CN110499026B - Modified liquid crystal polymer film and preparation method and application thereof - Google Patents
Modified liquid crystal polymer film and preparation method and application thereof Download PDFInfo
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- CN110499026B CN110499026B CN201910857683.5A CN201910857683A CN110499026B CN 110499026 B CN110499026 B CN 110499026B CN 201910857683 A CN201910857683 A CN 201910857683A CN 110499026 B CN110499026 B CN 110499026B
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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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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
- H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
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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
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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Abstract
The invention belongs to the technical field of liquid crystal polymers, and particularly relates to a modified liquid crystal polymer film and a preparation method and application thereof. The modified liquid crystal polymer film comprises the following components: polyphenylene benzothiazole, a cross-linking agent, conductive particles, an ultraviolet absorbent, a coupling agent and a filler; the cross-linking agent is aniline methyl triethoxysilane, and the coupling agent is phthalic anhydride modified triethoxysilane. According to the technical scheme provided by the invention, the problem of processing and film forming of the liquid crystal polymer is solved by adding a proper cross-linking agent and a proper coupling agent, the produced PBT film has excellent performances of low moisture absorption, low dielectric constant, low dielectric loss, high temperature resistance and the like, and no organic solvent is involved in the processing process, so that the environment-friendly effect is achieved.
Description
Technical Field
The invention belongs to the technical field of liquid crystal polymers, and particularly relates to a modified liquid crystal polymer film and a preparation method and application thereof.
Background
A Flexible Printed Circuit Board (also called "FPC Flexible Board") is a Printed Circuit made of a Flexible insulating base material, and has many advantages that a rigid Printed Circuit Board does not have. The device can be freely bent, wound and folded, can be randomly arranged according to the space layout requirement, and can be randomly moved and stretched in a three-dimensional space, so that the integration of component assembly and wire connection is realized. The FPC flexible board can greatly reduce the volume of electronic products, and is suitable for the development of the electronic products in the directions of high density, miniaturization and high reliability.
A Flexible Copper foil substrate (abbreviated as FCCL: Flexible Copper Clad Laminate), also called: the flexible copper clad laminate comprises a flexible copper clad laminate, a flexible copper clad laminate and a flexible copper clad laminate, wherein the FCCL is a processing base material of the FPC. FCCL compositions mainly include three major classes of materials: a cover film material, a metal conductor foil and an adhesive. At present, the covering film materials mainly comprise Polyester (PET) films, Polyimide (PI) films, polyester imide films, fluorocarbon ethylene films, imide fiber paper, polybutylene terephthalate films and the like. Among them, currently, the most widely used are polyester films (PET films) and polyimide films (PI films).
At present, more polyimide is applied, the dielectric constant and the loss factor are larger, the heat is easy to generate, the moisture absorption is large, the thermal expansion coefficient is not controllable, the product performance is not stable enough, the high-frequency transmission loss is serious, the structural characteristics are poorer, and the high-frequency high-speed development trend of the current FPC cannot be adapted.
Liquid crystal polymers, also called liquid crystal polymers, are high molecular compounds that can exist in a liquid crystal phase under certain conditions and are characterized by having molecules with higher molecular weights and ordered orientations. The molecular chain of the high polymer belonging to the material contains rod-shaped or sheet-shaped mesomorphic units, so that the liquid crystal forms a rigid or semi-rigid chain structure. Liquid crystals have both liquid-like fluidity and continuity and crystal-like anisotropy. Because of its low moisture absorption, low dielectric constant and low dielectric loss, and with the coming age of 5G high-speed transmission, it must replace the PI film widely used in FCCL at present. Because they are too highly oriented in the mold, the molecular weight is too high and it is difficult to process into films.
Disclosure of Invention
The invention provides a modified liquid crystal polymer film and a preparation method and application thereof, which are used for solving the problem that the existing liquid crystal polymer is difficult to be used for FPC film forming.
In order to solve the technical problems, the technical scheme of the invention is as follows: the modified liquid crystal polymer film comprises the following components: polyphenylene Benzothiazole (PBT), a cross-linking agent, conductive particles, an ultraviolet absorbent, a coupling agent and a filler; the crosslinking agent is aniline methyl triethoxysilane, the coupling agent is a mixture of phthalic anhydride modified triethoxysilane, and the structure of the phthalic anhydride modified triethoxysilane is shown in formula I:
optionally, the PBT has an average number-average degree of polymerization of 12000-30000.
Optionally, the phthalic anhydride modified triethoxysilane is synthesized by taking phthalic anhydride, allyl amine and triethoxysilane as raw materials and performing imidization reaction and catalytic hydrosilylation.
Optionally, the conductive particles are in-situ synthesized nano silver colloid. The nano silver colloid has high dispersibility.
Optionally, the ultraviolet light absorber is selected from phenyl ortho-hydroxybenzoate, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole or 2, 4-dihydroxybenzophenone.
Optionally, the filler is silica.
Optionally, the components are as follows in parts by weight:
optionally, the modified liquid crystal polymer film has a dielectric constant of 2.5-2.9 at 3GHz, a Coefficient of Thermal Expansion (CTE) of 15-16 PPM/DEG C, a water absorption of 0.02-0.04%, a transverse tensile strength of 320-350MPa, a longitudinal tensile strength of 320-350MPa, and an dissipation factor of 0.001-0.003.
The invention also provides a preparation method of the modified liquid crystal polymer film, which comprises the following steps: melting and mixing the components in a double-screw extruder, extruding, cooling, drying and granulating, then melting the modified particles in the double-screw extruder again, carrying out secondary mixing, finally extruding, casting a sheet or blowing a film, and finally carrying out biaxial tension film forming.
Optionally, the mixing temperature is 350-380 ℃, the secondary mixing temperature is 320-350 ℃, the longitudinal stretching ratio is 5-20, and the transverse stretching ratio is 5-20. .
The invention also provides the application of the modified liquid crystal polymer film in the FPC industry.
According to the technical scheme provided by the invention, the problem of processing and film forming of the liquid crystal polymer is solved by adding a proper cross-linking agent and a proper coupling agent, the produced PBT film has excellent performances of low moisture absorption, low dielectric constant, low dielectric loss, high temperature resistance and the like, and no organic solvent is involved in the processing process, so that the environment-friendly effect is achieved.
Detailed Description
For the convenience of understanding, the modified liquid crystal polymer film and the preparation method and application thereof are described below with reference to examples, which are only for illustrating the present invention and are not intended to limit the scope of the present invention.
The raw materials used in the following examples are commercially available unless otherwise specified, and the processes and equipment used therein are those conventionally used in the art unless otherwise specified.
EXAMPLE 1 preparation of coupling agent
Adding 14.8g of phthalic anhydride and 180ml of glacial acetic acid into a reaction bottle, stirring for dissolving, adding 5.7g of allyl amine, reacting for 1h at room temperature, heating for refluxing for 4h, cooling to room temperature, adding 170ml of water, heating to boil, cooling to room temperature, separating out white solid, performing suction filtration, washing with water, and then recrystallizing for purification.
And (3) adding 7.4g of the product obtained in the previous step and 100ml of toluene into a reaction bottle, stirring and dissolving, adding a platinum-containing catalyst, an agent, activating at 50 ℃ for 30min under the protection of nitrogen, adding 8.21g of triethoxysilane, heating to 70 ℃ after adding, reacting for 3h, cooling to room temperature, removing the solvent, and recrystallizing to obtain the phthalic anhydride modified triethoxysilane coupling agent.
EXAMPLE 2 composition of PBT films
EXAMPLE 3 composition of PBT films
Example 4 preparation of PBT film
The components in example 2 or 3 were melted and kneaded in a twin-screw extruder at 350 ℃, extruded, cooled, dried and pelletized, then the modified particles were melted again in the twin-screw extruder, and subjected to secondary kneading at 320 ℃, and finally extruded, cast into a sheet and biaxially stretched into a film, which was stretched 8 times in the longitudinal direction and 8 times in the transverse direction.
Example 5 comparative experiment
The films prepared in example 4 according to the present invention from examples 2 and 3 were compared with commercially available PI films for FCP in performance tests, and the results are shown in Table 1.
TABLE 1
As shown in Table 1, the modified liquid crystal polymer film provided by the invention has more excellent performance and is more suitable for being used as a covering film material of FCP.
Finally, it should be noted that: the above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: it is to be understood that modifications may be made to the technical solutions described in the foregoing embodiments, or some or all of the technical features may be equivalently replaced, and such modifications or replacements may not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A modified liquid crystal polymer film is characterized by comprising the following components: polyphenylene benzothiazole, a cross-linking agent, conductive particles, an ultraviolet absorbent, a coupling agent and a filler; the crosslinking agent is aniline methyl triethoxysilane, the coupling agent is phthalic anhydride modified triethoxysilane, and the structure of the phthalic anhydride modified triethoxysilane is shown in formula I:
2. the modified liquid crystal polymer film of claim 1, wherein the average number-average degree of polymerization of the polyphenylene-benzothiazole is 12000-30000.
3. The modified liquid crystal polymer film of claim 1, wherein said phthalic anhydride-modified triethoxysilane is synthesized by two steps of imidization and catalytic hydrosilylation using phthalic anhydride, allyl amine and triethoxysilane as raw materials.
4. The modified liquid crystal polymer film of claim 1, wherein the conductive particles are in-situ synthesized nano-silver colloid.
5. The modified liquid crystal polymer film of claim 1, wherein the ultraviolet absorber is selected from phenyl o-hydroxybenzoate, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole or 2, 4-dihydroxybenzophenone.
6. The modified liquid crystal polymer film according to claim 1, wherein the filler is silica.
7. The method for preparing a modified liquid crystal polymer film according to any one of claims 1 to 6, comprising the steps of: melting and mixing the components in a double-screw extruder, extruding, cooling, drying and granulating, then melting the modified particles in the double-screw extruder again, mixing for the second time, finally extruding, casting a sheet and stretching the sheet bidirectionally to form a film.
8. The method as claimed in claim 7, wherein the mixing temperature is 350-380 ℃, the secondary mixing temperature is 320-350 ℃, the longitudinal stretching ratio is 5-20, and the transverse stretching ratio is 5-20.
9. Use of the modified liquid crystalline polymer film of any one of claims 1 to 6 in the FPC industry.
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| CN2019106120796 | 2019-07-08 | ||
| CN201910612079.6A CN110256850A (en) | 2019-07-08 | 2019-07-08 | Modified liquid crystal polymer film and its preparation method and application |
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| CN110499026B true CN110499026B (en) | 2021-11-26 |
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| CN111690326A (en) * | 2020-05-12 | 2020-09-22 | 深圳市信维通信股份有限公司 | Preparation method of liquid crystal polymer film or liquid crystal polymer copper-clad plate |
| 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 |
| CN112973637B (en) * | 2021-02-20 | 2022-06-21 | 杭州楠大环保科技有限公司 | High-efficiency waste gas treating agent and preparation method and application thereof |
| CN113308111A (en) * | 2021-06-03 | 2021-08-27 | 宁夏清研高分子新材料有限公司 | Liquid crystal polymer film for flexible printed circuit board and preparation method thereof |
| CN113480868B (en) * | 2021-06-29 | 2022-10-04 | 宁波长阳科技股份有限公司 | Liquid crystal polymer film and preparation method thereof |
| CN113246438B (en) * | 2021-07-06 | 2021-09-24 | 苏州固泰新材股份有限公司 | Single screw extruder for processing liquid crystal polymer and film forming method |
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- 2019-07-08 CN CN201910612079.6A patent/CN110256850A/en active Pending
- 2019-09-09 CN CN201910857683.5A patent/CN110499026B/en active Active
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