CN117021527A - Preparation method of thick biaxially oriented liquid crystal polymer film - Google Patents
Preparation method of thick biaxially oriented liquid crystal polymer film Download PDFInfo
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- CN117021527A CN117021527A CN202310945929.0A CN202310945929A CN117021527A CN 117021527 A CN117021527 A CN 117021527A CN 202310945929 A CN202310945929 A CN 202310945929A CN 117021527 A CN117021527 A CN 117021527A
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 200
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 199
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 58
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 52
- 239000010959 steel Substances 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000001125 extrusion Methods 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 36
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000009998 heat setting Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000155 melt Substances 0.000 claims description 15
- 238000009966 trimming Methods 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 230000035882 stress Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 5
- 238000010096 film blowing Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 238000010345 tape casting Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/28—Storing of extruded material, e.g. by winding up or stacking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/287—Raw material pre-treatment while feeding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/20—Edge clamps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention discloses a preparation method of a thick biaxially oriented liquid crystal polymer film, which is characterized by comprising the following steps: adding LCP resin into a drying tank for drying, and then adding the dried LCP resin into melt extrusion equipment for melt extrusion; the molten LCP resin is extruded through a T-die, the formed LCP sheet flows onto a lower steel belt, and the temperature of the steel belt is controlled by a lower hot air plate; the LCP sheet material runs on the steel belt, then the circulating needling belt is contacted with two sides of the LCP, the LCP sheet material transversely extends through uniform motion of the needling belt, and then the LCP sheet material is naturally cooled and then peeled off from the steel belt; and (3) carrying out high-temperature heat setting on the LCP film, and then cooling to obtain the thick biaxially oriented liquid crystal polymer film. The liquid crystal polymer film prepared by the invention has the characteristics of high mechanical strength, uniform longitudinal and transverse tensile strength, relatively thicker thickness and the like, and can be widely applied to the fields of rigid high-frequency high-speed copper-clad plates, high-temperature resistant sheets, wireless charging insulating sheets, flame-retardant sheets, chip carrier plates and the like.
Description
Technical Field
The invention belongs to the preparation of liquid crystal polymer films, and relates to a preparation method of a thick biaxially oriented liquid crystal polymer film. The thick biaxially oriented liquid crystal polymer film prepared by the invention can be widely applied to the fields of rigid high-frequency high-speed copper-clad plates, high-temperature resistant sheets, wireless charging insulating sheets, flame-retardant sheets, chip carrier plates and the like.
Background
The liquid crystal polymer (Liquid Crystalline Polymer, abbreviated as LCP) is a polymer with liquid crystal property, belongs to special engineering plastics, and has a structure composed of rigid molecular chains, and can be a polymer material with liquid fluidity and crystal physical property anisotropy state under certain physical conditions. The liquid crystal polymer has high strength, high modulus, outstanding heat resistance, extremely small linear expansion coefficient, excellent flame resistance, electrical insulation, chemical corrosion resistance, weather aging resistance, microwave permeability and excellent molding processability, and meanwhile, the liquid crystal polymer has lower dielectric constant and dielectric loss at high frequency, and is particularly suitable for antenna substrates under 5G millimeter waves.
In the prior art, the thickness of LCP film is generally 25-125 μm, the maximum thickness can be 175 μm, and thicker LCP film can not be produced due to the adoption of the film blowing production process. When the film blowing process is adopted to produce the LCP film, synchronous biaxial stretching can be carried out, and the anisotropic problem of the LCP film is overcome, but the film blowing process has larger thickness tolerance deviation, and the melt sheet is too thick and cannot be effectively blown.
In the research of thick LCP films, the orientation problem of the LCP films still needs to be overcome, so that molecular chains are randomly arranged in two directions, and the mechanical properties in the two directions are kept stable. CN109664563a discloses a method for producing LCP film by two-direction staggered stacking and then multilayer lamination, which can obtain thicker film, but the method has no continuity, and the production waste is large, and delamination problem may exist. CN109648850a discloses a method for preparing an LCP film by using a 3D printing method, which forms a film with a certain porosity due to a manufacturing process similar to spinning, is more similar to a non-woven fabric structure, and can change the orientation problem of the LCP, but has defects in strength and the like, and simultaneously has a production thickness of only 25-100 μm, so that the thick film cannot be effectively prepared.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a thick biaxially oriented liquid crystal polymer film. Aiming at the defects of high equipment requirement, incapability of continuous production, low transverse strength and the like in the prior art, the invention provides the preparation method of the thick biaxially oriented liquid crystal polymer film, which has the characteristics of simple equipment, stability, controllability, continuous production, high longitudinal and transverse strength, difficult tearing, thicker thickness (being used as a sheet), good dimensional stability and the like, by adopting the mode that the LCP is firstly subjected to melt extrusion, then is subjected to semi-fixation through a heated steel belt, and then is subjected to transverse stretching on a semi-fixing piece at the edge to prepare the film.
The invention comprises the following steps: a preparation method of a thick biaxially oriented liquid crystal polymer film is characterized by comprising the following steps:
a. adding LCP resin into a drying tank for drying to obtain dried resin;
b. putting the dried resin into a melt extrusion device for melt extrusion, wherein the extrusion temperature is 280-330 ℃;
c. the melted LCP resin flows out into a sheet shape through a T-shaped die, the formed LCP sheet directly flows onto a steel belt below, the temperature of the steel belt is controlled through a hot air plate below, and the temperature of the hot air plate is controlled at 230-240 ℃;
d. the incompletely cooled LCP sheet material runs on a steel belt, then a circulating needling belt is contacted with two sides of the LCP sheet material, the needling belt fixes the two sides of the LCP sheet material, the LCP sheet material transversely extends at a uniform speed, the speed of the circulating needling belt is 0.5-1 m/min, the stretching multiple is 1.3-1.7 times, and the LCP sheet material is peeled off from the steel belt after natural cooling to obtain an LCP film;
e. and (3) carrying out high-temperature setting on the peeled LCP film to eliminate the stress, cooling the LCP film at the temperature of 190-210 ℃, and carrying out trimming and thickness measurement, and then independently rolling the LCP film at the speed of 3-15 m/min to obtain the thick biaxially oriented liquid crystal polymer film.
In the content of the invention: the LCP resin in the step a is one or more than two of marks A950 (polymers, seranis), C950 (polymers, seranis), E950i (polymers, seranis), vicrystr80 (Jinfa technologies Co., ltd.), vicrystr84 (Jinfa technologies Co., ltd.), V400P (Seranis), KD100 (Watertian materials Co., ltd.), KE100 (Watertian materials Co., ltd.), F600BB (Shiyang technologies resin (Beijing Co., ltd.), and A5000 (Shangye pharmaceutical Co., ltd.);
in the content of the invention: the drying temperature in the step a is preferably 150 ℃ and the drying time is preferably 4h.
In the content of the invention: the melt extrusion apparatus in step b is a single screw extruder, preferably having a screw diameter of 45mm and an aspect ratio of 35:1.
in the content of the invention: the opening degree of the T-shaped die head in the step c is preferably 0.65mm.
In the content of the invention: the thickness of the prepared thick biaxially oriented liquid crystal polymer film is 0.3-0.45 mm.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) According to the invention, the LCP resin is firstly melted to form the semi-shaped sheet, the LCP resin is not completely solidified, and the lateral stretching force is applied to the edge of the semi-shaped sheet by carrying out needling treatment on the edge of the semi-shaped sheet so as to enable the sheet to be laterally stretched; the LCP casting sheet is cooled too quickly to harden the sheet and prevent the sheet from being transversely stretched, and the circulating needling belt applies acting force when the LCP sheet is not cooled, so that the problem that the traditional LCP sheet cannot be transversely stressed is solved;
(2) According to the invention, the LCP resin flows out of the die head after being melted, and the melt is subjected to the action of gravity and extrusion force, so that the LCP resin is longitudinally stretched to a certain extent, thereby forming longitudinal orientation and realizing a biaxial stretching process;
(3) According to the invention, the LCP resin is carried by adopting the heating steel belt, the temperature of the steel belt is controlled by the hot air plate below, so that the LCP melt can not be rapidly cooled, and the steel belt and the LCP film are easy to strip, so that the production efficiency is not influenced;
(4) According to the invention, the peeled LCP film is subjected to heat treatment by a high-temperature furnace, so that the internal application force of the film can be eliminated, the shrinkage is reduced, and the dimensional stability is good;
(5) The method is different from a film blowing method, has relatively thicker film thickness, can be used for large-scale industrial production, has higher film rigidity, can be used on a rigid copper-clad plate, has low dielectric constant and dielectric loss, and has better application on high-frequency high-speed transmission equipment;
(6) The thick biaxially oriented liquid crystal polymer film prepared by the invention has good temperature resistance, can be used for a long time at high temperature, and can be applied to the fields of high temperature environment and chip carrier plates; the thick biaxially oriented liquid crystal polymer film prepared by the invention can reach V-0 grade, and can be used as an electronic insulating and flame-retardant sheet;
(7) The invention adopts a longitudinal pulling technology and then transverse pulling technology, does not adopt other film carriers and does not need a post-lamination treatment process, the prepared thick biaxially oriented liquid crystal polymer film has the characteristics of high mechanical strength, uniform longitudinal and transverse tensile strength, relatively thick thickness and the like, the preparation process is simple, the operation is easy, and the prepared thick biaxially oriented liquid crystal polymer film can be widely applied to the fields of rigid high-frequency high-speed copper-clad plates, high-temperature resistant sheets, wireless charging insulating sheets, flame-retardant sheets, chip carrier plates and the like, and has strong practicability.
Drawings
FIG. 1 is a schematic illustration of a production process flow of an embodiment of the present invention;
FIG. 2 is a diagram showing a process for preparing a thick biaxially oriented liquid crystal polymer film according to the present invention;
in fig. 2: 1 is a steel belt, 2 and 7 are endless needling belts, 3 and 6 are steel belt driving wheels, 4 and 5 are steel belt auxiliary driving wheels, 8 is a biaxially oriented LCP film, and 9 is a hot air plate;
FIG. 3 is a schematic view of a endless needled belt in accordance with one embodiment of the present invention;
in fig. 3: 10 is a needling structure, 11 is a needling belt, 12 and 13 are drive wheels;
FIG. 4 is a schematic view of a hot air plate of the present invention positioned directly below a steel strip, primarily to maintain the temperature of the strip, to ensure that the LCP melt does not cool rapidly, forming a semi-permanent sheet of some strength;
in fig. 4: 14 is a hot air outlet hole, 15 is a hot air inlet pipe, and 16 is a hot air plate fixing position.
Detailed Description
The following examples are intended to further illustrate the present invention but are not to be construed as limiting its scope, as many insubstantial modifications and adaptations of the invention that are within the scope of the invention as described above would be within the skill of the art.
Example 1:
a preparation method of a thick biaxially oriented liquid crystal polymer film comprises the following steps: LCP resin C950 was added to the drying pot and dried at 150 ℃ for 4h. Putting the dried resin into an extruder, wherein the extrusion temperature is 330 ℃, the screw diameter is 45mm, and the length-diameter ratio is 35:1, the molten LCP resin flows through a T-shaped die, the opening of the die is 0.65mm, the formed LCP sheet directly flows onto a lower steel belt, the temperature of the steel belt is controlled by a lower hot air plate, the temperature of the hot air plate is 240 ℃, a circulating needling belt penetrates into two sides of the LCP to be fixed, the speed of the circulating needling belt is 0.75m/min, and the transverse stretching multiple is 1.5 times. And cooling and stripping the stretched film, performing high-temperature heat setting at 208 ℃, and performing trimming, thickness measurement and rolling at a speed of 15m/min to obtain the thick biaxially oriented liquid crystal polymer film.
Example 2:
a preparation method of a thick biaxially oriented liquid crystal polymer film comprises the following steps: the LCP resin A950 and VicrystR80 mixed resin (mass ratio 1:2) were added to a drying pot and dried at 150℃for 4h. Adding the dried resin into an extruder, wherein the extrusion temperature is 283 ℃, the screw diameter is 45mm, and the length-diameter ratio is 35:1, the molten LCP resin flows through a T-shaped die, the opening of the die is 0.65mm, the formed LCP sheet directly flows onto a lower steel belt, the temperature of the steel belt is controlled by a lower hot air plate, the temperature of the hot air plate is 230 ℃, a circulating needling belt penetrates into two sides of the LCP to be fixed, the speed of the circulating needling belt is 0.5m/min, and the transverse stretching multiple is 1.3 times. And cooling and stripping the stretched film, performing high-temperature heat setting at 190 ℃, and performing trimming, thickness measurement and rolling at a speed of 8m/min to obtain the thick biaxially oriented liquid crystal polymer film.
Example 3:
a preparation method of a thick biaxially oriented liquid crystal polymer film comprises the following steps: LCP resin F600BB was added to the drying pot and dried at 150 ℃ for 4h. Adding the dried resin into an extruder, wherein the extrusion temperature is 280 ℃, the screw diameter is 45mm, and the length-diameter ratio is 35:1, the molten LCP resin flows through a T-shaped die, the opening of the die is 0.65mm, the formed LCP sheet directly flows onto a steel belt below, the temperature of the steel belt is controlled by a hot air plate below, the temperature of the hot air plate is 233 ℃, a circulating needling belt penetrates into two sides of the LCP to be fixed, the speed of the circulating needling belt is 1m/min, and the transverse stretching multiple is 1.7 times. And cooling and stripping the stretched film, performing high-temperature heat setting at 200 ℃, and performing trimming, thickness measurement and rolling at a speed of 3m/min to obtain the thick biaxially oriented liquid crystal polymer film.
Example 4:
a preparation method of a thick biaxially oriented liquid crystal polymer film comprises the following steps: a mixture of LCP resins a5000, E950i and KD100 (mass ratio 1:3:6) was added to a drying pot and dried for 4h at 150 ℃. Adding the dried resin into an extruder, wherein the extrusion temperature is 303 ℃, the screw diameter is 45mm, and the length-diameter ratio is 35:1, the molten LCP resin flows through a T-shaped die, the opening of the die is 0.65mm, the formed LCP sheet directly flows onto a lower steel belt, the temperature of the steel belt is controlled by a lower hot air plate, the temperature of the hot air plate is 238 ℃, a circulating needling belt penetrates into two sides of the LCP to be fixed, the speed of the circulating needling belt is 0.95m/min, and the transverse stretching multiple is 1.5 times. And cooling and stripping the stretched film, performing high-temperature heat setting at 210 ℃, and performing trimming, thickness measurement and rolling at a speed of 12m/min to obtain the thick biaxially oriented liquid crystal polymer film.
The performance index conditions of the thick biaxially oriented liquid crystal polymer films prepared in examples 1 to 4 are shown in Table 1 below.
Table 1: performance index Table of Thick biaxially oriented liquid Crystal Polymer films prepared in examples 1 to 4
As can be seen from the data shown in Table 1, the thick biaxially oriented liquid crystal polymer film prepared by the invention has the characteristics of relatively thick film, high mechanical strength, small anisotropy, good flame retardance, low dielectric constant and low dielectric loss. According to the method, the LCP sheet is subjected to semi-fixing treatment, the LCP is not immediately cooled, the edge of the LCP sheet is fixed through the circulating needling belt, and the transverse stretching force is provided through synchronous transverse movement, so that the semi-fixed sheet is transversely stretched, and the method has higher processing formability. The method overcomes the defect that the film blowing method in the prior art can not prepare the thick LCP film, and simultaneously overcomes the defect that the LCP sheet material is easy to tear in the transverse direction by the tape casting method.
Example 5:
a preparation method of a thick biaxially oriented liquid crystal polymer film comprises the following steps:
a. adding LCP resin into a drying tank for drying to obtain dried resin;
b. putting the dried resin into a melt extrusion device for melt extrusion, wherein the extrusion temperature is 330 ℃;
c. the molten LCP resin is extruded through a T-shaped die, the formed LCP sheet material directly flows onto a lower steel belt, the temperature of the steel belt is controlled by a lower hot air plate, and the temperature of the hot air plate is controlled at 240 ℃;
d. the incompletely cooled LCP sheet material runs on a steel belt, then a circulating needling belt is contacted with two sides of the LCP sheet material, the needling belt fixes the two sides of the LCP sheet material, the LCP sheet material transversely extends at a uniform speed, the speed of the circulating needling belt is 1m/min, the stretching multiple is ensured to be 1.7 times, and the LCP sheet material is peeled off from the steel belt after natural cooling to obtain an LCP film;
e. the peeled LCP film is subjected to high-temperature heat setting to eliminate the stress, the heat setting temperature is 210 ℃, then cooling is carried out, and the film is independently rolled after trimming and thickness measurement, and the speed of the film is 15m/min, so that the thick biaxially oriented liquid crystal polymer film is prepared.
Example 6:
a preparation method of a thick biaxially oriented liquid crystal polymer film comprises the following steps:
a. adding LCP resin into a drying tank for drying to obtain dried resin;
b. putting the dried resin into a melt extrusion device for melt extrusion, wherein the extrusion temperature is 280 ℃;
c. the molten LCP resin is extruded through a T-shaped die, the formed LCP sheet material directly flows onto a lower steel belt, the temperature of the steel belt is controlled by a lower hot air plate, and the temperature of the hot air plate is controlled at 230 ℃;
d. the incompletely cooled LCP sheet material runs on a steel belt, then a circulating needling belt is contacted with two sides of the LCP sheet material, the needling belt fixes the two sides of the LCP sheet material, the LCP sheet material transversely extends at a uniform speed, the speed of the circulating needling belt is 0.5m/min, the stretching multiple is 1.3 times, and the LCP sheet material is peeled off from the steel belt after natural cooling to obtain an LCP film;
e. and (3) carrying out high-temperature heat setting on the peeled LCP film to eliminate the stress, cooling the LCP film at the heat setting temperature of 190 ℃, carrying out trimming and thickness measurement, and then rolling the LCP film at the speed of 3m/min to obtain the thick biaxially oriented liquid crystal polymer film.
Example 7:
a preparation method of a thick biaxially oriented liquid crystal polymer film comprises the following steps:
a. adding LCP resin into a drying tank for drying to obtain dried resin;
b. putting the dried resin into a melt extrusion device for melt extrusion, wherein the extrusion temperature is 305 ℃;
c. the melted LCP resin flows out into a sheet through a T-shaped die, the formed LCP sheet directly flows onto a steel belt below, the temperature of the steel belt is controlled by a hot air plate below, and the temperature of the hot air plate is controlled at 235 ℃;
d. the incompletely cooled LCP sheet material runs on a steel belt, then a circulating needling belt is contacted with two sides of the LCP sheet material, the needling belt fixes the two sides of the LCP sheet material, the LCP sheet material transversely extends at a uniform speed, the speed of the circulating needling belt is 0.75m/min, the stretching multiple is ensured to be 1.5 times, and the LCP sheet material is peeled off from the steel belt after natural cooling to obtain an LCP film;
e. the peeled LCP film is subjected to high-temperature heat setting to eliminate the stress, the heat setting temperature is 200 ℃, then cooling is carried out, and the film is independently rolled after trimming and thickness measurement, and the speed of the film is 9m/min, so that the thick biaxially oriented liquid crystal polymer film is prepared.
Example 8:
a preparation method of a thick biaxially oriented liquid crystal polymer film comprises the following steps:
a. adding LCP resin into a drying tank for drying to obtain dried resin;
the drying temperature of the drying is 150 ℃ and the drying time is 4 hours;
b. putting the dried resin into a melt extrusion device for melt extrusion, wherein the extrusion temperature is 280 ℃;
the melt extrusion apparatus was a single screw extruder having a screw diameter of 45mm and an aspect ratio of 35:1, a step of;
c. the molten LCP resin is extruded through a T-shaped die, the formed LCP sheet material directly flows onto a lower steel belt, the temperature of the steel belt is controlled by a lower hot air plate, and the temperature of the hot air plate is controlled at 230 ℃;
the opening degree of the T-shaped die head is 0.65mm;
d. the incompletely cooled LCP sheet material runs on a steel belt, then a circulating needling belt is contacted with two sides of the LCP sheet material, the needling belt fixes the two sides of the LCP sheet material, the LCP sheet material transversely extends at a uniform speed, the speed of the circulating needling belt is 0.5m/min, the stretching multiple is 1.3 times, and the LCP sheet material is peeled off from the steel belt after natural cooling to obtain an LCP film;
e. and (3) carrying out high-temperature heat setting on the peeled LCP film to eliminate the stress, cooling the LCP film at the heat setting temperature of 190 ℃, carrying out trimming and thickness measurement, and then rolling the LCP film at the speed of 3m/min to obtain the thick biaxially oriented liquid crystal polymer film.
Example 9:
a preparation method of a thick biaxially oriented liquid crystal polymer film comprises the following steps:
a. adding LCP resin into a drying tank for drying to obtain dried resin;
the drying temperature of the drying is 150 ℃ and the drying time is 4 hours;
b. putting the dried resin into a melt extrusion device for melt extrusion, wherein the extrusion temperature is 330 ℃;
the melt extrusion apparatus was a single screw extruder having a screw diameter of 45mm and an aspect ratio of 35:1, a step of;
c. extruding molten LCP resin into sheets through a T-die, forming LCP sheets which directly flow onto a lower steel belt, the temperature of the steel belt being controlled by a lower hot air plate, the temperature of the hot air plate being controlled at 240 ℃;
the opening degree of the T-shaped die head is 0.65mm;
d. the incompletely cooled LCP sheet material runs on a steel belt, then a circulating needling belt is contacted with two sides of the LCP sheet material, the needling belt fixes the two sides of the LCP sheet material, the LCP sheet material transversely extends at a uniform speed, the speed of the circulating needling belt is 1m/min, the stretching multiple is ensured to be 1.7 times, and the LCP sheet material is peeled off from the steel belt after natural cooling to obtain an LCP film;
e. the peeled LCP film is subjected to high-temperature heat setting to eliminate the stress, the heat setting temperature is 210 ℃, then cooling is carried out, and after trimming and thickness measurement, the film is rolled, and the speed of the film is 15m/min, so that the thick biaxially oriented liquid crystal polymer film is prepared.
Example 10:
a preparation method of a thick biaxially oriented liquid crystal polymer film comprises the following steps:
a. adding LCP resin into a drying tank for drying to obtain dried resin;
the drying temperature of the drying is 150 ℃ and the drying time is 4 hours;
b. putting the dried resin into a melt extrusion device for melt extrusion, wherein the extrusion temperature is 310 ℃;
the melt extrusion apparatus was a single screw extruder having a screw diameter of 45mm and an aspect ratio of 35:1, a step of;
c. the molten LCP resin is extruded through a T-die, the formed LCP sheet (directly) flows onto a lower steel belt, the temperature of the steel belt is controlled by a lower hot air plate, and the temperature of the hot air plate is controlled at 235 ℃;
the opening degree of the T-shaped die head is 0.65mm;
d. the incompletely cooled LCP sheet material runs on a steel belt, then a circulating needling belt is contacted with two sides of the LCP sheet material, the needling belt fixes the two sides of the LCP sheet material, the LCP sheet material transversely extends at a uniform speed, the speed of the circulating needling belt is 0.8m/min, the stretching multiple is 1.5 times, and the LCP sheet material is peeled off from the steel belt after natural cooling to obtain an LCP film;
e. and (3) carrying out high-temperature heat setting on the peeled LCP film to eliminate the stress, cooling the LCP film at the heat setting temperature of 200 ℃, carrying out trimming and thickness measurement, and then rolling the LCP film at the speed of 9m/min to obtain the thick biaxially oriented liquid crystal polymer film.
In examples 5-10 above: the LCP resin in the step a is one or more than two of marks A950 (polymers, seranis), C950 (polymers, seranis), E950i (polymers, seranis), vicrystr80 (Jinfa technologies Co., ltd.), vicrystr84 (Jinfa technologies Co., ltd.), V400P (Seranis), KD100 (Watertian materials Co., ltd.), KE100 (Watertian materials Co., ltd.), F600BB (Shiyang technologies resin (Beijing Co., ltd.), and A5000 (Shangye pharmaceutical Co., ltd.);
in examples 5-10 above: the thickness of the prepared thick biaxially oriented liquid crystal polymer film is one of 0.3-0.45 mm.
In the above embodiment: the process parameters (temperature, time, speed, etc.) and the amount of each component in each step are within the range, and any point is applicable.
The technical contents of the invention and the technical contents not specifically described in the above embodiments are the same as the prior art, and the raw materials are all commercial products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (7)
1. A preparation method of a thick biaxially oriented liquid crystal polymer film is characterized by comprising the following steps:
a. adding LCP resin into a drying tank for drying to obtain dried resin;
b. putting the dried resin into a melt extrusion device for melt extrusion, wherein the extrusion temperature is 280-330 ℃;
c. the melted LCP resin is extruded into a sheet shape through a T-shaped die, the formed LCP sheet flows onto a lower steel belt, the temperature of the steel belt is controlled through a lower hot air plate, and the temperature of the hot air plate is controlled to be 230-240 ℃;
d. the LCP sheet material runs on a steel belt, then a circulating needling belt is contacted with two sides of the LCP sheet material, the needling belt fixes the two sides of the LCP sheet material, the LCP sheet material transversely extends at a uniform speed, the speed of the circulating needling belt is 0.5-1 m/min, the stretching multiple is 1.3-1.7 times, and the LCP sheet material is peeled off from the steel belt after natural cooling to obtain an LCP film;
e. and (3) carrying out high-temperature heat setting on the LCP film, cooling at 190-210 ℃, trimming, measuring thickness, and rolling at a speed of 3-15 m/min to obtain the thick biaxially oriented liquid crystal polymer film.
2. The method for preparing a thick biaxially oriented liquid crystal polymer film according to claim 1, wherein: the LCP resin in the step a is one or more than two of the marks A950, C950, E950i, vicrystR80, vicrystR84, V400P, KD100, KE100, F600BB and A5000.
3. The method for preparing a thick biaxially oriented liquid crystal polymer film according to claim 1 or 2, wherein: the drying temperature of the drying in the step a is 150 ℃ and the drying time is 4 hours.
4. The method for preparing a thick biaxially oriented liquid crystal polymer film according to claim 1 or 2, wherein: the melt extrusion apparatus in step b was a single screw extruder having a screw diameter of 45mm and an aspect ratio of 35:1.
5. the method for preparing a thick biaxially oriented liquid crystal polymer film according to claim 1 or 2, wherein: the die opening of the T-shaped die in the step c is 0.65mm.
6. The method for preparing a thick biaxially oriented liquid crystal polymer film according to claim 4, wherein: the die opening of the T-shaped die in the step c is 0.65mm.
7. The method for preparing a thick biaxially oriented liquid crystal polymer film according to claim 1 or 2, wherein: the thickness of the prepared thick biaxially oriented liquid crystal polymer film is 0.3-0.45 mm.
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