TW201934673A - Integrated molding, method for producing same, and primer composition - Google Patents

Abstract

This integrated molding in which a metal and a resin are attached through a primer layer is characterized in that the primer layer is formed from a primer composition containing an oxazoline group-containing polymer as a base polymer. Said integrated molding has excellent bonding strength (adhesive strength) between the metal and the resin.

Description

Integrated molding, manufacturing method thereof, and coating composition

The present invention relates to an integrally formed article, a manufacturing method thereof, and a primer composition.

Focusing on the electrical and automotive fields, we have developed technologies that allow metals and resins to adhere to a wide range of fields. In the past, various studies have been conducted in order to make metals and resins adhere to each other, including improving the bonding strength (adhesion strength) of these bonding interfaces, or improving the adhesion of the bonding interfaces.

For example, Patent Document 1 discloses a resin-metal bonded body in which an aluminum metal member and a thermoplastic resin member are bonded via an anodized film in which triazinethiol is present, so as to increase the above-mentioned bonding strength (adhesive strength).

In addition, Patent Document 2 discloses a laminated body for battery exterior, in which a stainless steel plate and a heat-fusible polyolefin-based resin having a thickness of 10 to 100 μm are made of a resin composition (containing: a carboxyl group-containing resin, an oxazole-containing resin). The organic-inorganic composite resin layer formed by a phosphine-based resin and a basic phosphorus oxy compound) is brought into an adhered state to improve the above-mentioned adhesion.

[Prior technical literature]

[Patent Literature]

Patent Document 1: WO2009 / 078377.

Patent Document 2: Japanese Patent Application Laid-Open No. 2012-164565.

The joint or laminate of metal and resin disclosed in the aforementioned patent document is expected to improve the bonding strength (adhesion strength) to a certain degree or the effect of improving the adhesion to a certain degree. However, the market has demanded stronger joint strength (adhesive strength) for one-piece molded articles manufactured by integral molding such as injection molding and transfer molding.

The present invention is made in view of the above-mentioned facts, and provides a molded body having excellent bonding strength (adhesive strength) and a method for producing the same.

In addition, the present invention provides a primer composition for obtaining the aforementioned one-piece molded article.

The present invention relates to an integrally formed article in which a metal and a resin are in an adhered state through a primer layer; the primer layer is formed of a primer composition, and the primer composition contains a oxazoline group-containing polymer as a basis polymer.

In addition, the present invention relates to a method for manufacturing the integrated molded article, and includes the step of adhering the metal and the resin through the primer layer formed by the primer composition.

Furthermore, the present invention relates to a primer composition, which is the aforementioned primer composition, and In the primer composition, the proportion of the oxazoline group-containing polymer is 0.001% by weight to 50% by weight.

Although the details of the action mechanism of the effect of the molded body of the present invention are partially unknown, it is estimated as follows. However, the present invention can be explained without being limited to this mechanism of action.

One of the molded articles of the present invention (molded articles manufactured by integral molding such as injection molding, transfer molding, etc.) is formed by a primer layer (a primer composition containing a polymer containing an oxazoline group as a base polymer). (Formation) to make the metal and resin adhere to each other. It is presumed that the base coating composition contains a polymer containing an oxazoline group as a main component, and the oxazoline group may react with a carboxyl group, a hydroxyl group, a thiol group, an amine group, etc., and may interact with a resin of an integrally formed product. The metal and the resin form coordination or intermolecular bonds, and thus the formed article of one metal and resin obtained by using the primer has excellent joint strength (adhesive strength). In particular, the bonding strength (adhesion strength) of the metal and the resin as a single body formed article directly through the primer is more excellent.

Further, the present invention is integrally molded product, even if the primer layer of the oxazoline group-containing polymer is ² or less degree of 0.05μg / cm ² or more 2500μg / cm content (deposition amount), since the bonding strength (adhesive strength ) Is excellent, so it is useful from the viewpoint of improving the productivity of the integrated molded article.

In addition, it is estimated that the molded body of the present invention is strongly adhered to the metal and the resin, and that the sealing interface between the metal and the resin is excellent. Therefore, the molded article can also be applied to a member that may cause leakage of moisture, gas, or the like.

Furthermore, the molded body of the present invention can further improve the bonding interface between the metal and the resin by using a metal roughened by spraying, etching, or the like, or a metal activated by plasma treatment, or the like. Bonding strength (adhesive strength).

1‧‧‧ metal

2‧‧‧ resin

FIG. 1 is a diagram showing a molded body used in the evaluation of the bonding strength (adhesion strength) in the examples. Fig. 1 (a) is a perspective view, Fig. 1 (b) is a top view, and Fig. 1 (c) is a sectional view taken along the line A-A 'of Fig. 1 (a).

FIG. 2 is a SEM photograph showing the metal surface roughened by the sandblasting treatment of Example 18. FIG.

FIG. 3 is a SEM photograph showing the metal surface roughened by the etching treatment of Example 35. FIG.

FIG. 4 is a SEM photograph of the metal surface after roughening treatment by the sandblasting treatment and the etching treatment of Example 37. FIG.

FIG. 5 is a diagram showing a molded body used in the evaluation of the sealing characteristics in the examples. Fig. 5 (a) is a plan view, and Fig. 5 (b) is a cross-sectional view taken along the line B-B 'in Fig. 5 (a).

<Integrated molded product>

One of the molded articles of the present invention is such that a metal and a resin are in an adhered state through a primer layer formed of a primer composition (containing an oxazoline group-containing polymer as a base polymer).

<Coating composition>

The primer composition of the present invention contains an oxazoline group-containing polymer as a base polymer. The base polymer referred to here is the aforementioned content of the solid content of the aforementioned primer composition. The proportion of the oxazoline-based polymer is at least 65% by weight, and more preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, or more preferably 95% by weight or more, 98 More preferably, it is more than% by weight.

Examples of the oxazoline group-containing polymer include a polymer containing a main chain composed of a (meth) acrylic acid skeleton and / or a styrene skeleton and having an oxazoline group in a side chain of the main chain. Wait. Among these, an oxazoline group-containing (meth) acrylic polymer containing a main chain composed of a (meth) acrylic skeleton and having an oxazoline group in a side chain of the main chain is preferred. The oxazoline group-containing polymer may be used alone or in combination of two or more kinds.

Examples of the oxazoline group include 2-oxazoline group, 3-oxazoline group, and 4-oxazoline group. Among these, 2-oxazoline group is preferred. The 2-oxazoline group is generally represented by the following general formula (1).

(Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a phenyl group, or a substituted phenyl group)

The aforementioned oxazoline group-containing polymer may have functional groups other than the oxazoline group. From the viewpoint of avoiding reducing the storage stability of the oxazoline group-containing polymer, the polymer Reactive functional groups, such as polyoxyalkenyl, alcoholic hydroxyl, etc.

The aforementioned oxazoline group-containing polymer is based on the viewpoint of increasing the solution viscosity of the oxazoline group-containing polymer and forming a uniformly coated bottom film. The oxazoline value is preferably 50 gsolid / eq. Or more, and 100 g solid / eq. The above is more preferable. In addition, from the viewpoint of preventing a decrease in the bonding strength caused by unreacted oxazoline groups during integral molding, it is preferably 1,500 gsolid / eq. Or less, 1,000 gsolid / eq. Or less, and 500 gsolid / eq. The following is particularly good. In addition, the weight average molecular weight of the oxazoline group-containing polymer is preferably 5,000 or more, more preferably 10,000 or more, and more preferably 1,000,000 or less.

The primer composition preferably contains a medium from the viewpoint of improving the paintability of the oxazoline group-containing polymer. The medium is not particularly limited as long as it can dissolve or disperse the oxazoline group-containing polymer, and examples thereof include water, methanol, ethanol, isopropanol, and n-butanol. Organic solvents, such as alcohols, are particularly preferred, with water as the main component. From the viewpoint of workability, the oxazoline group-containing polymer is preferably water-soluble.

When the said primer composition contains the said medium, it is preferable that the ratio of the said oxazoline group containing polymer in the said primer composition is 0.001 weight%-50 weight%. Based on the viewpoint of controlling the content (adhesion amount) of the oxazoline group-containing polymer in the coating layer described later to a predetermined range, the proportion of the oxazoline group-containing polymer in the coating composition is 0.005 weight. % Or more is preferable, 0.01% or more is more preferable, 0.03% or more is particularly preferable, and 25% or less is preferable, and 10% or less is more preferable. Furthermore, from the viewpoint of improving the productivity of the integrally molded product, the proportion of the oxazoline group-containing polymer in the primer composition is preferably 5% by weight or less, more preferably 3% by weight or less, and 1% by weight. % Is particularly preferred.

Specific examples of the aforementioned oxazoline group-containing polymer (solution) include "EPOCROS WS-300", "EPOCROS WS-500", and "EPOCROS WS-700" (all of which are companies in Japan) (Meth) acrylic polymer (solution) containing oxazoline group, etc .; "EPOCROS K-1000 series", "EPOCROS K-2000 series" (both (Co., Ltd.) Japan Catalyst (Meth) acrylic acid / styrene polymer (solution) containing oxazoline group and the like.

In addition, from the viewpoint of not impairing the effect of the present invention and further improving the stability of the primer composition over time, other components may be added to the primer composition. Examples of other components include silane coupling agents, titanate coupling agents, inorganic fillers such as silicon dioxide and zirconium compounds. When the other components are added, the content is usually about 0.1% to 40% by weight in the solid content of the primer composition.

<Coating layer>

The primer layer of the present invention is a layer formed of the aforementioned primer composition.

In the coating layer, the content (adhesion amount) of the oxazoline group-containing polymer is preferably from 0.05 μg / cm ^{2 to} 2000 μg / cm ² . From the viewpoint of improving the bonding strength (adhesion strength) of the bonding interface between the metal and the resin, the aforementioned oxazoline group-containing polymer in the coating layer is more preferably 0.1 μg / cm ² or more, and 0.2 μg / cm ² or more Particularly preferred, 1 μg / cm ² or higher is particularly preferred, 5 μg / cm ² or higher is particularly preferred, 10 μg / cm ² or higher is most preferred, and more preferably 2000 μg / cm ² or lower, and 1750 μg / cm ² or lower is particularly preferred. , 1500μg / cm ² or less being especially preferable, 1250μg / cm ² or less is very good.

<Metal>

The metal of the present invention is not particularly limited as long as it can be applied to integral molding described later, and examples thereof For example, stainless steel, aluminum, aluminum alloy, magnesium alloy, titanium, titanium alloy, copper, copper alloy, nickel, nickel alloy, chromium, chromium alloy, and the like.

The shape of the metal is not particularly limited as long as it has a shape that allows the resin to adhere to form a metal-resin composite. The shape of the aforementioned metal can be used, for example, from a metal block, a plate, a bar, or the like through individual plastic processing, sawing, milling, electrical discharge machining, drilling, pressing, grinding, grinding, etc., or a combination of these. Processing and machining to a desired shape.

In addition, the metal may roughen a metal surface at a bonding interface between the metal and the resin into a concave-convex shape by a roughening step described later, and may also activate a metal surface by a later-described activation step. The metal surfaces in the bonding interface may be roughened and / or activated to further increase the bonding strength (and then the strength) of the bonding interface.

From the viewpoint of improving the bonding strength (adhesion strength) of the bonding interface between metal and resin, the surface roughness (Ra) of the uneven shape is preferably 0.2 μm or more, more preferably 0.3 μm or more, and more preferably 3 μm or less. It is more preferably 2 μm or less.

<Resin>

The resin of the present invention is not particularly limited as long as it can be applied to integral molding described later, and examples thereof include thermoplastic resins and thermosetting resins.

The thermoplastic resin is not particularly limited, and examples thereof include polyethylene resin (PE), polypropylene resin (PP), polystyrene resin (PS), polyvinyl chloride resin (PVC), and polyvinylidene chloride resin (PVDC). , Acrylonitrile / styrene copolymer resin (AS), acrylonitrile / butadiene / styrene Copolymer resin (ABS), polyethylene terephthalate resin (PET), polyethylene terephthalate resin (PEN), acrylic resin, polyvinyl alcohol resin (PVA), ethylene / vinyl acetate copolymer resin Common resins such as ethylene / acrylic copolymer resin, ethylene / methacrylic copolymer resin; polyamide 6, polyamide 66, polyphthalamide and other polyamide resins (PA); polycarbonate resin (PC), polyacetal resin (POM), polyphenylene ether resin (PPE), modified polyphenylene ether resin, polybutylene terephthalate resin (PBT), polyvinylidene fluoride (PVDF), poly碸 Resin (PSU), Polyether 碸 Resin (PES), Polyphenylene Sulfide Resin (PPS), Polyacrylate Resin (PAR), Polyamidamine 醯 Imine Resin (PAI), Polyether 醯 Imide Resin (PEI) ), Polyether ketone resin (PEEK), aromatic polyether ketone resin, polyimide resin (PI), liquid crystalline polyester resin (LCP), polytetrafluoroethylene resin (PTFE), para-polystyrene resin (SPS), fluororesin, polyether fluorene resin (PES), and other engineering plastics; and the combination of two or more of these. In order to improve the characteristics (heat resistance, etc.) of the composite, the thermoplastic resin is preferably an engineering plastic. In addition, these resins may be blended with glass fibers, inorganic fillers, etc. in order to improve mechanical strength and the like, and these components may not be blended.

The thermoplastic resin may be a composition composed of the thermoplastic resin or a composition mainly composed of the thermoplastic resin. In addition, as long as the effect of the present invention is not impaired, various inorganic / organic fillers, flame retardants, flame retardant additives, ultraviolet absorbers, heat stabilizers, light stabilizers, and colorants that are conventionally known may be contained. Additives such as additives, carbon black, processing aids, nucleating agents, release agents, plasticizers, and fibrous reinforcing materials.

The thermosetting resin is not particularly limited, and examples thereof include phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, silicone resin, polyurethane resin, diallyl phthalate resin, and alkyd acid. Resins, isocyanate resins, and the like can also be exemplified by combinations of two or more of these. Among these, based on the From the viewpoint of the reactivity of the polymer, those containing functional groups such as a carboxyl group, a thiol group, a hydroxyl group, an epoxy group, an amine group, and a sulfinate group are preferred, and those containing an aromatic thiol group, a sulfinate group, A carboxyl functional group is more preferable.

The thermosetting resin may be a composition composed of the thermosetting resin, or may be a composition mainly containing the thermosetting resin. In addition, as long as the effect of the present invention is not impaired, various inorganic / organic fillers, flame retardants, flame retardant additives, ultraviolet absorbers, heat stabilizers, light stabilizers, and colorants that are conventionally known may be contained. Additives such as additives, carbon black, processing aids, nucleating agents, release agents, plasticizers, fibrous reinforcing materials, etc.

Examples of the thermoplastic resin or the resin other than the thermosetting resin include a photocurable resin composition containing acrylic resin, styrene resin, and the like; and a reaction hardening resin composition containing rubber, elastomer, and the like.

<Manufacturing method of integrated molded article>

A method for manufacturing a molded article according to the present invention includes a step of causing the metal and the resin to adhere to each other through the primer layer formed from the primer composition (adhesion step).

The primer layer may be formed by coating the primer composition on the surface of the metal and drying the medium or the like as necessary.

As the coating method, various well-known coating (coating) methods can be applied, and examples thereof include dip coating, spray coating, bar coating, roll coater, film applicator, spin coating, and screen printing.

The aforementioned drying conditions generally use a drying furnace, a blower, infrared rays, and the like, and the temperature is preferably about 50 ° C to 230 ° C, and more preferably about 65 ° C to 200 ° C. The aforementioned drying time cannot be determined uniformly due to the influence of the aforementioned drying temperature. Generally, it is preferably about 1 minute to 120 minutes, and more preferably about 5 minutes to 30 minutes.

The method for causing the aforementioned metal and the aforementioned resin to adhere through the aforementioned coating layer can be used: injection molding, extrusion molding, heat and pressure molding, compression molding, transfer molding, casting molding, laser welding molding, and reaction injection molding ( RIM molding), liquid injection molding (LIM molding) and other integrated molding methods. As the molding conditions of the aforementioned integral molding method, known conditions can be adopted in accordance with the aforementioned resin used.

In addition, the method for producing a molded body according to the present invention may include a step of roughening the surface of the metal into a concave-convex shape (roughening step) before the attaching step, and may further include activating the surface of the metal. Step of activation (activation step). By roughening and / or activating a metal surface at a joint interface between the metal and the resin, the joint strength (adhesion strength) of the joint interface can be further increased.

In the roughening step, mechanical roughening treatments such as sandblasting treatment, shot blasting treatment, grinding treatment, barrel grinding treatment, dry ice blasting treatment, and the like can be mentioned in the roughening treatment (method); chemical conversion treatment, etc. Chemical treatment; etching treatment using acid-based etchant, alkali-based etchant, etc .; anodizing, electrolytic polishing treatment, electrochemical treatment of roughening plating, etc., these roughening methods can be based on the use of the aforementioned metals Features are suitable for adoption. Among these, the mechanical polishing process is particularly preferable because it is based on the Kramer effect (external electron effect) and also serves as an activation step described later. In addition, the above-mentioned etching treatment may be performed under well-known conditions, and examples thereof include Japanese Patent Application Laid-Open No. 2013-52671 Newspaper, Japanese Patent Application Publication No. 2013-22761, Japanese Patent Application Publication No. 2014-111392, Japanese Patent Application Publication No. 2016-104896, and the like.

In the activation step, the activation treatment (method) includes a corona treatment, a plasma treatment, a flame treatment, an ozone treatment, and a UV modification. It is estimated that the metal surface is activated by such treatment, and polar groups such as a carboxyl group and a hydroxyl group are formed on the surface. In addition, since the formation of the aforementioned polar group is affected by the amount of moisture in the processing atmosphere, it is preferable that the processing is performed under a moderate humidity. Examples of the activation treatment (method) include ITRO treatment such as silicon oxide formation on a metal surface.

In addition, in the method for producing a molded body according to the present invention, other steps such as a degreasing step, a water washing step, an ultrasonic washing step, and a drying step may be suitably used according to necessity.

In addition, in the evaluation of the joint strength (adhesion strength) described below, the molded body of the present invention preferably has a tensile shear strength (MPa) of 15 MPa or more, more preferably 20 MPa or more, particularly preferably 25 MPa or more, and especially 30 MPa or more. Good, even better than 40MPa.

One of the molded articles of the present invention is used in the manufacture of various mechanical parts such as parts for electronic equipment, parts for household appliances, and parts for conveying machinery, and more specifically, it is suitable for various electronic devices such as mobile applications. Manufacturing of parts, parts for household appliances, parts for medical equipment, parts for vehicles, parts for vehicle mounting, other electrical parts, or parts for heat radiation.

[Example]

Next, examples of the present invention will be described together with comparative examples. Moreover, the present invention It is not limited to the following examples for explanation.

<Manufacturing of one-piece molding>

<Example 1>

Prepare a stainless steel plate (SUS316L manufactured by Standard Test Sheet Co., Ltd .; width 40mm, length 20mm, thickness 2mm in accordance with JIS G4305), and adjust this stainless steel plate to a concentration of 50g / L) Immersion at 50 ° C for 10 minutes. After that, it was immersed in water at 40 ° C for 1 minute, and then washed with water at normal temperature and dried to prepare a metal test piece. Next, the oxazoline group-containing polymer solution ("EPOCROS WS-300" (solid content of 10% by weight, (Company Co., Ltd.))) was diluted with water to prepare an oxazoline group-containing solution. The proportion of the polymer is 0.05% by weight of the primer composition. This base coating composition was applied to the entire surface of one side (40 mm × 20 mm) of the above-mentioned metal test piece, and the weight of the coated base coating composition was recorded, followed by drying in a drying oven at 75 ° C. for 90 minutes. Processing to obtain a metal test piece provided with a coating layer. In addition, the content (adhesion amount) (μg / cm ² ) of the oxazoline group-containing polymer in the primer layers shown in Tables 1 to 2 is the amount (weight part) from the primer composition applied to the metal To figure it out.

Using the obtained metal-coated test piece and polyphthalamide resin (manufactured by DSM, PPA resin, "NMX33"), injection molding was performed under the molding conditions shown in Table 4 (vertical injection molding machine) "STX20S2V", manufactured by Nissei Resin Industry Co., Ltd.) and annealed (constant temperature dryer "DRA330DB", manufactured by ADVANTECH), as shown in Figs. 1 (a) to 1 (c), to obtain a metal with a coating layer 1 and resin 2 are one-piece molded products with one end side overlapped (joining area 5 mm × 10 mm, in accordance with ISO19095).

<Example 2 to Example 17>

Except that the type of metal, the type of resin, and the ratio of the oxazoline group-containing polymer in the primer composition were changed to those shown in Table 1, the same operations as in Example 1 were performed to obtain Examples 2 to 3. The molded body of Example 17. In addition, the conditions for injection molding and annealing treatment of the resin used are shown in Table 4.

<Comparative Example 1 to Comparative Example 7>

Except that the primer composition was not used, and the types of metals and resins were changed to those shown in Table 1, the same operation as in Example 1 was performed to obtain a body molded article of Comparative Examples 1 to 7. In addition, the conditions for injection molding and annealing treatment of the resin used are shown in Table 4.

<Example 18>

A stainless steel plate (SUS316L manufactured by Standard Test Sheet Co., Ltd .; 40 mm in width, 20 mm in length, and 2 mm in thickness in accordance with JIS G4305) was prepared. The surface of the stainless steel plate was blasted with alumina (particle size # 120) using a sand blasting machine (blast cabinet BA-1, manufactured by Houcheng Engineering Co., Ltd., direct pressure condition: 0.5 MPa) (using a laser microscope ( 3CCD color confocal microscope "OPTELICSH1200" (manufactured by Laser Technology Corporation) Ra was 1.3 μm). Next, the stainless steel plate subjected to the spray treatment was immersed in an alkaline degreasing agent ("Eskelin 850" manufactured by Okano Pharmaceutical Industry Co., Ltd. to a concentration of 50 g / L) at 50 ° C for 10 minutes. After that, it was immersed in water at 40 ° C for 1 minute, and then washed and dried at normal temperature to prepare a metal test piece subjected to sandblasting. Next, the oxazoline group-containing polymer solution ("EPOCROS WS-300" (solid content of 10% by weight, (Company Co., Ltd.))) was diluted with water to prepare an oxazoline group-containing solution. The proportion of the polymer is 0.05% by weight of the primer composition. The primer composition was applied to the entire surface of one side (40 mm × 20 mm) of the above-mentioned sand-blasted metal test piece, and the weight of the applied primer composition was recorded. Then, a drying process was performed in a drying furnace at 75 ° C. for 90 minutes to obtain a metal test piece provided with a primer layer.

Using the obtained metal-coated test piece and polyphthalamide resin (manufactured by DSM, PPA resin, "NMX33"), injection molding was performed under the molding conditions shown in Table 4 (vertical injection molding machine) "STX20S2V", manufactured by Nissei Resin Industry Co., Ltd.) and annealed (constant temperature dryer "DRA330DB", manufactured by ADVANTECH), as shown in Figs. 1 (a) to 1 (c), to obtain a metal with a coating layer 1 and resin 2 are one-piece molded products with one end side overlapped (joining area 5 mm × 10 mm, in accordance with ISO19095).

<Example 19 to Example 34>

Except that the type of metal, resin, and ratio of the oxazoline group-containing polymer in the primer composition were changed to those shown in Table 2, the same operations as in Example 18 were performed to obtain Examples 19 to The molded article of Example 34. In addition, the conditions for injection molding and annealing treatment of the resin used are shown in Table 4.

<Example 35>

AZ-91D magnesium alloy die-casting (width 40mm, length 20mm, thickness 2mm) was placed in an etchant (aqueous solution containing 2% by weight of N, N-diethylhydroxylamine and 1.5% by weight of 35% by weight aqueous hydrochloric acid solution) Etching treatment (temperature 30 ° C, time 180 seconds, single-side etching amount (dissolving amount) in the depth direction is 2.7 μm), and washing with water and ultrasonic cleaning, and then drying to prepare an etched metal test piece . Next, the oxazoline group-containing polymer solution ("EPOCROS WS-300" (solid content of 10% by weight, (Company Co., Ltd.))) was diluted with water to prepare an oxazoline group-containing solution. The proportion of the polymer is 0.1% by weight of the primer composition. Apply this primer composition to The entire surface of the single side (40mm × 20mm) of the above-mentioned etched metal test piece was recorded. After the weight of the applied primer composition was recorded, the drying treatment was performed in a drying furnace at 75 ° C. for 90 minutes to obtain a setting. Coated metal test piece.

Using the obtained metal-coated test piece and polybutylene terephthalate resin (TORAY Co., Ltd., PBT resin, "1101G"), injection molding was performed under the molding conditions shown in Table 4 (vertical injection molding). Machine "STX20S2V", manufactured by Nissei Resin Industry Co., Ltd.) and annealed (constant temperature dryer "DRA330DB", manufactured by ADVANTECH), as shown in Fig. 1 (a) to Fig. 1 (c). The metal 1 and the resin 2 are one-piece molded products with one end side overlapped (joining area 5 mm × 10 mm, in accordance with ISO19095).

<Example 36>

Except that the AZ-31D magnesium alloy die-casting (width 40mm, length 20mm, thickness 2mm) was used in an etchant (aqueous solution containing 6% by weight of N, N-diethylhydroxylamine and 4.5% by weight of 35% by weight hydrochloric acid) Etching was performed by immersion treatment (temperature: 30 ° C., time: 135 seconds, single-side etching amount (dissolution amount) in the depth direction was 6.2 μm), and a metal test piece subjected to the etching treatment was obtained by the same operation as in Example 35. A molded body of Example 36 was obtained. In addition, the conditions for injection molding and annealing treatment of the resin used are shown in Table 4.

<Example 37>

A stainless steel plate (SUS316L manufactured by Standard Test Sheet Co., Ltd .; 40 mm in width, 20 mm in length, and 2 mm in thickness in accordance with JIS G4305) was prepared. The surface of the stainless steel plate was blasted with alumina (particle size # 120) using a sand blasting machine (blast blasting cabinet BA-1, manufactured by Hou Metro Engineering Co., Ltd., direct pressure condition: 0.5 MPa). Next, the stainless steel plate subjected to the spray treatment was immersed in an alkaline degreasing agent ("Eskelin 850" manufactured by Okano Pharmaceutical Industry Co., Ltd. to a concentration of 50 g / L) at 50 ° C for 10 minutes. After that, it was immersed in water at 40 ° C for 1 minute, and then washed and dried at normal temperature to prepare a metal test piece subjected to sandblasting. Next, the metal test piece was etched in an etchant (aqueous solution containing 10% by weight of 38% by weight FeCl ₃ aqueous solution and 10% by weight of 35% by weight aqueous hydrochloric acid solution) by etching (temperature: 50 ° C., time: 240 seconds, The amount of single-sided etching (dissolved amount) in the depth direction is 1 μm). After washing with water, immerse it in a 35 wt% nitric acid aqueous solution (24 ° C) (passivation treatment), and perform water washing and ultrasonic cleaning. Etching metal test piece. Next, the oxazoline group-containing polymer solution ("EPOCROS WS-300" (solid content of 10% by weight, (Company Co., Ltd.))) was diluted with water to prepare an oxazoline group-containing solution. The proportion of the polymer is 0.1% by weight of the primer composition. This primer composition was applied to the entire surface of one side (40 mm × 20 mm) of the above-mentioned sandblasted and etched metal test piece, and the weight of the primer composition was recorded, and then dried in a drying oven at 75 ° C. Drying was performed for 90 minutes under the conditions to obtain a metal test piece provided with a primer layer.

Using the obtained metal-coated test piece and polybutylene terephthalate resin (TORAY Co., Ltd., PBT resin, "1101G"), injection molding was performed under the molding conditions shown in Table 4 (vertical injection molding). Machine "STX20S2V", manufactured by Nissei Resin Industry Co., Ltd.) and annealed (constant temperature dryer "DRA330DB", manufactured by ADVANTECH), as shown in Fig. 1 (a) to Fig. 1 (c). The metal 1 and the resin 2 are one-piece molded products with one end side overlapped (joining area 5 mm × 10 mm, in accordance with ISO19095).

<Example 38 to Example 40>

In addition to changing the types of metals and resins to those shown in Table 2, The same operation as in Example 37 was performed to obtain a body molded article of Examples 38 to 40. In addition, the conditions for injection molding and annealing treatment of the resin used are shown in Table 4.

<Comparative Example 8 to Comparative Example 9>

Except that the primer composition was not used, and the type of resin was changed to that shown in Table 2, the same operation as in Example 18 was performed to obtain a body molded article of Comparative Examples 8 to 9. In addition, the conditions for injection molding and annealing treatment of the resin used are shown in Table 4.

<Comparative Example 10 to Comparative Example 11>

In addition to using the 2,4,6-trimercapto-s-triazine monosodium salt (manufactured by Sankyo Chemical Co., Ltd., "Sangiolu N-1", 0.004% by weight aqueous solution) for the primer composition, The same operation as in Example 1 and Example 18 was performed to obtain a molded body of Comparative Example 10 or Comparative Example 11. In addition, the conditions for injection molding and annealing treatment of the resin used are shown in Table 4.

<Evaluation of bonding strength (adhesion strength)>

The bonding strength (adhesion strength) refers to the molded body of one of the examples and comparative examples obtained as described above. The metal was directed toward FIG. 1 at a drawing speed of 10 mm / min by an AUTOGRAPH (manufactured by Shimadzu Corporation, "AGX-10kNX"). c) Stretching is performed in the direction Z shown, and the evaluation is based on the tensile shear strength (MPa) when the metal and the resin are peeled off. The results are shown in Tables 1 to 3. In addition, 0 MPa in the table indicates that the metal and the resin are not bonded.

Among the metals in Tables 1 to 3, SUS316L, SUS420, and SUS430 are stainless steel plates (manufactured by the standard test piece company) specified by JIS G4305; A5052 and A6063 are aluminum alloy plates (manufactured by the standard test piece company) specified by JIS H4000; TP340 is Pure titanium plate (manufactured by standard test piece company) specified by ASTM2 Grade2 (two types of JIS H4600); 64Ti is titanium alloy plate (manufactured by standard test piece company) specified by ASTM5 Grade5 (60 types of JIS H4600); AZ91 is AZ91D of ASTM standard (MDC1D of JIS H5303) Specified magnesium alloy die-castings (made by Standard Test Sheet Co., Ltd.); AZ31 is a magnesium alloy die-casting (manufactured by Standard Test Sheet Co., Ltd.) specified by ASTM Specification AZ31 Spreading Material (MP1 of JIS H5303).

Among the resins in Tables 1 to 3, PPA is a polyphthalamide resin (manufactured by DSM, "NMX33"); PBT is a polybutylene terephthalate resin (manufactured by TORAY, "1101G"); PPS is a polyphenylene sulfide resin (manufactured by Polyplastics Corporation, "1135MF1").

In the coating layers of Tables 1 to 2, WS-300 is an oxazoline group-containing polymer (manufactured by Japan Catalyst Corporation, "EPOCROS WS-300"); WS-700 is an oxazoline group-containing polymer ( "EPOCROS WS-700" manufactured by Japan Catalyst Corporation).

In addition, in the coating base of Table 3, Sangeolu is 2,4,6-trimercapto-s-triazine monosodium salt (manufactured by Sankyo Chemical Co., Ltd., "Sangeolu N-1").

<Example 41, Comparative Example 12>

<Evaluation of sealing characteristics>

The sealing characteristics were evaluated by the following methods.

Cut the stainless steel plate SUS316L (thickness: 2mm) specified by JIS G4305 into A size of 55 mm was formed, and a hole of 20 mmφ was perforated in the center to prepare a test piece for evaluating the sealing characteristics. The cross section of this metal test piece joined with the resin was sandblasted with alumina (particle size # 120) using a sand blasting machine (blast blasting cabinet BA-1 type, manufactured by Hou Metro Engineering Co., Ltd., direct pressure condition: 0.5 MPa). deal with. The Ra obtained by a laser microscope (3CCD color confocal microscope "OPTELICSH1200", manufactured by Laser Technology Corporation) was 1.3 μm. Next, the SUS316L subjected to the spray treatment was immersed in an alkaline degreasing agent ("Eskolin 850" manufactured by Okuno Pharmaceutical Industry to a concentration of 50 g / L) at 50 ° C for 10 minutes. After that, it was immersed in water at 40 ° C for 1 minute, and then washed and dried at normal temperature to prepare a metal test piece subjected to sandblasting. Next, the oxazoline group-containing polymer solution ("EPOCROS WS-300" (solid content of 10% by weight, (Company Co., Ltd.))) was diluted with water to prepare an oxazoline group-containing solution. The proportion of the polymer is 0.1% by weight of the primer composition. This primer composition was applied to the resin-bonded portion of the above-mentioned sand-blasted metal test piece and dried in a drying oven at 75 ° C. for 90 minutes to obtain a metal test piece provided with a primer layer. Using the obtained metal-coated test piece and polyphthalamide resin (manufactured by DSM, PPA resin, "NMX33"), injection molding was performed under the molding conditions shown in Table 4 (vertical injection molding machine) "STX20S2V", manufactured by Nissei Resin Industry Co., Ltd.) and annealed (constant temperature dryer "DRA330DB", manufactured by ADVANTECH Co., Ltd.) to obtain metal 1 and resin 2 having shapes shown in Figs. 5 (a) to 5 (b). Bonded one-piece molded body (according to ISO19095). The obtained molded article was mounted on a helium leak detector (manufactured by Shimadzu Corporation, MSE-2000S), and the partial pressure of helium in the detector was reduced to a vacuum (partial pressure before blowing), and then the measurement was performed on the integrated body Partial pressure of helium in the detector when the formed object blows helium (partial pressure after blowing). If there is no change in the partial pressure before and after blowing, or the change is small, it has excellent sealing characteristics. This measurement was performed 10 times. The results are shown in Table 5. In addition, as a comparative example, a one-piece molded article in which the primer composition was not used in the above-mentioned operation was produced, and its sealing characteristics were evaluated.

<Example 42>

An aluminum alloy plate (A6063 manufactured by Standard Test Sheet Co., Ltd. was 45 mm in width, 18 mm in length, and 2 mm in thickness) was prepared. The surface of this aluminum alloy plate was immersed in an alkaline degreasing agent ("Eskolin 850" manufactured by Okuno Pharmaceutical Industry to a concentration of 50 g / L) at 50 ° C for 10 minutes. After that, it was immersed in water at 40 ° C for 1 minute, and then washed with water at normal temperature and dried to prepare a metal test piece. Next, a dry ice blasting device (dry ice and snow washing system, manufactured by AIR WATER, conditions: sweep speed 3 mm / min) was used for dry ice blasting treatment on this surface, and a metal test piece subjected to dry ice blasting treatment was prepared. Next, the oxazoline group-containing polymer solution ("EPOCROS WS-300" (solid content of 10% by weight, (Company Co., Ltd.))) was diluted with water to prepare an oxazoline group-containing solution. The proportion of the polymer is 0.1% by weight of the primer composition. This base coating composition was applied to the entire surface of one side of the above-mentioned dry ice blast-treated metal test piece, and after recording the weight of the coated base coating composition, it was carried out in a drying furnace at 75 ° C for 90 minutes. A drying process was performed to obtain a metal test piece provided with a primer layer. In addition, the content (adhesion amount) (μg / cm ² ) of the oxazoline group-containing polymer in the primer layer shown in Table 6 was calculated from the amount (weight part) of the primer composition applied to the metal.

The above-obtained metal test piece and the polybutylene terephthalate resin (TORAY Co., Ltd., PBT resin, "2107G") were used, and the polybutylene terephthalate resin (TORAY shown in Table 4) was used. Company, PBT resin, "1101G") for injection molding (vertical injection molding machine "STX20S2V", manufactured by Nissei Resin Industry Co., Ltd.) and annealing (constant temperature dryer "DRA330DB", manufactured by ADVANTECH), As shown in FIGS. 1 (a) to 1 (c), a metal molded body 1 and a resin 2 provided with a primer layer are obtained as a single body molded product (joining area 5 mm × 10 mm, in accordance with ISO19095) with one end side overlapping one another. Next, regarding this integrated molded article, the above-mentioned joint strength (adhesive strength) was evaluated. The results are shown in Table 6.

<Example 43>

An aluminum alloy plate (A6063 manufactured by Standard Test Sheet Co., Ltd. was 45 mm in width, 18 mm in length, and 2 mm in thickness) was prepared. The surface of this aluminum alloy plate was immersed in grade 1 methanol and subjected to ultrasonic cleaning at room temperature for 10 minutes. Thereafter, it was rinsed with first-grade methanol at normal temperature and then dried to prepare a metal test piece. Next, the surface of this metal test piece was treated with an ITRO processing device (ITRO processing system, manufactured by ITRO, conditions: WD20mm, processing speed 500mm / sec, 4 pass, air 200NL / min, combustible gas 8NL / min, ITRO 1.2NL / min), to prepare metal test pieces after ITRO treatment. Next, the oxazoline group-containing polymer solution ("EPOCROS WS-300" (solid content of 10% by weight, (Company Co., Ltd.))) was diluted with water to prepare an oxazoline group-containing solution. The proportion of the polymer is 0.1% by weight of the primer composition. Apply this primer composition to the entire surface of one side of the above-mentioned ITRO-treated metal test piece, record the weight of the primer composition applied, and perform a drying treatment in a drying oven at 75 ° C for 90 minutes. A metal test piece provided with a coating layer was obtained.

The above-obtained metal test piece and the polybutylene terephthalate resin (TORAY Co., Ltd., PBT resin, "2107G") were used, and the polybutylene terephthalate resin (TORAY shown in Table 4) was used. Company, PBT resin, "1101G") for injection molding (vertical injection molding machine "STX20S2V", manufactured by Nissei Resin Industry Co., Ltd.) and annealing (constant temperature dryer "DRA330DB", manufactured by ADVANTECH), As shown in FIGS. 1 (a) to 1 (c), a metal molded body 1 and a resin 2 provided with a primer layer are obtained as a single body molded product (joining area 5 mm × 10 mm, in accordance with ISO19095) with one end side overlapping one another. Next, regarding this integrated molded article, the above-mentioned joint strength (adhesive strength) was evaluated. The results are shown in Table 6.

<Example 44>

An aluminum alloy plate (A6063 manufactured by Standard Test Sheet Co., Ltd. was 45 mm in width, 18 mm in length, and 2 mm in thickness) was prepared. The surface of this aluminum alloy plate was immersed in grade 1 methanol and subjected to ultrasonic cleaning at room temperature for 10 minutes. Thereafter, it was rinsed with first-grade methanol at normal temperature and then dried to prepare a metal test piece. Next, a plasma treatment device was used on the surface of this metal test piece (atmospheric piezoelectric system, manufactured by Japan Plasma Treatment Co., Ltd., conditions: WD5mm, processing speed 5m / min, transmission frequency 21kHz, output voltage 280V, current value 9.6A , Gas consumption 30L / min), prepare metal test piece after plasma treatment. Next, the oxazoline group-containing polymer solution ("EPOCROS WS-300" (solid content of 10% by weight, (Company Co., Ltd.))) was diluted with water to prepare an oxazoline group-containing solution. The proportion of the polymer is 0.1% by weight of the primer composition. This base coating composition was applied to the entire surface of one side of the above-mentioned plasma-treated metal test piece, and after the weight of the coated base coating composition was recorded, it was dried in a drying oven at 75 ° C for 90 minutes. Processing to obtain a metal test piece provided with a coating layer.

The above-obtained metal test piece and the polybutylene terephthalate resin (TORAY Co., Ltd., PBT resin, "2107G") were used, and the polybutylene terephthalate resin (TORAY shown in Table 4) was used. Company, PBT resin, "1101G") for injection molding (vertical injection molding machine "STX20S2V", manufactured by Nissei Resin Industry Co., Ltd.) and annealing (constant temperature dryer "DRA330DB", manufactured by ADVANTECH), As shown in FIGS. 1 (a) to 1 (c), a metal molded body 1 and a resin 2 provided with a primer layer are obtained as a single body molded product (joining area 5 mm × 10 mm, in accordance with ISO19095) with one end side overlapping one another. Next, regarding this integrated molded article, the above-mentioned joint strength (adhesive strength) was evaluated. The results are shown in Table 6.

<Example 45 to Example 46>

Except that the type of metal was changed as shown in Table 6, the same operation as in Example 44 was performed to obtain a body molded article of Examples 45 to 46. Next, regarding this integrated molded article, the above-mentioned joint strength (adhesive strength) was evaluated. The results are shown in Table 6.

In Table 6, SUS316L is a stainless steel plate (manufactured by a standard test piece company) specified by JIS G4305; A5052 and A6063 are aluminum alloy plates (a standard test piece company) specified by JISH4000 ); PBT is polybutylene terephthalate resin (manufactured by TORAY, "2107G"); WS-300 is an oxazoline group-containing polymer (manufactured by Japan Catalyst Company, "EPOCROS WS-300") .

Claims (9)

An integrally formed article in which a metal and a resin are attached to each other through a primer layer; the primer layer is formed of a primer composition, and the primer composition contains a oxazoline group-containing polymer as a base polymer. As an integrally molded product described in item request, wherein the primer layer, the polymer of the oxazoline group of 0.05μg / cm ² or more 2500μg / cm ² or less. The molded article according to claim 1 or 2, wherein the proportion of the oxazoline group-containing polymer in the solid content of the primer composition is 65% by weight or more. The formed article according to claim 1 or 2, wherein the metal-based stainless steel, aluminum, aluminum alloy, magnesium alloy, titanium, titanium alloy, copper, copper alloy, nickel, nickel alloy, chromium, or chromium alloy. The body molded article according to claim 1 or 2, wherein the resin-based thermoplastic resin or the thermosetting resin is used. A method for manufacturing a one-piece molded article, which is used to manufacture one-piece molded article according to any one of claims 1 to 5; including the following steps: the aforementioned metal and the aforementioned resin are formed by the aforementioned undercoating composition Apply a base coat to attach. The method for producing a body-formed article according to claim 6, further comprising a step of roughening the surface of the metal and / or a step of activating the surface of the metal. The method for manufacturing a body molded article according to claim 6 or 7, wherein the attaching step is injection molding or transfer molding. The primer composition according to any one of claims 1 to 5, wherein the proportion of the oxazoline group-containing polymer in the primer composition is 0.001% by weight or more and 50% by weight or less.