CN111497173A - Method for preparing liquid crystal polymer film - Google Patents
Method for preparing liquid crystal polymer film Download PDFInfo
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- CN111497173A CN111497173A CN202010356909.6A CN202010356909A CN111497173A CN 111497173 A CN111497173 A CN 111497173A CN 202010356909 A CN202010356909 A CN 202010356909A CN 111497173 A CN111497173 A CN 111497173A
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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
- B29C48/03—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
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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
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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
- B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
- B29C48/146—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration in the die
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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
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92942—Moulded article
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (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 relates to a preparation method of a liquid crystal polymer film, which comprises the steps of blending 5-25% of polytetrafluoroethylene granules and 75-95% of liquid crystal high molecular polymer granules according to the mass percentage, carrying out melt granulation by an extruder to obtain surface layer blending granules, respectively feeding the surface layer blending granules and the liquid crystal high molecular polymer core layer granules into corresponding screw extruders for melt extrusion, controlling the melting point of an extruded product to be Tm-10-Tm-30 ℃ during extrusion, discharging a melt with two surfaces and two core layers after passing through a melt pipe, a three-layer adapter and a three-layer die head, ultrasonic vibration perpendicular to the flow direction of the melt is applied to the three-layer die head and acts on the melt, after the melt is shaped through a middle gap of the first and second shaping rollers, and transversely stretching, slitting, drawing and rolling to obtain the liquid crystal polymer film with the two surface layers and the core layer structure. The invention simplifies the processing procedure, has small anisotropy and low dielectric constant, and can reduce the manufacturing cost.
Description
Technical Field
The invention relates to a preparation method of a liquid crystal polymer film, belonging to the technical field of liquid crystal polymer film manufacturing.
Background
The liquid Crystal high Polymer L CP (L iquid Crystal Polymer) is an anisotropic aromatic polyester-based high Polymer material composed of rigid molecular chains, can exist in a liquid Crystal phase under certain conditions, has liquid fluidity and Crystal anisotropy, and is a novel high-performance special engineering plastic developed in the early 80 s.
L CP material has excellent physical property, high dimension stability and precision, almost zero creep, abrasion resistance, linear expansion rate close to metal, excellent heat resistance and flame retardant property, good chemical stability, excellent weather resistance and electrical property, etc., wherein the electrical property is in the whole radio frequency range up to 110GHz, the dielectric constant is almost constant, the consistency is good, the tangent loss is very small, only 0.002, even 110GHz, only 0.0045 is increased, which is very suitable for millimeter wave application, the thermal expansion property is very small, and the material can be used as ideal high frequency packaging material.
The requirements for L CP are increasing rapidly with the development of thinner and more complex electronic equipment, 5G communication is moving to the world, and the new technology is located in a high frequency range, so higher requirements are put on materials, L CP has extremely low water absorption and better dielectric stability, L CP has ultralow warpage, high fluidity and dimensional stability and is suitable for being applied to a 5G high-speed connector, L CP material has strong anisotropy in the flowing direction due to the fact that the apparent viscosity of the material is greatly influenced by the shearing speed and the temperature, so that the film forming rate in the actual manufacturing process is low, so that high technical difficulty is set for the preparation of L CP film, and the manufacturing technology, patents or products of L CP films are disclosed in the market, mainly US Superex, Japan Colorado, Japan Toyota maker, Japan Sumitomo chemistry, the enterprises relate to film blowing and hot pressing manufacturing processes, or the manufacturing method of peeling off a support body before the L CP film is adopted, and the manufacturing cost is high.
Disclosure of Invention
The invention aims to provide a preparation method of a liquid crystal polymer film, which can simplify the processing procedure, has small anisotropy and low dielectric constant and can reduce the manufacturing cost.
The technical scheme for achieving the aim of the invention is as follows: a method for preparing a liquid crystal polymer film is characterized by comprising the following steps: the method comprises the following steps of (1),
(1) blending 5-25% of polytetrafluoroethylene granules and 75-95% of liquid crystal high polymer granules according to mass percentage, and carrying out melt granulation by an extruder to obtain surface layer blended granules, wherein the melting point Tm of the liquid crystal high polymer is more than or equal to 300 ℃;
(2) feeding the surface layer blended granules into a double-screw extruder, feeding the core layer granules of a liquid crystal high polymer with the mass percentage of 100% into another single-screw extruder, carrying out melt extrusion on the surface layer blended granules and the core layer granules through the respective corresponding screw extruders, controlling the melting point of an extruded product to be within Tm-10-Tm-30 ℃ during extrusion, allowing the extruded product to flow out of a melt with two surface layers and the core layer thereof through a melt pipe, a three-layer adapter and a three-layer die head, and applying ultrasonic vibration perpendicular to the flow direction of the melt at the three-layer die head to act on the melt so as to improve the homodromous of the melt in the flow direction;
(3) the melt flowing out of the die head vertically passes through the middle gap of a first group of shaping rollers for primary shaping, then vertically enters the middle gap of a second group of shaping rollers and flows out from the horizontal direction for secondary shaping, the temperature of the first group of shaping rollers is controlled between Tm-5 ℃ and Tm-50 ℃, the temperature of the second group of shaping rollers is lower than the temperature of the first group of shaping rollers by 10 ℃ to 20 ℃, and the temperature of the shaped soft sheet is more than or equal to Tm-80 ℃;
(4) the soft sheet starts to be transversely stretched at the outlet of the second group of shaping rollers, the transverse stretching multiple is 3-15 times, and the temperature of the soft sheet during stretching is controlled to be more than or equal to Tm-60 ℃;
(5) and cutting, drawing and rolling the stretched film material to obtain the liquid crystal polymer film with two surface layers and a middle core layer structure.
According to the invention, the liquid crystal polymer film is prepared in a three-layer co-extrusion mode, and the polytetrafluoroethylene granules with a specific proportion are added into the surface layer blending granules of the liquid crystal polymer film, so that the characteristics of non-adhesiveness, lubricating effect and the like of the surface of the polytetrafluoroethylene material are utilized, the obvious anisotropy of the liquid crystal high polymer material and a core layer caused by contact friction with a wall in the flowing process is effectively reduced, and the defect that the pure liquid crystal high polymer material is easy to skin in the extrusion process is overcome. The invention utilizes the polytetrafluoroethylene material with extremely high melt viscosity, reduces the melting point of an extruded material during extrusion, and can melt the material by utilizing the shearing force of an extruder so as to solve the technical problem that the fluidity of the liquid crystal high polymer melt is not beneficial to subsequent film forming by stretching. The dielectric constant of the polytetrafluoroethylene material in the surface layer is lower than that of the liquid crystal high polymer material, and the polytetrafluoroethylene material is added in a certain proportion, so that the dielectric constant of the liquid crystal polymer film can be reduced. In the three-layer co-extrusion manufacturing process, the melting point of an extrudate, the temperatures of the front and rear two groups of shaping roller sets, the temperature of the shaped soft sheet and the temperature of the soft sheet during transverse stretching are controlled, so that the phenomenon of hydration caused by overheating of a liquid crystal high polymer material can be reduced, and the yield of a film product is improved. The invention adopts the directional linear propagation characteristic of ultrasonic waves in a uniform medium, and before a melt flows out of a die head, the melt is subjected to ultrasonic vibration in the direction vertical to the flow direction of the melt to reduce the mechanical anisotropy of the melt in the flow direction, and meanwhile, the melt is subjected to transverse stretching in the direction vertical to the flow direction of the liquid crystal high polymer to offset the longitudinal mechanical strength of the melt, thereby simplifying the processing procedures, reducing the equipment investment by adopting conventional equipment, improving the yield, reducing the manufacturing cost and obtaining a liquid crystal polymer film product with better isotropy.
Detailed Description
The preparation method of the liquid crystal polymer film is carried out according to the following steps.
(1) According to the invention, 5-25% of polytetrafluoroethylene PTFE granules and 75-95% of liquid crystal high molecular polymer L CP granules are blended according to the mass percentage, and are melted and granulated by an extruder to prepare surface layer blended granules, wherein the melting point Tm of the liquid crystal high molecular polymer is more than or equal to 300 ℃, and the liquid crystal high molecular polymer comprises thermotropic liquid crystal polymer or modified liquid crystal polymer or polymer containing the thermotropic/modified liquid crystal polymer component.
(2) The method comprises the following steps of feeding surface layer blended granules into a double-screw extruder, feeding liquid crystal high polymer core layer granules with the mass percentage of 100% into another single-screw extruder, carrying out melt extrusion on the surface layer blended granules and the core layer granules through the respective corresponding screw extruders, controlling the melting point of an extruded product to be Tm-10-Tm-30 ℃ during extrusion, wherein the melting point is measured by a DSC method, if the two melting point peaks occur in the blend due to the fact that the melting point peaks are used as the reference, melting the granules by utilizing shearing force as the melting point of the extruded product is reduced to 10-30 ℃, further reducing the phenomenon that L CP materials are easy to cause hydration due to overheating, and improving the yield of thin film products.
(3) The melt flowing out of the die head vertically passes through the middle gap of the first group of shaping rollers for primary shaping, then vertically enters the middle gap of the second group of shaping rollers and flows out from the horizontal direction for secondary shaping, the sheet is changed from the vertical direction to the horizontal direction, the temperature of the first group of shaping rollers is controlled between Tm-5 ℃ and Tm-50 ℃, the temperature of the second group of shaping rollers is lower than the temperature of the first group of shaping rollers by 10-20 ℃, and the temperature of the shaped soft sheet is more than or equal to Tm-80 ℃.
The middle gap of the first group of shaping rollers and the middle gap of the second group of shaping rollers can be adjusted, a melt is slightly extruded when flowing through the middle gap of the first group of shaping rollers and the middle gap of the second group of shaping rollers, the thickness tolerance of the soft sheet can be adjusted by adjusting the middle gap, the length of the second group of shaping rollers is smaller than the width of the shaped soft sheet, and enough space is ensured to enter the transverse zipper clamp at the two edges of the soft sheet. The first set of shaping rollers and the second set of shaping rollers are ceramic rollers or metal rollers, the surfaces of which are plated with Teflon layers, and the Teflon layers are not adhered to the surface layer at a high temperature, so that the yield of liquid crystal polymer film products is further improved.
(4) And transversely stretching the soft sheet at the outlet of the second set of shaping rollers, wherein the transverse stretching multiple is 3-15 times, the temperature of the soft sheet during stretching is controlled to be more than or equal to Tm-60 ℃, and transversely stretching the soft sheet in the direction perpendicular to the flow direction of L CP to offset the longitudinal mechanical strength of the melt, so that better isotropy can be obtained.
(5) And cutting, drawing and rolling the stretched film material to obtain the liquid crystal polymer film with two surface layers and a middle core layer structure, wherein the surface layer thickness of the liquid crystal polymer film is more than or equal to 2 mu m.
Example 1
Selecting L CP granules Tm of 305 ℃, blending 5% of PTFE granules and 95% of L CP granules according to mass percent, and carrying out melt granulation by an extruder to obtain surface layer blended granules, sending the surface layer blended granules into a double-screw extruder, sending L CP core layer granules with the mass percent of 100% into another single-screw extruder, wherein the temperature of the two-screw extruder is 275 ℃, the surface layer blended granules and the core layer granules are melted and extruded by the corresponding screw extruders respectively, the melting point of an extruded product is controlled to be Tm-30 ℃, the extruded product flows out of a melt pipe, a three-layer adapter and a three-layer die head to obtain a melt with two surface layers and a core layer, the temperature of the melt pipe and the three-layer die head is 285 ℃, the melt flowing out of the die head vertically passes through a middle gap of a first group of sizing rollers to be primarily sized, then vertically enters the middle gap of a second group of sizing rollers at the temperature, flows out from the horizontal direction to be secondarily sized, the first group of sizing rollers is 255 ℃, the second group of sizing rollers is controlled to be rolled at the temperature of 225 ℃ after being sized, the temperature of the second group of the soft sheets is rolled at the second group of sizing rollers, the temperature, the thickness of the transversely stretched sheets is controlled to be rolled at 245 mu, the thickness of the central layer of the liquid crystal film, and the central layer of the liquid.
Example 2
Selecting L CP granules Tm being 310 ℃, blending 10% of PTFE granules and 90% of L CP granules according to mass percent, and carrying out melt granulation by an extruder to obtain surface layer blended granules, sending the surface layer blended granules into a double-screw extruder, sending L CP core layer granules with the mass percent being 100% into another single-screw extruder, wherein the temperature of the two screw extruders is 290 ℃, the surface layer blended granules and the core layer granules are melted and extruded by the respective corresponding screw extruders, the melting point of an extruded product is controlled to be Tm-20 ℃, the extruded product flows out of a melt pipe, a three-layer adapter and a three-layer die head, the melt with two surface layers and a core layer is controlled to be 300 ℃, the melt flowing out of the die head vertically passes through a middle gap of a first group of sizing rollers to be primarily sized, then vertically enters a middle gap of a second group of sizing rollers with the temperature being 250 ℃ and flows out from the horizontal direction to be secondarily sized, the sheets are changed from the vertical direction to the horizontal direction, the temperature of the first group of sizing rollers is 270 ℃, the second group of sizing rollers is rolled at the soft sheet with the temperature being 250 ℃, the temperature, the stretching and the thickness of the second group of the soft sheets is controlled to be stretched and the total thickness of the liquid crystal film is controlled to be 50 mu, and the total thickness of the liquid crystal layer is controlled to be stretched at the central part of the central layer, and the central part of.
Example 3
Selecting L CP granules Tm of 318 ℃, blending 25% of PTFE granules and 75% of L CP granules according to mass percent, and carrying out melt granulation by an extruder to obtain surface layer blended granules, sending the surface layer blended granules into a double-screw extruder, sending L CP core layer granules with the mass percent of 100% into another single-screw extruder, wherein the temperature of the two screw extruders is 293 ℃, the surface layer blended granules and the core layer granules are melted and extruded by the respective corresponding screw extruders, the melting point of an extruded product is controlled to be Tm-25 ℃, the extruded product flows out of a melt pipe, a three-layer adapter and a three-layer die head through a melt pipe, a melt with two surface layers and a core layer, the temperature of the melt pipe and the three-layer die head is 313 ℃, the melt flowing out of the die head vertically passes through a middle gap of a first group of sizing rollers to be primarily sized, then vertically enters a middle gap of a second group of sizing rollers at the temperature of 278 ℃ and flows out from the horizontal direction to be secondarily sized, the sheets are changed from the vertical direction to the horizontal direction, the temperature of the first group of sizing rollers is 313 ℃, the second group of sizing rollers is rolled at the soft rollers at the position of 278 ℃, the stretching and the temperature of the second group of rollers is controlled to be stretched, the surface layer, the thickness of the surface layer stretched and the liquid crystal film is stretched, the thickness of the total stretched film is controlled to be 298 mu of the liquid crystal.
Example 4
Selecting L CP granules Tm being 309 ℃, blending 12% of PTFE granules and 88% of L CP granules according to mass percent, and carrying out melt granulation by an extruder to obtain surface layer blended granules, sending the surface layer blended granules into a double-screw extruder, sending L CP core layer granules with the mass percent of 100% into another single-screw extruder, controlling the temperature of the two-screw extruder to be 285 ℃, carrying out melt extrusion on the surface layer blended granules and the core layer granules by the respective corresponding screw extruders, controlling the melting point of an extruded product to be Tm-24 ℃, flowing out a melt with two surface layers and a core layer through a melt pipe, a three-layer adapter and a three-layer die head, controlling the temperature of the melt flowing out of the die head to be 295 ℃, carrying out primary shaping by vertically passing through a middle gap of a first group of shaping rollers, then vertically entering the middle gap of a second group of shaping rollers at the temperature after shaping, carrying out secondary shaping by flowing out from the horizontal direction, changing the temperature of the first group of shaping rollers to be 290 ℃, rolling the second group of shaping rollers at the soft rollers at the temperature after shaping, carrying out secondary shaping, carrying out transverse stretching and carrying out transverse drawing on a central layer of the surface layer, controlling the thickness of a liquid crystal film to be 12 mu, and controlling the thickness of the liquid crystal film to be 100 mu after the total thickness of the surface layer is pulled, and the liquid crystal film is pulled in the central layer.
Example 5
Selecting L CP granules Tm being 300 ℃, blending 8% of PTFE granules and 92% of L CP granules according to mass percent, and carrying out melt granulation by an extruder to obtain surface layer blended granules, sending the surface layer blended granules into a double-screw extruder, sending L CP core layer granules with the mass percent of 100% into another single-screw extruder, wherein the temperature of the two screw extruders is 275 ℃, the surface layer blended granules and the core layer granules are melted and extruded by the respective corresponding screw extruders, the melting point of an extruded product is controlled to be Tm-25 ℃, the extruded product flows out of a melt pipe, a three-layer adapter and a three-layer die head to form a melt with two surface layers and a core layer, the temperature of the melt pipe and the three-layer die head is 285 ℃, the melt flowing out of the die head vertically passes through a middle gap of a first group of sizing rollers to be primarily sized, then vertically enters a middle gap of a second group of sizing rollers at the temperature, flows out of the middle gap of the second group of sizing rollers from the horizontal direction to be secondarily sized, the sheets are changed from the vertical direction to the horizontal direction, the first group of sizing rollers is at 255 ℃, the temperature of the soft group of the second group of sizing rollers, the soft sheets at the temperature of the second group of the rollers, the soft rollers, the surface layer of.
Example 6
Selecting L CP granules Tm being 300 ℃, blending 28% of PTFE granules and 72% of L CP granules according to mass percent, and carrying out melt granulation by an extruder to obtain surface layer blended granules, sending the surface layer blended granules into a double-screw extruder, sending L CP core layer granules with the mass percent being 100% into another single-screw extruder, wherein the temperature of the two-screw extruder is 300 ℃, the surface layer blended granules and the core layer granules are melted and extruded by the respective corresponding screw extruders, the melting point of the extruded product is controlled to be Tm-0 ℃, the phenomenon that skin is easy to generate in the extrusion process is found to cause extrusion difficulty, the melt with the two surface layers and the core layer flows out through a melt pipe, a three-layer adapter and a three-layer die head, the temperature of the melt pipe and the three-layer die head is 300 ℃, the melt flowing out from the die head vertically passes through a middle gap of a first group of sizing rollers to carry out primary sizing, vertically enters a middle gap of a second group of sizing rollers at the temperature and flows out from the horizontal direction to carry out secondary sizing, the first group of sizing rollers has the temperature of 300 ℃, the second group of sizing rollers at the temperature of 280 ℃ after sizing rollers, the second group of soft sheets is stretched and the sheets transversely stretched and the film is not controlled to form films at the.
Example 7
Selecting L CP granules Tm being 325 ℃, blending 15% of PTFE granules and 85% of L CP granules according to mass percent, and carrying out melt granulation by an extruder to obtain surface layer blended granules, sending the surface layer blended granules into a double-screw extruder, sending L CP core layer granules with the mass percent of 100% into another single-screw extruder, controlling the temperature of the two-screw extruder to be 315 ℃, carrying out melt extrusion on the surface layer blended granules and the core layer granules by the respective corresponding screw extruders, controlling the melting point of an extruded product to be Tm-10 ℃, flowing out a melt with two surface layers and a core layer through a melt pipe, a three-layer adapter and a three-layer die head, changing the temperature of the melt flowing out of the die head from the melt pipe to the three-layer die head from the melt pipe to the three-layer die head to be primarily shaped by vertically passing through a middle gap of a first group of sizing rollers, then vertically entering the middle gap of a second group of sizing rollers with the temperature being 255 ℃ and flowing out from the horizontal direction to carry out secondary sizing, changing the temperature of the first group of sizing rollers from the first group of sizing rollers to 300 ℃ after sizing rollers, rolling, controlling the thickness of a horizontal stretching and controlling the thickness of a liquid crystal film of the surface layer to be in a total thickness of a liquid crystal film to be 50 mu of a middle layer, and controlling the thickness of the liquid crystal film to be in a central layer of.
The main properties of the prepared liquid crystal polymer film are as follows GB/T13542.2-2009 and IEC 62631-2-1: 2018, and the detection results are shown in Table 1.
TABLE 1
The invention adopts a method of three-layer coextrusion and transverse stretching to obtain the liquid crystal polymer film product with uniform tolerance, small anisotropy and lower dielectric constant.
Claims (7)
1. A method for preparing a liquid crystal polymer film is characterized by comprising the following steps: the method comprises the following steps of (1),
(1) blending 5-25% of polytetrafluoroethylene granules and 75-95% of liquid crystal high polymer granules according to mass percentage, and carrying out melt granulation by an extruder to obtain surface layer blended granules, wherein the melting point Tm of the liquid crystal high polymer is more than or equal to 300 ℃;
(2) feeding the surface layer blended granules into a double-screw extruder, feeding the core layer granules of a liquid crystal high polymer with the mass percentage of 100% into another single-screw extruder, carrying out melt extrusion on the surface layer blended granules and the core layer granules through the respective corresponding screw extruders, controlling the melting point of an extruded product to be within Tm-10-Tm-30 ℃ during extrusion, allowing the extruded product to flow out of a melt with two surface layers and the core layer thereof through a melt pipe, a three-layer adapter and a three-layer die head, and applying ultrasonic vibration perpendicular to the flow direction of the melt at the three-layer die head to act on the melt so as to improve the homodromous of the melt in the flow direction;
(3) the melt flowing out of the die head vertically passes through the middle gap of a first group of shaping rollers for primary shaping, then vertically enters the middle gap of a second group of shaping rollers and flows out from the horizontal direction for secondary shaping, the temperature of the first group of shaping rollers is controlled between Tm-5 ℃ and Tm-50 ℃, the temperature of the second group of shaping rollers is lower than the temperature of the first group of shaping rollers by 10 ℃ to 20 ℃, and the temperature of the shaped soft sheet is more than or equal to Tm-80 ℃;
(4) the soft sheet starts to be transversely stretched at the outlet of the second group of shaping rollers, the transverse stretching multiple is 3-15 times, and the temperature of the soft sheet during stretching is controlled to be more than or equal to Tm-60 ℃;
(5) and cutting, drawing and rolling the stretched film material to obtain the liquid crystal polymer film with two surface layers and a middle core layer structure.
2. The method for producing a liquid-crystalline polymer film according to claim 1, characterized in that: the temperature of the melt pipe and the temperature of the three-layer die head are controlled within the range of Tm-5 ℃ to Tm-10 ℃.
3. The method for producing a liquid-crystalline polymer film according to claim 1, characterized in that: the first group of shaping rollers and the second group of shaping rollers are ceramic rollers or metal rollers, and the surfaces of the first group of shaping rollers and the second group of shaping rollers are plated with Teflon layers and are used for preventing the rollers from being adhered to the surface layer at a high temperature.
4. The method for producing a liquid-crystalline polymer film according to claim 1 or 3, characterized in that: the middle gap of first group design roller group and the middle gap of second group design roller can be adjusted, and the fuse-element appears slightly crowded state when flowing through the middle gap of first group design roller group and the middle gap of second group design roller.
5. The method for producing a liquid-crystalline polymer film according to claim 1, characterized in that: the length of the second group of shaping rollers is less than the width of the shaped soft sheet.
6. The method for producing a liquid-crystalline polymer film according to claim 1, characterized in that: the thickness of the single-side surface layer of the liquid crystal polymer film is more than or equal to 2 mu m.
7. The method for producing a liquid-crystalline polymer film according to claim 1, characterized in that: the liquid crystal high molecular polymer comprises thermotropic liquid crystal polymer or modified liquid crystal polymer or polymer containing the thermotropic/modified liquid crystal polymer component.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112172210A (en) * | 2020-09-18 | 2021-01-05 | 江苏中际信通讯材料有限公司 | Preparation method of liquid crystal polymer film with low dielectric constant and low dielectric loss |
| CN112549475A (en) * | 2020-11-24 | 2021-03-26 | 中国科学技术大学 | Method and device for preparing liquid crystal polymer film |
| CN113681852A (en) * | 2021-07-23 | 2021-11-23 | 华南理工大学 | Production equipment and method for LCP film under action of space electric field |
| CN114106579A (en) * | 2020-08-31 | 2022-03-01 | 宁波长阳科技股份有限公司 | Hollow mesoporous silicon sphere modified liquid crystal polymer film and preparation method thereof |
| JP7446710B2 (en) | 2018-12-12 | 2024-03-11 | 日東電工株式会社 | How to pass optical film |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02178016A (en) * | 1988-12-28 | 1990-07-11 | Daicel Chem Ind Ltd | Liquid crystalline polymer film and manufacture thereof |
| CN1238355A (en) * | 1999-06-25 | 1999-12-15 | 清华大学 | Process for preparing teflon composites reinforced by liquid crystal polymers |
| CN1860389A (en) * | 2003-09-29 | 2006-11-08 | 日东电工株式会社 | Polarizing film manufacturing method, polarizing film, and image display apparatus using this film |
| CN101259748A (en) * | 2007-03-05 | 2008-09-10 | 扬中市星鑫工程管道厂 | Method for preparing large-diameter pipe from super-high molecular weight polyethylene material |
| CN101318393A (en) * | 2008-07-08 | 2008-12-10 | 常州裕兴绝缘材料有限公司 | Electrostatic resistant heavy duty polyester film and method of preparing the same |
| CN103171223A (en) * | 2013-03-11 | 2013-06-26 | 常州百佳薄膜科技有限公司 | Bidirectional-stretching online-coating optical base film and its making method |
| CN103407140A (en) * | 2013-07-26 | 2013-11-27 | 常州大学 | Preparation method for PP/PE/PE three-layer compound microporous film |
| CN106633680A (en) * | 2016-12-29 | 2017-05-10 | 江苏沃特特种材料制造有限公司 | Modified liquid crystal polyester resin composition, preparation method thereof and application of composition |
| CN109280515A (en) * | 2018-09-03 | 2019-01-29 | 刘旭 | A kind of liquid crystal pressure-sensitive film of high contrast |
| CN110062786A (en) * | 2016-12-05 | 2019-07-26 | 株式会社村田制作所 | Black liquid crystalline polymer film and multilager base plate |
| CN110117374A (en) * | 2018-02-06 | 2019-08-13 | 佳胜科技股份有限公司 | The manufacturing method of liquid crystal polymer film and the flexible copper foil substrate with liquid crystal polymer film |
| CN110181829A (en) * | 2019-05-27 | 2019-08-30 | 陈祚 | A kind of liquid crystal polyester thin film industrial manufacture process |
-
2020
- 2020-04-29 CN CN202010356909.6A patent/CN111497173B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02178016A (en) * | 1988-12-28 | 1990-07-11 | Daicel Chem Ind Ltd | Liquid crystalline polymer film and manufacture thereof |
| CN1238355A (en) * | 1999-06-25 | 1999-12-15 | 清华大学 | Process for preparing teflon composites reinforced by liquid crystal polymers |
| CN1860389A (en) * | 2003-09-29 | 2006-11-08 | 日东电工株式会社 | Polarizing film manufacturing method, polarizing film, and image display apparatus using this film |
| CN101259748A (en) * | 2007-03-05 | 2008-09-10 | 扬中市星鑫工程管道厂 | Method for preparing large-diameter pipe from super-high molecular weight polyethylene material |
| CN101318393A (en) * | 2008-07-08 | 2008-12-10 | 常州裕兴绝缘材料有限公司 | Electrostatic resistant heavy duty polyester film and method of preparing the same |
| CN103171223A (en) * | 2013-03-11 | 2013-06-26 | 常州百佳薄膜科技有限公司 | Bidirectional-stretching online-coating optical base film and its making method |
| CN103407140A (en) * | 2013-07-26 | 2013-11-27 | 常州大学 | Preparation method for PP/PE/PE three-layer compound microporous film |
| CN110062786A (en) * | 2016-12-05 | 2019-07-26 | 株式会社村田制作所 | Black liquid crystalline polymer film and multilager base plate |
| CN106633680A (en) * | 2016-12-29 | 2017-05-10 | 江苏沃特特种材料制造有限公司 | Modified liquid crystal polyester resin composition, preparation method thereof and application of composition |
| CN110117374A (en) * | 2018-02-06 | 2019-08-13 | 佳胜科技股份有限公司 | The manufacturing method of liquid crystal polymer film and the flexible copper foil substrate with liquid crystal polymer film |
| CN109280515A (en) * | 2018-09-03 | 2019-01-29 | 刘旭 | A kind of liquid crystal pressure-sensitive film of high contrast |
| CN110181829A (en) * | 2019-05-27 | 2019-08-30 | 陈祚 | A kind of liquid crystal polyester thin film industrial manufacture process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7446710B2 (en) | 2018-12-12 | 2024-03-11 | 日東電工株式会社 | How to pass optical film |
| CN114106579A (en) * | 2020-08-31 | 2022-03-01 | 宁波长阳科技股份有限公司 | Hollow mesoporous silicon sphere modified liquid crystal polymer film and preparation method thereof |
| CN114106579B (en) * | 2020-08-31 | 2024-01-09 | 宁波长阳科技股份有限公司 | Hollow mesoporous silicon sphere modified liquid crystal polymer film and preparation method thereof |
| CN112172210A (en) * | 2020-09-18 | 2021-01-05 | 江苏中际信通讯材料有限公司 | Preparation method of liquid crystal polymer film with low dielectric constant and low dielectric loss |
| CN112549475A (en) * | 2020-11-24 | 2021-03-26 | 中国科学技术大学 | Method and device for preparing liquid crystal polymer film |
| CN113681852A (en) * | 2021-07-23 | 2021-11-23 | 华南理工大学 | Production equipment and method for LCP film under action of space electric field |
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