JP2006198993A - Thermoplastic resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin laminate having good adhesiveness, chemical resistance, heat resistance, electrical properties, and laminating workability, and can be suitably used for an electronic circuit board, a printed wiring board, a machine member, an automobile part and the like. provide.
SOLUTION: The polyaryl ketone resin (A) contains 100 parts by mass of a fluororesin (B) in a proportion of 0 to 100 parts by mass and the filler (C) in a proportion of 0 to 100 parts by mass. One layer and a polyarylketone-based resin (A) with a thermoplastic transition resin (D) having a glass transition temperature of 180 to 350 ° C. (A) / (D) = 95 to 5/5 to 95 mass The second layer comprising 0 to 100 parts by mass of the fluororesin (B) and 0 to 100 parts by mass of the filler (C) with respect to 100 parts by mass of the resin component contained in the ratio, A thermoplastic resin laminate is formed adjacent to one layer.
[Selection figure] None

Description

  The present invention has a good adhesiveness, chemical resistance, heat resistance, electrical properties, and laminate processability, and can be suitably used for an electronic circuit board, a printed wiring board, a machine member, an automobile part, and the like. About.

Polyaryl ketone resins such as polyetheretherketone resin and polyetherketone resin have excellent heat resistance, flame resistance, chemical resistance, electrical properties, etc., so aircraft parts, automobile parts, mechanical parts, Used for applications such as electronic parts.
On the other hand, epoxy resin substrates and glass cloth reinforced epoxy resin substrates that are frequently used as electronic circuit substrates are inferior to polyaryl ketone resins in terms of solvent resistance, etc., and components such as circuit components and circuit substrates made of polyaryl ketone resins There was a limit to using it in the same environment. For this reason, an attempt has been made to make a composite with a member made of a polyaryl ketone-based resin, but an adhesive is required. However, in long-term use, the adhesive may induce a short circuit due to electromigration between metal circuits (for example, copper foil or aluminum foil) on the surface of the epoxy resin substrate, and a lamination method that does not use an adhesive is required. It was.
In recent years, an electronic circuit board substrate that needs to be laminated with copper foil or aluminum foil, a polyaryl ketone resin having a high melting point and excellent heat resistance, and a polyetherimide resin having good adhesion to metal Including resin compositions have attracted attention.
It is disclosed that these resin compositions exhibit good adhesion with copper foil and are useful for circuit board substrates (see, for example, Patent Document 1). Furthermore, a thermoplastic resin laminate with a printed wiring board or a metal body using the resin composition and a method for producing the same are disclosed (for example, Patent Document 2 and Patent Document 3).
However, a resin composition containing a polyaryl ketone-based resin and a polyetherimide resin is not sufficiently resistant to organic solvents and has limited chemical resistance such as alkali resistance. As a member for an electronic circuit, it is not necessarily sufficient, and its use has a limit.

A heat-resistant composite film composed of a polyether ether ketone resin layer and a polyetherimide resin layer has been proposed (see, for example, Patent Document 4).
However, when this product is laminated with an epoxy resin circuit board by a press molding method, the polyetherimide resin layer melts and flows out, and burrs are likely to occur at the end, which causes problems in dimensional accuracy and appearance after lamination. In some cases, the removal of burrs is not easy, and there is a practical problem that it takes time.

JP 59-115353 A JP 2002-212314 A Japanese Patent No. 3514667 JP-A-62-148260

  The present invention has been made in view of the above circumstances, and has good adhesiveness, laminating workability, electrical characteristics, heat resistance, chemical resistance, and particularly excellent adhesion to an epoxy resin circuit board material. In the case of the laminated body, since the dielectric constant of the adherend is rarely increased, and the burr at the time of press lamination processing can be reduced, the surface protective layer of the printed circuit board used for the circuit of the electronic device, It is an object of the present invention to provide a thermoplastic resin laminate that can be suitably used as an electronic circuit forming substrate, as well as a machine member, an automotive part, and the like.

As a result of intensive studies, the present inventor has found that the polyaryl ketone-based resin (A) and, if necessary, the first layer containing the fluororesin (B) and the filler (C) in specific ratios, and the polyaryl ketone A ketone-based resin (A), at least one thermoplastic adhesion-imparting resin (D) selected from a thermoplastic polyimide resin, a polyethersulfone resin, and a polysulfone resin; and, if necessary, a fluororesin (B) and The present inventors have found that a thermoplastic resin laminate in which the second layer containing the filler (C) at a specific ratio is arranged adjacent to each other can solve the above problems, and based on this finding, the present invention has been completed.
That is, the present invention provides the following thermoplastic resin laminate.
(1) 1st comprising 0 to 100 parts by mass of fluororesin (B) and 0 to 100 parts by mass of filler (C) with respect to 100 parts by mass of polyaryl ketone-based resin (A). The layer and the polyarylketone resin (A) are mixed with a thermoplastic adhesiveness-imparting resin (D) having a glass transition temperature of 180 to 350 ° C. (A) / (D) = 95/5 to 5/95 The second layer comprising 0 to 100 parts by mass of the fluororesin (B) and 0 to 100 parts by mass of the filler (C) with respect to 100 parts by mass of the resin component contained in A thermoplastic resin laminate disposed adjacent to the layer.
(2) The thermoplastic resin laminate according to (1), wherein the thermoplastic adhesion-imparting resin (D) is at least one selected from a thermoplastic polyimide resin, a polyethersulfone resin, and a polysulfone resin.
(3) The thermoplastic resin according to (1) or (2), wherein the ratio of the thickness of the first layer to the thickness of the second layer is first layer / second layer = 99/1 to 1/99. Laminated body.
(4) The component (A) is mainly composed of a crystalline polyetheretherketone resin having a repeating unit represented by the following structural formula (1), and the component (D) is represented by the following structural formula (2). The above-mentioned (1) to (3) characterized in that the main component is a polyetherimide resin having a repeating unit represented by or a polyetherimide resin having a repeating unit represented by the following structural formula (3). The thermoplastic resin laminate according to any one of the above.

(5) The fluororesin as component (B) is at least one selected from polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer The thermoplastic resin laminate according to any one of (1) to (4).
(6) The thermoplastic resin laminate according to any one of (1) to (5), wherein the filler of component (C) is a plate-like material.
(7) The thermoplastic resin laminate according to any one of (1) to (5), wherein the filler of component (C) is at least one selected from mica, glass flakes, and silicon dioxide powder.

  According to the present invention, adhesiveness, laminating workability, electrical properties, heat resistance, chemical resistance are good, especially excellent adhesion to epoxy resin circuit board materials, and a laminate with circuit board materials In addition, since the dielectric constant of the adherend is rarely increased and the burrs at the time of press lamination can be reduced, the surface protective layer of the printed circuit board used for the circuit of the electronic device and the electronic circuit forming substrate It is possible to provide a thermoplastic resin laminate that can be suitably used as a mechanical member, an automotive part, and the like.

The thermoplastic resin laminate of the present invention is a thermoplastic resin laminate comprising a thermoplastic resin having a different composition and a first layer and a second layer disposed adjacent to each other. Here, the first layer is a layer that mainly exhibits solvent resistance and heat resistance, and the second layer is a layer that mainly exhibits adhesion and heat resistance to the adherend.
In the first layer constituting the present invention, the polyaryl ketone resin as the component (A) is an essential component, and contains a fluororesin (B) and / or a filler (C) as necessary.
The (A) component polyarylketone resin used in the first layer is a thermoplastic resin having an aromatic nucleus bond, an ether bond and a ketone bond in its structural unit, and a representative example thereof is polyetherketone (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 other repeating units such as a biphenyl structure and a sulfonyl group may be included without departing from the scope of the present invention. Moreover, in order to improve the heat resistance of the thermoplastic resin laminate of the present invention, for example, solder heat resistance and reflow heat resistance, it preferably exhibits crystallinity and has a crystal melting peak temperature of 260 ° C. or higher. The crystal melting peak temperature is preferably 300 to 380 ° C. In the present invention, the following structural formula (1)

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

If necessary, the fluororesin of the component (B) used in the first layer is not particularly limited as long as it is a synthetic polymer having a structural unit 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 ] — and repeating units represented by — (CF ₂ CF ₂ ) —, preferably 99-80% by mass Tetrafluoroethylene-hexafluoropropylene copolymer (FEP) consisting of 1 to 20% by mass of a repeating unit represented by [CF (CF ₃ ) CF ₂ ] —, (c) In the molecule, — (CF ₂ A repeating unit represented by CF ₂ ) — and — [CF (OC _m F _{2m + 1} ) CF ₂ ] — (wherein m is a positive integer in the range of 1 to 16, preferably 1 to 10). Having a repeating structural unit represented by And a repeating unit 1-8 wt%, represented by - _{is, - (CF 2 CF 2)} - represented repeating units 99-92 wt% and are in - _{[CF (OC m F 2m + 1} ) CF 2 ] Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), (d) having repeating structural units represented by — (CF ₂ CF ₂ ) — and — (CH ₂ CH ₂ ) — in the molecule. Preferably, a tetra unit consisting of 90 to 74% by mass of a repeating unit represented by — (CF ₂ CF ₂ ) — and 10 to 26% by mass of a repeating unit represented by — (CH ₂ CH ₂ ) — Fluoroethylene-ethylene copolymer (ETFE), (e) chlorotrifluoroethylene-ethylene copolymer having repeating structural units represented by-(CFClCF ₂ )-and-(CH ₂ CH ₂ )-in the molecule Coalescence, (f In the _{molecule, - (CF 2 CH 2)} - polyvinylidene fluoride having a repeating structural unit represented by (PVDF) and the like, further, these fluororesins, within the range not impairing the essential properties of the resin It may be one containing repeating structural units based on other monomers. 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 Cl, Br, or I, 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, (a) polytetrafluoroethylene (PTFE) (b) tetrafluoroethylene-hexafluoropropylene copolymer (FEP), (c) tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer It is selected from coalescence (PFA), more preferably (a) PTFE.

The molecular weight of the fluororesin is not particularly limited, but in the case of PTFE that melts, one having a melt viscosity of 1 million Pa · s or less at 380 ° C. is preferable. 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.

The amount of the component (B) used as necessary in the first layer is in the range of 0 to 100 parts by mass with respect to 100 parts by mass of the polyaryl ketone-based resin of the component (A) described above. Since the dielectric constant can be reduced by the addition of the fluororesin, adverse effects on the transmission characteristics of the circuit board can be reduced when it is laminated on the circuit board. In addition, when used as a sliding member for machine parts, automobile parts, etc., the sliding characteristics can be improved.
On the other hand, when the fluororesin (B) is 100 parts by mass or less with respect to 100 parts by mass of the polyaryl ketone resin as the component (A), the interlayer adhesion with the second layer is good. Therefore, the preferable addition amount of the component (B) is 10 to 70 parts by mass, more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the component (A).
The form of the component (B) in the first layer may be any form such as particulate, amorphous, spherical, layered, fibrous, mutual continuous network structure, etc., but it is resistant to chlorinated organic solvents such as chloroform. In order to improve, the form in which (A) component exists in the layer surface, or the form in which (A) component forms a continuous layer and (B) component forms a dispersed layer is preferable. In addition, the dispersed particle diameter and fiber diameter of the component (B) affect the irregularities on the surface of the thermoplastic resin laminate, and thus are appropriately selected according to the necessity of controlling the surface form.

The first layer of the thermoplastic resin laminate of the present invention may contain a filler (C) as necessary. Use of the filler (C) has an effect of reducing the coefficient of linear expansion and reducing warping and deformation of the thermoplastic resin laminate. Known fillers can be used, such as clay, glass, alumina, spherical alumina, plate-like alumina, silicon dioxide powder (silica, spherical silica, natural or synthetic quartz powder, etc.), nitriding Fillers such as aluminum, silicon nitride, and graphite, fibers such as glass fiber and carbon fiber, preferably inorganic scaly powder such as synthetic mica, natural mica (mascobite, phlogopite, sericite, szolite Etc.), and calcined inorganic or synthetic mica, boehmite, talc, illite, kaolinite, montmorillonite, vermiculite, smectite, plate-like alumina and the like are preferred. Further, in order to lower the dielectric constant of the thermoplastic resin laminate and make the dielectric constant of the laminate with the adherend equal to or less than that of the adherend alone, the relative dielectric constant of the filler (C) is 10 The following are preferable, and more preferably 8 or less. Preferably for this purpose, silicon dioxide powder, specifically quartz powder (relative permittivity 3.6 to 3.8 at 1 MHz), amorphous or spherical synthetic silica (relative permittivity 3 to 4), Furthermore, glass flakes (same dielectric constant 4-7), synthetic mica (same dielectric constant 6.2), natural mica (same dielectric constant 5-9), and phlogopite (relative dielectric constant 5-6) are more preferable. These fillers can be used alone or in combination of two or more.
In order to reduce the linear expansion coefficient in the surface direction of the thermoplastic resin laminate of the present invention and obtain the effect of reducing warping and deformation of the thermoplastic resin laminate, the shape of the filler (C) is preferably a plate shape. .
The average particle size of the filler (C) is about 0.01 to 200 μm, preferably 0.1 to 20 μm, more preferably 1 to 10 μm. If the average particle size is 0.01 μm or more, handling with the resin component or melt kneading is not so difficult, and if it is 200 μm or less, the toughness of each layer of the thermoplastic resin laminate and the entire thermoplastic resin laminate. Is not significantly impaired.
The average aspect ratio (particle size / thickness) of the filler (C) is preferably about 1 to 30, preferably 30 or more. The higher the average aspect ratio, the greater the effect of reducing the linear expansion coefficient of the thermoplastic resin laminate.

  As the filler for 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, a wet method in which a solvent is removed after contacting a filler and a surface treatment agent in a solution in which the surface treatment agent is dissolved, and a solution in which the surface treatment agent is dissolved and the filler are brought into contact with each other by a method such as spraying or stirring. After the surface treatment agent is coated on the surface of the filler, a semi-wet method in which the solvent is removed, and an integral blend method in which the resin and the filler and the surface treatment agent dissolved in a small amount of solvent are mixed and stirred. Etc. From the viewpoint of efficiently attaching the surface treatment agent to the surface of the filler material, 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 with a solvent are contact-mixed and then left in the air for several hours to several days, and then contacted 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. The temperature is usually about 80 to 150 ° C, preferably 100 to 130 ° C. The treatment time is usually 4 to 200 hours, preferably 24 to 100 hours.

In the first layer, the amount of the filler of component (C) used as necessary is in the range of 0 to 100 parts by mass with respect to 100 parts by mass of the polyaryl ketone-based resin of component (A) described above. . When the component (C) is 100 parts by mass or less, the first layer does not become extremely brittle. On the other hand, the addition of the component (C) improves the shape stability of the thermoplastic resin laminate due to the effect of reducing the linear expansion coefficient, and a clear effect is obtained at 5 parts by mass or more. Therefore, the preferable addition amount of the component (C) is 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, and further preferably 15 to 50 parts by mass with respect to 100 parts by mass of the component (A). Range.
In the first layer, the total mass in the case where the component (B) and the component (C) that are used as needed are combined is 0 to 100 parts by mass of the polyaryl ketone-based resin of the component (A) described above. 100 parts by mass, preferably 0 to 55 parts by mass, more preferably 0 to 50 parts by mass. When the total mass of the component (B) and the component (C) is 100 parts by mass or less, problems such as surging during melt-kneading are unlikely to occur.

The second layer constituting the present invention contains a polyaryl ketone resin (A) and a thermoplastic adhesion-imparting resin (D).
The (A) polyaryl ketone-based resin used for the second layer is selected from the same group as that used for the first layer, and is preferably polyetheretherketone. The polyaryl ketone resin used for the second layer may be the same as or different from the polyaryl ketone resin used for the first layer.
(D) component used for a 2nd layer is thermoplastic adhesive provision resin whose glass transition temperature is 180-350 degreeC. (D) The glass transition temperature of a component is measured by the method of prescription | regulation of JISK7122-1987. The range of the glass transition temperature is 180 to 350 ° C, preferably 200 to 300 ° C, more preferably 205 to 270 ° C. If it is 180 degreeC or more, the heat resistance of a laminated body with a specific adhesion body will not fall remarkably, and if it is 350 degrees C or less, a shaping | molding process will be comparatively easy.
Specific examples of the thermoplastic adhesion imparting resin as component (D) include thermoplastic polyimide resins, aromatic polyether sulfone resins, and aromatic polysulfone resins.
Thermoplastic polyimide resin is a thermoplastic resin containing aromatic nucleus bond and imide bond in its structural unit, and aromatic polysulfone (PSF, glass transition temperature 190 ° C) is a thermoplastic resin containing aromatic nucleus bond and sulfonyl bond in the structural unit. Aromatic polyethersulfone (PES, glass transition temperature 230 ° C.) is a thermoplastic resin containing aromatic nucleus bonds, ether bonds and sulfonyl bonds in its structural unit. PES is mainly composed of dichlorodiphenylsulfone. It is obtained by a polycondensation reaction as a raw material, and all have excellent heat resistance. Among these, a plastic polyimide resin having better adhesion to the first layer is preferable.

  Specific examples of the thermoplastic polyimide resin include polyetherimide resin, but are not particularly limited. Specifically, the following structural formula (2)

[Product name “Ultem 1000” (glass transition temperature: 216 ° C.), “Ultem 1010” (glass transition temperature: 216 ° C.) manufactured by General Electric Co., Ltd.]], the following structural formula ( 3)

Polyetherimide having a repeating unit represented by the formula [“Ultem CRS5001” (glass transition temperature Tg 226 ° C.)], and other specific examples, trade name “Ultem XH6050” (glass transition temperature) manufactured by General Electric Co., Ltd. : 247 ° C.), trade name “Aurum PL500AM” (glass transition temperature 258 ° C.) manufactured by Mitsui Chemicals, Inc., and the like.

Of these, those having no crystallinity are preferred, and polyetherimide resins having a repeating unit represented by the structural formula (2) or (3) are more preferred. The method for producing the polyetherimide resin is not particularly limited. Usually, the amorphous polyetherimide resin having the above structural formula (2) is 4,4 ′-[isopropylidenebis (p-phenylene). As a polycondensate of oxy) diphthalic dianhydride and m-phenylenediamine, and polyetherimide resin having the above structural formula (3) is 4,4 ′-[isopropylidenebis (p-phenyleneoxy) diphthalate. It is synthesized by a known method as a polycondensate of acid dianhydride and p-phenylenediamine.
The polyetherimide resin used in the present invention may contain other monomer units that can be copolymerized such as amide group, ester group, sulfonyl group and the like within the scope of the present invention. Absent. In addition, polyetherimide resin can be used individually by 1 type or in combination of 2 or more types.

In the resin composition constituting the second layer of the present invention, the mixing mass ratio of the (A) component polyarylketone resin and the (D) component thermoplastic adhesion-imparting resin is (A) / (D) = It is in the range of 95/5 to 5/95, preferably 70/30 to 15/85, more preferably 50/50 to 25/75.
With respect to the total of 100% by mass of the component (A) and the component (D), when the component (A) is 5% by mass or more, the polyaryl ketone resin of the component (A) has excellent heat resistance and low water absorption The characteristics can be exhibited, and the occurrence of burrs during press bonding with the adherend is small. Moreover, the adhesiveness of a 2nd layer and a to-be-adhered body is favorable in (D) component being 5 mass% or more.
Moreover, when using crystalline polyaryl ketone-type resin as (A) component, (A) component is 15 mass% or more with respect to a total of 100 mass% of (A) component and (D) component, The crystallinity itself as a resin component constituting the second layer is high, the crystallization rate is high, and the heat resistance is good. In the same case, if the component (D) is 30% by mass or more, volume shrinkage (dimensional change) accompanying crystallization of the crystalline polyaryl ketone resin is less likely to occur, and in adhesion to the adherend. Reliability is improved. Therefore, when a crystalline polyaryl ketone resin is used as the component (A), the mixing mass ratio of the component (A) to the component (D) is (A) / (D) = 70 to 15/30 to 85, and more preferably 45 to 25/55 to 75.

The second layer can contain a fluororesin (B), and is effective in reducing the relative dielectric constant as in the first layer. (B) As a fluororesin of a component, what is chosen from the group similar to what is used for a 1st layer is mentioned, It can use. The kind of fluororesin used for the second layer may be the same as or different from the fluororesin used for the first layer.
The quantity of (B) component used in a 2nd layer is the range of 0-100 mass parts with respect to 100 mass parts of total amounts of (A) component and (D) component. Since the dielectric constant can be reduced by adding a fluororesin, there is little adverse effect on the transmission characteristics of the circuit board when laminated on the circuit board. On the other hand, when the fluororesin (B) is 100 parts by mass or less, interlayer adhesion with the first layer is good. From this, the suitable addition amount of a fluororesin (B) component is 10-70 mass parts with respect to 100 mass parts of total amounts of (A) component and (D) component, More preferably, 15-50 It is the range of mass parts.
The form of the component (B) in the second layer is the same as the form of the component (B) in the first layer, any of particulate, amorphous, spherical, layered, fibrous, mutual continuous network structure, etc. In order to improve the adhesion to the adherend, the form in which the mixture of the component (A) and the component (D) is present on the surface of the layer, or the component (A) and the component (D) A form in which the mixture forms a continuous layer and the component (B) forms a dispersed layer is preferable. In addition, the dispersed particle diameter and fiber diameter of the component (B) affect the irregularities on the surface of the form body, and thus are appropriately selected according to the necessity of controlling the surface form.

Examples of the type of filler (C) used for the second layer as needed include those selected from those used for the first layer. The type of filler used for the second layer may be the same as or different from the filler used for the first layer. Further, the amount of filler used in the first layer and the second layer may be the same or different.
The amount of the filler of the component (C) is in the range of 0 to 100 parts by mass with respect to 100 parts by mass of the total mass of the components (A) and (D) described above. When the component (C) is 100 parts by mass or less, the second layer does not become extremely brittle. On the other hand, the addition of the component (C) improves the shape stability of the thermoplastic resin laminate due to the effect of reducing the linear expansion coefficient, and a clear effect is obtained at 5 parts by mass or more. Therefore, the preferable addition amount of the component (C) is 5 to 70 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the component (A).
In the second layer, the total mass in the case where the (B) component and the (C) component used together as necessary is 0 with respect to the total of 100 parts by mass of the above-described (A) component and (D) component. -100 mass parts, Preferably, it is 0-55 mass parts, More preferably, it is 0-50 mass parts. When the total mass of the component (B) and the component (C) is 100 parts by mass or less, problems such as surging during melt-kneading are unlikely to occur.

Resin composition constituting the first layer [including the case of component (A) alone. ], If necessary, various additives other than the resin other than the component (A) and the component (B) and the filler of the component (C), for example, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a core You may mix | blend an agent, a coloring agent, a lubricant, a flame retardant, etc. suitably. A known method can be used as a method of mixing various additives including the case of using the filler of component (C). As an example of a mixing combination,
(I) A method of mixing and dispersing the two components (A) and (B) at the same time when the component (A) and the component (B) are included.
(II) When composed of (A) component and (B) component, melt one of (A) component or (B) component and add the remaining one in solid state, semi-molten state or molten state and mix How to disperse.
(III) Method of mixing and dispersing (A) component and (C) component simultaneously when consisting of (A) component and (C) component (IV) When consisting of (A) component and (C) component, A method in which the component (A) is in a molten or semi-molten state, and then the component (C) is added and mixed and dispersed.
(V) A method of mixing and dispersing the three components (A), (B) and (C) at the same time when the component (A), (B) and (C) are comprised,
(VI) In the case of comprising (A) component, (B) component and (C) component, after mixing and dispersing (C) component in at least one of (A) component or (B) component, the remaining other The method of mixing and dispersing simultaneously or sequentially with the component of [When (C) component is mixed and dispersed in both (A) component and (B) component, (C) in (A) component and (B) component ) Component concentrations may be the same or different. ],
(VII) In the case of comprising (A) component, (B) component and (C) component, after mixing and dispersing (C) component in at least one of (A) component or (B) component, the remaining other A method of mixing and dispersing simultaneously or sequentially with the components of
(VIII) When the component (A), the component (B) and the component (C) are used and a plurality of types (A) and / or a plurality of types (B) are used, the components (A) and (B) At least one of the components is mixed with (C) component mixed and dispersed at a high concentration with other components (A) and (B) to be blended, or with the above mixture and others to be blended A method of mixing and dispersing a mixture of (A) component and / or (B) component (C) component mixed and dispersed at a low concentration simultaneously or sequentially;
Etc. Mixing / dispersing can be performed by the same method as that used in the lower layer.

In the resin composition constituting the second layer, various additives other than the resin (A), the component (B), the resin other than the component (D) and the filler (C), for example, to such an extent that the properties are not impaired. , 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 case where (B) component and a filler (C) are used. As an example of a mixing combination,
(IX) A method of mixing and dispersing the two components (A) and (D) at the same time when the component (A) and the component (D) are included.
(X) It consists of (A) component and (D) component, and when at least one of (A) component and / or (D) component is plural, at least one (A) component and / or (D) component Mixing and dispersing the remaining ingredients in this mixture,
(XI) A combination of (A) component and (D) component and (B) component and / or (C) component, when these components are mixed and dispersed simultaneously,
(XII) When the combination of component (A) and component (D) is combined with component (B) and / or component (C), component (B) and / or component (A) and component (D) Or (C) a method of mixing and dispersing at least one of the components, and then mixing and dispersing the mixed and dispersed components and the remaining components simultaneously or sequentially;
(XIII) When the combination of the component (A) and the component (D) and the component (B) and / or the component (C) are included, at least one of the component (A), the component (B), and the component (D) (C ) Method of mixing and dispersing the components in advance, then mixing and dispersing the mixed and dispersed components and the remaining components simultaneously or sequentially,
(XIV) When the combination of (A) component and (D) component, (B) component and / or (C) component, and at least one of (A) component and (D) component is a combination of plural types, Prepare a mixture in which component (B) and / or component (C) is mixed and dispersed in at least one of component (A) and component (D), and mix and disperse these mixture and the remaining components simultaneously or sequentially. [In this case, the ratio of the component (B) and / or the component (C) to the component (A) and the ratio of the component (B) and / or the component (C) to the component (D) may be the same or different. Good. ], Etc. are mentioned.

  As a method of mixing and dispersing each component of the resin composition constituting the first layer and the second layer, each resin component, filler (C) and various additives used as desired are separately uniaxially melt-kneaded. The components can be supplied to and mixed with a machine or a biaxial melt kneader, and each component can be sequentially supplied to the melt kneader using a melt kneader having a plurality of supply parts such as a side feed. Moreover, after premixing them beforehand using mixers, such as a Henschel mixer (brand name), a super mixer, a ribbon blender, and a tumbler mixer, it supplies to a melt kneader, for example, the temperature of 300 to 430 degreeC. Can be melt kneaded. 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 fluororesin (B), the filler (C) and various additives are highly concentrated (typically about 5 to 60% by mass) with the component (A) and / or the component (D) as the base resin. And the like, and a method of preparing a masterbatch mixed in (2) separately, adjusting the concentration of the masterbatch to the resin to be used, and mechanically blending 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 shape following the melt mixing and dispersion of the components, or once extruded into a strand shape or a sheet shape and cut to form pellets, granules, powders, etc. It may be obtained in a form suitable for processing.

The thickness of the first layer is not particularly limited, but is usually about 2 to 1000 μm, and preferably 10 to 100 μm from the viewpoint that molding is relatively easy. When the thickness is 2 μm or more, the strength of the surface becomes higher, and when the thickness is 1000 μm or less, troubles are hardly caused in cooling during molding.
The thickness of the second layer is not particularly limited, but is usually about 2 to 1000 μm, and is preferably 5 to 100 μm from the viewpoint that molding is relatively easy. When the thickness is 2 μm or more, the reliability of adhesion to the adherend is improved, and when the thickness is 1000 μm or less, troubles in cooling during molding hardly occur.
The ratio of the thickness of the first layer to the second layer is usually such that the ratio of the thickness of the first layer / the thickness of the second layer is 1/99 to 99/1, preferably 5/95 to 95/5. Range. In addition, when the first layer and the second layer are combined and formed as a laminated film by coextrusion and laminated with an adherend before or after cooling, each layer is stably within the above range of thickness ratios. Can be molded. Further, when the thickness of the thermoplastic resin laminate of the present invention is a relatively thin range, for example, a thickness of 120 μm or less, the solvent resistance of the first layer and the second layer are limited within the limited overall thickness. In order to achieve both layer adhesion, if the thickness ratio of the first layer is large, it is easy to avoid a decrease in solvent resistance due to scratches, and if the thickness ratio of the second layer is large, the adhesion strength to the adherend Becomes higher. From this viewpoint, more preferably, the ratio of the thickness of the first layer / the thickness of the second layer is 90/10 to 30/70.
In the thermoplastic resin laminate of the present invention, within the range not exceeding the gist of the present invention, between the first layer and the second layer, a layer containing the same component as the first layer or the second layer, or other components It may have a layer.
The shape of the thermoplastic resin laminate may be a flat shape such as a film or sheet, a corrugated plate shape, a tubular shape, or the like, and is appropriately selected so as to suit the shape of the object to be laminated. In the case of a printed wiring board used for an electronic device, the shape of a flat film or sheet is preferable.

As a method of molding and laminating the first layer and the second layer constituting the thermoplastic resin laminate of the present invention, a commonly used method such as a multilayer injection molding method, a multilayer extrusion molding method, a compression molding method, etc. A well-known method is mentioned. As specific examples, a method of so-called coextrusion in which a plurality of extruders are connected to a feed block type or multi-manifold type die for a first layer and a second layer, a die connected to an extruder, such as a T die, After extruding either the first layer or the second layer from the I die to form a film, and subsequently unwinding the film as a film, the other layer was connected to another extruder on the surface. A method of extruding and laminating from a die and thermocompression bonding using a roll or a press plate, a method of extruding a first layer and a second layer separately to form a film, heating at least one of them, and laminating both by pressure bonding Can be given.
The melt molding temperature of the thermoplastic resin laminate is appropriately adjusted depending on the flow characteristics, film formability, etc. of the composition, and is generally from the glass transition temperature or the melting point to 430 ° C. Furthermore, the temperature of the extruder connected to the first layer side is preferably 350 to 410 ° C, more preferably 370 ° C to 395 ° C, and the temperature of the extruder connected to the second layer side is 340 to 410 ° C. More preferably, it is 370-395 degreeC. The temperature of the die is 350 to 410 ° C, preferably 370 to 395 ° C.

It is preferable that the melt-molded thermoplastic resin laminate is rapidly cooled by being brought into contact with a cooling body such as a rotating casting roll (cooling drum) or a seamless belt. The surface temperature of the cooling body is selected from a temperature lower than the glass transition temperature or the melting point of the resin component such as the component (A) or the component (D) constituting the first layer or the second layer, 25 to 140 ° C., preferably 80-135 ° C. At 25 ° C. or higher, moisture in the air can be prevented from freezing and adhering to the surface of the cooling body, and the shape formed by contact with the cooling body at 140 ° C. or lower can be prevented from changing. If necessary, the thermoplastic resin laminate is further cooled by another roll or cooling air between the cooling body and the winder and sent to the winder.
The cooling body surface temperature 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 temperature control mechanism of the roll and the temperature of the heat medium such as circulating refrigerant such as oil and water are selected so as to realize a preferable range of the surface temperature of the roll. Moreover, when the thermoplastic resin laminate is cylindrical (tube), the cylindrical thermoplastic laminate extruded from a multi-layered round die connected with a plurality of extruders is cooled with a casting roll, water, A method of quenching and solidifying with compressed air or the like is mentioned.

  In the lamination of the thermoplastic resin laminate of the present invention and the adherend, it is recommended that the laminate be laminated so that the second layer is in contact with the adherend. The second layer excellent in heat-fusibility bears adhesion to the adherend, and the first layer excellent in solvent resistance covers the surface, thereby improving the solvent resistance of the adherend surface.

As the adherend of the thermoplastic resin laminate of the present invention, a glass cloth reinforced epoxy resin plate, a glass fiber reinforced epoxy resin plate, a polyimide film, a bismaleimide / triazine resin plate, an allylated polyphenylene ether resin plate, etc. Resin plates and films, thermoplastic resin plates and films such as thermoplastic polyimide and wholly aromatic polyester-based liquid crystal polymers, ceramic substrates, and laminates in which copper foil and aluminum foil are laminated on these substrates and films, Further examples include printed boards on which metal circuits such as copper, aluminum, and nickel are formed by the additive method and subtract method, and metal bodies such as copper foil, copper plate, aluminum foil, aluminum plate, and stainless steel plate. The method of laminating with the adherend is not particularly limited. For example, the adherend such as a glass cloth reinforced epoxy resin plate and the thermoplastic resin laminate previously formed into a film are superposed and heated while applying pressure. Press molding method of laminating and laminating, heating the adherend by heating roll contact, infrared rays, hot air, etc., and laminating the thermoplastic resin laminate of the present invention, and applying pressure by roll or press, stamping molding Law.
When the thermoplastic resin laminate and the adherend are laminated by applying pressure with a press, the lamination temperature is appropriately selected according to the properties of the adherend in a temperature range of usually 200 to 380 ° C. Good adhesiveness can be obtained at a temperature lower than the melting temperature of the polyaryletherketone resin, preferably 220 to 300 ° C, more preferably 230 to 260 ° C. In order to improve the adhesion between the thermoplastic resin laminate and the adherend, various adhesives and silane coupling agents are applied to the adherend surface or the lower layer surface of the thermoplastic resin laminate, and after heating as necessary. A method of laminating a thermoplastic resin laminate prepared in advance is also included.

The thermoplastic resin laminate of the present invention exhibits the heat resistance and solvent resistance of the first layer by laminating the adherend so that the first layer is the outside and the second layer is in contact with the adherend. The adhesiveness of the second layer can be expressed. Moreover, solvent resistance and alkali resistance can be imparted to the laminated surface of the adherend by laminating on one or both sides of the adherend.
The thermoplastic resin laminate of the present invention has good resistance to organic solvents and alkali chemicals, and has a dielectric constant equivalent to or lower than that of various insulating materials such as ordinary epoxy resin printed wiring boards. Because it can be thermocompression-bonded with various insulating materials such as printed wiring boards and metal-based adherends such as copper, aluminum, and iron at a temperature in the range of about 200 ° C. to 380 ° C., and has good adhesion, Examples of the use include a surface protective layer of a printed wiring board in the electrical industry and the electronic industry, a surface protective layer of a multilayer printed wiring board, and a surface cover layer of a multichip package. In addition, because it has good heat resistance, it protects the surface of circuit boards for space and aircraft equipment, chemical plant linings, fuel cell parts, energy generation equipment parts, heat shields, housings for various equipment, etc. Use as a layer, a machine member, an automobile part, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, the various measured value 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) Thickness of each layer The thickness of each layer of the thermoplastic resin laminates of the examples and comparative examples and the thermoplastic resin laminate of the adherend was observed by magnifying the cross section with a microscope, and the thickness of each layer was determined. It was measured.
(2) Adhesion state of first layer and second layer of thermoplastic resin laminate A cut piece having a length of 1 cm is cut with a cutter knife at a right angle to one side of the produced thermoplastic resin laminate to obtain a test piece. The evaluator sits on a chair facing the flat desk, and the test piece is placed in front of the evaluator on the desk so that the first layer is the upper surface and the notch is on the side opposite to the evaluator side. Place the left and right ends of the incision with the left and right thumbs and index fingers, and lift the side sandwiched between the fingers of the right hand in the direction of about 135 to 150 degrees counterclockwise starting from the incision. The first layer was peeled off from the second layer by pulling it while drawing. The state of adhesion and peeling was visually observed and divided into the following 5 ranks and evaluated.
Rank 1: The first layer does not peel from the second layer, and the thermoplastic resin laminate breaks (adhesion is very good)
Rank 2: The first layer is peeled off from the second layer, but remains in a part, and the thermoplastic resin laminate breaks (adhesion is good).
Rank 3: The first layer is peeled off from the second layer from the stretched part, and can be spread and peeled to the whole (adhesion is weak)
Rank 4: Peeling occurs from the notched part, and if it is left as it is without being pulled, the peeling gradually spreads to the whole (adhesion failure)
Rank 5: Not bonded at all (adhesion impossible)

(3) Relative permittivity measurement Relative permittivity was measured according to the method of JIS C2151-1999 (disc plate electrode method).
(4) Solvent resistance Each of the thermoplastic resin laminates of the examples and the sample of the comparative example was cut into a circular shape having a diameter of 52 cm to obtain a test piece. Stainless steel container with a cylindrical lid (outer diameter 53mm, length 63mm, inner diameter 46mm, depth 59mm, wall thickness approx. 2mm, packing installed in the opening, with a screw about 13mm in width to close the lid around the opening) The lid is provided with a screw on the inner side, 60 ml of chloroform is put in an outer diameter of 60 mm, a length of 16 mm, an inner diameter of 53 mm, and a depth of 14 mm), and the above test piece or the comparative example test piece is placed thereon (thermoplastic resin). In the case of a laminate, the first layer side is placed on the lower side so as to be in contact with the opening of the stainless steel container, or in the case of a laminate of a thermoplastic resin laminate and a glass cloth reinforced epoxy plate. The bottom of the laminate is in contact with the opening side of the stainless steel container.), Tighten the lid, turn the container upside down, and place the first layer side of the thermoplastic resin laminate on chloroform. Is touch, after it was left at room temperature for 4 hours, wiped lightly chloroform removed test pieces were left to dry in the room for 20 minutes. The change in the surface appearance was visually observed, and the evaluation was divided into the following three ranks as compared with the sample not contacted with chloroform.
Rank 1: No change in surface appearance (good)
Rank 2: Surface appearance changes at least partially (defect)
Rank 3: at least partially dissolved (very poor)

(5) Lamination with Glass Cloth Reinforced Epoxy Resin Plate Stacked in the following order from bottom to top, a high-performance high-temperature vacuum press molding machine (made by Kitagawa Seiki Co., Ltd., molding press, model: VH1- 1747), and press molding at a set maximum temperature of 240 ° C., a set maximum temperature holding time of 30 minutes, and a set pressure of the press molding machine of 10.1 MPa (pressure at the bonding part is about 4.9 MPa) It produced (it may abbreviate as an epoxy laminated body hereafter).
(I) A cushion paper having a square of about 30 cm on one side and a thickness of 1.6 mm (trade name: RA board RAB N 0016, manufactured by Mitsubishi Paper Industries Co., Ltd.), (j) a square having a side of 30 cm and a thickness of 1. 5 mm stainless steel plate, (k) rectangular 30 cm long, 25.5 cm wide, 50 μm thick polyimide film (Ube Industries, trade name: Upilex 50S, 50 μm thick), (l) 20 cm on one side A glass cloth reinforced epoxy resin plate having a thickness of 1 mm (GE-4F by the display method according to JIS C6484-1997, FR-4 by the display method by ANSI / NEMA standard, and 18 μm electrolytic copper foil bonded together, What was obtained by removing the copper foil by etching from the copper-clad plate cured to the C stage, and the abbreviation is “FR-4”.), (M) One side is 20 cm Square thermoplastic resin laminate of the present invention (first layer on top, second layer on bottom) or comparative film or laminate film (first layer on top, second layer on bottom), (n) Polyimide film similar to (k) above, (o) Stainless steel plate similar to (j) above, (p) Cushion paper similar to (i) above.
The above (i) to (p) 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 observed 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 conduct a visual inspection again. After confirming that was removed, they were overlaid.

(6) Adhesive state of laminate of thermoplastic resin laminate and glass cloth reinforced epoxy resin plate The surface of the prepared laminate was rubbed with a finger, and the adhesive state was divided into the following three ranks and evaluated.
Rank 1: No peeling, no change (good adhesion)
Rank 2: Peel off when rubbed strongly (adhesive)
Rank 3: peeled off without rubbing, not bonded at all (adhesion failure)

(7) Solder heat resistance and heat resistant adhesiveness A laminate obtained by laminating the thermoplastic resin laminate of each example and the sample of the comparative example using a glass cloth reinforced epoxy resin plate is cut into a square having a side of 5 cm. A test piece was obtained. In accordance with JIS C6481 normal solder heat resistance, the test piece was floated in a solder bath at 260 ° C. for 20 seconds so that the first layer side of the thermoplastic resin laminate of the present invention and the solder bath were in contact with each other. After taking out and cooling to room temperature, the presence or absence of swelling, peeling, etc. was examined by visual inspection, and the quality was judged.
Rank 1: No swelling or peeling occurs (very good)
Rank 2: Although swelling and peeling occur, the generated area is 5% or less (good)
Rank 3: Dandruff or peeling occurs in an area of more than 5% and less than 50% (defect)
Rank 4: Dandruff or peeling occurs in an area exceeding 50% of the whole (very bad)
(8) State of burrs during hot press lamination (generation evaluation)
In order to quantitatively evaluate the degree of burrs at the edges that occur in the lamination of the thermoplastic resin laminate of the present invention and the adherend by hot pressing, in the lamination with the above (5) glass cloth reinforced epoxy resin plate, The set pressure of the press molding machine is 2.6 MPa (adhesion part pressure is about 4.9 MPa), and instead of (L) FR-4, a 10 cm square stainless steel plate with a side of 0.4 mm in thickness ( SUS304, and a stick paste (made by KOKUYO Co., Ltd., trade name: Plit, product number: Ta-310N) attached to the center of this stainless steel plate in a circular shape with a diameter of about 17 mm, (m) Example or comparison The thermoplastic resin laminate of the example was aligned with the four sides of the stainless steel plate and cut with a cutter knife to match the dimensions of the stainless steel plate. In addition to changes to fixed so as not shift the scan plate and a (m) is the same manner as the above (5), to produce a stainless steel laminate. Using a loupe with a scale for measuring dimensions (magnification 10 times), the length from each side of the stainless steel plate to the tip of the resin (burr) that protrudes outward (abbreviated as “burr length”) was measured. The measurement locations were a total of three locations, the central portion of each side and the largest burr length near both ends, and the average value and the maximum value of the 12 burr lengths including the four sides were recorded.

Example 1
(Mixing / kneading of each layer resin component and molding / evaluation of thermoplastic resin laminate)
Polyetheretherketone resin [manufactured by Victrex, PEEK450G, Tg: 143 ° C., melting point Tm: 334 ° C.] (hereinafter sometimes simply referred to as PEEK-1) 10 kg (100 parts by mass) pellets at 180 ° C. And then extruded as a first 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.
4 kg of PEEK-1 (40% by mass with respect to the total mass of PEEK-1 and the thermoplastic polyimide resins PEI-1 and PEI-2 described later), amorphous polyetherimide resin [manufactured by General Electric Co., Ltd., product Name: Ultem 1000, glass transition temperature Tg: 216 ° C.] (hereinafter sometimes simply referred to as PEI-1) 3 kg (30% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) ) And polyetherimide resin [General Electric Co., Ultem CRS5001, Tg: 226 ° C.] (hereinafter sometimes simply referred to as PEI-2) 3 kg (PEI-1, PEI-2 and PEEK-1) Each pellet was dry blended and dried in hot air at 180 ° C. for 8 hours. The pellet mixture was extruded as a second layer from the multi-manifold die (set temperature 390 ° C.) connected to a single screw extruder having a diameter of 30 mmφ set at 380 ° C.
The coextruded film, that is, the first layer side of the thermoplastic resin laminate was rapidly cooled with a casting roll set at 125 ° C., and a silicon rubber roll was pressed against the second 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. Next, the coextruded film was wound up to obtain a thermoplastic resin laminate. The amount of molten resin discharged from the extruder and the line speed were adjusted so that the thermoplastic resin laminate had a thickness of 100 μm, the first layer had a thickness of 50 μm, and the second layer had a thickness of 50 μm. When the cross section of the produced thermoplastic resin laminate was observed with a microscope and the thickness of each layer was measured, the thickness of the first layer was 50 μm, and the thickness of the second layer was 50 μm. From these values, the ratio of the first layer to the second layer was calculated to be 50/50. The abbreviation for this thermoplastic resin laminate is “F1”.
This was cut with a knife and tried to peel it off with a fingertip, but could not be peeled off. The adhesion between the first layer and the second layer was rank 1, and the adhesion was judged to be very good.
When the relative dielectric constant was measured according to the method of JIS C2151-1999, it was 3.2. When the solvent resistance to chloroform was evaluated according to the above method, it was ranked 1.

(2) Production and evaluation of laminate of the thermoplastic resin laminate and glass cloth reinforced epoxy resin plate A high-performance high-temperature vacuum press molding machine (Kitakawa Seiki) (Made by Co., Ltd., molding press, model: VH1-1747), set maximum temperature 240 ° C., set maximum temperature holding time 30 minutes, set pressure of press molding machine 10.1 MPa (pressure of adhesive part is about 4 0.9 MPa) to obtain a laminate (hereinafter sometimes abbreviated as an epoxy laminate).
(I) A square paper with a side of about 30 cm and a thickness of 1.6 mm (Paper name: RA board RAB N 0016, manufactured by Mitsubishi Paper Industries Co., Ltd.), (j) a square with a side of about 30 cm and a thickness of 1 .5mm stainless steel plate, (k) rectangle of 30cm length and 25.5cm width, 50μm thick polyimide film (Ube Industries, trade name: Upilex 50S, 50μm thickness), (L) one side 20 cm square, 1 mm thick glass cloth reinforced epoxy resin plate (FR-4 above), (m) 20 cm square thermoplastic resin laminate (F1, first layer on top, second layer on bottom) Side), (n) a polyimide film similar to (k) above, (o) a stainless steel plate similar to (j) above, and (p) a cushion paper similar to (i) above.
The above (i) to (p) 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 observed 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 conduct a visual inspection again. After confirming that was removed, they were overlaid.

  When the cross section of the obtained epoxy laminate was observed with a microscope and the thickness of each layer was measured, the thickness of the first layer was 47 μm, the thickness of the second layer was 48 μm, and the thickness of FR-4 was 1 mm. ,Met. From this value, the ratio of the first layer to the second layer was calculated as 49:51. When the adhesion state of this thing was evaluated, it was rank 1, and it was judged that the adhesion state was good. When the solder heat resistance was evaluated by the above method in a 260 ° C. solder bath, it was ranked 1 and judged to be good. The relative dielectric constant was 4.2, which was the same level as that of the non-laminated FR-4, and the relative dielectric constant was not increased by the lamination. When the solvent resistance was evaluated by the above method, it was ranked 1 and was good. The average burr length during lamination by press molding was 0.08 mm, and the maximum value was 0.18 mm. These evaluation results are shown in Table 1. Hereinafter, in each table, the thermoplastic resin laminate of the present invention is abbreviated as “laminate”.

Comparative Example 1
The PEEK-1 and 10 kg (100 parts by mass) were dried with hot air at 180 ° C. for 8 hours, and then a film was formed at 390 ° C. using a single-screw extruder having a diameter of 40 mm connected to a T-die having a width of 320 mm. Extrusion, contact with the surface of a metal cast roll whose temperature is adjusted with circulating oil having a set temperature of 125 ° C., and pressing with a silicon rubber roll from the opposite side to form a rapidly cooled film, The abbreviation is R1). The above R1 was used in place of F1, and an attempt was made to laminate the glass cloth reinforced epoxy resin plate by the same operation as in Example 1, but no adhesion was made, and it was judged as “Rank 3”, and other evaluations were performed. There wasn't. The results are shown in Table 1.

Comparative Example 2
4.4 kg of PEI-1 pellets (44% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1), 0 kg of PEI-2 and 5.6 kg of PEEK-1 pellets (PEI- 1, 56% by mass based on the total mass of PEI-2 and PEEK-1), dry with hot air at 180 ° C. for 8 hours, and then use a single-screw extruder with a 40 mm diameter connected to a 300 mm wide T-die Extruded into a film at 380 ° C., brought into contact with the surface of a metal cast roll whose temperature was adjusted with a circulating oil at a set temperature of 155 ° C., and pressed with a silicon rubber roll from the opposite side to form a rapidly cooled film, A single-layer film (abbreviated as R2) having a thickness of 40 μm was obtained. Evaluation similar to Example 1 was performed except having used said R2 instead of F1. The results are shown in Table 1.

Comparative Example 3
The thickness of the first layer is 50 μm, PEI-1 is used alone without using PEEK-1 and PEI-2, and the thickness of the second layer is 50 μm. The thermoplastic resin laminate was obtained in the same manner as in Example 1 (abbreviated as R3).
Evaluation similar to Example 1 was performed except having used said R3 instead of F1. The results are shown in Table 1.

Comparative Example 4
The above-mentioned solvent resistance test was conducted on the simple substance of FR-4, and the evaluation result was rank 2 (defect).

Example 2
The thickness of the first layer of the thermoplastic resin laminate is changed to 20 μm, and the constituent component of the second layer is 4.4 kg of the above PEEK-1 (total mass of PEEK-1, PEI-1, and PEI-2) 44 mass%), PEI-1 is 5.6 kg (56 mass% with respect to the total mass of PEEK-1, PEI-1, and PEI-2), PEI-2 is 0 kg, A thermoplastic resin laminate (abbreviated as F2) was obtained in the same manner as in Example 1 except that the thickness was 15 μm. The evaluation results of this product are shown in Table 1.

Example 3
(Preparation of resin composition used for first layer)
10 kg (100 parts by mass) of PEEK-1 and 1.5 kg (PEEK-1 100) of polytetrafluoroethylene resin (manufactured by Asahi Glass Co., Ltd., grade name Fullon PTFE L-169J, abbreviated as B1) as fluororesin. 15 parts by mass with respect to parts by mass) were kneaded at a set temperature of 390 ° C. using a twin screw extruder with side feed, extruded into a strand, and cut into pellets. (The abbreviation is G3.)
(Molding and evaluation of thermoplastic resin laminate)
The above G3 is used for the first layer, the resin component of the second layer is 4 kg of PEEK-1 (40% by mass with respect to the total mass of PEEK-1, PEI-1, and PEI-2), and 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 (30% by mass with respect to the total mass of PEI-1, PEI-2 and PEEK-1) A thermoplastic resin laminate (abbreviated as F3) was obtained in the same manner as in Example 1, except that the resin composition was changed to a thickness of 90 μm for the first layer and 10 μm for the second layer. .
Evaluation similar to Example 1 was performed. The results are shown in Table 2.

Example 4
(Preparation of resin composition used for first layer)
Resin composition (abbreviated as G4) used in the first layer by performing the same operation as in Example 3 except that B1 was changed to 2.5 kg (PEEK-1, 25 parts by mass with respect to 100 parts by mass). .)
(Preparation of resin composition used for second layer)
2.8 kg of the above PEEK-1 (28% by mass with respect to the total mass of PEEK-1, PEI-1, and PEI-2), 3.8 kg of PEI-1 (PEEK-1, PEI-1, and 38 mass% with respect to the total mass of PEI-2), 3.4 kg of PEI-2 (34 mass% with respect to the total mass of PEEK-1, PEI-1, and PEI-2), and B1 described above. A component consisting of 5 kg (15 parts by mass with respect to a total of 100 parts by mass of PEEK-1, PEI-1, and PEI-2) is kneaded at a set temperature of 390 ° C. using a twin screw extruder with side feed, and in a strand form And then cut into pellets (abbreviated as H4).
(Molding and evaluation of thermoplastic resin laminate)
The same operation as in Example 1 was carried out except that G4 was used for the first layer, H4 was used for the second layer, the thickness of the first layer was 30 μm, and the thickness of the second layer was 60 μm. A resin laminate (abbreviated as F4) was obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 2.

Example 5
(Preparation of resin composition used for first layer)
Resin composition used for the first layer by performing the same operation as in Example 3 except that B1 is changed to 4 kg (PEEK-1, 40 parts by mass with respect to 100 parts by mass) (abbreviated as G5). Got.
(Preparation of resin composition used for second layer)
3 kg of PEEK-1 (30% by mass with respect to the total mass of PEEK-1, PEI-1, and PEI-2), 3 kg of PEI-1 (total of PEEK-1, PEI-1, and PEI-2) 30% by mass), 4 kg of PEI-2 (40% by mass with respect to the total mass of PEEK-1, PEI-1, and PEI-2), and synthetic mica that is commercially available instead of B1 (average particles) Except that the diameter is 6 μm, the aspect ratio is 25, and the abbreviation is C1) is changed to 2.5 kg (25 parts by mass with respect to 100 parts by mass of PEEK-1, PEI-1, and PEI-2). The same operation as in Example 3 was performed to obtain a resin composition for the second layer (abbreviated as H5).
(Molding and evaluation of thermoplastic resin laminate)
The same operation as in Example 1 was performed except that G5 was used for the first layer, H5 was used for the second layer, the thickness of the first layer was 80 μm, and the thickness of the second layer was 40 μm. A resin laminate (abbreviated as F5) was obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 2.

Example 6
(Preparation of resin composition used for first layer)
Resin used for the first layer in the same manner as in Example 3 except that 0 kg of B1 and 2.5 kg of synthetic mica (C1) (PEEK-1, 25 parts by mass with respect to 100 parts by mass) were added. A composition (abbreviated as G6) was obtained.
(Preparation of resin composition used for second layer)
4 kg of the above PEEK-1 (40% by mass with respect to the total mass of PEEK-1, PEI-1 and PEI-2), 6 kg of PEI-1 (of PEEK-1, PEI-1 and PEI-2) 60 mass% with respect to the total mass), PEI-2 is 0 kg, B1 is 2 kg (20 mass parts with respect to a total of 100 mass parts of PEEK-1, PEI-1, and PEI-2). The same procedure as in Example 3 was performed except that 2 kg of surface-treated synthetic mica obtained by the operation (20 parts by mass with respect to 100 parts by mass in total of PEEK-1, PEI-1, and PEI-2) was added. A two-layer resin composition (abbreviated as H6) was obtained.
(Production of surface-treated synthetic mica)
The surface-treated synthetic mica was produced by the following method. A surface treatment agent hexyltrimethoxysilane (Tokyo Kasei Co., Ltd.) dissolved in 160 g of isopropyl alcohol having a water content of about 3% by weight was placed in a Henschel mixer with 2 kg of commercially available synthetic mica (average particle size: 6 μm, aspect ratio: 25). 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 mica) of Kogyo Co., Ltd., reagent grade) 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 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 C2). ) Further, the same operation was repeated 10 times to obtain about 20 kg of surface-treated synthetic mica.
(Molding and evaluation of thermoplastic resin laminate)
The same operation as in Example 1 was performed except that G6 was used for the first layer, H6 was used for the second layer, the thickness of the first layer was 50 μm, and the thickness of the second layer was 40 μm. A resin laminate (abbreviated as F6) was obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 2.

Example 7
(Preparation of resin composition used for first layer)
The same procedure as in Example 3 was performed except that the surface-treated synthetic mica (C2) was changed to 2 kg (20 parts by mass with respect to PEEK-1, 100 parts by mass) instead of B1 and 2.5 kg. A resin composition (abbreviated as G7) used for one layer was obtained.
(Preparation of resin composition used for second layer)
3.5 kg of the above PEEK-1 (35% by mass with respect to the total mass of PEEK-1, PEI-1, and PEI-2), 2 kg of PEI-1 (PEEK-1, PEI-1, and PEI- 20 mass%), PEI-2 is 4.5 kg (45 mass% with respect to the total mass of PEEK-1, PEI-1, and PEI-2). The same as in Example 3 except that the surface-treated mica (C3) obtained by the operation was changed to 2.5 kg (25 parts by mass with respect to 100 parts by mass in total of PEEK-1, PEI-1, and PEI-2). Operation was performed to obtain a resin composition for the second layer (abbreviated as H7).
(Production of surface-treated mica)
The surface-treated 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 2% by weight was placed in a Henschel mixer (trade name) with 2 kg of commercially available phlogopite (average particle size: 4 μm, aspect ratio: 20). 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 synthetic 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 and left standing indoors for 4 days, then heated in an oven at 120 ° C. for 48 hours, cooled to room temperature and surface-treated mica (abbreviated as C3). Got. Further, this operation was repeated 10 times to obtain about 20 kg of surface-treated mica.
(Molding and evaluation of thermoplastic resin laminate)
The same operation as in Example 1 was performed except that G7 was used for the first layer, H7 was used for the second layer, the thickness of the first layer was 50 μm, and the thickness of the second layer was 50 μm. A resin laminate (abbreviated as F7) was obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 2.

Example 8
(Preparation of resin composition used for first layer)
B1 is changed to 0.5 kg (5 parts by mass for PEEK-1, 100 parts by mass), C2 is added to 1.5 kg (15 parts by mass for PEEK-1, 100 parts by mass), and Surface treated synthetic silica prepared by the following method (abbreviated as C4) 0.5 kg (PEEK-1, 5 parts by mass with respect to 100 parts by mass) A resin composition (abbreviated as G8) used for the first layer was obtained by operating.
(Production of surface-treated spherical silica)
The surface-treated spherical silica was produced by the following method. A surface treatment agent hexyltrimethoxysilane (Tokyo Kasei Kogyo Co., Ltd.) dissolved in 160 g of isopropyl alcohol having a water content of about 2% by weight was placed in a Henschel mixer (trade name) with 2 kg of commercially available spherical silica (average particle size: 1 μm). 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) 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 bat and allowed to stand indoors for 4 days, then heated in an oven at 120 ° C. for 48 hours, cooled to room temperature, and surface-treated spherical silica (abbreviated as C4). ) Further, this operation was repeated 5 times to obtain about 10 kg of surface-treated spherical silica.
(Preparation of resin composition used for second layer)
3.5 kg of PEEK-1 (35% by mass with respect to the total mass of PEEK-1, PEI-1, and PEI-2), 6 kg of PEI-1 (PEEK-1, PEI-1, and PEI- 2) and 60 kg PEI-2 (5 wt% based on the total weight of PEEK-1, PEI-1 and PEI-2), tetrafluoro instead of B1 Copolymer of ethylene and perfluoroalkyl vinyl ether (manufactured by Daikin Industries, Ltd., trade name: NEOFLON PFA AP-230, melting point: 310 ° C., measurement temperature: 372 ° C., melt flow rate at a load of 5 kg: 2 g / 10 minutes, abbreviated as B2. ) 0.5 kg (PEEK-1,
5 parts by mass with respect to a total of 100 parts by mass of PEI-1 and PEI-2), and 1.5 kg of surface-treated synthetic mica (C2) (total 100 parts by mass of PEEK-1, PEI-1, and PEI-2) And 15 kg of the surface-treated synthetic silica (C4) (5 parts by mass with respect to a total of 100 parts by mass of PEEK-1, PEI-1, and PEI-2). Except for this change, the same operation as in Example 3 was performed to obtain a resin composition for the second layer (abbreviated as H8).
(Molding and evaluation of thermoplastic resin laminate)
The same operation as in Example 1 was performed except that G8 was used for the first layer, H8 was used for the second layer, the thickness of the first layer was 60 μm, and the thickness of the second layer was 30 μm. A resin laminate (abbreviated as F8) was obtained. Evaluation similar to Example 1 was performed and the results are shown in Table 3.

Example 9
(Preparation of resin composition used for first layer)
B1 is changed to B2, 1.5 kg (15 parts by mass with respect to 100 parts by mass of PEEK-1), 1 kg of C2 (10 parts by mass with respect to 100 parts by mass of PEEK-1) is added, and C4 is further added. Resin composition used for the first layer by performing the same operation as in Example 3 except that 0.5 kg (5 parts by mass with respect to 100 parts by mass of PEEK-1) was added (abbreviated as G9). Got.
(Preparation of resin composition used for second layer)
3 kg of the above PEEK-1 (30% by mass with respect to the total mass of PEEK-1, PEI-1, and PEI-2), 4 kg of PEI-1 (of PEEK-1, PEI-1, and PEI-2) 40 mass% with respect to the total mass), 3 kg of PEI-2 (30 mass% with respect to the total mass of PEEK-1, PEI-1, and PEI-2), B1 with the above B2, 1 kg (PEEK-1, 10 parts by mass with respect to a total of 100 parts by mass of PEI-1 and PEI-2), and C2 of 2 kg (20 parts by mass with respect to a total of 100 parts by mass of PEEK-1, PEI-1, and PEI-2) Part) The same operation as in Example 3 was carried out except that the addition was made to obtain a resin composition for the second layer (abbreviated as H9).
(Molding and evaluation of thermoplastic resin laminate)
Thermoplasticity is the same as in Example 1 except that G9 is used for the first layer, H9 is used for the second layer, the thickness of the first layer is 35 μm, and the thickness of the second layer is 25 μm. A resin laminate (abbreviated as F9) was obtained. Evaluation similar to Example 1 was performed and the results are shown in Table 3.

  From Tables 1 to 3, when the thermoplastic resin laminates of Examples 1 to 9 within the scope of the present invention are epoxy resin laminates, the adhesiveness is good, and the printed wiring board before making the laminates The glass cloth-reinforced epoxy resin plate for use does not have a high relative dielectric constant, and is unlikely to adversely affect the transmission speed of electrical signals. Moreover, it can be seen that the solvent resistance of the laminate is improved, and further, burrs during press lamination are reduced, and the effects of the present invention can be confirmed.

The thermoplastic resin laminate of the present invention has good resistance to organic solvents and alkali chemicals, and has a dielectric constant equivalent to or lower than that of various insulating materials such as ordinary epoxy resin printed wiring boards. Because it can be thermocompression-bonded with various insulating materials such as printed wiring boards and metal-based adherends such as copper, aluminum, and iron at a temperature in the range of about 210 ° C to 340 ° C, and has good adhesion, Applications include surface protection layers for printed wiring boards in the electrical and electronic industries, surface protection layers for multilayer printed wiring boards, surface cover layers for multichip packages, and applications that coexist with PEEK circuit boards. Can be mentioned. In addition, because it has good heat resistance, it protects the surface of circuit boards for space and aircraft equipment, chemical plant linings, fuel cell parts, energy generation equipment parts, heat shields, housings for various equipment, etc. Use as a layer, a machine member, an automobile part, and the like.

Claims (7)

  A first layer comprising 0 to 100 parts by mass of the fluororesin (B) and 0 to 100 parts by mass of the filler (C) with respect to 100 parts by mass of the polyaryl ketone resin (A); Resin containing a thermoplastic adhesiveness-imparting resin (D) having a glass transition temperature of 180 to 350 ° C. in a polyaryl ketone resin (A) in a mass ratio of (A) / (D) = 95/5 to 5/95 Adjacent to the first layer is a second layer comprising 0 to 100 parts by mass of the fluororesin (B) and 0 to 100 parts by mass of the filler (C) with respect to 100 parts by mass of the component. A thermoplastic resin laminate.   The thermoplastic resin laminate according to claim 1, wherein the thermoplastic adhesion-imparting resin (D) is at least one selected from a thermoplastic polyimide resin, a polyethersulfone resin, and a polysulfone resin.   The thermoplastic resin laminate according to claim 1 or 2, wherein the ratio of the thickness of the first layer to the thickness of the second layer is first layer / second layer = 99/1 to 1/99. The component (A) is composed mainly of a crystalline polyetheretherketone resin having a repeating unit represented by the following structural formula (1), and the component (D) is represented by the following structural formula (2). The thermoplastic resin laminate according to any one of claims 1 to 3, which comprises a polyetherimide resin having a repeating unit or a polyetherimide resin having a repeating unit represented by the following structural formula (3) as a main component. body.

  The component (B) fluorine resin is at least one selected from polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. 5. The thermoplastic resin laminate according to any one of 4 above.   The thermoplastic resin laminate according to any one of claims 1 to 5, wherein the filler of component (C) is a plate. The thermoplastic resin laminate according to any one of claims 1 to 5, wherein the filler of component (C) is at least one selected from mica, glass flakes, and silicon dioxide powder.