阅读说明：本技术 一种双轴延伸lcp膜的制备方法 (Preparation method of biaxial extension LCP film ) 是由 刘勇 张威 李永刚 王帅 于 2021-09-07 设计创作，主要内容包括：本发明公开了一种双轴延伸LCP膜的制备方法。该制备方法包括以下步骤：S1：疏解分散,对空白LCP料、母切料以及回收料进行疏解分散；S2：分筛,对疏解分散后的原料进行分筛,保证原料的粒度的一致性；S3：配料,分筛后的原料加入适量二氧化硅、碳酸钙进行配料；S4：金属过滤,配料完成后对原料进行金属分离过滤；S5：干燥,对原料进行真空转鼓干燥,去除原料聚合物中微量的水,真空干燥后进行气流干燥,本发明在横向拉伸时,通过承载膜的承载以及隔离防粘剂的润滑,使得承载膜与LCP膜一同变形,提高了LCP的横向拉伸比,防止横向拉伸时LCP膜撕裂,提高了成品率,且制备出的LCP膜的各向力学性能均匀,满足柔性电路板的使用需求。(The invention discloses a preparation method of a biaxially oriented LCP film. The preparation method comprises the following steps: s1: carrying out defibering and dispersion, namely defibering and dispersing the blank LCP material, the mother cut material and the reclaimed material; s2: screening, namely screening the fluffed and dispersed raw materials to ensure the consistency of the particle sizes of the raw materials; s3: proportioning, namely adding a proper amount of silicon dioxide and calcium carbonate into the sieved raw materials for proportioning; s4: metal filtration, namely performing metal separation and filtration on the raw materials after the batching is finished; s5: the invention has the advantages that during transverse stretching, the bearing of the bearing film and the lubrication of the isolation anti-sticking agent ensure that the bearing film and the LCP film deform together, the transverse stretching ratio of LCP is improved, the LCP film is prevented from being torn during transverse stretching, the yield is improved, the prepared LCP film has uniform mechanical properties in all directions, and the use requirement of the flexible circuit board is met.)

1. A method for producing a biaxially stretched LCP film, comprising the steps of:

s1: carrying out defibering and dispersion, namely defibering and dispersing the blank LCP material, the mother cut material and the reclaimed material;

s2: screening, namely screening the fluffed and dispersed raw materials to ensure the consistency of the particle sizes of the raw materials;

s3: proportioning, namely adding a proper amount of silicon dioxide and calcium carbonate into the sieved raw materials for proportioning;

s4: metal filtration, namely performing metal separation and filtration on the raw materials after the batching is finished;

s5: drying, namely performing vacuum drum drying on the raw material to remove trace water in the raw material polymer, and performing airflow drying after vacuum drying to remove acid or alkaline impurities in the raw material polymer;

s6: melt extrusion, heating and melting the dried raw materials through an extruder, and uniformly conveying the melt to a die head to cast a sheet to form an LCP membrane under the pushing of extrusion pressure;

s7: calendering, namely extruding and extending the LCP membrane for multiple times through a hot roller;

s8: longitudinal stretching, namely gradually heating the LCP film to be above the glass transition temperature and close to a high elastic state in a preheating and mixing group by a longitudinal stretcher, and then stretching the LCP film in a stretching region;

s9: laying a bearing film, laying the bearing film at the bottom of the LCP film after longitudinal stretching through a guide roller, coating an isolation anti-sticking agent between the bearing film and the LCP film, and extruding and laminating through an extrusion roller after laying to form a combined film;

s10: transverse stretching, namely fully and uniformly preheating the combined film in a preheating section of a transverse stretcher, and further heating the film in a high-elasticity state through preheating in a tentering section and gradually widening the film under the action of transverse tension;

s11: separating the carrier film: separating the bearing film and the LCP film by a separation roller;

s12: and (4) drawing and rolling, wherein the separated LCP film is firstly cooled and shaped and then trimmed, and then drawing and rolling are carried out.

2. The method of claim 1, wherein in the step of S6, the gear pump is installed after the extruder, the melt coarse filter is installed before the gear pump, the melt fine filter is installed after the gear pump, the static mixer is installed in the pipeline, and the cooling drum is installed at the end of the head of the extruder.

3. The method of claim 1, wherein in step S8, the longitudinal drawing machine comprises pre-heating and mixing, stretching and rolling, cooling and rolling, tension rolling, rubber rolling, infrared heater, hot water unit of sheet passing mechanism, and driving system.

4. The method of claim 1, wherein the combined film after cross-drawing is heat-set in the shaping stage of the cross-drawing machine, and the final stage of the shaping stage is provided with a film relaxation stage in the preparation method S10.

5. The method of claim 1, wherein the extruder inside the apparatus of the process S6 comprises a head, and the cooling drum comprises a water bath and jacket cooling water.

6. The method of producing a biaxially stretched LCP film according to claim 1, wherein in the production method S6, the extruder is provided with a pressure detecting point P1 at the outlet, a pressure detecting point P2 before the gear metering pump, a pressure detecting point P3 before the melt finishing filter, a pressure detecting point P4 after the melt finishing filter, and a pressure detecting point P5 at the inlet of the head.

7. The method of producing a biaxially stretched LCP film according to claim 1, wherein the ratio of the speed of the rear roll to the speed of the front roll of the longitudinal stretching machine in the production method S8 is referred to as longitudinal stretching ratio.

8. The method of claim 1, wherein the ratio of the width of the transverse drawing port of the transverse drawing machine to the width of the transverse drawing port of the preparation method S10 is called transverse drawing ratio.

9. The method of claim 1, wherein in the step of S9, the carrier film is either PEEK or PP.

10. The method of producing a biaxially stretched LCP film according to claim 1, wherein in the production method S9, the release antiblocking agent is any one of a silica antiblocking agent and a glass bead antiblocking agent.

Technical Field

The invention relates to the technical field of LCP films, in particular to a preparation method of a biaxially oriented LCP film.

Background

Along with the great pursuit of miniaturization of mobile phones, wearable products and the like, embedding components in multilayer circuit boards is a long-term development trend of industry technologies. The number of components in the 5G antenna and the radio frequency front end is increased sharply, and the demand for embedding and packaging the millimeter wave circuit in the multilayer circuit board is increasingly urgent. LCP (liquid crystal polymer) with a multi-layer structure can realize modular packaging of high-frequency circuits such as an antenna, a radio frequency front end and the like, and the LCP antenna and the LCP soft board are used for improving the high-frequency performance of the antenna and reducing the space occupation, and the functional attribute and the product value of the LCP antenna are both improved.

At present, the preparation method of the liquid crystal polymer film mainly comprises a film blowing method and a biaxial stretching method, and because the liquid crystal polymer has high orientation under the action of shearing force, when the biaxial stretching method is adopted to prepare the LCP film, the mechanical properties of the film in two directions have larger difference, namely anisotropy,

when longitudinal stretching is adopted firstly and then transverse stretching is carried out, LCP films are stretched longitudinally, generally, an extruder extrudes cast sheets and then are directly stretched, the thickness of the cast sheets is large, the change of the stretching ratio is large at the moment, the longitudinal mechanical property of the films is excellent, then, when transverse stretching is carried out, the thickness of the films is reduced, the change of the transverse stretching ratio is small, the transverse tensile property is poor, when the biaxial synchronous stretching is adopted, although the in-plane is uniform, the change of the stretching ratio is small, the thickness is limited, the anisotropic liquid crystal films cannot meet the use requirements of the flexible circuit board, and the difficulty in film processing and preparation is very high.

Disclosure of Invention

In order to achieve the purpose, the invention adopts a technical scheme that: provided is a method for preparing a biaxially stretched LCP film, the method comprising the steps of:

s1: carrying out defibering and dispersion, namely defibering and dispersing the blank LCP material, the mother cut material and the reclaimed material;

s2: screening, namely screening the fluffed and dispersed raw materials to ensure the consistency of the particle sizes of the raw materials;

s3: proportioning, namely adding a proper amount of silicon dioxide and calcium carbonate into the sieved raw materials for proportioning;

s4: metal filtration, namely performing metal separation and filtration on the raw materials after the batching is finished;

s5: drying, namely performing vacuum drum drying on the raw material to remove trace water in the raw material polymer, and performing airflow drying after vacuum drying to remove acid or alkaline impurities in the raw material polymer;

s6: melt extrusion, heating and melting the dried raw materials through an extruder, and uniformly conveying the melt to a die head to cast a sheet to form an LCP membrane under the pushing of extrusion pressure;

s7: calendering, namely extruding and extending the LCP membrane for multiple times through a hot roller;

s8: longitudinal stretching, namely gradually heating the LCP film to be above the glass transition temperature and close to a high elastic state in a preheating and mixing group by a longitudinal stretcher, and then stretching the LCP film in a stretching region;

s9: laying a bearing film, laying the bearing film at the bottom of the LCP film after longitudinal stretching through a guide roller, coating an isolation anti-sticking agent between the bearing film and the LCP film, and extruding and laminating through an extrusion roller after laying to form a combined film;

s10: transverse stretching, namely fully and uniformly preheating the combined film in a preheating section of a transverse stretcher, and further heating the film in a high-elasticity state through preheating in a tentering section and gradually widening the film under the action of transverse tension;

s11: separating the carrier film: separating the bearing film and the LCP film by a separation roller;

s12: and (4) drawing and rolling, wherein the separated LCP film is firstly cooled and shaped and then trimmed, and then drawing and rolling are carried out.

As a further illustration of the invention, in preparation method S6, a gear metering pump is installed behind an extruder, a melt coarse filter is installed in front of the gear metering pump, a melt fine filter is installed behind the gear metering pump, a static mixer is installed in a conveying pipeline, and a cooling rotary drum is installed at the tail of a head of the extruder.

As a further explanation of the invention, in preparation method S8, the longitudinal drawing machine consists of preheating mixing, stretching rolling, cooling rolling, tension rolling, rubber rolling, an infrared heater, a sheet penetrating mechanism hot water unit and a driving system.

As a further explanation of the present invention, in preparation method S10, the combined film after being transversely drawn is subjected to heat setting treatment in a shaping section of a transverse drawing machine, and a film relaxation section is provided at the last section of the shaping section.

As a further explanation of the invention, in the preparation method S6, the temperature of the extruder head is controlled by electric heating or fan air cooling, and the temperature of the cooling drum is controlled by water bath and jacket cooling water.

As a further explanation of the present invention, in the preparation method S6, a pressure detection point P1 is provided at the outlet of the extruder, a pressure detection point P2 is provided before the gear metering pump, a pressure detection point P3 is provided before the melt polishing filter, a pressure detection point P4 is provided after the melt polishing filter, and a pressure detection point P5 is provided at the inlet of the head.

As a further illustration of the invention, the ratio of the speed of the back roll to the speed of the front roll of the longitudinal stretcher in preparation S8 is referred to as the longitudinal stretch ratio.

As a further explanation of the present invention, the ratio of the width of the film at the transverse drawing outlet to the width of the film at the transverse drawing inlet of the transverse drawing machine in the preparation method S10 is referred to as transverse drawing ratio.

As a further explanation of the present invention, in the preparation method S9, the carrier film is either a PEEK film or a PP film.

As a further explanation of the present invention, in preparation method S9, the release antiblocking agent is either a silica antiblocking agent or a glass bead antiblocking agent.

Above scheme, the LCP diaphragm is through calendering before longitudinal stretching, then longitudinal stretching again, although longitudinal stretching ratio has been reduced, but because thickness reduces, under the condition of stretching to same thickness, the homogeneity in the face has been improved, thereby be convenient for subsequent transverse stretching even, simultaneously before transverse stretching, lay the carrier film to LCP film bottom after longitudinal stretching, through adding the isolation antiadhesion agent, and vacuum extrusion process forms the combined film, the toughness and the percentage of elongation of LCP film have been improved greatly, when transverse stretching, through the bearing of carrier film and the lubrication of isolation antiadhesion agent, make carrier film and LCP film together warp, the transverse stretching ratio of LCP has been improved, prevent that the LCP film tears when transverse stretching, the yield has been improved, and the each direction mechanical properties of the LCP film prepared is even, satisfy flexible circuit board's user demand.

Drawings

FIG. 1 is a flow chart of the preparation method of the present invention;

FIG. 2 is a flow diagram of the extruder apparatus of the present invention;

FIG. 3 is a schematic diagram of the apparatus of the preparation process S9 according to the present invention.

Detailed Description

Hereinafter, various embodiments of the present invention will be described with reference to the accompanying drawings.

The first embodiment is as follows: referring to fig. 1 to 3, a method for preparing a biaxially stretched LCP film, the method comprising the steps of:

s1: carrying out defibering and dispersion, namely defibering and dispersing the blank LCP material, the mother cut material and the reclaimed material; the three raw materials are dispersed by a pulverizer to prepare LCP solid powder particles.

S2: screening, namely screening the fluffed and dispersed raw materials to ensure the consistency of the particle sizes of the raw materials; and putting the powdery LCP into a sieving machine for sieving to obtain LCP particles with the particle size of 200-400 mm.

S3: batching, wherein a proper amount of silicon dioxide and calcium carbonate are added into the sieved raw materials for batching, so that the roughness of the surface of the film is increased, the adhesion between the films is avoided, and 3-5 parts by weight of silicon dioxide or calcium carbonate are added into each 100 parts by weight of LCP particles;

s4: metal filtration, namely performing metal separation and filtration on the raw materials after the batching is finished, and performing metal filtration on the batched raw materials through a magnetic separator;

s5: drying, namely performing vacuum drum drying on the raw material to remove trace water in the raw material polymer, wherein the drying temperature is 100-120 ℃, the drying time is 30min, performing airflow drying after vacuum drying to remove acid or alkaline impurities in the raw material polymer, the drying temperature is 100-120 ℃, the drying time is 15min, and the airflow pressure is 1.5-2 MPa;

s6: melt extrusion, heating and melting the dried raw materials through an extruder, and uniformly conveying the melt to a die head to cast a sheet to form an LCP membrane under the pushing of extrusion pressure;

the gear metering pump is arranged behind the extruder, in order to ensure the uniformity of the longitudinal thickness of the film, the gear metering pump is controlled in a mode that the speed of the gear metering pump is unchanged in the production process, and when the resistance of the filter is increased, the linear speed of the cooling rotary drum is automatically adjusted to adapt to the change.

The melt coarse filter is arranged in front of the gear metering pump, the melt fine filter is arranged behind the gear metering pump, the static mixer is arranged in the conveying pipeline, and the cooling rotary drum is arranged at the tail part of the machine head of the extruder.

The inside of the extruder is controlled by electric heating or fan air cooling, the cooling drum controls the temperature by water bath and jacket cooling water, and the cooling drum is convenient to quench the LCP film to below the vitrification temperature and form an amorphous thick sheet.

The pressure detection point P1 is arranged at the outlet of the extruder, the pressure detection point P2 is arranged in front of the gear metering pump, the pressure detection point P3 is arranged in front of the melt fine filter, the pressure detection point P4 is arranged behind the melt fine filter, and the pressure detection point P5 is arranged at the inlet of the machine head. The pressure of the extruder system is convenient to detect, and the pressure in front of the gear metering pump is controlled by controlling the rotating speed of the extruder, so that the gear metering pump can ensure stable output of materials and uniformity of sheets.

S7: calendering, namely extruding and extending the LCP membrane for multiple times through a hot roller; used for controlling the longitudinal stretching ratio and ensuring the isotropic uniformity of the film.

S8: longitudinal stretching, namely gradually heating the LCP film to be above the glass transition temperature and close to a high elastic state in a preheating and mixing group by a longitudinal stretcher, and then stretching the LCP film in a stretching region; the longitudinal drawing machine consists of preheating mixing, stretching rolling, cooling rolling, tension rolling, rubber rolling, infrared heater, sheet penetrating mechanism, hot water unit and driving system. The ratio of the speed of the rear roll to the front roll of the longitudinal stretcher is called the longitudinal stretch ratio.

S9: laying a bearing film, laying the bearing film at the bottom of the LCP film after longitudinal stretching through a guide roller, coating an isolation anti-sticking agent between the bearing film and the LCP film, and extruding and laminating the bearing film and the LCP film in a vacuum environment through an extrusion roller after laying is finished to form a combined film; the carrier film is any one of a PEEK film or a PP film, the isolating anti-sticking agent is any one of a silicon dioxide anti-sticking agent or a glass bead anti-sticking agent, and the sum of the thickness of the carrier film and the thickness of the LCP film is the same as the thickness of the film before longitudinal stretching.

S10: transverse stretching, namely fully and uniformly preheating the combined film in a preheating section of a transverse stretcher, and further heating the film in a high-elasticity state through preheating in a tentering section and gradually widening the film under the action of transverse tension; the transversely pulled combined film is subjected to heat setting treatment in a shaping section of a transverse pulling machine so as to further improve the crystallization process of the film, eliminate internal stress and increase the dimensional stability of the film, and meanwhile, a film relaxation section is arranged at the last section of the shaping section so as to reduce the heat shrinkage rate of the film. And finally, a cooling section is arranged, and the cooling section is used for cooling the film subjected to heat treatment as soon as possible, so that crystal lattices of the stretched and oriented film are quickly frozen, the continuous growth of the crystal is limited, and the situation that the film is too high in crystallinity and brittle and is prevented from being de-oriented is avoided. The ratio of the width of the transverse drawing outlet film to the width of the transverse drawing inlet film of the transverse drawing machine is called transverse drawing ratio

S11: separating the carrier film: the separation roller is used for separating the bearing film from the LCP film, and the air knife is arranged between the bearing film and the LCP on one side of the separation roller, so that compressed air is blown between the LCP film and the bearing film to assist in the separation of the bearing film and facilitate the air blowing removal of the isolation anti-sticking agent;

s12: and (4) drawing and rolling, wherein the separated LCP film is firstly cooled and shaped and then trimmed, and then drawing and rolling are carried out.

Example two: in this embodiment, in the preparation method S6 of the first embodiment, in the production process, the control mode of the gear metering pump is to automatically adjust the speed of the gear metering pump to increase the pumping amount appropriately along with the increase of the resistance of the fine filter, so as to ensure that the pressure of the melt entering the machine head is not changed.

Example three: in this embodiment, in the preparation method S9 of the first embodiment, the carrier films made of different materials and the release and anti-sticking agents made of different materials are used for the tensile property test;

wherein, the sample specification: the width is 15mm, the sampling length is 150mm, and the sampling interval is 100 mm;

test tensile speed: 500+30 mm/min;

sample clamping: the sample is placed in two clamps of the testing machine, so that the longitudinal axis of the sample is superposed with the central connecting line of the upper clamp and the lower clamp, and the tightness of the clamps is proper.

Wherein: the longitudinal tensile strength and longitudinal maximum stretch ratio samples were taken from the film before the longitudinal stretching step, and the transverse tensile strength and transverse maximum stretch ratio samples were taken from the film before the transverse stretching step.

Wherein:

longitudinal tensile strength = tensile force/amount of deformation at longitudinal tear;

longitudinal maximum draw ratio = back roll speed before tearing/front roll speed;

tensile strength in the cross direction = tensile force/amount of deformation at tear in the cross direction;

maximum draw ratio in the cross direction = cross-draw exit film width before tearing/cross-draw entrance film width.

The test results are shown below:

comparing the data in the longitudinal stretching and the transverse stretching under the same other conditions

The control group is prepared by the existing double shaft, the test 1 group is PEEK film + silicon dioxide anti-adhesion agent, the test 2 group is PEEK film + glass bead anti-adhesion agent, the test 3 group is PP film + silicon dioxide anti-adhesion agent, and the test 4 group is PP film + glass bead anti-adhesion agent.

According to test data, compared with the existing biaxial stretching preparation, the four groups of tests show that the longitudinal tensile strength of the film before longitudinal stretching is improved by adding the rolling procedure before longitudinal stretching, the thickness of the film is reduced before longitudinal stretching by repeated rolling of the rolling procedure, but the longitudinal tensile strength is improved along with longitudinal multiple lamination, and the longitudinal maximum stretching ratio is reduced, so that the improvement of the uniformity of the film is facilitated by reducing the longitudinal stretching ratio after the rolling procedure is added.

The working procedure of laying the bearing film is added before transverse stretching, the transverse tensile strength and the transverse maximum stretching ratio of the film are greatly improved by four groups of data, the increase of the transverse tensile strength by using the combination of the PEEK + silicon dioxide anti-blocking agent and the combination of the PEEK film + glass bead anti-blocking agent is obviously superior to that of two combinations of the PP film, and the increase of the transverse maximum stretching ratio by using the combination of the PEEK + silicon dioxide anti-blocking agent, the combination of the PEEK film + glass bead anti-blocking agent and the combination of the PP film is almost the same.

In conclusion, by the preparation method designed by the invention, through calendering before longitudinal stretching, and then, the longitudinal stretching is performed again, although the longitudinal stretching ratio is reduced, since the thickness is reduced, under the condition of stretching to the same thickness, the uniformity in the plane is improved, thereby facilitating the subsequent transverse stretching to be uniform, and simultaneously before the transverse stretching, laying a bearing film at the bottom of the LCP film after longitudinal stretching, adding an isolation anti-sticking agent and forming a combined film by a vacuum extrusion process, greatly improving the toughness and the elongation of the LCP film, when stretching transversely, the bearing of the bearing film and the lubrication of the isolation anti-sticking agent cause the bearing film and the LCP film to deform together, thereby improving the transverse stretching ratio of the LCP, preventing the LCP film from tearing when stretching transversely, improving the yield, and the prepared LCP film has uniform mechanical properties in all directions, and meets the use requirements of the flexible circuit board.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.