CN109651632A - A kind of liquid crystal polymer film and preparation method thereof - Google Patents
A kind of liquid crystal polymer film and preparation method thereof Download PDFInfo
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- CN109651632A CN109651632A CN201811343546.1A CN201811343546A CN109651632A CN 109651632 A CN109651632 A CN 109651632A CN 201811343546 A CN201811343546 A CN 201811343546A CN 109651632 A CN109651632 A CN 109651632A
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
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- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
- C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor
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Abstract
The invention discloses a kind of liquid crystal polymer films and preparation method thereof, liquid crystal polymer film includes at least two first orientation unit and at least two second orientation unit, the first orientation unit intersects with the differently- oriented directivity of the second orientation unit, the at least two first orientation unit and at least two second orientation unit are arranged in netted braiding structure, and the netted braiding structure obtains the liquid crystal polymer film through hot press molding.The different first orientation unit of differently- oriented directivity and second orientation unit are arranged in netted braiding structure, and liquid crystal polymer film is by the way of hot-forming, available isotropic liquid crystal polymer film, make it that there is comparable mechanical property in the direction MD and the direction TD, and the phenomenon that layering will not occur in a thickness direction in obtained film.
Description
Technical field
The present invention relates to materials processing technology fields more particularly to a kind of liquid crystal polymer film and preparation method thereof.
Background technique
Liquid crystal polymer (Liquid Crystalline Polymer, LCP) is to grow up phase early 1980s
A kind of novel high polymer material.Since (1~40GHz) has lower dielectric constant and dielectric loss, liquid crystal in high frequency
Thin polymer film is widely applied in high-frequency high-speed communication flexible circuit board.
The main preparation methods of liquid crystal polymer film have: extrusion blow molding processes and extrusion are cast double daraf(reciprocals of farad).Application No. is
03156468.2 Chinese invention patent discloses a kind of production method of inflation film, and the inflation film of production has smooth
Surface not will form gap and/or fold.Application No. is 200410080693.6 Chinese invention patents to disclose a kind of thermoplastic
The manufacturing method of property liquid crystal polymer film, can manufacture at low temperature for flexibility circuit substrate or Mulitilayer circuit board etc.
Insulating materials, the liquid crystal polymer films that control thermal expansion coefficient.
Since liquid crystal polymer has height-oriented property under shearing force, using the film of conventional method preparation in MD
Mechanical property with higher on direction (Machine Direction, mechanical direction), and in the direction TD (Transverse
Direction, perpendicular to mechanical direction) on tearing strength it is very poor, that is, there is anisotropy, anisotropic films are unable to satisfy
The use demand of flexible circuit board.Further, since the height-oriented property of liquid crystal polymer, also brings to film in a thickness direction
The risk of layering.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of liquid crystal polymer film and preparation method thereof, liquid crystal is poly-
Close object film has comparable mechanical property on the direction MD and the direction TD.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
A kind of liquid crystal polymer film, including at least two first orientation unit and at least two second orientation list
Member, the first orientation unit intersect with the differently- oriented directivity of the second orientation unit, at least two first orientation list
First second orientation unit at least two is arranged in netted braiding structure, and the netted braiding structure is through hot press molding
Obtain the liquid crystal polymer film.
Another technical solution that the present invention uses are as follows:
A kind of production method of liquid crystal polymer film, by be used to make liquid crystal polymer film first orientation unit and
Second orientation unit is woven, and netted braiding structure is obtained；The netted braiding structure progress is hot-forming, it obtains described
Liquid crystal polymer film.
The beneficial effects of the present invention are: by the different first orientation unit of differently- oriented directivity and second orientation unit in netted
Braiding structure setting, and liquid crystal polymer film is by the way of hot-forming, available isotropic liquid crystal polymer
Film makes it have comparable mechanical property in the direction MD and the direction TD, and obtained film in a thickness direction will not
The phenomenon that being layered.Liquid crystal polymer film of the invention, manufacturing process is simple, and obtained thin film mechanical performance is good, fits
For making flexible circuit board.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the liquid crystal polymer film of the embodiment of the present invention one；
Fig. 2 is the partial structure diagram of the netted braiding structure of the embodiment of the present invention two；
Fig. 3 is another part structural schematic diagram of the netted braiding structure of the embodiment of the present invention two.
Label declaration:
1, first orientation unit；2, second orientation unit.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, below in conjunction with embodiment and cooperate attached
Figure is explained.
The most critical design of the present invention is: first orientation unit and second orientation unit are arranged in netted braiding structure,
Liquid crystal polymer film is hot-forming, and available isotropic liquid crystal polymer film makes it in the direction MD and the direction TD
With comparable mechanical property.
Please refer to Fig. 1, a kind of liquid crystal polymer film, including at least two first orientation unit 1 and at least two
Second orientation unit 2, the first orientation unit 1 intersect with the differently- oriented directivity of the second orientation unit 2, at least two institute
The second orientation unit 2 for stating first orientation unit 1 and at least two is arranged in netted braiding structure, and the netted braiding
Structure obtains the liquid crystal polymer film through hot press molding.
As can be seen from the above description, the beneficial effects of the present invention are: by the different first orientation unit of differently- oriented directivity and
Two orientation units are arranged in netted braiding structure, and liquid crystal polymer film is by the way of hot-forming, it is available respectively to
The liquid crystal polymer film of the same sex makes it have comparable mechanical property in the direction MD and the direction TD, and obtained film exists
Will not occur the phenomenon that layering on thickness direction.
Further, the cross-sectional area of the first orientation unit 1 and second orientation unit 2 is 10-6~1mm2。
Seen from the above description, the cross-sectional area of first orientation unit and second orientation unit, which can according to need, is selected
It selects, the bigger number that can reduce orientation unit of cross-sectional area, the smaller number that can increase orientation unit of cross-sectional area.
Further, at least two first orientation unit 1 is arranged in parallel, and described the second of at least two takes
It is arranged in parallel to unit 2.
Seen from the above description, the orientation unit of same orientation is arranged in parallel, and can increase the mechanical property of differently- oriented directivity.
Further, the first orientation unit 1 is vertically arranged relative to the second orientation unit 2.
Seen from the above description, the orientation unit of different orientation is arranged in a mutually vertical manner, can be averaged it is each to mechanical property.
Further, the material of the liquid crystal polymer film is poly- for the liquid crystal polymer containing phenyl ring, naphthalene-ring containing liquid crystal
Close object, the liquid crystal polymer of fatty race's segment or the liquid crystal polymer of the group containing cyclic polyester.
Seen from the above description, the material of liquid crystal polymer film, which can according to need, is selected.
Referring to figure 2. and Fig. 3, another technical solution of the present invention are as follows:
A kind of production method of liquid crystal polymer film will be used to make the first orientation unit 1 of liquid crystal polymer film
It is woven with second orientation unit 2, obtains netted braiding structure；The netted braiding structure progress is hot-forming, it obtains
The liquid crystal polymer film.
Seen from the above description, the count of netted braiding structure, which can according to need, is configured, first orientation list
Member and second orientation unit can be the mass of fibers that spinning obtains, the fiber being also possible to after oriented film is cut, and first
Orientation unit and second orientation unit can use identical fiber, and only modes of emplacement difference leads to final differently- oriented directivity not
Together.The manufacturing process of liquid crystal polymer film is simple, and obtained thin film mechanical performance is good, is suitable for production flexible circuit board.
Further, the cross section of the first orientation unit 1 in the netted braiding structure and the second orientation list
The cross section of member 2 is circle, and the distance between two neighboring described first orientation unit 1 value is less than the first orientation unit
1 diameter value, the distance between two neighboring described second orientation unit 2 value are less than the diameter value of the second orientation unit 2.
Seen from the above description, by the distance between two neighboring orientation unit value setting it is smaller, can be to avoid hot pressing after
Gap is generated, the uniform liquid crystal polymer film of thickness is obtained.
Further, the first orientation unit 1 is vertically arranged relative to the second orientation unit 2.
Further, the hot-forming temperature is (Ts+20)~(Tm-5) DEG C, wherein Ts is the first orientation
The Vicat softening point of unit 1, Tm are the fusing point of the first orientation unit 1.
Seen from the above description, hot-forming temperature is unsuitable excessively high or too low, and too low should not to form thickness uniform
Film, it is excessively high, it will affect the original orientation of orientation unit.
Further, the first orientation unit 1 and second orientation are obtained by the method for melt spinning or electrostatic spinning
Unit 2.
Seen from the above description, spinning is conducive to the orientation of high molecular material, first orientation unit and second orientation unit
It can be fibre bundle.
Please refer to Fig. 1, the embodiment of the present invention one are as follows:
A kind of liquid crystal polymer film, including at least two first orientation unit 1 and at least two second orientation list
Member 2, the differently- oriented directivity of the first orientation unit 1 intersects with the differently- oriented directivity of the second orientation unit 2, at least two institute
The second orientation unit 2 for stating first orientation unit 1 and at least two is arranged in netted braiding structure.Preferably, at least two
A first orientation unit 1 is arranged in parallel, and at least two second orientation unit 2 is arranged in parallel, institute
First orientation unit 1 is stated to be vertically arranged relative to the second orientation unit 2.In the present embodiment, 1 He of first orientation unit
The cross-sectional area of second orientation unit 2 is 10-6~1mm2.It is poly- that the netted braiding structure obtains the liquid crystal through hot press molding
Close object film, the material of the liquid crystal polymer film is liquid crystal polymer containing phenyl ring, naphthalene-ring containing liquid crystal polymer, contains rouge
The liquid crystal polymer of fat race segment or the liquid crystal polymer of the group containing cyclic polyester.
Referring to figure 2. and Fig. 3, the embodiment of the present invention two are as follows:
A kind of production method of liquid crystal polymer film, for obtaining the liquid crystal polymer film in embodiment one, including
Following steps:
Firstly, carrying out melt spinning or electrostatic spinning using thermoplastic liquid crystal polymer, height-oriented threadiness is obtained
Intermediate products can also be realized in such a way that anisotropic films are by cutting.In the present embodiment, the thermoplastic polymer is
The liquid crystal polymer of liquid crystal polymer, naphthalene-ring containing liquid crystal polymer, fatty race's segment containing phenyl ring or base containing cyclic polyester
The liquid crystal polymer of group.Melt spinning generally uses extruder to be plasticized material resin, prepares liquid crystal by spinning die head
Polymer fiber, this method are easy to get the fiber of circular cross section, and diameter range is 5~1000 μm.Electrostatic spinning is molten
Body carries out jet spinning in strong electrical field, and under electric field action, molten melt drop can be become cone from spherical shape, i.e., " taylor cone ",
And extend to obtain fiber filaments from conical tip, this mode is easy to produce the very thin fiber of diameter, diameter range 10nm
~50 μm.The single diameter of fine fibre of electrostatic spinning preparation is smaller, can spin and be prepared into the yarn containing plurality of fibers, in order to
It carries out the next step (braiding reticulates braiding structure).Spin the yarn prepared, can use twisting process.It is squeezed using common
Blow moulding or the film of extrusion curtain coating method preparation, polymer segment are orientated towards mechanical direction out, are anisotropy, will be this thin
Film is cut, and the fiber that cross section is rectangle can be prepared.In the present embodiment, select cross-sectional area for 10-6~1mm2Fibre
Dimension is used as first orientation unit and second orientation unit, and first orientation unit and second orientation unit use identical fiber, only
It is disposing way difference.
As shown in Figures 2 and 3, it will be used to make the first orientation unit 1 and second orientation unit 2 of liquid crystal polymer film
It is woven, obtains netted braiding structure.In the present embodiment, the first orientation unit 1 is relative to the second orientation unit 2
It is vertically arranged, multiple first orientation units 1 are arranged in parallel, and multiple second orientation units 2 are arranged in parallel.When the net
When the cross section of first orientation unit 1 in shape braiding structure and the cross section of the second orientation unit 2 are circle, phase
The distance between adjacent two first orientation units 1 value is less than the diameter value of the first orientation unit 1, two neighboring described
The distance between second orientation unit 2 value is less than the diameter value of the second orientation unit 2.In the present embodiment, title can be passed through
Weight method calculates the effective thickness of netted braiding structure, provides pressing parameter for hot pressing, the effective thickness of netted braiding structure is than real
The film thickness of border demand is high by 1~5%, to obtain void-free film.
The netted braiding structure progress is hot-forming, obtain the liquid crystal polymer film.It is described hot-forming
Temperature is (Ts+20)~(Tm-5) DEG C, wherein Ts is the Vicat softening point of the first orientation unit, and Tm takes for described first
To the fusing point of unit.
Embodiment three
The embodiment of the present invention three is a kind of production method of liquid crystal polymer film, is existed with the difference of embodiment two
In:
Using melt spinning machine, spinning is carried out to thermoplastic liquid crystal polymer resin (VECTRA A950) at 310 DEG C,
The fiber of circular section is obtained, diameter is 80 μm.Due to the effect of spinning die head shearing force, the polymer segment of fibrous inside is in take
To distribution.Spinning temperature is generally Tm~(Tm+80 DEG C), and Tm is the fusing point of thermoplastic liquid crystal polymer.Using braider to fibre
Dimension carries out plain weave, and the spacing control between two neighboring orientation unit is 60 μm, obtains netted braiding structure.Weighed survey
Amount, effective thickness are 71.8 μm.
Band intermediate products are pressed using calender, isotropic liquid crystal polymer film is prepared.Pressure
Prolong temperature be 220 DEG C, rolling velocity be 1m/min (generally 0.1m/min~20m/min), pressure be 10MPa (generally 1~
100MPa), stack spacing be 70 μm, lower than effective thickness 2.5%.
Comparative example
Using extrusion blow molding machine, thermoplastic liquid crystal polymer resin (VECTRA A950) is blow molded at 310 DEG C
Film.Extruder screw speed is 80rpm, and extrusion die diameter is 60mm, and gap 1mm, blow-up ratio 1:3 obtain thickness about
70 μm of inflation film.
Performance test
By the liquid crystal polymer film that embodiment three obtains and the inflation film that comparative example obtains respectively in omnipotent examination
It tests and carries out test for tensile strength on machine, obtain test result as shown in Table 1.
1 tensile strength test of table
From the test result of table 1 it is found that the prepared liquid crystal polymer film of the present invention is in MD and TD both direction
Mechanical property is suitable, and isotropic is presented；The film that conventional blown is prepared, mechanical property is preferable in the MD direction, but
The direction TD mechanics poor performance.
In conclusion a kind of liquid crystal polymer film provided by the invention and preparation method thereof, liquid crystal polymer film exists
The direction MD and the direction TD have a comparable mechanical property, and obtained film showing of will not occurring being layered in a thickness direction
As；Its manufacturing process is simple, at low cost, is suitable for production flexible circuit board.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright specification and accompanying drawing content are applied directly or indirectly in relevant technical field, similarly include
In scope of patent protection of the invention.
Claims (10)
1. a kind of liquid crystal polymer film, which is characterized in that including at least two first orientation unit and the of at least two
Two orientation units, the first orientation unit intersect with the differently- oriented directivity of the second orientation unit, and described the of at least two
One orientation unit is arranged at least two second orientation unit in netted braiding structure, and the netted braiding structure passes through
It is hot-forming to obtain the liquid crystal polymer film.
2. liquid crystal polymer film according to claim 1, which is characterized in that the first orientation unit and second orientation
The cross-sectional area of unit is 10-6~1mm2。
3. liquid crystal polymer film according to claim 1, which is characterized in that at least two first orientation unit
Arranged in parallel, at least two second orientation unit is arranged in parallel.
4. liquid crystal polymer film according to claim 1, which is characterized in that the first orientation unit is relative to described
Second orientation unit is vertically arranged.
5. liquid crystal polymer film according to claim 1, which is characterized in that the material of the liquid crystal polymer film is
The liquid crystal polymer of liquid crystal polymer, naphthalene-ring containing liquid crystal polymer, fatty race's segment containing phenyl ring or base containing cyclic polyester
The liquid crystal polymer of group.
6. a kind of production method of liquid crystal polymer film, which is characterized in that will be used to make the first of liquid crystal polymer film
Orientation unit and second orientation unit are woven, and netted braiding structure is obtained；The netted braiding structure is hot pressed into
Type obtains the liquid crystal polymer film.
7. the production method of liquid crystal polymer film according to claim 6, which is characterized in that the netted braiding structure
In the cross section of first orientation unit and the cross section of the second orientation unit be circle, two neighboring described first
The distance between orientation unit value is less than the diameter value of the first orientation unit, between the two neighboring second orientation unit
Distance value be less than the second orientation unit diameter value.
8. the production method of liquid crystal polymer film according to claim 6, which is characterized in that the first orientation unit
It is vertically arranged relative to the second orientation unit.
9. the production method of liquid crystal polymer film according to claim 6, which is characterized in that the hot-forming temperature
Degree is (Ts+20)~(Tm-5) DEG C, wherein Ts is the Vicat softening point of the first orientation unit, and Tm is the first orientation
The fusing point of unit.
10. the production method of liquid crystal polymer film according to claim 6, which is characterized in that by melt spinning or
The method of electrostatic spinning obtains the first orientation unit and second orientation unit.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110978576A (en) * | 2019-12-20 | 2020-04-10 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of liquid crystal polymer film |
| CN112549688A (en) * | 2019-09-25 | 2021-03-26 | 深圳大学 | Flexible copper-clad plate and preparation method and application thereof |
| CN113550139A (en) * | 2020-04-24 | 2021-10-26 | 深圳市劢全新材料科技有限责任公司 | Preparation method of aromatic polyester electrospun membrane compounded with ceramic |
| CN114438815A (en) * | 2020-11-03 | 2022-05-06 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of tear-resistant liquid crystal polyester film with small anisotropy |
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2018
- 2018-11-13 CN CN201811343546.1A patent/CN109651632A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112549688A (en) * | 2019-09-25 | 2021-03-26 | 深圳大学 | Flexible copper-clad plate and preparation method and application thereof |
| CN110978576A (en) * | 2019-12-20 | 2020-04-10 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of liquid crystal polymer film |
| WO2021120535A1 (en) * | 2019-12-20 | 2021-06-24 | 江门市德众泰工程塑胶科技有限公司 | Method for preparing liquid crystal polymer film, liquid crystal polymer film and application thereof |
| CN110978576B (en) * | 2019-12-20 | 2021-09-10 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of liquid crystal polymer film |
| CN113550139A (en) * | 2020-04-24 | 2021-10-26 | 深圳市劢全新材料科技有限责任公司 | Preparation method of aromatic polyester electrospun membrane compounded with ceramic |
| CN114438815A (en) * | 2020-11-03 | 2022-05-06 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of tear-resistant liquid crystal polyester film with small anisotropy |
| CN114438815B (en) * | 2020-11-03 | 2022-12-09 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of tear-resistant liquid crystal polyester film with small anisotropy |
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Application publication date: 20190419 |