Classifications

• • 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
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F1/00—Etching metallic material by chemical means
  • C23F1/10—Etching compositions
  • C23F1/14—Aqueous compositions
  • C23F1/16—Acidic compositions
  • C23F1/20—Acidic compositions for etching aluminium or alloys thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/17—Component parts, details or accessories; Auxiliary operations
  • B29C45/26—Moulds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
  • B29C65/56—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using mechanical means or mechanical connections, e.g. form-fits
  • B29C65/64—Joining a non-plastics element to a plastics element, e.g. by force
• • 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
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/54—Contact plating, i.e. electroless electrochemical plating
• • 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
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F1/00—Etching metallic material by chemical means

Definitions

• the present invention is an etching agent for roughening the surface of a substrate (hereinafter sometimes referred to as "aluminum-containing substrate") in which at least all or part of the surface is aluminum or an aluminum alloy
• aluminum-containing substrate in which at least all or part of the surface is aluminum or an aluminum alloy
• the present invention relates to a method for producing a base, a roughened base, a method for producing a base-resin cured product, and a base-resin cured product.
• Injection molding bonding, adhesive bonding, and the like have been studied as a bonding technology between metal and resin.
• the aluminum component is made of an alkaline etching agent containing an amphoteric metal ion, an oxidizing agent, and an alkali source, or an acid etching agent containing at least one of a ferric ion and a cupric ion, and an acid.
• a method of producing an aluminum-resin composite comprising the step of roughening the surface of
• an object of this invention is to provide the etching agent etc. which can form the rough surface excellent in the joint strength with resin with respect to the aluminum containing base material.
• the present inventors roughly contact the aluminum-containing substrate with an etching agent containing a peroxodisulfate ion and a chloride ion to obtain a rough bonding strength with the resin. It has been found that a surface can be formed, and the present invention has been completed.
• the present invention (1) An etching agent for roughening the surface of a substrate at least the whole surface of which is partially or entirely made of aluminum or an aluminum alloy, the etching agent containing at least peroxodisulfate ion and chloride ion.
• the method for producing a roughened substrate according to (2) including a zincate step of forming a zincate film on the surface of the substrate before the etching step.
• the etching agent etc. which can form the rough surface which is excellent in the joint strength with resin with respect to an aluminum containing base material can be provided.
• the etching agent according to the embodiment of the present invention is an aqueous solution containing at least peroxodisulfate ion and chloride ion.
• the substrate can be roughened by bringing the etching agent into contact with the surface or surface of the aluminum-containing substrate.
• the etchant is prepared by dissolving a peroxodisulfuric acid compound and a chlorine compound in water.
• an element such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, zinc or the like derived from the base material may be present.
• elements, such as zinc may be mixed by melt
• An etchant according to an embodiment of the present invention comprises peroxodisulfate ion (S 2 O 8 2 ⁇ ).
• peroxodisulfate ion As a source of peroxodisulfate ion, for example, one or more suitable ones can be selected from peroxodisulfate compounds such as sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, etc. It is not something to be done.
• the etching agent according to the embodiment of the present invention is preferably 0.02 mol / L or more and 0.90 mol / L or less, more preferably 0.10 mol / L or more and 0.50 mol / L or less, more preferably peroxodisulfate ion. Including 0.15 mol / L or more and 0.40 mol / L or less.
• An etchant according to an embodiment of the present invention comprises chloride ion (Cl ⁇ ).
• chloride ion chloride ion
• a chloride ion source for example, one or more suitable ones can be selected from chlorine compounds such as lithium chloride, sodium chloride, potassium chloride, calcium chloride, ammonium chloride and the like, but are limited thereto It is not a thing. However, it is preferable not to use a chloride of a transition metal such as iron chloride. In addition, it is preferable not to use hydrochloric acid because it may generate mist, which may cause health damage to workers and may corrode surrounding metal parts and devices.
• the etching agent according to the embodiment of the present invention preferably has a chloride ion of 0.40 mol / L or more and 2.50 mol / L or less, more preferably 0.80 mol / L or more and 2.00 mol / L or less, still more preferably 1 20 mol / L or more and 1.70 mol / L or less are included.
• the etching agent according to the embodiment of the present invention may be substantially free of phosphoric acid. Substantially not included means below the detection limit.
• the pH of the etching agent according to the embodiment of the present invention is preferably in the range of 6.0 or less, more preferably in the range of 2.0 to 4.0.
• the pH of the etching agent is not limited to commercially available pH measuring devices and electrodes, and can be measured using these.
• the pH measuring device can be calibrated by adjusting the internal solution of the pH electrode and the commercially available pH standard solution to the same temperature as the etching agent etc. using the pH measuring device and the device having a temperature compensation function. For example, it is also possible to measure the pH at the temperature used of the etching agent and the like.
• the method for producing a roughened substrate according to an embodiment of the present invention includes an etching step of contacting the surface or surface of the substrate with an etchant containing at least peroxodisulfate ion and chloride ion. Further, in the method of manufacturing a bonded base material-cured resin product according to an embodiment of the present invention, the etching step and the recess formed by bringing the etching agent into contact to roughen the base material are used. And D. placing the resin composition.
• the surface or surface of the roughened substrate obtained by the method for producing a roughened substrate according to an embodiment of the present invention is formed by roughening such as injection molding bonding and adhesive bonding.
• the base material and the resin composition can be firmly bonded.
• a zincate film is formed on the surface of the substrate before performing the etching step.
• a zincate step is carried out to form
• other steps may be present.
• the surface cleaning process of which the surface of the said base material is cleaned before performing each process can be mentioned.
• the method for producing a roughened substrate according to the embodiment of the present invention may include the etching step and other optional steps described below as exemplified below. Step of degreasing the substrate (optional) ⁇ step of alkaline cleaning the substrate (optional) ⁇ step of pickling the substrate (optional) ⁇ zincate step (optional) ⁇ etching step
• the order of the process of carrying out the alkali washing process of a base material, and the process of carrying out an acid washing process of a base material may be reverse, may contain only any one, and does not need to contain both.
• the method for producing a bonded base material-cured resin product includes an etching step, a step of putting a resin composition in a recess, and other optional steps described below as exemplified below. May be. Step of degreasing the substrate (optional) ⁇ step of alkaline cleaning the substrate (optional) ⁇ step of pickling the substrate (optional) ⁇ zincate step (optional) ⁇ etching step ⁇ post treatment step (optional) ⁇ A step of putting the resin composition into a recess.
• the order of the process of carrying out the alkali washing process of a base material, and the process of carrying out an acid washing process of a base material may be reverse, may contain only any one, and does not need to contain both.
• a base material and each process are explained in full detail.
• the base material applied to the embodiment of the present invention is not particularly limited as long as at least all or part of the surface is a base material composed of aluminum or an aluminum alloy.
• the base material may include a cast material and a die cast material, and may be heat-treated.
• the base material may be subjected to other processing and / or other processing, for example, processing such as cutting, grinding, blasting, polishing (lapping), and the like may be performed.
• the shape of the said base materials such as a rod, a band, a pipe
• the base material may be a molded product or a material before molding.
• all or part of the surface of the substrate may be a film of aluminum or an aluminum alloy, and the method of forming the film may be, for example, a plating method or a thermal spraying method, but is not limited thereto.
• parts other than the surface of the substrate may be materials other than aluminum or aluminum alloy, for example, metals other than aluminum or aluminum alloy, Examples include, but are not limited to, resins, rubbers, woods, ceramics, and composite materials.
• alloy components other than aluminum in aluminum alloy magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, zinc can be mentioned, for example.
• a zincate step may be performed to form a zincate film on the surface of the substrate as a pretreatment of the etching step.
• the zincate process any known process can be used as long as it is a zincate process for aluminum.
• the bath temperature is maintained at 40.0 ° C. or less, and the substrate is immersed for about 1.0 seconds to 5.0 minutes to allow natural oxidation.
• the zincate film can be formed at the same time as removing the film.
• the formed film may be dissolved with the etching agent or nitric acid, and the operation of forming the film again may be performed once or more.
• metals such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, zinc and the like derived from the base may be present in addition to the essential components.
• the pH of the treatment liquid used in the zincate step is not limited as long as it is within a known range, and may be, for example, 10.0 or more and 13.0 or more in the case of a treatment liquid exhibiting a pH on the alkaline side. It is also good. Preferably, it is in the range of 11.0 to 13.0.
• Sodium hydroxide or potassium hydroxide can be used to raise the pH to adjust the pH of the zincate solution.
• etching step in which the etching agent is brought into contact with the surface or the surface of the substrate. is there.
• the etchant preferably has a solution temperature of 10.0 to 70.0 ° C.
• the substrate is brought into contact with the etchant, for example, by immersion.
• the etching agent is brought into contact with the substrate after the zincate step.
• the contact time varies depending on the liquid temperature and pH but is, for example, in the range of 1.0 second to 3600.0 seconds.
• the temperature of the etching step is preferably 5.0 to 70.0 ° C., and more preferably 20.0 to 40.0 ° C.
• the manufacturing method according to the embodiment of the present invention may include a surface cleaning step of cleaning the surface of the substrate in advance before performing all the steps.
• the process of degreasing the surface of the said base material can be mentioned as an example of a surface cleaning process.
• the method of the degreasing treatment is not particularly limited, and examples thereof include a method using a solvent-based, water-based or emulsion-based degreasing agent.
• the degreasing agent may contain an alkali salt, a surfactant and the like.
• the time of the above-mentioned degreasing process is preferably 0.5 to 30.0 minutes.
• the temperature of the degreasing step is preferably 30.0 to 70.0 ° C.
• the process of carrying out the alkali cleaning process of the surface of the said base material can be mentioned as an example of a surface cleaning process.
• a publicly known thing can be applied as an agent used by alkaline washing treatment. After the degreasing step, an alkaline washing step may be performed. It is preferable that the time of the process of the said alkali cleaning treatment is 0.5 to 30.0 minutes. It is preferable that the temperature of the said process of carrying out the said alkali cleaning is 30.0 to 70.0 degreeC.
• the process of pickling the surface of the said base material can be mentioned as an example of a surface cleaning process.
• a publicly known thing can be applied as a medicine used by acid wash processing.
• a step of pickling may be performed after the step of degreasing. It is preferable that the time of the process of the said acid wash process is 0.5 to 30.0 minutes. It is preferable that the temperature of the process of the said acid wash process is 30.0 to 70.0 degreeC.
• a film may be formed on the surface of the substrate.
• the film may be formed by a coating method or a reaction method.
• the film to be formed include an alumite film, a chemical conversion film (phosphate film, chromate film, silicate film, lithium conversion film, calcium conversion
• a film, a zirconium oxide film, etc., a silane coupling agent hardened film, a plating film, etc. are mentioned, it is not limited to these.
• the water washing step may be performed after all steps ⁇ all kinds of processing (for example, surface cleaning step and zincate step) performed before etching step, etching step, post treatment step, etc. ⁇ .
• a resin composition is provided in the depression of the roughened substrate formed by roughening after obtaining the roughened substrate through an etching step of bringing the etching agent into contact with the surface or the surface of the substrate.
• thermoplastic resin and adhesive agent which are mentioned later can be mentioned.
• Injection molding or adhesive bonding can be mentioned as an example of the process of putting the said resin composition in the dent of the said roughening base material.
• Injection molding may include insert molding and outsert molding.
• insert molding it is preferable to prepare a mold, insert an aluminum alloy into an injection mold, inject a resin composition, and once bonded and integrated as it is after mold release. It is possible to firmly bond the base and the resin by placing the resin composition by injection molding in the depression formed by roughening the base.
• this method may be referred to as injection molding bonding.
• membrane formed at the post-process process may exist on the surface or surface of a rough surface.
• the resin constituting the resin composition mainly used for injection molding may be a thermoplastic resin or a thermosetting resin.
• the resin may contain a filler, for example, suitable from glass fiber, carbon fiber, metal fiber, ceramic fiber, glass bead, carbon powder, metal powder, ceramic powder, aluminum oxide powder, pigment and the like. Although 1 type, or 2 or more types of things can be selected, it is not limited to these.
• an adhesive as a resin composition is applied to the rough surface, an adhesive is put in a recess of the roughened substrate, and then a mating material is pasted, and the adhesive is The aspect which hardens
• the mating material may be any material including metal, rubber, wood, ceramic and composite material as well as resin material.
• the shape of the mating material is not particularly limited, and may be a plate, a bar, a band, a tube, a line, a film, or the like.
• the adhesive includes, for example, vinyl chloride resin adhesives, vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyacrylic adhesives, polyamide adhesives, cellulose adhesives, ⁇ -olefin adhesives, aqueous Polymer-isocyanate adhesive, cyanoacrylate adhesive, urea resin adhesive, melamine resin adhesive, phenol resin adhesive, resorcinol resin adhesive, epoxy resin adhesive, silicone resin adhesive, Polyester adhesive, polyurethane adhesive, polyaromatic adhesive, chloroprene rubber adhesive, nitrile rubber adhesive, styrene butadiene rubber adhesive, polysulfide adhesive, butyl rubber adhesive, silicone rubber Suitable from adhesives, acrylic rubber adhesives, urethane rubber adhesives, etc. It can be selected one or more, but is not limited thereto.
• the bonded substrate-resin cured product according to the embodiment of the present invention may be composed only of the roughened substrate and the cured product of the resin composition, or the roughened group. In addition to the cured product of the material and the resin composition, it may include a counterpart material in contact with the cured product.
• the resin composition is cooled by cooling if the resin composition is a thermoplastic resin composition after the step of placing the resin composition in the depression of the roughened base material formed by roughening.
• the resin composition is an adhesive, it is cured by being left or heated to form a bonded substrate-resin cured product.
• the surface or surface of the roughened substrate obtained by the method for producing a roughened substrate according to the embodiment of the present invention may be subjected to lamination to form one or more laminate layers.
• the roughened substrate is useful as a material for a heat dissipating member and a sliding member.
• the bonded base-resin cured product obtained by the method for producing a bonded base-resin cured product according to the embodiment of the present invention is a member for automobiles, a member for aircraft, a member for electronic devices, a member for mobile devices It is useful as a member for office automation equipment, a member for home appliances, and a member for medical equipment.
• the surface-roughened base material and the base material-cured resin composite obtained by the manufacturing method of the embodiment of the present invention are not limited to the above applications.
• the bonded base material-cured resin products according to Examples 1 to 13 and Comparative Examples 1 to 4 are [surface cleaning step ⁇ zincate step ⁇ etching step ⁇ injection molding bonding step and adhesive bonding step, unless otherwise noted. It manufactured through the process process of any process of].
• the bonded base material-cured resin product according to Comparative Examples 5 to 12 was manufactured through the same processing steps as described above except that it did not include the zincate step. Hereinafter, each process of the said process process is demonstrated.
• injection molding joining process polyphenylene sulfide (PPS resin) containing 30% of glass fibers as a resin composition was injection molded and bonded to the base material having undergone the steps up to the etching step.
• PPS resin polyphenylene sulfide
• an electric servo injection molding machine Si-50 III manufactured by Toyo Machine Metals Co., Ltd. was used.
• the injection molding conditions were: preheat 125 ° C., molding temperature 320 ° C., mold temperature 135 ° C., injection speed 30 mm / sec, injection pressure 1000 kgf, holding pressure 1200 kgf, and cooling time 15 seconds.
• the bonded base material-cured resin product is 10 mm ⁇ 45 mm ⁇ t3 mm.
• the bonding area with a base material is 10 mm x 5 mm.
• Adhesive bonding process In the adhesive bonding step, an epoxy-based adhesive AR-S30 manufactured by Nichiban Co., Ltd. containing 10% of glass beads BZ-02 manufactured by As One Co., Ltd. is applied to the two base materials subjected to the steps up to the etching step. , Joined.
• the bonding area of the two base materials is 10 mm ⁇ 20 mm.
• Example 1 (Examples and Comparative Examples Using a Substrate Consisting of A5052)
• A5052 standardized by JIS H4000 was used.
• the zincate step was not performed.
• the substrate was immersed for 480 seconds using the following etchant (1).
• Etchant (1) ⁇ Component> -Water-Sodium peroxodisulfate: 0.35 mol / L Sodium chloride: 1.70 mol / L ⁇ PH> 3.0
• Example 2 A base-resin cured product was produced in the same manner as in [Example 1] except that the zincate step was carried out. Specifically, the substrate was immersed for 30 seconds using the following zincate solution as the zincate step. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Example 2 were obtained. The pH of the zincate solution was adjusted to 12.5 using a hydrochloric acid aqueous solution.
• Zincate liquid ⁇ component> ⁇ Water ⁇ Zinc oxide: 0.25 mol / L Sodium hydroxide: 3.80 mol / L -Tartaric acid: 0.07 mol / L ⁇ PH> 12.5 ⁇ Temperature of zincate process> 40.0 ° C
• Example 3 A base-resin cured product was produced in the same manner as in [Example 2] except that the etching step was changed. Specifically, the substrate was immersed for 480 seconds using the following etchant (2) as an etching step. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Example 3 were obtained.
• Etchant (2) ⁇ Component> -Water-Potassium peroxodisulfate: 0.30 mol / L -Potassium chloride: 1.40 mol / L ⁇ PH> 3.0
• Example 4 A base-resin cured product was produced in the same manner as in [Example 2] except that the etching step was changed. Specifically, the substrate was immersed for 480 seconds using the following etchant (3) as an etching step. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Example 4 were obtained.
• Etchant (3) ⁇ Component> ⁇ Water ⁇ Ammonium peroxodisulfate: 0.36 mol / L -Sodium chloride: 1.70 mol / L ⁇ PH> 3.0
• Example 5 A base-resin cured product was produced in the same manner as in [Example 2] except that the etching step was changed. Specifically, the substrate was immersed for 480 seconds using the etching agent (4) in Table 1 as an etching step. In this manner, a bonded substrate-cured resin product according to Example 5 and a bonded substrate-substrate bonded product according to adhesive bonding were obtained.
• Etchant (4) ⁇ Component> -Water-Sodium peroxodisulfate: 0.35 mol / L -Calcium chloride: 0.90 mol / L ⁇ PH> 3.0
• Comparative Example 1 A bonded substrate-resin cured product was obtained by the same method as in [Example 2] except that the etching step was changed. Specifically, the substrate was immersed for 480 seconds using the following etchant (5) as an etching step. In this way, a bonded base-resin cured product by injection molding bonding and a bonded base-resin cured product by adhesive bonding according to Comparative Example 1 were obtained.
• Etchant (5) ⁇ Component> -Water-Sodium peroxodisulfate: 0.35 mol / L ⁇ PH> 3.0
• Comparative Example 2 A bonded substrate-resin cured product was obtained by the same method as in [Example 2] except that the etching step was changed. Specifically, as the etching step, the substrate was immersed for 480 seconds using the following etchant (6). In this way, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Comparative Example 2 were obtained.
• Etchant (6) ⁇ Component> -Water-Sodium chloride: 1.70 mol / L ⁇ PH> 3.0
• Comparative Example 3 A bonded base-resin composite was obtained in the same manner as in [Example 1] except that the etching step was changed. Specifically, the substrate was immersed for 300 seconds using the following etchant (7) as an etching step. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Comparative Example 3 were obtained.
• Etchant (7) ⁇ Component> Water and phosphoric acid: 5.10 mol / L Sodium chloride: 0.85 mol / L ⁇ PH> 1.0
• Comparative Example 4 A bonded base-resin composite was obtained in the same manner as in [Example 1] except that the etching step was changed. Specifically, as the etching step, the substrate was immersed for 300 seconds using the following etchant (8). In this manner, a bonded base-resin cured product by injection molding bonding and a bonded base-resin cured product by adhesive bonding according to Comparative Example 4 were obtained.
• Etchant (8) ⁇ Component> Water and sulfuric acid: 0.50 mol / L -Sodium chloride: 1.70 mol / L ⁇ PH> 1.0
• Example 6 A base-resin cured product was produced in the same manner as in [Example 2] except that the base was changed. Specifically, A1050 standardized by JIS H4000 was used as a base material. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Example 6 were obtained.
• Example 7 A base-resin cured product was produced in the same manner as in [Example 2] except that the base was changed. Specifically, A2017 standardized by JIS H4000 was used as a base material. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Example 7 were obtained.
• Example 8 A base-resin cured product was produced in the same manner as in [Example 2] except that the base was changed. Specifically, A3003 standardized by JIS H4000 was used as a substrate. In this way, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Example 8 were obtained.
• Example 9 A base-resin cured product was produced in the same manner as in [Example 2] except that the base was changed. Specifically, A4032 standardized by JIS H4140 was used as a base material. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Example 9 were obtained.
• Example 10 A base-resin cured product was produced in the same manner as in [Example 2] except that the base was changed. Specifically, A6063 standardized by JIS H4040 was used as a base material. In this way, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to [Example 10] were obtained.
• Example 11 A base-resin cured product was produced in the same manner as in [Example 2] except that the base was changed. Specifically, A7075 standardized by JIS H4000 was used as a base material. In this way, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to [Example 11] were obtained.
• Example 12 A base-resin cured product was produced in the same manner as in [Example 2] except that the base was changed. Specifically, AC 8A standardized by JIS H5202 was used as a substrate. In this way, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Example 12 were obtained.
• Example 13 A base-resin cured product was produced in the same manner as in [Example 2] except that the base was changed. Specifically, ADC 12 standardized by JIS H5302 was used as a substrate. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to [Example 13] were obtained.
• Comparative Example 5 A base-resin cured product was produced in the same manner as in [Comparative Example 4] except that the base was changed. Specifically, A1050 standardized by JIS H4000 was used as a base material. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Comparative Example 5 were obtained.
• Comparative Example 6 A base-resin cured product was produced in the same manner as in [Comparative Example 4] except that the base was changed. Specifically, A2017 standardized by JIS H4000 was used as a base material. In this way, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Comparative Example 6 were obtained.
• Comparative Example 7 A base-resin cured product was produced in the same manner as in [Comparative Example 4] except that the base was changed. Specifically, A3003 standardized by JIS H4000 was used as a substrate. In this manner, a bonded base-resin cured product by injection molding bonding and a bonded base-resin cured product by adhesive bonding according to Comparative Example 7 were obtained.
• Comparative Example 8 A base-resin cured product was produced in the same manner as in [Comparative Example 4] except that the base was changed. Specifically, A4032 standardized by JIS H4140 was used as a base material. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Comparative Example 8 were obtained.
• Comparative Example 9 A base-resin cured product was produced in the same manner as in [Comparative Example 4] except that the base was changed. Specifically, A6063 standardized by JIS H4040 was used as a base material. In this manner, a bonded base-resin cured product by injection molding bonding and a bonded base-resin cured product by adhesive bonding according to Comparative Example 9 were obtained.
• Comparative Example 10 A base-resin cured product was produced in the same manner as in [Comparative Example 4] except that the base was changed. Specifically, A7075 standardized by JIS H4000 was used as a base material. In this manner, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Comparative Example 10 were obtained.
• Comparative Example 11 A base-resin cured product was produced in the same manner as in [Comparative Example 4] except that the base was changed. Specifically, AC 8A standardized by JIS H5202 was used as a substrate. In this way, a bonded substrate-cured resin product by injection molding bonding and a bonded substrate-cured resin product by adhesive bonding according to Comparative Example 11 were obtained.
• Comparative Example 12 A bonded base-resin composite of Comparative Example 12 was produced in the same manner as in Comparative Example 4 except that the base material was changed. Specifically, ADC 12 was used as a substrate. In this manner, a bonded base-resin cured product and a base-base bonded body according to Comparative Example 12 were obtained.

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