JP2012045920A - Resin-metal composite laminate, resin-metal composite injection molding, and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-metal composite laminate which has excellent heat resistance and material strength as well as excellent press processability and good adhesion between a coating resin layer and a metal plate, and which is excellent in adhesion with an injection resin such as an ABS-based resin, a polycarbonate/ABS based-alloy resin, a polyester-based elastomer.SOLUTION: The resin-metal composite laminate includes a polyester-based resin layer formed on the metal plate as top surface. In the polyester-based resin layer, a storage elastic modulus at 90°C, which is measured under the condition that an oscillation frequency is 10 Hz, a strain is 0.1%, a rate of temperature rise is 3°C/min, and a distance between chucks is 25 mm, is 10 MPa or more and tanδ is less than 0.2, and the storage elastic modulus at 130°C is less than 30 MPa, and tanδ is 0.1 or more.

Description

  The present invention is a resin / metal composite laminate suitable for use in producing a resin / metal composite injection molded body by injecting a molten resin onto its surface by in-mold molding or insert molding, and fixing and integrating the injection molding convex portions. The present invention relates to a body, a resin / metal composite injection-molded body using the resin / metal composite laminate, and a method for producing the same.

Cases (housings) such as OA equipment, electronic equipment, and video equipment are required to have characteristics such as electromagnetic wave shielding, strength, and lightness. Therefore, by in-mold molding of a synthetic resin on a base made of metal such as aluminum. It is manufactured by fixing and integrally forming a screw boss, a reinforcing rib or the like (see Patent Document 1). The housing with such a structure ensures electromagnetic shielding and strength by a base made of a metal such as aluminum, and provides workability and functionality by providing integrally molded parts such as bosses and ribs with a synthetic resin. And lighter and thinner.
However, the case disclosed in Patent Document 1 in which a synthetic resin is directly injection-molded by in-mold molding on a metal base has a drawback that adhesion between the synthetic resin and the metal base is poor.

  In contrast, a metal plate having at least one surface coated with a resin such as polyester resin is inserted and fixed in the cavity of the injection mold, and the molten resin is injected onto the coated resin surface of the metal plate. A method of manufacturing an injection molded product 40 as shown in FIG. 6 by forming injection molded parts such as ribs and screwing bosses and integrating the metal plate and the injection molded part is disclosed ( Patent Document 2). In FIG. 6, 41 is an aluminum plate (metal plate), 42 is a polybutylene terephthalate film (coating resin), and 43a and 43b are injection-molded bosses and ribs.

In the injection-molded product described in Patent Document 2, since the molten resin is injected onto the surface of the coated resin on the metal plate, it adheres more than the resin directly injected onto the metal substrate described in Patent Document 1. However, it is difficult to obtain sufficient adhesive strength when injecting ABS resin, polycarbonate / ABS alloy resin, and polyester elastomer. was there.
In addition, the coating resin layer has high adhesion to the injected molten resin, high adhesion to the metal plate, excellent press workability, and heat resistance that can withstand the mold temperature (80 to 120 ° C). A material strength that does not cause deformation due to the injection pressure is required, but Patent Document 2 does not make such a study.

JP-A-6-29669 JP 2001-315159 A

  The present invention is a further technical improvement based on the above prior art documents, has excellent heat resistance and material strength, is excellent in press workability, has good adhesion between the coating resin layer and the metal plate, In addition, a resin / metal composite laminate having excellent adhesion to an injection resin such as ABS resin, polycarbonate / ABS alloy resin, and polyester elastomer, and resin / metal composite injection using the resin / metal composite laminate It aims at providing a molded object and those manufacturing methods.

  As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by forming a polyester resin layer having specific viscoelastic temperature characteristics as a coating resin layer formed on a metal plate. As a result, the present invention has been completed.

  That is, the gist of the present invention is as follows.

[1] A resin / metal composite laminate having a metal plate and an outermost layer made of a polyester resin layer formed on the metal plate, the polyester resin layer having a vibration frequency of 10 Hz, a strain of 0. The storage elastic modulus at 90 ° C. measured at 1%, the heating rate of 3 ° C./min, and the gap between chucks of 25 mm is 10 MPa or more, tan δ is less than 0.2, and the storage elastic modulus at 130 ° C. is less than 30 MPa, Tan / δ is 0.1 or more, a resin / metal composite laminate.

[2] The resin / metal composite laminate according to [1], which is a resin / metal composite laminate for integrally forming a convex portion made of a synthetic resin on the outermost layer by injection molding. body.

[3] The synthetic resin constituting the convex portion is at least one selected from the group consisting of ABS resin, ABS / polycarbonate alloy resin, polycarbonate resin, and polyester elastomer resin. 2] The resin / metal composite laminate according to [2].

[4] The resin / metal composite laminate according to any one of [1] to [3], wherein the outermost layer is composed of two or more polyester resin layers.

[5] The resin / metal composite laminate according to any one of [1] to [4], wherein a thickness of the outermost layer is 5 μm or more and 200 μm or less.

[6] The resin / metal composite laminate according to any one of [1] to [5], wherein a surface of the outermost layer is embossed.

[7] A synthetic resin molten resin is injection-molded on the outermost layer of the resin / metal composite laminate according to any one of [1] to [6], so that the convex portions made of the synthetic resin are integrated. A resin / metal composite injection-molded article characterized by being molded into.

[8] A housing for OA equipment or electronic equipment, comprising the resin / metal composite injection molded article according to [7].

[9] A method for producing a resin / metal composite laminate according to any one of [1] to [6], comprising a laminating step of welding a polyester resin layer to the metal plate. Manufacturing method of resin / metal composite laminate.

[10] A method for producing a resin / metal composite injection molded product according to [7], wherein the molten resin is injected into an injection mold in which the resin / metal composite laminate is disposed, and the convex A method for producing a resin / metal composite injection molded article, comprising a step of integrally molding a portion.

  The outermost layer made of the polyester resin of the resin / metal composite laminate of the present invention has high adhesion to a synthetic resin to be injection-molded, for example, ABS resin or polycarbonate resin, and is flexible so that it can be pressed. Furthermore, it has heat resistance that can withstand the mold temperature (80 to 120 ° C.). Therefore, for example, after pressing the resin / metal composite laminate of the present invention into a predetermined shape as necessary, it is inserted and fixed in a cavity of an injection mold, and a molding method such as in-mold molding or insert molding By injecting molten resin such as ABS-based resin or polycarbonate-based resin on the surface of the outermost layer to form convex portions that become reinforcing ribs, screw bosses, etc., the injection-molded convex portions are made of resin / metal. It can be firmly fixed and integrated with the outermost layer of the composite laminate.

  The resin / metal composite injection of the present invention is formed by integrally forming a convex portion made of synthetic resin by injection molding a synthetic resin molten resin on the outermost layer of the resin / metal composite laminate of the present invention. Since the molded body has an outermost layer made of a metal plate and a polyester-based resin, it has electromagnetic wave shielding properties and insulating properties, and since the metal plate is a base material, it can be thinned with sufficient strength. , Because the convex portions to be reinforcing ribs, screw bosses and the like are firmly and integrally formed with respect to the outermost layer, various structural materials, especially housings of OA equipment, electronic equipment, video equipment ( It is suitable for various members such as a housing), especially as a casing of a mobile phone, and is effective in improving the light weight, thinness, and miniaturization.

It is sectional drawing which shows an example of embodiment of the resin-metal composite laminated body of this invention. It is sectional drawing which shows an example of embodiment of the resin and metal composite injection molding of this invention. It is a schematic diagram which shows an example of the manufacturing process of the resin and metal composite laminated body of this invention. It is sectional drawing which shows an example of the manufacturing process of the resin and metal composite injection molding of this invention. It is explanatory drawing of an Erichsen test method. It is sectional drawing which shows a conventional product.

  Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the scope of the embodiments described below.

[Explanation of terms]
In the present invention, the “main component” includes the meaning of allowing other components to be contained within a range that does not interfere with the function of the main component, unless otherwise specified. At this time, although the content ratio of the main component is not specified, the main component (when two or more components are main component resins, the total amount thereof) is 50% by mass or more, particularly 70% in the composition. It is preferable to occupy at least 90% by mass, particularly 90% by mass to 100% by mass.

In general, the term “sheet” refers to a product that is thin by definition in JIS and generally has a thickness that is small and flat for the length and width. In general, “film” refers to the length and width. This is a thin flat product whose thickness is extremely small as compared to, and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japanese Industrial Standard JIS K 6900). For example, in terms of thickness, in the narrow sense, a film having a thickness of 100 μm or more is sometimes referred to as a sheet, and a film having a thickness of less than 100 μm is sometimes referred to as a film. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
Further, in the present invention, when expressed as “X to Y” (X and Y are arbitrary numbers), unless otherwise specified, “X is preferably greater than X” and “ Is less than Y.

[Resin / metal composite laminate]
The resin / metal composite laminate of the present invention (hereinafter sometimes referred to as “the present laminate”) has a metal plate and an outermost layer comprising a polyester resin layer formed on the metal plate. A storage modulus at 90 ° C. measured under the conditions of a vibration frequency of 10 Hz, a strain of 0.1%, a rate of temperature increase of 3 ° C./min, and a gap between chucks of 25 mm, is a metal composite laminate. Hereinafter, it may be described as “E ′ (90)”.) 10 MPa or more, tan δ (hereinafter sometimes referred to as “tan δ (90)”) is less than 0.2, and storage elasticity at 130 ° C. The ratio (hereinafter sometimes referred to as “E ′ (130)”) is less than 30 MPa, and tan δ (hereinafter sometimes referred to as “tan δ (130)”) is 0.1 or more. To do.

  1A and 1B are cross-sectional views showing an example of an embodiment of the resin / metal composite laminate of the present invention. The resin / metal composite laminate 1A, 1B is one of the metal plates 2. FIG. The outermost layer 4 made of a polyester resin layer is formed on the surface. In the resin / metal composite laminate 1 </ b> A in FIG. 1A, the outermost layer 4 has a single-layer structure of the polyester resin layer 3. In the resin / metal composite laminate 1B of FIG. 1B, the outermost layer 4 includes a first polyester resin layer 3a in the lower layer (layer on the metal plate 2 side) and a second polyester system in the upper layer (surface side). It is a two-layer laminated structure with the resin layer 3b.

<Storage elastic modulus E ′ and tan δ>
The inventors of the present invention have disclosed the heat resistance of the resin / metal composite laminate in the injection molding process, that is, the releasability between the heated mold of the injection molding machine and the resin / metal composite laminate, and the heated injection resin As a result of intensive studies on the compatibility of the softening conditions of the resin layer for ensuring the heat-sealing property with the metal plate, a resin / metal composite laminate having a polyester resin layer satisfying these conditions as the outermost layer was found.

  That is, this laminate has a storage elastic modulus at 90 ° C. measured under the conditions of a vibration frequency of 10 Hz, a strain of 0.1%, a temperature increase rate of 3 ° C./min, and a chuck interval of 25 mm for the polyester resin layer constituting the outermost layer. E ′ (90) is 10 MPa or more and tan δ (90) is less than 0.2. When the storage elastic modulus E ′ (90) is 10 MPa or more and tan δ (90) is less than 0.2, when the laminate is set in a heated injection molding machine, it is fused with the mold of the injection molding machine. Alternatively, it is possible to maintain a good appearance without causing blocking and without causing the outermost surface of the polyester-based resin layer to be rough when taken out from the mold. The storage elastic modulus E ′ (90) is preferably 20 MPa or more, more preferably 30 MPa or more. On the other hand, the upper limit of the storage elastic modulus E ′ (90) is about 1,000 MPa. Further, tan δ (90) is preferably 0.15 or less, more preferably 0.13 or less, and its lower limit is 0.01.

  In addition, this laminate has a storage elasticity at 130 ° C. measured for a polyester resin layer constituting the outermost layer under the conditions of vibration frequency 10 Hz, strain 0.1%, temperature increase rate 3 ° C./min, and chuck 25 mm. The rate E ′ (130) is less than 30 MPa, and tan δ (130) is 0.1 or more. When the storage elastic modulus E ′ (130) is less than 30 MPa and tan δ (130) is 0.1 or more, the outermost layer of the polyester-based resin layer can be softened by the heat during injection, and the injection heated by injection molding Sufficient adhesion between the resin and the outermost layer of the polyester resin layer can be obtained. The storage elastic modulus E ′ (130) is preferably 20 MPa or less, more preferably 10 MPa or less, and its lower limit is usually about 0.1 MPa. On the other hand, tan δ (130) is preferably 0.10 or more, more preferably 0.13 or more, and the upper limit is preferably about 10.

In addition, although the outermost layer which concerns on this invention is comprised with a polyester-type resin layer, this outermost layer is comprised from one polyester-type resin layer, as shown to Fig.1 (a). As shown in FIG. 1 (b), two polyester resin layers different from each other, or a laminated structure of three or more layers may be used.
Here, a different polyester resin layer means that the component composition of the polyester resin composition which comprises the said polyester resin layer differs, for example. When the outermost layer has a laminated structure of two or more polyester resin layers, all the polyester resins constituting the outermost layer have a storage elastic modulus E ′ (90) of 10 MPa or more and a tan δ (90) of 0. .2 and storage elastic modulus E ′ (130) need not be less than 30 MPa and tan δ (130) need not be 0.1 or more, and at least on the surface side of the laminated polyester resin layers. Only the uppermost exposed layer has a storage elastic modulus E ′ (90) of 10 MPa or more, a tan δ (90) of less than 0.2, a storage elastic modulus E ′ (130) of less than 30 MPa, and a tan δ (130) of 0. Any material satisfying the viscoelastic temperature characteristic defined in the present invention, ie, 1 or more. Thus, only the uppermost layer satisfies the viscoelastic temperature characteristics defined in the present invention, and the uppermost polyester resin layer exposed on the surface has a specific viscoelastic temperature characteristic. The above-mentioned polyester-based resin layer is used as a layer that ensures adhesion resistance with the mold in the above-described injection molding machine, blocking resistance, and adhesion to the injection resin. By using a layer that functions as an intermediate adhesive layer for enhancing the adhesiveness between the resin layer and the metal plate, it is possible to form a good resin / metal composite laminate.

<Single-layered outermost layer>
When the outermost layer according to the present invention is composed of only one polyester resin layer, as the polyester resin forming the polyester resin layer, a resin obtained by condensation polymerization of a dicarboxylic acid component and a diol component, Among these, an aromatic polyester resin obtained by condensation polymerization of an aromatic dicarboxylic acid component and a diol component is preferable from the viewpoint of heat resistance.

  Here, representative examples of the “aromatic dicarboxylic acid component” include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc., but a part of terephthalic acid is substituted with “other dicarboxylic acid component”. It may be.

  At this time, as "other dicarboxylic acid components", oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, neopentylic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, p-oxybenzoic acid Etc. These may be one kind or a mixture of two or more kinds, and the amount of other dicarboxylic acids to be substituted can be appropriately selected.

  Typical examples of the above “diol component” include ethylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol and the like, but a part of ethylene glycol may be substituted with “other diol component”.

  At this time, as "other diol components", propylene glycol, butanediol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, Examples include pentaerythritol, trimethylol, and methoxypolyalkylene glycol. These may be one kind or a mixture of two or more kinds, and the amount of other diols to be substituted can be appropriately selected.

  Further, as the other polyester-based resin, “copolyester” containing a dicarboxylic acid component other than terephthalic acid and / or a diol component other than ethylene glycol can also be used.

  Specific examples of such aromatic copolymer polyesters include, for example, “Novapex” series (for example, Novapex PS600) manufactured by Mitsubishi Chemical Corporation, which is a modified product of polyethylene terephthalate, and Mitsubishi Engineering, which is a modified product of polybutylene terephthalate. A “Novaduran” series (for example, Novaduran 5008) manufactured by Plastics may be mentioned. In addition, “Easter 6673” manufactured by Eastman Chemical Co., which is a polyester resin in which about 30 mol% of ethylene glycol in polyethylene terephthalate is substituted with 1,4-cyclohexanedimethanol, has a slightly low melt viscosity composed of the same components. “Easter” series including “Easter GN119” can be mentioned. In addition, polyethylene glycol terephthalate glycol component modified with 1,4-butanediol, acid component modified with adipic acid and sebacic acid, "PES" series made by Toagosei Co., Ltd. (eg PES111EE), Toyobo "Byron" series (For example, Byron GA5410, Byron GM470) etc. can be mentioned.

  In particular, as a polyester-based resin that can improve adhesion with ABS-based injection resin and maintain heat resistance, polybutylene terephthalate (PBT) using butanediol as the diol component and terephthalic acid as the aromatic dicarboxylic acid component is the most. preferable.

  Polybutylene terephthalate is a crystalline resin that has excellent heat resistance and strength, and is a polyester that constitutes the outermost polyester resin layer because it is completely compatible with polycarbonate resin and becomes a polymer alloy. Particularly preferred as a base resin.

  Specific examples of such polybutylene terephthalate products include, for example, “Juranex” series manufactured by Wintech Polymer, and “Novaduran” series manufactured by Mitsubishi Engineering Plastics.

  A mixture of polybutylene terephthalate and the above copolymerized polyester can also be used.

  There is no particular limitation on the method for controlling the viscoelastic temperature characteristics of the polyester resin layer constituting the outermost layer according to the present invention within the specific range. For example, a dicarboxylic acid component and a diol that are components of the polyester resin are used. The method of selecting an ingredient and its combination is mentioned. Depending on the molecular structure, molecular weight, etc., for example, when it is desired to increase the storage modulus E ′ (90) (when tan δ (90) is to be decreased), dicarboxylic acid components include terephthalic acid (melting point: 427 ° C.), isophthalic acid Select a polyester resin with a high blending ratio of diol components such as aromatic dicarboxylic acid components (melting point 348 ° C.) and 1,4 butanediol having higher crystallinity than ethylene glycol as the diol component. Use it. Further, when the storage elastic modulus E ′ (130) is to be lowered (when tan δ (130) is to be raised), an aliphatic dicarboxylic acid such as adipic acid (melting point 153 ° C.) or sebacic acid (melting point 134 ° C.) is used as the dicarboxylic acid component. As the acid component or diol component, a polyester resin having a high blending ratio of a diol component such as ethylene glycol having low crystallinity as compared with 1,4 butanediol or the like may be selected and used.

  In order to obtain adhesion to the injection resin, it is possible to blend components other than the polyester resin component with the polyester resin forming the polyester resin layer. Examples of the components to be blended include polyester elastomers, styrene resins, olefin resins and the like. Examples of commercially available products include Hytrel 2521 (manufactured by Toray DuPont) and Primalloy A1700 (manufactured by Mitsubishi Chemical Corporation).

  By blending components other than these polyester resins, it is possible to control the viscoelastic temperature characteristics of the polyester resin layer within the aforementioned range.

  Moreover, in order to prevent blocking with a heating metal mold | die, it is also possible to control the surface adhesiveness with a metal mold | die by controlling the crystallinity of a polyester-type resin layer, or embossing the surface. As a method for controlling crystallinity, there is a method of improving the crystallization speed by adding a nucleating agent in addition to the selection of the dicarboxylic acid and diol components. Core materials include metal oxides such as zinc oxide, magnesium oxide, silicon oxide, iron (III) oxide, and titanium oxide; calcium carbonate, magnesium carbonate, calcium silicate, lead silicate, magnesium silicate, calcium phosphate, calcium sulfate Inorganic salts such as barium sulfate and potassium titanate; organic acid salts such as calcium oxalate and sodium oxalate; clays such as talc, kaolin, clay mica and wollastonite. In addition, the shape of the crystal nucleating agent is not particularly limited, and may be amorphous, in addition to a plate shape and a spherical shape. Examples of commercially available products include Pine Crystal K1500 (manufactured by Arakawa Chemical Co., Ltd.) and SG-95 (manufactured by Nippon Talc Co., Ltd.).

  On the other hand, as an embossing method, for example, after laminating a metal plate and a polyester resin film for forming the outermost layer by a method described later, the embossing is performed on the surface of the outermost layer by passing through a heating furnace and passing an embossing roll. Can be applied.

  The thickness of the outermost layer composed of a single layer polyester resin layer is usually 5 μm or more, preferably 10 μm or more, more preferably 30 μm or more, and usually 200 μm or less, preferably 100 μm or less, more preferably 60 μm or less. . If the thickness of the outermost layer is 5 μm or more, the occurrence of pinholes during processing such as drawing and bending can be suppressed, and the adhesiveness with the injection molded part can be improved. In addition, when the thickness of the outermost layer is 200 μm or less, the press workability does not deteriorate and the laminate can be thinned, which is economically advantageous.

<Outermost layer of laminated structure>
If it is difficult to satisfy all of the adhesion with the injection resin such as ABS resin, mold heat resistance, and metal adhesion in the outermost layer consisting of a single polyester resin layer, the outermost layer is made of a different type of polyester. Functional separation can also be performed as a laminated structure in which a series resin layer is laminated. For example, in the case of a two-layer laminated structure of different polyester resin layers, the lower polyester resin layer is provided with adhesion to a metal plate, and the upper polyester resin layer satisfies the viscoelastic temperature characteristics described above. As a thing, the required performance can be satisfied by imparting heat resistance to the mold and adhesion to the injection resin.

  When the outermost layer has a laminated structure of two or more polyester resin layers, the lower polyester resin layer in contact with the metal plate is composed of the upper polyester resin layer and the metal plate in contact with the lower polyester resin layer. It is preferable to use a polyester-based resin having excellent adhesion to both, for example, a copolymerized polyester-based resin.

  That is, for the purpose of enhancing the adhesion to the metal plate, the polyester resin of the polyester resin layer contains a copolymer component in the range of 1 mol% or more, for example, 1 to 50 mol% of the entire polyester resin. You can also. Examples of such a copolymer component include a dicarboxylic acid component, an oxycarboxylic acid component, a tricarboxylic acid component, a diol component, and a triol component.

  Examples of the dicarboxylic acid component include oxalic acid, succinic acid, adipic acid, sebacic acid, maleic acid, dimer acid, indane dicarboxylic acid, isophthalic acid, diphenyl dicarboxylic acid, and sulfoisophthalic acid metal salt. Examples of the oxycarboxylic acid component include oxybenzoic acid, and examples of the tricarboxylic acid component include trimellitic acid.

  As diol components, propanediol, butanediol, pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol S, polyethylene glycol, polytetramethylene glycol Examples of the triol component include trimethylolpropane.

  The copolymerization of these components may be performed at any stage such as in the initial stage of polymerization, in the middle of polymerization, or in an extruder after polymerization.

  Specific examples of copolyester resins that are preferred as polyester resins in the polyester resin layer in contact with the metal plate include polyethylene terephthalate / ethylene isophthalate copolymer (PETI) and ethylene glycol of polyethylene terephthalate (PET). Examples thereof include a copolymer (PETG) in which about 30 mol% of the portion is 1,4-cyclohexanedimethanol, or a blend resin in which two or more of these resins are mixed.

  When the outermost layer has a laminated structure of two or more polyester-based resin layers, the lower polyester-based resin layer in contact with the metal plate has an ethylene-vinyl acetate copolymer (EVA) as a resin other than the polyester-based resin. Also, a resin such as ethylene-ethyl acrylate copolymer (EEA) or a copolymer of these copolymers and polyolefin can be used in combination.

  When the outermost layer is a laminated structure of two or more polyester resin layers, the uppermost polyester resin layer exposed on the surface of the outermost layer is the polyester resin layer in the case of the outermost layer having a single layer structure. Applied.

Even when the outermost layer has a laminated structure of two or more polyester resin layers, the thickness (the total thickness of the laminated polyester resin layers constituting the outermost layer) is the above-described single-layer structure. As in the outermost layer, the thickness is usually 5 μm or more, preferably 10 μm or more, more preferably 30 μm or more, usually 200 μm or less, preferably 100 μm or less, more preferably 60 μm or less. It is possible to suppress the occurrence of pinholes during processing such as, and to reduce the thickness of this laminate without lowering the adhesiveness to the injection molded part and press workability, and it can be used economically it can.
For the thickness of each layer, the uppermost polyester-based resin layer serving as the exposed surface for ensuring mold heat resistance, adhesion to the injection resin, etc. is a polyester-based material that satisfies the viscoelastic temperature characteristics defined in the present invention. In order to sufficiently obtain the effect of forming the resin layer, it is usually 5 μm or more, particularly 10 μm or more, preferably 100 μm or less, particularly preferably 50 μm or less. For the polyester resin layer in contact with the lowermost metal plate, In order to ensure adhesion to the metal plate and adhesion to the upper polyester resin layer, it is usually 5 μm or more, particularly 10 μm or more, and preferably 100 μm or less, particularly 50 μm or less.

<Metal plate>
The metal plate as the metal member of this laminate includes a hot-rolled steel plate, a stainless steel plate (SUS), a single-layer plated steel plate formed by plating a metal such as nickel, zinc and copper, and two or more of these metals. Various steel plates such as a multi-layer plated steel plate formed by multi-layer plating, various metal plate materials such as an aluminum plate, an aluminum alloy plate, and a magnesium alloy plate can be used.

  As a metal plate, metal foil can also be used depending on a use, and it is preferable that the thickness is about 100 micrometers-about 2 mm. For example, in the present laminate for forming a housing such as an OA device, an electric product, or an electronic product, the thickness of the metal plate is preferably 200 μm to 1.5 mm, particularly preferably 300 μm to 1.0 mm. If the thickness of the metal plate is 100 μm or more, deformation does not occur due to the injection pressure, and if it is 2 mm or less, there is no problem in press workability.

  The surface of the metal plate is formed by electrolytic treatment in a dichromic acid solution for forming a monolayer film made of chromium hydrated oxide, and a two-layer film made of chromium hydrated oxide on the upper layer and metal chromium on the lower layer. Various chemical conversion treatments such as electrolytic chromic acid treatment, immersion chromic acid treatment, phosphoric acid chromic acid treatment, etching treatment with an alkali solution or acid solution, and anodizing treatment may be performed.

Further, various primer and adhesive layers can be formed on the surface of the metal plate for the purpose of improving the adhesion between the metal plate and the polyester resin layer constituting the outermost layer. This primer and adhesive are conventionally known coupling agents such as aluminum, titanium, and silane, acrylic resin adhesive, urethane resin adhesive, epoxy resin adhesive, and polyester resin adhesive. An agent etc. can be mentioned. However, it is not limited to these.
The thickness of the primer layer and the adhesive layer is usually about 0.1 to 15 μm in order to sufficiently obtain the effect of improving the adhesion between the metal plate and the outermost layer without inhibiting the thinning.

  Moreover, when an aluminum alloy plate is used as the metal plate, the surface of the metal plate on the side opposite to the outermost layer forming surface may be anodized. By anodizing, scratch resistance, rust prevention, and colorability required when used as a casing of an electronic device can be imparted to the surface of a metal plate.

  Anodizing is a processing method that forms an alumite layer on the aluminum surface by performing surface finishing, degreasing, anodizing, dyeing, sealing treatment, etc. on this laminate with the outermost layer formed on one side. It is.

  Examples of the surface finishing process include physical finishing such as mirror finishing by buffing, mat finishing by blasting, and hairline finishing, and mat finishing using an aqueous ammonium fluoride solution, phosphoric acid-sulfuric acid aqueous solution, or It can also be performed by chemical polishing using a phosphoric acid-nitric acid aqueous solution, electrolytic polishing using a phosphoric acid aqueous solution, or the like.

  Examples of degreasing include degreasing with sulfuric acid and electrolytic degreasing in an aqueous sodium hydroxide solution.

For the anodization, a sulfuric acid method, an oxalic acid method, a phosphoric acid method, or the like can be employed. The specific conditions will be described. For example, in the sulfuric acid method, an electrode is connected to the resin / metal composite laminate, immersed in a 10 to 30% by mass sulfuric acid aqueous solution adjusted to 15 to 25 ° C., and a current density of 50 to 300 A / By applying current at m ² , an aluminum oxide layer can be formed on the surface of the metal plate. The thickness of the aluminum oxide layer to be produced is not particularly limited, but if it is too thin, sufficient performance will not be exhibited. Conversely, if it is too thick, the treatment time will be long, which is not economical. Preferably, the aluminum oxide layer has a thickness in the range of 1 to 20 μm.

  If necessary, the alumite layer can be dyed before the sealing treatment. Examples of the dyeing method include a method of dyeing using an organic dye, a method of dyeing by dipping in a dyeing solution containing a metal salt, and the like.

  Examples of the sealing treatment include a method of exposing to water vapor and a method of immersing in boiling water, whereby the alumite layer becomes a hydrate and the corrosion resistance can be greatly improved.

  Anodizing may be performed at any stage before or after injection molding, but in order to avoid appearance defects due to the metal surface coming into contact with the mold during injection molding, anodizing is performed after injection molding. Is preferably performed.

  This laminated body may decorate by the coating the surface on the opposite side to the outermost layer formation surface of a metal plate. In this case, a coating film layer is formed on the surface opposite to the outermost layer forming surface of the metal plate, and after the injection molding is performed on the surface on which the outermost layer is formed, the coating film layer is coated on the surface. To form a resin coating layer.

  When direct coating is performed on a metal plate without forming a coating film layer on the surface opposite to the outermost layer forming surface of the metal plate, a high baking temperature of 120 to 130 ° C. is required, so injection molding If coating is performed after this, the injection molded resin will be softened and deformed. In addition, the adhesive strength between the metal plate and the coating resin is generally insufficient, and there is a problem that it is easy to peel off when used.

  On the other hand, when the coating film layer is formed on the metal plate, it is possible to use a paint conventionally used for polycarbonate resin, MXD6 nylon, or the like. By laminating the coating film layer in this way, the drying temperature of the coated resin can be suppressed to about 60 to 80 ° C., and the softening and deformation of the injection molding resin does not occur during drying, and further to the metal plate The adhesive strength of the paint resin can be greatly improved.

  Examples of resins that can be used for the coating film layer include polycarbonate resins, polyamide resins, polyester resins, urethane resins, ABS resins, and acrylic resins. The thickness of the coating film layer is preferably about 5 to 50 μm. When the thickness of the coating film layer is in the range of 5 to 50 μm or more, an adhesive force with the paint can be expressed, which is economically advantageous.

  As a method of laminating and forming a coating film layer on a metal plate, a method of laminating a molten resin of a coating film forming resin onto a surface of a metal plate in a film form, a pre-formed coating film on a metal plate The method of laminating etc. is mentioned.

Examples of the paint that can be used in the resin coating layer include urethane resins, acrylic resins, and polyamide resins, and these can be applied by any method such as spraying.
A hard coat layer may be further provided on the surface of the resin coating layer thus formed.
The thickness of the resin coating layer is not particularly limited, and the thickness is appropriately determined according to the purpose.

  In particular, when the resin constituting the coating film layer is matched with the injection resin that forms the convex portion, for example, the same resin is selected as the resin that constitutes the coating film layer and the injection resin that forms the convex portion. Then, when the convex forming resin is injection-molded on the outermost layer composed of the polyester-based resin layer of this laminate, injection molding can be performed by selecting a grade for MXD6 nylon as the paint used in the resin coating layer. Since the projecting portion and the coating film layer that have been applied can be applied together, the process can be simplified. Similarly, when the resin constituting the coating film layer is a polyester resin layer similar to the outermost polyester resin layer, a convex portion made of a polycarbonate resin is injection-molded on the outermost layer, and the resin coating is performed. By selecting a polycarbonate grade as the coating material used in the layer, the injection-molded convex portion and the coating film layer can be applied in a lump, thereby simplifying the process.

<Thickness of resin / metal composite laminate>
Suitable thicknesses of the metal plate and outermost layer constituting this laminate and other layers provided as necessary are as described above, but these metal plate and outermost layer, primer layer provided as necessary The total thickness of the laminate including other constituent layers varies depending on the application, but is usually 0.1 to 3.0 mm, particularly 0.1 to 2.0 mm. In addition, in applications where thinning is required, the thickness is preferably about 0.1 to 1.0 mm.

<Method for producing this laminate>
This laminated body can be manufactured by laminating the polyester resin layer as the outermost layer on the metal plate. As a method of laminating, a method of laminating a thermoplastic resin composition for forming an outermost layer for forming a polyester-based resin layer into a film in advance and laminating it on the surface of a metal plate, melting on a metal plate heated to 100 to 250 ° C. Although the method of extruding and laminating the thermoplastic resin composition for forming the outermost layer into a film shape can be mentioned, a method of laminating by a laminating method is preferable because it can be produced in a continuous process.

  As a method of forming the outermost layer of a laminated structure composed of two or more polyester resins, for example, the outermost layer of a two-layer laminated structure, a thermoplastic resin composition and a second polyester that form the first polyester resin layer A method of forming a first polyester resin layer by coextruding a thermoplastic resin composition for forming a resin layer on a surface of a metal plate heated to 100 to 250 ° C. And a thermoplastic resin composition forming the second polyester resin layer are coextruded into a film to form a laminated film, and the laminated film is laminated on the surface of the metal plate, and the first polyester resin is formed. The first polyester resin fill by extruding the thermoplastic resin composition forming the second polyester resin and the thermoplastic resin composition forming the second polyester resin into a film shape, respectively. And a second polyester resin film, and after laminating the first polyester resin film on the surface of the metal plate, the second polyester resin film is laminated on the first polyester resin film. In this case as well, it is preferable to employ a laminating method.

  FIG. 3 is a schematic diagram showing a process for producing the present laminate by laminating a polyester resin film for forming the outermost layer on a metal plate, and a pair of metal plates 21 from a wound body 21 of the metal plate. A pair of rollers 27 is formed by laminating a polyester resin film 26 fed from a wound body 25 of a resin film after heating in a direction indicated by an arrow between the rollers 23 and 23 and passing through a heating furnace 24. , 27, and further pressed in a reheating furnace 28 to fuse and integrate the resin film 26 to the metal plate 22 to form a resin / metal composite laminate 29, which is wound around the wound body 30. take.

The metal plate may have a primer layer formed in advance, or the primer layer may be formed on the metal plate sent out in the resin film laminating process.
In addition, the resin film may be subjected to a surface treatment such as a corona discharge treatment for the purpose of improving the adhesion with the metal plate.

  Further, the surface of the metal plate opposite to the outermost surface layer formation surface can be coated with a paint or subjected to chemical plating as described above. Moreover, you may laminate | stack the other protective resin film which peels easily. In the process of molding the injection-molded part by the injection molding method, there is a risk of scratching the metal plate. In this way, the protective resin film is laminated on the surface opposite to the surface layer forming surface of the metal plate. If the resin film is peeled after the injection molded part is molded, a beautiful resin / metal composite injection molded body can be obtained by preventing damage in the injection molding process.

  In the present invention, the heating conditions for laminating the outermost layer-forming resin film on the metal plate differ depending on the type of polyester resin constituting the outermost layer, but usually the heating temperature of the metal plate (the heating temperature of the heating furnace 24). ) Is 300 to 500 ° C., the reheating temperature (the temperature of the reheating furnace 28) after fusion of the resin film is 250 to 450 ° C., and the reheating time (the time for the laminate to pass through the reheating furnace 28) is 3. It is preferable to be about 10 to 10 seconds.

[Resin / Metal Composite Injection Molded Body]
The resin / metal composite injection molded article of the present invention is a convex part made of a synthetic resin by injection molding a molten resin of the synthetic resin on the outermost layer made of the polyester-based resin layer of the laminate as described above. Are integrally formed.

  FIG. 2 is a cross-sectional view showing an example of the resin / metal composite injection molded article of the present invention. The resin / metal composite injection molded article 5 is formed by forming the outermost layer 4 on one surface of the metal plate 2. After bending the resin / metal composite laminate 1A (or 1B) of the present invention, a convex portion 6 made of a synthetic resin is integrally molded by injection molding.

<Convex-forming synthetic resin>
The synthetic resin for forming the convex portions by injection molding is not particularly limited, and is a styrene resin such as polystyrene, ABS resin and MBS resin, an acrylic resin such as polymethyl methacrylate, a polyester resin, and a polyolefin. Resin, polyamide resin, polycarbonate, polyphenylene oxide, and a mixture of these resins. As the synthetic resin for forming the convex portion, polycarbonate resin, ABS resin, ABS / polycarbonate alloy resin, and polyester are particularly preferable because they are compatible with the polyester resin layer constituting the outermost layer. It is preferable that it is at least one selected from the group consisting of a series elastomer resin.
The convex forming synthetic resin is usually different from the resin of the resin layer of the resin / metal composite laminate.

There is no restriction | limiting in particular in the shape and magnitude | size of the convex part formed by injection molding, According to the objective, it determines suitably.
In addition, this convex part is not limited to the above-mentioned reinforcing rib and screwing boss, and is formed as a partition plate, an insulating plate in the housing, a protective wall of a member in the housing, a surrounding member, or the like.

<Method for producing resin / metal composite injection molded article>
Hereinafter, an example of a method for producing the resin / metal composite injection molded product of the present invention using the laminate will be described with reference to FIGS. 4 (a) to 4 (e). The manufacturing method of a body is not limited to the method shown to Fig.4 (a)-(e) at all.

  First, the resin / metal composite laminate (this laminate) 1A (or 1B) of the present invention in which the metal plate 2 and the outermost layer 4 are laminated is cut into an appropriate size (FIG. 4 (a)), and thereafter Then, if necessary, drawing, bending, and punching are performed to obtain a desired shape such as a flat plate shape, an L-shaped section, and a U-shaped section (FIGS. 4B and 4C). ).

  Next, the molded resin / metal composite laminate 1 </ b> A (or 1 </ b> B) is inserted and fixed in the cavity of the injection mold 7. The insertion / fixing position may be either the male mold side or the female mold side of the injection mold, and in the case of a box-shaped molded body, it may be one surface or a plurality of surfaces. The fixing method may be any one of a method of inserting into a female mold, a method of covering the male mold surface, and a method of applying a reduced pressure to a vacuum hole communicating from the outside of the mold to the cavity surface. Next, the molten resin 9 of the convex forming synthetic resin is poured from the injection molding machine 8 toward the outermost layer 4 to perform injection molding (FIG. 4D). Thereafter, the molded body is taken out from the mold to obtain the resin / metal composite injection molded body 5 of the present invention in which the convex portions 6 of the synthetic resin are formed on the surface 4 of the outermost layer of the resin / metal composite laminate 1A (or 1B). (FIG. 4 (e)).

  For example, when manufacturing a box-type housing for a book-type computer, the metal plate on which the outermost layer of the polyester-based resin layer is formed is cut into a rectangle, the outermost surface is turned inside, and bending is performed on all four sides. After forming a shallow box shape and drilling it at the required position, insert it into the female mold side of the injection mold cavity, close the mold, and inject molten resin into the remaining part of the cavity The injection molding convex portions such as ribs and screw fixing bosses may be formed on the outermost layer surface inside the box-shaped housing.

  In this injection molding process, the outermost layer of the laminate is melted quickly by the heat of the injected molten resin and becomes compatible with the injected resin because the viscoelastic temperature characteristics are in an appropriate range. In order to fuse, the convex part formed by injection molding is firmly bonded and integrated with the outermost layer.

About this injection molding condition, although it varies depending on the kind of synthetic resin for forming the convex portion, when an ABS / polycarbonate alloy resin (melting point: about 250 to 300 ° C.) is used as the synthetic resin for forming the convex portion,
Molten resin temperature: 270-290 ° C
Injection mold temperature: 70-100 ° C
It is preferable to perform injection molding.
Moreover, when using polycarbonate-type resin (melting | fusing point: about 230-260 degreeC) as a synthetic resin for convex part formation,
Molten resin temperature: 270-300 ° C
Injection mold temperature: 60-120 ° C
It is preferable to perform injection molding.

  The resin / metal composite injection-molded article of the present invention thus obtained may be further subjected to a surface treatment such as painting or plating on the surface of the metal plate opposite to the outermost layer forming surface.

<Application>
The resin / metal composite injection molded product of the present invention is an electronic device such as a personal computer, a desktop computer, various printing machines, various copiers, office automation equipment such as telephones, electronic dictionaries / dictionaries, audio equipment, video equipment, television, radio, etc. It is useful for casings (housings) of devices and parts, and is particularly suitable as a casing for mobile phones by taking advantage of its features such as being thin and having convex parts such as ribs and screw bosses. It is done. However, the use of the resin / metal composite injection molded article of the present invention is not limited to these.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Film raw resin]
The resin used as a raw material of the resin film for outermost layer formation used in the following examples and comparative examples is as follows.
A-1: Low melting point polyester resin (“PES111EE” manufactured by Toa Gosei Co., Ltd.)
62 mol% terephthalic acid, 20 mol% adipic acid, 18 mol% sebacic acid
1,4 butanediol 34 mol%, ethylene glycol 66 mol%,
Point: 105 ° C)
A-2: Low melting point polyester resin (Toyobo "Byron GA5410"
44 mol% terephthalic acid, 30 mol% isophthalic acid, 26 mol adipic acid
%, 1,4 butanediol 100 mol%, melting point: 117 ° C.)
B-1: High melting point polyester resin (Toyobo "Byron GM470"
86 mol% terephthalic acid, 14 mol% adipic acid, 1,4 butanediol
86 mol%, ethylene glycol 14 mol%, melting point: 185 ° C, Toyobo
Made)
C-1: Polyester elastomer (acid component is 77 mol% terephthalic acid,
Consisting of 23 mol% of isophthalic acid, the glycol component is 1,4 butanediol
Polyester comprising 46 mol% and polytetramethylene glycol 54 mol%
90 parts by mass of a sulfur component, 8 parts by mass of a styrene component, and 2 parts by mass of a butadiene component
Polyester-based elastomer, melting point: 190 ° C)
D-1: Maleic acid-modified SEBS ("Tuftec M1913" manufactured by Asahi Kasei Corporation,
Styrene content: 30% by mass)
E-1: Polyester elastomer (100 mol% terephthalic acid as an acid component,
As a glycol component, 11 mol% of 1,4 butanediol and polytetramethyle
A polyester elastomer comprising 89 mol% of glycol,
Melting point: 160 ° C)

[Raw material composition]
The raw material composition of the resin film for outermost layer formation of the following compositions (mass ratio) was prepared using the said raw material resin.
Film composition No. 1: A-1 / A-2 / B-1 = 40/30/30
Film composition No. 2: A-2 / C-1 = 40/60
Film composition No. 3: A-1
Film composition No. 4: A-2
Film composition No. 5: C-1
Film composition No. 6: D-1
Film composition No. 7: B-1
Film composition No. 8: E-1

[Evaluation of viscoelastic temperature characteristics of film]
The viscoelastic temperature characteristics of the outermost layer-forming resin films used in Examples and Comparative Examples were evaluated by the following methods.
A sample with a length of 4 mm and a width of 60 mm was cut out from the resin film for forming the outermost layer before laminating on a metal plate, and using a viscoelastic spectrometer DVA-200 (manufactured by IT Measurement Co., Ltd.), a vibration frequency of 10 Hz, a strain of 0. Starting from -50 ° C in the MD direction (extrusion direction during film deposition) under the conditions of 1%, temperature increase rate of 3 ° C / min, and 25 mm between chucks, storage modulus at 90 ° C or 130 ° C, respectively. (E ′) and loss elastic modulus (E ″) were measured. Loss tangent tan δ = E ″ / E ′ was calculated from these measured values.

[Preparation of sample for evaluation]
<Example 1>
Film composition No. 1 raw materials are mixed, supplied to an extruder heated to 200 ° C., kneaded at 200 ° C. using this extruder, and a mold release PET using a laminator in which the molten resin composition is heated to 200 ° C. A film having a thickness of 60 μm was produced by sand lamination between (polyethylene terephthalate) films. The viscoelastic temperature characteristics of the outermost layer-forming resin film are as shown in Table 1.
After the film was peeled off from the release PET, a stainless steel plate (SUS304, 1 / 2H, thickness 0.3 mm passed through a heating furnace at 350 ° C. The same stainless steel was used in Examples 2 and Comparative Examples 1 to 4 below. A sample for evaluation was prepared by thermally fusing one surface of a steel plate at a surface temperature of 215 ° C.

<Example 2>
Film composition No. 1, no. Each of the two raw materials was sand laminated in the same manner as in Example 1 to prepare films each having a thickness of 30 μm. After peeling the release PET, the film composition No. 1 film was laminated at 205 ° C. to a stainless steel plate passed through a 350 ° C. heating furnace to form a first polyester resin layer. After lamination, the film composition No. was passed through a heating furnace at 250 ° C. on this first polyester resin layer. A film made of 2 was laminated at 215 ° C. to prepare a sample for evaluation.
In addition, film composition No. The viscoelastic temperature characteristics of the film made of 2 are as shown in Table 1.

<Example 3>
Film composition No. 1, no. In place of the raw material of No. 2, film composition No. 1, no. A sample for evaluation was produced in the same manner as in Example 2 except that the raw material No. 5 was used.
In addition, film composition No. The viscoelastic temperature characteristics of the film consisting of 5 are as shown in Table 1.

<Comparative Example 1>
Film composition No. 1, no. In place of the raw material of No. 2, film composition No. 3, no. A sample for evaluation was produced in the same manner as in Example 2 except that the raw material No. 4 was used.
In addition, film composition No. The viscoelastic temperature characteristics of the film consisting of 4 are as shown in Table 1.

<Comparative example 2>
Film composition No. 1, no. In place of the raw material of No. 2, film composition No. 1, no. A sample for evaluation was produced in the same manner as in Example 2 except that the raw material No. 4 was used.

<Comparative Example 3>
Film composition No. 1, no. In place of the raw material of No. 2, film composition No. 1, no. A sample for evaluation was produced in the same manner as in Example 2 except that the raw material No. 7 was used.
In addition, film composition No. The viscoelastic temperature characteristics of the film made of 7 are as shown in Table 1.

<Comparative example 4>
Film composition No. 1, no. In place of the raw material of No. 2, film composition No. 1, no. A sample for evaluation was produced in the same manner as in Example 2 except that the raw material No. 6 was used.
In addition, film composition No. Table 1 shows the viscoelastic temperature characteristics of the film made of 6.

<Comparative Example 5>
Film composition No. 1, no. In place of the raw material of No. 2, film composition No. 1, no. A sample for evaluation was produced in the same manner as in Example 2 except that the raw material No. 8 was used.
In addition, film composition No. The viscoelastic temperature characteristics of the film consisting of 8 are as shown in Table 1.

[Sample Evaluation]
The following evaluation was performed about the sample for evaluation obtained by the Example and the comparative example.

<Adhesiveness and durability with injection resin>
(Adhesiveness)
A polycarbonate / ABS alloy resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) melted by heating to 270 ° C. was injection-molded onto the outermost polyester resin layer of the sample for evaluation (injection shape: circle with a radius of 3.425 mm). Columnar). Next, a tensile test (tensile speed: 5 mm / min) was performed in the vertical direction, the fracture strength was measured, and the adhesiveness was evaluated according to the following evaluation criteria.
○: Breaking strength 8 MPa or more ×: Breaking strength less than 8 MPa

(durability)
An injection-molded sample obtained in the same manner as in the evaluation of adhesiveness was held at 60 ° C. and 95% RH for 96 hours in a constant temperature and humidity chamber, and then subjected to the same tensile test as in the evaluation of adhesiveness. The durability of adhesion was evaluated according to the following evaluation criteria.
○: Breaking strength 8 MPa or more ×: Breaking strength less than 8 MPa

<Mold heat resistance>
The mold temperature was set to 90 ° C., and the heat-melted polycarbonate / ABS alloy resin (Mitsubishi Engineering Plastics Co., Ltd.) was injection-molded onto the outermost polyester resin layer of the sample for evaluation (injection shape: (Cylindrical shape with a radius of 3.425 mm) At this time, the presence or absence of changes in the appearance of the surface and the inside was visually observed and evaluated according to the following criteria.
○: No change ×: Surface roughness due to mold surface transfer

<Erichsen test>
The Eriksen test was conducted by the method shown in FIGS. 5 (a) to 5 (c).
First, as shown in FIG. 5 (a), cuts 32 are made on the surface of the evaluation sample 31 (5 mm interval), and then, as shown in FIG. 5 (b), the Eriksen test defined by JIS K 6744 is performed. Using the apparatus, a punch 33 having a spherical tip is pushed into the center portion of the sample 31 by 5 mm (in FIG. 5B, 34 is a die and 35 is a wrinkle presser), as shown in FIG. 5C. Further, the sample 31 was observed for floating and cracking, and evaluated according to the following criteria.
○: No peeling ×: With peeling

[Evaluation results]
The evaluation results are shown in Table 1.

Table 1 shows the following.
Examples 1 to 3 in which E ′ (90), tan δ (90), E ′ (130), and tan δ (130) all satisfy the requirements of the present invention are adhesiveness to the injection resin, durability, and mold heat resistance. The Eriksen test also showed good results. On the other hand, since E ′ (90) is low in Comparative Examples 1 and 2, and tan δ (90) is high in Comparative Example 4, the releasability from the mold is poor after an injection test with an injection molding machine. The resin layer on the outermost layer had a mold mark and was inferior in appearance. In Comparative Example 3 where E ′ (130) is high and tan δ (130) is low and Comparative Example 5 where tan δ (130) is low, the mold release property from the mold is good, but the outermost resin layer is It did not soften in the injection test and was inferior in adhesiveness with the injection resin.

1A, 1B Resin / metal composite laminate 2 Metal plate 3, 3a, 3b Polyester resin layer 4 Outermost layer 5 Resin / metal composite injection molded body 6 Convex part 7 Injection mold 8 Injection molding machine 9 Molten resin 24 Heating furnace 26 Resin film 28 Reheating furnace 29 Resin / metal composite laminate 31 Sample 32 Notch 33 Punch 34 Die 35 Wrinkle presser

Claims (10)

  A resin / metal composite laminate having a metal plate and an outermost layer comprising a polyester resin layer formed on the metal plate, the polyester resin layer having a vibration frequency of 10 Hz, a strain of 0.1%, The storage elastic modulus at 90 ° C. measured at a temperature rising rate of 3 ° C./min and 25 mm between chucks is 10 MPa or more, tan δ is less than 0.2, the storage elastic modulus at 130 ° C. is less than 30 MPa, and tan δ is 0. A resin-metal composite laminate characterized by being 1 or more.   2. The resin / metal composite laminate according to claim 1, which is a resin / metal composite laminate for integrally forming a convex portion made of a synthetic resin on the outermost layer by injection molding.   The synthetic resin constituting the convex portion is at least one selected from the group consisting of an ABS resin, an ABS / polycarbonate alloy resin, a polycarbonate resin, and a polyester elastomer resin. The resin / metal composite laminate described.   The resin / metal composite laminate according to any one of claims 1 to 3, wherein the outermost layer is composed of two or more polyester resin layers.   The resin / metal composite laminate according to any one of claims 1 to 4, wherein the outermost layer has a thickness of 5 µm to 200 µm.   The resin / metal composite laminate according to any one of claims 1 to 5, wherein a surface of the outermost layer is embossed.   The resin-metal composite laminate according to any one of claims 1 to 6, wherein a convex portion made of the synthetic resin is integrally molded by injection molding a synthetic resin molten resin on the outermost layer. A resin / metal composite injection molded product characterized by the above.   A housing for OA equipment or electronic equipment, comprising the resin / metal composite injection molded article according to claim 7.   A method for producing a resin / metal composite laminate according to any one of claims 1 to 6, further comprising a laminating step of welding a polyester resin layer to the metal plate. Body manufacturing method.   8. The method for producing a resin / metal composite injection molded body according to claim 7, wherein the molten resin is injected into the injection mold in which the resin / metal composite laminate is disposed to integrate the convex portions. A method for producing a resin / metal composite injection molded article, comprising a step of molding.

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