CN113844149B - Method for producing laminated body - Google Patents
Method for producing laminated body Download PDFInfo
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- CN113844149B CN113844149B CN202011410648.8A CN202011410648A CN113844149B CN 113844149 B CN113844149 B CN 113844149B CN 202011410648 A CN202011410648 A CN 202011410648A CN 113844149 B CN113844149 B CN 113844149B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/144—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers using layers with different mechanical or chemical conditions or properties, e.g. layers with different thermal shrinkage, layers under tension during bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
- B32B37/18—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only
- B32B37/182—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only one or more of the layers being plastic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention discloses a method for manufacturing a laminate, comprising: a step of performing plasma treatment on the surface of the liquid crystal polymer film (10) to impart a functional group that is a hydrophilic group to the surface of the liquid crystal polymer film; a step of forming a laminate (12) by hot-pressing the liquid crystal polymer film and the copper foil at a first temperature at which the movement of the functional group is activated, with the surface of the liquid crystal polymer film that has been subjected to the plasma treatment being opposed to the copper foil (11); a step of heat-treating the laminate at a second temperature at which the molecular orientation of the liquid crystal polymer film becomes random; and a step of quenching the laminate to a temperature at which the liquid crystal polymer film is not promoted to be reoriented. The laminate is formed by laminating a liquid crystal polymer film and a copper foil, and has sufficient peel strength.
Description
Technical Field
The present invention relates to a method for producing a laminate comprising a liquid crystal polymer film and a copper foil laminated together.
Background
Most flexible wiring boards are composed of a laminate of an insulating polymer film and a copper foil. The circuit pattern is formed by etching the copper foil of the laminate.
In recent years, devices have been increasingly high-frequency in order to achieve higher communication rates. As the insulating polymer film, a liquid crystal polymer film having a small dielectric loss and dielectric loss tangent has been used.
As a method for producing a laminate formed by laminating a liquid crystal polymer film and a copper foil, for example, patent document 1 discloses the following method: the liquid crystal polymer film and the copper foil are overlapped, and the laminate is formed by hot pressing at a temperature equal to or higher than the melting point of the liquid crystal polymer film.
Patent document 2 discloses a method adopted to improve dimensional stability: the liquid crystal polymer film and the copper foil are hot-pressed at a temperature of 260 ℃ to form a laminate, and the laminate is heat-treated at a temperature of not less than the melting point of the liquid crystal polymer film.
Patent document 1: japanese laid-open patent publication No. 2010-221694
Patent document 2: japanese laid-open patent publication No. 2000-343610
Disclosure of Invention
Technical problem to be solved by the invention
However, the laminate formed by the methods disclosed in patent document 1 and patent document 2 has the following problems: the peel strength at the time of peeling the copper foil from the liquid crystal polymer film cannot be sufficiently obtained, and the deviation of the peel strength is large.
The inventors of the present application found that: the problem of not obtaining sufficient peel strength is that inherent in liquid crystal polymer films.
That is, a liquid crystal polymer film produced by a melt method, a solution method, or the like has small intermolecular cohesive energy in the thickness direction because molecules are oriented in a direction parallel to the plane (in-plane direction). Therefore, when the copper foil is peeled from the liquid crystal polymer film, the copper foil is peeled from the liquid crystal polymer film by being broken in the thickness direction, not from the interface between the copper foil and the liquid crystal polymer film.
That is, the peel strength of the polymer films other than the liquid crystal polymer film is generally determined by the adhesion of the interface between the copper foil and the liquid crystal polymer film; the peel strength of the liquid crystal polymer film is determined by the weak intermolecular cohesive energy in the thickness direction of the liquid crystal polymer film.
The present invention has been made to solve the above-mentioned problems, and its main purpose is: a method for producing a laminate which is formed by laminating a liquid crystal polymer film and a copper foil and has sufficient peel strength with little deviation.
Technical solution for solving the technical problems
The method for producing a laminate according to the present invention is a method for producing a laminate comprising a liquid crystal polymer film and a copper foil laminated together, the method comprising: a step of performing plasma treatment on the surface of the liquid crystal polymer film, and imparting a functional group that is a hydrophilic group to the surface of the liquid crystal polymer film; a step of forming a laminate by thermally pressing the liquid crystal polymer film and the copper foil at a first temperature at which the movement of the functional group is activated, with the surface of the liquid crystal polymer film that has been subjected to the plasma treatment being opposed to the copper foil; a step of heat-treating the laminate at a second temperature higher than the first temperature and at which the molecular orientation of the liquid crystal polymer film becomes random; and a step of quenching the laminate to a temperature at which the liquid crystal polymer film is not promoted to be reoriented.
Effects of the invention
According to the present invention, a method for producing a laminate which is formed by laminating a liquid crystal polymer film and a copper foil and has sufficient peel strength with less variation can be provided.
Drawings
Fig. 1 (a) to (E) are diagrams schematically showing a method of manufacturing a laminate in an embodiment of the present invention;
fig. 2 illustrates a method of forming a laminate in a roll-to-roll manner.
Symbol description-
10-a liquid crystalline polymer film; 10 a-the surface of a liquid crystal polymer film; 11-copper foil; 12-laminate; 12A-laminate roll; 23. 31-atmospheric pressure plasma device; 40-preheating device; 41-a hot press roll; 42-heating means; 43-insulating walls; 51-cooling means.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The present invention is not limited to the following embodiments, and may be appropriately modified within a range that does not depart from the scope of the present invention.
Fig. 1 (a) to (E) schematically show a method for producing a laminate according to an embodiment of the present invention. The laminate in this embodiment has a structure in which a liquid crystal polymer film and a copper foil are laminated. Here, the liquid crystal polymer film is formed of a thermotropic liquid crystal polymer which becomes liquid crystal in a molten state, and the liquid crystal polymer film is subjected to molecular alignment in a lamination front direction.
As shown in fig. 1 (a), the surface 10a of the liquid crystal polymer film 10 is subjected to plasma treatment. Examples of gases that can be used for plasma treatment include: any one of argon, nitrogen, air, steam, and carbon dioxide, or a gas obtained by mixing two or more of the above gases. The plasma treatment can be, for example, atmospheric pressure plasma treatment.
Functional groups, which are hydrophilic groups, are imparted to the surface of the liquid crystal polymer film 10 that has been subjected to plasma treatment. The functional group to be given to the surface of the liquid crystal polymer film 10 includes any one of a hydroxyl group, a carbonyl group, and a carboxyl group.
If argon or nitrogen is used as the gas for plasma treatment, the plasma easily becomes stable. If water vapor and carbon dioxide are mixed into the gas for plasma treatment, hydroxyl groups, carbonyl groups, carboxyl groups, that is, functional groups, are easily introduced into the surface of the liquid crystal polymer film 10.
The generation of the atmospheric pressure plasma can be performed by using a barrier discharge, an arc discharge, a microwave discharge, or the like, and the barrier discharge irradiates a wide area with the plasma, so that the barrier discharge can be easily applied to a roll-to-roll process.
As a plasma irradiation method for irradiating the liquid crystal polymer film 10 with plasma, a direct irradiation method in which the liquid crystal polymer film 10 is inserted into a gap between barrier discharge electrodes may be used, and a remote irradiation method in which the liquid crystal polymer film 10 is irradiated with plasma generated by barrier discharge by an air flow, radicals, or the like may be used.
The irradiation power of the plasma is preferably 1 W.min/cm per unit area of the liquid crystal polymer film 10 2 The above. If the irradiation power of the plasma is set to 10 W.min/cm 2 As described above, the molecular structure of the surface of the liquid crystal polymer film 10 is destroyed, and the peeling strength is lowered. Therefore, the irradiation power of the plasma was 10 W.min/cm 2 The above is not preferable.
Next, as shown in fig. 1 (B), the surface 10a of the liquid crystal polymer film 10, which has been subjected to plasma treatment, is opposed to the copper foil 11. As shown in fig. 1 (C), the liquid crystal polymer film 10 and the copper foil 11 are hot pressed to form a laminate 12. Here, the temperature of the hot pressing (first temperature) is set to a temperature at which the movement of the functional group imparted to the surface of the liquid crystal polymer film 10 is activated.
When the liquid crystal polymer film 10 and the copper foil 11 are hot-pressed at this temperature, the functional group (hydrophilic group) such as hydroxyl group introduced into the surface of the liquid crystal polymer film 10 is dehydrated and condensed with the surface of the copper foil 11. As a result, an adhesive force between the liquid crystal polymer film 10 and the copper foil 11 can be obtained. In the case where the hydrophobic group of the silane coupling agent and the organic rust inhibitor are exposed on the outermost surface of the copper foil 11, it is preferable to remove the hydrophobic group of the silane coupling agent and the organic rust inhibitor by performing plasma treatment or the like on the outermost surface of the copper foil 11 or to impart a hydrophilic group such as a hydroxyl group to the outermost surface of the copper foil 11.
For example, in the case where hydroxyl groups (C-OH) are introduced into carbon atoms on the surface of the liquid crystal polymer film 10, OH-Cu (copper) is dehydrocondensed to form C-O-Cu. In the case where hydroxyl groups are given to the surface of the copper foil 11, OH groups are hydrogen-bonded to each other, and then, finally, dehydration-condensed to form C-O-Cu. In the case where a thin oxide film (CuO) is formed on the surface of the copper foil 11, and after OH and O are bonded by hydrogen, C-OH-O-Cu is dehydrogenated and condensed to finally form C-O-O-Cu.
The hot-pressing temperature (first temperature) may be a temperature at which the movement of the functional group given to the surface of the liquid crystal polymer film 10 is activated. Specifically, it is preferable to set the temperature of the hot pressing (first temperature) to be equal to or higher than the β relaxation temperature and equal to or lower than the α relaxation temperature of the liquid crystal polymer film 10. In general, the values of the β relaxation temperature in the width direction and the length direction when the liquid crystal polymer film 10 is formed are different, and the values of the α relaxation temperature in the width direction and the length direction when the liquid crystal polymer film 10 is formed are also different. Here, a lower temperature among the above temperatures is taken as a representative value.
Here, the β relaxation temperature is defined as being determined by the rotational movement of small segments or side chains within the chain molecule, and the α relaxation temperature is defined as being determined by the microscopic brownian movement of the main chain segment. The liquid crystal polymer film 10 has a beta relaxation temperature of approximately 100 ℃ to 120 ℃ and an alpha relaxation temperature of approximately 230 ℃ to 250 ℃. The alpha relaxation temperature and the beta relaxation temperature can be measured by a dynamic viscoelasticity measurement (DMA) device respectively.
If the temperature of the hot pressing (first temperature) is lower than the beta relaxation temperature, the adhesion between the liquid crystal polymer film 10 and the copper foil 11 cannot be sufficiently obtained. The temperature of the hot pressing (first temperature) is thus lower than the beta relaxation temperature, which is not preferable. If the hot-pressing temperature (first temperature) is higher than the alpha relaxation temperature, the hardness (Young's modulus) of the liquid crystal polymer film 10 is drastically decreased. Therefore, it is difficult to control the pressure at the time of hot pressing, the thickness of the liquid crystal polymer film 10 may be changed, or the liquid crystal polymer film 10 may be protruded from the copper foil 11. The hot-pressing temperature (first temperature) is higher than the alpha relaxation temperature, which is not preferable.
The pressure of the hot pressing is set appropriately according to the temperature of the hot pressing, and is preferably in the range of 0.5MPa to 100MPa, more preferably in the range of 5MPa to 50 MPa.
As the copper foil 11, for example, electrolytic copper foil, rolled copper foil, or the like can be used. If the copper foil 11 having the surface formed with irregularities is used, the adhesion between the liquid crystal polymer film 10 and the copper foil 11 can be further improved. When the copper foil 11 having a surface roughness (Rz) of 1.5 μm or less is used, transmission loss can be suppressed even at a high frequency of about 10 GHz.
By forming a copper diffusion barrier layer (also referred to as an adhesive layer) formed of nickel, chromium, cobalt, manganese, titanium, or the like on the copper foil 11, coordination bonding is performed with respect to the metal element forming the copper diffusion barrier layer while maintaining the molecular structure of the liquid crystal polymer film 10. As a result, the adhesive force can be further improved. Further, by letting the metal element function as a copper diffusion barrier layer, the occurrence of the following phenomenon can be suppressed: the copper element catalyzes the decomposition of the liquid crystal polymer film 10 (damage caused by copper) to deteriorate the liquid crystal polymer film 10, and the adhesion between the liquid crystal polymer film 10 and the copper foil 11 is reduced.
Next, as shown in fig. 1D, the laminate 12 is heat-treated at a temperature (second temperature) at which the molecular orientation of the liquid crystal polymer film 10 becomes random orientation. Here, the second temperature is set to a temperature higher than the hot pressing temperature (first temperature) and in the vicinity of the melting point of the liquid crystal polymer film 10. Specifically, the second temperature is preferably at a temperature of 20 ℃ or higher than the melting point of the liquid crystal polymer film 10 and 20 ℃ or lower than the melting point of the liquid crystal polymer film.
If the second temperature does not reach a temperature 20 deg.c lower than the melting point of the liquid crystal polymer film 10, the molecular orientation of the liquid crystal polymer film 10 becomes insufficiently random, and therefore the second temperature does not reach a temperature 20 deg.c lower than the melting point of the liquid crystal polymer film 10, which is not preferable. If the second temperature exceeds a temperature 20 ℃ higher than the melting point of the liquid crystal polymer film 10, the liquid crystal polymer film 10 and the copper foil 11 are oxidized and deteriorated, so that it is not preferable that the second temperature exceeds a temperature 20 ℃ higher than the melting point of the liquid crystal polymer film 10.
The heating method of the laminate 12 can be, for example, a heater heating method, a lamp heating method, an infrared heating method, an induction heating method, or the like. In the case of heating by a heater, as shown in fig. 1 (D), the heating member 13 is preferably brought into contact with the copper foil 11.
When the laminate 12 is heat-treated, it is not necessary to apply pressure to the laminate 12, but if a pressure of 5MPa or more is applied to the laminate 12, the molecular orientation of the liquid crystal polymer film 10 in the in-plane direction is enhanced. Therefore, the application of a pressure of 5MPa or more is not preferable.
Next, after the laminate 12 is heat-treated, the laminate 12 is quenched to a temperature at which the liquid crystal polymer film 10 is not accelerated as shown in fig. 1 (E). Specifically, the laminate 12 is preferably quenched to 80 ℃ or less. For example, as shown in fig. 1 (E), when the laminate 12 is cooled, the cooling member 14 is preferably brought into contact with the copper foil 11.
According to the present embodiment, the molecular orientation of the liquid crystal polymer film 10 can be randomized by performing the heat treatment on the laminate 12 after the laminate 12 is formed by hot-pressing the liquid crystal polymer film 10 and the copper foil 11 which have been subjected to the plasma treatment. Thus, intermolecular cohesive energy in the thickness direction of the liquid crystal polymer film can be increased. As a result, when the copper foil 11 is peeled from the liquid crystal polymer film 10, a large amount of intermolecular cohesive energy is consumed to break the liquid crystal polymer film 10 in the thickness direction. So that higher peeling strength can be obtained.
That is, the peel strength between the liquid crystal polymer film 10 and the copper foil 11 is not determined by the weak intermolecular cohesive energy in the thickness direction of the liquid crystal polymer film 10 oriented in the plane direction, but the adhesive force of the interface between the copper foil and the liquid crystal polymer film is maximally exerted. Thus, the peeling strength can be made sufficiently high, and the peeling strength can be prevented from being deviated.
It should be noted that if it takes time to cool the laminate 12 to room temperature after the heat treatment is performed on the laminate 12, the following may occur: the liquid crystal polymer film 10 becomes fragile because of its excessively high crystallinity, and the peel strength of the laminate 12 decreases by promoting the re-orientation of the liquid crystal polymer film 10. Therefore, in order to suppress the promotion of the reorientation, it is preferable that the laminate 12 is quenched to a temperature at which the crystallization of the liquid crystal polymer film 10 is not promoted and the reorientation of the liquid crystal polymer film 10 is not promoted after the laminate 12 is heat-treated. Specifically, the temperature is 80℃or lower.
In the present embodiment, the laminate 12 is formed by hot-pressing the liquid crystal polymer film 10 and the copper foil 11, which have been subjected to the plasma treatment, before randomizing the molecular orientation of the liquid crystal polymer film 10, so that it is not necessary to apply excessive pressure to the laminate 12 in the process of heat-treating the laminate 12 later. As a result, since excessive pressure is not applied to the liquid crystal polymer film 10, randomization of the molecular orientation of the liquid crystal polymer film 10 is not hindered.
In the present embodiment, the laminate 12 is formed by hot-pressing the liquid crystal polymer film 10 and the copper foil 11 which have been subjected to the plasma treatment, and therefore, the adhesion between the liquid crystal polymer film 10 and the copper foil 11 can be sufficiently ensured. So that the peeling strength between the liquid crystal polymer film 10 and the copper foil 11 can be ensured to be sufficiently high.
(method for producing roll-to-roll laminate)
Fig. 2 shows a method of manufacturing the laminate 12 by performing a process of plasma-treating the surface of the liquid crystal polymer film 10, a process of hot-pressing the liquid crystal polymer film 10 and the copper foil 11 to form the laminate 12, a process of heat-treating the laminate 12, and a process of quenching the laminate 12 as a series of processes by a roll-to-roll method.
As shown in fig. 2, the rolled liquid crystal polymer film 10 fed from the transport drum 20 is plasma-treated by the atmospheric pressure plasma device 23 while being supported by the metal belt transport device 22 via the heating roller 21.
A plasma gas such as argon, nitrogen, air, or steam is supplied to the atmospheric pressure plasma device 23 through a flow meter (not shown), and the atmospheric pressure plasma device 23 is connected to a high-frequency power supply (not shown) for generating plasma. The use of a plurality of atmospheric pressure plasma devices 23 as necessary can increase the processing speed.
On the other hand, the rolled copper foil 11 fed from the feeding roller 30 is simultaneously fed and laminated with the liquid crystal polymer film 10 which has been plasma-treated by the atmospheric pressure plasma device 23. The surface of the copper foil 11 may be subjected to plasma treatment by the atmospheric pressure plasma device 31 before lamination.
The liquid crystal polymer film 10 and the copper foil 11 in a laminated state are preheated by a preheating device 40 composed of a heating roller and a metal belt, and then laminated by a pair of hot press rollers 41 to form a laminate 12. The laminated body 12 obtained by lamination is immediately subjected to heat treatment by a heating device 42 composed of a heating roller and a metal belt. The preheating device 40, the pair of hot press rollers 41, and the heating device 42 are covered with a heat insulating wall 43, and the inside is replaced with nitrogen gas or the like.
After the heat-treated laminate 12 passes through the roll 50, it is cooled to 80 ℃ or lower by a cooling device 51 comprising a cooling roll and a metal belt. Thereafter, the cooled laminate 12 is wound as a laminate roll 12A around a carrying drum 52.
If the atmospheric pressure plasma devices 23 and 31 are barrier discharge type atmospheric pressure plasma devices, a wide and uniform treatment is easily performed, and thus the atmospheric pressure plasma devices 23 and 31 are preferably barrier discharge type atmospheric pressure plasma devices. If the atmospheric pressure plasma devices 23, 31 are remote atmospheric pressure plasma devices, it is difficult to excessively destroy molecules on the surface of the liquid crystal polymer film 10, and thus the atmospheric pressure plasma devices 23, 31 are preferably remote atmospheric pressure plasma devices. The gas used for the discharge is preferably nitrogen as a main component from the viewpoints of stability of plasma and suppression of cost. If about several% to 10% of air is added to nitrogen, hydroxyl groups, carbonyl groups, carboxyl groups, etc. are easily introduced into the surface of the liquid crystal polymer film 10, and therefore about several% to 10% of air is preferably added to nitrogen.
The preheating device 40 is constituted by a plurality of heating rollers and a metal belt. If a stainless steel seamless belt is used as the metal belt, a state in which the contact state of the metal belt with the copper foil 11 is uniform is easily obtained, and thus the stainless steel seamless belt is used as the metal belt. If an induction heating type roller is used as the heating roller, a predetermined temperature can be easily and efficiently obtained, and therefore, the induction heating type roller is preferable. The nip pressure of the heating roller may be a pressure sufficient to ensure heat conduction with the copper foil 11. If the preheating temperature of the copper foil 11 is controlled by the temperature set by the heating roller and the preheating temperature of the copper foil 11 is set in the range of 150 to the hot pressing temperature, the moisture adsorbed on the liquid crystal polymer film 10 and the copper foil 11 can be removed, and wrinkles and the like generated by thermal expansion at the time of hot pressing can be easily suppressed. Therefore, the preheating temperature of the copper foil 11 is controlled by the temperature set by the heating roller, and the preheating temperature of the copper foil 11 is preferably set in the range of 150 to the hot pressing temperature.
If a pressure-controlled roller is used for the pair of heat-press rollers 41, the lamination condition is easily and stably reproduced even in the case where the thickness of the liquid crystal polymer film 10 and the copper foil 11 is slightly changed, and therefore, the pair of heat-press rollers 41 is preferably a pressure-controlled roller. The upper and lower heating rolls in the heat press roll 41 may have the same temperature, but if the temperature of the heating roll on the copper foil 11 side is increased, excessive heat load is not applied to the liquid crystal polymer film 10 when the bonding interface is heated, and therefore, it is preferable to increase the temperature of the heating roll on the copper foil 11 side.
The heating device 42 is constituted by a plurality of heating rollers and a metal belt. If a stainless steel seamless belt is used as the metal belt, a state in which the contact state of the metal belt with the copper foil 11 is uniform is easily obtained, and therefore, a stainless steel seamless belt is preferably used as the metal belt. If an induction heating type roller is used as the heating roller, it is easy to efficiently obtain a temperature of 300℃or higher, and therefore, it is preferable to use an induction heating type roller as the heating roller. The nip pressure of the heating roller may be a pressure sufficiently large enough to ensure heat conduction with the laminate 12. In the heat treatment, the temperature of the surface of the liquid crystal polymer film 10 may be measured by a radiation thermometer or the like, and the measured value may be fed back to control the temperature of the heating roller.
The cooling device 51 is constituted by a plurality of cooling rolls and a metal belt. If a stainless steel seamless belt is used as the metal belt, a state in which contact with the copper foil 11 is uniform is easily obtained, and therefore the stainless steel seamless belt is used as the metal belt. The nip pressure of the heating roller may be a pressure sufficient to ensure heat conduction with the laminate. If the temperature of the cooled laminate 12 is 80 ℃ or lower, preferably 40 ℃ or lower, the change in internal stress when the wound laminate roll 12A is cooled to normal temperature can be reduced, and therefore the temperature of the cooled laminate 12 is preferably 80 ℃ or lower, preferably 40 ℃ or lower.
Example (example)
The above embodiments are described in more detail below with reference to examples and comparative examples.
[ common conditions ]
The specific cases of the liquid crystal polymer films 10 used in the examples and comparative examples are as follows: product number "Vecstar CTS50N", thickness: 50 μm, width: 270mm, melting point: 325 ℃, alpha relaxation temperature: the width direction of 236 ℃ during film forming and the length direction of 237 ℃ during film forming; beta relaxation temperature: the width direction at the time of film formation was 105℃and the length direction at the time of film formation was 110 ℃. The specific cases of the copper foil 11 used are as follows: the product number "JXEFL-V2" manufactured by JX Metal Co., ltd., electrolytic copper foil, thickness 18 μm, width 270mm.
The laminate 12 is formed using the roll-to-roll method shown in fig. 2. At this time, the processing speed was 1m/min, the pull-out tension of the liquid crystal polymer film 10 was 100N/m, the pull-out tension of the copper foil 11 was 100N/m, and the winding tension of the laminate 12 was 150N/m.
The preheating device 40 of the liquid crystal polymer film 10 sets the temperature of the heating roller to 100 ℃.
Five devices with a width of 270mm were placed as the atmospheric pressure plasma device 23, and the power was: 1.85 W.min/cm 2 Frequency: plasma irradiation was performed at 35kHz to 55 kHz. The gap between the atmospheric pressure plasma device 23 and the liquid crystal polymer film 10 was set to 2mm, the plasma gas was set to 95% nitrogen, the dry air was set to 5%, and the total flow rate was set to 100L/min/stage.
The pair of heat pressing rollers 41 uses a diameter: 6 inches, width: 500mm, area of pressurization: 5.4cm 2 And the pressing pressure was set to 30MPa. The inner environment of the heat insulating wall 43 is set to 2% or less of oxygen.
[ evaluation method ]
Peel strength between the liquid crystal polymer film 10 and the copper foil 11 was measured in accordance with IPC-TM-650.
Example 1
The laminate 12 of 20m was produced with the rolling temperature (the temperatures of the upper and lower heating rolls in the hot press roll 41) set at 200℃and the heat treatment temperature (the temperatures of the respective heating rolls in the heating device 42) set at 340 ℃. 340 ℃ is the temperature of 325 ℃ +15 ℃ of the melting point of the liquid crystal polymer film 10.
Example 2
The roll-in temperature (the temperatures of the upper and lower heating rolls in the hot press roll 41) was set to 200℃and the heat treatment temperature (the temperatures of the heating rolls in the heating device 42) was set to 310℃to produce a 20m laminate 12. 310 ℃ is the temperature of 325 ℃ to 15 ℃ of the melting point of the liquid crystal polymer film 10.
Comparative example 1
The laminate 12 of 20m was produced with the rolling temperature (the temperatures of the upper and lower heating rolls in the hot press roll 41) set at 200℃and the heat treatment temperature (the temperatures of the respective heating rolls in the heating device 42) set at 360 ℃. 360℃is the temperature at which the melting point of the liquid crystal polymer film 10 is 325 ℃ +35℃.
Comparative example 2
The laminate 12 of 20m was produced by setting the rolling temperature (temperature of the upper and lower heating rolls in the hot press roll 41) to a non-heating temperature (25 ℃) and the heat treatment temperature (temperature of each heating roll in the heating device 42) to 340 ℃.
Comparative example 3
The laminate 12 of 20m was produced with the rolling temperature (the temperatures of the upper and lower heating rolls in the hot press roll 41) set at 80℃and the heat treatment temperature (the temperatures of the respective heating rolls in the heating device 42) set at 340 ℃. 80 ℃ is the temperature of 105 ℃ to 25 ℃ of the beta relaxation temperature of the liquid crystal polymer film 10.
Comparative example 4
The laminate 12 of 20m was produced with the rolling temperature (the temperatures of the upper and lower heating rolls in the hot press roll 41) set at 260℃and the heat treatment temperature (the temperatures of the respective heating rolls in the heating device 42) set at 340 ℃. 260℃is the temperature of 236℃ +24℃ for the alpha-relaxation temperature of the liquid crystal polymer film 10.
Comparative example 5
The laminate 12 of the laminate 20m was produced by setting the rolling temperature (the temperatures of the upper and lower heating rolls in the hot press roll 41) to 340℃and the heat treatment temperature to non-heating (25 ℃). 340 ℃ is the temperature of 325 ℃ +15 ℃ of the melting point of the liquid crystal polymer film 10.
Table 1 shows the results of the peel strength measurements of the laminates 12 formed in examples 1 to 2 and comparative examples 1 to 5.
(Table 1)
As shown in Table 1, the peel strength of examples 1 and 2 was 6.7N/cm or more, and the strength was not problematic in practical use. In addition, the appearance was also normal.
The peel strength of comparative example 1 was 8.1N/cm, and the strength was not problematic, but the liquid crystal polymer film 10 turned brown. Consider that: this is because the liquid crystal polymer film 10 is deteriorated by oxidation when the heat treatment temperature is higher than the melting point.
In comparative example 2, the peel strength was 2.8 to 4.8N/cm, and the deviation was large and insufficient in practical use. Consider that: the reason why the peel strength is insufficient is that the roll temperature is too low and the adhesion between the liquid crystal polymer film 10 and the copper foil 11 is hardly obtained. Consider that: the reason for the large variation is that the region in which the local plane direction of the liquid crystal polymer film 10 is oriented remains.
In comparative example 3, the peel strength was 5.8N/cm, which is a value insufficient in practical use. Consider that: this is because the rolling temperature is low, and the adhesion between the liquid crystal polymer film 10 and the copper foil 11 cannot be sufficiently obtained.
In comparative example 4, the peel strength was 5.5N/cm, which is a value insufficient in practical use. Consider that: this is because the liquid crystal polymer film 10 has a high rolling temperature, and the molecules are strongly aligned in the planar direction, and cannot be sufficiently randomized by the heat treatment. In addition, the film thickness of the liquid crystal polymer film 10 was reduced, and a portion of the end portion of the liquid crystal polymer film 10 protruding from the copper foil was seen. Consider that: this is because the rolling is excessive in comparison with the state in which the liquid crystal polymer film 10 has been softened when the rolling is performed.
In comparative example 5, the peel strength was 3.4 to 5.2N/cm, and the deviation was large and insufficient in practical use. Consider that: this is because the molecular orientation of the liquid crystal polymer film 10 remains, and the liquid crystal polymer film 10 is broken in the thickness direction. The liquid crystal polymer film 10 has a residual molecular orientation, and the liquid crystal polymer film 10 is broken in the thickness direction because the laminate 12 is formed by hot-pressing the liquid crystal polymer film 10 and the copper foil 11 at a temperature equal to or higher than the melting point of the liquid crystal polymer film.
The present invention has been described above with reference to preferred embodiments, but the present invention is not limited to the above, and various modifications are of course possible.
Claims (4)
1. A method for producing a laminate comprising a liquid crystal polymer film and a copper foil, characterized by comprising the steps of:
the liquid crystal polymer film is oriented with the molecules in a direction parallel to the plane prior to lamination,
the method for manufacturing the laminate comprises the following steps: a step (A) of performing plasma treatment on the surface of the liquid crystal polymer film, and imparting a functional group that is a hydrophilic group to the surface of the liquid crystal polymer film;
a step (B) of forming the laminate by thermally pressing the liquid crystal polymer film and the copper foil at a first temperature at which the movement of the functional group is activated, with the surface of the liquid crystal polymer film that has been subjected to the plasma treatment being opposed to the copper foil;
a step (C) of heat-treating the laminate at a second temperature higher than the first temperature and at which the molecular orientation of the liquid crystal polymer film becomes random; and
a step (D) of quenching the laminate to a temperature of 80 ℃ or less which does not promote the reorientation of the liquid crystal polymer film,
in the step (B), the first temperature is equal to or higher than the beta relaxation temperature of the liquid crystal polymer film and equal to or lower than the alpha relaxation temperature,
in the step (C), the second temperature is a temperature of 20 ℃ or higher than the melting point of the liquid crystal polymer film and 20 ℃ or lower than the melting point of the liquid crystal polymer film,
the steps (a), (B), (C) and (D) are performed as a series of steps in a roll-to-roll method.
2. The method for producing a laminate according to claim 1, wherein:
in the step (a), the gas used for the plasma treatment is one of argon, nitrogen, air, steam, and carbon dioxide, or a gas obtained by mixing two or more of argon, nitrogen, air, steam, and carbon dioxide.
3. The method for producing a laminate according to claim 1, wherein:
in the step (a), the functional group to be added to the surface of the liquid crystal polymer film is any one of a hydroxyl group, a carbonyl group, and a carboxyl group.
4. The method for producing a laminate according to claim 1, wherein:
in the step (a), the plasma treatment is an atmospheric pressure plasma treatment.
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| JP2020-111005 | 2020-06-27 | ||
| JP2020123076A JP7312461B2 (en) | 2020-06-27 | 2020-07-17 | Laminate manufacturing method |
| JP2020-123076 | 2020-07-17 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000280341A (en) * | 1999-03-30 | 2000-10-10 | Kuraray Co Ltd | Thermoplastic liquid crystal polymer film and modifying method thereof |
| JP2006272744A (en) * | 2005-03-29 | 2006-10-12 | Nippon Steel Chem Co Ltd | Method for producing laminate |
| KR20080064803A (en) * | 2005-09-14 | 2008-07-09 | 닛토덴코 가부시키가이샤 | Polarizing plate with optical compensation layer, liquid crystal panel using polarizing plate with optical compensation layer, and image display device |
| KR20130049827A (en) * | 2011-01-05 | 2013-05-14 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Copper-clad laminate and method for manufacturing same |
| JP2015037841A (en) * | 2013-08-19 | 2015-02-26 | 東洋紡株式会社 | Method of manufacturing laminate and method of manufacturing device structure using the laminate |
| WO2016170779A1 (en) * | 2015-04-20 | 2016-10-27 | 株式会社クラレ | Metal-clad laminate sheet manufacturing method, and metal-clad laminate sheet using same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4337279A (en) * | 1981-01-23 | 1982-06-29 | Uop Inc. | Method for increasing the peel strength of metal-clad polymers |
| JPH03155936A (en) * | 1989-11-14 | 1991-07-03 | Matsushita Electric Works Ltd | Manufacture of laminated sheet |
| JP4216433B2 (en) * | 1999-03-29 | 2009-01-28 | 株式会社クラレ | Method for producing metal-clad laminate for circuit board |
| JP2008229995A (en) * | 2007-03-20 | 2008-10-02 | Nippon Steel Chem Co Ltd | Method of manufacturing laminate |
| JP5411656B2 (en) | 2009-02-24 | 2014-02-12 | パナソニック株式会社 | Manufacturing method of laminated board for flexible printed wiring board, laminated board for flexible printed wiring board, and flexible printed wiring board |
| JP6871910B2 (en) * | 2016-03-08 | 2021-05-19 | 株式会社クラレ | Manufacturing method of metal-clad laminate and metal-clad laminate |
| TWI647261B (en) * | 2018-02-06 | 2019-01-11 | 佳勝科技股份有限公司 | Liquid crystal polymer film and method for producing flexible copper foil substrate having liquid crystal polymer film |
-
2020
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- 2020-12-04 CN CN202011410648.8A patent/CN113844149B/en active Active
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000280341A (en) * | 1999-03-30 | 2000-10-10 | Kuraray Co Ltd | Thermoplastic liquid crystal polymer film and modifying method thereof |
| JP2006272744A (en) * | 2005-03-29 | 2006-10-12 | Nippon Steel Chem Co Ltd | Method for producing laminate |
| KR20080064803A (en) * | 2005-09-14 | 2008-07-09 | 닛토덴코 가부시키가이샤 | Polarizing plate with optical compensation layer, liquid crystal panel using polarizing plate with optical compensation layer, and image display device |
| KR20130049827A (en) * | 2011-01-05 | 2013-05-14 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Copper-clad laminate and method for manufacturing same |
| JP2015037841A (en) * | 2013-08-19 | 2015-02-26 | 東洋紡株式会社 | Method of manufacturing laminate and method of manufacturing device structure using the laminate |
| WO2016170779A1 (en) * | 2015-04-20 | 2016-10-27 | 株式会社クラレ | Metal-clad laminate sheet manufacturing method, and metal-clad laminate sheet using same |
| CN107530979A (en) * | 2015-04-20 | 2018-01-02 | 株式会社可乐丽 | The manufacture method of metal-coated laminated board and the metal-coated laminated board manufactured with the manufacture method |
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| KR102493270B1 (en) | 2023-01-30 |
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