JP2010005838A - Metal member for joining and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal member for joining that is obtained by activating the surface of a metal represented by an aluminum alloy, a magnesium alloy and the like and making a primer layer excellent in adhesiveness firmly adhere thereto, and to provide its manufacturing method and further a jointed member formed by using the member for joining. <P>SOLUTION: The surface of a metal substrate 2 is energized by, for example, a laser treatment, coated with primer comprising a predetermined compound in the state that a metal hydroxide 2a is formed on the substrate surface, and the compound in the primer layer 3 is directly bonded by covalent bonding to the hydroxyl group of the metal hydroxide 2a. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a joining technique using a metal adhesive typified by aluminum or magnesium alloy, activates the surface of these metals, and a metal member for joining provided with a primer layer rich in adhesiveness on the surface of a metal substrate, The manufacturing method further relates to a joining member using the joining member.

In recent years, light metal materials mainly composed of aluminum, magnesium, etc. have been applied along with resin materials such as polyethylene and polypropylene for the purpose of reducing vehicle weight from the viewpoint of improving fuel efficiency and reducing CO ₂ emissions. It is expanding.

The technologies for bonding these light metal materials or by bonding these light metal materials and members made of other materials into a wide range of fields such as the metal processing field, resin processing field, functional material manufacturing field, machine assembly field, etc. Is required. A number of adhesives have been developed to meet these requirements, some of which are very good.
The development of such adhesion technology is supported by the surface modification of the light metal material as the adherend and the development of the adhesive technology. Among these, the surface modification of the light metal material as the adherend, that is, before bonding As a processing method, the following methods are generally mentioned.

First, for aluminum alloys, chromic acid treatment is generally performed after removing dirt and oil film adhering to the surface, and this chromic acid treatment produces a strong metal oxide film. In addition to stabilization, the surface is roughened by etching.
On the other hand, in magnesium alloys, zinc phosphate treatment is performed after complete degreasing with sodium phosphate or sodium silicate, thereby generating a zinc phosphate film having a large uneven shape.

  As described above, surface modification of the light metal material as an adherend, that is, a pretreatment method for adhesion, is to form a solid metal oxide film or a zinc phosphate film that has a stable surface etched uneven shape. It is a common method to make, and these pretreatments can cope with adhesion and painting.

However, in the surface treatment with zinc phosphate, the metal materials that can be applied are limited from the viewpoint of the corrosion resistance after the treatment, and sludge is generated as a by-product of the reaction. high.
In addition, due to recent environmental regulations, chromic acid treatment containing hexavalent chromium harmful to the treatment liquid is also being avoided.

Therefore, as a treatment method that does not include such harmful components in the treatment liquid, for example, a compound containing a nitrogen atom having a lone pair of electrons and a non-chromium coating agent for a metal surface containing this compound and a zirconium compound have been proposed. (See Patent Document 1).
Further, a surface treatment method using a chromium-free acidic composition, for example, a surface treatment method for immobilizing a film by treating with an aqueous solution of a component capable of forming a film having excellent corrosion resistance and then baking and drying without washing with water is proposed. (See Patent Document 2).
JP 2000-204485 A JP-A-5-195244

  However, the method described in Patent Document 1 is to obtain a surface-treated film excellent in adhesion and corrosion resistance after treatment without using hexavalent chromium, which is a harmful component, by treating with the above composition. Although possible, the target material is limited to aluminum alloys. Moreover, since a surface treatment film is formed by treatment and drying, it is difficult to uniformly treat complicated structures such as vehicle members.

  Moreover, since the method described in Patent Document 2 does not involve a chemical reaction in the formation of the film, it can be applied to various metal materials such as a magnesium alloy and an aluminum alloy. However, since a surface treatment film is formed by treatment and drying, it is difficult to uniformly treat a complicated structure such as a vehicle member as in the invention described in Patent Document 1.

On the other hand, methods of physically treating the surface, such as shot blasting using sand, iron, alumina, stainless steel powder, etc., surface polishing methods using sandpaper, wire brushes, and grinders, are also generally performed. However, when the processed member is an extruded material or a casting, the thickness of the oxide film or mold release material present on the surface is not uniform, so it is difficult to process uniformly. Variations in adhesiveness and coating adhesion occur.
Furthermore, since the alloy surface after the treatment is adhered with fine powder of the alloy generated during the treatment, there is a problem that the surface must be cleaned and degreased.

  The present invention has been made in view of the above problems in the conventional metal material surface treatment method and surface modification method. And the purpose is to activate a metal surface typified by an aluminum alloy or a magnesium alloy, and to firmly bond a primer layer excellent in adhesiveness, a manufacturing method thereof, Is to provide a joining member using the joining member.

  As a result of intensive studies to solve the above problems, the present inventors have applied energy by, for example, laser treatment, thereby forming a metal hydroxide on the metal surface, and constituting an OH group and a primer of the hydroxide The present inventors have found that the above object can be achieved by forming a covalent bond with a compound to be completed, and have completed the present invention.

  That is, the present invention is based on the above knowledge, and the metal member for bonding of the present invention is provided with a primer layer on the surface of a metal substrate, and is used by being bonded to another member via this primer layer. The bonding metal member is characterized in that a hydroxyl group exists on the surface of the base material, and at least a part of the hydroxyl group is covalently bonded to a compound constituting the primer layer.

In the joining member of the present invention, the primer layer in the joining metal member is joined to another member directly or via an adhesive layer.
And in the manufacturing method of the metal member for joining of this invention, after adding energy to the surface of a metal base material and forming a metal hydroxide on the surface of a base material, it is directly with the hydroxyl group of the said metal hydroxide. It is characterized by applying a primer containing a compound that binds covalently.

  According to the present invention, at least one hydroxyl group of the metal hydroxide formed on the metal substrate is applied by applying a primer containing a predetermined compound in a state where the metal hydroxide is formed on the surface of the metal substrate. Part is covalently bonded to the compound constituting the primer layer. Therefore, the adhesive force of the primer layer with respect to a metal base material can be improved, and it can join firmly with another member via the said primer layer and an adhesive bond layer as needed.

  Hereinafter, the present invention will be described in more detail.

In the bonding metal member of the present invention, a primer layer is provided on the surface of the metal substrate, and is a bonding metal member for use by bonding to another member through the primer layer, as described above, Hydroxyl groups exist on the surface of the metal substrate, and at least a part of these hydroxyl groups are covalently bonded to the compound constituting the primer layer.
In addition, such a bonding member includes a compound that directly applies a covalent bond to a hydroxyl group of the metal hydroxide after energy is applied to the surface of the metal substrate to form a metal hydroxide on the surface of the substrate. It can be manufactured by applying a primer.

That is, by applying energy to the surface of the metal substrate, a metal hydroxide is generated on the surface, and a primer containing, for example, an isocyanate compound or an epoxy compound as a resin component is applied thereon. As a result, the hydroxyl group of the metal hydroxide present on the surface of the base material undergoes an addition reaction with the above-mentioned primer component directly and promptly without being hydrated or altered by water intervening in advance or water generated in the reaction process. A strong covalent bond can be formed between the metal hydroxide and the primer layer.
The covalent bond formed in this way is stronger and stronger than the hydrogen bond and van der Waals force formed between the molecules, and even after the primer is cured, it remains at the interface between the substrate surface and the primer layer. Water, oil, and other foreign substances can be prevented from entering, and the durability of the primer layer can be improved.

In this invention, it does not specifically limit as a kind of metal base material, The metal and alloy conventionally used can be used.
Specific examples include iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), magnesium (Mg), aluminum (Al), silver (Ag), platinum (Pt), gold (Au ), Lead (Pb), tin (Sn), titanium (Ti), cobalt (Co), manganese (Mn), chromium (Cr), molybdenum (Mo), cadmium (Cd), tungsten (W), iridium (Ir ) And the like, and alloys containing two or more of these metals are used.

  The present invention is effective when applied to aluminum, aluminum alloys, and magnesium alloys that form a strong oxide film on the surface and generally have a problem of adhesion among the metals and alloys described above. It is. Moreover, since these metals and alloys have a lighter specific gravity than conventional steel materials and steel plates, they can be suitably used from the viewpoint of reducing the weight of the members.

Here, the type of aluminum alloy is not particularly limited, and specifically, for example, AC1A, AC1B, AC2A, AC2B, AC3A, AC4A, AAC4B, AC4C, AC4CH, AC4D, AC5A defined in JIS H5202 Aluminum alloy castings such as AC7A, AC8A, AC8B, AC8C, AC9A, AC9B, etc., ADC1, ADC3, ADC5, ADC6, ADC10, ADC10Z, ADC12, ADC12Z, ADC14, etc., as defined in JIS H 5302, Examples include aluminum alloy wrought materials such as alloy numbers 2017, 2219, 3003, 3104, 4032, 5005, 5154, 6101, 6061, 7075, and 8021 defined in JIS H4000. That.
Typical examples of these aluminum alloys are AC4C, ADC12, 5005, 5154, 6106, 6061, and 7075.

Further, the type of magnesium alloy is not particularly limited, and specifically, for example, AZ31, AZ31B, AZ61, AZ91, AZ91D, AM50, AM60, AM60B, etc. defined in SAE (American Automotive Engineering Standard) J465. Can be mentioned.
Here, the notations “AZ” and “AM” represent added metal elements, “A” is aluminum, “M” is manganese, and “Z” is zinc. The numbers following these notations indicate the addition ratio of these additive elements. For example, in the case of AZ91, aluminum is 9% and zinc is 1%. Among these magnesium alloys, AZ31, AZ61, AZ91, AM60, and AM60B can be given as representative examples.

  The form of the metal substrate is not particularly limited, and a metal substrate obtained by a molding method such as casting using a metal mold or sand mold, extrusion, forging, or pressing can be used.

  The means for applying energy to the surface of the metal substrate and forming a metal hydroxide on the surface of the substrate is particularly limited as long as energy can be applied directly or indirectly to the metal surface. It is not a thing and conventionally well-known various apparatuses can be used.

  As a specific example of such an apparatus, laser (LASER: Light Amplification by Stimulation of Radiation) light of various wavelengths ranging from ultraviolet rays to infrared rays can be irradiated, marking, surface fine processing, metal welding, etc. Laser processing equipment used for plasma, equipment that generates plasma by glow discharge under reduced pressure, mainly used for plasma polymerization to form a thin film, low pressure mercury lamp and high pressure mercury lamp as light source Corona discharge is a device used for the purpose of improving the wettability of the resin surface in the form of a film or a sheet, and performing corona discharge near the substrate surface. Processing equipment, polyethylene resin and polypropylene Flame treatment equipment using mixed combustion of propane gas and air used for the purpose of activating olefin resin surfaces such as carbon resin, electrons that accelerate electrons with acceleration voltage and irradiate the substrate surface with a high energy electron beam An irradiation device, an ozone treatment device that generates ozone using a low-pressure mercury lamp or excimer lamp as a light source, an ion implantation device (ion beam irradiation device) that injects arbitrary ions into the substrate surface by accelerating them in an electric field, infrared light Examples thereof include an infrared irradiation device that directly irradiates with a lamp, a method of heating with a heating device such as a heater, and a method of generating frictional heat on the substrate surface by directly polishing the substrate surface, such as blasting or sanding.

  In addition, the method of applying energy directly to the surface of the metal substrate using the apparatus as described above is, for example, applying energy generated from the apparatus directly to the metal surface in the air or under vacuum conditions. Means that. On the other hand, the method of indirectly applying energy to the metal surface is, for example, applying energy indirectly to the metal surface previously coated with any material in the air or under vacuum conditions, or immersing it in oil or chemicals. This means that energy is applied to the surface of the metal through these oils and chemicals.

  In the present invention, it is preferable to apply laser treatment, plasma treatment, ultraviolet irradiation treatment, corona treatment and flame treatment alone or in combination among the various treatments described above. With these treatment devices, sufficient energy can be applied to the surface of the base material to modify the metal, so that the metal hydroxide can be uniformly formed. An efficient and highly reliable process can be performed without causing deterioration of the quality layer.

  In particular, in the present invention, it is preferable to apply laser irradiation among the various processes described above.

The type of laser used in the present invention is not particularly limited, and specific examples include YAG laser (yttrium, aluminum, garnet), YVO ₄ laser (yttrium vanadate), semiconductor laser, and CO ₂ laser.
Among these, a YAG laser and a YVO ₄ laser are preferable, and a laser processing apparatus used for marking and fine processing can be diverted, so that the equipment cost can be kept low.

The compound included in the primer and constituting the primer layer is not particularly limited as long as it does not require water in the reaction process and can be directly added to the hydroxyl group of the metal hydroxide on the substrate surface. Specifically, for example, the following compounds can be used.
(A-1) Isocyanate compound (A-2) Epoxy compound (A-3) Acid anhydride (A-4) Carboxylic acid can be mentioned, but (A-1) Isocyanate compound, (A-2) It is preferable to use an epoxy compound and (A-3) acid anhydride.

  The isocyanate compound is not particularly limited as long as it contains a compound having two or more isocyanate groups in the molecule, and various isocyanate compounds can be used.

Specific examples of such compounds include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate ( 4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylidene diisocyanate (TMXDI), tolidine diisocyanate ( TODI), aromatic diisocyanates such as 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (N Aliphatic diisocyanates such as BDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H6-XDI (hydrogenated XDI), H12-MDI (hydrogenated MDI), and the like Examples thereof include carbodiimide-modified diisocyanates of diisocyanates, or isocyanurate-modified diisocyanates, and two or more of these may be used in combination.
Among these, 4,4′-MDI, 2,4′-MDI, HDI, XDI, or those obtained by prepolymerizing these compounds is preferable.

Moreover, the isocyanate compound may contain a catalyst as necessary in addition to the compound having two or more isocyanate groups in the molecule as described above. The catalyst is not particularly limited as long as it accelerates or delays the curing rate of the isocyanate compound as necessary, and various catalysts can be used.
Specific examples include monoamines such as triethylamine (TEA) and N, N′-dimethylcyclohexylamine (DMEDA), N, N, N ′, N′-tetramethylethylenediamine (TMEDA), N, N, N Diamines such as', N'-tetramethylhexane-1,6-diamine (TMHMDA), N, N, N ′, N ″, N ″ -pentamethyldipropylene-triamine (PMDPTA), tetramethylguanidine (TMG) triamines, triethylenediamine (TEDA), N, N′-dimethylpiperazine (DMP), cyclic amines such as N-methylmorpholine (NMMO), dimethylaminoethanol (DMEA), N-methyl-N Examples include alcohol amines such as'-(2-hydroxyethyl) -piperazine (MHEP). Of these catalysts, triamines and cyclic amines are preferable.

Furthermore, the said isocyanate compound may also contain an additive as needed. Such additives include:
(1) Antioxidants such as hindered amines, hydroquinones, hindered phenols, sulfur-containing compounds (2) Ultraviolet absorbers such as benzophenones, benzotriazoles, salicylic acid esters, metal complexes, etc. (3) Metal soaps, heavy metal inorganics and organics Weather-resistant stabilizers such as salts and organotin compounds (4) Plasticizers such as phthalate esters, phosphate esters and fatty acid esters (5) Paraffin wax, polymer wax, beeswax, whale wax, low molecular weight polyolefin, etc. Waxes (6) Organic and inorganic fillers such as calcium carbonate, kaolin, talc, mica, bentonite, clay, carbon black, glass balloon, acrylic resin powder, phenol resin powder, ceramic powder, zeolite, titanium oxide (7) Glass fiber, aramid fiber, carbon fiber, Organic and inorganic fibers such as nylon fiber, nylon fiber, polyester fiber, alumina fiber, boron fiber, etc. (8) Antistatic agents (9) Antibacterial agents (10) Dehydrating agents (11) Flame retardants (12) Solvents (13) Pigments (14) perfumes (15) curing accelerators and the like. Two or more of these additives can be used in combination.

The epoxy compound is not particularly limited as long as it contains an epoxy resin having two or more epoxy groups in the molecule and a curing agent, and various epoxy resins can be used.
Specific examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, biphenyl type epoxy resins, and glycidyl ester type epoxies. Examples thereof include resins, alicyclic epoxy resins, and heterocyclic epoxy resins. Bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferable.

  Specific examples of the curing agent described above include ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), isophoronediamine (IPDA), N-aminoethylpiperazine ( N-AEP) aliphatic amines, m-xylenediamine (MXDA) and other aromatic aromatic amines, metaphenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS) and other aromatics Amines, other amines such as dicyandiamide (DICY), adipic acid dihydrazide (AADH), modified polyamines such as epoxy compound-added polyamine, Michael added polyamine, and Mannich added polyamine, polyamide amine Phthalic anhydride (PA), tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MeTHPA), methylhexahydrophthalic anhydride (MeHHPA), methyl nadic anhydride (MNA) , Dodecyl succinic anhydride (DDSA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic anhydride (BTDA), ethylene glycol bis (anhydrotrimate) (TMEG), trimellitic anhydride (TMA), polyazeline Examples of the acid anhydride (PAPA) include anhydrides, aliphatic amines, other amines, modified polyamines, and polyamidoamines.

Moreover, the said epoxy compound may also contain a catalyst as needed other than the epoxy resin and hardening | curing agent which have 2 or more of epoxy groups in a molecule | numerator. As such a catalyst, any catalyst can be used without particular limitation as long as it accelerates or delays the curing rate of the epoxy compound as necessary.
Specific examples include 2- (dimethylaminomethyl) phenol (DMP-10), 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30), triethanolamine, tetramethylguanidine, pyridine, Although tertiary amines such as picoline, piperidine, pyrrolidine, 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU) and the like can be mentioned, DMP-10 and DMP-30 can be preferably used.

  Furthermore, as an epoxy compound, you may contain an additive as needed other than the epoxy resin and hardening | curing agent which have 2 or more of epoxy groups in a molecule | numerator. As this additive, it is the same as that of the above-mentioned additive, and can also use 2 or more types together.

The acid anhydride is not particularly limited as long as it has one or more acid anhydride groups in the molecule, and various acid anhydrides can be used.
Specific examples of such acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, ethylene glycol bis (anhydrotrimate), maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecyl succinic anhydride, succinic anhydride, methylcyclohexenedicarboxylic anhydride, alkylstyrene-maleic anhydride copolymer, methyl nadic anhydride, chlorendic anhydride, poly Examples thereof include azelaic anhydride, and preferred are phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

  Furthermore, the acid anhydride may contain an additive as necessary. As this additive, it is the same as that of the above-mentioned additive, and can use 2 or more types together.

  As a form of such a primer, for example, as a solution in which a compound constituting the primer is previously diluted in a solvent, as an emulsion (emulsion) dispersed in water using an emulsifier, or water-solubilized using a surfactant It can be used as an aqueous solution. Among these usage forms, a solution excellent in workability is preferable.

  As a method for applying such a primer to the substrate surface, it can be applied directly with a brush or brush, or impregnated into a cloth in advance, or spray, blade coater, air knife coater, roll coater, bar coater, gravure, etc. There are a coating method using a coating apparatus such as a coater, a flow coater, a curtain coater, and a coating method using dipping, a coating gun, etc., but it is not limited to these.

The bonding member of the present invention uses the bonding metal member of the present invention, and the primer layer in the bonding metal member is directly or, if necessary, via an adhesive layer different from the primer layer. It is joined with other members.
Here, there is no limitation as to other members, that is, mating members, and members and articles made of various materials can be applied. Of course, joining the metal members for joining of the present invention is also included.

At this time, depending on the type of the mating member, that is, a member made of a material that can obtain sufficient adhesion by the primer layer component of the joining metal member, the metal base material of the joining metal member and the mating member are the primer layer. It will be joined directly via.
On the other hand, in the case of a material for which sufficient adhesive strength cannot be obtained only by the primer layer, the primer layer of the bonding metal member is bonded to the mating member via an adhesive layer having sufficient adhesion to the mating member. Will be.

  Specific examples of the mating member include, for example, polyolefin resins including polyethylene (PE) resin and polypropylene (PP) resin, polystyrene (PS) resin, polyvinyl chloride (PVC) resin, polyester resin, polyamide (PA) resin, Polyamideimide (PAI) resin, acrylonitrile butadiene styrene (ABS) resin, polycarbonate (PC) resin, polyacetal (POM) resin, acrylic resin, urea resin, melamine resin, epoxy resin, phenol (PF) resin, polyphenylene sulfide ( Plastic molded products made of PPS resin, etc., metal molded products made of steel materials, aluminum alloys, magnesium alloys, copper alloys, titanium alloys, woven fabrics made of carbon fibers, aramid fibers, glass fibers, natural fibers, natural rubber, etc. The sti Down-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), ethylene propylene rubber (EPDM) rubber molded article and the like, and the like glass and ceramic products. Among these members, resin molded products and metal molded products are preferable.

  Specific examples of metal molded products include iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), magnesium (Mg), aluminum (Al), silver (Ag), and platinum (Pt). , Gold (Au), lead (Pb), tin (Sn), titanium (Ti), cobalt (Co), manganese (Mn), chromium (Cr), molybdenum (Mo), cadmium (Cd), tungsten (W) And metals and alloys containing iridium (Ir) as a main component, and alloys containing two or more of these metals.

  When the mating member is a metal molded product, particularly when it is made of an aluminum alloy or a magnesium alloy, the metal hydroxide is similarly generated on the mating member side, and then a primer is applied to form a covalent bond. It is desirable to use the metal member for bonding of the present invention.

At this time, the primer layers of both members can be joined via an adhesive layer different from these, or the primer layers of both members can be joined directly. At this time, it is not essential that the primer layers of both members are of the same type.
In addition, after forming a metal hydroxide on the joint surface of the metal base by the above-described means, after applying a primer on one or both sides, the two are bonded together, that is, the metal hydroxide. It is also possible to join both metal substrates subjected to the generation treatment through a single primer layer.

The adhesive is not particularly limited as long as it is a compound that is applied to at least a part of the primer application surface, typically the entire primer application surface, and is cured after being joined to a mating member made of any material. Various curable compositions can be used. In particular,
(B-1) Isocyanate compound (B-2) Epoxy compound (B-3) Acid anhydride (B-4) Carboxylic acid (B-5) Polyolefin type (polyethylene (PE) type, ethylene-vinyl acetate (EVA) Etc.), synthetic rubber type (polybutadiene (SBS) type, polyisoprene (SIS) type, etc.), polyamide type, polyester type compound, etc.
(B-6) Polyolefin compound (B-7) natural rubber, styrene / butadiene rubber (SBR), acrylonitrile / butadiene rubber (NBR), ethylene / propylene rubber (EPDM), chloroprene rubber (CR) Synthetic rubbers such as butyl rubber (IIR) and butadiene rubber (BR) (B-8) acrylic compounds (B-9) urea compounds (B-10) melamine compounds (B-11) phenolic compounds (B-12) Examples include silicone compounds containing modified silicones, preferably (B-1) isocyanate compounds, (B-2) epoxy compounds, (B-6) polyolefin compounds, (B-8) acrylic compounds, (B -12) A silicone compound.

As an isocyanate compound, it is the same as that of the isocyanate compound described previously, A polyol compound can be used together as needed besides the compound which has two or more isocyanate groups in a molecule | numerator. The polyol compound is not particularly limited as long as it contains a compound having two or more hydroxyl groups in the molecule.
Specific examples include polyether polyols such as polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene ether glycol (PTMG), and condensation and lactone polyester polyols. Of these polyol compounds, polyether polyols are preferred.

  The epoxy compound is the same as the above-described epoxy compound, and is not particularly limited as long as it contains an epoxy resin having two or more epoxy groups in the molecule and a curing agent, and various epoxy resins can be used. .

Examples of the acrylic compound include a thermoplastic acrylic compound, a thermosetting acrylic compound, and a moisture curable acrylic compound, but are not particularly limited, and various acrylic compounds can be used.
Specific examples of the thermoplastic acrylic compound include acrylic acid esters such as methyl methacrylate and ethyl acrylate, and polymers and copolymers of methacrylic acid esters. In this case, the ester group of the esterified product may be an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, lauryl, and stearyl. In the case of a copolymer, two or more types of ester groups can be used in combination.

  Specific examples of thermosetting acrylic compounds include monomers having a functional group (carboxyl group, hydroxyl group, amino group, methylol group, epoxy group, etc.) that can form a crosslinked structure in the molecule, such as acrylic acid and methacrylic acid. , Acrylamide, methacrylamide, N-methylol acrylamide, allyl glycidyl ether, glycidyl methacrylate, and the like, and those having no such functional group, for example, styrene and the above-mentioned acrylic acid or methacrylic acid ester group. And a polymer obtained by copolymerizing two or more monomers.

  Specific examples of the moisture curable acrylic compound include methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylate, and butyl cyanoacrylate. Among these acrylic compounds, a thermosetting acrylic compound or a moisture curable acrylic compound is preferable.

  Furthermore, the acrylic compound may contain an additive as necessary. Such additives are the same as those described above, and two or more kinds can be used in combination.

Examples of the silicone compound include a thermosetting silicone compound and a moisture curable silicone compound, but are not particularly limited, and various silicone compounds can be used.
Specific examples of the thermosetting silicone compound include a composition mainly composed of an organopolysiloxane having a vinyl group and an organohydropolysiloxane having an Si-H group, and a platinum complex as a catalyst. . Specific examples of the moisture curable silicone compound include dealcohol-free silicone compounds, deoxime-type silicone compounds, deacetate-type silicone compounds, deamidation-type silicone compounds, and deacetone-type silicone compounds. Of these silicone compounds, moisture-curable silicone compounds are preferred.

  The silicone compound may contain an additive as necessary. As this additive, it is the same as that of the above-mentioned additive, and can also use 2 or more types together.

  When using the said isocyanate compound or an epoxy compound as an adhesive agent, the composition of a primer and a compound may correspond, and the effort by overcoating can be skipped.

The adhesive may be used in the same manner as the primer described above, but it is desirable to use it as it is without diluting with a solvent or water.
And as an application method to the primer application surface of an adhesive agent, the application method similar to a primer is employable.

At this time, after applying the primer, it is preferable to apply the curable composition B after confirming that the surface is sufficiently dried. In addition, after applying the adhesive, it is preferable to quickly join the mating member before the surface is dried.
As a means for confirming the degree of drying of the primer and the adhesive surface after application, for example, a confirmation method by dry-to-touch specified in JIS K-5400 can be mentioned, and lightly touch the application surface with a fingertip. As long as the fingertips are not soiled with these coatings, it can be considered that the coating is sufficiently dry.

In order to accelerate the drying and curing of the primer and adhesive surface, heat treatment and humidification treatment can be appropriately performed as necessary. In particular, it is preferable to promote drying and curing of the primer at a temperature of 40 ° C to 150 ° C.
Moreover, about an adhesive agent, when it consists of an epoxy compound or an acrylic compound, when it consists of an isocyanate compound or a silicone compound in an environment of 40 degreeC-150 degreeC, temperature 40 to 150 degreeC and humidity 30-100 It is preferable to promote drying and curing in a% RH environment.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited only to these Examples.

Example 1
Using a YVO ₄ laser irradiation device (ML-7111A, manufactured by Miyachi Technos Co., Ltd.) on the surface of a base material (AZ91: 25 × 100 × 4 mm) made of a magnesium alloy plate, current 25 A, frequency 15 kHz, processing speed 500 mm / s. By irradiating laser light under the conditions of a wavelength of 1064 nm and an irradiation intensity of 3800 W / mm ² , the entire surface of one side of the substrate was subjected to surface modification treatment to generate a metal hydroxide.
And the surface state after laser irradiation processing was investigated by the method shown below, and the joining test piece using these base materials was produced, and initial adhesiveness and durable adhesiveness were each evaluated.

<Initial adhesiveness>
As shown in FIG. 1, an isocyanate-based primer (Hamatite RC-50E, manufactured by Yokohama Rubber Co., Ltd .: hereinafter referred to as “Primer A”) is brushed in the region of 10 mm end of the treated surface 2a of the treated substrate 2. Then, the primer layer 3 was formed by drying and curing for 10 minutes in a room temperature environment to obtain a joining metal member 1.
Next, after lightly touching the primer application surface with a finger and confirming that the primer does not adhere to the fingertip, a silicone adhesive (TB-1217H, manufactured by Three Bond Co., Ltd .: “Adhesive K” is applied to the primer application surface. 2) is applied using an application gun, and as shown in FIG. 2, the primer layer 3 of the other joining metal member 1 produced in the same manner is bonded through the adhesive layer 4, It joined and it was set as the test piece. Then, for the purpose of curing the “adhesive K”, it is left in a constant temperature and humidity chamber (PL-3K, manufactured by Tabai Espec Co., Ltd.) previously adjusted to 20 ° C. and 65% RH for 7 days, and further 24 hours at room temperature. Cured for hours.

  And the tensile shear test was done using such a joining test piece. The tensile shear test was performed using an autograph (AG-I 20 kN, manufactured by Shimadzu Corporation), and the shear strength was measured under a tensile speed of 50 mm / min. After the test, the ratio of the area where the adhesive is cohesive to the coated area of the adhesive was determined visually to obtain the cohesive failure rate.

<Durable adhesiveness>
After preparing a test piece by the same method as the above initial adhesiveness, after leaving it in a constant temperature and humidity chamber (PL-3K, manufactured by Tabai Espec Co., Ltd.) that has been previously adjusted to 50 ° C. and 95% RH, Furthermore, after curing at room temperature for 24 hours, the same tensile shear test was performed. These results are shown in Table 1.

<Surface condition>
In Example 1, as a representative example of a magnesium alloy substrate, the substrate after laser irradiation treatment was allowed to cool at room temperature for 5 minutes, and then cooled by an X-ray photoelectron spectrometer (JPS-9200, manufactured by JEOL). Was used to confirm the bonding state of the metal atoms from the bond energy value (chemical shift) of each metal atom present on the irradiation-treated surface.
That is, in the case of a magnesium atom, strong absorption occurs around 49.8 eV for metal magnesium, around 49.5 eV for magnesium hydroxide, and around 50.8 eV for magnesium oxide. Next, the bonding state of magnesium atoms on the modified surface was determined. This X-ray photoelectron spectroscopic analysis chart is shown in FIG.

(Example 2)
A test piece obtained by repeating the same operation as in Example 1 except that an isocyanate-based adhesive (Hamatite WS-201, manufactured by Yokohama Rubber Co., Ltd .: hereinafter referred to as “adhesive L”) was used as the adhesive. Thus, initial adhesiveness and durable adhesiveness were evaluated. The results are also shown in Table 1.

(Example 3)
As the primer, the same operation as in Example 1 was performed, except that the isocyanate-based adhesive L was used and the treated substrates were directly bonded to each other through a primer layer containing the isocyanate-based compound. The test piece obtained by repeating was evaluated about initial adhesiveness and durable adhesiveness, respectively. The results are also shown in Table 1.

Example 4
Test obtained by repeating the same operation as in Example 1 except that a hot-melt type olefin-based adhesive (HM712, manufactured by Cemedine Co., Ltd .: hereinafter referred to as “adhesive M”) was used as the adhesive. Each piece was evaluated for initial adhesion and durable adhesion. The results are also shown in Table 1.

(Example 5)
As a primer, an epoxy adhesive (Sandyne 2403, manufactured by Asahi Rubber Co., Ltd .: hereinafter referred to as “adhesive N” was used, and the treated substrates were directly bonded to each other via a primer layer containing the adhesive and containing an epoxy compound. .
At this time, the adhesive N is a heat curable adhesive, and is left to stand in an oven (PH-301, manufactured by Tabai Espec Co., Ltd.) heated and adjusted to 170 ° C. for 20 minutes for the purpose of curing the adhesive N. Further, after curing at room temperature for 24 hours, the initial adhesiveness was evaluated by conducting the same tensile shear test. For durable adhesion, the sample was left in a pressure cooker tester (EHS-220M, manufactured by Tabay Espec Co., Ltd.) that had been previously adjusted to 120 ° C. for 72 hours, and after curing at room temperature for 24 hours, the same tensile shear test was performed. Evaluated by doing. The results are also shown in Table 1.

(Example 6)
Except that an aluminum alloy plate (ADC12) was used as the metal substrate, initial adhesion and durability adhesion were similarly evaluated using test pieces obtained by repeating the same operation as in Example 1 above. did. The results are also shown in Table 1.
Moreover, about the said Example 6, as a typical example of an aluminum alloy base material, about the base material after a laser irradiation process, it carries out X-ray photoelectron spectroscopy analysis similarly to the said Example 1, and the metal which exists in an irradiation process surface The state of atomic bonding was confirmed. In other words, in the case of aluminum atoms, strong absorption occurs at around 72.9 eV for metal aluminum, around 74.0 eV for aluminum hydroxide, around 74.7 eV for oxide film, and around 73 to 74 eV for aluminum oxide. Therefore, the bonding state of aluminum atoms on the modified surface was determined. This X-ray photoelectron spectroscopic analysis chart is shown in FIG.

(Comparative Example 1)
The surface of the base material composed of a magnesium alloy plate is irradiated with laser light under the same conditions, and the silicone is formed without applying a primer to the treated surfaces of both base materials on which metal hydroxide is generated. Direct bonding was performed using a system adhesive K. Except for this, initial adhesiveness and durable adhesiveness were evaluated in the same manner as in Example 1 above. The results are also shown in Table 1.

(Comparative Example 2)
It is obtained by repeating the same operation as in Example 1 except that a terminal glycidyl group-modified silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd .: hereinafter referred to as “Primer B”) is used as a primer. The test specimens were evaluated for initial adhesion and durable adhesion. The results are also shown in Table 1.

(Comparative Example 3)
Obtained by repeating the same operation as in Example 1 except that a terminal thiol group-modified silane coupling agent (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd .: hereinafter referred to as “Primer C”) was used as a primer. The initial adhesiveness and the durable adhesiveness were similarly evaluated using the test pieces. The results are also shown in Table 1.

(Comparative Example 4)
A test piece obtained by repeating the same operation as in Example 1 except that a ketimine compound (hereinafter referred to as “primer D”) was used as a primer and an isocyanate-based adhesive L was used as an adhesive. The adhesiveness and the durable adhesiveness were evaluated. The results are also shown in Table 1.
The primer D was prepared by adding triethylenetetramine (TETA, Tosoh Corporation) to a glass container with a lid of 300 mL, which was previously filled with molecular sieve (Molecular sieve 3A 1/16, manufactured by Kanto Chemical Co., Ltd.) until about 5 minutes. 50 parts by weight and 50 parts by weight of acetone (reagent grade 1, manufactured by Kanto Chemical Co., Inc.) were added in this order, and the mixture was stirred and sealed, and then placed in a room temperature environment for 2 days. . And after arranging for 2 days, as a result of analyzing the transparent liquid in the glass container with an infrared spectrophotometer (FTIR-8400S, manufactured by Shimadzu Corporation), the amino group disappeared and a ketimine group was newly generated. It has been confirmed that

(Comparative Example 5)
The primer D comprising a ketimine compound as a primer and an epoxy adhesive N as an adhesive were cured and cured under the same conditions as in Example 5 to cure the primer. Except for this, initial adhesiveness and durable adhesiveness were evaluated by test pieces obtained by repeating the same operation as in Example 1. The results are also shown in Table 1.

(Comparative Example 6)
Except that an aluminum alloy plate (ADC12) was used as the metal base material, initial adhesiveness and durable adhesiveness were similarly evaluated using a test piece obtained by repeating the same operation as in Comparative Example 1 above. did. The results are also shown in Table 1.

(Comparative Example 7)
The same operation as in Example 1 except that an aluminum alloy plate (ADC12) was used as the metal substrate, the primer D made of a ketimine compound was used as the primer, and the silicone-based adhesive K was used as the adhesive. The test pieces obtained by repeating the above were evaluated for initial adhesion and durable adhesion. The results are also shown in Table 1.

  As a representative example of the investigation result of the surface state, in FIG. 3 which is an X-ray photoelectron spectroscopic analysis chart regarding the magnesium alloy substrate, an absorption peak was observed in the vicinity of 50.8 eV indicating the presence of magnesium oxide. Moreover, in FIG. 4 regarding the aluminum alloy base material, a peak is recognized in the vicinity of 74.0 eV indicating the presence of aluminum hydroxide, and in any case, the surface of the base material is It was confirmed that a modified surface containing aluminum or magnesium hydroxide was formed.

  Further, as is apparent from Table 1, a primer containing a curable resin capable of addition reaction with a hydroxyl group is directly applied to the surface, such as an isocyanate compound or an epoxy compound, without requiring water during the reaction process. In the joining test piece of Examples 1-6 using the metal member for joining of this invention, it was recognized that the outstanding initial adhesiveness and durable adhesiveness are shown.

On the other hand, even in the case of using a metal substrate subjected to the same treatment, the bonding test pieces of Comparative Examples 1 and 6 directly bonded with an adhesive without providing a primer layer were compared with the above examples. It was confirmed that the initial adhesiveness and the durable adhesiveness were inferior.
Even when a primer layer is formed, a silane coupling agent (alkoxysilane compound) or ketimine compound cannot react directly with a hydroxyl group to form a covalent bond. After that, in the joining test pieces of Comparative Examples 2 to 5 and 7 using a compound that forms a covalent bond with a hydroxyl group only after dehydration condensation, initial adhesiveness and durable adhesion are compared with the corresponding examples. It was confirmed that it was inferior in sex.

It is a schematic explanatory drawing which shows the dimension and shape of the metal member for joining used for the Example of this invention. It is the schematic which shows the preparation points of the joining test piece which joined the said metal member for joining. It is a graph which shows an example (Example 1) of the X-ray photoelectron spectroscopy analysis chart of the magnesium alloy base material surface after a laser irradiation process. It is a graph which shows an example (Example 6) of the X-ray photoelectron spectroscopy analysis chart of the aluminum alloy base material surface after a laser irradiation process.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Metal member for joining 2 Metal base material 3 Primer layer 4 Adhesive layer

Claims (8)

  A metal member provided with a primer layer on the surface of a metal substrate and joined to another member via the primer layer, wherein a hydroxyl group is present on the surface of the substrate, and at least one of the hydroxyl groups. A bonding metal member, wherein the part is covalently bonded to a compound constituting the primer layer.   The joining metal member according to claim 1, wherein the metal substrate is made of an aluminum alloy or a magnesium alloy.   The joining metal member according to claim 1 or 2, wherein the primer layer contains at least one compound selected from the group consisting of an isocyanate compound, an epoxy compound, and an acid anhydride.   A joining member, wherein the primer layer of the joining metal member according to any one of claims 1 to 3 is joined to another member directly or via an adhesive layer.   The joining member according to claim 4, wherein the adhesive layer contains at least one compound selected from the group consisting of an acrylic compound, an isocyanate compound, an epoxy compound, and a silicone compound.   Applying energy to the surface of the metal substrate to form a metal hydroxide on the surface of the substrate, and then applying a primer containing a compound that directly and covalently bonds to a hydroxyl group of the metal hydroxide Method for manufacturing a metal member.   The metal hydroxide is formed on the surface of the metal substrate by at least one treatment selected from the group consisting of laser treatment, plasma treatment, ultraviolet irradiation treatment, corona treatment and flame treatment. Item 7. A method for producing a joining metal member according to Item 6.   The method for producing a metal member for joining according to claim 6 or 7, wherein the compound contained in the primer is at least one compound selected from the group consisting of an isocyanate compound, an epoxy compound, and an acid anhydride. .

Images