WO2014157289A1 - Corps lié métal/résine, et procédé de fabrication de celui-ci - Google Patents

Corps lié métal/résine, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2014157289A1
WO2014157289A1 PCT/JP2014/058435 JP2014058435W WO2014157289A1 WO 2014157289 A1 WO2014157289 A1 WO 2014157289A1 JP 2014058435 W JP2014058435 W JP 2014058435W WO 2014157289 A1 WO2014157289 A1 WO 2014157289A1
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WIPO (PCT)
Prior art keywords
resin
metal
oxygen
film
containing film
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PCT/JP2014/058435
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English (en)
Japanese (ja)
Inventor
正憲 遠藤
令子 高澤
みゆき 吉田
秀水 近藤
敦子 石田
三典 松島
亮太 高橋
Original Assignee
日本軽金属株式会社
ポリプラスチックス株式会社
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Application filed by 日本軽金属株式会社, ポリプラスチックス株式会社 filed Critical 日本軽金属株式会社
Priority to JP2015508577A priority Critical patent/JP6017675B2/ja
Priority to CN201480017983.8A priority patent/CN105073375B/zh
Priority to KR1020157030218A priority patent/KR102016783B1/ko
Publication of WO2014157289A1 publication Critical patent/WO2014157289A1/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
    • B29C45/14311—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 using means for bonding the coating to the 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts

Definitions

  • the present invention relates to a metal resin joined body in which a metal base material made of metal and a resin molded body made of a thermoplastic resin are integrally and firmly joined by injection molding or thermocompression bonding of a thermoplastic resin, and a method for manufacturing the same. .
  • the present inventors have already made an aluminum / resin injection integrated molded product in which an aluminum shaped body and a resin molded body are already locked together by a concave portion of an aluminum material and a fitting portion of a thermoplastic resin.
  • Patent Document 1 an aluminum alloy member excellent in resin bondability characterized by having a convex portion made of silicon crystal
  • Patent Document 2 an aluminum alloy member excellent in resin bondability characterized by having a convex portion made of silicon crystal
  • a technique for integrating an aluminum alloy material and a thermoplastic resin composition obtained through a pretreatment immersed in one or more aqueous solutions selected from ammonia, hydrazine, and a water-soluble amine compound by injection molding (Patent Documents 3 and 4), an aqueous solution of triazine dithiols, or a solution using various organic solvents as a solvent is used as an electrodeposition solution, and after the electrochemical surface treatment of the metal, the metal after the surface treatment (Patent Document 5) that joins rubber and plastic has been proposed. Further, an adhesive is applied on a metal plate, or an organic film is formed by surface treatment, and then injection molding is performed.
  • Technology for integrating metal and resin (Patent Document 6), or treating the surface of the metal with an acid or alkali and then treating with a silane coupling agent, followed by injection molding Techniques for joining the (Patent Document 7) have been proposed respectively.
  • Patent Document 8 a technique for injecting a thermoplastic resin onto the surface of a metal on which a microporous hydroxyl group-containing film is formed and integrating the metal and the thermoplastic resin through the film
  • Patent Document 9 polyarylene A technique
  • a metal terminal or the like is inserted and joined using a resin material mainly composed of a sulfide resin and a specific olefin copolymer and an inorganic filler blended therein.
  • Patent Document 1 and Patent Document 2 the present inventors have so far proposed a physical bonding mainly based on the fitting of the anchor effect, and a special treatment in which halogen ions are contained in the treatment bath as the technique.
  • a method by a simple etching process has been proposed. Although these methods have no problem in performance such as bonding strength and airtightness of the bonded portion, gas derived from halogen is generated during this etching process, and the surrounding metal parts and equipment are not corroded. There was another issue of having to take measures to prevent polluting the environment.
  • Patent Document 8 describes the anchor effect and chemical action of a porous hydroxyl group-containing film, and the effect of using a thermoplastic resin composition to which a thermoplastic elastomer is added.
  • Patent Document 9 discloses polyarylene sulfide resin. However, it is not clear about the effect on the bonding strength and adhesion by combining the metal surface treatment and the functional group of the resin composition. there were.
  • an oxygen-containing film containing oxygen is formed on the surface of a metal substrate by intentionally increasing the oxygen content.
  • an additive compound having a specific functional group that reacts with the oxygen-containing film is added to the thermoplastic resin composition.
  • an object of the present invention is to provide a metal-resin joint that exhibits excellent metal-resin bond strength and that does not cause a decrease in strength after a durability test and that can maintain excellent metal-resin bond strength over a long period of time. To provide a body.
  • the present invention includes a metal substrate made of metal, an oxygen-containing film containing oxygen formed by intentionally increasing the oxygen content on the surface of the metal substrate, and the oxygen-containing film.
  • the thermoplastic resin composition contains an additive compound having a functional group that reacts with an oxygen-containing film,
  • the additive compound is selected from the group consisting of carboxyl groups and salts thereof and esters thereof, epoxy groups, glycidyl groups, isocyanate groups, carbodiimide groups, amino groups and salts thereof, and acid anhydride groups and esters thereof.
  • thermoplastic resin composition contains an additive compound having a functional group that reacts with an oxygen-containing film, and the additive compound comprises a carboxyl group and a salt thereof and an ester thereof, an epoxy group, a glycidyl group, an isocyanate group, and a carbodiimide. It is a method for producing a gold resin joined body having at least one functional group selected from the group consisting of a group, an amino group and a salt thereof, and an acid anhydride group and an ester thereof.
  • the present invention relates to a film forming step of forming an oxygen-containing film by intentionally increasing the oxygen content on the surface of a metal substrate made of metal, and injection molding of a thermoplastic resin composition.
  • the resin molded body obtained in the resin molding step is formed by injection molding or thermocompression bonding on the resin-containing process for forming the molded body and the oxygen-containing film of the surface-treated metal base material obtained in the film forming process.
  • a metal resin bonding process for bonding It is a method for producing a metal resin joined body for producing a metal resin joined body in which a metal substrate and a resin molded body are joined through the oxygen-containing film,
  • the thermoplastic resin composition contains an additive compound having a functional group that reacts with an oxygen-containing film, and the additive compound comprises a carboxyl group and a salt thereof and an ester thereof, an epoxy group, a glycidyl group, an isocyanate group, and a carbodiimide. It is a method for producing a metal resin joined body having at least one functional group selected from the group consisting of a group, an amino group and a salt thereof, and an acid anhydride group and an ester thereof.
  • the metal base material used as a base is particularly limited, such as a copper base material made of copper or a copper alloy, an iron base material made of iron or an iron alloy, an aluminum base material made of aluminum or an aluminum alloy, or the like.
  • a copper base material made of copper or a copper alloy such as copper base material made of copper or a copper alloy, an iron base material made of iron or an iron alloy, an aluminum base material made of aluminum or an aluminum alloy, or the like.
  • it can be determined on the basis of various physical properties such as strength, corrosion resistance, and workability required for the use of the metal-resin bonded body formed by using the metal-resin bonded body.
  • the material and shape of the aluminum base material are not particularly limited as long as it is made of aluminum or an aluminum alloy, and the strength required for the use of the aluminum resin joined body formed using the aluminum base material. It can be determined based on various physical properties such as corrosion resistance and workability.
  • the oxygen-containing film formed on the surface of such a metal substrate is not particularly limited as long as the adhesion with the metal substrate is good, but the metal substrate is copper.
  • a substrate for example, an oxygen-containing film obtained by blackening treatment or an oxygen-containing film (thermal oxide film) obtained by laser treatment can be exemplified, and the metal substrate is iron-based.
  • a material for example, an oxygen-containing film derived from a zinc film obtained by galvanizing treatment can be mentioned.
  • the metal substrate is an aluminum substrate, a zinc ion-containing alkaline aqueous solution is used.
  • a zinc-containing film containing zinc element obtained by the film forming process used, a film forming process using hot water of 91 ° C. or higher and 100 ° C. or lower, or a film using hot water of 60 ° C. or higher and 90 ° C. or lower The hydrated oxide film obtained by the forming process It can be exemplified obtained oxide film or the like with a film forming process for performing laser processing on a surface of the aluminum substrate.
  • the surface of the aluminum base material is oxidized with zinc oxide (ZnO) and oxidized with the zinc element. It is only necessary to be able to form a coating containing zinc iron (ZnFeO), zinc oxide aluminum (ZnAlO), etc., and when molding a resin molded body by injection molding of a thermoplastic resin composition, this thermoplasticity By thermocompression bonding with a resin molded body obtained by molding the resin composition, a strong aluminum-resin bonding strength is achieved between the resin molded body formed on the oxygen-containing film.
  • the film-forming process using the zinc ion containing aqueous alkali solution preferably an alkali hydroxide (MOH) and zinc ion (Zn 2+) in a weight ratio (MOH / Zn 2+) ratio of 1 to 100 inclusive
  • a zinc ion-containing aqueous alkali solution that is preferably contained in a proportion of 2 or more and 20 or less, more preferably 3 or more and 10 or less
  • the zinc ion-containing alkaline aqueous solution is brought into contact with the surface of the aluminum substrate at room temperature, thereby producing A zinc-containing film containing oxygen is preferably formed on the surface of the substrate.
  • the alkali source in the zinc ion-containing alkaline aqueous solution preferably one or more selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide is used, and this zinc ion-containing alkaline aqueous solution is used.
  • the zinc ion source is preferably at least one selected from zinc oxide, zinc hydroxide, zinc peroxide, zinc chloride, zinc sulfate, and zinc nitrate.
  • the alkali hydroxide concentration is 10 g / L or more and 1000 g / L or less, preferably 50 g / L or more and 300 g / L or less. It may be 1 g / L or more and 200 g / L or less, preferably 10 g / L or more and 100 g / L or less.
  • the composition of the aqueous solution containing zinc ions within the above range, aluminum and zinc ions cause a substitution reaction on the surface of the aluminum base material, aluminum is dissolved, and zinc ions are precipitated as fine particles, As a result, an oxygen-containing film (zinc-containing film) containing an oxygen element and a zinc element is formed on the surface of the aluminum substrate. That is, aluminum melts while forming a concave portion, and zinc is precipitated in the concave portion to form a zinc-containing film containing zinc element.
  • the alkali hydroxide concentration is less than 10 g / L, there is a problem that the formation of a zinc-containing film containing zinc element becomes insufficient.
  • the electrical conductivity is 0.01 mS / m or more and 20 mS / m or less, preferably 0.01 mS / m.
  • m hot water of not less than 10 mS / m and not less than 91 ° C. and not more than 100 ° C.
  • the aluminum substrate is usually immersed in this hot water for not less than 0.5 minutes and not more than 30 minutes, preferably not less than 1 minute and not more than 10 minutes.
  • a hydrated oxide film or hot water having an electrical conductivity of 0.01 mS / m to 20 mS / m, preferably 0.01 mS / m to 10 mS / m, and 60 ° C. to 90 ° C.
  • the aluminum substrate is usually immersed for 0.5 minutes to 30 minutes, preferably 1 minute to 10 minutes to form a hydrated oxide film.
  • the hot water or hot water used in the film forming treatment for forming the hydrated oxide film is pure water.
  • the electrical conductivity of hot water or hot water used in the film formation process for forming this hydrated oxide film is less than 0.01 mS / m, it will be in the region of ultrapure water, resulting in high production costs of pure water. On the other hand, when it exceeds 20 mS / m, the hydrated oxide film may not be formed, and the film formation rate becomes extremely slow, and the presence of impurities. There is also a problem that film defects of the hydrated film easily occur.
  • boehmite or pseudoboehmite (boehmite) or pseudoboehmite ( This is a film with a broad peak mainly composed of pseudoboehmite), and in the film formation treatment using hot water of 60 ° C. or more and 90 ° C. or less, the peak derived from the crystalline component is not mainly observed. It is a film mainly composed of (amorphous).
  • the X-ray diffraction measurement of the hydrated oxide film was performed by measuring 30 mm ⁇ from the surface-treated aluminum base material after the hydrated oxide film was formed as the oxygen-containing film on the surface of the aluminum base material by the film forming process.
  • a sample for measurement was prepared with a thickness of 30 mm, and this sample was fixed to a glass sample plate (sample part 24 mm square / penetration) of an X-ray diffraction apparatus [manufactured by Rigaku Corporation: RAD-rR].
  • Cu rotating anti-cathode target (used X-ray and wavelength: CuK ⁇ 1.5418 ⁇ ), X-ray output: 50 kV, 200 mA, detector: scintillation detector, optical system attributes: Bragg-Brentano optical system (concentration method), diverging slit 1 ° , Measured under conditions of a scattering slit of 1 ° and a light receiving slit of 0.3 mm, the contained components are identified, and then, among the peaks representing each detected phase, the peaks are high in intensity and derived from other components Integral diffraction strength for one non-overlapping peak To calculate the which it was sought.
  • the vicinity of the surface of the aluminum substrate is partially made of aluminum. Heating to above the melting temperature of the base material to oxidize and deposit aluminum oxide (Al 2 O 3 ) near the surface of the aluminum base material to form an oxygen-containing film containing this aluminum oxide (Al 2 O 3 )
  • a laser etching apparatus or the like can be used.
  • the surface-treated aluminum base material obtained by forming the oxygen-containing film on the surface of the aluminum base material in the above-described film forming step is measured by EPMA on the surface layer from the outermost surface to a depth of 3 ⁇ m.
  • the oxygen content is 0.1 to 50% by weight, preferably 1.0 to 30% by weight.
  • the coating is too thin to achieve sufficient aluminum-resin bonding strength between the aluminum base material and the resin molding.
  • the oxygen content is increased beyond 50% by weight, the film becomes too thick, causing film cohesive failure, and sufficient aluminum-resin bonding strength cannot be obtained. .
  • the thickness of the oxygen-containing film formed on the surface of the aluminum substrate in this film forming process is usually 0.06 ⁇ m or more and 2 ⁇ m or less, preferably 0.1 ⁇ m or more and 1 ⁇ m or less. Good. If the film thickness of the oxygen-containing film is less than 0.06 ⁇ m, the film may be too thin to obtain sufficient aluminum-resin bonding strength. Conversely, if the film thickness exceeds 2 ⁇ m, the film will be thick. Thus, cohesive failure of the film may occur, and sufficient aluminum-resin bonding strength may not be obtained.
  • the thickness of the hydrated oxide film formed on the surface of the aluminum base material by the film forming process using hot water of 91 ° C. or higher and 100 ° C. or lower is usually 0.1 ⁇ m or more and 1 ⁇ m or less.
  • the thickness is preferably 0.2 ⁇ m or more and 0.5 ⁇ m or less. If the film thickness of this oxygen-containing film is less than 0.1 ⁇ m, the film may be too thin to obtain sufficient aluminum-resin bonding strength. Conversely, if the film thickness exceeds 1 ⁇ m, the film will be thick. Thus, cohesive failure of the film may occur, and sufficient aluminum-resin bonding strength may not be obtained.
  • the thickness of the hydrated oxide film formed on the surface of the aluminum substrate by the film forming process using hot water of 60 ° C. or more and 90 ° C. or less is usually 0.1 ⁇ m or more and 1 ⁇ m or less.
  • the thickness is preferably 0.2 ⁇ m or more and 0.5 ⁇ m or less. If the film thickness of this oxygen-containing film is less than 0.1 ⁇ m, the film may be too thin to obtain sufficient aluminum-resin bonding strength. Conversely, if it exceeds 1 ⁇ m, the film will be thick. Thus, cohesive failure of the film may occur, and sufficient aluminum-resin bonding strength may not be obtained.
  • the resin molded body is integrated on the oxygen-containing film by injection molding of a thermoplastic resin composition.
  • the resin molding process for forming the resin molded body by injection molding of the thermoplastic resin composition, and the obtained resin molded body with the surface-treated aluminum base Aluminum that is integrally bonded by thermocompression using means such as laser welding, vibration welding, ultrasonic welding, hot press welding, hot plate welding, non-contact hot plate welding, or high frequency welding on the oxygen-containing film of the material.
  • An aluminum resin bonded body is manufactured by a resin bonding process.
  • the thermoplastic resin composition used in the above resin molding step specifically includes a sulfur element such as a polyarylene sulfide resin such as polyphenylene sulfide (PPS) or a sulfone resin.
  • a sulfur element such as a polyarylene sulfide resin such as polyphenylene sulfide (PPS) or a sulfone resin.
  • Resins such as polyester resins such as polybutylene terephthalate (PBT), resins containing oxygen atoms such as liquid crystal polymers, polycarbonate resins, polyacetal resins, polyether resins, polyphenylene ether resins, such as polyamide (PA) , ABS, polyimide, polyetherimide, and other resin compositions comprising a thermoplastic resin containing a nitrogen atom.
  • PA polyamide
  • ABS polyimide
  • polyetherimide polyetherimide
  • automotive parts that have a great need for metal-resin bonded bodies are particularly preferred in terms of heat resistance and rigidity.
  • PPS is used from the viewpoint of rigidity.
  • PBT liquid crystal polymer
  • engineering plastics such as polyacetal particularly preferred.
  • thermoplastic resin composition used in the resin molding step a resin composition containing an additive compound having a specific functional group that reacts with the oxygen-containing film is used.
  • the additive compound means a substance other than the thermoplastic resin constituting the thermoplastic resin composition, and is particularly limited as long as it is used by being added to the thermoplastic resin composition. It is not intended to be added for various purposes in consideration of the production of thermoplastic resin compositions, the moldability and processability of thermoplastic resin compositions, the properties of resin moldings obtained by molding thermoplastic resin compositions, etc.
  • Examples include various additives such as antioxidants, mold release agents, plasticizers, UV absorbers, heat stabilizers, antistatic agents, dyes, pigments, lubricants, silane coupling agents, fillers, and elastomers.
  • an elastomer is particularly preferable as the additive from the viewpoint of alleviating the distortion between the metal and the resin caused by the difference in linear expansion.
  • the additive compound includes a carboxyl group and a salt thereof and an ester thereof, an epoxy group, a glycidyl group, an isocyanate group, a carbodiimide group, an amino group and a salt thereof, and an acid anhydride group and an ester thereof.
  • a compound having at least one functional group selected from among them is preferable, and among them, a compound having a glycidyl group is particularly preferable.
  • the additive compound is preferably an olefin copolymer containing a structural unit derived from ⁇ -olefin and a structural unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid, and is further a (meth) acrylic copolymer.
  • (meth) acrylic acid ester is also referred to as (meth) acrylate.
  • glycidyl (meth) acrylate is also referred to as glycidyl (meth) acrylate.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid
  • (meth) acrylate” means both acrylate and methacrylate.
  • the ⁇ -olefin is not particularly limited, and examples thereof include ethylene, propylene, butylene and the like, and ethylene is particularly preferable.
  • the ⁇ -olefin can be used alone or in combination of two or more.
  • the additive compound contains a structural unit derived from ⁇ -olefin, flexibility is easily imparted to the resin molded body. By providing this flexibility, the resin molded body becomes soft, and excellent metal-resin bonding strength is exhibited, and strength reduction after a durability test is prevented, and excellent metal-resin bonding strength over a long period of time. Is easily maintained.
  • the glycidyl ester of ⁇ , ⁇ -unsaturated acid is not particularly limited and includes, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, and glycidyl methacrylate is particularly preferable.
  • the glycidyl ester of ⁇ , ⁇ -unsaturated acid can be used alone or in combination of two or more. When the additive compound contains a glycidyl ester of ⁇ , ⁇ -unsaturated acid, an effect of improving the bonding strength between the metal and the resin can be obtained.
  • the (meth) acrylic acid ester is not particularly limited.
  • methyl acrylate is particularly preferable.
  • the (meth) acrylic acid ester can be used alone or in combination of two or more.
  • the structural unit derived from (meth) acrylic acid ester contributes to the improvement of the bonding strength between the metal and the resin.
  • a coalescence can be manufactured by superposing
  • the copolymer can be obtained by performing copolymerization by a well-known radical polymerization reaction.
  • the type of the copolymer is not particularly limited.
  • the copolymer may be a random copolymer or a block copolymer.
  • An olefin-based graft copolymer in which polyacrylonitrile / styrene copolymer, butyl acrylate / styrene copolymer, or the like is chemically bonded in a branched or cross-linked structure may be used.
  • the olefin copolymer used in the present invention can contain structural units derived from other copolymer components as long as the effects of the present invention are not impaired.
  • the functional group of the additive compound is contained in the thermoplastic resin composition at a rate of 0.5 to 150 ⁇ mol / g, preferably 0.5 to 50 ⁇ mol / g, more preferably 2 to 25 ⁇ mol / g.
  • the ratio of the functional group in this thermoplastic resin composition is lower than 0.5 ⁇ mol / g, the metal-resin bonding strength tends to be lowered, and conversely if it is higher than 150 ⁇ mol / g, characteristics as a resin material, particularly fluidity It is not preferable because it tends to adversely affect mechanical strength such as tensile strength and bending strength, and rigidity.
  • the ratio of the functional group in the thermoplastic resin composition is as follows.
  • M molecular weight per functional group
  • the amount of the functional group is 1 / M (mol / g)
  • the additive compound is added to the thermoplastic resin composition in a proportion of 1% by mass
  • (1 / M) ⁇ (1/100 ) 1/100 M (mol / g)
  • the “molecular weight per functional group” M is 1 ⁇ 2 of the molecular weight Mw of the additive compound itself if the additive compound has a plurality of, for example, two functional groups.
  • an oxygen-containing film is formed on the entire surface of the metal base material to be a base, and resin molding is performed by injection molding only at a necessary portion of the obtained surface-treated metal base material or by thermocompression bonding.
  • the body may be joined, or in consideration of cost, an oxygen-containing film is formed only on a part of the surface of the metal substrate or only at a necessary portion, and the obtained surface-treated metal substrate is necessary. You may join a resin molding to a location by injection molding or thermocompression bonding.
  • the oxygen-containing film when forming the oxygen-containing film only on a part of the surface of the metal substrate or only necessary portions, the oxygen-containing film is masked after masking portions other than the part that forms the oxygen-containing film, for example, with a masking tape or the like.
  • a process for forming the mask may be performed, and then the masking tape or the like of the masked portion may be removed.
  • a pre-treatment of the surface of the metal substrate if necessary, as a pretreatment of the surface of the metal substrate, if necessary, a degreasing treatment, an etching treatment, a desmut treatment, and a rough surface. Any one type or two or more types of processing selected from a chemical conversion treatment, a chemical polishing treatment, and an electrolytic polishing treatment may be performed.
  • the degreasing process performed as said pre-processing it can carry out using the normal degreasing bath which consists of sodium hydroxide, sodium carbonate, sodium phosphate, surfactant, etc.
  • immersion temperature is usually 15
  • the immersion time is 1 minute or more and 10 minutes or less, preferably 3 minutes or more and 6 minutes or less.
  • an alkali aqueous solution such as sodium hydroxide or an acid aqueous solution such as a sulfuric acid-phosphoric acid mixed aqueous solution is usually used.
  • concentration of 20 g / L or more and 200 g / L or less is used, Preferably it is 50 g / L or more and 150 g / L or less, Immersion temperature 30 to 70 degreeC, Preferably it is 40 to 60 degreeC.
  • the immersion treatment may be performed under a treatment condition of not more than ° C. and a treatment time of 0.5 to 5 minutes, preferably 1 to 3 minutes.
  • the sulfuric acid concentration is 10 g / L or more and 500 g / L or less, preferably 30 g / L or more and 300 g / L or less
  • the phosphoric acid concentration is 10 g / L or more and 1200 g. / L or less, preferably 30 g / L or more and 500 g / L, immersion temperature 30 ° C. or more and 110 ° C. or less, preferably 55 ° C. or more and 75 ° C. or less, and immersion time 0.5 minutes or more and 15 minutes or less, preferably
  • the immersion treatment is preferably performed under a treatment condition of 1 minute or more and 6 minutes or less.
  • a desmut bath made of an aqueous nitric acid solution having a concentration of 1 to 30% is used, an immersion temperature of 15 ° C. to 55 ° C., preferably 25 ° C. to 40 ° C., and an immersion time of 1
  • the immersion treatment may be performed under a treatment condition of not less than 10 minutes and not more than 10 minutes, preferably not less than 3 minutes and not more than 6 minutes.
  • the roughening treatment performed as the pretreatment for example, after the pretreatment of the aluminum base material, in the treatment liquid mainly composed of ammonium acid fluoride (trade name: JCB-3712 manufactured by Nippon Sea Hey Chemical) The method etc. which are immersed in can be illustrated.
  • the treatment liquid mainly composed of ammonium acid fluoride (trade name: JCB-3712 manufactured by Nippon Sea Hey Chemical)
  • JCB-3712 manufactured by Nippon Sea Hey Chemical
  • the metal is an aluminum substrate
  • a plurality of surface-treated aluminum substrates having an oxygen-containing film are formed on the surface of the aluminum substrate, and some of the surface-treated aluminum substrates have a glycidyl group on the surface.
  • the PPS molded body was joined by injection molding of polyphenylene sulfide (PPS) having an aluminum PPS joined body.
  • PPS polyphenylene sulfide
  • For the remaining surface-treated aluminum substrate first, stearic acid is volatilized in an electric furnace maintained at 100 ° C., and the surface-treated aluminum substrate is exposed therein for 24 hours.
  • a stearic acid-treated aluminum base material having a monomolecular film of stearic acid, and a PPS molded body is joined to the surface of the stearic acid-treated aluminum base material by injection molding of PPS having a glycidyl group, thereby stearic acid-treated aluminum PPS joining.
  • the body The difference in bonding strength between the aluminum PPS bonded body and the stearic acid-treated aluminum PPS bonded body was measured. As a result, the bonding strength in the stearinized aluminum PPS bonded body is the bonding strength of the aluminum PPS bonded body. Compared with, it was clearly reduced.
  • Stearic acid has both a carboxyl group (COOH) which is a hydrophilic group and an alkyl group (C 17 H 35 ) which is a hydrophobic group, and has a property of forming a monomolecular film having a thickness of one molecule.
  • COOH carboxyl group
  • C 17 H 35 alkyl group
  • Stearic acid has both a carboxyl group (COOH) which is a hydrophilic group and an alkyl group (C 17 H 35 ) which is a hydrophobic group, and has a property of forming a monomolecular film having a thickness of one molecule.
  • COOH carboxyl group
  • C 17 H 35 alkyl group
  • the surface-treated aluminum base material before and after the stearic acid treatment was compared and examined by observing the surface, but no difference was found in the surface structure depending on the presence or absence of the stearic acid monomolecular film.
  • the contact angle was close to 180 °, and the droplet was almost spherical. This is a result of supporting that the alkyl group side of stearic acid is unevenly distributed on the outermost layer side of the aluminum base material.
  • the metal-resin bonded body of the present invention is a specific material in which the surface of a metal substrate is coated with an oxygen-containing film by intentionally increasing the oxygen content and reacts with the oxygen-containing film as a thermoplastic composition.
  • a resin composition containing an additive compound having a functional group of by injection molding of this thermoplastic resin composition, or by thermocompression bonding of a resin molded body obtained by injection molding of this thermoplastic resin composition It is obtained by joining a resin molded body on the oxygen-containing film on the surface of the metal substrate, and the metal substrate and the resin molded body are not only firmly bonded via the oxygen-containing film, but also for a long time. In addition, excellent metal-resin bonding strength can be maintained.
  • the method for producing a metal-resin joined body of the present invention in the film formation step of forming an oxygen-containing film by intentionally increasing the oxygen content on the surface of the metal substrate, gas generation, etc.
  • it can be operated at room temperature, has no problems with surrounding equipment and environment, is easy to operate and low cost, and can exhibit excellent metal-resin bonding strength over a long period of time.
  • the body can be manufactured.
  • FIG. 1 is an explanatory view for explaining a metal resin bonded body produced in Example 1 of the present invention.
  • FIG. 2 is an explanatory diagram for explaining a method for evaluating a bonding strength between a metal and a resin performed in Example 1 of the present invention.
  • the metal resin joined body of this invention and its manufacturing method are demonstrated concretely. 1.
  • the surface roughening treatment and the film formation treatment for forming the oxygen-containing film performed as pretreatment are as follows.
  • the aluminum substrate was immersed in an aqueous nitric acid solution adjusted to 30% by mass at room temperature for 0.5 minutes, and then 50 ° C. in an aqueous sodium hydroxide solution adjusted to 5% by mass, After dipping for 0.5 minutes and further dipping in an aqueous nitric acid solution adjusted to 30% by weight at room temperature for 0.5 minutes, the pretreated aluminum substrate was then adjusted to a concentration of 20% by weight.
  • a roughened aluminum base material was prepared by immersing in a treatment liquid (JCB-3712, manufactured by Nippon CB Chemical Co., Ltd.) containing adjusted acidic ammonium fluoride as a main component at a temperature of 40 ° C. for 10 minutes.
  • Treatment method A Formation of zinc-containing film
  • Zinc ion-containing aqueous solution of sodium of (NaOH-Zn 2+ solution) was prepared (20 g / L as Zn 2+) sodium hydroxide as a film-forming treatment agent concentration 100 g / L and the zinc oxide concentration 25 g / L.
  • the aluminum base material was immersed in this zinc ion-containing sodium aqueous solution for 1 minute at room temperature (Note: only in the case of Comparative Example 1 was immersed for 5 minutes), then washed with water, and an oxygen-containing film on the surface.
  • a surface-treated aluminum base material for testing in which a zinc-containing film containing zinc element was formed was produced.
  • Treatment method B formation of hydrated oxide film by hot water
  • a test in which an aluminum substrate was immersed in hot water (pure water) at 91 to 100 ° C. for 0.5 to 30 minutes to form a hydrated oxide film mainly composed of boehmite or pseudoboehmite as an oxygen-containing film on the surface.
  • a surface-treated aluminum substrate was prepared.
  • Treatment method C formation of hydrated oxide film by hot water
  • Treatment method D formation of oxide film by laser treatment
  • laser etching processing device name: Miyachi Technos / ML-7112A; laser wavelength: 1064 nm, spot diameter: 50-60 ⁇ m, oscillation mode: Q switch pulse, frequency: 10 kHz
  • pitch width is 50 ⁇ m intervals on the surface of aluminum substrate
  • PPS (1) PPS-based resin composition [trade name: DURAFIDE (registered trademark) RSF-10719 manufactured by Polyplastics Co., Ltd .; additive compounds a and b described later; and inorganic filler 50%.
  • PPS (2) PPS resin [trade name: Fortron KPS W203A manufactured by Kureha Co., Ltd.
  • the above aromatic polyester liquid crystal resin (LCP) is manufactured as follows. Using a reactor equipped with a stirrer, a distillation pipe, a gas introduction pipe, a discharge hole, etc., p-hydroxybenzoic acid 345 parts by weight (73 mol%), 6-hydroxy-2-naphthoic acid 175 parts by weight (27 mol%), 0.02 part by weight of potassium acetate and 350 parts by weight of acetic anhydride were charged into the reactor, and the reactor was sufficiently replaced with nitrogen. Then, the temperature was raised to 150 ° C. under normal pressure, and stirring was started. The mixture was stirred at 150 ° C. for 30 minutes, and the temperature was gradually raised, and acetic acid produced as a by-product was distilled off.
  • Additive compound in resin composition [Additive compound in resin composition]
  • Additive Compound a Glycidyl group-containing elastomer [trade name: Modiper A4300, manufactured by NOF Corporation]
  • Additive compound b Elastomer not containing functional group [Dow Chemical Japan Co., Ltd. trade name: Engage 8440]
  • Additive compound c Elastomer containing glycidyl group [trade name: Bondfast 7L, manufactured by Sumitomo Chemical Co., Ltd.]
  • Additive compound d isocyanate compound [Degussa Japan Co., Ltd.
  • Additive compound e Epoxy compound [Mitsubishi Chemical Corporation product name: Epicoat JER1004K]
  • Additive compound f Ester elastomer (trade name: NUC-6570, manufactured by Nihon Unicar Co., Ltd.)
  • Additive Compound g Dicyandiamide [Nippon Carbide Industries, Ltd., trade name: Dicyandiamide G]
  • Additive compound h Carbodiimide compound [Rhein Chemie Japan Co., Ltd. trade name: Stavacsol P400]
  • Additive compound i Glycidyl group-containing elastomer (trade name: Bond First E, manufactured by Sumitomo Chemical Co., Ltd.)
  • the “oxygen content” and “film thickness” of the oxygen-containing film formed on the surface of the aluminum substrate and the “film thickness of the aluminum resin joined body” are as follows: And measured. [Measurement of oxygen content of oxygen-containing film]
  • the surface-treated aluminum base material obtained in the manufacturing process of the aluminum resin joined body was subjected to mapping analysis using EPMA (manufactured by Shimadzu: EPMA 1610) and measuring 512 steps in the vertical and horizontal directions at an irradiation diameter of 40 ⁇ m / step.
  • the measurement area is 20.48 mm ⁇ 20.48 mm
  • the sampling time for one step is 20 ms
  • the acceleration voltage is 15 kV
  • the resolution in the depth direction of oxygen is 3 ⁇ m or less.
  • the detected oxygen intensity was calculated as a weight percentage (wt%) from a calibration curve prepared in advance.
  • the calibration curve used was calculated and prepared from two points: the oxygen intensity of the Al 2 O 3 standard sample (oxygen content: 48 wt%) and the oxygen intensity of the high-purity Al foil.
  • the aluminum resin bonded body and the surface-treated aluminum base material obtained in the manufacturing process of the aluminum resin bonded body are each focused on the sample surface using a type focused ion beam processing apparatus (manufactured by FEI: Quanta 3D type).
  • the observation site was extracted by applying an ion beam to repel atoms on the surface and processed into a thin film having a thickness of about 100 nm to prepare an observation sample.
  • the observation was performed using a transmission electron microscope (TEM) (manufactured by FEI: Tecnai G2 F20 S-TWIN) under an acceleration voltage of 200 kV.
  • TEM transmission electron microscope
  • Example 1 Production of surface-treated aluminum substrate An aluminum substrate having a size of 50 mm x 25 mm was cut out from a commercially available aluminum plate (A5052; plate thickness 2.0 mm). Next, the surface-treated aluminum base material for the test by which the oxygen-containing film
  • thermoplastic resin composition As the thermoplastic resin composition, a PPS resin composition [PPS (1)] containing additive compound a and additive compound b shown in Table 1 and 50% inorganic filler was used. .
  • This PPS resin composition [PPS (1)] is a resin composition having a melt viscosity of 230 Pa ⁇ s (310 ° C., 1000 s ⁇ 1 ).
  • Example 2 to 47 The aluminum substrate, the film formation treatment of the oxygen-containing film, the oxygen-containing film, the resin composition, and the resin molding conditions are as shown in Tables 1 to 8, respectively. Went. In Example 29, a 30 wt% HNO 3 solution was used, and in Example 30, the electrical conductivity of hot water was adjusted to the values shown in Table 5 using 0.1 M NaOH water.
  • Example 3 4, 12 to 14, 18, 23, 24, 29 to 34, 42, 43, 45, and 46, the same PPS resin composition [PPS (1)] as in Example 1 was used. Using. In Example 2 using PPS resin [PPS (2)], 40% by mass of a glass-based filler was added to the resin composition, and Examples 5 to 9 using PBT were used. 15 to 17, 19 to 22, 25 to 28, 35, 36, 44, and 47, and Examples 10 and 11 using PP, 30% by mass of glass-based filler was added to the resin composition. Furthermore, in Examples 37 to 40 using POM, 25% by mass of glass-based filler is added, and in Example 41 using LCP, 50% by mass of glass is added. System filler material is added.
  • Example 3 (Cool thermal shock test) Using a thermal shock tester (manufactured by ESPEC Corporation), a thermal shock test is performed under predetermined cycle conditions, taken out after 100 cycles, and a joint strength evaluation test is performed in the same manner as in Example 1 to evaluate durability. did.
  • the cycle conditions are as follows. In Example 3, after heating at 160 ° C. for 1.5 hours, the temperature was lowered to ⁇ 40 ° C., cooled for 1.5 hours, and then heated to 160 ° C. again. In Example 27, after heating at 140 ° C. for 1.5 hours, the heating-cooling process in which the temperature is lowered to ⁇ 40 ° C., cooled for 1.5 hours, and then heated again to 140 ° C. is 1 cycle. It was. The results are shown in Tables 1 to 8.
  • Comparative Examples 4 and 7 to 10 the same PPS resin composition [PPS (1)] as in Example 1 was used.
  • Comparative Examples 1, 11, 17, and 18 using PPS resin [PPS (2)] 40% by mass of a glass-based filler was added to the resin composition, and PBT was used.
  • Comparative Examples 2, 5, 12 and 16, and Comparative Examples 3, 6 and 15 using PP 30% by mass of a glass filler is added to the resin composition, and POM is used.
  • Comparative Example 13 25% by mass of the glass-based filler was added, and in Comparative Example 14 using LCP, 30% by mass of the glass-based filler was added.
  • Comparative Examples 4 to 6 the roughening treatment as the pretreatment and the film formation treatment (surface treatment) for forming the oxygen-containing film were not performed, and in Comparative Examples 9 and 10, the oxygen-containing film was formed.
  • An aluminum resin joined body was prepared in the same manner as in the above example except that an aluminum substrate was used without performing the film forming process (surface treatment) to be performed, and the joint strength was evaluated in the same manner as in Example 1. A test was conducted.
  • Comparative Examples 7 and 8 the electrical conductivity of hot water was adjusted to the values shown in Table 10 using 0.1 M NaOH water. The results are shown in Tables 9 to 11.
  • the metal resin bonded body of the present invention has excellent bonding strength before and after the durability test, it is suitably used for manufacturing various parts such as parts for various sensors for automobiles, parts for home appliances and parts for industrial equipment. Is possible.
  • SYMBOLS 1 Aluminum resin joined body, 2 ... Surface-treated aluminum base material, 3 ... PPS molded object (resin molded object), 4 ... Tip joint part, 5 ... Pin gate, 6 ... Jig, 7 ... Load.

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Abstract

L'invention fournit un corps lié métal/résine qui tout en développant une excellente résistance, et sans baisse de résistance après essai de fatigue, permet de préserver une excellente résistance de liaison sur le long terme. Ce corps lié métal/résine possède : un matériau de base métallique ; un revêtement à teneur en oxygène comprenant un oxygène qui est formé à la surface du matériau de base métallique par exécution d'un traitement augmentant volontairement la teneur en oxygène ; et un corps moulé de résine qui est lié sur ce revêtement à teneur en oxygène, et qui est formé par une composition de résine thermodurcissable comprenant un composé additif doté d'un groupe fonctionnel spécifique réagissant avec le revêtement à teneur en oxygène. Le groupe fonctionnel dudit composé additif consiste en au moins un élément choisi dans un groupe constitué d'un groupe carboxyle, d'un sel de celui-ci ainsi que d'un ester de celui-ci, d'un groupe époxy, d'un groupe glycidylique, d'un groupe isocyanate, d'un groupe carbodiimide, d'un groupe amino ainsi que d'un sel de celui-ci, et d'un groupe anhydride acide ainsi que d'un sel de celui-ci.
PCT/JP2014/058435 2013-03-26 2014-03-26 Corps lié métal/résine, et procédé de fabrication de celui-ci WO2014157289A1 (fr)

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