CN111634090A - ABA (abscisic acid) composite film and preparation method thereof - Google Patents
ABA (abscisic acid) composite film and preparation method thereof Download PDFInfo
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- CN111634090A CN111634090A CN202010529023.7A CN202010529023A CN111634090A CN 111634090 A CN111634090 A CN 111634090A CN 202010529023 A CN202010529023 A CN 202010529023A CN 111634090 A CN111634090 A CN 111634090A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/10—Removing layers, or parts of layers, mechanically or chemically
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Abstract
The invention relates to the technical field of liquid crystal high polymer materials, in particular to an ABA composite film and a preparation method thereof. The technical problem to be solved by the invention is as follows: the film forming performance of the Type II LCP is poor, the molecules in the LCP film have strong orthodrology, the tensile strength in the TD direction after film forming is very small, the stress is easy to damage, no enterprise can continuously and stably produce the Type II LCP film in China.
Description
Technical Field
The invention relates to the technical field of liquid crystal high polymer materials, in particular to an ABA composite film and a preparation method thereof.
Background
Liquid Crystal Polymer, abbreviated as LCP, is a novel Polymer material, and generally becomes a Liquid Crystal form in a certain heating state.
The basic structure of the liquid crystalline polymer is a wholly aromatic polyester whose main monomer is p-hydroxybenzoic acid, and the LCP material obtained by polymerizing only this monomer cannot be melted and therefore cannot be processed. However, if the monomer is copolymerized with other different monomers to find a balance between the molten state and the liquid crystal state, the LCP material can be processed, and has good processability, and can be subjected to injection molding, extrusion, stretching, film forming, and the like.
LCP films have high tensile strength and modulus, excellent thermal stability, heat resistance and chemical resistance, excellent wear resistance and abrasion resistance, good weather resistance and radiation resistance, excellent flame retardancy (UL94 vtm-0), outstanding corrosion resistance, low thermal expansion coefficient, high insulating properties, low dielectric constant and the like.
LCP film is mainly used in electronics and communication industry, and under the high frequency transmission requirement of 5G in the future, LCP material is expected to replace the PI material which is generally used at present.
The currently known application is a mobile phone antenna of iPhone X, and the industry analyzes the main reason for adopting LCP material:
(1) in the future, mobile phones develop towards the direction of 5G (higher and higher frequency), and LCP materials are adopted to have smaller dielectric loss and conductor loss; after the iPhoneX adopts a full-face screen, the clearance space reserved for the antenna is reduced, the design of the antenna needs to be changed, and the LCP antenna can save space; LCP antennas may also replace radio frequency coaxial connectors.
(2) Except for electrical property, LCP material has obvious advantages in water vapor absorption, thermal expansion and light weight compared with traditional antenna, and is suitable for light weight and waterproof development of future mobile phones. Has very small thermal expansion characteristic and can be used as an ideal high-frequency packaging material.
(3) LCP films are attracting attention from industry because of their low moisture absorption, good chemical resistance, high gas barrier properties, and low dielectric constant/dielectric dissipation factor (Dk/Df). The mobile phone antenna for iPhone X is up to $ 5 in value, and employs a multi-layer LCP antenna. The novel resin multilayer substrate produced by combining the multilayer technology, the design technology and the unique LCP film of the Primatec has excellent high-frequency characteristics and flexibility, can be bent into various shapes according to use requirements, is very suitable for smart phones with continuously reduced internal space, and enables thin and free-shaped circuit design.
The main classification methods for liquid crystal polymers at present are classified into three types according to heat resistance:
the second type, which is the main type currently used for film production, is a raw material resin for LCP films, the global market of which is mainly focused on the us and japan, and for example, the invention patent CN104220236A by kohli discloses a thermoplastic liquid crystal polymer film and a method for producing the same, and further discloses that by stretching a film having a specific dielectric constant in a plane under specific stretching conditions, the film can be stretched alone, whereby a thermoplastic liquid crystal polymer film with reduced thickness unevenness can be efficiently produced, and the resulting thermoplastic liquid crystal polymer film with less thickness unevenness can improve the reliability of a substrate when used for, for example, a printed circuit board. Wherein, the major factories in the United states are Ticona (Ticona), Japanese relatively large-scale companies are Japanese treasury (polyplasics) and Sumitomo chemical (Sumitomo), but the materials of the enterprises are closed to China and are very expensive, the domestic existing production enterprises have Peste, Watt shares, Jinfa technologies and the like, but have defects in the aspect of product film forming property, and no enterprise in China can continuously and stably produce the film.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: the film forming performance of Type II LCP is poor, the molecules in the LCP film have strong anterograde, the tensile strength in TD direction after film forming is very small, the stress is easy to damage, and no enterprise can continuously and stably produce Type II LCP films in China. The LCP film prepared by utilizing a special high-density polyethylene (HDPE) film and a special processing technology has good film forming performance and high tensile strength in the TD direction, and can be continuously and stably produced in the actual production process.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides an ABA composite film which is characterized in that an intermediate layer is an LCP film, and the outer sides of two surfaces of the intermediate layer are polytetrafluoroethylene films.
Specifically, the thickness of the LCP film is 25-50 μm, and the thickness of the polytetrafluoroethylene film is 50-100 μm.
Specifically, the LCP film is a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.
Specifically, the copolymer has a melting point of 290 ℃ to 300 ℃, and a melt viscosity of 900 ℃ to 1600 poise.
Specifically, the preparation method of the ABA composite film comprises the following steps:
the copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid and polytetrafluoroethylene are melted and extruded from an ABA adapter connecting die head of an annular blow molding machine, the ABA adapter connecting die head is a three-layer concentric circular die head, the die head temperature is 290-.
Specifically, an ABA composite film is flattened by a pair of film clamping rollers to obtain a folded pressing sheet, the folded pressing sheet of a tubular film is divided into two flat films, the two flat films are respectively wound and wound on rollers to obtain a pre-peeled film, the pre-peeled film is subjected to continuous heat treatment at the temperature of 260-265 ℃, and then polytetrafluoroethylene films on the upper layer and the lower layer of the pre-peeled film are peeled at an angle of 180 degrees to obtain a continuous LCP film with the thickness of 25-50 mu m.
Specifically, the heat treatment method of the pre-stripping film comprises the following steps: the pre-peeled film is conveyed to a hot air circulation type heat treatment furnace with the furnace length of 1.5m at the temperature of 260-265 ℃ at the speed of 3-5m/min for continuous heat treatment.
The invention has the beneficial effects that:
(1) the preparation method of the LCP film overcomes the film forming defect of LCP and can realize the continuous and stable production of Type II LCP films.
(2) The invention compounds LCP and polytetrafluoroethylene as a supporting film during melt extrusion, simplifies the process and improves the production efficiency of the LCP film.
(3) The LCP film prepared by the invention has better TD direction tensile strength.
Drawings
FIG. 1: an ABA adapter for an annular blow molding machine is attached to a schematic representation of the cross section of the die.
Detailed Description
The present invention will now be described in further detail with reference to examples.
Example 1
(1) Respectively adding a copolymer formed by p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid with a melting point of 280 ℃ and 2 parts of polytetrafluoroethylene into feed openings of two extruders according to a weight ratio of 1:4, carrying out melt extrusion from an ABA adapter connecting die head of an annular blow molding machine, wherein the die head temperature is 290 ℃, the blow molding ratio is 5, the stretching ratio is 2.2, carrying out blow molding to obtain an ABA composite film, wherein a layer A is polytetrafluoroethylene, a layer B is a copolymer formed by hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the thickness ratio of polytetrafluoroethylene layers on the outermost two layers in the ABA composite film is 1:1, and the thickness of the ABA composite film is 250 mu m;
(2) flattening the ABA composite film by a pair of film clamping rollers to obtain a folded pressing sheet, dividing the folded pressing sheet of the tubular film into two flat films, respectively winding and rolling the two flat films on the rollers to obtain a pre-peeled film, conveying the pre-peeled film to a hot air circulating type heat treatment furnace with the furnace length of 1.5m and the temperature of 260 ℃ at the speed of 3m/min for continuous heat treatment, and peeling polytetrafluoroethylene films on the upper layer and the lower layer of the pre-peeled film at an angle of 180 ℃ to obtain a continuous LCP film with the thickness of 50 mu m.
Example 2
(1) Respectively adding a copolymer formed by p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid with a melting point of 283 ℃ and 2 parts of polytetrafluoroethylene into feed openings of two extruders according to a weight ratio of 1:4, carrying out melt extrusion from an ABA adapter connecting die head of an annular blow molding machine, wherein the die head temperature is 295 ℃, the blow molding ratio is 4, the stretching ratio is 2, and carrying out blow molding to obtain an ABA composite film, wherein a layer A is polytetrafluoroethylene, a layer B is a copolymer formed by hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the thickness ratio of the outermost two polytetrafluoroethylene layers in the ABA composite film is 1:1, and the thickness of the ABA composite film is 125 mu m;
(2) flattening the ABA composite film by a pair of film clamping rollers to obtain a folded pressing sheet, dividing the folded pressing sheet of the tubular film into two flat films, respectively winding and rolling the two flat films on the rollers to obtain a pre-peeled film, conveying the pre-peeled film to a hot air circulating type heat treatment furnace with the furnace length of 1.5m and the temperature of 265 ℃ at the speed of 4m/min for continuous heat treatment, and peeling polytetrafluoroethylene films on the upper layer and the lower layer of the pre-peeled film at an angle of 180 ℃ to obtain a continuous LCP film with the thickness of 25 mu m.
Example 3
(1) Respectively adding a copolymer formed by p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid with a melting point of 283 ℃ and 2 parts of polytetrafluoroethylene into feed openings of two extruders according to a weight ratio of 1:4, carrying out melt extrusion from an ABA adapter connecting die head of an annular blow molding machine, wherein the die head temperature is 300 ℃, the blow molding ratio is 4.5, the stretching ratio is 2.1, carrying out blow molding to obtain an ABA composite film, wherein a layer A is polytetrafluoroethylene, a layer B is a copolymer formed by hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the thickness ratio of polytetrafluoroethylene layers on the outermost layer in the ABA composite film is 1:1, and the thickness of the ABA composite film is 130 mu m;
(2) flattening the ABA composite film by a pair of film clamping rollers to obtain a folded pressing sheet, dividing the folded pressing sheet of the tubular film into two flat films, respectively winding and rolling the two flat films on the rollers to obtain a pre-peeled film, conveying the pre-peeled film to a hot air circulating type heat treatment furnace with the furnace length of 1.5m and the temperature of 265 ℃ at the speed of 5m/min for continuous heat treatment, and peeling polytetrafluoroethylene films on the upper layer and the lower layer of the pre-peeled film at an angle of 180 ℃ to obtain a continuous LCP film with the thickness of 30 mu m.
The technical solutions of examples 1 to 3 of the present application allow the continuous production of LCP films.
Comparative example 1 differs from example 1 in that: the HDPE pellet in example 1 is replaced by high-density polyethylene, and the high-density polyethylene cannot be continuously formed into a film after ring blow molding and stretching and is easy to break.
Comparative example 2 is a commercially available PI film (Kapton).
Comparative example 3 is a commercially available LCP film (plersted).
The results of the performance tests of the LCP film prepared in example 1 and the commercially available films of comparative examples 2-3 are shown in tables 1 and 2:
TABLE 1
TABLE 2
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (7)
1. An ABA composite film is characterized in that an intermediate layer is an LCP film, and the outer sides of two surfaces of the intermediate layer are polytetrafluoroethylene films.
2. An ABA composite film according to claim 1 wherein: the thickness of the LCP film is 25-50 mu m, and the thickness of the polytetrafluoroethylene film is 50-100 mu m.
3. An ABA composite film according to claim 1 wherein: the LCP film is a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.
4. An ABA composite film according to claim 1 wherein: the copolymer has a melting point of 280 ℃ and 300 ℃, and a melt viscosity of 900 ℃ and 1600 poises.
5. The preparation method of the ABA composite film is characterized by comprising the following steps of:
the copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid and polytetrafluoroethylene are melted and extruded from an ABA adapter connecting die head of an annular blow molding machine, the ABA adapter connecting die head is a three-layer concentric circular die head, the die head temperature is 290-.
6. The method for preparing an ABA composite film according to claim 5, wherein:
flattening the ABA composite film by a pair of film clamping rollers to obtain a folded pressing sheet, dividing the folded pressing sheet of the tubular film into two flat films, respectively winding and rolling the two flat films on a roller to obtain a pre-peeled film, carrying out continuous heat treatment on the pre-peeled film at the temperature of 260-265 ℃, and then peeling polytetrafluoroethylene films on the upper layer and the lower layer of the pre-peeled film at an angle of 180 ℃ to obtain a continuous LCP film with the thickness of 25-50 mu m.
7. The method for preparing an ABA composite film according to claim 6, wherein the heat treatment method of the pre-peeled film is as follows: the pre-peeled film is conveyed to a hot air circulation type heat treatment furnace with the furnace length of 1.5m at the temperature of 260-265 ℃ at the speed of 3-5m/min for continuous heat treatment.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010529023.7A CN111634090A (en) | 2020-06-11 | 2020-06-11 | ABA (abscisic acid) composite film and preparation method thereof |
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| CN202010529023.7A CN111634090A (en) | 2020-06-11 | 2020-06-11 | ABA (abscisic acid) composite film and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616526A (en) * | 2003-09-30 | 2005-05-18 | 可乐丽股份有限公司 | Method of making liquid crystal polymer films |
| TW201213406A (en) * | 2010-03-26 | 2012-04-01 | Kuraray Co | Light-reflective film, light-reflective laminate, and light-reflective circuit board |
| CN106317810A (en) * | 2015-06-25 | 2017-01-11 | 财团法人工业技术研究院 | Liquid crystal polymer composite film |
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- 2020-06-11 CN CN202010529023.7A patent/CN111634090A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616526A (en) * | 2003-09-30 | 2005-05-18 | 可乐丽股份有限公司 | Method of making liquid crystal polymer films |
| TW201213406A (en) * | 2010-03-26 | 2012-04-01 | Kuraray Co | Light-reflective film, light-reflective laminate, and light-reflective circuit board |
| CN106317810A (en) * | 2015-06-25 | 2017-01-11 | 财团法人工业技术研究院 | Liquid crystal polymer composite film |
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