WO2020137007A1 - Matériau métallique façonné et prérevêtu, procédé de production de composite, et composite - Google Patents

Matériau métallique façonné et prérevêtu, procédé de production de composite, et composite Download PDF

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Publication number
WO2020137007A1
WO2020137007A1 PCT/JP2019/034527 JP2019034527W WO2020137007A1 WO 2020137007 A1 WO2020137007 A1 WO 2020137007A1 JP 2019034527 W JP2019034527 W JP 2019034527W WO 2020137007 A1 WO2020137007 A1 WO 2020137007A1
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Prior art keywords
rubber
metal
inorganic
layer
organic
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PCT/JP2019/034527
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English (en)
Japanese (ja)
Inventor
隆秀 林田
幸太 池田
和泉　圭二
晋 上野
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日鉄日新製鋼株式会社
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Publication of WO2020137007A1 publication Critical patent/WO2020137007A1/fr

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Classifications

    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
    • C23C22/06—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 acidic solutions with pH less than 6
    • C23C22/40—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 acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—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 acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D

Definitions

  • the present invention relates to a precoated coated metal base material, a method for producing a composite, and a composite.
  • a metal plate or its press-molded product which is given a shape by heat or pressure on a metal, or a so-called "metal raw material” which is a metal member molded by casting, forging, cutting, powder metallurgy, etc.
  • a composite body in which molded articles of a resin composition are joined is known.
  • a composite in which a metal base material and a molded body of a resin composition are joined is lighter in weight than a component made of only metal and has higher strength than a component made of only resin, so that a mobile phone, a personal computer, etc. Used in various electronic devices.
  • Patent Document 1 a surface of an electrogalvanized metal that has been subjected to a specific chromate treatment and a chlorinated vulcanized rubber are joined using a synthetic resin adhesive. A method of making a metal bonded composite is described.
  • the vulcanized rubber can be bonded to the metal by the above method, and it is not necessary to vulcanize the rubber at the time of bonding, so that it is possible to easily and inexpensively manufacture the rubber-metal adhesive composite. ing.
  • the present invention has been made in view of the above points, and is a metal raw material that has been pre-coated to have a bondability with rubber by precoating, and exhibits adhesiveness that affects these during storage and movement.
  • a precoated metal base material having sufficient jointability to vulcanized rubber, a composite of metal and rubber joined using the precoated metal base material
  • a pre-coated metal casting material according to an embodiment of the present invention for solving the above-mentioned problems is a metal casting material, an inorganic-organic composite layer arranged on the metal casting material, and the inorganic-organic composite.
  • the method for producing a composite body according to one embodiment of the present invention for solving the above-mentioned problems the surface of the precoated metal base material, a rubber molded body containing a vulcanized rubber composition, the rubber And a step of arranging the rubber layer in contact with the layer, and heating the rubber layer in contact with the rubber molded body to bond the precoated metal base material and the rubber molded body.
  • a composite body according to an embodiment of the present invention for solving the above-mentioned problems, a metal matrix, an inorganic-organic composite layer arranged on the metal matrix, and a surface of the inorganic-organic composite layer.
  • a rubber layer containing a vulcanized halogen rubber, and a rubber molded body containing a vulcanized rubber composition arranged in contact with the surface of the rubber layer.
  • the metal raw material is preliminarily provided with the bondability with the rubber by the pre-coating, and does not exhibit the adhesiveness that affects these during storage and movement, while it is bonded with the rubber.
  • a precoated metal matrix having sufficient bondability to vulcanized rubber a method for producing a composite in which metal and rubber are bonded using the precoated metal matrix, and the precoat Provided is a composite made from the prepared metal profile.
  • Pre-coated metal matrix material is a metal matrix material, an inorganic/organic composite layer arranged on the metal matrix material, and a metal/organic composite layer arranged in contact with the surface of the inorganic/organic composite layer.
  • the rubber layer includes a halogen rubber and a vulcanizing agent for the halogen rubber.
  • the precoated metal matrix has a bondability with a rubber molded body containing a vulcanized rubber composition, and thus the metal matrix and the rubber molded body are bonded together (hereinafter, (Also referred to simply as "complex").
  • the rubber layer since the halogen rubber is partially vulcanized at the time of forming the rubber layer, the rubber layer does not have adhesiveness enough to affect storage and movement. On the other hand, in the rubber layer, since the halogen rubber is partially unvulcanized, the rubber layer can be satisfactorily joined to the rubber molded body by thermocompression bonding. In addition, in the present embodiment, the inorganic-organic composite layer has an action of increasing the bonding strength of the rubber layer to the metal matrix material.
  • Metal forming material refers to a metal that has been given a shape by being formed or subjected to a force.
  • the metal blank is a metal plate, a press-molded product thereof, or a metal member molded by casting, forging, cutting, powder metallurgy, or the like.
  • the type of metal blank is not particularly limited. Examples of metal blanks include metal plates, pressed products of metal plates, and metal members.
  • the metal plate examples include a zinc-plated steel plate, a Zn-Al alloy-plated steel plate, a Zn-Al-Mg-alloy plated steel plate, a Zn-Al-Mg-Si alloy-plated steel plate, an aluminum-plated steel plate, a stainless steel plate (austenitic steel, martens). (Including site-based, ferrite-based, and ferrite-martensite two-phase systems), aluminum plates, aluminum alloy plates, and copper plates.
  • the metal plate may be a rolled steel plate such as a cold rolled steel plate.
  • the metal member include various metal members formed by casting, forging, cutting, powder metallurgy, etc., including aluminum die casting and zinc die casting.
  • the metal base material may be subjected to known pretreatments such as degreasing and pickling, if necessary.
  • Inorganic-organic composite layer The inorganic-organic composite layer is in contact with the surface of the metal matrix or through another layer such as the plating layer between the surface of the metal matrix and the metal matrix. It is placed on the surface of the profile.
  • the above-mentioned inorganic-organic composite layer is a layer containing an inorganic compound and an organic compound.
  • the above-mentioned inorganic compound may be any compound capable of reacting with the above-mentioned organic compound to form a bond or form a chelate.
  • the inorganic compound preferably contains a metal that forms a polyvalent ion. More preferably, it is an oxide, hydroxide or fluoride of a metal selected from the group consisting of Group 4 metals, Group 5 metals or Group 6 metals.
  • the metal is preferably a metal other than chromium, and is Ti, Zr, Hf, V, Nb, Ta, Mo or W. It is preferable.
  • These metals are metal ions eluted from the surface of the metal base material (for example, when the metal base material is a stainless steel plate, metal ions such as Cr, Ni, Mo, and Fe, and the metal base material is plated. When it has a layer, it reacts with the ions of the metal constituting the plating such as Zn, Mg and Al) to form a poorly soluble chemical conversion coating having excellent corrosion resistance. Further, these metals react with an organic compound to crosslink the organic compound and form a sparingly soluble inorganic-organic composite compound in which the inorganic compound and the organic compound are composited.
  • the inorganic-organic composite layer having a dense skeleton made of the inorganic-organic composite compound thus formed has high adhesion to the metal base material and can also improve the corrosion resistance of the metal base material.
  • these metals can act as a vulcanizing agent for the halogen rubber contained in the rubber layer. Therefore, these metals are bonded to the halogen rubber in the rubber layer when the rubber molded body is thermocompression-bonded to the precoated metal base material, and the bonding strength between the inorganic-organic composite layer and the rubber layer is increased. It is possible to further improve the bonding strength of the rubber molded body bonded to the rubber layer to the metal base material.
  • the inorganic-organic composite layer contains an inorganic compound containing Ti (hereinafter, also referred to as “titanium compound”)
  • the amount of Ti (titanium atom) conversion is 1 mg/m 2 or more and 100 mg/m 2 or less. It is preferable to contain the titanium compound of.
  • the inorganic-organic composite layer contains an inorganic compound containing Zr (hereinafter, also referred to as “zirconium compound”)
  • the amount of Zr (zirconium atom) conversion is 0.1 mg/m 2 or more and 30 mg/m 2 or more. It is preferable to contain 2 or less zirconium compounds.
  • the inorganic-organic composite layer may be a so-called chromate-free chemical conversion coating that does not substantially contain chromium as the metal. Therefore, the pre-coated metal matrix having the inorganic-organic composite layer can be chromate-free.
  • chromate-free means that the precoated metal matrix material does not substantially contain hexavalent chromium. “Chromate-free” means that, for example, four 50 mm ⁇ 50 mm test pieces are cut out from the precoated metal base material, immersed in 100 mL of boiling pure water for 10 minutes, and then immersed in the pure water.
  • concentration analysis method according to JIS H8625 (1993) Annex 2.4.1 “Diphenylcarbazide colorimetric method”
  • the metal mainly forms an amorphous oxide or hydroxide in the inorganic-organic composite layer to form the dense skeleton.
  • the metal may be present in the inorganic-organic composite layer as a poorly soluble fluoride. After the fluoride is dissolved in the water in the atmosphere, it is re-precipitated as a hardly soluble oxide or hydroxide on the surface of the metal matrix exposed from the defect portion to fill the defect portion. That is, the so-called self-repairing action can be exhibited, which is preferable.
  • organic compounds examples include organic acids and organic resins.
  • the organic compound is an organic acid from the viewpoint of facilitating the formation of a chelate with the metal and forming a dense inorganic-organic composite layer having excellent adhesion to a metal matrix and corrosion resistance. Is preferred.
  • the above organic compounds have a high action of forming intermolecular forces and hydrogen bonds. Therefore, the organic compound forms an interaction with the halogen rubber constituting the rubber layer to enhance the adhesiveness of the rubber layer to the inorganic-organic composite layer, whereby the rubber molded body to be bonded to the rubber layer is formed. It is possible to increase the bonding strength to the metal base material.
  • the above-mentioned organic compound acts as a binder of the rubber layer and enhances the adhesion of the rubber layer to the inorganic-organic composite layer.
  • the organic compound is transferred from the rubber layer of the precoated metal matrix to the rubber layer of the other precoated metal matrix in a non-heated state such as during transfer and storage. (Hereinafter, also referred to as “blocking”, in which the rubber layer of the precoated metal matrix is unintentionally adhered to another surface when not heated and cannot be easily separated).
  • the organic acid when the inorganic-organic composite treatment liquid is applied to the metal base material and dried by heating to form the inorganic-organic composite layer, water is removed and the treatment liquid is concentrated. The pH of the liquid locally drops. Due to this local decrease in pH, the surface in contact with the inorganic-organic composite layer on the side of the metal matrix is finely etched. Therefore, the organic acid, by the etching, to widen the contact area between the surface of the metal matrix and the inorganic-organic composite layer, it is also possible to increase the bonding strength of the inorganic-organic composite layer to the metal matrix. it can.
  • the organic acid causes metal salts and oxides to be eluted from the metal matrix into the inorganic-organic composite layer during the etching. Since the eluted metal salts and oxides also act as a vulcanizing material for halogen rubber, the inorganic-organic composite layer (metal salts and oxides) and rubber layer (metal salts and oxides) are heated by heating when joining the rubber moldings. It is also possible to increase the bonding strength of the inorganic-organic composite layer to the metal matrix after bonding the rubber molded body by bonding with a halogen rubber).
  • the organic acid may be an organic compound having a hydroxyl group in the molecule, and is preferably an organic compound having a carboxyl group in the molecule. Further, the organic acid is preferably a polyvalent organic acid having two or more hydroxyl groups or carboxyl groups in the molecule. Examples of such organic acids include tartaric acid, tannic acid, citric acid, oxalic acid, malonic acid, lactic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and the like.
  • PBTC 2-phosphonobutane-1,2,4-tricarboxylic acid
  • polyhydric phenols such as tannic acid and organic phosphonic acids such as PBTC easily form stable inorganic-organic composite compounds, and also have an action of complementing the self-repairing action of the above-mentioned metal fluorides. Since it has, the adhesiveness of the said inorganic organic composite layer can be improved more. Further, since the polyhydric phenols and the organic phosphonic acid are soluble even in strong acidity, even when concentrated in the treatment liquid when forming the inorganic-organic composite layer, the surface of the metal matrix is etched by the etching. The effect of improving the bonding strength can be more remarkably exhibited.
  • organic acid may form a salt with Mg, Al, Fe, Ni, Zn, Mo and the like.
  • organic resin examples include phenol resin, acrylic resin, acrylic olefin resin, and urethane resin.
  • the above-mentioned inorganic-organic composite layer may further contain components other than the above-mentioned components.
  • examples of such other ingredients include anticorrosive ingredients, waxes and inorganic lubricants.
  • examples of the rust preventive components include porous silica, metal phosphates and complex phosphates.
  • examples of the above wax include various organic waxes of fluorine type, polyethylene type and styrene type.
  • Examples of the above inorganic lubricants include silica, molybdenum disulfide and talc.
  • composition in the inorganic-organic composite layer can be confirmed by, for example, a Fourier transform infrared spectrophotometer for organic components and a fluorescent X-ray analyzer for inorganic components.
  • the amount of the inorganic-organic composite layer attached is preferably 10 mg/m 2 or more and 300 mg/m 2 or less, and more preferably 30 mg/m 2 or more and 200 mg/m 2 or less.
  • the inorganic-organic composite layer is formed by applying a water-based inorganic-organic composite treatment liquid (dispersion or solution) containing the inorganic compound and the organic compound, and optionally other components, onto the metal casting. It can be formed by a method of heating and drying.
  • the above-mentioned inorganic-organic composite treatment liquid is, for example, when forming an inorganic-organic composite layer containing a titanium compound as the above-mentioned inorganic compound, K n TiF 6 (K: alkali metal or alkaline earth metal, n: 1 or 2) , K 2 [TiO(COO) 2 ], (NH 4 ) 2 TiF 6 , H 2 TiF 6 , TiCl 4 , TiOSO 4 , Ti(SO 4 ) 2 , Ti(OH) 4 , (NH 4 ) 2 TiF 6 , H 2 TiF 6 and KnTiF 6 may be contained.
  • K n TiF 6 K: alkali metal or alkaline earth metal, n: 1 or 2
  • K 2 [TiO(COO) 2 K 2 [TiO(COO) 2
  • (NH 4 ) 2 TiF 6 , H 2 TiF 6 , TiCl 4 , TiOSO 4 Ti(SO 4 ) 2
  • zirconate such as zirconium oxide and sodium zirconate, or fluorinated It suffices to contain zirconic acid and a fluorozirconate such as sodium fluorozirconate.
  • the inorganic-organic composite treatment liquid may contain the above-mentioned organic acid or its salt or the above-mentioned organic resin as the above-mentioned organic compound.
  • the method of applying the inorganic-organic composite treatment liquid is not particularly limited and may be appropriately selected from known methods including a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping and pulling method and the like.
  • the conditions for heating and drying the inorganic-organic composite treatment liquid may be appropriately set according to the composition and amount of the inorganic-organic composite treatment liquid. For example, by putting the metal base material coated with the inorganic-organic composite treatment liquid in a drying oven and drying it with a hot air dryer so that the surface temperature of the metal base material falls within the range of 110 to 200° C., A uniform inorganic-organic composite layer can be formed on the surface of the metal matrix.
  • the rubber layer is a layer containing a halogen rubber as a main component and a vulcanizing agent for the halogen rubber.
  • the term “main component” means that 50% by mass or more of the organic resin contained in the rubber layer is a halogen rubber.
  • halogen rubber Since the above-mentioned halogen rubber has high adhesion to both the inorganic-organic composite layer and the rubber molded body, it is possible to increase the bonding strength of the rubber molded body to the metal base material.
  • halogen rubber examples include vinylidene fluoride rubber, fluorine-containing vinyl ether rubber, and fluorine-containing fluorinated rubber such as phosphazene rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, chlorinated butyl rubber, chlorinated polyethylene. It includes rubber, chlorinated rubber containing maleic acid-modified chlorinated polyethylene rubber, chlorinated rubber obtained by chlorinating natural rubber, and brominated rubber containing brominated butyl rubber.
  • chlorinated rubbers are preferable, and chloroprene rubbers, chlorosulfonated polyethylene rubbers, and chlorinated rubbers are more preferable, from the viewpoint of further enhancing the bondability to the inorganic-organic composite layer and the rubber molded body.
  • the vulcanizing agent may be any compound that can vulcanize the halogen rubber.
  • examples of the vulcanizing agent include metal oxides, metal salts of unsaturated fatty acids, organic peroxides, thiourea compounds, and the like.
  • metal oxides as the vulcanizing agent include magnesium oxide and zinc oxide.
  • Examples of unsaturated fatty acid metal salts as the vulcanizing agent include zinc salts and magnesium salts of unsaturated fatty acids having 3 to 8 carbon atoms.
  • organic peroxide as the vulcanizing agent examples include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne. , 2,5-Dimethyl-2,5-di(t-butylperoxy)hexane, dialkyl peroxides including 1,3-bis(t-butylperoxyisopropyl)benzene, benzoyl peroxide, and iso Diacyl peroxides including butyryl peroxide, and peroxyesters including 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane and t-butylperoxyisopropyl carbonate, etc. are included. ..
  • thiourea compounds as the vulcanizing agent include ethylene thiourea, diethyl thiourea, dibutyl thiourea, and trimethyl thiourea.
  • the inorganic-organic composite layer contains, in addition to the components described above, an aldehyde-ammonia system, an aldehyde-amine system, an imidazoline system, a thiourea system, a guanidine system, a thiazole system, a sulfenamide system, a thiuram system, a dithiocarbamate system, It may contain a vulcanization accelerator such as xanthate.
  • the halogen rubber is partially vulcanized by the vulcanizing agent during heating when forming the rubber layer, and the reactivity and fluidity of the halogen rubber are reduced. Therefore, the adhesiveness to other rubber layers and the like is not so high in the unheated state such as during transfer and storage.
  • the halogen rubber since the halogen rubber remains partially unvulcanized, the halogen rubber becomes fluid when heated. Therefore, when the rubber molded body is brought into contact with the rubber layer and is thermocompression-bonded, the molecules of the halogen rubber having fluidity permeate into the outermost layer of the rubber molded body and are entangled with the molecules constituting the rubber molded body. When the heating is continued in this state, the halogen rubber is vulcanized and cured by the vulcanizing agent while being entangled with the molecules forming the rubber molded body. Therefore, the rubber layer can increase the bonding strength of the rubber molded body to the metal base material.
  • partially vulcanized (or partially unvulcanized) can be confirmed by a known method.
  • the rubber layer contains a vulcanizing agent in an amount of 1% by mass or more and 50% by mass or less based on the total mass of the halogen rubber. Is preferable, and it is more preferable that the amount is 10% by mass or more and 30% by mass or less.
  • the adhesion thickness of the rubber layer is preferably 1 ⁇ m or more and 200 ⁇ m or less, more preferably 5 ⁇ m or more and 60 ⁇ m or less.
  • the rubber layer is preferably a non-vulcanized halogen rubber and a vulcanizing agent, and other components optionally added, a pre-coat film liquid dispersed or dissolved in an organic solvent on the surface of the inorganic-organic composite layer. It can be formed by a method of coating, heating and drying.
  • the method for applying the precoat film liquid is not particularly limited, and may be appropriately selected from known methods including a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping and pulling method and the like.
  • the conditions for heating and drying the precoat film liquid may be appropriately set according to the composition of the precoat film liquid and the amount to be applied, but it is preferable to perform the conditions such that the rubber layer is partially vulcanized.
  • the metal base material coated with the precoat film liquid is put into a drying oven so that the surface temperature of the metal base material falls within the range of 120 to 200° C., and the hot air dryer is used for 10 seconds to 3 minutes. By drying for about a minute, the rubber layer in which the halogen rubber is partially vulcanized can be formed. Under the heating conditions of this level, the halogen rubber is not completely vulcanized but remains partially vulcanized.
  • the rubber molded body is a molded body having a desired shape and containing a vulcanized rubber composition.
  • the rubber composition may be a rubber composition having a bondability with the halogen rubber contained in the rubber layer, but particularly a natural rubber, a chloroprene rubber, a nitrile butadiene rubber, or a diene-based polymer having an unsaturated bond in its main chain. Rubber is preferred.
  • the above rubber composition is a vulcanized rubber composition.
  • the precoated metal matrix has sufficient bondability with the vulcanized rubber composition. Therefore, the rubber molded body does not need to be vulcanized at the time of joining, does not require an apparatus for vulcanization and preparations, and enables a simple and inexpensive production of a composite.
  • the above rubber molded body may have a shape according to the application. From the viewpoint of enhancing the bondability to the pre-coated metal base material, the surface of the molded body that contacts the rubber layer has substantially the same shape as the surface of the rubber layer that contacts the molded body. It is preferable to have.
  • the composite is a step of arranging a rubber molding containing a vulcanized rubber composition in contact with the rubber layer on the surface of the precoated metal matrix, and the step of contacting with the rubber molding. It can be manufactured by a method including a step of heating the rubber layer to bond the precoated metal base material and the rubber molded body.
  • Step of arranging the rubber molded body on the surface of the precoated metal base material In this step, the above-mentioned precoated metal base material is prepared, and the rubber molded body is placed on the surface thereof in contact with the rubber layer. To do.
  • the pre-coated metal matrix, the above-mentioned inorganic-organic composite treatment liquid is applied on the metal matrix and heated and dried to form an inorganic-organic composite layer, and then the inorganic-organic composite layer is formed.
  • the prepared product may be prepared by applying the above-mentioned precoating film liquid on the surface, heating and drying.
  • the rubber molded body is arranged in contact with the rubber layer with respect to the pre-coated metal base material.
  • the rubber molded body has at least a portion to be joined of the rubber molded body and a portion to be joined of the pre-coated metal base material which are in contact with each other via the rubber layer, Placed against a pre-coated metal blank.
  • the part to be joined of the rubber molded body and the part to be joined of the precoated metal base material are at least at the time of performing a heating step described later, via a rubber layer. All you have to do is contact.
  • the rubber molded body and the precoated metal base material are pressed and attached to each other by a fixing jig or the like from the viewpoint of preventing misalignment.
  • Step of heating the rubber layer In this step, the contact portion between the rubber layer of the preformed metal material and the rubber molded body is heated to heat-bond the rubber layer and the rubber molded body. Then, the rubber molded body is bonded to the metal base material. At this time, at the same time, since the halogen rubber contained in the rubber layer is further vulcanized, it is possible to more firmly bond the rubber molded body and the metal base material.
  • the heating may be performed on at least a part of the surface in contact with the rubber layer and the rubber molded body, but from the viewpoint of further improving the adhesiveness, it is performed on the entire surface in contact. It is preferable.
  • the heating method is not particularly limited and may be appropriately selected from known methods. Examples of such heating methods include heating by hot press, heating by hot roller, electromagnetic induction heating, direct current heating, heating by resistance heating, heating by ultrasonic wave, laser heating, heating by hot air heating furnace, and heater chip. Heating by etc. is included.
  • Molecules of the halogen rubber contained in the rubber layer are sufficiently entangled with the molecules constituting the rubber molded body, and from the viewpoint of further increasing the bonding strength between the rubber molded body and the metal raw material, at the time of heating. It is preferable to press either or both of the rubber molded body and the precoated metal base material so that they are biased toward each other.
  • the conditions such as temperature and pressure during heating may be set so that the halogen rubber is sufficiently vulcanized.
  • the halogen rubber is sufficiently vulcanized by heating for 10 to 30 minutes so that the surface temperature of the metal raw material falls within the range of 150 to 300° C. It can be bonded to the metal base material with sufficient strength.
  • a pressure of 0.5 MPa or more may be applied between the rubber molded body and the precoated metal base material, and a pressure of 2 MPa or more is preferably applied. ..
  • the upper limit of the pressure is not particularly limited, but may be 100 MPa or less, for example.
  • Composite Body Another embodiment of the present invention relates to a composite body manufactured by the above manufacturing method.
  • the composite includes a metal matrix, an inorganic-organic composite layer disposed on the metal matrix, and a vulcanized halogen rubber disposed in contact with the surface of the inorganic-organic composite layer. It has a rubber layer and a rubber molded object which is arranged in contact with the surface of the rubber layer and which contains a vulcanized rubber composition.
  • the above metal matrix and inorganic-organic composite layer have substantially the same components as the metal matrix and inorganic-organic composite layer described above for the precoated metal matrix.
  • the vulcanized rubber layer is a layer derived from the rubber layer described above for the precoated metal matrix, provided that the halogen rubber contained in the rubber layer is vulcanized in the present embodiment. ..
  • the above-mentioned rubber molded body is a rubber molded body joined to the above-mentioned pre-coated metal base material.
  • a clear boundary may not be formed between the rubber molded body and the vulcanized rubber layer, and an interface region in which both rubbers are mixed in the thickness direction may be formed.
  • Preparation of precoated metal base material 1-1 Preparation of Inorganic-Organic Composite Treatment Liquid As organic acids, tannic acid, which is a polyhydric phenol, and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), which is an organic phosphonic acid, were prepared.
  • tannic acid which is a polyhydric phenol
  • PBTC 2-phosphonobutane-1,2,4-tricarboxylic acid
  • treatment liquid 1 An organic compound (organic acid) and an inorganic compound (compound containing a metal that forms a polyvalent ion) in the combinations shown in Table 1 were dissolved in ion-exchanged water so that each content was 2% by mass.
  • Inorganic-organic composite treatment liquid 1 to inorganic-organic composite treatment liquid 8 (hereinafter referred to as “treatment liquid 1" to “treatment liquid 8", respectively) were prepared.
  • Comparative Treatment Liquid 1 Ion-exchanged water to which neither organic compounds nor inorganic compounds were added was designated as Comparative Treatment Liquid 1. Further, the organic compounds or the inorganic compounds shown in Table 2 were dissolved in ion-exchanged water so that the content was 2% by mass to prepare Comparative Treatment Liquids 2 to 6.
  • precoat film liquid Chlorosulfonated polyethylene rubber (15 parts by mass), which is a halogen rubber, was dissolved in toluene (85 parts by mass). Furthermore, zinc oxide (5 parts by mass), which is a vulcanizing agent, was added to this solution, and the mixture was uniformly stirred to give Precoat film liquid 1 (hereinafter, "precoat film liquid” is referred to as "film liquid”). Prepared.
  • a film liquid 2 was prepared in the same manner as the film liquid 1 except that the halogen rubber was changed to chloroprene.
  • Comparative coating solution 1 prepared in the same manner as coating solution 1 except that the vulcanizing agent was not added, and comparative coating solution prepared in the same manner as coating solution 1 except that the vulcanizing agent was added in a small amount of 100% based on the total amount of the halogen rubber. Liquid 2 was prepared.
  • pre-coated metal base material A hot-dip galvanized steel sheet having a plate thickness of 1.6 mm was prepared, degreased with ethanol as a solvent, and dried.
  • the inorganic-organic composite treatment liquid 1 was applied to the surface of the plated layer of the steel sheet by a bar coater so that the coating thickness was 4 ⁇ m (adhesion amount when dried: 65 mg/m 2 ).
  • the steel plate was put into an electric hot air oven, and the inorganic-organic composite treatment liquid 1 was dried at an atmospheric temperature of 300° C. for 5 to 10 seconds so that the steel plate surface temperature was 150° C., to form an inorganic-organic composite layer.
  • the steel plate temperature was measured by directly attaching a thermocouple to the hot-dip galvanized steel plate of the base material.
  • the precoat film liquid 1 was applied to the surface of the inorganic-organic composite layer with a bar coater so that the coating thickness was 50 ⁇ m and the thickness after drying was 20 ⁇ m. After that, the steel plate is put into an electric hot air oven, and the precoat film liquid 1 is dried at an ambient temperature of 300°C so that the steel plate surface temperature is 160°C to form a partially vulcanized rubber layer. A metal blank 1 was obtained.
  • the combination of the inorganic-organic composite treatment liquid and the precoat film liquid was changed to the combination shown in Table 3 to obtain precoated metal matrix materials 2 to precoat metal matrix material 10.
  • the pre-coated metal element shown in Table 3 is prepared by using one of Comparative Treatment Liquids 1 to 6 instead of the Inorganic-organic composite treatment liquid 1 or by using the Comparative Pre-coat film liquid 1 instead of the Pre-coat treatment liquid 1. Profile 11 to pre-coated metal matrix 18 were obtained.
  • the precoated metal matrix 23 and the precoated metal matrix 24 shown in Table 3 were obtained in the same manner as the precoated metal matrix 1 or the precoated metal matrix 6 except that the rubber layer was not formed.
  • Pre-coated metal base material 1 to pre-coated metal base material 20 are cut into 25 mm width x 60 mm length, respectively, so that the surface of the rubber layer is exposed in a 25 mm square area. Both ends of the metal base material in the long side direction were sealed with heat-resistant fluorine tape of 17.5 mm.
  • a vulcanized nitrile rubber having a hardness of 60 degrees and a thickness of 6 mm cut out into a width of 25 mm and a length of 125 mm is aligned with one end face in the long side direction of the cut out precoated metal base material, and the exposed rubber layer I also made contact.
  • the precoated metal base material and the vulcanized nitrile rubber were thermocompression bonded under the conditions of 170° C. and 98 MPa for 15 minutes to bond them to each other to obtain a composite.
  • the obtained composite was fixed to the test jig shown in FIG. 1 of JIS K6256-1-2, and the end surface of the vulcanized nitrile rubber that did not come into contact with the precoated metal matrix was grasped with a width of 50 mm, and the tensile tester ( Shimadzu Corp., device name "Autograph AG-IS") was used to peel 90 degrees at a speed of 50 mm/min, and the peeling force at which cohesive failure of the vulcanized nitrile rubber occurred was measured. The bonding strength of the vulcanized rubber was evaluated. ⁇ Cohesive failure occurred when maximum peeling force was 4 N/mm or more. ⁇ Cohesive failure occurred when maximum peeling force was 2 N/mm or more and less than 4 N/mm ⁇ Cohesive failure occurred when maximum peeling force was less than 2 N/mm.
  • Table 4 shows the evaluation results.
  • the preparation conditions presence or absence of addition of an inorganic compound, an organic compound, a halogen rubber and a vulcanizing agent
  • “ ⁇ ” means that each of the above components was added
  • "X” indicates that the above components were not added.
  • Pre-coated metal casting materials 1 to pre-coat having a metal casting material, an inorganic-organic composite layer arranged on the metal casting material, and a rubber layer arranged in contact with the surface of the inorganic organic composite layer
  • the metal base material 10 was less likely to cause blocking and had a high bonding strength with the vulcanized rubber.
  • the pre-coated metal base material 14 to pre-coated metal base material 16 to which the organic compound was not added to the inorganic-organic composite layer were likely to cause blocking, and it was difficult to increase the bonding strength of the vulcanized rubber. This is because there is no interaction between the organic acid and the halogen rubber, and the organic acid etches the metal matrix and the metal salts and oxides eluted from the metal matrix and the halogen rubber. It is probable that the bond between and did not occur.
  • the pre-coated metal base material 17 and the pre-coated metal base material 18 in which the vulcanizing agent was not added to the rubber layer were likely to cause blocking, and it was difficult to increase the bonding strength of the vulcanized rubber. This is because the rubber layer was not partially vulcanized during the production of the precoated metal blank, so the bondability to other rubber layers did not deteriorate, and the halogen rubber was added during thermocompression bonding with the rubber molding. It is considered that the halogen rubber did not cure sufficiently because it did not vulcanize.
  • the pre-coated metal base material of the present invention hardly causes blocking during storage and movement, and has good bondability to a vulcanized rubber molding.
  • the composite body obtained by joining the pre-coated metal base material and the rubber molded body of the present invention is suitable for various electronic devices, household appliances, medical devices, automobile bodies, vehicle mounted articles, building materials, etc. Used.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Un objet de la présente invention est de fournir un matériau métallique façonné prérevêtu ayant une aptitude à la liaison à des caoutchoucs qui lui a été conférée par prérevêtement. Le matériau métallique façonné prérevêtu, lorsqu'il est stocké ou transporté, ne présente pas d'adhésivité qui affecte négativement le stockage ou le transport, mais, lorsqu'il est lié à des caoutchoucs, présente une capacité de liaison suffisante aux caoutchoucs vulcanisés. La présente invention concerne un matériau métallique façonné prérevêtu qui comprend un matériau métallique façonné, une couche composite inorganique/organique disposée sur le matériau métallique façonné, et une couche de caoutchouc disposée en contact avec la surface de la couche composite inorganique/organique. La couche de caoutchouc comprend un caoutchouc halogéné et un agent de vulcanisation pour le caoutchouc halogéné.
PCT/JP2019/034527 2018-12-28 2019-09-03 Matériau métallique façonné et prérevêtu, procédé de production de composite, et composite WO2020137007A1 (fr)

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JP2018247246A JP7163769B2 (ja) 2018-12-28 2018-12-28 プレコートされた金属素形材、および複合体の製造方法
JP2018-247246 2018-12-28

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0725954A (ja) * 1993-07-09 1995-01-27 Asahi Glass Co Ltd 接着性弗素ゴムおよびそれを用いた積層体
JP2003328143A (ja) * 2002-05-10 2003-11-19 Nisshin Steel Co Ltd ガスケット用表面処理ステンレス鋼板およびゴム被覆ステンレス鋼板
WO2014087939A1 (fr) * 2012-12-04 2014-06-12 Nok株式会社 Agent de traitement de surface métallique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0725954A (ja) * 1993-07-09 1995-01-27 Asahi Glass Co Ltd 接着性弗素ゴムおよびそれを用いた積層体
JP2003328143A (ja) * 2002-05-10 2003-11-19 Nisshin Steel Co Ltd ガスケット用表面処理ステンレス鋼板およびゴム被覆ステンレス鋼板
WO2014087939A1 (fr) * 2012-12-04 2014-06-12 Nok株式会社 Agent de traitement de surface métallique

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