JP5276925B2 - Composite sheet and composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite sheet in which a support layer and a thin film layer are releasably bonded, and the thin film layer and a joining layer are completely integrated, and a composite body using the composite sheet. <P>SOLUTION: The composite sheet 10 includes the resin or metal sheet-like support layer 11, the thin film layer 12 formed on one side (or both sides) of the support layer 11, and the joining layer 13 formed on one principal plane of the support layer 11 through the thin film layer 12. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a composite sheet and a composite using a part of the composite sheet. The present invention particularly relates to a composite sheet used for compression connection between an electrode terminal portion of an electronic device such as a liquid crystal display and a conductive portion of a flexible printed circuit board on which a drive circuit is mounted, a surface material of a conveyor belt, or a tube. The present invention relates to a surface material of a gasket or a surface material of a cushion material of a substrate press used for a joint part of a body.

  Conventionally, a fluororesin film (or film) is excellent in properties such as wear resistance, releasability, and slipperiness, and thus has been used for various applications. Specifically, the following uses are mentioned.

1) It is used as a gasket used at the joint of pipes.
Usually, rubber or resin packing is used to prevent leakage at the connection part in a pipe-like pipe for transporting fluid such as liquid or gas. However, due to aging and deterioration of chemical solution penetration, the packing may adhere to the connection surface during periodic replacement, and it may take time to replace. Therefore, it can be easily replaced by attaching a fluororesin film to the gasket surface.

2) Used as a surface release of a substrate press cushion material.
Recent glass epoxy substrates and FP substrates are markedly multi-layered. In this laminated press molding, a fluororesin film is used on the surface of a heat-resistant rubber sheet or a non-woven cushion sheet.

3) Used as a surface thin film of a thermocompression bonding sheet.
In the electronic device manufacturing process, a crimping process as shown in FIG. 7 is performed.
Reference numeral 1 in the figure indicates a glass substrate on which an electrode terminal portion 2 is formed at an end portion. On the end of the glass substrate 1, the end of a flexible printed circuit board (FPC) 3 is laminated by thermocompression bonding. Here, the FPC 3 includes a film 5 on which the drive circuit 4 is formed, and an anisotropic conductive film (ACF) 6 formed on a part of the drive circuit 4. A heater 8 having a silicone rubber sheet 7 at the lower end is disposed on the thermocompression-bonded portion between the glass substrate 1 and the flexible printed circuit board 3. Reference numeral 9 denotes a ray film (protective film).

In FIG. 7, with the ACF 6 interposed between the terminal 2 of the glass substrate 1 and the drive circuit 4 of the FPC 3, heat is applied by the heater 8 via the silicone rubber sheet 7 between the flexible printed board 3 on the ACF 6 and the heater 8. The electrode terminal portion 2 of the glass substrate 1 and the drive circuit 4 of the FPC 3 are electrically connected by crimping.
However, when a silicone rubber sheet is used as the cushion sheet, the ACF 6 that protrudes from the electrode terminal portion 2 or the drive circuit 4 that is a material to be bonded adheres to the silicone rubber sheet 7, causing a problem. Accordingly, an ethylene tetrafluoride ethylene resin (PTFE) sheet having a good releasability with respect to the ACF 6 is usually used between the silicone rubber sheet 7 and the material to be bonded.

  By the way, in the crimping step, the silicone rubber sheet can usually use the same press portion a plurality of times. However, since the PTFE sheet used for mold release is easily deformable and does not have elasticity, it is deformed by one press and the same press portion cannot be used a plurality of times.

4) Used as a surface material for conveyor conveyor belts.
A fluororesin film is used as a surface material for a conveyor belt when continuously transporting highly adhesive objects such as synthetic resins, rubber materials, and foods.
Conventionally, as a technique using a fluororesin film or a fluororesin film, for example, the following Patent Documents 1 to 3 are known.
Patent Document 1: This patent relates to a transfer foil for a fluororesin film and a method for producing the fluororesin film. Here, the transfer foil for fluororesin film has a structure in which a transfer layer in which a fluororesin powder and a thermoplastic resin are appropriately blended is formed on a support film, and a resin adhesive layer is provided on the transfer layer as necessary. It has become.

Patent Document 2: This patent has a structure in which a fluororesin film is laminated on a support layer made of polyethylene terephthalate resin through a resin anchor coat layer.
Patent Document 3: This patent relates to a fluorine-containing thin film formed on the surface of a substrate and a method for producing a substrate having the thin film.
JP-A-1-128900 JP 2002-120335 A JP 2006-1014 A

An object of the present invention is to provide a composite sheet in which a support layer and a thin film layer are bonded so as to be peelable, and the thin film layer and the bonding layer are completely integrated.
Another object of the present invention is to provide a composite that can be easily bonded to a flat or curved adherend by peeling the support layer from the thin film layer of the composite sheet.

The composite sheet of the present invention comprises a resin- or metal-made sheet-like support layer and a completely sintered PTFE simple substance having a specific gravity of 2.13 to 2.20 formed on one or both sides of the support layer. And a bonding layer formed on the thin film layer and formed of a fluororesin layer containing a bonding component .
Further, the composite sheet of the present invention comprises a resin or metal sheet-like support layer and a specific gravity formed on one or both sides of the support layer, the surface of which is electrically or chemically treated so as to be bonded. 2. A thin film layer made of a sintered layer of PTFE alone, which is completely sintered of 2.13 to 2.20 .

The composite of the present invention comprises an adherend and a laminate having the support layer peeled off from the composite sheet according to any one of claims 1 to 3 , which is bonded to the adherend. The composite sheet is laminated and integrated with the adherend by any one of pressure, heating, or pressure so that the bonding layer side or the surface treatment side of the thin film layer is in contact with the main surface of the adherend. After the formation , the support layer is peeled off.

  According to the composite sheet of the present invention, when the bonding layer is provided, the support layer and the thin film layer are bonded so as to be peelable, and the thin film layer and the bonding layer are completely integrated. It is done. Further, according to the composite of the present invention, the support layer can be peeled off from the thin film layer and easily joined to a curved surface such as a rubber-based flat sheet or piping.

Hereinafter, the composite sheet and composite of the present invention will be described in detail.
As shown in FIG. 1, the basic structure of the composite sheet 10 of the present invention is a resin or metal sheet-like support layer 11, a thin film layer 12 formed on one side of the support layer 11, and the support. The body layer 11 includes a bonding layer 13 formed on one main surface via a thin film layer 12. The thin film layer 12 may be formed on both surfaces of the support layer 11. Here, it is preferable that the thin film layer 12 and the bonding layer 13 are completely integrated, and the support layer 11 is lightly attached so that it can be peeled off from the thin film layer 12.

  The thickness of the support layer is preferably 5 to 500 μm, more preferably 25 to 100 μm. Here, in order to obtain a sintered thin film of various fluororesins as the thin film layer, the support layer needs to withstand heat of 200 to 330 ° C. or more which is the melting temperature of the fluororesin.

  As the material for the support layer, in order to withstand the melting temperature of the fluororesin, resins such as aromatic polyimide, aromatic polyamide, polyether ether ketone resin, aromatic polyester resin, polysulfide resin, or stainless steel, aluminum, aluminum alloy , Zinc foil, copper, lead, nickel, nickel alloys and the like. Here, when the main surface of the adherend is flat, the material of the support layer is preferably made of resin, and when the main surface of the adherend is curved like a pipe, it is preferable to use metal. . In addition, as a material for the support layer, the resin and metal may be used in appropriate combination depending on the surface shape of the adherend in consideration of the transfer followability of the thin film layer to the surface.

  The thin film layer is preferably a PTFE sheet completely sintered with a specific gravity of 2.13 to 2.20. Moreover, it is preferable that the thickness of a thin film layer is 0.2-20 micrometers. Here, if the thickness exceeds 20 μm, cracks are likely to occur in the support layer, and if the thickness is less than 0.2 μm, it is difficult to form a thin film layer. Examples of the thin film layer include a layer made of a single fluorine resin, or a layer in which at least one of a conductive material, a reinforcing material, and a heat conductive material is filled in the fluorine resin layer.

  In the case of a fluorine resin alone, examples of the material include, for example, ethylene tetrafluoride resin (PTFE), tetrafluoroethylene perfluoroalkoxyethylene copolymer resin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin ( FEP), trifluorinated ethylene chloride resin (PCTFE), tetratetrafluoroethylene / ethylene copolymer (ETFE), trifluorinated ethylene chloride / ethylene copolymer resin (ECTFE), and vinyl fluoride resin (PVDF). . Among these, when the composite sheet of the present invention is used in the ACF pressure bonding step, PTFE and PFA are preferable in consideration of heat resistance.

  Examples of the conductive material include carbon black. Examples of the reinforcing material include potassium titanate whiskers and quartz powder. Examples of the thermally conductive material include metal oxides such as zinc oxide, magnesium oxide, alumina, silicon oxide, iron oxide, beryllium oxide, and chromium oxide, metal nitrides such as boron nitride and aluminum nitride, or boron carbide, Examples of the metal carbide include titanium carbide and silicon carbide.

When the bonding layer does not contain a bonding component, it is preferable that the surface of the thin film layer be subjected to electrical treatment or chemical treatment so as to be bonded. Here, examples of the electrical treatment include plasma treatment such as corona discharge, and examples of the chemical treatment include treatment with a silane coupling agent and a metal sodium-naphthalene complex solution.
Examples of the bonding layer include a fluorine resin layer in which a bonding component (for example, fine powder silica) is blended.

  In the present invention, when forming the composite, if it is difficult to release the support layer from the thin film layer, it is preferable to take a release means so as not to adhere to the support layer. Here, as a mold release means, for example, embossing is performed on the surface of the support layer.

  As shown in FIG. 2, the basic configuration of the composite 14 of the present invention includes an adherend 15 and a laminate 16 formed of the bonding layer 13 and the thin film layer 12 formed on the adherend 15. It has a configuration. Here, the laminate 16 is obtained by heating the composite sheet 10 on the adherend 15 by pressurization or under pressure so that the bonding layer 13 is in contact with the main surface of the adherend 15. After bonding, the support 15 is peeled off.

Examples of the adherend include silicone rubber and fluorine rubber. As silicone rubber, K ₂ O · 6Ti ₂ O / SnO ₂ (Sb) (trade name: DENTOR WK200B, manufactured by Otsuka Chemical), carbon black, graphite, Au, Ag, Cu, Silicone rubber filled with metals such as Ni, SnO ₂ , ZnO, MgO, etc., or BN, AlN, SiO, BeO, ZnO, Al ₂ O ₃ , MgO, SiC, etc. are added to impart thermal conductivity to the rubber Silicone rubber can be used.

Examples of the adherend include resin, metal, and ceramics. Here, as the resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, ABS resin, AS resin, acrylic resin, polyamide resin, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polyphenylene sulfate Fido, polysulfone, liquid crystal polymer, polyetheretherketone, thermoplastic polyimide, polyamideimide and other thermoplastic resins, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, polyurethane resin, thermosetting polyimide, etc. These thermosetting resins can be mentioned.
Examples of the metal include stainless steel, aluminum, aluminum alloy, zinc foil, copper, lead, nickel, and nickel alloy. Examples of the ceramic include barium titanate, boron nitride, silicon carbide, silicon nitride, zirconia, and alumina.

Hereinafter, composite sheets and composites according to specific examples of the present invention will be described with reference to the drawings.
Example 1
The composite sheet 20 according to the first embodiment will be described with reference to FIG. Reference numeral 21 in the drawing indicates a resin film (support layer) having a thickness of 50 μm made of a polyimide film. On the resin film 21, a PTFE sintered layer (thin film layer) 22 having a thickness of about 2 to 3 μm is formed. On the PTFE sintered layer 22, a PTFE layer (bonding layer) 23 having a thickness of about 4 to 5 μm containing fine powder silica is formed.

The composite sheet 20 having such a configuration is manufactured as follows.
First, after coating PTFE dispersion on one side of a resin film made of a polyimide film (thickness 50 μm, width 500 mm, length 500 mm), it is baked at 350 to 370 ° C. and has a thickness of about 2 to 3 μm on the polyimide film surface. The PTFE sintered layer 22 was formed.
Next, a PFA dispersion to which silica fine particles are added is coated on the PTFE sintered layer 22 and then fired at 350 to 370 ° C. to form a PTFE layer (bonding) having a thickness of about 4 to 5 μm on the PTFE sintered layer 22. Layer) 23 was formed, and a composite sheet 24 was produced.

  The composite sheet 20 according to Example 1 includes a PTFE sintered layer (thin film layer) 22 having a thickness of about 2 to 3 μm and fine powder silica on a resin film (support layer) 21 having a thickness of 50 μm made of a polyimide film. A PTFE layer (bonding layer) 23 having a thickness of about 4 to 5 μm is sequentially formed. According to the composite sheet 20, when the composite is formed, the resin film 21 can be easily peeled off from the PTFE sintered layer 22 and laminated on the adherend.

(Example 2)
The complex according to Example 2 will be described with reference to FIGS.
First, separately from the composite sheet 20 of FIG. 3, carbon black as a conductive component, magnesium oxide as a heat conductive component, and silica powder as a reinforcing component are added to a millable silicone rubber and dispersed uniformly with a kneader. Thus, a silicone rubber composition was obtained. Next, a peroxide vulcanizing agent was further mixed into the silicone composition, and a calender rubber having a thickness of 0.2 mm was extruded to obtain a calender rubber layer 25 having a thickness of 0.2 mm.

  Next, the composite sheet 20 of FIG. 3 was laminated on the calender rubber layer 25 as an adherend so that the PTFE layer 23 was in contact with the calender rubber layer 25 (see FIG. 4A). Thereafter, the composite sheet 20 laminated with the calendar rubber layer 25 was vulcanized at 170 ° C. for 10 minutes with a flat press. Subsequently, after cooling and peeling off the resin film 21, it was treated in a hot air drying furnace at 200 ° C. for 4 hours to provide a 0.2 mm thick vulcanized sheet having a PTFE sintered layer 22 completely sintered on the surface. (Composite) 26 was produced. The PTFE layer 23, the PTFE sintered layer 22, and the calendar rubber layer 25 are collectively referred to as a composite body 26 (see FIG. 4B).

The composite 26 manufactured in this manner has a configuration in which a PTFE layer 23 and a PTFE sintered layer 22 are sequentially formed on a calendar rubber layer 25 as an adherend. When the composite body 26 having such a configuration is used as a cushion sheet for thermocompression bonding between the electrode terminal portion of the circuit board and the conductive portion of the FPC, it is resistant to deformation and ensures releasability from the anisotropic conductive film. be able to.
In fact, when the composite 26 as a sample was subjected to a durability test between the press lower plate and the press-heated upper plate (press plate surface width: 1.5 mm) using the following tester, each component of the composite 26 of the present invention was measured. It was confirmed that the calender rubber layer 25, the PTFE layer 23, and the PTFE sintered layer 22 were not defective.

  Test machine: small press, upper panel: 230 ° C., lower panel: normal temperature, pressure 3.9 MPa, holding time: 20 sec.

(Example 3)
The composite according to Example 3 will be described with reference to FIG.
A reference numeral 35 in the drawing is an adherend, and is composed of a cotton canvas 36 and NBR rubber layers 37a and 37b formed on both sides of the cotton canvas 36. A PTFE sintered layer 22 is formed on one NBR rubber layer 37 a of the adherend 35 via a PTFE layer 23.

The composite having such a structure is manufactured as follows. That is, first, as in Example 1, the composite sheet 20 was manufactured by forming the PTFE sintered layer 22 and the PTFE layer 23 on the resin film 21. Separately, after applying a rubber coating of 0.2 mm with white NBR rubber paste dissolved in xylene solvent on both sides of a cotton canvas 36 with a thickness of 0.3 mm, the solvent is removed in a drying oven at 50 ° C. And dried. Thereby, the adherend 35 in which the NBR rubber layers 37a and 37b were formed on both surfaces of the cotton canvas 36 was obtained. Subsequently, after laminating the composite sheet 20 of FIG. 3 on the adherend 35 so that the PTFE layer 23 is in contact with the NBR rubber layer 37a of the adherend 35, it is 150 ° C., 20 kg / cm ² , 10 with a flat press machine. Partially vulcanized. Further, after taking out from the flat press machine and cooling, the resin film was peeled off to produce an NBR rubberized sheet (composite) 38 in which the completely sintered PTFE sintered layer 22 having a thickness of 4 to 5 μm was transferred to the surface layer. .

  According to the third embodiment, the completely sintered PTFE sintered layer 22 can be formed on the surface of the heat-resistant white NBR rubber layer 37a that is lower than the molding temperature of the fluororesin. Therefore, the release property and slipperiness of the fluororesin body can be imparted without impairing the inherent flexibility, rebound resilience, and hue of the NBR rubber.

Example 4
A composite body in which the composite sheet 20 manufactured in Example 1 is laminated on an adherend and integrated will be described.
First, as the adherend, both sides of an aluminum plate having a thickness of 1 mm were buffed with a sander, degreased with xylol, applied with a primer (model manufactured by Road Far East Incorporated: Chemlock 5150) and dried at room temperature. did. Next, an unvulcanized fluoro rubber calendar sheet having a thickness of 0.5 mm is disposed on both surfaces of the aluminum plate, and the thin film layer surface side of the composite sheet 20 is further disposed on both surfaces of the unvulcanized fluoro rubber calendar sheet. The laminated body was obtained by butting.

This laminate was placed between a heating and pressure press machine (not shown), and vulcanized under the conditions of a heating temperature of 170 ° C., a pressing pressure of 20 kgf / cm ³ , and a pressurization holding time of 10 minutes. Next, the polyimide film was peeled off, and secondary vulcanization was performed by a treatment in a heating electric furnace at a heating temperature of 200 ° C. and a heating and holding time of 8 hours. Thereby, the composite body with which the PTFE thin film was integrated on the fluororubber surface formed in both surfaces of the core which consists of an aluminum plate was obtained.

  The composite thus obtained is used as a cushion material for a substrate press. However, since the cushion material does not contain a siloxane component, it is a cushion board that can withstand heat and repeatedly compress. Moreover, since the core body is lightweight because it uses an aluminum material, and the outermost surface is a PTFE layer, the releasability is extremely high, so that the handling is good and the production efficiency is expected to be improved. Furthermore, since it is possible to follow minute irregularities of the substrate circuit pattern, it is possible to apply pressure uniformly.

(Example 5)
Hereinafter, the composite according to Example 5 will be described with reference to FIG. However, the same members as those of FIG. As the composite sheet 40, a PTFE sintered layer (thin film) having a thickness of about 2 to 3 μm whose surface is treated with a metal sodium-naphthalene complex solution on a resin film (support layer) 21 made of polyimide film and having a thickness of 50 μm. Layer) 22 and a layer (bonding layer) 41 made of an epoxy adhesive having a thickness of 10 μm is used.

The composite sheet having such a configuration is manufactured as follows.
First, after coating PTFE dispersion on one surface of a resin film (thickness 50 μm, width 500 mm, length 500 mm) 21 made of a polyimide film, it is baked at 350 to 370 ° C. and has a thickness of about 2 to 3 μm on the polyimide surface. The PTFE sintered layer 22 was formed. Next, after treating the PTFE sintered layer surface with a metal sodium-naphthalene complex solution, the composite sheet 40 was manufactured by applying an epoxy adhesive to the PTFE sintered layer surface to form a bonding layer 41.
Next, the bonding layer surface side of this composite sheet 40 and a copper foil (adhered body / thickness 35 μm, width 500 mm, length 500 mm) 42 were overlapped and pressure-molded at room temperature. As a result, a composite 44 in which a PTFE sintered layer (thin film layer) 43 was joined and integrated on the surface of the copper foil 42 was obtained.

  The composite 44 thus obtained was sintered by firing at 350 to 370 ° C. after the PTFE dispersion was applied as a process for forming the PTFE sintered layer (thin film layer) 43 on the copper foil (adhered body) 42 in the conventional method. Therefore, a copper foil (adhered body) that is free from oxidation or residual strain due to heating can be obtained.

Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage. Further, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, you may combine the component covering different embodiment suitably. Specifically, in Example 1, the PFA layer (bonding layer) containing fine powder silica was described. However, the present invention is not limited to this, and in the case of using a bond layer not containing fine powder silica, the surface of the thin film layer is used. In addition, electrical and chemical surface treatment can be applied for the purpose of improving adhesion. Further, the materials, thicknesses, and the like of the composite sheet are not limited to those described in the above examples.
Hereinafter, the invention described in the scope of claims of the present application will be appended.
[1] A sheet-like support layer made of resin or metal, a thin film layer formed on one or both sides of the support layer, and a bonding layer formed on the thin film layer. Composite sheet.
[2] A composite comprising a sheet-like support layer made of resin or metal, and a thin film layer formed on one side or both sides of the support layer and processed so that the surfaces can be joined. Sheet.
[3] The composite sheet according to [1] or [2], wherein the thin film layer is a completely sintered PTFE sheet having a specific gravity of 2.13 to 2.20.
[4] The composite sheet according to any one of [1] to [3], wherein the thin film layer has a thickness of 0.2 to 20 μm.
[5] The composite sheet according to any one of [1] to [4], wherein the surface of the thin film layer is electrically or chemically treated.
[6] The composite sheet according to [1], wherein the bonding layer is a fluororesin layer containing a bonding component.
[7] An adherend and a laminate having a support peeled from the composite sheet according to any one of [1] to [6] joined to the adherend, the laminate being a composite After the sheet is laminated and integrated on the adherend by any one of pressure, heating or pressure so that the bonding layer side or the surface treatment side of the thin film layer is in contact with the main surface of the adherend A composite comprising the support being peeled off.

Sectional drawing which shows the basic composition of the composite sheet which concerns on this invention. Sectional drawing which shows the basic composition of the composite_body | complex which concerns on this invention. Sectional drawing of the composite sheet which concerns on Example 1 of this invention. Sectional drawing which shows the manufacturing method of the composite_body | complex which concerns on Example 2 of this invention in order of a process. Sectional drawing of the composite_body | complex which concerns on Example 3 of this invention. Sectional drawing of the composite_body | complex which concerns on Example 5 of this invention. Explanatory drawing in the case of performing thermocompression bonding with the electrode terminal part of a circuit board, and the electroconductive part of FPC using a cushion sheet.

Explanation of symbols

  10, 20, 24, 40 ... composite sheet, 11 ... support, 12 ... thin film layer, 13, 23, 41 ... bonding layer, 14, 26 ... composite, 16 ... laminate, 21 ... polyimide film (support layer) ), 22, 43 ... PTFE sintered layer (thin film layer), 25 ... adherend, 42 ... copper foil.

Claims (4)

A thin film comprising a resin or metal sheet-like support layer, and a sintered layer of a completely sintered PTFE having a specific gravity of 2.13 to 2.20 formed on one or both surfaces of the support layer composite sheet, wherein the layer that comprises the this formed thin film layer, the bonding layer made of fluorine resin layer formulated bonding component. A resin or metal sheet-like support layer and a complete specific gravity of 2.13 to 2.20 formed on one side or both sides of the support layer and electrically or chemically treated so that the surfaces can be joined. A composite sheet comprising a thin film layer made of a sintered layer of PTFE alone sintered . The composite sheet according to claim 1, wherein the thin film layer has a thickness of 0.2 to 20 μm. An adherend and a laminate that is bonded to the adherend and peeled off the support layer from the composite sheet according to any one of claims 1 to 3 , wherein the laminate joins the composite sheet. After the layer side or the surface treatment side of the thin film layer is in contact with the main surface of the adherend, it is laminated and integrated on the adherend by any means of pressure, heating or pressurization, and then the support layer It is comprised by peeling off, The composite body characterized by the above-mentioned.

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