JP2006044224A - Laminated body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated body suitably usable as machine parts, car parts or the like and good in sliding property, surface scratching resistance, heat resistance, adhesion to a metal and further less susceptible to peeling of a cut edge on shearing processing. <P>SOLUTION: The laminated body has a metal contacting layer and a surface layer laminated in order on at least one surface of a metallic body and the metal contacting layer is comprised of a resin composition containing a resin component of 100 mass parts comprising (A) a thermoplastic polyimide resin and (B) a polyarylketone resin in a ratio of (A)/(B)= 95/5-5/95 by mass ratio, (C) a filler of 0-100 mass parts and/or (D) a solid lubricant of 0-100 mass parts, and the surface layer is comprised of a resin composition containing (B) a polyarylketone resin of 100 parts mass and (C) the filler of 0-100 parts mass and/or (D) the solid lubricant of 0-100 parts mass. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminate of a thermoplastic resin composition and a metal having excellent adhesion between layers, and in particular, there is little peeling at the cut end due to slidability, heat resistance, surface scratch resistance, shearing, etc. In addition, the present invention relates to a laminate that has good chemical resistance and can be suitably used as a machine member, an automobile part, or the like.

Resin-coated metals in which metal surfaces are coated with resins containing various solid lubricants are used as mechanical members, automobile parts, and the like that are required to have slidability, heat resistance, and surface scratch resistance. As a method of coating, a method of solvent coating on a metal surface using a thermosetting resin such as a polyimide resin or a polyamideimide resin is common. However, the solvent coating method has a problem that the solvent used at the time of coating is volatilized and easily affects the environment, and other methods that do not use a solvent are desired.
As a specific method, the use of a thermoplastic resin excellent in recyclability instead of a thermosetting resin has been studied, and among these thermoplastic resins, in particular, a polyether ether ketone resin or a polyether ketone resin. Such polyaryl ketone resins are excellent in heat resistance, flame retardancy, chemical resistance, etc., and are therefore widely used mainly in aircraft parts, automobile parts, machine parts, and electrical / electronic parts.
However, a polyaryl ketone resin alone is difficult to adhere to a metal, so that it is difficult to laminate on a metal surface.
Usually, as a method of laminating the polyaryl ketone resin on a metal surface, solvent coating is extremely difficult because it is hardly dissolved in a solvent, and a thermal spraying method (HVOF process, for example, see Patent Document 1), powder The painting method (for example, refer patent document 2) is examined.
However, in the HVOF process, fuel gas such as hydrogen and oxygen gas are used for thermal spraying the polyaryletherketone resin, and internal combustion is used. Yes, in order to laminate the polyaryl ether ketone resin on the surface of the metal body in the powder coating method, after the polyaryl ether ketone resin powder is attached to the surface of the metal body, for example, high temperature baking at about 400 ° C. is required Since heating and cooling take time and production efficiency is not good, there is a problem that the production cost at the time of baking is high. Further, since the resin layer is formed by fusing powder, internal voids and pinholes are likely to occur in the resin layer. Furthermore, there is a problem that annealing occurs in aluminum and the strength of the aluminum base material decreases.

On the other hand, in an electronic circuit board substrate that requires lamination on a metal surface such as copper foil or aluminum foil, in order to take advantage of the heat resistance as a crystalline resin having a high melting point, the adhesion between the polyaryl ketone resin and the metal is Mixtures with good polyetherimide resins have been noted.
For example, it is disclosed that this mixture exhibits good adhesion with a copper foil and is useful for a circuit board substrate (see, for example, Patent Document 3). Furthermore, the laminated body with a printed wiring board and a metal body using this mixture, its manufacturing method, and a heat-fusible insulating sheet are disclosed (for example, refer patent document 4 and patent document 5).
However, the mixture of polyarylketone resin and polyetherimide resin has good adhesion to metal, but there is a limit to chemical resistance such as wear resistance and alkali resistance and slidability. In the field of automobile parts and the like, it is not always sufficient, and there are limits to applications.

JP 2002-39203 A JP 2003-48273 A JP 59-115353 A JP 2002-212314 A Japanese Patent No. 3514667

  The present invention has been made in view of the above circumstances, and is suitable as a machine part, an automobile part, etc., particularly excellent in adhesion between a metal body and a thermoplastic resin layer, and excellent in slidability, heat resistance, and chemical resistance. Another object of the present invention is to provide a laminate of a thermoplastic resin and a metal.

As a result of intensive studies, the present inventors have found that at least one surface of the metal body has (A) a metal contact layer containing a thermoplastic polyimide resin and (B) a polyaryl ketone resin, and (B) a polyaryl. The present inventors have found that a laminate obtained by sequentially laminating a surface layer containing a ketone resin can solve the above problems, and based on this finding, the present invention has been completed.
That is, this invention provides the following laminated bodies.
(1) A laminate in which a metal contact layer and a surface layer are sequentially laminated on at least one surface of a metal body, wherein the metal contact layer comprises (A) a thermoplastic polyimide resin and (B) a polyaryl ketone resin. A laminate comprising the resin composition comprising the resin composition, wherein the surface layer comprises a resin composition comprising the polyaryl ketone resin (B).
(2) The laminate according to (1), wherein the metal contact layer and / or the surface layer further comprises (C) a resin composition containing a filler.
(3) The laminate according to (1) or (2), wherein the metal contact layer and / or the surface layer further comprises (D) a resin composition containing a solid lubricant.
(4) 100 parts by mass of a resin composition in which the metal contact layer contains (A) a thermoplastic polyimide resin and (B) a polyarylketone resin at a mass ratio of (A) / (B) = 95/5 to 5/95. And (D) a resin composition containing 0 to 100 parts by mass of a filler and / or (D) a solid lubricant in a proportion of 0 to 400 parts by mass, and the surface layer is (B) a polyaryl ketone resin. Said (1)-(3) which consists of a resin composition which contains 0-100 mass parts of (C) filler and / or (D) 0-100 mass parts of solid lubricant with respect to 100 mass parts. The laminate according to any one of the above.
(5) 100 parts by mass of a resin composition in which the metal contact layer contains (A) a thermoplastic polyimide resin and (B) a polyaryl ketone resin in a mass ratio of (A) / (B) = 95/5 to 30/70. Or (D) any one of (1) to (3) above, comprising a resin composition containing 0 to 100 parts by mass of filler and / or (D) 0 to 100 parts by mass of solid lubricant. The laminate according to Item 1.
(6) The laminate according to any one of (1) to (5), wherein the thickness ratio between the metal contact layer and the surface layer is in the range of 1/99 to 99/1.
(7) Any one of the above (1) to (5), wherein the thickness of the metal body is 0.01 to 50 mm, the thickness of the metal contact layer is 0.1 to 800 μm, and the thickness of the surface layer is 1 to 1000 μm. The laminate according to Item.

(8) A polyetherimide resin having a repeating unit represented by the following structural formula (2) or a polyetherimide resin having a repeating unit represented by the following structural formula (2), wherein the thermoplastic polyimide resin of component (A) Wherein the polyaryl ketone resin as the component (B) is mainly composed of a crystalline polyetheretherketone resin having a repeating unit represented by the following structural formula (3) ( The laminate according to any one of 1) to (7).

(9) The laminate according to any one of (2) to (8), wherein the filler of component (C) is plate-shaped.
(10) The laminate according to any one of (2) to (9), wherein the average particle size of the filler of component (C) is in the range of 0.01 to 200 μm.
(11) The laminate according to any one of (2) to (10), wherein the filler of component (C) is mica.
(12) The laminate according to any one of (3) to (8), wherein the solid lubricant of component (D) is at least one selected from graphite, fluororesin, and transition metal sulfide.

According to the present invention, it has excellent adhesion to metal, heat resistance, solvent resistance, surface scratch resistance, slipperiness, slidability, and can be suitably used as a machine member, automobile part, etc. A laminate of a thermoplastic resin and a metal can be provided.
In addition, because it can be formed at a low temperature, it is possible to form a sliding layer made of a polyaryl ketone resin composition even for sliding parts made of metal materials that could not be used due to problems such as a decrease in metal substrate hardness. It becomes.
Furthermore, compared with conventional sliding parts such as resin coating by the solvent coating method, since no solvent is used, there is no volatilization diffusion of the solvent to the environment, and the environmental load can be reduced.

The laminate of the present invention is a laminate of a thermoplastic resin and a metal, and is a laminate in which a metal contact layer made of a thermoplastic resin composition and a surface layer are sequentially laminated on at least one surface of the metal body. .
As the metal body used in the present invention, iron, chromium, nickel, zinc, aluminum, aluminum alloy, aluminum-silicon alloy, magnesium, magnesium alloy, titanium, titanium alloy, copper, silver, gold, brass, brass, bronze, Examples thereof include stainless steel, carbon steel, cast iron, superalloy (for example, NCF800, NCF600) and the like. Further, steel materials obtained by plating iron or carbon steel with zinc, tin, chromium, nickel, zinc-aluminum, or the like can also be used. Of these, iron, cast iron, carbon steel, stainless steel, aluminum, and aluminum alloy are preferable from the viewpoint of high rigidity and low cost. Furthermore, stainless steel, aluminum, and an aluminum alloy are more preferable from the viewpoint that rust hardly occurs.

  Stainless steel has various alloy compositions, for example, SUS301, SUS301L, SUS302, SUS302B, SUS303, SUS303Se, SUS304, SUS304L, SUS304J1, SUS304J2, SUS305, SUS309S, SUS310S, SUS316, SUS316L, SUS317, SUS32, SUS329J1, SUS329J3L, SUS329J4L, SUS343, SUS403, SUS405, SUS410, SUS430, SUS434, SUS436L, SUS436J1L, SUS444, SUS447J1, SUS304cul, SUSXM7, USXM27, USXM27 L, and the like.

  Examples of aluminum and aluminum alloy include JIS H2118-2000, JIS H2211-1999, JIS H4000-1999, JIS H4040-1999, JIS H4080-1999, JIS H4090-1990, JIS H4100-1999, JIS H4140-1988, JIS. The alloy number shown in H5202-1999, JIS H5302-1999, and the classification symbol shown in JIS H0001-1998 can be mentioned, specifically, A1050, A1070, A1080, A1085, A1100, A1200. A1N00, A3203, A2011, A2014, A2017, A2023, A2024, A2219, A3003, A3004, A3104, A3203, A40 32, A4043, A5005, A5052, A5056, A5083, A5086, A5454, A5652, A5N01, A6005A, A6060, A6061, A6063, A6082, A6N01, A7005, A7020, A7050, A7075, A7N01, A8021, A8021, A8079, AC80B AC4A, AC4B, AC4C, AC4D, AC5A, AC7A, AC8A, AC8B, AC8C, AC9A, AC9B, ADC1, ADC2, ADC3, ADC5, ADC6, ADC8, ADC10, ADC12, ADC14, A390, BA11, BA12, and the like. Moreover, what added rolling, extension, and heat processing to the said metal can be used.

Although the shape of a metal body is not specifically limited, For example, a flat body, a curved body, a corrugated body, a cylinder, a tubular body, a disk shape etc. are mentioned. Among these, it is a flat body that can be easily processed, and examples of the flat body include a single wafer, a continuous strip (coil), and the like. Although the thickness of a metal body is not specifically limited, From the ease of a process, it is about 0.01-50 mm normally, Preferably, it is about 0.05-20 mm, More preferably, it is about 0.1-15 mm.
The surface finish of the metal body can be performed by various methods. Examples of the treated surface include surfaces subjected to treatment such as rolling treatment, heat treatment, pickling treatment (for example, JIS G0203-2000, JIS G4305). -1999, No. 1, No. 2D, No. 2B defined in AISI standards, etc., and further polished surfaces (for example, No. 3, No. 4, No. 4, # 240, # 320, # 400), surface subjected to cold rolling and brightening treatment (for example, BA defined in the above standards), polished surface (for example, hairline defined in the above standards, etc.) HL, No. 7 which is a vibration meaning non-directional hairline polishing finish, No. 8) which is a mirror finish. Other surface treatment methods include shot blasting by blasting, silver-white dull finish, bead blasting, satin finish by blasting, bright finish, chemical coloring, embossing, etching, plating with a metal different from the base Finishing (for example, plating with gold, silver, copper, aluminum, chromium, etc.) and the like can be mentioned.

Among these, the surface roughness parameter specified in JIS B0601-1994 has a ten-point average roughness (Rz) of about 0.01 to 80 μm, more preferably 0.4 to 20 μm. It is about. When Rz is 0.01 μm or more, the adhesion between the thermoplastic resin and the metal contact layer containing the filler is good, and when Rz is 80 μm or less, the influence on the irregularities of the surface layer is small.
Further, the maximum height (Ry) of the surface roughness parameter defined in JIS B0601-1994 is usually in the range of about 0.01 to 100 μm, and preferably about 0.5 to 25 μm. When Ry is 0.01 μm or more, the adhesive strength between the surface of the metal body and the metal contact layer is good, and when it is 100 μm or less, the influence on the unevenness of the surface layer is small.
Similarly, the arithmetic mean roughness (Ra) of the surface roughness parameter defined in JIS B0601-1994 of the metal body is usually in the range of about 0.001 to 10 μm, preferably about 0.05 to 2.5 μm. Range.
The surface roughness (Rz, Ry, Ra) specified in JIS B0601-1994 is a commercially available surface roughness measuring device (as an example, a surface roughness measuring device manufactured by Kosaka Laboratory Ltd., model SE3-FK, etc.). Can be measured using.

  The metal contact layer which comprises the laminated body of this invention consists of a resin composition containing (A) thermoplastic polyimide resin and (B) polyaryl ketone resin. The thermoplastic polyimide resin of component (A) is a thermoplastic resin containing an aromatic nucleus bond and an imide bond in its structural unit, and specific examples include polyetherimide resin, but are not particularly limited. Specifically, the following structural formula (1)

[Product name “Ultem 1000” (glass transition temperature Tg: 216 ° C.), “Ultem 1010” (glass transition temperature: 216 ° C.) manufactured by General Electric Co., Ltd.]], the following structural formula (2)

And a polyetherimide having a repeating unit represented by the formula [trade name “Ultem CRS5001” (glass transition temperature: 226 ° C.) manufactured by General Electric Co., Ltd.]. ULTEM XH6050 ”(glass transition temperature: 247 ° C.), trade name“ Aurum PL500AM ”(glass transition temperature: 258 ° C.) manufactured by Mitsui Chemicals, Inc., and the like. Among these, it is preferably an amorphous one, and more preferably a polyetherimide resin having a repeating unit represented by the structural formula (1) or (2) as a main component. Here, the main component means a resin component whose content exceeds 50% by mass.
The method for producing the polyetherimide resin is not particularly limited. Usually, the amorphous polyetherimide resin having a repeating unit represented by the structural formula (1) is 4,4 ′-[isopropylene. As a polycondensate of redenebis (p-phenyleneoxy) diphthalic dianhydride and m-phenylenediamine, an amorphous polyetherimide resin having a repeating unit represented by the above structural formula (2) is 4 4,4 '-[isopropylidenebis (p-phenyleneoxy) diphthalic dianhydride and p-phenylenediamine can be synthesized by a known method.
Moreover, the polyetherimide resin used in the present invention may contain other monomer units having a copolymerizable group such as an amide group, an ester group, and a sulfonyl group as necessary. In addition, the thermoplastic polyimide resin of (A) component can be used individually by 1 type or in combination of 2 or more types.

  In the laminate of the present invention, the component (B) polyaryl ketone resin used in the metal contact layer is a thermoplastic resin containing an aromatic nucleus bond, an ether bond and a ketone bond in its structural unit. , Polyether ketone (glass transition temperature: 157 ° C., crystal melting peak temperature: 373 ° C.), polyether ether ketone (glass transition temperature: 143 ° C., crystal melting peak temperature: 334 ° C.), polyether ether ketone ketone (glass transition Temperature, 153 ° C., crystal melting peak temperature: 370 ° C.) and the like, and may contain other repeating units having a copolymerizable structure or group such as a biphenyl structure or a sulfonyl group, if necessary. Absent. In the present invention, the following structural formula (3)

What has a polyether ether ketone resin which has a repeating unit represented by these as a main component is used suitably. Here, the main component means a component whose content exceeds 50% by mass.
Polyether ether ketones having this repeating unit are commercially available as trade names “PEEK151G”, “PEEK381G”, “PEEK450G”, etc., manufactured by Victrex. All of these have a glass transition temperature of 143 ° C. and a crystal melting peak temperature of 334 ° C. In addition, the polyaryl ketone resin of (B) component can be used individually by 1 type or in combination of 2 or more types.

In the resin composition constituting the metal contact layer according to the present invention, the mixing mass ratio of the thermoplastic polyimide resin (A) and the polyaryl ketone resin (B) is (A) / (B) = 95 / The range of 5-5 / 95 is preferable, more preferably (A) / (B) = 85 / 15-30 / 70, and still more preferably (A) / (B) = 80 / 20-45 / It is in the range of 55, particularly preferably in the range of 85/15 to 50/50.
When the (A) component is 95% by mass or less with respect to the total of 100% by mass of the (A) component and the (B) component, the polyaryl ketone resin of the (B) component has excellent heat resistance and low water absorption Can be demonstrated. Moreover, the adhesiveness of a metal contact layer and a metal body will become favorable as (A) component is 5 mass% or more.
Moreover, when using crystalline polyaryl ketone resin as (B) component, when (A) component is 80 mass% or less with respect to a total of 100 mass% of (A) component and (B) component, The resin composition constituting the contact layer has high crystallinity, a high crystallization speed, and good heat resistance. In the same case, if the component (A) is 55% by mass or more, volume shrinkage (dimensional change) accompanying crystallization of the crystalline polyaryl ketone resin is difficult to increase, and reliability in adhesion to a metal body is high. Is obtained. Accordingly, when a crystalline polyaryl ketone resin is used as the component (B), the mixing mass ratio of the component (A) to the component (B) is (A) / (B) = 75/25. It is preferable to set it to -55/45.

  Here, a resin composition of a polyaryl ketone resin (A) and a polyetherimide resin (B) is used as a metal contact layer on at least one surface of a relatively hard metal plate such as a stainless steel plate having a thickness of 0.4 mm. In the laminate obtained by laminating the polyaryl ketone resin (B) as a surface layer, the adhesion between the metal plate and the resin layer is good, but cannot be cut with a cutter knife, so when cutting with a method such as shearing, Separation may occur at the end. For this reason, in this invention, addition of the filler to a metal contact layer is preferable, and there exists an effect which reduces peeling of an edge part.

As the filler of the component (C) used in the present invention, a known material can be used, for example, a filler such as clay, glass, alumina, silica, aluminum nitride, silicon nitride, glass fiber or aramid fiber, Fibrous fillers such as carbon fibers, scale-like (plate-like) powders such as synthetic mica, natural mica (mascobite, phlogopite, sericite, szolite, etc.), calcined synthetic mica, natural mica, boehmite, talc , Illite, kaolinite, montmorillonite, vermiculite, smectite, plate-like alumina, scaly titanate (for example, scaly magnesium potassium titanate, scaly lithium potassium titanate, etc.). Among these, synthetic mica, natural mica, calcined synthetic mica and natural mica, boehmite, talc, illite, kaolinite, montmorillonite, vermiculite, smectite and other scaly (plate-like) powders, plate-like alumina, scaly A titanate is preferred, and synthetic mica and natural mica are more preferred. These fillers can be used alone or in combination of two or more.
The shape of the filler is preferably a plate shape, and the average particle size is about 0.01 to 200 μm, preferably about 0.1 to 20 μm, more preferably about 1 to 10 μm, and the average aspect ratio (particle size / thickness). ) Is usually about 1 to 100, preferably about 5 to 50, more preferably about 10 to 30.

  As the filler for the component (C), a filler that has been surface-treated with a surface treatment agent may be used. As the surface treatment agent, aminosilane, epoxy silane, vinyl silane, silane coupling agent such as silane compound having acryloxy group or methacryloxy group, linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms in silicon atom 1 or 2 bonded alkoxysilanes, titanate coupling agents, aluminate coupling agents, zirconate coupling agents and the like. The usage-amount of a surface treating agent is 0.1-8 mass parts normally with respect to 100 mass parts of fillers, Preferably it is the range of 0.5-3 mass parts.

Various known methods can be applied as the surface treatment method. For example, after contacting the filler and the surface treatment agent in a solution in which the surface treatment agent is dissolved, the wet method is used to remove the solvent, and the solution and filler in which the surface treatment agent is dissolved is contacted by a method such as spraying or stirring. After the surface treatment agent is applied to the surface of the filler, the semi-wet method for removing the solvent, the thermoplastic resin and the filler and the surface treatment agent or the surface treatment agent dissolved in a small amount of solvent are mixed and then stirred. Examples include the integral blend method. From the viewpoint of efficiently attaching the surface treatment agent to the surface of the filler, a wet method or a semi-wet method is preferable.
The concentration of the surface treating agent in the solvent can be about 0.1 to 80% by mass. As the solvent, for example, isopropyl alcohol, ethanol, methanol, hexane and the like that are easy to remove are preferable. This solvent may contain a small amount of water or a small amount of an acid component that promotes hydrolysis.
By the above surface treatment method, the filler and the surface treatment agent diluted or not diluted in a solvent are contact-mixed, and then left in the air for several hours to several days, and contact with moisture in the air to cause hydrolysis. It is recommended that the used solvent be removed by evaporation.
This evaporation removal treatment is performed under normal pressure or reduced pressure by hydrolyzing alkoxysilyl groups or by dehydrating condensation of the generated hydroxysilyl groups with hydroxyl groups on the surface of the filler and removing the generated alcohol and the solvent used. Below, it is normally performed at about 80 to 150 ° C, preferably about 100 to 130 ° C. The treatment time is usually about 4 to 200 hours, preferably about 24 to 100 hours.
The amount of the filler of component (C) used in the resin composition constituting the metal contact layer is 100 parts by mass of the total amount of the thermoplastic polyimide resin of component (A) and the polyaryl ketone resin of component (B) described above. The amount is preferably 0 to 100 parts by mass, more preferably 10 to 55 parts by mass, and still more preferably 15 to 45 parts by mass. When the filler is 100 parts by mass or less, the metal contact layer does not become extremely brittle. On the other hand, when it is 10 parts by mass or more, peeling of the end portion is reduced when the laminate of the present invention is cut by shearing or the like, adhesion between the metal contact layer and the metal body is improved, and a linear expansion coefficient is increased. The shape stability of the laminate due to the reduction effect is improved.

  The resin composition constituting the metal contact layer may contain a solid lubricant. The solid lubricant in the metal contact layer improves the slidability and wear of the metal contact layer, and has the effect of delaying subsequent wear reaching the metal layer when the surface layer is worn. Moreover, in the resin composition which comprises a metal contact layer by recycling and using the end material, the ear | edge, etc. of the surface film used for the laminated body of this invention, or the laminated film by which the metal contact layer and the surface layer were laminated | stacked A solid lubricant may be mixed. Examples of the solid lubricant contained in the resin composition constituting the metal contact layer and the surface layer include materials such as fluororesin, graphite, transition metal sulfide, and hexagonal boron nitride.

The fluororesin is not particularly limited as long as it is a polymer compound containing a fluorine atom in the molecule, and a known one can be used. As such, for example, (a) polytetrafluoroethylene (PTFE) having a repeating structural unit represented by — (CF ₂ CF ₂ ) — in the molecule; (b) — (CF ₂ CF ₂ )-and-[CF (CF ₃ ) CF ₂ ]-, preferably 99 to 80% by mass of the repeating structural unit represented by-(CF ₂ CF ₂ )- And tetrafluoroethylene-hexafluoropropylene copolymer (FEP) comprising 1 to 20% by mass of a repeating structural unit represented by-[CF (CF ₃ ) CF ₂ ]-; (c) (CF ₂ CF ₂₎ - and - table by (wherein, m is 1-16, preferably in the range of a positive integer ranging from 1 to 10) - _{[CF (OC m F 2 m +} 1) CF 2 ] Having a repeating structural unit, preferably- 99 to 92% by mass of the repeating structural unit represented by (CF ₂ CF ₂ ) — and 1 to 8% by mass of the repeating structural unit represented by — [CF (OC _m F _{2 m + 1} ) CF ₂ ] — A tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), (d) a repeating structural unit represented by-(CF ₂ CF ₂ )-and-(CH ₂ CH ₂ )-in the molecule. Preferably, 90 to 74% by mass of a repeating structural unit represented by — (CF ₂ CF ₂ ) — and 10 to 26% by mass of a repeating structural unit represented by — (CH ₂ CH ₂ ) —. A tetrachloroethylene-ethylene copolymer (ETFE); (e) a chlorotrifluoroethylene having a repeating structural unit represented by-(CFClCF ₂ )-and-(CH ₂ CH ₂ )-in the molecule (F) Polyvinylidene fluoride (PVDF) having a repeating structural unit represented by-(CF ₂ CH ₂ )-in the molecule, and further, these fluororesins are made of this resin. And those containing repeating structural units based on other monomers as long as the essential properties are not impaired.

Examples of other monomers include tetrafluoroethylene (excluding PFA, FEP and ETFE), hexafluoropropylene (excluding FEP), perfluoroalkyl vinyl ether (excluding PFA), and perfluoro. Alkylethylene (alkyl group having 1 to 16 carbon atoms), perfluoroalkyl allyl ether (alkyl group having 1 to 16 carbon atoms), and formula: CF ₂ = CF [OCF ₂ CF (CF ₃ )] _n OCF ₂ ( CF ₂ ) _p Y (wherein Y represents a halogen, n represents an integer of 0 to 5, and p represents an integer of 0 to 2). The amount of repeating structural units based on other monomers is 50% by mass or less, preferably 0.01 to 45% by mass of the polymer.

  Among these fluororesins, preferably, (a) polytetrafluoroethylene (PTFE), (b) tetrafluoroethylene-hexafluoropropylene copolymer (FEP), (c) tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer It is selected from polymers (PFA), more preferably (a) PTFE.

The molecular weight of the fluororesin is not particularly limited, but in the case of PTFE that melts, it is particularly preferable that the melt viscosity is 1 million Pa · s or less at 380 ° C. These fluororesins may be used alone or in combination of two or more.
The fluororesin may be a molding powder or a fine powder for a solid lubricant. Examples of commercially available products of polytetrafluoroethylene include Teflon 7J and TLP-10 manufactured by Mitsui / Dupont Fluorochemicals, Fullon G163 manufactured by Asahi Glass Co., Ltd., Polyflon M15 manufactured by Daikin Industries, Ltd., and Lubron L5. It is done.

Examples of the graphite used as the solid lubricant in the present invention include natural flake graphite, natural earth graphite, artificial graphite, pyrolytic graphite, and the like, preferably natural flake graphite and artificial graphite. Natural scaly graphite is a naturally occurring graphite that contains most of its appearance in the form of plates, scaly, leaves, and needles. The artificial graphite is preferably one obtained by pulverizing a lump obtained by firing a carbon source such as a mixture of coke and pitch at a high temperature, or one having a high degree of crystallinity produced by vapor phase growth. Pyrolytic graphite is obtained by calcinating a carbon source such as coke at a high temperature of about 2500 ° C. to 3000 ° C. These natural flake graphite, artificial graphite, and pyrolytic graphite have less ash, impurities, and volatile components such as silicon dioxide and silicate compounds than natural earth graphite, and are excellent in heat resistance and lubricity. Even when blended in the resin, the resin is hardly deteriorated. The average particle size of the graphite used in the present invention is about 1 to 100 μm, preferably about 4 to 80 μm, more preferably about 5 to 60 μm, as measured by laser diffraction. .
If the average particle size is 100 μm or less, uniform dispersion in the resin component and good molded film appearance can be easily obtained. If the average particle size is 1 μm or more, handling troubles such as powder scattering occur during blending into the resin component and kneading. In the case of melt kneading using an extruder or the like, problems such as unstable measurement due to poor engagement with the screw and poor take-up due to unstable shape of the extrudate are less likely to occur.
The amount of ash content in the graphite used in the present invention is preferably as small as possible, usually 2% by mass or less, and more preferably 0.05 to 1% by mass. When it is in the range of 2% by mass or less, when blended and used in the resin component, thermal degradation of the resin component during processing hardly occurs.
Further, it is preferable that the volatile content in graphite is small, and it is usually 2% by mass or less, preferably 1% by mass or less. When it is in the range of 2% by mass or less, foaming is reduced during melt-kneading with the resin component.
Examples of these commercially available graphite products include trade names CPB-3 (natural scaly graphite), CPB-30, CPB-3000, and trade names CP of Nippon Graphite Industries Co., Ltd. CP, CPB, manufactured by Timcal, Timrex KS-44 (artificial graphite), and the like.

  Examples of the transition metal sulfide used as the solid lubricant in the present invention include molybdenum disulfide and tungsten disulfide. In the thermoplastic resin constituting the metal contact layer and / or the thermoplastic resin constituting the surface layer. In order to disperse the powder, it is preferably a powder. The average particle size is preferably about 0.1 to 20 μm, more preferably about 0.3 to 11 μm. When the average particle size is 0.1 μm or more, handling troubles due to powder scattering or the like hardly occur during melt kneading with the thermoplastic resin component, and when it is 20 μm or less, poor dispersion in the thermoplastic resin component or Defects in film appearance are unlikely to occur.

As specific examples of molybdenum disulfide powder, product name Mori powder A (average particle size 0.5 μm), product name Mori powder B (average particle size 3 μm), product name Mori powder C (average particle size) manufactured by Nippon Graphite Industries Co., Ltd. 0.3-0.4 μm), manufactured by Sumiko Lubricant Co., Ltd., trade name MOS and the like.
Specific examples of tungsten disulfide include Nippon Lubricant Co., Ltd., trade names Tanmic A (average particle size 1 μm), Tanmic B (average particle size 0.6 μm), and the like.
The hexagonal boron nitride (abbreviation: h-BN) is preferably a powder in order to be dispersed in the metal contact layer resin and / or the surface layer resin. The average particle diameter of this is 0.01-100 μm, preferably 0.1-20 μm, more preferably 3-15 μm. When the average particle size is 0.1 μm or more, handling troubles due to powder scattering or the like hardly occur during melt kneading with the resin component, and when it is 100 μm or less, poor dispersion in the resin component or poor film appearance occurs. Hard to happen. The specific surface area is 0.1 to 100 m ² / g, preferably 1 to ²⁰ m ² / g. If the specific surface area is 0.1 m ² / g or more and 100 m ² / g or less, poor dispersion hardly occurs.

  Specific examples of hexagonal boron nitride used as a solid lubricant in the present invention include those sold by Mizushima Alloy Iron Co., Ltd., GE Specialty Materials Japan Co., Ltd. and the like.

Among these solid lubricants of component (D), the above PTFE and natural scaly graphite are more preferable.
The amount of the solid lubricant of the component (D) used in the metal contact layer is 100 parts by mass of the total amount of the thermoplastic polyimide resin of the component (A) and the polyaryl ketone resin of the component (B) described above. 0-100 mass parts is preferable, More preferably, it is 5-55 mass parts, More preferably, it is the range of 10-45 mass parts.
Even if the metal contact layer does not contain the component (D), the adhesion to the metal body and the surface layer is good, but when the component (D) is contained due to the recycling of the edge during film formation, (D ) If the component is 100 parts by mass or less, the metal workability of the metal contact layer is hardly lowered.
When the component (C) and the component (D) are used in combination in the resin composition constituting the metal contact layer, the component (C) and the component (D) with respect to a total of 100 parts by mass of the component (A) and the component (B). The total mass is 0 to 100 parts by mass, preferably 0 to 55 parts by mass. When the total mass of the component (C) and the component (D) is 100 parts by mass or less, problems such as surging during melt-kneading are unlikely to occur.
In the resin composition constituting the metal contact layer, other than (A) component, (B) component resin, (C) component filler, (D) component solid lubricant to the extent that the properties are not impaired These additives, for example, heat stabilizers, ultraviolet absorbers, light stabilizers, nucleating agents, colorants, lubricants, flame retardants and the like may be appropriately blended. Moreover, a well-known method can be used for the mixing method of various additives including the filler of (C) component and the solid lubricant of (D) component.

As an example of the combination of mixing, the example of 3 components of (A) component, (B) component, and (C) component is shown below.
(I) A method of mixing and dispersing the three components (A), (B) and (C) at the same time,
(II) A method in which the component (A) and the component (B) are mixed in advance, and the component (C) is mixed and dispersed in the mixture,
(III) Component (C) is mixed and dispersed in advance in component (A) or component (B) to prepare a mixture of component (A) and component (C) or a mixture of component (B) and component (C). And then mixing the component (B) with the mixture of the component (A) and the component (C), or mixing the component (A) with the mixture of the component (B) and the component (C),
(IV) A method of preparing a mixture in which (C) component is mixed and dispersed in each of (A) component and (B) component, and further mixing these mixtures [in this case, (C) component to (A) component] The ratio and the ratio of component (C) to (B) may be the same or different. ],
(V) When using a plurality of types of (A) component and / or a plurality of types of (B) component, at least one of them is blended with a mixture in which component (C) is mixed and dispersed at a high concentration The other component (A) and / or the component (B) to be mixed are mixed, or the component (C) is mixed at a low concentration with the above mixture and the other component (A) and / or the component (B) to be blended. Examples thereof include a method of mixing and dispersing the mixed and dispersed mixture.
Also when (D) component is used, it can mix and disperse | distribute according to the said mixing method.

As a method of mixing and dispersing, (A) component and (B) component, (C) component and / or (D) component and various additives used as required are separately uniaxial melting kneader or biaxial melting. The components can be supplied to the kneader and mixed, and each component can be sequentially supplied to the melt kneader using a melt kneader having a plurality of supply units. Moreover, after premixing them beforehand using a mixer such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a tumbler mixer, etc., the mixture is supplied to a melt kneader, specifically 350 ° C. to 430 ° C. It is also possible to melt-knead at a temperature of Further, depending on the purpose, it can be dispersed in an aqueous medium or an organic solvent and mixed by a wet method.
Furthermore, the component (C) and / or the component (D) and various additives, the component (A) and / or the component (B) as a base resin at a high concentration (typically about 10 to 60% by mass) A master batch mixed in (1) is prepared separately, and the resin used is mixed and adjusted in concentration, and mechanically blended using a kneader or an extruder. Among the mixing methods, a method of preparing and mixing a master batch is preferable from the viewpoint of dispersibility and workability.
The mixed resin composition may be directly formed into a film after the melt mixing and dispersion of the components, or once extruded into a strand or a sheet and cut to form a pellet, granule, powder or the like. It may be obtained in a form suitable for.
In the present invention, the thickness of the metal contact layer is not particularly limited, but is usually about 0.1 to 800 μm, and preferably about 2 to 200 μm from the viewpoint that molding is relatively easy.

The surface layer constituting the laminate of the present invention comprises (B) a polyaryl ketone resin or a resin composition containing this and (C) a filler, and / or (D) a resin composition containing a solid lubricant. (B) The polyaryl ketone resin can use the same thing as what was illustrated in the said metal contact layer, The kind of the polyaryl ketone resin is the same as what is used in a metal contact layer, May be different. In the surface layer, it is preferable to use a polyether ether ketone having a repeating unit represented by the structural formula (3).
The filler (C) used in the surface layer can be the same as that exemplified in the metal contact layer, and the kind of the filler is the same as that used in the metal contact layer. May be different.
The amount of (C) filler used for the surface layer is in the range of 0 to 100 parts by mass with respect to 100 parts by mass of (B) polyaryl ketone resin. When the filler to be added is 100 parts by mass or less, the surface layer does not become extremely brittle. The addition of this filler improves the pencil hardness of the surface layer, and improves the shape stability of the laminate by reducing the linear expansion coefficient. From this, the suitable addition amount of the filler is preferably in the range of 10 to 55 parts by mass, more preferably in the range of 15 to 45 parts by mass with respect to 100 parts by mass of the polyaryl ketone resin (B). is there.
(D) The solid lubricant used for the surface layer can be the same as that exemplified in the metal contact layer, and the type of the solid lubricant is the same as that used in the metal contact layer. It may or may not be.

The amount of (D) solid lubricant used for the surface layer is preferably in the range of 0 to 400 parts by mass with respect to 100 parts by mass of (B) polyaryl ketone resin, and the solid lubricant to be added is 100 parts by mass or less. It is preferable that the surface layer does not become extremely brittle. By adding this solid lubricant, the friction coefficient of the surface layer can be reduced. Therefore, the preferable addition amount of the solid lubricant (D) is more preferably in the range of 10 to 55 parts by mass, more preferably in the range of 15 to 45 parts by mass with respect to 100 parts by mass of the component (B). .
When the component (C) and the component (D) are used in combination with the resin composition constituting the surface layer, the total mass of the component (C) and the component (D) with respect to a total of 100 parts by mass of the component (A) and the component (B). Is preferably 0 to 100 parts by mass, and more preferably 0 to 55 parts by mass. When the total mass of the component (C) and the component (D) is 100 parts by mass or less, problems such as surging during melt-kneading are unlikely to occur.

Resin composition constituting the surface layer [including the case of the component (B) alone. ], If necessary, resins other than the component (B), fillers of the component (C), various additives other than the solid lubricant of the component (D), such as heat stabilizers, ultraviolet absorbers, light Stabilizers, nucleating agents, coloring agents, lubricants, flame retardants, and the like may be appropriately blended.
As a method for mixing the filler of component (C) and / or the solid lubricant or component of component (D), known methods can be used. As an example of the combination of mixing, the example of 2 components which consist of (B) component and (D) component is shown below.
(VI) A method of simultaneously mixing and dispersing the two components (B) and (D),
(VII) A method of preparing a mixture in which the component (D) is mixed and dispersed in a high concentration in the component (B) in advance, and further mixing and dispersing the component (B) in the mixture,
(VIII) A method of preparing in advance a mixture of a plurality of types in which component (D) is mixed and dispersed in component (B) at different concentrations, and mixing these mixtures,
(IX) When using a plurality of types of the component (B) and / or a plurality of types of the component (D), a mixture obtained by mixing and dispersing the component (D) at a high concentration in at least one of the components (B); A method of mixing or dispersing another (B) component to be blended, or mixing and dispersing the above mixture with a mixture of (D) component mixed and dispersed at a low concentration in the other (B) component to be blended;
Etc. Mixing / dispersing can be performed by the same method as that used in the metal contact layer.

The thickness of the surface layer is not particularly limited, but is usually about 1 to 1000 μm, and preferably 10 to 200 μm from the viewpoint that molding is relatively easy.
The ratio of the thickness of the metal contact layer to the surface layer is usually such that the ratio of the thickness of the metal contact layer / the thickness of the surface layer is 1/99 to 99/1, preferably 10/90 to 90/10. . When the ratio of the surface layer is higher than 1, the slidability, the wearability and the mechanical strength of the surface layer are excellent, and when the ratio of the metal contact layer is higher than 1, the mechanical strength and the adhesive strength of the metal contact layer are excellent.
In addition, when the metal contact layer and the surface layer are combined and formed as a laminated film by coextrusion and laminated with a metal body before cooling or after cooling, each layer can be stably molded as long as the thickness ratio is within the above range. On the other hand, if the surface layer ratio, which is excellent in slidability and wear, is high, the life of the laminate is prolonged. From this viewpoint, the ratio of the thickness of the metal contact layer / the thickness of the surface layer is more preferably 10/90 to 70/30.

  In the laminate of the present invention, a layer containing the same component as the metal contact layer or the surface layer or a layer composed of other components is interposed between the metal contact layer and the surface layer within the range not exceeding the gist of the present invention. It may have a laminated structure.

Examples of methods for forming the metal contact layer and the surface layer constituting the laminate of the present invention include known methods such as injection molding, extrusion molding, compression molding, and calendar molding. For example, cooling is performed by contacting a cooling resin with a film-like resin composition extruded from a die for film extrusion, such as a die having a rectangular or rectangular-like cross section at the tip of the extruded portion, specifically a T die or an I die. Extrusion casting method, calendering method and the like can be adopted, and although not particularly limited, from the viewpoint of film forming property, stable productivity, etc., a die for film extrusion such as T die and I die An extrusion casting method using a cooling body is preferred. As the cooling body, the material of the surface is made of metal, rubber, fiber, etc., and the form includes a roll, a belt, a seamless belt, and the like.
Among these, it is preferable to use a roll as the cooling body because the cooling device is simple and easy to handle. As an example, a resin composition melted from an extruder is fed into a die through a conduit, extruded into a film shape from the tip of the die, and sandwiched between a metal roll and a rubber roll for cooling and fixed in a film shape and cooled. Subsequently, it is wound around the metal roll side, cooled, and sent to a winder. The film is cooled by another roll or cooling air between the metal roll and the winder as necessary.

The molding temperature in the extrusion casting method is appropriately adjusted depending on the flow characteristics and film-forming properties of the composition, but is generally about the glass transition temperature or the melting point to 430 ° C., preferably 350 to 400 ° C., more preferably 380. ~ 395 ° C.
The surface temperature of a cooling body such as a roll is usually a glass transition temperature of the resin component constituting each layer or a temperature not higher than the melting point. When forming a metal contact layer, the surface temperature of a cooling body is about 30-175 degreeC normally, Preferably it is the range of 90-140 degreeC. If it is 30 ° C. or higher, it can be avoided that water in the air freezes and adheres to the surface of the cooling body, and if it is 175 ° C. or lower, the shape formed by contact with the cooling body is prevented from changing. be able to. When forming the surface layer, the surface temperature of the cooling body is usually about 30 to 155 ° C, preferably about 90 to 141 ° C. If it is 30 ° C. or higher, it can be avoided that water in the air freezes and adheres to the surface of the cooling body, and if it is 175 ° C. or lower, the shape formed by contact with the cooling body is prevented from changing. be able to. It can be measured by a contact method in which a thermocouple or a temperature indicator is brought into contact with the upper surface of the cooling body, a non-contact method using light or electromagnetic waves, such as an infrared thermometer.
The preferable range of the surface temperature of the cooling body can be controlled by appropriately selecting the temperature control mechanism of the cooling body and the temperature of a heat medium such as a circulating refrigerant such as oil and water.

The method of laminating the metal body, the metal contact layer, and the surface layer when producing the laminate of the present invention is not particularly limited. For example, the metal body, the metal contact layer previously formed into a film shape, and the surface layer are overlapped. Press forming to heat and laminate while applying pressure, metal body, and metal contact layer and surface layer previously formed into a film shape are heated simultaneously by heating roll contact, infrared rays, hot air, etc. The resin composition constituting the metal contact layer and the resin composition constituting the surface layer are melt-kneaded in separate extruders and laminated in separate dies or multilayer dies, respectively. A method of extruding into a film and placing it on the surface of the metal body as it is without cooling, and laminating with the metal body between a heating press or a heating roll, or metal contact Examples include a method of extruding a layer and a surface layer as a laminated film and once cooling, and then laminating between a metal body and a heating press or a heating roll, etc. Lamination temperature is the melting temperature of the resin component used in each layer or glass transition The temperature is appropriately selected depending on the amount ratio of the filler and the solid lubricant, but is usually 350 to 390 ° C, preferably 360 to 370 ° C. Moreover, when using the laminated film of a metal contact layer and a surface layer, it is 210-390 degreeC, Preferably it is the range of 230-280 degreeC. Adhesive strength is good at 210 ° C. or higher, and rapid deterioration of the resin component can be avoided at 390 ° C. or lower.
The heating time is appropriately selected depending on the laminating method, the laminating temperature, and the required adhesive strength, but is usually 0.01 seconds or longer, preferably 0.1 second to 500 minutes. Selection of a time of 0.01 seconds or more is effective in improving the adhesive strength, and deterioration of the resin component can be avoided by selection of a short time of 500 minutes or less.
The pressure is appropriately selected depending on the laminating apparatus, temperature, time, required adhesive strength, and strength of the metal body, but is usually 0.1 MPa or more, preferably 1 MPa to 100 MPa. Moreover, when laminating | stacking by press molding, Preferably it is the range of 2-10 Mpa. The effect of increasing the adhesive strength is obtained at 0.1 MPa or more, and abnormal deformation of the metal adhesive layer or the surface layer can be avoided at 100 MPa or less.

The metal body used in the above lamination may be in the form of a continuous coil, a strip or a cut plate, and the metal contact layer and the surface layer may also be subjected to lamination in the form of continuous winding or cut sheets. .
Moreover, in order to improve the adhesion between the metal body and the metal contact layer, a silane coupling agent such as aminosilane or epoxysilane can be used.
Applications of the laminate of the present invention include mechanical parts having rotational sliding and reciprocating sliding parts, automobile parts, various bearings such as thrust bearings and journal bearings, automobile engine compartment parts, partition walls, door sliding parts, brakes Examples include parts, energy generation equipment parts, heat shielding plates, swash plates of air compressors, shoes, and housings of various equipment.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, the various measured values and evaluation about the film displayed in this specification were performed as follows. Here, the flow direction from the extruder of the film is called the vertical direction, and the orthogonal direction is called the horizontal direction.

(1) Exfoliation state of cut end For a laminate having a metal part thickness of 1 mm or less, shirring (blade span about 1000 mm, stepping type) manufactured by Ikuno Machinery Co., Ltd. is used, and the laminate is 3 cm wide and 20 cm long. The strips were cut into three pieces, and the presence or absence of peeling occurring at the end of the long side was visually observed, and the evaluation was divided into the following four ranks. When the state of occurrence of peeling between the cutting edge on the fixed blade side and the cutting edge on the movable blade side is different, the peeling state of the edge with the larger peeling length or width is evaluated, and the strip-shaped test piece The state of peeling of the cut end of the remaining part after cutting was also observed, and if the length and width of the peeling were large, it was regarded as the evaluation result.
Rank 1: No peeling of the end portion occurs or the maximum value of the peeling width is 0.5 mm or less.
Rank 2: The maximum value of the peeling width is more than 0.5 mm and 1 mm or less.
Rank 3: Peeling occurs across the entire end, and the peel width is at least partially greater than 1 mm.
Rank 4: After cutting by shearing, during the conditioning for 2 days at room temperature, the peeling gradually spreads beyond the peeling width of 1 mm from the end, and at least 10% of the laminated surface peels off.

(2) Peeling around the cut line Laminated bodies with a metal part thickness exceeding 1 mm cannot be cut by shearing, so put three straight straight cuts at 2 cm intervals on the resin surface with a cutter knife. Further, three parallel cuts on a straight line having a width of 2 cm in the direction perpendicular to the straight line were made in the vicinity of the center of the straight line, and the state of peeling was visually observed. Moreover, the cutter knife tip was inserted into the cut portion to try to peel off the cut portion. The presence or absence of peeling occurring at the cut portion was visually observed, and the evaluation was divided into the following four ranks.
Rank 1: No peeling of the cut occurs or the maximum value of the peeling width is 0.5 mm or less.
Rank 2: The maximum peel width of the cut is more than 0.5 mm and 1 mm or less.
Rank 3: Peeling occurs across the entire cut and the peel width is at least partially greater than 1 mm.
Rank 4: After cutting with a cutter knife, during the conditioning for 2 days at room temperature, the peeling gradually spreads beyond the cut width of 1 mm from the cut portion, and at least 10% of the laminated surface peels off.

(3) Peel strength For a laminate having a metal part thickness of 1 mm or less, the obtained laminate was cut into strips having a width of 3 cm and a length of 20 cm by the above shearing, and a thermoplastic resin surface length of 20 cm. A straight cut is made with a cutter knife at a position 5 mm inward from the ends of both sides, and further approximately 3 to 5 cm inward of one side with a length of 3 cm, approximately parallel to a side with a length of 3 cm. A cut was made with a cutter knife, and the position was repeatedly bent up and down on the surface of the laminate to produce a peeled portion for peel strength measurement, which was used as a test piece.
In addition, for laminates having a thickness of the metal body portion exceeding 1 mm, cutting by shearing is not performed, and five parallel straight cuts of 2 cm intervals are put on the laminate resin surface with a cutter knife. A straight cut was made in a direction perpendicular to the straight line at a position 2 to 3 cm from the end of the straight line, and the tip of the cutter knife was inserted into the cut to make a peeled portion. When the resin layer portion was broken or broken during the peeled portion preparation operation, it was determined that the material was broken (abbreviated as “material breakage”).
Further, in order to pull the resin layer at the peeled portion for the purpose of measuring the adhesive strength, a cellophane tape having a width of 18 mm was attached to the peeled portion to provide a pulling margin. Specifically, a cellophane tape having a width of 18 mm (trade name: Nichiban Cello Tape, model number: CT405A-18) is cut to a length of about 33 cm, and the adhesive surface is left inside, leaving both ends at about 1.5 cm, and is divided into two at the center. Folded and bonded together, both ends were pasted to the peeled portion, and a tensile margin of 18 mm width and 15 cm length was obtained.
The peeled portion was stretched from the peeled portion with a thermoplastic resin layer or the cellophane tape in a direction perpendicular to the surface of the laminate. The one where the peeled portion spread was pulled in the direction of 180 degrees at a speed of 50 mm / min with a tensile tester, and the peel strength was measured. When the film was torn during the spreading operation, it was judged that the peel strength was stronger than the material strength, and it was judged that the material was broken (abbreviated as “material break”).

(4) Friction coefficient measurement The static friction coefficient and the dynamic friction coefficient were measured according to JIS K 7125-1987.
(5) Pencil hardness Pencil hardness was measured in accordance with JIS K 3312-1994.
(6) Surface roughness of the metal body used for the laminate The surface roughness parameter defined in JIS B0601-1994 was measured using a surface roughness measuring device, model SE3-FK, manufactured by Kosaka Laboratory Ltd. did. The measured parameters are ten-point average roughness (Rz), maximum height (Ry), and arithmetic average roughness (Ra).
(7) Solvent resistance The laminate was immersed in chloroform for 4 hours at room temperature, the change in surface appearance was visually observed, and the evaluation was divided into the following five ranks compared with the unimmersed sample.
Rank 1: No change in appearance.
Rank 2: The surface gloss changes.
Rank 3: Surface roughness occurs partially.
Rank 4: Surface roughness occurs throughout.
Rank 5: at least partially dissolved.

Example 1
(1) Preparation of film used for metal contact layer Amorphous polyetherimide resin [manufactured by General Electric, trade name: Ultem 1000, glass transition temperature Tg: 216 ° C.] (hereinafter simply abbreviated as PEI-1) 2.016 kg (28% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), polyetherimide resin [manufactured by General Electric, Ultem CRS5001, Tg: 226 ° C.] (hereinafter, simply 2.304 kg (sometimes abbreviated as PEI-2) (32 mass% based on the total mass of PEI-1, PEI-2 and PEEK-1), polyetheretherketone resin [manufactured by Victrex, PEEK450G, Tg: 143 ° C., melting point Tm: 334 ° C.] (hereinafter simply abbreviated as PEEK-1) 2.8 kg (40 mass% with respect to the total mass of PEI-1, PEI-2 and PEEK-1), and synthetic mica (average particle size: 6 μm, aspect ratio: 25) as a filler 2.8 kg (PEI-1, PEI) -2 and PEEK-1 in a total of 100 parts by mass, the components consisting of 38.9 parts by mass, abbreviation C1) were kneaded at a set temperature of 380 ° C. using a twin screw extruder with side feed, extruded into a strand, and cut To give pellets.
The pellets were dried with hot air at 180 ° C. for 12 hours, then extruded into a film at 380 ° C. using a 40 mm uniaxial extruder connected with a T-die, and the temperature was adjusted with circulating oil at a preset temperature of 160 ° C. The film was brought into contact with the surface of the cast metal roll and pressed with a silicone rubber roll from the opposite side to form a quenched film, thereby obtaining a 100 μm-thick metal contact layer film (abbreviated as S1).

(2) Preparation of film used for surface layer 7.2 kg (100 parts by mass) of PEEK-1 and 2.8 kg of synthetic mica (C1) as a filler (38.9 parts by mass with respect to 100 parts by mass of PEEK-1) These components were kneaded using a twin screw extruder with side feed at a set temperature of 390 ° C., extruded into a strand, and cut into pellets.
The pellets were dried with hot air at 180 ° C. for 12 hours, then extruded into a film at 390 ° C. using a 40 mm uniaxial extruder connected with a T-die, and the temperature was adjusted with circulating oil at a preset temperature of 130 ° C. A surface film (abbreviated as T1) having a thickness of about 110 μm was obtained by bringing it into contact with the surface of the cast metal roll and pressing it with a silicone rubber roll from the opposite side to form a quenched film.

(3) Manufacture of a laminated body The materials stacked in the following order from bottom to top are set in a high-performance high-temperature vacuum press molding machine (Kitakawa Seiki Co., Ltd., molding press, model: VH1-1747). Then, press molding was performed at a preset maximum temperature of 360 ° C., a preset maximum temperature holding time of 20 minutes, and a preset pressure of the press molding machine of 9.7 MPa (pressure at the bonding portion was about 3.9 MPa) to obtain a laminate.
(I) Cushion paper (product name: RA board RAB N 0016, manufactured by Mitsubishi Paper Industries Co., Ltd.) having a square of about 30 cm on one side covered with 35 μm copper foil on both sides and a thickness of 1.6 mm,
(J) a stainless steel plate with a side of about 30 cm and a thickness of 2 mm;
(K) A polyimide film having a length of 30 cm and a width of 25 cm and a thickness of 50 μm (manufactured by Ube Industries, Ltd., trade name: Upilex 50S, thickness 50 μm),
(L) A stainless steel plate (SUS304, degreased by chloroform cleaning, abbreviation A1) having a square of 22 cm on one side and a thickness of 0.4 mm,
(M) a square metal contact layer film (abbreviated S1) having a side of 24 cm;
(N) a square surface film (abbreviated as T1) having a side of 24 cm,
(O) the same polyimide film as in (k) above,
(P) a stainless steel plate similar to (j) above,
(Q) Cushion paper covered with a copper foil similar to (i) above.
The above (i) to (q) are used to remove dirt and foreign matter on the surface with a wiping paper soaked with a small amount of ethanol before superimposing, and the above (k) to (o) are visually checked before superimposing. Check the foreign matter on the front and back by inspection, wipe off the foreign matter using a wiping cloth (trade name: Microstar-CP, manufactured by Teijin Limited) soaked with a small amount of ethanol, and then perform a visual inspection again. After confirming that was removed, they were overlaid.
The surface roughness parameters of the metal body A1 used were Ra of 0.18 μm, Ry of 1.5 μm, and Rz of 1.4 μm.

  When the cross section of the obtained laminate was observed with a microscope and the thickness of each layer was measured, the metal body was 0.4 mm, the metal contact layer was 96 μm, and the surface layer was 107 μm. From this value, the ratio of the metal contact layer to the surface layer was calculated as 47:53. This laminate was cut by the above shearing, and the peeled state of the end portion was visually observed. The static friction coefficient was 0.235, and the dynamic friction coefficient was 0.163. An attempt was made to create a peeled part at the end to measure the peel strength, but the peeled part was not peeled off, a cut was made with a cutter knife, the laminate was bent several times up and down the surface, and the peeled part was produced. First, when the thermoplastic resin layer was pulled and peeled off with the fingertip, the thermoplastic resin layer was cut, and thus it was determined that the material was destroyed (hereinafter abbreviated as “material failure”). The pencil hardness was H. Further, when the solvent resistance was evaluated by the above method, no change in appearance was observed, and the rank was 1.

Example 2
Of the constituent components of the metal contact layer film, 4.4 kg of PEI-1 (55% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), PEEI-2 was not used, and PEEK- 1 was changed to 3.6 kg (45% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), and synthetic mica (C1) was produced by the following method 2 kg of surface-treated mica (PEI- 1, 25 parts by mass with respect to a total of 100 parts by mass of PEI-2 and PEEK-1, and a film for metal contact layer (abbreviation) except that the film thickness was 35 μm. To S2.) Was obtained.
The surface-treated mica was produced by the following method. A surface treatment agent hexyltrimethoxysilane in which 2 kg of commercially available mica (average particle size: 10 μm, aspect ratio: 20) was put into a Henschel mixer (trade name) and dissolved in 160 g of isopropyl alcohol having a water content of about 3% by mass was added. 200 g of a 20% by mass solution obtained by dissolving 40 g (2 parts by mass with respect to 100 parts by mass of synthetic mica) (manufactured by Tokyo Chemical Industry Co., Ltd.) was sprinkled, and the upper part of the mixer was covered. While supplying nitrogen, the mixer was operated for 10 minutes to stir and mix. This product was spread on a stainless steel bat and allowed to stand indoors for 4 days, then heat-treated in an oven at 120 ° C. for 48 hours, cooled to room temperature, and surface-treated mica (abbreviated as C2). Got. Further, this operation was repeated 10 times to obtain about 20 kg of surface-treated mica.
Of the constituents of the surface layer film, the amount of PEEK-1 is 7.6 kg (100 parts by mass), and the synthetic mica (C1) is 2.4 kg of the surface-treated mica (C2) (with respect to 100 parts by mass of PEEK-1). 31.6 parts by mass), and a film for surface layer (abbreviated as T2) was obtained in the same manner as in Example 1 except that the film thickness was 40 μm.
Example 1 except that the metal body was changed to SUS301 ½ H material (abbreviated as A2) with a thickness of 0.4 mm, the metal contact layer film was changed to S2, and the surface layer film was changed to T2. The same press molding was performed to obtain a laminate. The surface roughness parameters of the metal body A2 were Ra 0.08 μm, Ry 1.0 μm, and Rz 0.92 μm.
The thickness of each layer of the obtained laminate was 0.4 mm metal body, 33 μm metal contact layer, and 38 μm surface layer. The evaluation results of this product are shown in Table 1.

Example 3
Of the constituent components of the metal contact layer film, PEI-1 is 3.04 kg (40 mass% with respect to the total mass of PEI-1, PEI-2 and PEEK-1), and PEI-2 is 1.9 kg (PEI- 1, 25% by mass with respect to the total mass of PEI-2 and PEEK-1, and PEEK-1 to 2.66 kg (35% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) Then, the synthetic mica (C1) was changed to 2.4 kg of the surface-treated mica (C2) (31.6 parts by mass with respect to 100 parts by mass in total of PEI-1, PEI-2, and PEEK-1), and the film thickness A film for metal contact layer (abbreviated as S3) was obtained in the same manner as in Example 1 except that the thickness was changed to 80 μm.
The composition of the surface layer film is PEEK-1 only, synthetic mica is not blended, it is dried at 180 ° C. for 12 hours without using a twin screw extruder, and then directly supplied to a single screw extruder having a diameter of 40 mm. Except that the film thickness was 30 μm, the same operation as in Example 1 was performed to obtain a surface layer film (abbreviated as T3).
Press forming similar to Example 1 except that the metal body was changed to SUS304 (abbreviated as A3) with a thickness of 0.5 mm, the metal contact layer film was changed to S3, and the surface layer film was changed to T3. To obtain a laminate. The surface roughness parameters of the metal body A3 were Ra 0.17 μm, Ry 1.67 μm, and Rz 1.37 μm.
The thickness of each layer of the obtained laminate was 0.5 mm metal body, 76 μm metal contact layer, and 27 μm surface layer. The evaluation results of this product are shown in Table 1.

Comparative Example 1
The constituents of the film for the surface layer are only PEEK-1 10 kg (100 parts by mass), the same operation as in Example 1 is carried out except that the synthetic mica is blended and melt-kneaded, and the extrusion molding is performed as it is. A film for surface layer of 110 μm (abbreviated as TR1) was obtained.
A laminate was obtained by performing the same press molding as in Example 1 except that the metal contact layer film was not used and the surface layer film was changed to TR1. The thickness of each layer of the obtained laminate was a metal body of 0.4 mm and a surface layer of 106 μm.
This laminate was cut by shirring similar to that of Example 1, and the peeled state of the end portion was visually observed. As a result, it was ranked 3 and was being conditioned for 2 days in a temperature-controlled room at 23 ° C. and 50% humidity. The peeling gradually exceeded the peeling width of 1 mm from the end portion and spread over the entire laminated surface, and about 60% of the laminated surface was peeled off. Furthermore, since about 80% of the bonded surface was peeled after 2 days, it was determined that the adhesion was poor. The thickness of the peeled TR1 layer was 106 μm. No other evaluation was performed due to poor adhesion.

Comparative Example 2
The metal contact layer film was set to S1, and the same press molding as in Example 1 was performed except that the surface layer film was not used to obtain a laminate. The thickness of each layer of the obtained laminate was a metal body of 0.4 mm and a metal contact layer of 96 μm. The evaluation results of this product are shown in Table 1.
Comparative Example 3
The surface of the stainless steel plate A1 was roughened by shot blasting (abbreviated as RA1). The surface roughness parameter Ra was 1.4 μm, Ry was 14.9 μm, and Rz was 10.7 μm. Pellets prepared by melting and kneading 0.2% by mass of carbon black for coloring into PEEK-1 were pulverized to an average particle size of about 0.1 mm (abbreviated as PEEK-1P), applied onto RA1, and heated to 420 ° C. After heating for 60 minutes in the set oven to melt PEEK-1P, the oven was cooled to room temperature over 6 hours. This product had a static friction coefficient of 0.262 and a dynamic friction coefficient of 0.198.

Example 4
Of the constituent components of the metal contact layer film, 3.28 kg of PEI-1 (40 mass% with respect to the total mass of PEI-1, PEI-2 and PEEK-1) and 2.87 kg of PEI-2 (PEI- 1, 35 mass% with respect to the total mass of PEI-2 and PEEK-1), PEEK-1 was changed to 2.05 kg (25 mass% with respect to the total mass of PEI-1, PEI-2 and PEEK-1) Then, the synthetic mica (C1) was changed to 1.8 kg (22 parts by mass with respect to a total of 100 parts by mass of PEI-1, PEI-2 and PEEK-1) of the surface-treated mica produced by the following method, and the film thickness A film for metal contact layer (abbreviated as S4) was obtained in the same manner as in Example 1 except that the thickness was changed to 50 μm.
The surface-treated synthetic mica was produced by the following method. A surface treatment agent phenyltrimethoxy dissolved in 160 g of isopropyl alcohol having a water content of about 3% by weight was added 2 kg of commercially available synthetic mica (average particle size: 6 μm, aspect ratio: 25) to a Henschel mixer (trade name). 200 g of a 20% by mass solution obtained by dissolving 40 g of silane (manufactured by Tokyo Chemical Industry Co., Ltd., reagent grade) (2 parts by mass with respect to 100 parts by mass of mica) was sprinkled, and the top of the mixer was covered. While supplying nitrogen, the mixer was operated for 10 minutes to stir and mix. This was spread on a stainless steel vat, left in a room for 4 days, then heat-treated in an oven at 120 ° C. for 48 hours, cooled to room temperature, and surface-treated synthetic mica (abbreviated as C3). ) Further, the same operation was repeated 30 times to obtain about 60 kg of surface-treated synthetic mica.
Of the constituent components of the surface layer film, the amount of PEEK-1 is 8.2 kg (100 parts by mass), and the same surface-treated synthetic mica (C3) 1.8 kg as that used in the above S4 synthetic mica (C1) The surface layer film (abbreviated as T4) was obtained in the same manner as in Example 1 except that the film thickness was changed to 22 parts by mass with respect to 100 parts by mass of PEEK-1 and the film thickness was changed to 70 μm. .
Except that the metal contact layer film was changed to S4 and the surface layer film was changed to T4, press forming was performed in the same manner as in Example 1 to obtain a laminate. The thickness of each layer of the obtained laminate was 0.4 mm metal body, 46 μm metal contact layer, and 66 μm surface layer. The evaluation results of this are shown in Table 2.

Example 5
Of the components of the metal contact layer film, 2.25 kg of PEI-1 (30% by mass with respect to the total mass of PEI-1, PEI-2, and PEEK-1) and 2.25 kg of PEI-2 (PEI- 1, 30% by mass with respect to the total mass of PEI-2 and PEEK-1), PEEK-1 was changed to 3.0 kg (40% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) The synthetic mica (C1) is changed to 2.5 kg (33.3 parts by mass with respect to 100 parts by mass in total of PEI-1, PEI-2, and PEEK-1) of the above-mentioned surface-treated synthetic mica (C3), and the film thickness A film for metal contact layer (abbreviated as S5) was obtained in the same manner as in Example 1 except that the thickness was changed to 50 μm.
Of the constituent components of the surface layer film, the amount of PEEK-1 is 7.5 kg (100 parts by mass), and the same surface-treated synthetic mica (C3) 2.5 kg as used in S4 above. The surface layer film (abbreviated as T5) is obtained in the same manner as in Example 1 except that the film thickness is changed to 33.3 parts by mass with respect to 100 parts by mass of PEEK-1 and the film thickness is set to 50 μm. Obtained.
Press forming similar to Example 1 except that the metal body was changed to SUS316 (abbreviated as A4) with a thickness of 0.3 mm, the metal contact layer film was changed to S5, and the surface layer film was changed to T5. To obtain a laminate. The surface roughness parameters of the metal plate A4 were Ra 0.07 μm, Ry 1.87 μm, and Rz 1.15 μm.
The thickness of each layer of the obtained laminate was 0.3 mm metal body, 45 μm metal contact layer, and 47 μm surface layer. The evaluation results of this are shown in Table 2.

Example 6
Among the constituent components of the metal contact layer film, 4.4 kg of PEI-1 (55% by mass with respect to the total mass of PEI-1, PEI-2, and PEEK-1), PEEI-2 was not used, and PEEK- 1 was changed to 3.6 kg (45% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), and synthetic mica (C1) was replaced with 2 kg of the surface-treated synthetic mica (C3) (PEI-1, The film was changed to 25 parts by mass with respect to 100 parts by mass in total of PEI-2 and PEEK-1, and the same operation as in Example 1 was performed except that the film thickness was 28 μm. And obtained.
8 kg (100 parts by mass) of the above PEEK-1 and 2 kg of polytetrafluoroethylene resin (manufactured by Asahi Glass Co., Ltd., grade name Fullon PTFE L-169J, abbreviation: D1) as a solid lubricant (25 to 100 parts by mass of PEEK-1) The mass part) was kneaded at a set temperature of 390 ° C. using a twin screw extruder with side feed, extruded into a strand shape, and cut into pellets.
A surface layer film (abbreviated as T6) was obtained in the same manner as in Example 1 except that the pellet was used and the film thickness was changed to 60 μm.
Except that the metal contact layer film was changed to S6 and the surface layer film was changed to T6, the same press molding as in Example 1 was performed to obtain a laminate.
The thickness of each layer of the obtained laminate was 0.4 mm metal body, 24 μm metal contact layer, and 55 μm surface layer. The evaluation results of this are shown in Table 2.

Example 7
Of the constituent components of the metal contact layer film, 3.2 kg of PEI-1 (40% by mass with respect to the total mass of PEI-1, PEI-2, and PEEK-1) and 2.4 kg of PEI-2 (PEI- 1, 30% by mass with respect to the total mass of PEI-2 and PEEK-1), PEEK-1 was changed to 2.4 kg (30% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) The synthetic mica (C1) was changed to 2 kg of the surface-treated synthetic mica (C3) (25 parts by mass with respect to a total of 100 parts by mass of PEI-1, PEI-2, and PEEK-1), and the film thickness was 24 μm. Otherwise, the same operation as in Example 1 was performed to obtain a metal contact layer film (abbreviated as S7).
The above PEEK-1 8.33 kg (100 parts by mass) and a fluorine resin as a solid lubricant, scaly graphite (manufactured by Nippon Graphite Co., Ltd., trade name, special CP, average particle diameter measured under a microscope is 6 μm, abbreviation: D2) Changed to 1.67 kg (20 parts by mass with respect to 100 parts by mass of PEEK-1), kneaded at a set temperature of 390 ° C. using a twin screw extruder with side feed, extruded into a strand, cut and pelletized It was.
Using this pellet, the same operation as in Example 1 was carried out except that the extrusion temperature was set to 390 ° C. and the film thickness was set to 100 μm to obtain a surface layer film (abbreviated as T7).
Except that the metal contact layer film was changed to S7 and the surface layer film was changed to T7, press molding was performed in the same manner as in Example 1 to obtain a laminate.
The thickness of each layer of the obtained laminate was 0.4 mm metal body, 20 μm metal contact layer, and 96 μm surface layer. The evaluation results of this are shown in Table 2.

Example 8
Of the constituent components of the metal contact layer film, 3 kg of PEI-1 (30% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) and 3 kg of PEI-2 (PEI-1, PEI- 2 and 30% by mass of PEEK-1), 4 kg of PEEK-1 (40% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), and synthetic mica (C1) above Surface treatment mica (C2) 1.5 kg (15 parts by mass with respect to a total of 100 parts by mass of PEI-1, PEI-2 and PEEK-1), and the solid lubricant is 1.5 kg (PEI-) of the fluororesin (D1). 1, 15 parts by mass with respect to a total of 100 parts by mass of PEI-2 and PEEK-1, and 10 kg with respect to 1 kg of the above graphite (D2) (100 parts by mass of PEI-1, PEI-2 and PEEK-1) ) A side feed with a twin-screw extruder extruding into strands and kneaded at a set temperature of 390 ° C. using, and cut to pellets.
Using this pellet, the same operation as in Example 1 was carried out except that the extrusion temperature was 390 ° C. and the film thickness was 50 μm, to obtain a metal contact layer film (abbreviated as S8).
10 kg (100 parts by mass) of the above PEEK-1; 1 kg of the surface-treated synthetic mica (C3) (10 parts by mass with respect to 100 parts by mass of PEEK-1); 2 kg of the fluororesin (D1) as a solid lubricant (PEEK-1) 20 parts by mass with respect to 100 parts by mass) and 1 kg of the above scaly graphite (D2) (10 parts by mass with respect to 100 parts by mass of PEEK-1) at a set temperature of 390 ° C. using a twin screw extruder with side feed. Kneaded, extruded into strands, and cut into pellets.
A surface layer film (abbreviated as T8) was obtained in the same manner as in Example 1 except that this pellet was used and the film thickness was 35 μm.
Except that the metal contact layer film was changed to S8 and the surface layer film was changed to T8, press forming was performed in the same manner as in Example 1 to obtain a laminate.
The thickness of each layer of the obtained laminate was 0.4 mm metal body, 45 μm metal contact layer, and 31 μm surface layer. The evaluation results of this are shown in Table 2.

Example 9
(Production of laminated film by coextrusion)
2.8 kg of PEI-1 (28 mass% with respect to the total mass of PEI-1, PEI-2 and PEEK-1), 3 kg of PEI-2 (total mass of PEI-1, PEI-2 and PEEK-1) 30 mass%), 4.2 kg of PEEK-1 (42 mass% with respect to the total mass of PEI-1, PEI-2 and PEEK-1), and 2.5 kg of the surface-treated mica (C2) (PEI- 1, 25 parts by mass with respect to a total of 100 parts by mass of PEI-2 and PEEK-1) was kneaded at a set temperature of 380 ° C. using a twin screw extruder with side feed, extruded into a strand, and cut into pellets. .
The pellets were dried with hot air at 180 ° C. for 8 hours and extruded as a metal contact layer from a multi-manifold die (set temperature: 390 ° C.) connected to a single screw extruder having a diameter of 30 mmφ set at 390 ° C.
The PEEK-1 pellets were dried with hot air at 180 ° C. for 8 hours and then extruded as a surface layer from the multi-manifold die (set temperature 390 ° C.) connected to a single screw extruder having a diameter of 40 mmφ set at 390 ° C.
The discharge amount of the molten resin was adjusted so that the thickness ratio of the metal contact layer to the surface layer was 16:84. The coextruded film, that is, the metal contact layer side of the laminated film was quenched with a 125 ° C. casting roll, and a silicon rubber roll was pressed against the surface layer side. Furthermore, the silicon rubber roll was cooled by pressing a hard chrome plating roll cooled with water of about 35 ° C. installed on the opposite side of the metal roll. Subsequently, this coextruded film was wound up to obtain a laminate. The amount of molten resin discharged from the extruder and the line speed were adjusted so that the thickness of this product was 50 μm. When the cross section of the produced laminated film was observed under a microscope and the thickness of each layer was measured, the thickness of the metal contact layer was 8 μm and the thickness of the surface layer was 42 μm. The abbreviation for this laminated film is “ST9”.
(Lamination with metal body)
The metal contact layer film (S1) and the surface layer film (T1) are changed to the laminated film (ST9), and the metal contact layer of the laminated film is overlaid on (A1) so as to be in contact with the metal body (A1). A laminate was obtained by press molding in the same manner as in Example 1 except that the set maximum temperature during press lamination was changed to 250 ° C. and the set maximum temperature holding time was changed to 30 minutes.
The evaluation results of this laminate are shown in Table 3.

Example 10
(Preparation of resin composition used for metal contact layer)
Among the components of the metal contact layer, 6 kg of PEI-1 (60% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), 4 kg of PEEK-1 without using PEI-2 ( 40 mass% with respect to the total mass of PEI-1, PEI-2 and PEEK-1, and 1.5 kg of surface-treated mica (C2) (15 with respect to a total of 100 mass parts of PEI-1, PEI-2 and PEEK-1) And 1.5 kg of the fluororesin (D1) as a solid lubricant (15 parts by mass with respect to a total of 100 parts by mass of PEI-1, PEI-2 and PEEK-1), twin-screw extrusion with side feed Using a machine, the mixture was kneaded at a preset temperature of 390 ° C., extruded into a strand shape, and cut into pellets (abbreviated as K101).
As a surface layer component, 10 kg (100 parts by mass) of the above PEEK-1; 0.8 kg of the above surface-treated synthetic mica (C3) (8 parts by mass with respect to 100 parts by mass of PEEK-1); and the above fluororesin as a solid lubricant (D1) 2.5 kg (25 parts by mass with respect to 100 parts by mass of PEEK-1) was kneaded at a set temperature of 390 ° C. using a twin screw extruder with side feed, extruded into a strand shape, cut into pellets (Abbreviated as K102).
(Production of laminated film by coextrusion)
The pellets of K101 were dried with hot air at 180 ° C. for 8 hours, and extruded as a metal contact layer from a multi-manifold die (set temperature: 390 ° C.) connected to a single screw extruder with a diameter of 30 mmφ set at 390 ° C.
The K102 pellets were hot-air dried at 180 ° C. for 8 hours and then extruded as a surface layer from the multi-manifold die (set temperature 390 ° C.) connected to a single screw extruder having a diameter of 40 mmφ set at 390 ° C.
The amount of molten resin discharged was adjusted so that the thickness ratio of the metal contact layer to the surface layer was 14:86. The coextruded film, that is, the metal contact layer side of the laminated film was quenched with a 125 ° C. casting roll, and a silicon rubber roll was pressed against the surface layer side. Furthermore, the silicon rubber roll was cooled by pressing a hard chrome plating roll cooled with water of about 35 ° C. installed on the opposite side of the metal roll. Subsequently, this coextruded film was wound up to obtain a laminate. The amount of molten resin discharged from the extruder and the line speed were adjusted so that the thickness of this product was 105 μm. When the cross section of the produced laminated film was observed under a microscope and the thickness of each layer was measured, the thickness of the metal contact layer was 15 μm, and the thickness of the surface layer was 90 μm. The abbreviation for this laminated film is “ST10”.
(Lamination with metal body)
Except for changing the laminated film (ST9) to (ST10), the same press molding operation as in Example 9 was performed to obtain a laminated body. The evaluation results of this laminate are shown in Table 3.

Example 11
Of the constituent components of the metal contact layer, 6 kg of PEI-1 (60% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) and 1.5 kg of PEI-2 (PEI-1, PEI- 2 and 15% by mass of PEEK-1), 2.5 kg of PEEK-1 (25% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), surface-treated synthetic mica (C3 ) 1.5 kg (15 parts by mass with respect to a total of 100 parts by mass of PEI-1, PEI-2, and PEEK-1), and 1 kg (PEI-1, PEI-2) of the graphite (D2) as a solid lubricant And 10 parts by mass of PEEK-1 with respect to a total of 100 parts by mass using a twin screw extruder with side feed, kneaded at a set temperature of 390 ° C., extruded into strands, and cut into pellets (abbreviated as abbreviations). 111 to.).
Among the surface layer components, 10 kg (100 parts by mass) of the PEEK-1; 1.0 kg of the surface-treated synthetic mica (C3) (10 parts by mass with respect to 100 parts by mass of PEEK-1); D1) 2 kg (20 parts by mass with respect to 100 parts by mass of PEEK-1) and 1 kg of graphite (D2) (10 parts by mass with respect to 100 parts by mass of PEEK-1) using a twin screw extruder with side feed The mixture was kneaded at a set temperature of 390 ° C., extruded into a strand, and cut into pellets (abbreviated as K112).
(Production of laminated film by coextrusion)
The K111 pellets were dried with hot air at 180 ° C. for 8 hours, and then extruded as a metal contact layer from a multi-manifold die (set temperature 390 ° C.) connected to a single screw extruder having a diameter of 30 mmφ set at 390 ° C.
The K112 pellets were dried with hot air at 180 ° C. for 8 hours, and then extruded as a surface layer from the multi-manifold die (set temperature 390 ° C.) connected to a single screw extruder having a diameter of 30 mmφ set at 390 ° C.
The amount of molten resin discharged was adjusted so that the thickness ratio of the metal contact layer to the surface layer was 57:43. The coextruded film, that is, the metal contact layer side of the laminated film was quenched with a 125 ° C. casting roll, and a silicon rubber roll was pressed against the surface layer side. Furthermore, the silicon rubber roll was cooled by pressing a hard chrome plating roll cooled with water of about 35 ° C. installed on the opposite side of the metal roll. Subsequently, this coextruded film was wound up to obtain a laminate. The amount of molten resin discharged from the extruder and the line speed were adjusted so that the thickness of this product was 70 μm. When the cross section of the produced laminated film was observed under a microscope and the thickness of each layer was measured, the thickness of the metal contact layer was 40 μm, and the thickness of the surface layer was 30 μm. The abbreviation for this laminated film is “ST11”.
(Lamination with metal body)
Except for changing the laminated film (ST9) to ST11, the same press molding operation as in Example 9 was performed to obtain a laminated body. The evaluation results of this laminate are shown in Table 3.

Example 12
Of the constituent components of the metal contact layer film, 3 kg of PEI-1 (30% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) and 3 kg of PEI-2 (PEI-1, PEI- 2 and 30% by mass of PEEK-1), PEEK-1 is changed to 4kg (40% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), and synthetic mica is used. First, it was the same as in Example 1 except that kneading by a twin screw extruder was not carried out and the mixture was sufficiently stirred and dried at 180 ° C. for 8 hours, then directly fed to a single screw extruder having a diameter of 40 mm and the thickness was 50 μm. The metal contact layer film was obtained (abbreviated as S12). The component of the surface layer film is PEEK-1 10 kg, synthetic mica is not used, kneading by a twin screw extruder is not performed, 180 ° C. is dried for 8 hours, and then directly supplied to a single screw extruder having a diameter of 40 mm. The same operation as in Example 1 was performed except that the thickness was changed to 50 μm to obtain a surface layer film (abbreviated as T12). A laminated body was obtained by the same operation as in Example 1 except that the metal body was a cast iron plate having a thickness of 4 mm, a length of 16 cm, and a width of 16 cm (abbreviated as A5), and the lamination method was changed as follows. . The metal body (A5) was surface-treated by shot blasting, and its surface roughness parameter Ra was 1.07 μm, Ry was 11.1 μm, and Rz was 8.5 μm. Table 4 shows the evaluation results of this laminate.
(Production of laminate)
The materials stacked in the following order from bottom to top are set in a high-performance high-temperature vacuum press molding machine (Kitakawa Seiki Co., Ltd., molding press, model: VH1-1747), and the maximum set temperature is 360 ° C. The laminate was obtained by press molding at a preset maximum temperature holding time of 30 minutes and a set pressure of the press molding machine of 5.2 MPa (pressure at the bonding portion was about 3.9 MPa).
(I-1) A stainless steel plate with a side of about 30 cm and a thickness of 1.5 mm,
(J-1) Cushion paper (trade name: RA board RAB N 0016 manufactured by Mitsubishi Paper Industries Co., Ltd.) having a square of about 20 cm on one side covered with 35 μm copper foil on both sides and a thickness of 1.6 mm,
(K-1) A square with a side of 16 cm and a thickness of 4 mm, a cast iron plate (degreased by chloroform cleaning, surface treatment surface up, abbreviation A5),
(L-1) The metal contact film (abbreviated as S12) having a square of 18 cm on a side,
(M-1) The above surface layer film (abbreviated as T12) having a square of 18 cm on one side,
(N-1) A polyimide film having a side of 20 cm and a thickness of 50 μm (manufactured by Ube Industries, trade name: Upilex 50S, thickness 50 μm), polyimide film,
(O-1) 125 μm-thick polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 500H),
(P-1) A polyimide film similar to (n-1) above,
(Q-1) A stainless plate (SUS304) having a square of 20 cm on a side and a thickness of 5 mm,
(R-1) Cushion paper covered with a copper foil, the same as (i-1) above, with a square of 18 cm on one side.
The above (i-1) to (r-1) are for removing dirt and foreign matter on the surface with a wiping paper soaked with a small amount of ethanol before superposition, and (k-1) is for dust and foreign matter on the surface. Using a rubber blower, the above (l-1) to (p-1) are wiping cloth (Teijin) that has been visually inspected for foreign matter on the front and back sides and a small amount of ethanol. The foreign matter was wiped off using a product name (trade name: Microstar-CP), and then visually inspected again to confirm that the foreign matter could be removed, and then superposed.

Example 13
Of the constituent components of the metal contact layer film, 5.5 kg of PEI-1 (55% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), PEEI-2 was not used, and PEEK- 1 4.5 kg (45% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), without using synthetic mica, solid lubricant (D1) 0.5 kg (PEI-1, PEI- 2 and 5 parts by mass with respect to 100 parts by mass of PEEK-1), 0.5 kg of fixed lubricant (D2) (5 parts by mass with respect to a total of 100 parts by mass of PEI-1, PEI-2 and PEEK-1), A metal contact layer film was obtained in the same manner as in Example 1 except that the extrusion temperature of the twin screw extruder and the extrusion temperature of the single screw extruder were changed to 390 ° C. and the thickness was changed to 25 μm (abbreviated as S13). To do.) Constituent components of the surface layer film are PEEK-1 10 kg, synthetic mica is not used, solid lubricant (D1) 2.5 kg (25 parts by mass with respect to 100 parts by mass of PEEK-1), and surface layer thickness is changed to 60 μm. A film for surface layer was obtained by the same operation as in Example 1 (abbreviated as T13). The same operation as in Example 12 except that the metal contact layer film was (S13), the surface layer film was (T13), and the metal body was a cast iron plate having a thickness of 6 mm (abbreviated as A6). To obtain a laminate. The metal body (A6) was surface-treated by shot blasting, and its surface roughness parameter Ra was 0.56 μm, Ry was 5.8 μm, and Rz was 4.9 μm. Table 4 shows the evaluation results of this laminate.

Example 14
Of the constituent components of the metal contact layer film, 3 kg of PEI-1 (30% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) and 3 kg of PEI-2 (PEI-1, PEI- 2 and 30% by mass of PEEK-1), 4 kg of PEEK-1 (40% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), 1 kg of surface-treated synthetic mica as a filler (10 parts by mass with respect to a total of 100 parts by mass of PEI-1, PEI-2 and PEEK-1), (D1) 0.5 kg as a solid lubricant (total 100 masses of PEI-1, PEI-2 and PEEK-1) 5 parts by weight), 1 kg of fixed lubricant (D2) (10 parts by weight with respect to a total of 100 parts by weight of PEI-1, PEI-2 and PEEK-1), extrusion temperature and single screw extrusion of the twin screw extruder Push the machine The temperature 390 ° C., and in addition were changed to 30μm metal contact layer thickness to obtain a film metallic contact layer in the same manner as in Example 1 (, S14 abbreviations.). Constituent components of the film for the surface layer are 10 kg of PEEK-1, 1 kg of surface-treated synthetic mica as a filler (10 parts by mass with respect to 100 parts by mass of PEEK-1), 2 kg of solid lubricant (D1) (100 parts by mass of PEEK-1) 20 parts by weight) and (D2) 1 kg (10 parts by weight with respect to 100 parts by weight of PEEK-1) and a surface layer thickness of 40 μm were obtained in the same manner as in Example 1 to obtain a surface layer film ( The abbreviation is T14). A laminate was obtained in the same manner as in Example 12 except that the metal body was A6, the metal contact layer was S14, and the surface layer was changed to T14. Table 4 shows the evaluation results of this laminate.

Example 15
Of the constituent components of the metal contact layer film, 4 kg of PEI-1 (40% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) and 3 kg of PEI-2 (PEI-1, PEI- 2 and 30% by mass with respect to the total mass of PEEK-1), 3 kg of PEEK-1 (30% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), and surface-treated synthetic mica 1 as a filler .5 kg (15 parts by mass with respect to a total of 100 parts by mass of PEI-1, PEI-2 and PEEK-1), (D1) 1.5 kg (total of PEI-1, PEI-2 and PEEK-1 as solid lubricant) 15 parts by mass with respect to 100 parts by mass), the same operation as in Example 1 except that the extrusion temperature of the twin screw extruder and the extrusion temperature of the single screw extruder were changed to 390 ° C. and the metal contact layer thickness was changed to 28 μm. Do the metal To obtain a catalyst film (and S15 abbreviations.). Constituent components of the film for the surface layer are 10 kg of PEEK-1, 1 kg of surface-treated synthetic mica as a filler (10 parts by mass with respect to 100 parts by mass of PEEK-1), 2 kg of solid lubricant (D1) (100 parts by mass of PEEK-1) 20 parts by mass) and the thickness of the surface layer was set to 60 μm, and the same operation as in Example 1 was performed to obtain a film for the surface layer (abbreviated as T15). The same operation as in Example 12 was performed except that the metal body was cast iron having a thickness of 10 mm (abbreviated as A7), the metal contact layer surface film was changed to S15, and the surface layer film was changed to T15. A laminate was obtained.
The metal body (A7) was surface-treated by shot blasting, and its surface roughness parameter Ra was 0.83 μm, Ry was 8.5 μm, and Rz was 6.6 μm. Table 4 shows the evaluation results of this laminate.

Example 16
Of the constituent components of the metal contact layer film, 3 kg of PEI-1 (30% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) and 3 kg of PEI-2 (PEI-1, PEI) -2 and 30% by mass of PEEK-1), 4 kg of PEEK-1 (40% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), surface treatment as a filler Synthetic mica 2.5kg (25 parts by mass for 100 parts by mass of PEI-1, PEI-2 and PEEK-1), the extrusion temperature of the twin screw extruder and the extrusion temperature of the single screw extruder are 390 ° C, metal Except for changing the contact film thickness to 40 μm, the same operation as in Example 1 was performed to obtain a metal contact film (abbreviated as S16). Constituent components of the surface layer film are 10 kg (100 parts by mass) of PEEK-1, 0.5 kg of surface synthetic mica as a filler (5 parts by mass with respect to 100 parts by mass of PEEK-1), and the above graphite (D2) as a solid lubricant. ) 0.5 kg (PEEK-1, 5 parts by mass with respect to 100 parts by mass) and polytetrafluoroethylene resin (manufactured by Daikin Industries, Ltd., trade name: Polyflon TFE L-5, abbreviated as D3) 2 kg (PEEK) -1 20 parts by mass with respect to 100 parts by mass), except that the surface layer film thickness was set to 70 μm, the same operation as in Example 1 was performed to obtain a surface layer film (abbreviated as T16). A laminate was obtained in the same manner as in Example 12 except that the metal body was A6, the metal contact layer film was S16, and the surface layer film was changed to T16. Table 4 shows the evaluation results of this laminate.

Example 17
As a surface layer component, 10 kg (100 parts by mass) of the above PEEK-1; 1 kg of the above surface-treated synthetic mica (C3) (10 parts by mass with respect to 100 parts by mass of PEEK-1); and the above fluororesin (D1) as a solid lubricant ) 2 kg (20 parts by mass with respect to 100 parts by mass of PEEK-1) and the above graphite (D2) 0.5 kg (5 parts by mass with respect to 100 parts by mass of PEEK-1) using a twin screw extruder with side feed. The mixture was kneaded at a set temperature of 390 ° C., extruded into strands, and cut into pellets (abbreviated as K172).
Of the constituent components of the metal contact layer, 3.5 kg of PEI-1 (35% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) and 3 kg of PEI-2 (PEI-1, PEI- 2 and 30% by mass with respect to the total mass of PEEK-1, and 3.5 kg with PEEK-1 (35% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1). After mixing and stirring, hot air drying was performed at 180 ° C. for 8 hours, and then extruded as a metal contact layer from a multi-manifold die (set temperature: 390 ° C.) connected to a single screw extruder having a diameter of 30 mmφ set at 390 ° C.
The K172 pellets were dried with hot air at 180 ° C. for 8 hours and then extruded as a surface layer from the multi-manifold die (set temperature 390 ° C.) connected to a single screw extruder having a diameter of 30 mmφ set at 390 ° C.
The amount of molten resin discharged was adjusted so that the thickness ratio of the metal contact layer to the surface layer was 24:76. The coextruded film, that is, the metal contact layer side of the laminate was quenched with a 125 ° C. casting roll, and a silicon rubber roll was pressed against the surface layer side. Furthermore, the silicon rubber roll was cooled by pressing a hard chrome plating roll cooled with water of about 35 ° C. installed on the opposite side of the metal roll. Subsequently, this coextruded film was wound up to obtain a laminate. The amount of molten resin discharged from the extruder and the line speed were adjusted so that the thickness of this product was 34 μm. When the cross section of the produced laminated film was observed under a microscope and the thickness of each layer was measured, the thickness of the metal contact layer was 8 μm and the thickness of the surface layer was 26 μm. The abbreviation for this laminated film is “ST17”.
Except that the metal contact film and the surface layer film were changed to the laminated film (ST17) and the metal body was changed to A6, a press molding operation was performed in the same manner as in Example 12 to obtain a laminated body. Table 5 shows the evaluation results of this laminate.

Example 18
Of the components of the metal contact layer, 5.8 kg of PEI-1 (58% by mass with respect to the total mass of PEI-1, PEI-2, and PEEK-1), PEEK-1 was used without using PEI-2. 4.2 kg (42 mass% with respect to the total mass of PEI-1, PEI-2, and PEEK-1), surface treatment synthetic mica (C3) 1.5 kg (total of PEI-1, PEI-2, and PEEK-1 100) 15 parts by mass with respect to parts by mass) and 1 kg of the fluororesin (D1) as a solid lubricant (10 parts by mass with respect to a total of 100 parts by mass of PEI-1, PEI-2, and PEEK-1) Were kneaded at a set temperature of 390 ° C., extruded into strands, and cut into pellets (abbreviated as K181).
As a surface layer component, 10 kg (100 parts by mass) of the above PEEK-1, no surface-treated synthetic mica as a filler, and 2.5 kg of the fluororesin (D1) as a solid lubricant (100 mass of PEEK-1) 25 parts by mass) was kneaded at a set temperature of 390 ° C. using a twin screw extruder with side feed, extruded into a strand, and cut into pellets (abbreviated as K182).
The K181 pellets were dried with hot air at 180 ° C. for 8 hours and extruded as a metal contact layer from a multi-manifold die (set temperature: 390 ° C.) connected to a single screw extruder having a diameter of 30 mmφ set at 390 ° C.
The K182 pellets were dried with hot air at 180 ° C. for 8 hours, and then extruded as a surface layer from the multi-manifold die (set temperature 390 ° C.) connected to a single screw extruder having a diameter of 40 mmφ set at 390 ° C.
The discharge amount of the molten resin was adjusted so that the thickness ratio of the metal contact layer to the surface layer was 14:86. The coextruded film, that is, the metal contact layer side of the laminate was quenched with a 125 ° C. casting roll, and a silicon rubber roll was pressed against the surface layer side. Furthermore, the silicon rubber roll was cooled by pressing a hard chrome plating roll cooled with water of about 35 ° C. installed on the opposite side of the metal roll. Subsequently, this coextruded film was wound up to obtain a laminate. The amount of molten resin discharged from the extruder and the line speed were adjusted so that the thickness of this product was 105 μm. When the cross section of the produced laminated film was observed under a microscope and the thickness of each layer was measured, the thickness of the metal contact layer was 15 μm, and the thickness of the surface layer was 90 μm. The abbreviation for this laminated film is “ST18”.
Except for changing the metal contact film and the surface layer film to the above laminated film (ST18) and changing the lamination temperature by pressing to 250 ° C., the same press molding operation as in Example 12 was performed to obtain a laminate. Table 5 shows the evaluation results of this laminate.

Example 19
Of the constituent components of the metal contact layer, 6 kg of PEI-1 (60% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) and 1.5 kg of PEI-2 (PEI-1, PEI- 2 and 15% by mass of PEEK-1), 2.5 kg of PEEK-1 (25% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), surface-treated synthetic mica (C3 ) 1.5 kg (15 parts by mass with respect to a total of 100 parts by mass of PEI-1, PEI-2 and PEEK-1), and (D2) 1 kg (of PEI-1, PEI-2 and PEEK-1 10 parts by mass with respect to 100 parts by mass in total was kneaded at a set temperature of 390 ° C. using a twin screw extruder with side feed, extruded into a strand, and cut into pellets (abbreviated as K191). .
As a surface layer component, 10 kg (100 parts by mass) of the above PEEK-1, 0.5 kg of surface treated synthetic mica (C3) as a filler (5 parts by mass with respect to 100 parts by mass of PEEK-1), and the above as a solid lubricant 2 kg of fluororesin (D1) (20 parts by mass with respect to 100 parts by mass of PEEK-1) and 0.5 kg of graphite (D2) (5 parts by mass with respect to 100 parts by mass of PEEK-1) are twin-screw extruded with side feed. The mixture was kneaded at a preset temperature of 390 ° C., extruded into a strand, and cut into pellets (abbreviated as K192).
The K191 pellets were dried with hot air at 180 ° C. for 8 hours and extruded as a metal contact layer from a multi-manifold die (set temperature: 390 ° C.) connected to a single screw extruder with a diameter of 30 mmφ set at 390 ° C.
The K192 pellets were dried with hot air at 180 ° C. for 8 hours, and then extruded as a surface layer from the multi-manifold die (set temperature 390 ° C.) connected to a single screw extruder with a diameter of 30 mmφ set at 390 ° C.
Adjust the amount of molten resin discharged so that the thickness ratio of the metal contact layer to the surface layer is 57:43, and adjust the amount of molten resin discharged from the extruder and the line speed so that the total thickness is 70 μm. A laminated film was obtained by performing the same operation as in Example 10. When the cross section of the produced laminated film was observed with a microscope and observed, and the thickness of each layer was measured, the thickness of the metal contact layer was 34 μm and the thickness of the surface layer was 26 μm. The abbreviation for this laminated film is “ST19”.
Press forming operation similar to that of Example 12 except that the metal contact film and the surface layer film are changed to the above laminated film (ST19), the metal body is changed to A6, and the lamination temperature by pressing is changed to 250 ° C. To obtain a laminate. Table 5 shows the evaluation results of this laminate.

Example 20
The metal contact film and the surface layer film were changed to the above laminated film (ST18), and the metal body was surface-treated by shot blasting to an 8 mm thick aluminum plate (material is A1100, silicon shown in JIS H4000-1999, silicon The total content of iron and iron was 0.7%. The abbreviation was changed to A8.) The laminate was obtained in the same manner as in Example 12 except that the lamination temperature by pressing was changed to 240 ° C. The metal body (A8) was surface-treated by shot blasting, and its surface roughness parameter Ra was 0.74 μm, Ry was 7.5 μm, and Rz was 6.1 μm. Table 5 shows the evaluation results of this laminate.

Example 21
The metal contact film and the surface layer film were changed to the above laminated film (ST19), and the metal body was subjected to surface treatment by shot blasting to a 6 mm thick aluminum-silicon alloy plate (the material was shown in JIS H4000-1999). A4043, silicon content 5.5%. The abbreviation was changed to A9), and the same operation as in Example 12 was performed except that the lamination temperature by pressing was changed to 240 ° C. to obtain a laminate. The surface roughness parameter Ra of the metal body (A9) was 0.85 μm, Ry was 9.1 μm, and Rz was 7.2 μm. Table 5 shows the evaluation results of this laminate.

From Tables 1 and 2, the laminated bodies of Examples 1 to 8 are less likely to be peeled off at the end of cutting by shearing, and the effects of the present invention are clear.
From Table 3, the laminated bodies of Examples 9 to 11 hardly peel off at the end of cutting by shearing, and the effect of the present invention is clear.
From Table 4, the laminated bodies of Examples 12 to 16 are less likely to be peeled around the cut by the cutter knife, and the effect of the present invention is clear.
From Table 5, the laminated bodies of Examples 17 to 21 are less likely to be peeled around the cut by the cutter knife, and the effect of the present invention is clear.

The laminate of the present invention is excellent in slidability, heat resistance, chemical resistance, solder heat resistance, dimensional stability, etc., and thus is suitably used for various applications. And partition walls, sliding parts for doors, brake parts, air compressor parts, bearings, bushes, energy generating equipment parts, battery parts, fuel cell parts, heat shielding plates, housings for various devices, electromagnetic shielding plates, aerospace equipment And a protective plate.

Claims (12)

  A laminate in which a metal contact layer and a surface layer are sequentially laminated on at least one surface of a metal body, wherein the metal contact layer includes (A) a thermoplastic polyimide resin and (B) a polyaryl ketone resin. And a surface layer comprising a resin composition containing a polyaryl ketone resin (B).   The laminate according to claim 1, wherein the metal contact layer and / or the surface layer further comprises (C) a resin composition containing a filler.   The laminate according to claim 1 or 2, wherein the metal contact layer and / or the surface layer further comprises (D) a resin composition containing a solid lubricant.   The metal contact layer comprises (A) a thermoplastic polyimide resin and (B) a polyarylketone resin at a mass ratio of (A) / (B) = 95/5 to 5/95 with respect to 100 parts by mass of the resin composition. And (C) a resin composition containing 0 to 100 parts by mass of a filler and / or (D) a solid lubricant in a ratio of 0 to 100 parts by mass, and the surface layer is 100 parts by mass of (B) a polyaryl ketone resin. In any one of Claims 1-3 which consists of a resin composition which contains 0-100 mass parts of (C) fillers, and / or (D) a solid lubricant in the ratio of 0-400 mass parts. The laminated body of description.   The metal contact layer comprises (A) a thermoplastic polyimide resin and (B) a polyarylketone resin at a mass ratio of (A) / (B) = 95/5 to 30/70 with respect to 100 parts by mass of the resin composition. The laminate according to any one of claims 1 to 3, comprising a resin composition containing 0 to 100 parts by mass of (C) a filler and / or 0 to 100 parts by mass of (D) a solid lubricant. body.   The laminate according to any one of claims 1 to 5, wherein the thickness ratio between the metal contact layer and the surface layer is in the range of 1/99 to 99/1.   The thickness of a metal body is 0.01-50 mm, the thickness of a metal contact layer is 0.1-800 micrometers, and the thickness of a surface layer is 1-1000 micrometers, The laminated body of any one of Claims 1-5 . The thermoplastic polyimide resin of component (A) is composed mainly of a polyetherimide resin having a repeating unit represented by the following structural formula (1) or a polyetherimide resin having a repeating unit represented by the following structural formula (2). The polyaryl ketone resin as the component (B) is mainly composed of a crystalline polyetheretherketone resin having a repeating unit represented by the following structural formula (3). The laminate according to any one of the above.

  The laminate according to any one of claims 2 to 8, wherein the filler of component (C) is plate-shaped.   The laminate according to any one of claims 2 to 9, wherein the average particle diameter of the filler of component (C) is in the range of 0.01 to 200 µm.   (C) The filler of a component is a mica, The laminated body of any one of Claims 2-10. The laminate according to any one of claims 3 to 8, wherein the solid lubricant as component (D) is at least one selected from graphite, a fluororesin, and a transition metal sulfide.