JPWO2019054426A1 - Laminate - Google Patents

Abstract

A laminate containing at least a metal plate, an adhesive layer, and a resin layer, and these layers are laminated in this order, and the resin constituting the resin layer is a semi-aromatic polyamide or polyimide resin, and the adhesive layer. However, the laminate contains a dimer acid-based polyamide resin and / or an epoxy compound, and has a peeling strength of 6 N / 25 mm or more between the metal plate and the resin layer after the heat cycle test.

Description

The present invention relates to a laminate containing a metal plate, an adhesive layer, and a resin layer, and these layers are laminated in this order.

2. Description of the Related Art In recent years, many products such as automobiles, home electric appliances and mobile phones use electric and electronic parts using a metal laminate. As a metal laminate, a sensor in which a metal such as copper or tin is covered with an insulating film, a flexible printed circuit board with a polyimide film as a base material and a circuit formed of copper foil, etc., a copper wire is sandwiched using a polyester adhesive Examples include flexible flat cables and rechargeable battery packs for electronic devices.
These metal laminates are required to have heat resistance, for example, because they are used in a harsh environment such as in-vehicle use or exposed to high temperatures in a reflow soldering process in a manufacturing process. Therefore, at present, as the metal laminated body, for example, a laminated body composed of a polyimide film, an epoxy adhesive, and a metal is used in this order.

As an adhesive sheet for producing such a laminate, for example, in Japanese Unexamined Patent Publication No. 2010-285463, a polyimide-based resin film which is a heat-resistant resin film is used as a base film, and thermosetting A heat resistant adhesive sheet in which an adhesive is laminated is disclosed.

However, in the adhesive sheet disclosed in Japanese Unexamined Patent Publication No. 2010-285463, in a so-called heat cycle test in which a temperature change is repeated in a temperature range such as −20 to 150° C., for example, a base film and a metal plate. There was a problem in practical use because the adhesive strength of was significantly reduced.

The present invention is to solve the above problems and is excellent in adhesiveness between a metal plate and a resin layer, and even in a heat cycle test in which a temperature change is repeated in a temperature range such as −20 to 150° C. An object of the present invention is to provide a laminate composed of a metal plate, an adhesive layer, and a resin layer, which has a small decrease in strength and excellent heat resistance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resin layer having a specific structure is laminated with a metal plate through an adhesive layer having a specific structure, so that peeling after a heat cycle test is performed. The present invention has been completed by finding that a laminate having excellent strength can be obtained and the above problems can be solved.

That is, the gist of the present invention is as follows.
(1) A laminate containing at least a metal plate, an adhesive layer, and a resin layer, and these layers being laminated in this order,
The resin constituting the resin layer is a semi-aromatic polyamide or polyimide resin,
The adhesive layer contains a dimer acid-based polyamide resin and/or an epoxy compound,
A laminate having a peel strength of 6 N/25 mm or more between a metal plate and a resin layer after a heat cycle test under the following conditions.
Heat cycle test conditions:
A cycle in which the laminated body is held at −20° C. for 30 minutes, heated to 150° C. over 2 hours, held at 150° C. for 30 minutes, and then cooled again to −20° C. over 2 hours is defined as one cycle. , This is repeated 100 cycles.
(2) The laminate according to (1), wherein the diamine component of the semi-aromatic polyamide contains a diamine having 9 or 10 carbon atoms.
(3) The laminate according to (1), wherein the dimer acid-based polyamide resin has an acid value of 3 to 12 mgKOH/g.
(4) An electric/electronic component using the laminate according to any one of (1) to (3).

INDUSTRIAL APPLICABILITY The layered product of the present invention has a heat resistance that does not cause a decrease in adhesive strength and an adhesive property between a resin layer and a metal plate even in a heat cycle test in which a temperature is repeatedly changed in a temperature range of −20 to 150° C. It is an excellent laminate. Therefore, the laminate of the present invention can be used in applications such as a sensor, a flexible printed circuit board, and a rechargeable battery pack for electronic equipment.

Hereinafter, the present invention will be described in detail.
The laminate of the present invention contains at least a metal plate, an adhesive layer, and a resin layer, and is configured in this order.

(Adhesive layer)
The adhesive layer constituting the laminate of the present invention contains a dimer acid-based polyamide resin (P) and/or an epoxy compound (Q).

The dimer acid-based polyamide resin (P) constituting the adhesive layer has an amide bond in the main chain and is obtained by a dehydration condensation reaction mainly using dimer acid as a dicarboxylic acid component and a diamine component. is there. The dimer acid-based polyamide resin (P) has flexibility because it has a larger hydrocarbon group than resins such as nylon 6, nylon 66, and nylon 12, which are widely used as polyamide resins.
In the present invention, the dimer acid-based polyamide resin (P) preferably contains dimer acid as a dicarboxylic acid component in an amount of 50 mol% or more, more preferably 60 mol% or more, and 70 mol% or more based on the entire dicarboxylic acid component. It is more preferable to contain the above. If the proportion of dimer acid is less than 50 mol %, it becomes difficult to achieve the characteristics and effects of the dimer acid-based polyamide resin (P).

Here, the dimer acid is obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid and linolenic acid. If it is 25% by mass or less of the dimer acid component, a monomeric acid (C18) which is a monomer, a trimer acid (C54) which is a trimer, and another polymerized fatty acid having a carbon number of 20 to 54 are included. However, it may be hydrogenated to reduce the degree of unsaturation. Dimer acid is commercially available as Haridimer series (manufactured by Harima Kasei Co., Ltd.), Pripol series (manufactured by Croda Japan Co., Ltd.), Tsunodim series (manufactured by Tsukino Food Industry Co., Ltd.), and these can be used.

When a component other than dimer acid is used as the dicarboxylic acid component of the dimer acid-based polyamide resin (P), it is preferable to use adipic acid, azelaic acid, sebacic acid, pimelic acid, suberic acid, nonanedicarboxylic acid, fumaric acid, or the like. By containing these in an amount of less than 50 mol %, it becomes easy to control the softening point and adhesiveness of the resin.
As the diamine component of the dimer acid-based polyamide resin (P), ethylenediamine, hexamethylenediamine, tetramethylenediamine, pentamethylenediamine, m-xylenediamine, phenylenediamine, diethylenetriamine, piperazine and the like can be used, and among them, ethylenediamine. , Hexamethylenediamine, diethylenetriamine, m-xylenediamine and piperazine are preferred.
When polymerizing the dimer acid-based polyamide resin (P), it is possible to control the polymerization degree and the acid value or amine value of the resin (P) by changing the charging ratio of the dicarboxylic acid component and the diamine component. Becomes

In the present invention, the amine value of the dimer acid polyamide resin (P) is preferably less than 1.0 mgKOH/g, more preferably less than 0.7 mgKOH/g, and less than 0.4 mgKOH/g. Is more preferable. When the dimer acid-based polyamide resin (P) having an amine value of 1.0 mgKOH/g or more is used for the adhesive layer, the heat resistance of the adhesive layer may decrease.
In addition, the acid value of the dimer acid-based polyamide resin (P) is 1 to 20 mgKOH/g because it can enhance the peel strength of the obtained laminate and suppress the decrease in the peel strength after the heat cycle test. It is more preferably 1 to 15 mgKOH/g, further preferably 3 to 12 mgKOH/g, and most preferably 3 to 7 mgKOH/g. If the acid value of the dimer acid-based polyamide resin is less than 1 mgKOH/g, it becomes difficult to obtain a stable adhesive layer-forming coating agent for forming the adhesive layer, while if it exceeds 20 mgKOH/g. However, the chemical resistance, which is a good characteristic of the original dimer acid-based polyamide resin, may decrease.
The acid value is defined as the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin. On the other hand, the amine value is represented by the number of milligrams of potassium hydroxide, which is a molar equivalent to the base component in 1 g of the resin. Both are measured by the method described in JIS K2501.

The softening point of the dimer acid-based polyamide resin (P) is preferably 70 to 250°C, more preferably 80 to 240°C, and further preferably 80 to 200°C. When the softening point is less than 70° C., the obtained adhesive layer tends to have low heat resistance, and the tackiness at room temperature tends to be high. On the other hand, when the softening point is higher than 250° C., it tends to be difficult to disperse the resin (P) in an aqueous medium to prepare an adhesive layer-forming coating agent, and the obtained adhesive layer has At the time of bonding, the fluidity of the resin becomes insufficient, and there is a possibility that sufficient adhesiveness cannot be obtained.

The adhesive layer may contain the dimer acid-based polyamide resin (P) alone. However, it is preferable to use it in combination with a crosslinking agent suitable for the dimer acid-based polyamide resin (P) from the viewpoint of improving the adhesiveness. By cross-linking the dimer acid-based polyamide resin (P) with a cross-linking agent, it is possible to obtain an adhesive layer that exhibits low fluidity (low fluidity at high temperature) even when heated above the softening point of the resin (P).

As the cross-linking agent, any one can be used as long as it can cross-link the dimer acid-based polyamide resins (P) with each other. For example, a hydrazide compound, an isocyanate compound, a melamine compound, a urea compound, a carbodiimide compound, and an oxazoline compound are preferable, and these compounds can be used alone or in combination. Of these, oxazoline compounds, carbodiimide compounds, and isocyanate compounds are preferable. In addition, as the cross-linking agent, a self-crosslinking agent, a polyvalent coordination site, or the like can be used.

In the present invention, a commercially available crosslinking agent may be used because it is easily available. Specifically, as the hydrazide compound, APA series manufactured by Otsuka Chemical Co., Ltd. (APA-M950, APAM980, APA-P250, APA-P280, etc.) can be used. As the isocyanate compound, BASONAT PLR8878 manufactured by BASF, BASONAT HW-100, Bayhydur 3100 manufactured by Sumitomo Bayer Urethane Co., Bayhydur VPLS2150/1 and the like can be used. As the melamine compound, Cymel 325 manufactured by Mitsui Cytec Co., Ltd. can be used. As the urea compound, Beckamine series manufactured by DIC can be used. As carbodiimide compounds, carbodilite series (SV-02, V-02, V-02-L2, V-04, E-01, E-02, V-01, V-03, V- manufactured by Nisshinbo Chemical Co., Ltd. 07, V-09, V-05) and the like can be used. As the oxazoline compound, Epocros series (WS-500, WS-700, K-1010E, K-1020E, K-1030E, K-2010E, K-2020E, K-2030E) manufactured by Nippon Shokubai Co., Ltd. can be used. These are commercially available as dispersions or solutions containing a crosslinking agent.

When the adhesive layer in the invention contains the dimer acid-based polyamide resin (P) and the crosslinking agent, the content of the crosslinking agent is 0.5 to 50 parts by mass with respect to 100 parts by mass of the dimer acid-based polyamide resin (P). It is preferably part. When the content of the cross-linking agent is less than 0.5 parts by mass, it becomes difficult for the adhesive layer to obtain a desired cross-linking effect such as low fluidity at high temperature. On the other hand, when it exceeds 50 parts by mass, the adhesive layer for forming an adhesive layer described later is formed. As a result of lowering the liquid stability and processability of the coating agent, it may be difficult to obtain the basic performance of the adhesive layer.

The epoxy compound (Q) forming the adhesive layer preferably has two or more epoxy groups, and examples thereof include a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and an alicyclic epoxy resin. .. You may use 2 or more types of these.
Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, halogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, hydrogenated bisphenol. A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin having ether bond, naphthalene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, etc. Is mentioned.
Commercially available products of epoxy compounds include ADEKA RESIN EP-4000, EP-4080, EP-4100, EP-4900, ED-505, ED-506 (manufactured by ADEKA), jER1001, 1002, 1003, 1055, 1004, 1007, 1009, 1010, 1031S, 1302H60, Epicoat 604, 630, 630LSD, YX4000, YX4000H (manufactured by Mitsubishi Chemical Corporation), Denacol EX-313, EX-314, EX-411, EX-421, EX-512, EX-614( Nagase Chemtex Co., Ltd.) and the like.

The adhesive layer may contain the epoxy compound (Q) alone. However, it is preferably used in combination with a curing accelerator suitable for the epoxy compound (Q).
Examples of the curing accelerator include aromatic polyamines, imidazole derivatives such as 2-alkyl-4-methylimidazole and 2-phenyl-4-alkylimidazole, dicyandiamide, triphenylphosphine, diazabicycloundecene, diaminodiphenylsulfone. Known examples can be exemplified. You may use 2 or more types of these.

The adhesive layer can also be configured by combining the dimer acid-based polyamide resin (P) and the epoxy compound (Q). The epoxy compound (Q) exhibits a function as a crosslinking agent for the dimer acid-based polyamide resin (P). The epoxy compound (Q) to be combined with the dimer acid-based polyamide resin (P) may be a single epoxy compound or a combination of two or more kinds. Commercially available products of the epoxy compound (Q) to be combined with the dimer acid-based polyamide resin (P) include Denacol EM-150, EM-101 (manufactured by Nagase Chemtech), Adeka Resin EM-0517, EM-0526, EM-051R. , EM-11-50B, EP-4085, EP-4088S and the like (made by ADEKA). Among these epoxy compounds (Q), a glycidyl ether type epoxy resin is preferable, and a dicyclopentadiene type epoxy resin is particularly preferable.

The dicyclopentadiene type epoxy resin is preferably a compound which is liquid at room temperature and has a structural unit derived from dicyclopentadiene and two or more epoxy groups in one molecule. Examples of the structural unit that can be contained in addition to the structural unit derived from dicyclopentadiene include structural units derived from cyclohexane and the like, and examples thereof include dicyclopentadiene diphenol and dicyclopentadiene dixylenol. To be done.
The epoxy equivalent of the dicyclopentadiene type epoxy resin is preferably 30 to 1000, more preferably 50 to 500, and further preferably 100 to 300. Further, the dicyclopentadiene type epoxy resin preferably has a viscosity at 25° C. of 1 Pa·s or less, and as commercially available products, EP-4085, EP-4088S (manufactured by ADEKA), HP-7200, HP-7200H( DIC), ZX-1658GS (Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.

The dimer acid-based polyamide resin (P) has flexibility. Therefore, when the adhesive layer contains the dimer acid-based polyamide resin (P), the laminate can have flexibility while having improved adhesiveness. Further, when the adhesive layer contains a diglycidyl ether type epoxy compound as the epoxy compound (Q) with respect to the dimer acid type polyamide resin (P), the adhesiveness with a metal plate is particularly improved. Moreover, the laminated body in this case also has flexibility, and thus is suitable for flexible cables and circuit boards.

In the adhesive layer, various agents such as a leveling agent, an antifoaming agent, an anti-armpitting agent, a pigment dispersant, an ultraviolet absorber, and titanium oxide may be used as necessary as long as the physical properties such as adhesiveness and heat resistance are not impaired. Pigments or dyes such as zinc oxide and carbon black can be added.

The thickness of the adhesive layer in the laminate is not particularly limited, and can be arbitrarily selected according to the type of metal plate or resin layer. Generally, the thickness of the adhesive layer is preferably in the range of 0.05 to 50 μm, more preferably 0.1 to 20 μm, and further preferably 0.5 to 10 μm. When the thickness of the adhesive layer is less than 0.05 μm, the adhesiveness may not be sufficiently exhibited, while when the thickness exceeds 50 μm, the adhesiveness may be saturated, which may be disadvantageous in terms of cost.

The adhesive layer forming the laminate may be transparent or opaque depending on the application of the laminate. For example, the metal plate in the laminate is visualized by making the resin layer or the adhesive layer transparent. The adhesive layer may be colored in order to hide the metal plate or enhance the design.
In the present invention, whether the adhesive layer is transparent or opaque can be arbitrarily selected as long as the predetermined characteristics are satisfied.

(Resin layer)
In the resin layer forming the laminate of the present invention, the resin forming the resin layer needs to be a semi-aromatic polyamide or polyimide resin from the viewpoint of heat resistance.

The semi-aromatic polyamide that constitutes the resin layer is composed of a dicarboxylic acid component and a diamine component, and has an aromatic component in the dicarboxylic acid component and/or the diamine component.
The dicarboxylic acid component constituting the semi-aromatic polyamide preferably contains terephthalic acid as a main component, and the dicarboxylic acid component other than terephthalic acid includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and sebacic acid. , Aliphatic carboxylic acids such as dodecanedioic acid, tetradecanedioic acid and octadecanedioic acid, and aromatic compounds such as 1,4-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid and isophthalic acid A dicarboxylic acid is mentioned. The content of terephthalic acid in the dicarboxylic acid component is preferably 60 to 100 mol %.

The diamine component constituting the semi-aromatic polyamide preferably contains an aliphatic diamine having 4 to 15 carbon atoms as a main component, and 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexane. Diamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,10-decanediamine 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine and the like. Among them, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine and other diamines having 9 carbon atoms, and 1,10-decanediamine and other carbon atoms. Diamines whose number is 10 are preferred. These may be used alone or in combination of two or more.

Lactams such as ε-caprolactam, ζ-enanthlactam, η-capryllactam, and ω-laurolactam may be copolymerized with the semi-aromatic polyamide within a range that does not impair the object of the present invention.

The type and copolymerization ratio of the monomers constituting the semi-aromatic polyamide are preferably selected so that the melting point (Tm) of the obtained semi-aromatic polyamide is in the range of 280 to 350°C. By setting the Tm of the semi-aromatic polyamide within the above range, thermal decomposition of the semi-aromatic polyamide during processing into the resin layer can be efficiently suppressed. When the Tm of the semi-aromatic polyamide is less than 280°C, the resulting resin layer may have insufficient heat resistance. On the other hand, a semi-aromatic polyamide having a Tm of more than 350°C may undergo thermal decomposition during the production of the resin layer.

A commercially available product can be preferably used as the semi-aromatic polyamide. Examples of such commercially available products include "Genestar (registered trademark)" manufactured by Kuraray Co., Ltd., "Zecot (registered trademark)" manufactured by Unitika, "Renny (registered trademark)" manufactured by Mitsubishi Engineering-Plastics, and Mitsui Chemicals, Inc. Examples include “Aren (registered trademark)” and “Ultramid (registered trademark)” manufactured by BASF.

The semi-aromatic polyamide can be produced using any known method. For example, a solution polymerization method or an interfacial polymerization method using an acid chloride and a diamine component as raw materials can be mentioned. Alternatively, a method in which a prepolymer is prepared using a dicarboxylic acid component and a diamine component as raw materials and the prepolymer is made to have a high molecular weight by melt polymerization or solid phase polymerization can be mentioned.

Further, an end cap may be used together with the diamine component, the dicarboxylic acid component and the polymerization catalyst, if necessary. The terminal blocking agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the terminal of the semi-aromatic polyamide from the viewpoint of suppressing thermal decomposition and suppressing increase in molecular weight, Examples thereof include monocarboxylic acids, monoamines, acid anhydrides, monoisocyanates, monohalides, monoesters and monoalcohols.

The polyimide-based resin forming the resin layer is a polymer having an imide bond in a repeating unit, and examples thereof include polyimide, polyetherimide, and polyamideimide.

The polyimide-based resin is produced by any known method, for example, in a polymer in which a tetracarboxylic acid component and a diamine component are imide-bonded, a polyimide-based resin obtained by reacting a tetracarboxylic dianhydride and a diamine compound. It is preferably obtained by imidizing a resin precursor (polyamic acid).

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and 2,2-bis(2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane Dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis[4-(2,3- Examples thereof include dicarboxyphenoxy)phenyl]propane dianhydride and bis(3,4-dicarboxyphenyl)sulfone dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.
Examples of the diamine compound include m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone. 2,2-bis(4-aminophenoxyphenyl)propane, 2,2-bis(4-aminophenoxyphenyl)hexafluoropropane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis( 4-aminophenoxy)benzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2-dimethylbiphenyl , 2,2-bis(trifluoromethyl)-4,4'-diaminobiphenyl. These diamine compounds may be used alone or in combination of two or more kinds.
Since polyimide resin is excellent in heat resistance, mechanical strength, electrical properties, and chemical resistance, tetracarboxylic dianhydride is pyromellitic dianhydride and diamine compound is 4,4′-diaminodiphenyl ether. It is preferable that the tetracarboxylic dianhydride be 3,3′,4,4′-biphenyltetracarboxylic dianhydride and the diamine compound be p-phenylenediamine.

Further, the polyimide resin may be polyamideimide, which is a polymer in which a tricarboxylic acid component and a diamine component are imide-bonded and amide-bonded.
Examples of the tricarboxylic acid component include trimellitic acid, diphenyl ether-3,3',4'-tricarboxylic acid, diphenylsulfone-3,3',4'-tricarboxylic acid, benzophenone-3,3',4'-tricarboxylic acid and the like. Examples of the diamine component include those exemplified as the diamine compound constituting the polyimide resin.
Polyamideimide can be usually produced by polymerizing by the reaction of trimellitic anhydride and diisocyanate or by the reaction of trimellitic anhydride chloride and diamine, and then imidizing.

From the above-mentioned semi-aromatic polyamide or polyimide resin, the method for producing a resin layer is not particularly limited, and examples thereof include an extrusion method and a solvent casting method, and the resin layer constituting the laminate of the present invention is It may be manufactured by any method.

The resin layer is required to be composed of the above resins, but known additives and stabilizers, such as antistatic agents, plasticizers, lubricants, antioxidants, pigments, etc., can be used as long as the effects of the present invention are not impaired. May be included.
Further, the resin layer may be subjected to a corona treatment, a plasma treatment, an ozone treatment, a chemical treatment, a solvent treatment, or the like as a pretreatment on the surface in consideration of the adhesiveness when laminated with the adhesive layer.
The thickness of the resin layer is preferably 0.5 μm to 1.5 mm, more preferably 15 to 200 μm, and further preferably 25 to 75 μm. If the thickness of the resin layer is less than 0.5 μm, it may be difficult to manufacture, and if it exceeds 1.5 mm, handling may be difficult. The resin layer may be stretched.

The resin layer forming the laminate may be transparent or opaque depending on the application of the laminate. For example, the metal plate in the laminate is visualized by making the resin layer or the adhesive layer transparent. The resin layer may be colored in order to hide the metal plate or improve the design.
Generally, the transparency of a film is represented by haze and total light transmittance. In the present invention, when the resin layer is transparent, the haze of the resin layer is preferably less than 15%, more preferably less than 10%, and the total light transmittance is preferably 60% or more. , 80% or more is more preferable.
In the present invention, whether the resin layer is transparent or opaque can be arbitrarily selected as long as the predetermined characteristics are satisfied.

In the present invention, a semi-aromatic polyamide or a polyimide resin is used as the resin forming the resin layer, and instead of this, an aliphatic polyamide such as polyamide 6 or polyamide 66 is not used.
For example, when the characteristics of the semi-aromatic polyamide polyamide 9T and the characteristics of the aliphatic polyamide polyamide 6 and the polyamide 66 are compared, the melting point of the polyamide 6 is 225°C, whereas the melting point of the polyamide 9T is 225°C. The melting point is 265° C., and these aliphatic polyamides have relatively low heat resistance. Therefore, the resin layer made of an aliphatic polyamide having low heat resistance is inferior in dimensional stability during lamination and dimensional stability in a heat cycle test after lamination, and is likely to cause a decrease in adhesiveness, floating, and the like.
Furthermore, regarding the water absorption rate (23° C., 24 hours, immersion in water), the water absorption rate of polyamide 9T is 0.25%, the water absorption rate of polyamide 6 is 1.6%, and the water absorption rate of polyamide 66 is 1%. 0.5%, and these aliphatic polyamides have relatively high water absorption.
Therefore, when a laminate including a resin layer made of an aliphatic polyamide having low heat resistance and high water absorption is used for a flexible printed circuit board or the like, the moisture-absorbed resin layer is, for example, 260 in a reflow soldering process. When exposed to an atmosphere of ℃ for several seconds, water contained in the resin layer is suddenly turned into steam, causing blister and the like to cause blister and deteriorating the appearance, and the adhesion to the metal plate may be deteriorated.

When the laminate of the present invention is used for a printed wiring board or an application involving chemical treatment such as etching using a strong alkali or the like, it is preferable that the resin layer is composed of a semi-aromatic polyamide. Polyimide-based resin has low durability against strong alkali, and the resin layer formed of the polyimide-based resin has a problem of chemical stress cracking such as brittle fracture when stress such as bending is applied after chemical treatment. I have a concern. On the other hand, since semi-aromatic polyamide has high durability against strong alkalis and there is little concern about chemical stress cracking, the laminate in which the resin layer is composed of semi-aromatic polyamide is applicable to a wide range of electronic component applications. Is.

(Metal plate)
The type of metal that constitutes the metal plate of the laminate is not particularly limited, and examples thereof include copper, tin, aluminum, stainless steel, gold, nickel, and mixtures and compounds thereof.
The thickness of the metal plate is not particularly limited, but is preferably 1 mm or less, and more preferably 0.5 mm or less. The surface of the metal plate may be a mirror surface, a rough surface, or may be surface-treated.

(Laminate)
The laminate of the present invention is excellent in adhesiveness between the metal plate and the resin layer even after the heat cycle test under the conditions described below, the peel strength between the metal plate and the resin layer is 6 N/25 mm or more, and the peel strength is It is preferably 7 N/25 mm or more, and more preferably 8 N/25 mm or more.

(Lamination of adhesive layer and resin layer)
The laminate of the present invention contains at least a metal plate, an adhesive layer, and a resin layer, and these layers are laminated in this order. The method for laminating the adhesive layer on the resin layer is to bond the resin layer to the resin layer. Examples thereof include a method of applying a layer forming coating agent and a method of coextruding a resin forming an adhesive layer and a resin forming a resin layer. Since the latter method depends on the melting temperature at the time of forming the resin layer, the former method of applying the adhesive layer forming coating agent is preferable.

The method of applying the adhesive layer-forming coating agent is a method of applying the coating agent to the biaxially stretched resin layer (post coating method) or a coating agent to the resin layer before biaxial stretching. Any method such as a method of stretching and heat treatment after coating (in-line coating method) can be selected.
Then, the adhesive layer can be laminated on the resin layer by a method of simultaneously drying, stretching and heat treating the resin layer coated with the adhesive layer forming coating agent, or by a method of stretching and heat treating after drying.

The adhesive layer-forming coating material is a resin component dispersed or dissolved in an aqueous medium or an organic solvent, and a uniform adhesive layer can be formed by applying and drying the resin component. The adhesive layer-forming coating material is preferably an aqueous dispersion dispersed in an aqueous medium in consideration of the working environment. The aqueous medium is a liquid containing water as a main component, and may contain a basic compound or a hydrophilic organic solvent described later.

In order to disperse the dimer acid-based polyamide resin (P) in an aqueous medium with good stability, it is preferable to use a basic compound. By using the basic compound, some or all of the carboxyl groups contained in the dimer acid-based polyamide resin (P) are neutralized to generate a carboxyl anion, and the electrical repulsive force thereof causes aggregation between the resin fine particles. Therefore, the dimer acid-based polyamide resin (P) can be stably dispersed in an aqueous medium and can maintain a stable form in an alkaline region. The pH of the aqueous dispersion is preferably in the range of 7-13. As the basic compound, a basic compound having a boiling point under atmospheric pressure of less than 185° C. is preferable.

Examples of the basic compound having a boiling point under atmospheric pressure of less than 185° C. include amines such as ammonia and organic amine compounds. Specific examples of the organic amine compound include triethylamine, N,N-dimethylethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, Examples thereof include methylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. Among the basic compounds having a boiling point under atmospheric pressure of less than 185° C., triethylamine and N,N-dimethylethanolamine are preferable.
When the boiling point of the basic compound at atmospheric pressure exceeds 185° C., it becomes difficult to volatilize the basic compound, particularly the organic amine compound by drying when applying the aqueous coating agent to form a coating film, It may adversely affect hygiene and coating properties.

The content of the basic compound in the aqueous dispersion is preferably 0.01 to 100 parts by mass, more preferably 1 to 40 parts by mass, and further preferably 1 to 15 parts by mass with respect to 100 parts by mass of the resin solid content. preferable. When the content of the basic compound is less than 0.01 part by mass, the effect of adding the basic compound is poor and it becomes difficult to obtain an aqueous dispersion having excellent dispersion stability. On the other hand, when the content of the basic compound exceeds 100 parts by mass, the aqueous dispersion tends to be colored or gelled, and the pH of the emulsion tends to be too high.

When an aqueous dispersion is used as the adhesive layer-forming coating material, it is preferable that the boiling point at atmospheric pressure is 185° C. or higher or that the non-volatile water-based auxiliary agent is not contained. The boiling point at atmospheric pressure of 185° C. or higher or a non-volatile hydration aid refers to an emulsifier component or a compound having a protective colloid action. That is, in the method described below, a stable aqueous dispersion having a fine resin particle size can be obtained without using an aqueous solubilizing agent. The use of the hydration aid does not immediately reduce the stability of the aqueous dispersion and therefore does not preclude the use of the hydration aid. In the method described below, the aqueous dispersion is clearly distinguished from that obtained by a method based on the so-called phase inversion emulsification method in which the aqueous solubilizing agent is an essential component, so the aqueous solubilizing agent is used as much as possible. It is preferable not to use it, and it is particularly preferable not to use it at all. However, after obtaining the aqueous dispersion, an hydration aid may be positively used depending on the purpose, for example, when another coating agent containing the aqueous dispersion is newly obtained, the purpose may be increased. It goes without saying that a water-based auxiliary agent may be added accordingly.

Examples of the emulsifier component include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier or an amphoteric emulsifier, and in addition to those generally used for emulsion polymerization, surfactants are also included. For example, as anionic emulsifiers, sulfuric acid ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulphates, polyoxyethylene alkyl phenyl ether sulphates, vinyl sulfosuccinates. Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide. Examples thereof include compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives. Examples of the amphoteric emulsifier include lauryl betaine and lauryl dimethylamine oxide.
Examples of the compound having a protective colloid action include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl pyrrolidone, polyacrylic acid and its salts, carboxyl group-containing polyethylene wax, and carboxyl group-containing compound. Acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less, such as polypropylene wax and carboxyl group-containing polyethylene-propylene wax, salts thereof, acrylic acid-maleic anhydride copolymers and salts thereof, styrene-(meth)acrylic acid. The unsaturated carboxylic acid content of the copolymer, ethylene-(meth)acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, etc. is 10 Compounds generally used as a dispersion stabilizer for fine particles, such as a polymer containing carboxyl group at a mass% or more and a salt thereof, polyitaconic acid and a salt thereof, a water-soluble acrylic copolymer having an amino group, gelatin, gum arabic, and casein. And so on.

Next, a method for dispersing the dimer acid-based polyamide resin (P) in water will be described. As described above, the adhesive layer in the laminate of the present invention is preferably an aqueous dispersion prepared by dispersing the dimer acid-based polyamide resin (P) in an aqueous medium from the viewpoint of working environment, but is not limited thereto. Not a thing.
In order to obtain the aqueous dispersion of the dimer acid type polyamide resin (P), it is preferable to use a container that can be closed. That is, a means of charging each component in a container that can be sealed, heating and stirring is preferably used.
Specifically, first, a predetermined amount of dimer acid-based polyamide resin (P), a basic compound, and an aqueous medium are put into a container. As described above, since a basic compound or a hydrophilic organic solvent described below may be contained in the aqueous medium, for example, if an aqueous medium containing a basic compound is used, the basic compound is separately prepared. Without adding, the basic compound will be charged in the container as a result.
Next, the container is closed and heated and stirred at a temperature of preferably 70 to 280°C, more preferably 100 to 250°C. When the temperature at the time of heating and stirring is less than 70° C., the dispersion of the dimer acid-based polyamide resin (P) is difficult to proceed, and it tends to be difficult to set the number average particle diameter of the resin to 0.5 μm or less. If the temperature is higher than 0°C, the molecular weight of the dimer acid-based polyamide resin (P) may decrease, and the internal pressure of the system may increase to a level that cannot be ignored.
When heating and stirring, it is preferable to heat and stir at 10 to 1000 revolutions per minute until the resin is uniformly dispersed in the aqueous medium.

Further, a hydrophilic organic solvent may be added together and placed in the container. As the hydrophilic organic solvent in this case, from the viewpoint of further reducing the particle size of the dimer acid-based polyamide resin (P) and at the same time further promoting the dispersion of the dimer acid-based polyamide resin (P) in the aqueous medium, 20° C. The solubility in water is preferably 50 g/L or more, more preferably 100 g/L or more, still more preferably 600 g/L or more, and particularly preferably when a hydrophilic organic solvent that can be dissolved in water at an arbitrary ratio is selected and used. Good. The boiling point of the hydrophilic organic solvent is preferably 30 to 250°C, more preferably 50 to 200°C. When the boiling point is lower than 30°C, the hydrophilic organic solvent is likely to be volatilized during the preparation of the aqueous dispersion, and as a result, the meaning of using the hydrophilic organic solvent is lost and the working environment is likely to be deteriorated. On the other hand, when the temperature exceeds 250°C, it tends to be difficult to remove the hydrophilic organic solvent from the aqueous dispersion, and as a result, when the coating film is formed, the organic solvent remains in the coating film, It may reduce solvent resistance.
As in the case of the basic compound described above, since a hydrophilic organic solvent may be contained in the aqueous medium, if an aqueous medium containing a hydrophilic organic solvent is used, a hydrophilic organic solvent is additionally added. Even if it does not, as a result, the hydrophilic organic solvent is charged in the container.

The content of the hydrophilic organic solvent is preferably 60% by mass or less with respect to the entire components (water, basic compound and various organic solvents including the hydrophilic organic solvent) constituting the aqueous medium. , 1 to 50 mass% is more preferable, 2 to 40 mass% is further preferable, and 3 to 30 mass% is particularly preferable. When the content of the hydrophilic organic solvent is more than 60% by mass, not only the effect of promoting hydration cannot be expected, but in some cases, the aqueous dispersion tends to gel, which is not preferable.

Specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-. Amyl alcohol, alcohols such as 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone and isophorone; tetrahydrofuran, Ethers such as dioxane; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate , Esters such as dimethyl carbonate; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Glycol derivatives such as diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate; and further 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile , Dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate and the like.

A part of the organic solvent and the basic compound added during the aqueous solution can be removed from the aqueous dispersion by a solvent removal operation called stripping. By such stripping, the content of the organic solvent can be reduced to 0.1% by mass or less, if necessary. Even when the content of the organic solvent is 0.1% by mass or less, no particular effect on the performance of the aqueous dispersion is confirmed. Examples of the stripping method include a method in which the aqueous dispersion is heated with stirring under normal pressure or reduced pressure, and the organic solvent is distilled off. At this time, it is preferable to select a temperature and a pressure at which the basic compound is not completely distilled off. In addition, since the solid content concentration in the aqueous dispersion becomes high when a part of the aqueous medium is distilled off at the same time, it is preferable to appropriately adjust the solid content concentration.

Examples of the hydrophilic organic solvent that can be easily desolvated include ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono Butyl ether and the like, and particularly ethanol, n-propanol, isopropanol, tetrahydrofuran and the like are preferably used. A hydrophilic organic solvent that is easy to remove the solvent is generally used because it greatly contributes to the promotion of water solubilization of the resin.

Further, when obtaining the aqueous dispersion, a hydrocarbon-based organic solvent such as toluene or cyclohexane constitutes the aqueous medium for the purpose of promoting the dispersion of the resin (P) in the aqueous medium containing the hydrophilic organic solvent. You may mix|blend in the range of 10 mass% or less with respect to the whole component. When the blending amount of the hydrocarbon-based organic solvent exceeds 10% by mass, separation from water becomes remarkable in the production process, and a uniform aqueous dispersion may not be obtained.

The aqueous dispersion of the dimer acid-based polyamide resin (P) can be obtained by the above method, but after the components are heated and stirred, the obtained aqueous dispersion may be cooled to room temperature if necessary. Good. Of course, the stability of the aqueous dispersion is naturally maintained without agglomeration even after the cooling process.
After cooling the aqueous dispersion, there is basically no problem even if it is immediately dispensed and subjected to the next step. However, since foreign matters and a small amount of undispersed resin may rarely remain in the container, it is preferable to once provide a filtration step before paying out the aqueous dispersion. The filtration step is not particularly limited, but, for example, means for performing pressure filtration (for example, air pressure 0.5 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) can be adopted.
After obtaining an aqueous dispersion of a dimer acid-based polyamide resin (P), an appropriate amount of this aqueous dispersion and a dispersion or solution containing a cross-linking agent are mixed to obtain a coating agent with better adhesiveness. You can

On the other hand, when the dimer acid-based polyamide resin (P) is dissolved in an aqueous medium to form an aqueous coating agent, for example, the resin (P) is added to a hydrophilic organic solvent such as n-propanol and the temperature is 30 to 100°C. After the resin (P) is once dissolved by heating and stirring under the temperature of 1, the appropriate amount of water or the dispersion or solution containing the above-mentioned cross-linking agent is added to obtain an aqueous coating agent for forming an adhesive layer. You can

The adhesive layer-forming coating material is preferably a water-based coating material as described above, but the coating material for forming the adhesive layer containing the epoxy compound (Q) is the epoxy compound (Q) in an organic solvent. It may be dispersed or dissolved in.
As the organic solvent, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1- Ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and other alcohols; methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone and other ketones; tetrahydrofuran, dioxane and other ethers Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, etc. Esters; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol Glycol derivatives such as ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate; and further 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethyl. Examples thereof include acetamide, diacetone alcohol, ethyl acetoacetate, toluene, xylene, and cyclohexane. If necessary, these organic solvents may be mixed and used.

The content (solid content concentration) of the dimer acid-based polyamide resin (P) and/or the epoxy compound (Q) in the adhesive layer-forming coating material can be appropriately selected according to the purpose of use and storage method, and is not particularly limited. Is preferably 3 to 40% by mass, and more preferably 10 to 35% by mass. When the content of the resin (P) or the compound (Q) in the adhesive layer-forming coating material is less than the above range, it may take time to form a coating film by the drying step, and a thick coating film may be formed. It tends to be difficult to obtain. On the other hand, when the content of the resin (P) or the compound (Q) in the adhesive layer-forming coating material is more than the above range, the storage stability of the coating material tends to decrease.

The viscosity of the adhesive layer-forming coating agent is not particularly limited, but it is preferable that the viscosity is low even at room temperature. Specifically, the rotational viscosity measured at 25° C. using a B type viscometer (DVL-BII type digital viscometer manufactured by Tokimec Co., Ltd.) is preferably 20000 mPa·s or less, more preferably 5000 mPa·s or less, and 500 mPa·s.・S or less is more preferable. When the viscosity of the adhesive layer-forming coating material exceeds 20000 mPa·s, it tends to be difficult to uniformly apply the coating material to the resin layer.

The adhesive layer-forming coating agent may contain additives such as an antistatic agent, a leveling agent, and an ultraviolet absorber depending on the application, and in particular, a basic material may be added as an additive. Dispersion stability is maintained.

As a method of applying the adhesive layer-forming coating material to the resin layer, a known method can be adopted. For example, gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating and the like can be adopted. By these methods, the surface of the resin film can be uniformly coated.

The medium can be removed by applying the adhesive layer-forming coating agent to the resin layer and then subjecting it to dry heat treatment, and the adhesive layer made of a dense coating film can be brought into close contact with the resin layer.

(Lamination of metal plates)
Examples of the method for adhering the metal plate on the adhesive layer laminated on the resin layer include a method such as hot pressing.
The adhesive layer in the present invention exhibits low fluidity at high temperature, and even when subjected to high temperature of hot pressing in adhering metal plates, shape change due to high temperature flow is suppressed, and adhesiveness between the resin layer and the metal plate It is possible to obtain a laminate excellent in heat resistance.
When the adhesive layer in the present invention contains the dimer acid-based polyamide resin (P), the heat pressing conditions such as temperature, pressure, and time are made milder than those of the adhesive layer containing the thermosetting resin. can do. The hot press can bond even at a temperature of 180° C., but from the viewpoint of increasing the peel strength, it is preferably 180 to 200° C., more preferably 190 to 200° C. Further, the heat press can bond for 15 minutes, but it is preferably 15 to 120 minutes, more preferably 60 to 120 minutes. For example, when the adhesive layer contains the epoxy compound (Q), the hot pressing is performed under the condition of 200° C.×2 hours, but by using the dimer acid type polyamide resin (P), the hot pressing condition is 180° C. It is possible to lower the temperature and shorten the temperature to 15°C for 15 minutes. However, the hot pressing conditions may be variously changed and selected depending on the characteristics required for the metal plate, the adhesive layer, the resin layer used, the type of the apparatus for hot pressing, the combination of capabilities, or the obtained laminate. This is not the case because you can.

In a laminate including a metal plate, an adhesive layer, and a resin layer in this order, the problem of curling may occur. That is, since the resin layer is laminated on the metal plate which is hardly affected by heat and humidity and whose dimensional change is extremely small, with the adhesive layer interposed, the dimensional shrinkage of the resin layer or the volumetric shrinkage of the adhesive layer occurs. The laminated body curls on the resin layer side. Therefore, by using a resin layer that does not easily shrink in size or an adhesive layer that does not easily shrink in volume, the laminate can suppress curling.
As the thickness of the resin layer increases, it is difficult for the resin layer to shrink in dimension, and curling of the laminate can be suppressed. On the other hand, the volume shrinkage of the adhesive layer is caused by the fact that the crosslinking density increases with the progress of curing due to the use of the curing agent or the combined use with the crosslinking agent or the like. Therefore, the thickness of the adhesive layer is made as thin as possible so that the influence of volume contraction is less likely to occur, and thus the curling of the laminate can be suppressed.
In consideration of the above, the type and thickness of the resin layer, the type of the adhesive layer, the type of crosslinking agent to be used, the compounding amount, and the thickness are determined to improve the adhesiveness of each interface as a laminate and suppress curling. Need to plan.

Since the laminate of the present invention can be manufactured while achieving both shortening of the time in the bonding step and handling property, and can withstand the heat cycle test, various circuit boards in the electric and electronic fields, display substrates, It can be used for display members, sensor members, rechargeable battery exterior members, cable members and the like. Among them, the laminate of the present invention can be used as a film by taking advantage of the heat resistance, bending resistance, and chemical resistance of the resin layer, and since the resin layer can be handled as a film, the sensor member, the flexible printed circuit board, the flexible It can be suitably used as a substrate material such as a flat cable, and a cable material rechargeable battery exterior member.

Hereinafter, the present invention will be specifically described with reference to examples. In addition, the measurement and evaluation of various values in the examples were performed as follows.
(1) Characteristic values of dimer acid-based polyamide resin [acid value, amine value]
It was measured by the method described in JIS K 2501.
[Softening point]
Using 10 mg of the resin as a sample, a microscope equipped with a heating (cooling) device heat stage for microscope (type of Heating-Freezing ATAGE TH-600 manufactured by Rincom Co., Ltd.) was used, and measurement was performed at a heating rate of 20° C./min. The temperature at which the resin melted was defined as the softening point.
[Content of dimer acid]
It was determined by performing ¹ H-NMR analysis (Varian Co., Ltd. 300 MHz) at 120° C. in tetrachloroethane (d ₂ ).

(2) Solid Content Concentration of Aqueous Dispersion An appropriate amount of the obtained aqueous dispersion was weighed, and this was heated at 150° C. until the mass of the residue (solid content) reached a constant amount, and the solid content concentration was determined.

(3) pH of aqueous dispersion
The pH was measured using a pH meter (F-52 manufactured by Horiba, Ltd.).

(4) Viscosity of Aqueous Dispersion The rotational viscosity (mPa·s) at a temperature of 25° C. was measured using a B type viscometer (DVL-BII type digital viscometer manufactured by Tokimec Co., Ltd.).

(5) Number-Average Particle Diameter of Resin in Aqueous Dispersion The number-average particle diameter of resin in the aqueous dispersion was determined by dynamic light scattering method using Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340) manufactured by Nikkiso Co., Ltd. Measured by

(6) Peel strength (6.1) Peel strength before heat cycle test Cellophane tape (LP-24, manufactured by Nichiban Co., Ltd.) was applied to the surfaces of the metal plates of the laminates A and B prepared in Examples and Comparative Examples, respectively. Bonding was performed and reinforcement was performed so that the metal plate was not immediately broken when the metal plate was pulled in a peeling test to be described later. Then, a measurement sample having a width of 25 mm and a length of 10 cm was cut out promptly so as not to absorb moisture, and a tensile tester (precision universal material testing machine 2020 manufactured by Intesco Co., Ltd.) was used under a 23° C., 50% RH atmosphere, and a pulling speed of 200 mm. The peel strength between the metal plate and the resin layer was measured by performing the T-type peel test under the condition of /minute, and the adhesiveness was evaluated by the magnitude of the value. The measurement was carried out on 5 samples, and the average value was taken as the peel strength before the heat cycle test.
(6.2) Peel strength after heat cycle test Further, the laminates A and B produced in Examples and Comparative Examples were held at -20°C for 30 minutes and then heated to 150°C over 2 hours, After holding at 150° C. for 30 minutes, the temperature was lowered to −20° C. over 2 hours again as one cycle, and this cycle was repeated 100 times. With respect to the laminates A and B after the heat cycle test, the peel strength was measured by the same method as described above, and the adhesiveness after the heat cycle test was evaluated.
Practically, it was judged that even if the required performance was not obtained with the laminate A, if the required performance was obtained with the laminate B, it could be used for the intended purpose.

(7) Appearance after heat resistance test Regarding the laminates A and B after the heat cycle test, those without peeling after the heat cycle test were further held at 260°C for 15 minutes, and the appearance after that was evaluated according to the following criteria. It was visually confirmed with. Note that this heat resistance test assumes a state in which the laminate of the present invention is actually used as a device component, particularly a state in which it is used for reflow soldering. Practically, it was judged that even if the required performance was not obtained with the laminate A, if the required performance was obtained with the laminate B, it could be used for the intended purpose.
The blisters indicate a state in which the metal plate/adhesive layer or the adhesive layer/resin layer interface strength is lowered and the metal plate or resin layer floats. Peeling means a state in which the metal plate/adhesive layer or the adhesive layer/resin layer is completely separated.
A: No blister or peeling is observed. Moreover, no abnormal appearance is observed in the laminate.
◯: No blister or peeling is observed. However, some distortion is seen in the laminate.
Δ: Blisters are seen.
X: Both blister and peeling are observed.

(8) Curl The laminate B produced in Examples and Comparative Examples was sufficiently cooled after production, and a test piece having a size of 100×100 mm was cut out. The test piece was allowed to stand for 24 hours in an environment of 23° C. and 65% RH, and the degree of curl of the test piece was evaluated by grounding with the metal plate side of the test piece as the lower surface. That is, when the test piece curls concavely (the adhesive layer or the resin layer contracts), the lifting height of both ends is measured, and when it curls convexly (the resin layer expands due to moisture absorption), the center The lifting height of the part was measured and evaluated according to the following criteria.
◎: Lifting height is less than 0.5 mm ◯: Lifting height is 0.5 mm or more and less than 3 mm △: Lifting height exceeds 3 mm

(9) Chemical resistance (alkali resistance)
The laminate B produced in each of the examples and comparative examples was sufficiently cooled after the production, and a test piece having a size of 100×100 mm was cut out. A tension of 60 N was applied to the test piece, a 5% sodium hydroxide aqueous solution at 45° C. was sprayed, and the presence or absence of cracks was visually observed and evaluated according to the following criteria.
◯: No cracks occurred at all Δ: Cracks occurred at one or more places.

The following were used as the resin and the coating material that constitute the adhesive layer forming coating material.
[Dimer acid-based polyamide resin (P-1)]
It contains 100 mol% of dimer acid as a dicarboxylic acid component and 100 mol% of ethylenediamine as a diamine component, and has an acid value of 10.0 mgKOH/g, an amine value of 0.1 mgKOH/g, and a softening point of 110° C., 200. A polyamide resin having a melt viscosity of 1,100 mPa·s at °C.

[Dimer acid-based polyamide resin (P-2)]
As the dicarboxylic acid component, 85 mol% of dimer acid and 15 mol% of azelaic acid are contained, and as the diamine component, 50 mol% of piperazine and 50 mol% of ethylenediamine are contained, and the acid value is 15.0 mgKOH/g and the amine value is A polyamide resin having 0.3 mgKOH/g, a softening point of 158° C., and a melt viscosity of 10,000 mPa·s at 200° C.

[Dimer acid-based polyamide resin (P-3)]
As the dicarboxylic acid component, 60 mol% of dimer acid and 40 mol% of azelaic acid are contained, and as the diamine component, 50 mol% of piperazine and 50 mol% of ethylenediamine are contained, and the acid value is 10.5 mgKOH/g and the amine value is A polyamide resin having 0.1 mgKOH/g, a softening point of 165° C., and a melt viscosity at 230° C. of 3,800 mPa·s.

[Dimer acid-based polyamide resin (P-4)]
As the dicarboxylic acid component, 90 mol% of dimer acid, 10 mol% of azelaic acid, 50 mol% of piperazine and 50 mol% of ethylenediamine as diamine components, the acid value is 33.0 mgKOH/g, and the amine value is A polyamide resin having 0.2 mgKOH/g and a softening point of 130°C.

[Dimer acid-based polyamide resin (P-5)]
It contains 100 mol% of dimer acid as a dicarboxylic acid component and 100 mol% of ethylenediamine as a diamine component, and has an acid value of 2.5 mgKOH/g, an amine value of 0.1 mgKOH/g and a softening point of 115°C. Polyamide resin.

[Dimer acid-based polyamide resin (P-6)]
As the dicarboxylic acid component, 90 mol% of dimer acid and 10 mol% of azelaic acid are contained, and as the diamine component, 70 mol% of piperazine and 30 mol% of ethylenediamine are contained, and the acid value is 5.0 mgKOH/g and the amine value is A polyamide resin having 0.1 mg KOH/g and a softening point of 140°C.

[Dimer acid-based polyamide resin aqueous dispersion (E-1)]
In a hermetically sealed 1 liter glass container with a stirrer and a heater, 75.0 g of dimer acid type polyamide resin (P-1), 37.5 g of isopropanol (IPA), 37.5 g of tetrahydrofuran (THF), 7 Charged 0.2 g of N,N-dimethylethanolamine and 217.8 g of distilled water. While stirring at a rotation speed of 300 rpm, the inside of the system was heated and heated and stirred at 120° C. for 60 minutes. Then, the mixture was cooled to around room temperature (about 30° C.) with stirring, 100 g of distilled water was added, and then the mixture was filtered with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) while slightly applying pressure. The obtained aqueous dispersion was placed in a 1 L eggplant flask, depressurized using an evaporator while being placed in a hot water bath heated to 80° C., and about 100 g of a mixed medium of IPA, THF and water was distilled off to obtain a milky white uniform dimer acid. A system polyamide resin aqueous dispersion (E-1) was obtained. The solid content concentration of E-1 was 20 mass %, the number average particle size of the resin in the dispersion was 0.040 μm, the pH was 10.4, and the viscosity was 36 mPa·s.

[Production of Aqueous Dispersion of Dimer Acid Polyamide Resin (E-2)]
In a pressure-resistant 1 liter glass container with a stirrer and a heater, which can be sealed, 75.0 g of dimer acid type polyamide resin (P-2), 93.8 g of IPA, 6.0 g of N,N-dimethylethanolamine and 200 Charged 0.3 g of distilled water. While stirring at a rotation speed of 300 rpm, the inside of the system was heated and heated and stirred at 120° C. for 60 minutes. Then, the mixture was cooled to around room temperature (about 30° C.) with stirring, added with 130 g of distilled water, and then filtered with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) while slightly applying pressure. The obtained aqueous dispersion was placed in a 1 L eggplant flask, depressurized using an evaporator while being placed in a hot water bath heated to 80° C., and about 130 g of a mixed medium of IPA and water was distilled off to obtain a milky white uniform dimer acid polyamide. An aqueous resin dispersion (E-2) was obtained. The solid content concentration of E-2 was 20% by mass, the number average particle diameter of the resin in the dispersion was 0.052 μm, the pH was 10.6, and the viscosity was 30 mPa·s.

[Production of Dimer Acid-Based Polyamide Resin Aqueous Dispersion (E-3)]
In a pressure-resistant 1 liter glass container with a stirrer and a heater, which can be sealed, 110.0 g of dimer acid-based polyamide resin (P-3), 110.0 g of IPA, 110.0 g of THF, 9.2 g of N,N were added. Dimethylethanolamine, 11.0 g of toluene, and 199.8 g of distilled water were charged. While stirring at a rotation speed of 300 rpm, the inside of the system was heated and heated and stirred at 120° C. for 60 minutes. Then, the mixture was cooled to around room temperature (about 30° C.) with stirring, 330 g of distilled water was added, and then filtered with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) while slightly applying pressure. The obtained aqueous dispersion was placed in a 1 L eggplant flask, depressurized using an evaporator while being immersed in a hot water bath heated to 80° C., and about 330 g of a mixed medium of IPA, THF, toluene and water was distilled off to obtain a milky white uniform A dimer acid-based polyamide resin aqueous dispersion (E-3) was obtained. The solid content concentration of E-3 was 20 mass %, the number average particle size of the resin in the dispersion was 0.065 μm, the pH was 10.3, and the viscosity was 8 mPa·s.

[Production of Aqueous Dispersion of Dimer Acid Polyamide Resin (E-4)]
In a pressure-resistant 1 liter glass container with a stirrer and a heater, which can be sealed, 110.0 g of dimer acid-based polyamide resin (P-4), 110.0 g of IPA, 110.0 g of THF, 28.9 g of N,N. Dimethylethanolamine, 11.0 g of toluene, and 180.1 g of distilled water were charged. While stirring at a rotation speed of 300 rpm, the inside of the system was heated and heated and stirred at 120° C. for 60 minutes. Then, the mixture was cooled to around room temperature (about 30° C.) with stirring, 330 g of distilled water was added, and then filtered with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) while slightly applying pressure. The obtained aqueous dispersion was placed in a 1 L eggplant flask, depressurized using an evaporator while being immersed in a hot water bath heated to 80° C., and about 330 g of a mixed medium of IPA, THF, toluene and water was distilled off to obtain a milky yellow uniform A dimer acid-based polyamide resin aqueous dispersion (E-4) was obtained. The solid content concentration of E-4 was 20 mass %, the number average particle diameter of the resin in the dispersion was 0.038 μm, the pH was 10.3, and the viscosity was 55 mPa·s.

[Production of Aqueous Dispersion of Dimer Acid Polyamide Resin (E-5)]
A hermetically sealed pressure-resistant 1 liter glass container equipped with a stirrer and a heater was used, and 75.0 g of dimer acid polyamide resin (P-5), 37.5 g of IPA, 37.5 g of THF, 1.4 g of N,N were used. -Dimethylethanolamine and 217.8 g of distilled water were charged. While stirring at a rotation speed of 300 rpm, the inside of the system was heated and heated and stirred at 120° C. for 60 minutes. Then, the mixture was cooled to around room temperature (about 30° C.) with stirring, 100 g of distilled water was added, and then the mixture was filtered with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) while slightly applying pressure. The obtained aqueous dispersion was placed in a 1 L eggplant flask, depressurized using an evaporator while being placed in a hot water bath heated to 80° C., and about 100 g of a mixed medium of IPA, THF and water was distilled off to obtain a milky white uniform dimer acid. A system polyamide resin aqueous dispersion (E-5) was obtained. The solid content concentration of E-5 was 21% by mass, the number average particle diameter of the resin in the dispersion was 0.150 μm, the pH was 10.1, and the viscosity was 10 mPa·s.

[Production of Aqueous Dispersion of Dimer Acid Polyamide Resin (E-6)]
In a pressure-resistant 1 liter glass container with a stirrer and a heater, which can be sealed, 75.0 g of dimer acid polyamide resin (P-6), 75.0 g of IPA, 75.0 g of THF, 6.0 g of N,N. Dimethylethanolamine, 7.5 g of toluene and 136.5 g of distilled water were charged. The system was heated while stirring at a rotation speed of 300 rpm, and heated and stirred at 130° C. for 60 minutes. Then, the mixture was cooled to around room temperature (about 30° C.) with stirring, added with 230 g of distilled water, and then filtered with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) while slightly applying pressure. The obtained aqueous dispersion was placed in a 1 L eggplant flask, depressurized using an evaporator while being immersed in a hot water bath heated to 80° C., and about 230 g of a mixed medium of IPA, THF, toluene and water was distilled off to obtain a milky white uniform mixture. An aqueous polyamide resin dispersion (E-2) was obtained. The solid content concentration of E-6 was 20.9 mass %, the number average particle diameter of the resin in the dispersion was 0.130 μm, the pH was 10.9, and the viscosity was 3 mPa·s.

[Polyolefin resin (R-1)]
Bondein LX4110 manufactured by Sumitomo Chemical Co., Ltd. was used as the polyolefin resin (R-1).

[Polyolefin resin aqueous dispersion (N-1)]
A hermetically sealed 1 liter glass container equipped with a stirrer and a heater was charged with 60.0 g of polyolefin resin (R-1), 28.0 g of IPA, 1.5 g of TEA and 210.5 g of distilled water in a glass container. When the mixture was charged and stirred at a rotation speed of a stirring blade of 300 rpm, no precipitation of resin particles was observed at the bottom of the container and it was confirmed that the resin particles were in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the temperature in the system was kept at 140° C., and the mixture was further stirred for 20 minutes. Then, after soaking in a water bath and cooling to room temperature (about 25° C.) while stirring at a rotation speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) is performed. Then, a milky white uniform polyolefin resin aqueous dispersion (N-1) was obtained.

The following materials were used as the resin constituting the resin layer and the resin layer.
[Semi-aromatic polyamide (PA9T)]
1264 g of 1,9-nonanediamine (NMDA), 316 g of 2-methyl-1,8-octanediamine (MODA), 1627 g of terephthalic acid (TPA) (average particle size: 80 μm) (NMDA:MODA:TPA=80: 20:99, molar ratio), 48.2 g of benzoic acid (4.0 mol% with respect to the total number of moles of dicarboxylic component and diamine component), 3.2 g of phosphorous acid (total amount of dicarboxylic component and diamine component) 0.1% by mass), 1100 g of water was put into the reactor and purged with nitrogen. Furthermore, after stirring at 80° C. for 0.5 hours at 28 rpm, the temperature was raised to 230° C. Then, it heated at 230 degreeC for 3 hours. Then, it was cooled and the reaction product was taken out. After pulverizing the reaction product, it was heated in a dryer under a nitrogen stream at 220° C. for 5 hours to perform solid phase polymerization to obtain a polymer. Then, the mixture was melted and kneaded at a cylinder temperature of 320° C. and extruded in a strand shape. Then, it cooled and cut|disconnected and the pellet-shaped semi-aromatic polyamide (PA9T) was prepared.

[Semi-aromatic polyamide (PA9T) film]
100 parts by weight of semi-aromatic polyamide (PA9T), and 0.2 parts by weight of 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-. 1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (Sumilyzer GA-80 manufactured by Sumitomo Chemical Co., Ltd., thermal decomposition temperature 392°C) was heated to a cylinder temperature of 320°C. It was put into a single-screw extruder having a screw diameter of 50 mm and melted to obtain a molten polymer. The molten polymer was filtered using a metal fiber sintered filter (NF-10 manufactured by Nippon Seisen Co., Ltd., filtration accuracy 30 μm). Then, it was extruded into a film form from a T-die at 320° C. to obtain a film-like melt. The melt was brought into close contact with a cooling roll set at 50° C. by an electrostatic application method and cooled to obtain a substantially non-oriented unstretched film (thickness 250 μm).
Next, while holding both ends of the unstretched film with clips, the unstretched film was guided to a tenter system simultaneous biaxial stretching machine (entrance width: 193 mm, outlet width: 605 mm) to perform simultaneous biaxial stretching. As for the stretching conditions, the temperature of the preheating part is 120° C., the temperature of the stretching part is 130° C., the MD stretching strain rate is 2400%/min, the TD stretching strain rate is 2760%/min, and the MD stretching ratio is 3.0. And the TD stretch ratio was 3.3.
Then, heat setting was performed at 270° C. in the same tenter, and a relaxation treatment of 5% was performed in the width direction of the film to obtain a biaxially stretched film having a thickness of 25 μm.
The obtained biaxially stretched semi-aromatic polyamide (PA9T) film (thickness 25 μm) was used as a resin layer.
In addition, the same operation was performed except that the thickness of the unstretched film was changed to 500 μm to obtain a biaxially stretched semi-aromatic polyamide (PA9T) film (thickness 50 μm), which was also used as a resin layer.

[Semi-aromatic polyamide (PA10T)]
A semi-aromatic polyamide (PA10T) was prepared in the same manner as the semi-aromatic polyamide (PA9T) except that 1,720 g of 1,10-decanediamine was used as the diamine.

[Semi-aromatic polyamide (PA10T) film]
A film was obtained in the same manner as the semi-aromatic polyamide (PA9T) film, except that the semi-aromatic polyamide (PA9T) was changed to the semi-aromatic polyamide (PA10T). The obtained semi-aromatic polyamide (PA10T) film was used as a resin layer.

[Semi-aromatic polyamide (PA6T) film]
A film was obtained in the same manner as the semi-aromatic polyamide (PA9T) film, except that the semi-aromatic polyamide (PA9T) was changed to nylon 6T (PA6T) (Aren E manufactured by Mitsui Chemicals, Inc.). The obtained semi-aromatic polyamide (PA6T) film was used as a resin layer.

[Polyimide (PI) film]
A polyimide (PI) film (Kapton 100H manufactured by Toray-Dupont, thickness 25 μm) was used as a resin layer.

[Polyetherimide (PEI) film]
A polyetherimide (PEI) film (Superiot, thickness 25 μm, manufactured by Mitsubishi Plastics, Inc.) was used as a resin layer.

[Polyethylene terephthalate (PET) film]
A polyethylene terephthalate (PET) film (Emblet S-25 manufactured by Unitika Ltd., thickness 25 μm) was used as a resin layer.

[Nylon 6 (N6) film]
Nylon 6 (N6) film (Emblem ON-25 manufactured by Unitika Ltd., thickness 25 μm) was used as a resin layer.

[Nylon 66 (N66) film]
A film was obtained in the same manner as the semi-aromatic polyamide (PA9T) film, except that the semi-aromatic polyamide (PA9T) was changed to nylon 66 (N66) (UBE nylon 66 manufactured by Ube Industries, Ltd.). The obtained nylon 66 (N66) film was used as a resin layer.

[Polypropylene (PP) film]
A polypropylene (PP) film (OPU-1, manufactured by Mitsui Chemicals Tohcello, thickness 25 μm) was used as a resin layer.

Example 1
Dimer acid-based polyamide resin aqueous dispersion (E-1) and oxazoline group-containing polymer aqueous solution (Nippon Shokubai Co., Ltd. Epocros WS-700, solid content concentration 25 mass%), each solid content was 100 parts by mass. It was blended so as to be 10 parts by mass, and mixed and stirred at room temperature for 5 minutes to obtain a coating material for forming an adhesive layer.
As the resin layer, a semi-aromatic polyamide (PA9T) film was used, and the above coating composition was dried and applied in a thickness of 3 μm and dried under the conditions of 150° C. and 30 seconds to laminate an adhesive layer on the resin layer. ..
Then, an electrolytic copper foil (Furukawa Electric Co., Ltd. surface CTS treatment, thickness 18 μm) was superposed on the surface of the adhesive layer and pressed with a heat press machine (180° C., 15 minutes, 2 MPa) to bond the metal plate and the adhesive. A layered product A (180° C.×15 min pressed product) including a layer and a resin layer in that order was obtained.
Further, pressing was performed with a heat press machine (200° C., 120 minutes, 2 MPa) to obtain a laminate B (200° C.×120 min pressed product) including a metal plate, an adhesive layer, and a resin layer in this order.

Examples 2 to 22, Comparative Examples 4 to 13
Same as Example 1 except that the type of the aqueous dispersion, the type and amount of the crosslinking agent, the thickness after drying, the type of resin of the resin layer, and the type of metal of the metal plate are as shown in Table 1. The operation was performed to obtain a laminated body.
In Example 4, an aluminum foil (A1N30, 15 μm, manufactured by Toyo Aluminum Co., Ltd.) was used as the metal plate, and in Example 5, a stainless foil (SUS-304-H-TA manufactured by Nisshin Steel Co., Ltd.) was used. , Thickness 20 μm) was used.
Further, in Example 7, a carbodiimide compound (Carbodilite series E-01, manufactured by Nisshinbo Chemical Co., solid content 40% by mass) was used as a crosslinking agent.
In Example 8, a dicyclopentadiene type epoxy resin (ADEKA Resin EP-4088S manufactured by ADEKA) was used as the epoxy compound (Q-1), and in Example 9, the epoxy compound (Q-2) was used as bisphenol A. The type epoxy compound (ADEKA RESIN EM-051R manufactured by ADEKA) was added to each of the dimer acid-based polyamide resin aqueous dispersions (E-1).

Examples 23 and 24, Comparative Examples 1 and 2
100 parts by mass of an epoxy compound (Q-3) (epoxy resin jER1001 manufactured by Mitsubishi Chemical Co., Ltd.) and 20 parts by mass of diaminodiphenyl sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing accelerator, methyl ethyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.). Was dissolved and dispersed in to obtain an adhesive layer-forming coating material having a concentration of 40%. A laminate was obtained in the same manner as in Example 1 except that this adhesive layer-forming coating material was applied to the resin layer shown in Table 1 by a wire bar so that the thickness after drying would be the value shown in Table 1. ..

Example 25
Same as Example 24 except that 100 parts by mass of the epoxy compound (Q-3) and 30 parts by mass of diaminodiphenyl sulfone were dissolved and dispersed in methyl ethyl ketone to prepare an adhesive layer-forming coating agent having a concentration of 40%. A laminate was obtained.

Comparative Example 3
In Comparative Example 3, a hot melt resin (STAYSTIK #383 manufactured by Techno Alpha Co., Ltd.) was heated and then made to have a thickness of 15 μm, and a laminate was obtained in the same manner as in Example 1.

Tables 1 to 4 show the configurations of the laminates in Examples and Comparative Examples and the evaluation results of the properties.

The laminates of Examples had excellent adhesiveness even after the heat cycle test, and did not cause blistering or peeling after the heat resistance test.
In Comparative Examples 1 and 2, the laminate A, which has a low press temperature during metal plate lamination and a short press time, has low adhesiveness, and even when the press temperature during metal plate lamination is increased and the press time is increased. The laminate B had low adhesiveness after the heat cycle test.
In Comparative Example 3 in which the adhesive layer is a hot-melt resin, the laminate A obtained by lowering the pressing temperature at the time of laminating the metal plates and shortening the pressing time has a decreased adhesiveness of the hot-melt resin in the heat cycle test. did. Further, when the pressing temperature at the time of laminating the metal plates was increased and the pressing time was lengthened, the hot melt resin flowed out, so that the laminated body B could not be obtained.
Since the laminates of Comparative Examples 4 and 5 did not use the adhesive layer specified in the present invention, the peel strength after the heat cycle test was low, and blisters were observed after the heat resistance test.
The resin layers of Comparative Examples 6 and 7 in which the constituent resin was polypropylene were inferior in heat resistance and melted at the time of pressing, so that the laminate A and the laminate B could not be obtained.
Further, in the resin layers of Comparative Examples 8 to 13 in which the constituent resin was nylon 6, nylon 66, or polyethylene terephthalate, both blistering and peeling were observed in the heat cycle test, so the peel strength of the laminate can be measured. could not.

Claims (4)

A laminated body containing at least a metal plate, an adhesive layer, and a resin layer, and these layers being laminated in this order,
The resin constituting the resin layer is a semi-aromatic polyamide or polyimide resin,
The adhesive layer contains a dimer acid-based polyamide resin and/or an epoxy compound,
A laminate having a peel strength of 6 N/25 mm or more between a metal plate and a resin layer after a heat cycle test under the following conditions.
Heat cycle test conditions:
A cycle in which the laminated body is held at −20° C. for 30 minutes, heated to 150° C. over 2 hours, held at 150° C. for 30 minutes, and then cooled again to −20° C. over 2 hours is defined as one cycle. , This is repeated 100 cycles. The laminate according to claim 1, wherein the diamine component of the semi-aromatic polyamide contains a diamine having 9 or 10 carbon atoms. The acid value of a dimer acid type polyamide resin is 3-12 mgKOH/g, The laminated body of Claim 1 characterized by the above-mentioned. An electric or electronic component using the laminate according to claim 1.