CN102753342B - Resin/metal composite laminate material, resin/metal composite injection moulding body, and manufacturing method for same - Google Patents

Resin/metal composite laminate material, resin/metal composite injection moulding body, and manufacturing method for same Download PDF

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Publication number
CN102753342B
CN102753342B CN201080062992.0A CN201080062992A CN102753342B CN 102753342 B CN102753342 B CN 102753342B CN 201080062992 A CN201080062992 A CN 201080062992A CN 102753342 B CN102753342 B CN 102753342B
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resin
metal composite
composite laminated
bed
resin bed
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CN102753342A (en
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田岛久生
西原俊一
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Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
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Mitsubishi Plastics Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—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 the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14811—Multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0011—Electromagnetic wave shielding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3431—Telephones, Earphones
    • B29L2031/3437—Cellular phones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2571/00—Protective equipment

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The invention provides a resin/metal composite laminate material in which a resin layer is laminated on the surface of a metal sheet, and in which convex sections composed of a synthetic resin can be integrally formed on the resin layer with high bonding strength by injection moulding. The resin/metal composite laminate material has a metal plate, and a resin layer a laminated on at least one side of the metal plate, said resin layer a having a polyamide resin as the main component. The crystallisation index (I) of the resin layer (a) is 0.40-0.80. (Hm1, Hc1, and Hm2 are the first crystal melting heat, the first crystallisation heat, and the second crystal melting heat as measured by DSC.)

Description

Resin/metal composite laminated material, resin/metal composite injection-molded article and manufacture method thereof
Technical field
The present invention relates to resin/metal composite laminated material and manufacture method thereof, in particular to following resin/metal composite laminated material and manufacture method thereof, described resin/metal composite laminated material is the resin/metal composite laminated material having the resin bed a using polyamide-based resin as principal component at least one superimposed layer of metallic plate, or further lamination has the resin/metal composite laminated material using the hybrid resin of polycarbonate resin and polyester resin as the resin bed b of principal component on this resin bed a, this resin/metal composite laminated material is used as the matrix material for manufacturing resin/metal composite injection-molded article, described resin/metal composite injection-molded article the protuberance be made up of synthetic resin integration is formed on the described resin bed a or resin bed b of this resin/metal composite laminated material by the injection mo(u)lding such as in-molded or be insert molded, it is suitable as various structural material, the particularly constituent material of the framework of OA equipment or electronic equipment.
The invention still further relates to the resin/metal composite injection-molded article and manufacture method thereof that the protuberance be made up of synthetic resin integration are formed on the resin bed a or resin bed b of described resin/metal composite laminated material by injection mo(u)lding.
The invention still further relates to by this resin/metal composite injection-molded article form for OA equipment or the framework for electronic equipment.
Background technology
In recent years, the framework of the such portable equipment of OA equipment, framework (shell), particularly mobile phone of electronic equipment, notebook computer of always waiting in expectation is day by day slim, miniaturized.In addition, for above-mentioned framework, except requiring insulating properties and further capability of electromagnetic shielding, also need surperficial side within it to form enhancing rib, be threaded with protuberances such as boss (ネ ジ only uses ボ ス), therefore, carry out seeking on its slim, miniaturized basis, the research and development (referenced patent document 1) that raised part and framework main body are molded as one securely.
In the past, what the framework of mobile phone adopted is the framework of structure shown in Fig. 6 a, 6b.
Framework 11 shown in Fig. 6 a is frameworks that the such high-intensity resin of glass fiber-reinforced polyamide-based resin (particularly nylon MXD 6) is made, it has the advantage that can be molded as one by main part 11a and protuberance 11b by injection mo(u)lding, but it has following shortcoming: in order to meet as the necessary intensity of framework by resin, even high-intensity resin, also the thickness of at least about 1mm is needed, restricted in slimming.
Framework 12 shown in Fig. 6 b obtains as follows: implement to process for the formation of the perforate of protuberance to metal framework main body 12a, then flows into resin and realizes physics engaging, thus form resin-made protuberance 12b.Because main part 12a is metal, therefore this framework 12 can slimming to thickness about 0.3mm.In addition, can capability of electromagnetic shielding be realized by metal and realize insulating properties by resin portion, but, need the step of main part 12a being carried out to perforate processing, from design aspect, be subject to severely restricts.In addition, owing to forming resin-made protuberance 12b in the mode taking physics to engage to the hole portion that metal main part 12a is formed, therefore there is the shortcoming that the poor air-tightness of this holding section, water proofing property are also poor.
For above-mentioned existing framework, following scheme is proposed: resin-coated by utilizing plate face carried out in die cavity that coated metallic plate is inserted into injection forming mold and has been fixed in patent document 2, resin-coated that molten resin is expelled to this metallic plate above forms injection mo(u)lding part, thus by metallic plate and injection mo(u)lding sectoral integration.
According to the method, the metallic plate being pre-formed with resin bed a is suitably processed, metallic plate after processing is arranged in injection forming mold, then the molten resin injected for the formation of protuberance to be molded as one with resin-coated, thus, can without the need to can protuberance be formed through complicated operation.
In addition, framework obtained above possesses metal main part and resin bed a, and it has insulating properties, electromagnetic wave shielding, can realize slimming in addition, and, can be formed by the protuberance of integration on resin bed a and strengthen rib, be threaded and use boss.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 6-29669 publication
Patent document 2: Japanese Unexamined Patent Publication 2001-315159 publication
Summary of the invention
The problem that invention will solve
Polyamide-based resin such as nylon 6 grade is listed as resin-coated in patent document 2, but all study to its degree of crystallinity and to its fusing point, therefore, there is following undesirable situation: when forming protuberance by injection mo(u)lding on described resin-coated layer a, sometimes cannot obtain sufficient adhesive strength.
Namely, the protuberance of high-adhesive-strength is molded as one on resin-coated layer in order to the injection mo(u)lding by molten resin, when injection mo(u)lding, the heat utilizing molten resin is needed to make resin-coated appropriate melting, form the state compatible with molten resin, and then carry out cooling curing, therefore, need strictly to control to resin-coated degree of crystallinity and then to its fusing point, and do not carry out above-mentioned research in patent document 2.
In addition, for resin-coated layer, require that the cementability between itself and the molten resin of injection is high, and require that it has the heat resistance of excellent press processability, tolerance mold temperature (80 ~ 120 DEG C), and the strength of materials etc. that can not deform under injection pressure, and in patent document 2, do not carry out above-mentioned research.
It should be noted that, in patent document 2, from the viewpoint of compatibility, preferably following combination: resin-coated is polyester resin, resin for the formation of protuberance is the mixture of Merlon (PC) and ABS resin, but for PC/ABS resin, it sometimes fully cannot meet enhancing rib, be threaded by the necessary intensity of boss, therefore, present requirement utilizes the MXD nylon 6 received much concern as high-strength engineering plastic to form protuberance, further, in this case, the resin-coated layer a selecting to realize high-adhesive-strength is also required.
The present invention completes in view of above-mentioned present situation, problem of the present invention is, a kind of resin/metal composite laminated material and resin/metal composite injection-molded article are provided, described resin/metal composite laminated material has resin bed a at the surface stack of metallic plate, and described resin/metal composite laminated material can be integrally formed by injection mo(u)lding the protuberance be made up of synthetic resin on its resin bed a with high-adhesive-strength; Described resin/metal composite injection-molded article the protuberance be made up of synthetic resin integration is formed on the resin bed a of described resin/metal composite laminated material by injection mo(u)lding, it is suitable as various structural material, particularly the constituent material of the framework of OA equipment or electronic equipment.
The method of dealing with problems
In order to solve the problem, the present inventor etc. conduct in-depth research, found that: as long as crystallization index is adjusted to the polyamide-based resin layer of given range, or the above-mentioned polyamide-based resin layer superimposed layer as intermediate layer formed using the hybrid resin of polycarbonate resin and polyester resin as the resin bed of principal component, just with high-adhesive-strength, desired protuberance can be molded as one.
The present invention completes based on above-mentioned discovery, and its main points are as follows.
The feature of the resin/metal composite laminated material of the present invention's (the 1st embodiment) is, it has metallic plate and is stacked in the resin bed a using polyamide-based resin as principal component at least one side of this metallic plate, wherein, the crystallization index of the above-mentioned resin bed a calculated by following formula (I) is 0.40 ~ 0.80.
[mathematical expression 1]
In above-mentioned (I) formula, H m1, H c1be respectively use differential scanning calorimeter (DSC) to measure in the temperature range of 30 ~ 300 DEG C, when heating up to this resin bed a with the programming rate of 10 DEG C/min crystal melting heat (the 1st crystal melting heat), crystallization heat release (the 1st crystallization heat release), H m2refer to after naturally cooling to 30 DEG C subsequently, again in the temperature range of 30 ~ 300 DEG C, the crystal melting heat (the 2nd crystal melting heat) that measures when this resin bed a being heated up with the programming rate of 10 DEG C/min.
Resin/metal composite the laminated material of the 2nd embodiment relates to the resin/metal composite laminated material described in the 1st embodiment, and wherein, the polyamide-based resin contained in described resin bed a is nylon 6.
Resin/metal composite the laminated material of the 3rd embodiment relates to the 1st embodiment or the resin described in the 2nd embodiment/metal composite laminated material, and wherein, the thickness of described resin bed a is 5 ~ 100 μm, and the thickness of described metallic plate is 0.03 ~ 3.0mm.
Resin/metal composite the laminated material of the 4th embodiment relates to the resin/metal composite laminated material in the 1st embodiment to the 3rd embodiment described in arbitrary embodiment, wherein, described resin bed a has further the 2nd resin bed b using the hybrid resin of polycarbonate resin and polyester resin as principal component.
Resin/metal composite the laminated material of the 5th embodiment relates to the resin/metal composite laminated material described in the 4th embodiment, wherein, the polycarbonate resin contained in described resin bed b and the mixing ratio of polyester resin are polycarbonate resin: polyester resin=20:80 ~ 70:30.
Resin/metal composite the laminated material of the 6th embodiment relates to the resin/metal composite laminated material described in the 4th embodiment or 5 embodiments, and wherein, the polyester resin contained in described resin bed b is for being polybutylene terephthalate (PBT).
Resin/metal composite the laminated material of the 7th embodiment relates to the resin/metal composite laminated material in the 4th embodiment to the 6th embodiment described in arbitrary embodiment, and this resin/metal composite laminated material is used for in-molded.
Resin/metal composite the laminated material of the 8th embodiment relates to the resin/metal composite laminated material in the 1st embodiment to the 3rd embodiment described in arbitrary embodiment, and this resin/metal composite laminated material for being integrally formed the protuberance be made up of synthetic resin by injection mo(u)lding on described resin bed a.
Resin/metal composite the laminated material of the 9th embodiment relates to the resin/metal composite laminated material in the 4th embodiment to the 7th embodiment described in arbitrary embodiment, and this resin/metal composite laminated material for being integrally formed the protuberance be made up of synthetic resin by injection mo(u)lding on described resin bed b.
Resin/metal composite the laminated material of the 10th embodiment relates to the 8th embodiment or the resin described in the 9th embodiment/metal composite laminated material, wherein, the fusing point of the resin forming described resin bed a, described resin bed b or form described resin bed a and resin bed b is lower 10 ~ 60 DEG C than the fusing point of the synthetic resin forming described protuberance.
Resin/metal composite the laminated material of the 11st embodiment relates to the resin/metal composite laminated material described in the 10th embodiment, and wherein, the synthetic resin forming described protuberance is nylon MXD 6.
Resin/metal composite the laminated material of the 12nd embodiment relates to the resin/metal composite laminated material described in the 10th embodiment, and wherein, the synthetic resin forming described protuberance is polycarbonate resin.
Resin/metal composite the laminated material of the 13rd embodiment relates to the resin/metal composite laminated material in the 1st embodiment to the 12nd embodiment described in arbitrary embodiment, wherein, described metallic plate carried out pellumina process (ア Le マ イ ト processes and processes) with the face of the opposition side, face being formed with described resin bed a or being formed with described resin bed a and resin bed b.
Resin/metal composite the laminated material of the 14th embodiment relates to the resin/metal composite laminated material in the 1st embodiment to the 13rd embodiment described in arbitrary embodiment, wherein, described metallic plate be formed with described resin bed a or be formed on the face of opposition side, face of described resin bed a and resin bed b, there is coating rete and resin coated layer successively.
The feature of the resin/metal composite injection-molded article of the present invention's (the 15th embodiment) is, the protuberance be made up of this synthetic resin and described resin/metal composite laminated material by the molten resin of injection mo(u)lding synthetic resin on the resin bed a or resin bed b of the resin/metal composite laminated material described in the present invention's (the 1st embodiment is to the arbitrary embodiment in the 14th embodiment), thus are molded as one by it.
The feature of the framework for OA equipment or electronic equipment of the present invention's (the 16th embodiment) is, it comprises the resin/metal composite injection-molded article described in the present invention's (the 15th embodiment).
The framework for OA equipment or electronic equipment of the 17th embodiment relates to the framework for OA equipment or electronic equipment described in the 16th embodiment, and this framework is the framework of mobile phone.
The manufacture method of the resin/metal composite laminated material of the present invention's (the 18th embodiment) is the method for the manufacture of the resin/metal composite laminated material described in (the 1st embodiment is to the arbitrary embodiment in the 14th embodiment), and the method has the lamination operation of deposition resin molding on described metallic plate.
The manufacture method of the resin/metal composite injection-molded article of the present invention's (the 19th embodiment) is the method for the manufacture of the resin/metal composite injection-molded article described in (the 15th embodiment), the method has following operation: in the injection forming mold being configured with described resin/metal composite laminated material, inject described molten resin, thus described protuberance and described resin/metal composite laminated material are molded as one.
The effect of invention
Owing to forming the resin of the resin bed a of resin of the present invention/metal composite laminated material using polyamide-based resin as principal component, and its crystallization index has been controlled in specific scope, thus when carrying out injection mo(u)lding to the resin for the formation of protuberance, resin appropriate melting under the effect of the heat of molten resin of this resin bed a, be cooled with the state fully compatible with the molten resin of injection and solidify, therefore, on this resin bed a, the protuberance of synthetic resin can be formed with high-adhesive-strength.
In addition, if further lamination is formed with the resin/metal composite laminated material of resin bed b on above-mentioned resin bed a, then high with the cementability of the resin of injection mo(u)lding, such as polycarbonate resin, and it is comparatively soft, therefore, press processability is excellent, and possesses the heat resistance that can tolerate mold temperature (80 ~ 120 DEG C), and described resin bed b is using the hybrid resin of polycarbonate resin and polyester resin as principal component.
For resin of the present invention/metal composite injection-molded article that plastic protuberance is integrally formed for the molten resin by injection mo(u)lding synthetic resin on the resin bed a or resin bed b of the invention described above resin/metal composite laminated material, because it possesses metallic plate and resin bed, therefore there is electromagnetic wave shielding, insulating properties, because it is matrix material with metallic plate, thus there is enough intensity, slimming can be realized, and, due to this resin/metal composite injection-molded article integrated molding enhancing rib securely on the resin layer, be threaded with protuberances such as boss, therefore, be suitable for use as various structural material, particularly OA equipment, the framework of electronic equipment, especially the framework of mobile phone, for its slimming of raising, miniaturization is effective.
Accompanying drawing explanation
Fig. 1 a ~ Fig. 1 b is profile, it illustrates an example of the embodiment of resin of the present invention/metal composite laminated material.
Fig. 2 is profile, it illustrates an example of the embodiment of resin of the present invention/metal composite injection-molded article.
Fig. 3 is schematic diagram, it illustrates an example of the manufacturing process of resin of the present invention/metal composite laminated material.
Fig. 4 a ~ Fig. 4 e is profile, it illustrates an example of the manufacturing process of resin of the present invention/metal composite injection-molded article.
Fig. 5 a ~ Fig. 5 c is the key diagram of AEG-process method.
Fig. 6 a ~ Fig. 6 b is the profile of the framework illustrated in the past.
Symbol description
1,1a, 1b resin/metal composite laminated material
1A metallic plate
1B resin bed (the laminated resin layer of resin bed a or resin bed a and resin bed b)
1C basalis
2 resins/metal composite injection-molded article
3 protuberances
4 injection forming molds
5 injection moulding machines
6 molten resins
24 heating furnaces
26 resin moldings
28 reheating furnaces
29 resins/metal composite laminated material
31 samples
32 otch
33 drifts
34 punch dies
35 blank holders
Detailed description of the invention
Below, embodiments of the present invention are described in detail.
[resin/metal composite laminated material]
Resin of the present invention/metal composite laminated material has metallic plate and is stacked in the resin bed a using polyamide-based resin as principal component at least one side of this metallic plate, or there is metallic plate, resin bed a and be stacked in the resin bed b using the hybrid resin of polycarbonate resin and polyester resin as principal component on this resin bed a further, wherein, the crystallization index of the above-mentioned resin bed a calculated by following formula (I) is 0.
[mathematical expression 2]
In above-mentioned (I) formula, H m1, H c1be respectively use differential scanning calorimeter (DSC) to measure in the temperature range of 30 ~ 300 DEG C, when heating up to this resin bed a with the programming rate of 10 DEG C/min crystal melting heat (the 1st crystal melting heat), crystallization heat release (the 1st crystallization heat release), H m2refer to after naturally cooling to 30 DEG C subsequently, again in the temperature range of 30 ~ 300 DEG C, the crystal melting heat (the 2nd crystal melting heat) that measures when this resin bed a being heated up with the programming rate of 10 DEG C/min.
Fig. 1 a, 1b are the profiles of an example of the embodiment that resin of the present invention/metal composite laminated material is shown, for this resin/metal composite laminated material 1a, 1b, define resin bed 1B across basalis 1C on a face of metallic plate 1A.In the resin/metal composite laminated material 1a of Fig. 1 a, resin bed 1B is the single layer structure of resin bed a (in fig 1 a, representing with symbol " 1B-a ").In the resin/metal composite laminated material 1b of Fig. 1 b, resin bed 1B is with resin bed a (in Figure 1b, represent using symbol " 1B-a ") as intermediate layer (priming coat), with 2 layer stacked structure of resin bed b (in Figure 1b, representing using symbol " 1B-b ") as superficial layer.
< metallic plate >
As the object lesson of metallic plate of the present invention, can enumerate: pure aluminum plate, aluminium alloy plate, corrosion resistant plate, steel plate, Titanium board, titanium alloy sheet, magnesium alloy plate, carried out the metals such as nickel, zinc, copper individual layer plating and the individual layer coated steel sheet formed, carried out two or more above-mentioned metal multilayer plating and the multilayer coated steel sheet formed, carried out two or more alloy formed in above-mentioned metal plating and the alloy plating steel plate formed, etc.
Can also enumerate: on above-mentioned steel plate and coated steel sheet, defined tunicle by chemical conversion treatment various surface treated steel plates, corrosion resistant plate, aluminium alloy plate, described chemical conversion treatment comprise the electrolytic treatments in bichromate solution of carrying out for the formation of the individual layer tunicle be made up of hydrated chromium oxide or for the formation of upper strata be hydrated chromium oxide, lower floor is the electrolysis chromic acid process etc. that 2 layers of tunicle of crome metal carry out; Implement the aluminium sheet, aluminium alloy plate, copper, copper alloy etc. that obtain for the formation of the above-mentioned chemical conversion treatment of the individual layer tunicle be made up of hydrated chromium oxide and other chemical conversion treatment, etch processes, anodized etc. that other chemical conversion treatment described comprises the process of dipping chromic acid, chromium phosphate acid treatment and adopts aqueous slkali or acid solution to carry out.
In above-mentioned metallic plate, from the viewpoint of the high and excellent corrosion resistance of intensity, the corrosion resistant plates such as preferred SUS304 or its surface treatment plate, such as coated steel sheet, in addition, light from the viewpoint of quality, preferred aluminium sheet, aluminium alloy plate or its surface treatment plate.
The thickness of metallic plate suitably can be selected according to resin/metal composite laminated material and the application target employing resin/metal composite injection-molded article that this resin/metal composite laminated material obtains, to obtain necessary intensity and thickness, the thickness of metallic plate is generally 0.03 ~ 3.0mm, particularly 0.1 ~ 2.0mm.
Particularly, in the purposes of the requirement slimming as the framework of mobile phone, the thickness of metallic plate is preferably about 0.1 ~ 1.0mm, when metallic plate is the corrosion resistant plates such as SUS304, its thickness is 0.1 ~ 0.6mm, when metallic plate is aluminum or aluminum alloy plate, preferably its thickness is about 0.3 ~ 1.0mm.
If the thickness of metallic plate is excessively thin, then cannot obtain necessary intensity, distortion can be produced due to resin pressure when injection mo(u)lding, or metallic plate distortion can be produced after shaping because of the contraction of resin, if and the thickness of metallic plate is blocked up, then slimming cannot be realized.
< substrate >
Basalis 1C in Fig. 1 a, 1b is not required, in order to improve the adaptation between metallic plate 1A and resin bed 1B, preferably there is various substrate, bond layer between which.As substrate, bonding agent, what can use in known aluminium class, titanium class, coupling agent, crylic acid resin bonding agent, polyurethane type resin bonding agent, epoxy resin bonding agent, the polyester resin bonding agent etc. such as silicone based is one kind or two or more, but is not limited to the above-mentioned material exemplified.
In order to fully obtain the raising effect of the adaptation between metallic plate and resin bed a, and do not harm slimming, the thickness of basalis, adhesive linkage is generally about 0.1 ~ 15 μm.
< resin bed a >
Resin bed a of the present invention (the resin bed 1B-a in Fig. 1 a, 1b) is formed using polyamide-based resin as principal component, and above-mentioned crystallization index is 0.40 ~ 0.80.
It should be noted that, " principal component " mentioned here refers to, more than the 50 quality % accounting for the resin forming resin bed a, the resin preferably accounting for more than 80 quality %, particularly preferably account for more than 95 quality %.
(polyamide-based resin)
As the polyamide-based resin of the resin bed a formed in the present invention, can enumerate: nylon 6, nylon 11, nylon 12, nylon66 fiber, NYLON610, nylon 612, nylon 46, aromatic polyamide resinoid etc. containing the construction units generated by polycondensation reaction by m-xylene diamine and adipic acid of more than 90 % by mole.In addition, can also enumerate: utilize carboxylic acid anhydrides etc. to carry out modification to above-mentioned resin and the sour modifier obtained, utilize GMA etc. to carry out modification to above-mentioned resin and the one matter or its mixture etc. of epoxide modified thing obtained etc.
Preferred polyamide resinoid, because it has the following advantages: with compatibility, the deposition excellence of the resin for the formation of protuberance of resin described later/metal composite injection-molded article; Excellent in workability, and when carrying out bending machining, extrusion process to resin/metal composite laminated material, not easily produce be full of cracks etc.; Due to excellent heat resistance, therefore when injection mo(u)lding described later, fully can tolerate mold temperature (being generally 100 ~ 160 DEG C).
Wherein, preferred nylon 6, because it easily meets the crystallization index specified in the present invention, and excellent with the compatibility of the resin of formation described later resin of the present invention/metal composite injection-molded article protuberance, deposition.
(other composition)
It should be noted that, the resin forming resin bed a can be with polyamide-based resin beyond the mixture of resin.Now, as the object lesson of the resin beyond polyamide-based resin, can enumerate: the polyester resin such as PETG, polybutylene terephthalate (PBT), polyethylene, polypropylene, take ethene as the olefine kind resin such as copolymer of principal component.But, from the viewpoint of compatibility, deposition to the control of crystallization index and the synthetic resin with formation protuberance described later, resin bed a of the present invention is preferably only formed using polyamide-based resin as resinous principle, is particularly preferably only formed using nylon 6 as resinous principle.
For resin bed a of the present invention, can in the above-mentioned resin using polyamide-based resin as principal component, add the resin additives such as cementability imparting agent, lubricant, pigment further as required and be formed.
(crystallization index)
If the crystallization index of resin bed a of the present invention is more than 0.80, then when injection mo(u)lding described later, the meltability under the effect of the heat of the molten resin of injection is insufficient, protuberance and resin bed a cannot be molded as one with high-adhesive-strength.Crystallization index lower than 0.40 time, heat resistance be deteriorated, thus not preferred.Therefore, the crystallization index of resin bed a is set as 0.40 ~ 0.80, is preferably set to 0.6 ~ 0.75.
It should be noted that, for the crystallization index of resin bed a, particularly, can carry out measuring, calculating according to method described in embodiment item described later.
As making the crystallization index of resin bed a be the method for above-mentioned scope, can enumerate and select suitable polyamide-based resin, and as below describe, after defining resin bed a on a metal plate, the method for suitable adjustment cooling condition.In addition, to add in selected polyamide-based resin in addition on the basis of filler etc., adjustment cooling condition, thus make crystallization index be the method for above-mentioned scope.
(fusing point)
For forming the resin of resin bed a, preferably meet above-mentioned crystallization index, and its fusing point is lower 10 ~ 60 DEG C, more preferably low 10 ~ 40 DEG C, especially preferably low 15 ~ 40 DEG C than the hereinafter described fusing point for the synthetic resin being formed protuberance by injection mo(u)lding.If the fusing point forming the resin of resin bed a is too high, then when injection mo(u)lding described later, the meltability under the effect of the heat of the molten resin of injection is insufficient, protuberance and resin bed a cannot be molded as one with high-adhesive-strength.And on the other hand, if its fusing point is too low, then heat resistance is deteriorated, the temperature of injection forming mold cannot be tolerated, not preferably.
(thickness)
In the present invention, the thickness of if tree lipid layer a is excessively thin, then when the injection mo(u)lding of protuberance described later, with high-adhesive-strength, protuberance and resin bed a cannot be molded as one, in addition, add man-hour at resin/metal composite laminated material, the situation that pin hole etc. is undesirable occurs to produce sometimes.The thickness of if tree lipid layer a is blocked up, then add man-hour in the bending machining etc. of carrying out resin/metal composite laminated material, resin bed a easily peels off, and can become the obstruction of resin/metal composite laminated material slimming simultaneously and then can become the obstruction of resin/metal composite injection-molded article slimming.
Therefore, the purposes that the thickness of resin bed a defines resin bed b described later, resin/metal composite laminated material and resin/metal composite injection-molded article according to whether at this resin bed a superimposed layer and the shape, structure etc. of protuberance that are formed on this resin bed a and different, but be preferably 5 ~ 100 μm, particularly, when not forming resin bed b on resin bed a, the thickness of resin bed a is preferably 15 ~ 100 μm, is more preferably 20 ~ 50 μm.
In addition, resin bed a is formed resin bed b, the thickness of resin bed a is preferably 5 ~ 50 μm, is more preferably 10 ~ 40 μm, is especially preferably 10 ~ 30 μm.
< resin bed b >
Using above-mentioned resin bed a as intermediate layer and when resin bed a superimposed layer formed resin bed b (the resin bed 1B-b in Fig. 1 b), this resin bed b can be formed by using the hybrid resin of polycarbonate resin and polyester resin as the resin combination of principal component.
For polycarbonate resin monomer, have problems, can crack after processing in press processability, by using the hybrid resin of polycarbonate resin and polyester resin, press processability is improved.
(polycarbonate resin)
As long as polycarbonate resin by carbonic acid and glycol or dihydric phenol is formed, the polycarbonate resin (R is dibasic aliphatic or aromatic group) that represents with general formula-(O-R-O-CO-) n-.
Can enumerate such as: use the bisphenol-A synthesized by phenol and acetone, by the polycarbonate resin that surface aggregate method, ester-interchange method, pyridine method etc. are manufactured; By bisphenol-A and dicarboxylic acid derivatives, such as copolymerization is carried out to () phthalyl chloride etc. and the polycarbonate resin obtained; Undertaken being polymerized by the derivative of bisphenol-A, such as tetramethylene bisphenol-A etc. and the polycarbonate resin obtained, etc.
Part or all that can also use bisphenol-A is by the polycarbonate resin of the structure after the displacement of other dihydric phenol.
Now, as other dihydric phenol, can enumerate: quinhydrones, 4, 4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) methane, two (4-hydroxy phenyl) alkanes such as two (4-hydroxy phenyl) ethane of 1-, 1, two (4-hydroxy phenyl) cycloalkane such as 1-bis(4-hydroxyphenyl)cyclohexane, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) sulfoxide, the compounds such as two (4-hydroxy phenyl) ether, such as 2, the alkylated bisphenols class that two (3-methyl-4-hydroxy phenyl) propane of 2-is such, such as 2, 2-two (3, 5-bis-bromo-4-hydroxy phenyl) the such halogenated bisphenol class of propane.
The viscosity average molecular weigh of polycarbonate resin is not particularly limited, and is preferably 10,000 ~ 100,000, is more preferably 20,000 ~ 30,000, be wherein particularly preferably 23,000 ~ 28, the scope of 000.
In addition, the melt flow rate (MFR) of polycarbonate resin is not particularly limited, and is preferably based on JISK7210 standard, 300 DEG C, the melt flow rate (MFR) that measures under 1.2Kg loading is 5 ~ 20.
As polycarbonate resin, " Lupilon " series of such as Mitsubishi engineering Plastics Co., Ltd's manufacture, " Calibre " series etc. of Sumitomo Dow company manufacture can be enumerated.
It should be noted that, as polycarbonate resin, can be used alone a kind of polycarbonate resin, also can mix two or more polycarbonate resin and use.
(polyester resin)
As polyester resin, be the resin that dicarboxylic acid component and diol component are formed through polycondensation, wherein, from the viewpoint of heat resistance, the aromatic polyester-based resin preferably formed through polycondensation by aromatic dicarboxylic acid composition and diol component.
Wherein, as the representative substances of above-mentioned " aromatic dicarboxylic acid composition ", terephthalic acid (TPA), M-phthalic acid, naphthalene dicarboxylic acids etc. can be enumerated, but also can be the part of terephthalic acid (TPA) by " other dicarboxylic acid component " displacement the material that obtains.
Here, as " other dicarboxylic acid component ", ethanedioic acid, malonic acid, succinic acid, adipic acid, azelaic acid, decanedioic acid, neopentanoic acid, M-phthalic acid, naphthalene dicarboxylic acids, oxydibenzoic acid, P-hydroxybenzoic acid etc. can be enumerated.These other dicarboxylic acid component can be wherein a kind, also can be mixtures of more than two kinds, and in addition, the amount of other replaced dicarboxylic acid component also can suitably be selected.
As the representative substances of above-mentioned " diol component ", ethylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol etc. can be enumerated, also with " other diol component ", a part for ethylene glycol can be replaced.
Here, as " other diol component ", propane diols, butanediol, trimethylene, tetramethylene glycol, hexamethylene glycol, diethylene glycol, neopentyl glycol, PAG, 1,4-CHDM, glycerine, pentaerythrite, trimethylolpropane, methoxypolyalkylene glycol etc. can be enumerated.These other diol components can be wherein a kind, also can be mixtures of more than two kinds, and in addition, the amount of other replaced glycol also can suitably be selected.
In addition, as other polyester resin, " copolyester " of the dicarboxylic acid component beyond containing terephthalic acid (TPA) and/or other diol component beyond ethylene glycol can be used.
The molecular weight of the polyester resins such as aromatic polyester-based resin used in the present invention is not particularly limited, but preferably in phenol/tetrachloro-ethylene=50/50 (volume ratio) solution, in the inherent viscosities of 30 DEG C be about 0.600 ~ 1.400.
As the concrete goods example of above-mentioned aromatic copolyester, can enumerate such as, " Novapex " that manufacture as the Mitsubishi chemical Co., Ltd of the modifier of PETG is serial (such as, Novapex PS600), " Novaduran " series (such as, Novaduran 5008) of manufacturing as the Mitsubishi engineering Plastics Co., Ltd of the modifier of polybutylene terephthalate (PBT).In addition, can enumerate as % by mole ethylene glycol of about 30 in PETG by 1, " Eastar 6763 " that the Eastman Chemical company of the mylar of 4-cyclohexanedimethanol displacement manufactures, comprise identical component but melt viscosity slightly low with " Eastar GN 119 " " Eastar " series that is representative.
Particularly, the polyester resin of heat resistance can be kept as the processability can improving polycarbonate resin, most preferably use butanediol as diol component, use terephthalic acid (TPA) as the polybutylene terephthalate (PBT) (PBT) of aromatic dicarboxylic acid composition.
Polybutylene terephthalate (PBT) is crystalline resin, and therefore heat resistance, intensity are all excellent, in addition, from completely compatible with polycarbonate resin and form the viewpoint of polymer alloy, particularly preferably it can be used as the polyester resin forming resin bed b.
As the concrete goods example of above-mentioned polybutylene terephthalate (PBT), can enumerate such as, " Novaduran " series that " Duranex " series that Wintech polymer company manufactures, Mitsubishi engineering Plastics Co., Ltd manufacture.
In addition, the mixture of polybutylene terephthalate (PBT) and above-mentioned copolyester can also be used.
(mixed proportion)
For the mixed proportion of the polyester resin and polycarbonate resin that form resin bed b, by quality ratio, preferably in the scope of 20:80 ~ 70:30, further preferred in the scope of 20:80 ~ 60:40, especially preferred in the scope of 30:70 ~ 50:50, wherein particularly preferably in the scope of 35:65 ~ 45:55.Time in the scope of described mixed proportion, can not crack when press process, when injection mo(u)lding, film surface also can not melting, therefore preferably.
(fusing point)
For forming the resin of resin bed b, preferably its fusing point is lower 10 ~ 60 DEG C, more preferably low 10 ~ 40 DEG C, especially preferably low 15 ~ 40 DEG C than the fusing point for the synthetic resin being formed protuberance by injection mo(u)lding described below.If the fusing point forming the resin of resin bed b is too high, then, when injection mo(u)lding described later, because the meltability under the effect of the heat of injected molten resin is insufficient, with high-adhesive-strength, protuberance cannot be molded as one.And on the other hand, if its fusing point is too low, then heat resistance is deteriorated, the temperature of injection forming mold cannot be tolerated, not preferably.
It should be noted that, resin bed a is formed resin bed b, for the fusing point of resin bed a, and not necessarily is defined as lower than the described fusing point for the synthetic resin being formed protuberance by injection mo(u)lding below, but the fusing point of if tree lipid layer a is too low, under then there is the effect of the heat of the moulding resin of resin bed a when injection mo(u)lding and mould and the worry peeled off from metallic plate, therefore not preferred.From the point of view, the fusing point of preferred resin layer a is lower 10 ~ 60 DEG C, more preferably low 10 ~ 40 DEG C, especially preferably low 15 ~ 40 DEG C than the fusing point for the synthetic resin being formed protuberance by injection mo(u)lding described below.
(thickness)
The thickness of resin bed b is preferably 10 ~ 200 μm.The thickness of if tree lipid layer b lower than 10 μm, then, when implementing extrusion process, bending machining etc., also existing and produces pin hole etc. and cannot improve the worry with the cementability of injection mo(u)lding part.On the contrary, the thickness of if tree lipid layer b more than 200 μm, then becomes blocked up, there is the situation that press processability reduces, unfavorable at economic aspect.
For be formed with the resin of the present invention/metal composite laminated material of above-mentioned resin bed b at resin bed a superimposed layer for, the cementability of the resin bed b on surface and the molten resin of injection is high, and press processability is excellent, in addition, also there is the heat resistance that can tolerate mold temperature (80 ~ 120 DEG C) and the speciality that can not cause the excellences such as the strength of materials of distortion because of injection pressure, therefore, it is suitable as the resin/metal composite laminated material of injection mo(u)lding thing cementation integration on its surface by in-molded injecting molten resin.
Other constituting layer > of <
For resin of the present invention/metal composite laminated material, when using aluminium alloy plate as metallic plate, can to metallic plate with formed resin bed opposition side, face face, be namely formed with resin bed a or pellumina process is carried out in the face of the opposition side, face that is formed with resin bed a and resin bed b.By carrying out pellumina process, can to traumatic resistance, rust-preventing characteristic, coloring required during the framework of metal sheet surface imparting as electronic equipment.
Pellumina process refers to, by carrying out Surface Finishing, degreasing processing, anodic oxidation, dyeing, sealing pores etc. to resin metallic laminated composite material one side being formed with resin bed a or being formed with resin bed a and resin bed b, make the processing method forming alumina layer on aluminium surface.
As Surface Finishing, can enumerate: the mirror finish of being undertaken by polishing, the Physical Processing such as delustring processing, hairline processing of being undertaken by blasting treatment, in addition, can also by employing the delustring process of ammonium fluoride aqueous solution, the chemical grinding employing the phosphorus acid-sulfur acid aqueous solution or employ phosphoric acid-aqueous solution of nitric acid, the electrolytic polishing etc. employing phosphate aqueous solution carry out above-mentioned Surface Finishing.
As degreasing processing, can enumerate: the degreasing utilizing sulfuric acid to carry out, the electrolytic degreasing etc. in sodium hydrate aqueous solution.
In anodic oxidation, sulfuric acid process, Oxalic Acid Method, phosphoric acid method etc. can be adopted.Being described as follows for actual conditions: such as in sulfuric acid process, connecting electrode on resin/metal composite laminated material, is impregnated in the aqueous sulfuric acid of 10 ~ 30 quality % being adjusted to 15 ~ 25 DEG C, with 50 ~ 300A/m 2current density energising, thus, alumina layer can be formed at metal sheet surface.The thickness of the alumina layer generated is not particularly limited, if but its thickness is excessively thin, then and cannot play sufficient performance, on the contrary, if the thickness of alumina layer is blocked up, then the processing time is elongated, economical not.The thickness of preferential oxidation aluminium lamination is the scope of 1 ~ 20 μm.
As required, the dyeing of aluminium oxide rete can be carried out before carrying out sealing pores.As decoration method, can enumerate: the method using organic dyestuff to carry out dyeing, be impregnated in comprise slaine dyeing liquor in carry out the method etc. that dyes.
As sealing pores, can enumerate the method be exposed in steam, the method that impregnated in boiling water, thus, aluminium oxide rete forms hydrate, thus can increase substantially corrosion resistance.
Pellumina process can any stage before carrying out injection mo(u)lding or afterwards be carried out, but, in order to avoid producing bad order when injection mo(u)lding because of metal covering and contacting dies, preferably after injection mo(u)lding, carry out pellumina process.
For resin of the present invention/metal composite laminated material, by coating to metallic plate with formed resin bed opposition side, face face, be namely formed with resin bed a or the face of opposition side, face that is formed with resin bed a and resin bed b processes when, this face has coating rete and resin coated layer successively.By being set to said structure, after injection mo(u)lding can being carried out on the face being formed with resin bed a or being formed with resin bed a and resin bed b, the face of coating rete applying, thus forming resin coated layer.
When directly applying on a metal plate at non-lamination coating rete, sintering temperature needs to be about 120 ~ 130 DEG C, and therefore, if applied after carrying out injection mo(u)lding, then softening, distortion occurs moulding resin.In addition, in general, scarcely abundant with the coating bonding force of metal, there is the problem easily occurring to peel off in use.
In contrast, if lamination coating rete on a metal plate in advance, then the coating used in Merlon in the past, nylon MXD 6 etc. can be used.By the above-mentioned coating rete of lamination, baking temperature can be controlled at about 60 ~ 80 DEG C, softening, the distortion of moulding resin can not occur when drying, and the bonding force of coating can be increased substantially.
As the resin that can use in coating rete, can enumerate: polycarbonate resin, polyamide-based resin, polyester resin, polyurethane based resin, ABS resin, acrylic resin.The thickness of coating rete is preferably about 5 ~ 50 μm.As long as the thickness of coating rete is in the scope of 5 ~ 50 μm, the bonding force with coating can be demonstrated, at economic aspect also advantageously.
Form the method for coating rete as lamination on a metal plate, can enumerate: the molten resin extruding the resin for the formation of coating film at metal sheet surface, and its lamination is formed as membranaceous method; By preformed coating rete pressure method on a metal plate, etc.
As the coating used in resin coated layer, can enumerate: polyurethane based resin, acrylic resin, polyamide-based resin, any means such as spraying process can be used to be coated with.Also hard conating can be set on the most top layer of resin coated layer.The thickness of resin coated layer is not particularly limited, and can suitably set its thickness according to its object.
Particularly, when making the resin of formation coating rete consistent with the resin forming protuberance, such as, the resin forming coating rete is selected to be same resin with the resin of formation protuberance, and on resin bed a injection mo(u)lding formed by nylon MXD 6 protuberance, by selecting nylon MXD 6 grade as the coating used in resin coated layer, can apply in the lump the protuberance carrying out injection mo(u)lding and coating rete, therefore, operation can be simplified.Similarly, when the resin selecting to form coating rete is same resin with the resin of formation resin bed b, the protuberance that injection mo(u)lding is formed by Merlon on resin bed b, by selecting Merlon grade as the coating used in resin coated layer, application can be carried out in the lump to the protuberance carrying out injection mo(u)lding and coating rete, therefore, operation can be simplified.
In addition, when lamination is formed as the resin bed a of resin bed and resin bed b, also can be formed between resin bed a and resin bed b and there is the resin bed of high adhesiveness as adhesive linkage to two resin beds.As above-mentioned adhesive linkage, the adhesive linkage formed by polyester resin, epoxylite, polyurethane based resin etc. can be enumerated, the adhesive linkage preferably formed by polyester resin.
The thickness G reatT.GreaT.GT of < resin/metal composite laminated material
Form the metallic plate of resin of the present invention/metal composite laminated material, resin bed (i.e. resin bed a or resin bed a and resin bed b), as required and the basalis arranged or the preferred thickness of adhesive linkage and other constituting layer described above, for the gross thickness of resin of the present invention/metal composite laminated material, different according to its purposes, but be generally 0.1 ~ 3.0mm, particularly 0.1 ~ 2.0mm, in the purposes of the such requirement slimming of the framework of such as mobile phone, be preferably about 0.1 ~ 1.0mm.
The manufacture method > of < resin/metal composite laminated material
Resin of the present invention/metal composite laminated material can be manufactured by following method: at least one side of metallic plate, form the resin bed a using polyamide-based resin as principal component meeting above-mentioned crystallization index or form this resin bed a and above-mentioned resin bed b.
As the method forming resin bed a on a metal plate, can enumerate: the molten resin extruding the resin for the formation of resin bed a at metal sheet surface, and its lamination is formed as membranaceous method; By molded for the preformed resin film layer for the formation of resin bed a method on a metal plate, etc.
In addition, the method of resin bed a and resin bed b is formed as lamination on a metal plate, can enumerate: carry out coextrusion by the molten resin of the resin for the formation of resin bed a with for the formation of the molten resin of the resin of resin bed b at metal sheet surface, and its lamination is formed as membranaceous method; The molten resin of the resin for the formation of resin bed b is extruded into membranaceous by the resin bed a of metallic plate being pre-formed with resin bed a according to the method described above, thus lamination form the method for resin bed b; By the resin for the formation of resin bed a shaping in advance and the stack membrane method on a metal plate laminated into type for the formation of the resin of resin bed b, etc.
Fig. 3 illustrates that resin molding laminated into type is to manufacture the schematic diagram of the operation of resin of the present invention/metal composite laminated material on a metal plate, 1 pair roller 23 is clipped in around the metallic plate 22 of body 21 by from metal plate coils, between 23, and send according to the direction of arrow, after making it be heated by heating furnace 24, the resin molding that lamination is sent by resin molding coiling body 25 is (for the formation of the film of the resin of resin bed a, or for the formation of the resin of resin bed a and the stack membrane for the formation of the resin of resin bed b) 26, be clipped in 1 pair roller 27, extrude between 27, then heated again by reheating furnace 28, thus make resin molding 26 and the integration of metallic plate 22 deposition, form resin/metal composite laminated material 29, and batched on coiling body 30.
Metallic plate can be pre-formed basalis, in addition, the metallic plate also can sent in the lamination operation of described resin molding forms basalis.
In addition, in order to improve the cementability with metallic plate, the surface treatments such as Corona discharge Treatment can also be implemented to resin molding.
In the lamination operation of described resin molding, the crystallization index of formed resin bed a can be adjusted by the heating condition again (heating-up temperature of reheating furnace 28 and heat time (linear velocity)) after control deposition resin molding.Namely, if improve again heating-up temperature and shorten rethermalization time, then can form the resin bed a that crystallization index is less, on the contrary, if reduce again heating-up temperature and/or extend rethermalization time, then can form the resin bed a that crystallization index is larger, therefore, crystallization index can be formed at the resin bed a of 0.40 ~ 0.80 by controlling heating condition again, thus obtaining resin of the present invention/metal composite laminated material.
In the present invention, heating condition during by resin film layer pressure is on a metal plate different according to the resin types of formation resin bed (resin bed a or resin bed a and resin bed b), but the heating-up temperature of metallic plate (heating-up temperature of heating furnace 24) is generally 300 ~ 500 DEG C, preferably the heating-up temperature again (temperature of reheating furnace 28) after deposition resin molding is set as 250 ~ 450 DEG C, about rethermalization time (laminated material is by the time in reheating furnace 28) was set as 3 ~ 10 seconds.
[resin/metal composite injection-molded article]
Resin of the present invention/metal composite injection-molded article is by the molten resin at the upper injection mo(u)lding synthetic resin of the resin bed (resin bed a or resin bed b) of the invention described above resin/metal composite laminated material, thus the protuberance formed by this synthetic resin and resin of the present invention/metal composite laminated material are molded as one and are obtained.
Fig. 2 is the profile of the example that resin of the present invention/metal composite injection-molded article is shown, this resin/metal composite injection-molded article 2 carries out bending machining to the resin of the present invention/metal composite laminated material forming resin bed (resin bed a or resin bed a and resin bed b) 1B on a face of metallic plate 1A, to be then molded as one with it by the protuberance 3 formed by synthetic resin by injection mo(u)lding and to obtain.
< protuberance is formed and uses synthetic resin >
As the synthetic resin for being formed protuberance by injection mo(u)lding, be not particularly limited, can enumerate: the mixture of the acrylic resin such as styrene resin, polymethyl methacrylate, polyester resin, polyolefin resin, polyamide-based resin, Merlon, polyphenylene oxide and the above-mentioned resins such as polystyrene, ABS resin, MBS resin.Particularly, when resin bed on metallic plate is only made up of above-mentioned resin bed a, preferred use nylon MXD 6 (the crystalline thermoplastic resin obtained by m-xylene diamine (MXDA) and adipic acid), because its intensity is high and mechanical property excellent.In addition, resin bed on metallic plate is by when resin bed a and resin bed b are formed and superficial layer is resin bed b, from the excellent compatibility with resin bed b, 1 kind or mixture of more than two kinds, particularly preferably polycarbonate resin in optimization polycarbonate resinoid, ABS resin or polycarbonate resin and above-mentioned resin.
It should be noted that, the resin that the above-mentioned synthetic resin for the formation of protuberance is normally different from the resin of the resin bed of resin/metal composite laminated material.
Shape, the size of the protuberance formed by injection mo(u)lding are not particularly limited, and suitably can determine according to its object.
It should be noted that, this protuberance is not limited to above-mentioned enhancing rib, is threaded with boss, also can be formed as the protective bulkhead of the dividing plate in framework, insulation board or framework inner member, surround component etc.
The manufacture method > of < resin/metal composite injection-molded article
Below, with reference to Fig. 4 a ~ 4e, the example of manufacture method of the resin of the present invention/metal composite injection-molded article employing resin of the present invention/metal composite laminated material is described, but the manufacture method of resin of the present invention/metal composite injection-molded article is not limited to the method shown in Fig. 4 a ~ 4e.
First, resin of the present invention/metal composite the laminated material 1 (also can have basalis 1C) of metallic plate 1A and resin bed (resin bed a or resin bed a and resin bed b) 1B is had by lamination to cut into suitable size (Fig. 4 a), then, carry out extrusion process, bending machining and punching processing etc. as required, give the shape (Fig. 4 b, 4c) that its tabular, cross section L font, cross section コ font etc. are desired.
Then, resin/metal composite laminated material 1 after giving shape is configured in the die cavity of injection forming mold 4, flow into protuberance by injection moulding machine 5 towards the direction of resin bed 1B and form molten resin 6 with synthetic resin, carry out injection mo(u)lding (Fig. 4 d).Then, from mould, take out formed body, obtain the resin of the present invention/metal composite injection-molded article 2 (Fig. 4 e) being formed with the protuberance 3 of synthetic resin on the resin bed 1B face of resin/metal composite laminated material 1.
In this injection molding processes, the resin bed a of resin of the present invention/metal composite laminated material is by being set in proper range by its crystallization index, rapid melting under the effect of the heat of injected molten resin, thus with injecting resin compatible and deposition, therefore, the protuberance formed by injection mo(u)lding and resin bed a are bonding integral securely.
In addition, resin bed a has resin bed b, resin bed b and polycarbonate resin, ABS resin or with polycarbonate resin and the excellent compatibility being selected from the one kind or two or more mixture in above-mentioned resin, therefore, the protuberance formed by injection mo(u)lding and resin bed b are bonding integral securely.In addition, by the resin bed a of excellent in workability is arranged between metallic plate, to the appropriateness (Fitness of stamped metal just can improve).
Described injection mo(u)lding condition is different according to the kind of protuberance formation synthetic resin, when using nylon MXD 6 (fusing point: about 240 ~ 245 DEG C) as protuberance formation synthetic resin, preferably at molten resin temperature: 270 ~ 300 DEG C, injection forming mold temperature: carry out injection mo(u)lding under the condition of 100 ~ 160 DEG C.
In addition, when using polycarbonate resin (fusing point: about 230 ~ 260 DEG C) as protuberance formation synthetic resin, preferably at molten resin temperature: 270 ~ 300 DEG C, injection forming mold temperature: carry out injection mo(u)lding under the condition of 60 ~ 120 DEG C.
For the resin of the present invention/metal composite injection-molded article as above obtained, can as required further to metallic plate implement with the face of opposition side, face forming resin bed apply, the surface treatment such as plating.
< purposes >
Resin of the present invention/metal composite laminated material is as OA equipment, telephone set, e-dictionary/dictionary, stereo sets such as notebook computer, desktop computer, various printing machine, various duplicators, the framework (shell) of the electronic equipment such as television set, radio, parts are useful, be particularly suitable as mobile phone framework use because its slimming can be played and have strengthen rib, be threaded by the feature of the protuberances such as boss.
Embodiment
Below, enumerate embodiment, comparative example and reference example and more specific detail is carried out to the present invention, but only otherwise exceed purport of the present invention, then not by the restriction of following examples.
[embodiment 1 ~ 4, comparative example 1 ~ 3]
After the coated on one side bisphenol A type epoxy resin of corrosion resistant plate (the thick 0.3mm of SUS3041/2H), define the basalis that thickness is 1 μm.
Then, according to method shown in Fig. 3, in the basalis forming surface of this corrosion resistant plate, lamination Nylon 6 Film (Mitsubishi Plastics Inc manufactures, fusing point: 220 DEG C), obtains resin/metal composite laminated material.
When lamination, the heating-up temperature in heating furnace 24 is set as 350 DEG C, and the heating-up temperature again of reheating furnace 28, cooling means and rethermalization time are set as shown in table 1, thus, the degree of crystallinity of the resin bed formed in each example are changed.It should be noted that, (resin bed thickness a) is 25 μm to the resin bed formed.
It should be noted that, for embodiment 3 and 4, make sample under the same conditions as example 1, it only changes used metal separately, and embodiment 3 changes to nickel plating stainless steel (the thick 0.3mm of SUS3041/2H), embodiment 4 changes to aluminium alloy (the thick 0.3mm of A5182H18).
[table 1]
In accordance with the following methods, be studied the crystallization index of the resin bed of obtained resin/metal composite laminated material respectively, its result is as shown in table 2.
[crystallization index]
Use the differential scanning calorimeter (DSC) that Perkin Elmer company manufactures, heat up in the temperature range of 30 ~ 300 DEG C, with the programming rate of 10 DEG C/min, measure resin/metal composite laminated material crystal melting heat at this moment (the 1st crystal melting heat H m1) and crystallization heat release (the 1st crystallization heat release H c1), after naturally cooling to 30 DEG C subsequently, again heat up in the temperature range of 30 ~ 300 DEG C, with the programming rate of 10 DEG C/min, measure crystal melting heat (the 2nd crystal melting heat H now m2) and crystallization heat release (the 2nd crystallization heat release H c2) (this value is as shown in table 2).Crystallization index is calculated by above-mentioned value according to following formula (I).
[mathematical expression 3]
Then, each resin/metal composite laminated material is arranged in injection forming mold, the molten resin (resin temperature 275 DEG C) of injection nylon MXD6 (" Reny (registration mark) NXG 5050 ", fusing point that Mitsubishi engineering Plastics Co., Ltd manufactures: 243 DEG C), be carry out injection mo(u)lding under the condition of 160 DEG C in mold temperature, in the resin aspect of resin/metal composite laminated material, integrally shaping radius is 3.425mm, is highly the cylindric protuberance of 15mm, thus has manufactured tension test sample.
Carry out tension test to the tension test sample obtained in accordance with the following methods, result is as shown in table 2.
[tension test]
With the draw speed of 5mm/ minute, the cylindric protuberance of tension test sample is stretched to the direction deviated from mutually with resin/metal composite laminated material, measure intensity when protuberance ruptures from resin bed, it can be used as adhesive strength.
When adhesive strength is more than 8MPa, as qualified.
[reference example 1]
Make nylon 66 resin (" CM3001-N ", fusing point 265 DEG C that Toray company manufactures) melting between 2 warm-up mills, obtain the Nylon 66 Membrane that thickness is 25 μm.
Use this Nylon 66 Membrane to replace Nylon 6 Film, form resin bed according to the step identical with embodiment 1 on corrosion resistant plate surface, obtain resin/metal composite laminated material.
Use this resin/metal composite laminated material, manufacture tension test sample similarly to Example 1, and similarly carry out tension test, result is as shown in table 2.
[reference example 2]
The corrosion resistant plate used in embodiment 1 is heated to 100 DEG C, and the commercially available acrylonitrile-butadiene rubber of deposition heats pressure viscosity band (Tesa tape manufactures, softening point 100 DEG C), and formation thickness is the resin bed of 38 μm, obtains resin/metal composite laminated material.
Use this resin/metal composite laminated material, manufacture tension test sample similarly to Example 1, and similarly carry out tension test, result is as shown in table 2.
It should be noted that, whether the resin (resin of the resin bed of resin/metal composite laminated material) when injection mo(u)lding in each example (has (zero), without (×)) and sticks on injection forming mold and be also recorded in the lump in table 2.
From the above results, employing define crystallization index be the polyamide-based resin layer of 0.40 ~ 0.80 as the resin of the present invention/metal composite laminated material of resin bed a, the protuberance formed by nylon MXD 6 and above-mentioned resin/metal composite laminated material can be molded as one with high-adhesive-strength by injection mo(u)lding.
It should be noted that, in reference example 1, compared with the fusing point of the molten resin of injection mo(u)lding, the fusing point of resin bed a is too high, and when injection mo(u)lding, resin bed a can not fully melting, and therefore, although can not stick on mould, the adhesive strength of protuberance is lower.
In reference example 2, compared with the fusing point of the molten resin of injection mo(u)lding, the fusing point (softening point) of resin bed a is too low, although the adhesive strength of protuberance is higher than comparative example 1 ~ 3, but still insufficient, in addition, the resin of resin bed a flows in mould, thus also there is the problem of resin adheres.
[embodiment 5 ~ 7]
According to the mass ratio shown in table 3 by polycarbonate resin (PC) (viscosity average molecular weigh 25000) and polybutylene terephthalate (PBT) (PBT) (30 DEG C, inherent viscosity in phenol/tetrachloro-ethylene=50/50 (volume ratio) solution is 1.2448) mixing, be supplied to the extruder being heated to 280 DEG C, this extruder is used to carry out mixing at 280 DEG C, by T-shaped die head, the resin combination of molten condition is extruded into sheet, by its cooling curing, the resin bed b having made thickness shown in table 3 and fusing point forms film.
As on the Nylon 6 Film (thickness: 20 μm, fusing point: 220 DEG C, crystallization index: the scope of 0.40 ~ 0.80, " Diamiron " that Mitsubishi Plastics Inc manufactures) of resin bed a, with 6g/m 2coating is according to 100 mass parts: the bonding agent that polyesters bonding agent and isocyanate crosslinking coordinate and obtain by the ratio of 12.5 mass parts, heated for 30 seconds in 60 DEG C in drying oven, after making its drying, use the nip rolls being heated to 60 DEG C to form film to above-mentioned resin bed b and carry out lamination, in 60 DEG C of slakings 5 days in baking oven, obtain laminated film.
The one side of corrosion resistant plate (SUS304,1/2H, thick 0.3mm) is coated with bisphenol A type epoxy resin, defines the basalis that thickness is 1 μm.
Then, above-mentioned laminated film is deposited on the corrosion resistant plate being heated to 300 DEG C, make Nylon 6 Film side become corrosion resistant plate side, obtain the resin/metal composite laminated material (assess sample) of " resin bed/bonding agent/nylon 6/ epoxy resin/SUS " structure.
[comparative example 4]
Use bar coater by silane coupler 1% aqueous solution with 20g/m 2be coated on the surface of corrosion resistant plate (SUS304,1/2H, thickness are 0.3mm), heated for 30 seconds at 110 DEG C, make it dry, then, on this coated face, (Kurabo company manufactures deposition polyurethane film, trade name " U-1250 "), obtain the laminated material (assess sample) of " resin bed/amino silane/SUS " structure.
[comparative example 5]
On the corrosion resistant plate (SUS304,1/2H, thick 0.3mm) being heated to 170 DEG C in advance, deposition thickness is polyesters adhesive film (the Kurabo company manufacture of 50 μm, trade name " Kuranbeter G13 "), obtain the laminated material (assess sample) of " resin bed/SUS " structure.
[comparative example 6]
On the corrosion resistant plate (SUS304,1/2H, thick 0.3mm) being heated to 170 DEG C in advance, deposition thickness is polyesters adhesive film (Toagosei Co., Ltd's manufacture of 30 μm, trade name " Aron-meltPES111EE ")), then be the POLYCARBONATE SHEET of 130 μm in 170 DEG C, thereon laminate thickness, obtain the laminated material (assess sample) of " resin bed/adhesive film/SUS " structure.
[evaluation method]
Be described for the evaluation method of the sample obtained in embodiment and comparative example 4 ~ 6 and evaluation result.
The cementability > of < and injection mo(u)lding resin
On the resin of assess sample, injection mo(u)lding is heated to 290 DEG C and the polycarbonate resin of melting (injection moulding shape: radius is the cylindric of 3.425mm).Then, carry out tension test (draw speed: 5mm/ minute) in the vertical direction, determine intensity during fracture.
Now, the Strength Changes after environmental test is determined.Environmental test is: use thermostat to keep 96 hours at 85 DEG C, on the other hand, use constant temperature and humidity cabinet 60 DEG C, keep 96 hours under the environment of 95%RH.
Result is as shown in table 3.
[table 3]
The sample of embodiment 5 ~ 7 all demonstrates good cementability (peel strength) after bonding and environmental test in the early stage.In contrast, for the sample of comparative example 4 and 5, although initial bond is good, after environmental test, cementability (peel strength) significantly reduces.The early strength of the sample of comparative example 6 is low.
< heat resistance >
By mold temperature set be 80 DEG C, 100 DEG C or 120 DEG C, the polycarbonate resin (injection moulding shape: radius is the cylindric of 3.425mm) of injection mo(u)lding heating and melting on the resin bed of assess sample, now, whether the outward appearance visually observing surface and inside changes, and evaluates according to following standard.
Zero: do not change
△: chap in surface
×: occur peeling off
[table 4]
For the sample of embodiment 5 ~ 7, even if mold temperature is 120 DEG C, all do not find that outward appearance changes on surface and inside.In contrast, although the sample of comparative example 4 is good at 80 DEG C, when reaching more than 100 DEG C, surface is dissolved.In addition, for the sample of comparative example 5, at two temperature of 80 DEG C and 100 DEG C, surface is dissolved, and surperficially chaps.In addition, for the sample of comparative example 6, same with the sample of embodiment 5 ~ 7, film surface and inside do not find cosmetic variation.
< AEG-process >
AEG-process has been carried out according to method shown in Fig. 5 a ~ 5c.
First, as shown in Figure 5 a, otch 32 (5mm interval) is marked on the surface of sample 31, then, as shown in Figure 5 b, using the AEG-process device of regulation in JIS K 6744, is that spherical drift is pressed into the core 5mm ~ 7mm of sample 31 (in Fig. 5 b, 34 is punch die by front end, 35 is blank holder), as shown in Figure 5 c, observe whether to there occurs on sample 31 and float or crackle, and evaluate according to following standard.Result is as shown in table 5.
Zero: be not peeling and crackle
△: have crackle
×: there is stripping
[table 5]
For the sample of embodiment 5 ~ 7 and comparative example 4, even if extrude distance for 7mm, sample does not produce yet and floats and crackle.
In contrast, for the sample of comparative example 5, under 5mm condition, just observed stripping, for the sample of comparative example 6, when extruding under 5mm and 7mm condition, all on film, produce a large amount of crackle.
[embodiment 8]
According to identical method, at aluminium alloy plate (A5182H18, the thick 0.3mm) laminated film that superimposed layer is identical with embodiment 6, obtain sample.Be 120 DEG C by mold temperature set, the shaping polycarbonate resin (injection moulding shape: radius is the cylindric of 3.425mm) through heating and melting on the film of assess sample.
[embodiment 9]
Injection mo(u)lding polycarbonate resin on the sample identical with embodiment 8, then in the aqueous solution of the phosphoric acid 50 quality % and nitric acid 5 quality % that are heated to 90 DEG C, flooded for 30 seconds, 10 quality % aqueous sulfuric acids are used to carry out stain (desmut) process, then installing electrodes on sample, and impregnated in and be adjusted in the 20 quality % aqueous sulfuric acids of 20 DEG C, with 150A/m 2current density be energized, obtain the pellumina of 12 μm on the metal surface.Then, use organic dyestuff to be colored as redness, and flood 2 minutes in the hot water of 95 DEG C, carried out sealing pores.
[embodiment 10]
On the sample identical with embodiment 8 after injection mo(u)lding polycarbonate resin, then in the NaOH 15 quality % aqueous solution being heated to 55 DEG C, flooded for 180 seconds, 10 quality % aqueous sulfuric acids are used to carry out stain process, then installing electrodes on sample, and impregnated in and be adjusted in the 20 quality % aqueous sulfuric acids of 20 DEG C, with 150A/m 2current density be energized, obtain the pellumina of 12 μm on the metal surface.Then, use organic dyestuff to be colored as gold, and flood 2 minutes in the hot water of 95 DEG C, carried out sealing pores.
The sample obtained embodiment 8 ~ 10 in the vertical direction carries out tension test (draw speed: 5mm/ minute), measures intensity during fracture, as injection moulding adhesive strength.Result is as shown in table 6.
[table 6]
As shown in Table 6, under having carried out the situation (embodiment 9 and 10) of pellumina process after moulding, all can obtain the bonding force equal with the situation of not carrying out pellumina process (embodiment 8), the scope being reduced to permission of injection moulding adhesive strength.
Use specific embodiment to invention has been detailed description, but those skilled in the art being known, when not departing from the intent and scope of the present invention, can various change being carried out.
In addition, the application proposes based on the Japanese patent application (Japanese Patent Application 2010-023143) proposed on February 4th, 2010, refer to its full content at this.

Claims (29)

1. resin/metal composite laminated material, it has metallic plate and is stacked in the resin bed a using polyamide-based resin as principal component at least one side of this metallic plate, wherein, the crystallization index of the described resin bed a calculated by following formula (I) is 0.40 ~ 0.80
In above-mentioned (I) formula, H m1, H c1the 1st the crystal melting heat using differential scanning calorimeter (DSC) to measure in the temperature range of 30 ~ 300 DEG C, when heating up to this resin bed a with the programming rate of 10 DEG C/min, the 1st crystallization heat release respectively, H m2refer to after naturally cooling to 30 DEG C subsequently, again in the temperature range of 30 ~ 300 DEG C, the 2nd crystal melting heat measuring when this resin bed a being heated up with the programming rate of 10 DEG C/min.
2. resin according to claim 1/metal composite laminated material, wherein, the polyamide-based resin contained in described resin bed a is nylon 6.
3. resin according to claim 1/metal composite laminated material, wherein, the thickness of described resin bed a is 5 ~ 100 μm, and the thickness of described metallic plate is 0.03 ~ 3.0mm.
4. resin according to claim 2/metal composite laminated material, wherein, the thickness of described resin bed a is 5 ~ 100 μm, and the thickness of described metallic plate is 0.03 ~ 3.0mm.
5. the resin according to any one of Claims 1 to 4/metal composite laminated material, wherein, described resin bed a also has the 2nd resin bed b using the hybrid resin of polycarbonate resin and polyester resin as principal component.
6. resin according to claim 5/metal composite laminated material, wherein, the polycarbonate resin contained in described resin bed b and the mixing ratio of polyester resin are polycarbonate resin by quality ratio: polyester resin=20:80 ~ 70:30.
7. resin according to claim 5/metal composite laminated material, wherein, the polyester resin contained in described resin bed b is polybutylene terephthalate (PBT).
8. resin according to claim 6/metal composite laminated material, wherein, the polyester resin contained in described resin bed b is polybutylene terephthalate (PBT).
9. resin according to claim 5/metal composite laminated material, it is for in-molded.
10. resin according to claim 6/metal composite laminated material, it is for in-molded.
11. resin according to claim 7/metal composite laminated materials, it is for in-molded.
12. resin/metal composite laminated materials according to any one of Claims 1 to 4, it for being integrally formed the protuberance be made up of synthetic resin by injection mo(u)lding on described resin bed a.
13. resin according to claim 5/metal composite laminated materials, it for being integrally formed the protuberance be made up of synthetic resin by injection mo(u)lding on described resin bed b.
14. resin according to claim 6/metal composite laminated materials, it for being integrally formed the protuberance be made up of synthetic resin by injection mo(u)lding on described resin bed b.
15. resin according to claim 7/metal composite laminated materials, it for being integrally formed the protuberance be made up of synthetic resin by injection mo(u)lding on described resin bed b.
16. resin according to claim 9/metal composite laminated materials, it for being integrally formed the protuberance be made up of synthetic resin by injection mo(u)lding on described resin bed b.
17. resin according to claim 12/metal composite laminated materials, wherein, the fusing point forming the resin of described resin bed a is lower 10 ~ 60 DEG C than the fusing point of the synthetic resin forming described protuberance.
18. resin according to claim 13/metal composite laminated materials, wherein, the fusing point forming the resin of described resin bed a, described resin bed b or described resin bed a and resin bed b is lower 10 ~ 60 DEG C than the fusing point of the synthetic resin forming described protuberance.
19. resin according to claim 17/metal composite laminated materials, wherein, the synthetic resin forming described protuberance is nylon MXD 6.
20. resin according to claim 18/metal composite laminated materials, wherein, the synthetic resin forming described protuberance is nylon MXD 6.
21. resin according to claim 17/metal composite laminated materials, wherein, the synthetic resin forming described protuberance is polycarbonate resin.
22. resin according to claim 18/metal composite laminated materials, wherein, the synthetic resin forming described protuberance is polycarbonate resin.
23. resin/metal composite laminated materials according to any one of Claims 1 to 4, wherein, described metallic plate have passed through pellumina process with the face of the opposition side, face being formed with described resin bed a.
24. resin/metal composite laminated materials according to any one of Claims 1 to 4, wherein, described metallic plate be formed on the face of opposition side, face of described resin bed a, there is coating rete and resin coated layer successively.
25. 1 kinds of resin/metal composite injection-molded articles, the molten resin of injection mo(u)lding synthetic resin on its resin bed a by the resin/metal composite laminated material according to any one of claim 1 ~ 24 or resin bed b, thus the protuberance be made up of this synthetic resin and described resin/metal composite laminated material are molded as one and obtain.
26. 1 kinds of frameworks for OA equipment or electronic equipment, it comprises resin according to claim 25/metal composite injection-molded article.
27. frameworks for OA equipment or electronic equipment according to claim 26, it is the framework of mobile phone.
The manufacture method of 28. 1 kinds of resin/metal composite laminated materials, it is the method for the resin/metal composite laminated material according to any one of manufacturing claims 1 ~ 24, and the method has the lamination operation of deposition resin molding on described metallic plate.
The manufacture method of 29. 1 kinds of resin/metal composite injection-molded articles, it is the method for the resin/metal composite injection-molded article described in manufacturing claims 25, the method has following operation: in the injection forming mold being configured with described resin/metal composite laminated material, inject described molten resin, thus described protuberance and described resin/metal composite laminated material are molded as one.
CN201080062992.0A 2010-02-04 2010-07-14 Resin/metal composite laminate material, resin/metal composite injection moulding body, and manufacturing method for same Active CN102753342B (en)

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JP5499741B2 (en) 2014-05-21
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