more selected from the group consisting of (c1) to (c7) below before forming the resin coating layer.
  • (c1) a silane coupling agent having one or more functional groups selected from the group consisting of an amino group, a mercapto group, a (meth)acryloyl group, an epoxy group and an isocyanato group; and (c2) a silane coupling agent having an amino group.
  • a combination with an epoxy compound (c3) one selected from the group consisting of a silane coupling agent having a mercapto group, an epoxy compound, an isocyanate compound, an epoxy-modified (meth)acrylate compound, and an amino group-containing (meth)acrylate compound Combination with the above compounds (c4)
  • Combination of a silane coupling agent having a (meth) acryloyl group and a thiol compound (c5)
  • a silane coupling agent having an epoxy group, an amine compound, a thiol compound and an amino group-containing Combination with one or more compounds selected from the group consisting of meth)acrylate compounds (c6) isocyanate compound (c7) thiol compound
  • (c1) to (c7) correspond to the respective groups or structures of (C1) to (C7) formed therefrom, respectively. That is, the treatment by (c1) forms a functional group-introduced layer into which the group of (C1) is introduced, and the treatment by (c2) forms a functional group-introduced layer into which the structure of (C2) is introduced. to form.
  • the treatment (c2) when the amino group is reacted with a polyfunctional epoxy compound, an epoxy group, which is a functional group possessed by the polyfunctional epoxy compound, is introduced at the end.
  • an isocyanato group which is a functional group possessed by the polyfunctional isocyanate compound, is introduced to the terminal.
  • the method for forming the functional group-introduced layer is not particularly limited. can be formed by coating with the coating method of For example, a metal substrate 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. method.
  • silane coupling agent for example, known agents used in surface treatment of glass fibers can be applied.
  • these functional groups react with functional groups of compounds other than the silane coupling agent used to form the functional group-introduced layer to produce functional groups that are compatible with the compound forming the resin coating layer. obtain. Therefore, in each of the treatments (c2) to (c5), it is preferable to treat the surface of the metal substrate with the silane coupling agent and then with a compound other than the silane coupling agent.
  • the silicon coupling agent is preferably used as a compound forming the functional group-introduced layer in order to firmly bond the metal substrate and the resin coating layer through the functional group-introduced layer.
  • the silane coupling agent is not particularly limited, but has one or more functional groups selected from the group consisting of an amino group, a mercapto group, a (meth)acryloyl group, an epoxy group and an isocyanato group. preferable. These silane coupling agents may be used singly or in combination of two or more.
  • Those having an amino group include, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2 -Aminopropyltrimethoxysilane hydrochloride and the like.
  • mercapto groups include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
  • Those having a (meth)acryloyl group include, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri ethoxysilane and the like.
  • Those having an epoxy group include, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyltrimethoxysilane, 3-glycid xypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.
  • Those having an isocyanato group include, for example, 3-isocyanatopropyltriethoxysilane.
  • the thiol compound in (c4), (c5) or (c7) is a compound other than the silane coupling agent.
  • the mercapto group of the thiol compound is likely to bond with the surface of the metal substrate, particularly with the hydroxyl group generated by surface treatment. Further, when used in combination with the silicon coupling agent, it reacts with a functional group such as a (meth)acryloyl group or an epoxy group derived from the silane coupling agent to form the resin coating layer on the surface of the metal substrate.
  • a thiol compound is preferably used as a compound forming the functional group-introduced layer in order to firmly bond the metal substrate and the resin coating layer through the functional group-introduced layer.
  • the thiol compound is not particularly limited. Trademark) QE-340M” (manufactured by Toray Fine Chemicals Co., Ltd.); ether-based primary thiol compound: “Cupcure (registered trademark) 3-800” (manufactured by Cognis); 1,4-bis(3-mercaptobutyric Ryloxy) butane: "Karenzu MT BD1” (manufactured by Showa Denko KK), pentaerythritol tetrakis (3-mercaptobutyrate): "Karenzu MT PE1" (manufactured by Showa Denko KK); 1,3,5-tris ( 3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione: "Karenzu MT NR1” (manufactured by Showa Denko KK) and the like. These thiol compounds may be used
  • the isocyanate compound in (c3) or (c6) is a compound other than the silane coupling agent.
  • the isocyanato group of the isocyanate compound is likely to bond with the surface of the metal base material, particularly with the hydroxyl group generated by the surface treatment. Further, when used in combination with the silicon coupling agent, it reacts with functional groups such as mercapto groups derived from the silane coupling agent, and is compatible with the compound that forms the resin coating layer on the surface of the metal substrate. can give rise to sensitive functional groups. Therefore, the isocyanate compound is preferably used as a compound forming the functional group-introduced layer in order to firmly bond the metal substrate and the resin coating layer through the functional group-introduced layer.
  • isocyanate compound examples include, but are not limited to, polyfunctional isocyanates such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), and isophorone diisocyanate (IPDI); Isocyanatoethyl methacrylate: "Karenzu MOI®", 2-isocyanatoethyl acrylate: “Karenzu AOI®” and “AOI-VM®”, 1,1-(bisacryloyloxyethyl) ethyl isocyanate : isocyanate compounds having a radical reactive group such as "Karenzu BEI (registered trademark)" (manufactured by Showa Denko KK). The said isocyanate compound may be used individually by 1 type, or may use 2 or more types together.
  • polyfunctional isocyanates such as diphenylmethane diisocyanate (MDI), he
  • the epoxy compound in (c2) or (c3) is a compound other than the silane coupling agent.
  • the epoxy group of the epoxy compound reacts with a functional group derived from the silane coupling agent, such as an amino group or a mercapto group, to produce a functional group that is compatible with the compound that forms the resin coating layer on the surface of the metal substrate.
  • a functional group derived from the silane coupling agent such as an amino group or a mercapto group
  • an epoxy compound is preferably used as a compound forming the functional group-introduced layer in order to firmly bond the metal substrate and the resin coating layer through the functional group-introduced layer.
  • the epoxy compound a known epoxy compound can be used, and a polyfunctional epoxy compound or a compound having an alkenyl group in addition to the epoxy group is preferable.
  • the epoxy compound include allyl glycidyl ether, 1,6-hexanediol diglycidyl ether, and bifunctional epoxy resins.
  • Alicyclic epoxy compounds may also be used, such as 1,2-epoxy-4-vinylcyclohexane: "Celoxide (registered trademark; hereinafter the same.) 2000", 3',4'-epoxycyclohexylmethyl-3,4-epoxy Cyclohexane carboxylate: "Celoxide 2021P” (manufactured by Daicel Corporation) and the like. These epoxy compounds may be used singly or in combination of two or more.
  • the amine compound in (c5) is a compound other than the silane coupling agent.
  • the amino group of the amine compound reacts with a functional group such as an epoxy group derived from the silane coupling agent to generate a functional group that is compatible with the compound that forms the resin coating layer on the surface of the metal substrate. Therefore, the amine compound is preferably used as a compound forming the functional group-introduced layer in order to firmly bond the metal substrate and the resin coating layer through the functional group-introduced layer.
  • amine compound a known amine compound or the like can be used, and amine compounds having two or more amino groups in one molecule and compounds having an alkenyl group in addition to an amino group (including an amide group) can be used.
  • amino compounds include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, hexamethylenediamine, 2,5-dimethyl-2,5-hexanediamine, 2, 2,4-trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4-aminomethyloctamethylenediamine, 3,3′-iminobis(propylamine), 3,3′-methylimino bis(propylamine), bis(3-aminopropyl)ether, 1,2-bis(3-aminopropyloxy)ethane, mensendiamine, isophoronediamine
  • Epoxy-modified (meth)acrylate compound The epoxy-modified (meth)acrylate compound in (c3) is a compound other than the silane coupling agent and has an epoxy group and a (meth)acryloyl group. Therefore, by reacting with a functional group such as a mercapto group derived from the silane coupling agent, a functional group that is easily compatible with the compound that forms the resin coating layer can be generated on the surface of the metal substrate. Therefore, the epoxy-modified (meth)acrylate compound is preferably used as a compound for forming the functional group-introduced layer in order to firmly bond the metal substrate and the resin coating layer through the functional group-introduced layer. be done.
  • epoxy-modified (meth)acrylate compound examples include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl methacrylate: "Cychromer (registered trademark) M100", and (c2) and (c3) described above.
  • Cychromer registered trademark
  • a compound obtained by (meth)acryloylating a part of the polyfunctional epoxy compound in is mentioned.
  • These epoxy-modified (meth)acrylate compounds may be used singly or in combination of two or more.
  • the amino group-containing (meth)acrylate compound in (c3) or (c5) is a compound other than the silane coupling agent and has an amino group and a (meth)acryloyl group. Therefore, by reacting with a functional group such as a mercapto group or an epoxy group derived from the silane coupling agent, a functional group that is easily compatible with the compound forming the resin coating layer can be generated on the surface of the metal substrate. Therefore, the amino group-containing (meth)acrylate compound is suitable as a compound for forming the functional group-introduced layer in order to firmly bond the metal substrate and the resin coating layer through the functional group-introduced layer. Used.
  • amino group-containing (meth)acrylate compound examples include (meth)acrylamide, and part of the amine compound having two or more amino groups in one molecule in (c5) described above is (meth)acryloylated. and the like. These amino group-containing (meth)acrylate compounds may be used singly or in combination of two or more.
  • FIG. 3 shows one embodiment of the conjugate of the present invention.
  • the substrate-resin bonded body 10 shown in FIG. 3 is obtained by joining and integrating the resin primer layer side surface of the composite laminate 1 and the resin material 5 . That is, the base material 2 and the resin material 5 are joined and integrated through the resin primer layer 3 .
  • the resin primer layer 3 on the surface of the composite laminate 1 can be formed under low-temperature conditions that do not affect resin with low heat resistance such as deformation, and can be welded and integrated under the low-temperature conditions, resulting in high bonding strength. Therefore, a substrate-resin bonded body having excellent workability can be obtained.
  • the base material 2 is a resin base material
  • a resin-resin bonded body is obtained
  • the base material 2 is a metal base material
  • a base-resin bonded body is obtained.
  • the resin material to be joined with the composite laminate is not particularly limited, and may be a general synthetic resin.
  • the resin primer layer of the composite laminate can exhibit high bonding strength even under low-temperature conditions that do not affect resin with low heat resistance such as deformation, so it can be suitably used even with resins with low heat resistance. .
  • resins with low heat resistance examples include thermoplastic resins such as polyvinyl chloride, polyethylene, and polypropylene, as well as thermoplastic resins reinforced with glass fibers and carbon fibers.
  • thermoplastic resins such as polyvinyl chloride, polyethylene, and polypropylene
  • thermoplastic resins reinforced with glass fibers and carbon fibers are used.
  • pipes used for infrastructure are used. It is also suitable for use in connecting metal and resin, and is useful for connecting resin pipes and metal pipes, for example.
  • the joined body of the present invention can also be obtained by joining the composite laminates of the present invention through at least one resin primer layer.
  • the base material 2 of each composite laminate is a resin base material
  • a resin-resin bonded body is obtained
  • the base material 2 of each composite laminate is a metal base material
  • a metal-resin bonded body is obtained
  • one of the substrates 2 of each composite laminate is a resin substrate and the other is a metal substrate
  • a metal-resin bonded body is obtained.
  • the thickness of the resin primer layer depends on the material to be bonded to the resin primer layer and the contact area of the bonded portion, but from the viewpoint of sufficient bonding strength and heat resistance, it is preferably 1 ⁇ m to 1 mm, more preferably 2 ⁇ m to 500 ⁇ m. , more preferably 5 ⁇ m to 100 ⁇ m.
  • the bonded body can be obtained by welding a resin material, a metal substrate, or another composite laminate to the resin primer layer of the composite laminate. Specifically, for example, they can be joined and integrated by thermal welding, ultrasonic welding, high-frequency induction welding, high-frequency dielectric welding, injection molding, and press molding.
  • the welding methods include heat welding, ultrasonic welding, high-frequency induction welding, high-frequency dielectric welding, and injection molding, as well as various welding methods such as vibration welding, spin welding, laser welding, hot air welding, and hot plate welding. is also mentioned.
  • the resin primer layer of one composite laminate is attached to the resin primer layer of the other composite laminate.
  • the non-bonded substrate surfaces may be welded together.
  • a primer film can be used in place of the resin primer layer.
  • the primer film means a film that functions as an adhesive layer between the base material A and the base material B.
  • a primer film made of at least one selected from the group consisting of a polymer of a plastic resin composition is prepared, and between a base material A made of metal or resin and a base material B made of metal or resin, The base material A and the base material B can be joined and integrated
  • A a combination of a bifunctional thiol compound and a phenol novolak-type epoxy resin and/or a cresol novolac-type epoxy resin
  • B a combination of a bifunctional amino compound and a phenol novolak-type epoxy resin and/or a cresol novolac-type epoxy resin
  • C a combination of a bifunctional carboxy compound and a phenol novolak type epoxy resin and/or a cresol novolak type epoxy resin
  • D a combination of a difunctional isocyanate compound and a phenol novolak resin and/or a cresol novolak resin
  • E Maleic anhydride-modified polyolefin and/or chlorinated polyolefin
  • the method for joining and integrating is selected from the group consisting of high-frequency induction welding, high-frequency dielectric welding, ultrasonic welding, laser welding, heat welding, injection welding, and press welding. It is preferable that at least one method is used.
  • [Metal substrate] ⁇ Aluminum plate: aluminum alloy; Al-Mg-Si system A6063, 18 mm ⁇ 45 mm, thickness 1.5 mm ⁇ Steel: Steel plate, SPHC (JIS G 3131: 2018), 18 mm x 45 mm, thickness 1.6 mm ⁇ SUS304 plate: Stainless steel SUS304 (Cr-Ni system), 18 mm ⁇ 45 mm, thickness 1.5 mm
  • Resin base material ⁇ Takiron C.I. Vinyl chloride plate Product number: ESS8800A, 10mm x 45mm, thickness 2.0mm ⁇ Sekisui Seisaku Kogyo Co., Ltd.
  • the aluminum test piece subjected to the etching treatment was prepared by dissolving 2 g of 3-aminopropyltrimethoxysilane (silane coupling agent "KBM-903" (manufactured by Shin-Etsu Silicone Co., Ltd.)) in 1000 g of industrial ethanol. After being immersed for 20 minutes in a solution containing a silane coupling agent at °C, the metal test piece was taken out and dried to perform a functional group imparting treatment to obtain an aluminum test piece to which a functional group was imparted.
  • ⁇ Steel plate, SUS-304 plate> The steel plate and SUS-304 plate used to manufacture the test pieces were degreased with acetone and subjected to surface treatment.
  • In-situ polymerizable thermoplastic resin compositions (1) to (9) were prepared as follows using the composition raw materials shown in Table 1 below.
  • thermoplastic resin composition (2) o-cresol novolac type epoxy resin "YDCN-704N" (manufactured by Nippon Steel Chemical & Materials Co., Ltd.) 100 g, 100 g, bifunctional thiol compound: 1,4-bis(3-mercaptobutyryloxy)butane "Karenzu MT BD1" (manufactured by Showa Denko Co., Ltd.) 35.6 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30) 0.54 g was dissolved in 252 g of methyl ethyl ketone to prepare an in-situ polymerization type thermoplastic resin composition (2). made.
  • thermoplastic resin composition (3) 100 g of hexamethylene diisocyanate (HDI) (manufactured by Tokyo Chemical Industry Co., Ltd.), 125.0 g of BRG-556 "Shaunol BRG-556" (manufactured by Aica Kogyo Co., Ltd.), and 0.90 g of triphenylphosphine were dissolved in 418 g of methyl ethyl ketone.
  • a polymerizable thermoplastic resin composition (3) was prepared.
  • thermoplastic resin composition (4) 100 g of hexamethylene diisocyanate (HDI) (manufactured by DIC Corporation), 113.1 g of ortho-cresol novolac resin "LF-200" (manufactured by Lignite Corporation), and 0.85 g of triphenylphosphine were dissolved in 396 g of methyl ethyl ketone to form an on-site polymerization type thermoplastic.
  • a resin composition (4) was prepared.
  • thermoplastic resin composition (6) o-Cresol novolak type epoxy resin "YDCN-704N" (manufactured by Nippon Steel Chemical & Materials Co., Ltd.) 100g, 100g, piperazine 41.0g, triphenylphosphine 0.56g dissolved in methyl ethyl ketone 262g to make an on-site polymerization type thermoplastic resin composition Item (6) was produced.
  • thermoplastic resin composition (7) 100 g of phenolic novolac type epoxy resin "N-740" (manufactured by DIC Corporation), 46.1 g of terephthalic acid, and 0.58 g of triphenylphosphine were dissolved in 271 g of methyl ethyl ketone to prepare an in-situ polymerization type thermoplastic resin composition (7). .
  • thermoplastic resin composition (8) In situ polymerization type thermoplastic resin composition (8)> In a solution of 10 g of maleic anhydride-modified polypropylene "Modic (registered trademark) ER321P" (manufactured by Mitsubishi Chemical Corporation) dissolved in 190 g of xylene, 6.0 g of the in-situ polymerization type thermoplastic resin composition (1) was mixed, A polymerizable thermoplastic resin composition (8) was prepared.
  • thermoplastic resin composition (9) In situ polymerization type thermoplastic resin composition (9)> In a solution of 10 g of chlorinated polypropylene "Superchron (registered trademark) 814HS" (manufactured by Nippon Paper Industries Co., Ltd.) dissolved in 190 g of xylene, 6.0 g of the in-situ polymerizable thermoplastic resin composition (2) was mixed and polymerized in situ. A type thermoplastic resin composition (9) was prepared.
  • thermoplastic resin compositions (1) to (9) were spray-coated onto each substrate so that the thickness after drying was 10 to 60 ⁇ m. After leaving it in the air at room temperature for 30 minutes to evaporate the solvent, it was left in a furnace at 70° C. for 30 minutes to cause a polyaddition reaction (only the in-situ polymerization type thermoplastic resin composition (7) was 6 hours). , and allowed to cool to room temperature to produce a composite laminate in which a resin primer layer was laminated on the surface of the base material. Table 2 shows the produced composite laminate.
  • Examples 37-46> Heat welding
  • the resin primer layer of the composite laminate (A) formed by forming the resin primer layer on the resin base material and the resin base material (C) were bonded together so that the joint portion was 1.0 cm x 0.5 cm. After being placed on top of each other so as to be 5 cm long, it was sandwiched with a double clip and allowed to stand in a drying oven at 75° C. for 5 minutes.
  • Examples 47 to 50> (Preparation of film for primer) In-situ polymerization type thermoplastic resin compositions (1), (3), and (8) are applied to a release film (PTFE film) so that the thickness after drying is 40 ⁇ m, and left at room temperature for 30 minutes. After volatilizing the solvent, the polymerization reaction was carried out at 80 ° C. for 30 minutes, and the temperature was returned to normal temperature and peeled off from the release film (PTFE film). ).
  • a primer film was sandwiched between the resin base material (A) and the resin base material (B) so that the joint area was 1.0 cm ⁇ 0.5 cm. After standing in the oven for 5 minutes, it was returned to room temperature.
  • a resin substrate (A) and a resin substrate are bonded using AV adhesive 32 manufactured by Asahi Organic Chemicals Co., Ltd., a vinyl chloride pipe adhesive manufactured by Cemedine Co., Ltd., and Cemedine PPX for PE and PP, which are commercially available adhesives for vinyl chloride.
  • the material (B) was applied and pasted together so that the joint area was 1.0 cm ⁇ 0.5 cm to prepare resin-resin joints (Comparative Examples 7 to 11).
  • Nominal diameter 40 polyvinyl chloride pipe VU40 manufactured by Kubota Chemix (outer diameter 48 mm, length 25 cm), 25 mm from the end, the in-situ polymerization type thermoplastic resin composition (1) is applied to the outer circumference to a thickness of 40 ⁇ m after drying. I sprayed it to make it look like it was. After leaving it in the air at room temperature for 30 minutes to volatilize the solvent, leave it in a furnace at 80 ° C. for 30 minutes to cause a polyaddition reaction, allow to cool to room temperature, and produce a polyvinyl chloride tube with a resin primer layer. formed.
  • the primer-applied part of the polyvinyl chloride pipe with the resin primer layer was pushed into a polyvinyl chloride cap with a nominal diameter of 40, and the joint part was heated for 3 minutes using a dryer.
  • the surface temperature reached 80°C in 2 minutes and was held for 1 minute.
  • the end was connected to a water pipe and a water pressure of 0.6 MPa was applied to check for leakage, and it was confirmed that there was no leakage.
  • Nominal diameter 40 polyvinyl chloride pipe VU40 manufactured by Kubota Chemix (outer diameter 48 mm, length 25 cm) was coated with an adhesive for vinyl chloride pipe manufactured by Cemedine Co., Ltd. on the outer periphery 25 mm from the end. Next, the adhesive coated portion of the polyvinyl chloride pipe with the resin primer layer was pushed into a polyvinyl chloride cap with a nominal diameter of 40 and left for 3 minutes. After 5 minutes, the end was connected to a water pipe and a water pressure of 0.6 MPa was applied to check for leakage.
  • the composite laminate of the present invention is joined and integrated with other materials or parts such as steel, aluminum, CFRP, etc., for example, door side panels, hoods, roofs, tailgates, steering hangers, A pillars, B pillar, C pillar, D pillar, crash box, power control unit (PCU) housing, electric compressor parts (inner wall, intake port, exhaust control valve (ECV) insertion part, mount boss, etc.), lithium ion battery ( LIB) It can be used as various automotive parts such as spacers, battery cases, and LED headlamps.
  • PCU power control unit
  • ECV exhaust control valve
  • LIB lithium ion battery
  • the composite laminate is, for example, by joining and integrating with a resin material such as nylon, polyphenylene sulfone, polyetherimide molding, etc., so that the metal-resin bonded body is required to have higher heat resistance. It is also expected to be used in fields such as parts and aerospace parts. However, the uses of the composite laminate are not limited to these exemplified uses.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un stratifié composite comprenant un matériau de base formé d'un métal ou d'une résine, et une ou plusieurs couches d'apprêt en résine stratifiées sur une surface du matériau de base, au moins l'une des couches d'apprêt en résine étant au moins une couche de polymère choisie dans le groupe constitué de couches de polymère chacune formée d'un polymère d'une composition de résine thermoplastique de type à polymérisation in situ qui contient les éléments (A) suivants, des couches de polymère formées chacune d'un polymère d'une composition de résine thermoplastique de type polymérisation in situ qui contient les éléments (B) suivants, des couches de polymère formées chacune d'un polymère d'une composition de résine thermoplastique de type polymérisation in situ qui contient les éléments (C) suivants, des couches de polymère formées chacune d'un polymère d'une composition de résine thermoplastique de type polymérisation in situ qui contient les éléments (D) suivants, et des couches de polymère formées chacune d'un polymère d'une composition de résine thermoplastique de type polymérisation in situ qui contient les éléments (E) suivants et l'un quelconque de (A)- (D), et ladite couche de polymère étant disposée au niveau de la surface la plus à l'extérieur. (A) Une combinaison entre un composé thiol bifonctionnel et une résine époxy de type novolaque phénolique et/ou une résine époxy de type novolaque de crésol. (B) Une combinaison entre un composé amino bifonctionnel et une résine époxy de type novolaque phénolique et/ou une résine époxy de type novolaque de crésol. (C) Une combinaison entre un composé carboxy bifonctionnel et une résine époxy de type novolaque phénolique et/ou une résine époxy de type novolaque de crésol. (D) Une combinaison entre un composé isocyanate bifonctionnel et une résine novolaque phénolique et/ou une résine novolaque de crésol. (E) Une polyoléfine modifiée par un anhydride maléique et/ou une polyoléfine chlorée.
PCT/JP2022/007818 2021-02-26 2022-02-25 Stratifié composite et corps assemblé WO2022181754A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000143942A (ja) * 1998-11-13 2000-05-26 Toto Kasei Co Ltd 合成樹脂用難燃剤及び難燃性樹脂組成物
JP2001348419A (ja) * 2000-06-06 2001-12-18 Nagase Chemtex Corp リサイクル可能なエポキシ樹脂組成物
US20100044914A1 (en) * 2004-05-21 2010-02-25 Minh-Tan Ton-That Primer composition and uses thereof
JP2011126942A (ja) * 2009-12-15 2011-06-30 Toyota Motor Corp ホットメルト型接着剤及びｒｔｍ成形方法
JP2013533338A (ja) * 2010-06-08 2013-08-22 ヘンケル コーポレイション デュアル硬化接着剤
JP2020202349A (ja) * 2019-06-13 2020-12-17 昭和電工株式会社 電子基板筐体及びその製造方法
WO2021024978A1 (fr) * 2019-08-06 2021-02-11 昭和電工株式会社 Élément en résine thermoplastique équipé d'un apprêt, et conjugué résine-résine

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000143942A (ja) * 1998-11-13 2000-05-26 Toto Kasei Co Ltd 合成樹脂用難燃剤及び難燃性樹脂組成物
JP2001348419A (ja) * 2000-06-06 2001-12-18 Nagase Chemtex Corp リサイクル可能なエポキシ樹脂組成物
US20100044914A1 (en) * 2004-05-21 2010-02-25 Minh-Tan Ton-That Primer composition and uses thereof
JP2011126942A (ja) * 2009-12-15 2011-06-30 Toyota Motor Corp ホットメルト型接着剤及びｒｔｍ成形方法
JP2013533338A (ja) * 2010-06-08 2013-08-22 ヘンケル コーポレイション デュアル硬化接着剤
JP2020202349A (ja) * 2019-06-13 2020-12-17 昭和電工株式会社 電子基板筐体及びその製造方法
WO2021024978A1 (fr) * 2019-08-06 2021-02-11 昭和電工株式会社 Élément en résine thermoplastique équipé d'un apprêt, et conjugué résine-résine

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