CN111070832A - Strippable polyimide composite film - Google Patents
Strippable polyimide composite film Download PDFInfo
- Publication number
- CN111070832A CN111070832A CN201811214312.7A CN201811214312A CN111070832A CN 111070832 A CN111070832 A CN 111070832A CN 201811214312 A CN201811214312 A CN 201811214312A CN 111070832 A CN111070832 A CN 111070832A
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- Prior art keywords
- polyimide film
- polyimide
- dianhydride
- film
- oda
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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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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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
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A strippable polyimide composite film comprises a first polyimide film having opposite first and second surfaces; and a second polyimide film attached to the first surface of the first polyimide film, wherein the difference in thermal expansion coefficient between the first polyimide film and the second polyimide film is 9 μm/m DEG C or more so that the first polyimide film and the second polyimide film can be peeled from each other.
Description
Technical Field
The invention relates to a strippable polyimide composite film, in particular to a strippable polyimide composite film capable of being prepared into an ultrathin polyimide film.
Background
In a printed circuit board, a polyimide protective layer (coverlay) is generally provided thereon in order to protect metal lines. With the development of technology and product demand, the size of the printed circuit board tends to be light, thin and multifunctional, and it is also an important development goal in the field to reduce the overall thickness of the printed circuit board, wherein the thinning of the polyimide passivation layer has become one of the important indexes of the overall design of the printed circuit board.
However, the ultra-thin polyimide film is limited by the existing polyimide film preparation process, and the development of the ultra-thin polyimide film is difficult. It is known that the thinnest polyimide protective layers currently commercially available can be less than 10 microns thick; however, it is almost impossible to achieve the object of producing a polyimide film having a thickness of less than 5 μm by the conventional biaxial stretching process. Furthermore, the problem of the workability of the adhesive application in downstream applications must also be considered.
Accordingly, there remains a need for ultra-thin polyimide film products and related processes for making the same.
Disclosure of Invention
The invention provides a strippable polyimide composite film, which comprises a first polyimide film, a second polyimide film and a third polyimide film, wherein the first polyimide film is provided with a first surface and a second surface which are opposite; and a second polyimide film attached to the first surface of the first polyimide film, wherein the difference between the thermal expansion coefficients of the first polyimide film and the second polyimide film is greater than 9 μm/m DEG C, so that the first polyimide film and the second polyimide film can be peeled off from each other.
Drawings
FIG. 1 is a cross-sectional view of a peelable polyimide composite film of the present invention;
FIG. 2 is a schematic view of a peelable polyimide composite film of the present invention.
[ description of reference ]
Detailed Description
In the present embodiment, referring to fig. 1, the first polyimide film 10 has a thickness of 6 microns or less, preferably 5 microns or less, for example: 0.1 to 5 microns. In embodiments, the thickness of the first polyimide film 10 may be 0.1, 1, 2, 2.5, 3, 4, 4.5 microns or any value therebetween.
The thickness of the second polyimide film 12 is not particularly limited, and the thickness of a general polyimide film can be employed. In some embodiments, the second polyimide film 12 has a thickness of 5 to 50 micrometers. In some embodiments, the thickness of the second polyimide film 12 may be 20 micrometers or more.
Referring to FIG. 2, the difference between the thermal expansion coefficients of the first polyimide film 10 and the second polyimide film 12 is greater than or equal to 9 μm/m.DEG.C, so that the films can be peeled off from each other.
If necessary, a biaxial stretching process may be further performed after the first polyimide film 10 and the second polyimide film 12 are formed, whereby the strength of the polyimide films may be improved. Since the thinner the thickness of the polyimide film, the more difficult it is to carry out the biaxial stretching treatment, it is known that the ultrathin polyimide films currently commercially available are hardly subjected to the biaxial stretching treatment in the production process, and the film strength thereof is adversely affected. In contrast, since the polyimide composite film of the present invention directly forms the first polyimide film 10 on the second polyimide film 12, it is possible to perform a biaxial stretching process without adversely affecting the film, such as cracking, if necessary.
The polyimide composite film of the present invention may be formed by thermal or chemical conversion. If chemical conversion is employed, a dehydrating agent and a catalyst may be added to the polyamic acid solution before the coating step. The solvents, dehydrating agents and catalysts used as described above can be those known in the art. The solvent may be an aprotic polar solvent, such as Dimethylacetamide (DMAC), N ' -Dimethylformamide (DMF), N-methylpyrrolidinone (NMP), Dimethylsulfoxide (DMSO), tetramethylsulfone, N ' -dimethyl-N, N ' -propyleneurea (DMPU), and the like. The dehydrating agent can be aliphatic acid anhydride (such as acetic anhydride and propionic anhydride), aromatic acid anhydride (such as phthalic anhydride and phthalic anhydride), etc. The catalyst may be a heterocyclic tertiary amine (e.g., picoline (picoline), pyridine, etc.), an aliphatic tertiary amine (e.g., Triethylamine (TEA), etc.), an aromatic tertiary amine (e.g., xylidine, etc.), etc. Polyamic acid: dehydrating agent: the molar ratio of the catalyst was 1: 2: 1, i.e., about 2 moles of dehydrating agent and about 1 mole of catalyst were used per mole of polyamic acid.
In the present invention, a polyimide is formed by a condensation reaction of a diamine monomer and a dianhydride monomer, and the diamine and dianhydride are reacted in an approximately equimolar ratio (1: 1), such as 0.9: 1.1, or 0.98: 1.02.
The polyimide constituting the releasable base layer main structure and the polyimide of the polyimide film are not particularly limited.
In examples, the diamine monomer may be 4, 4 '-diaminodiphenyl ether (4, 4' -oxydianiline (4, 4 '-ODA)), p-phenylenediamine (p-PDA)), 2' -bis (trifluoromethyl) benzidine (2, 2 '-bis (trifluoromethylphenyl) benzidine (tfmb)), 1, 3-bis (4' -aminophenoxy) benzene (1, 3-bis (4-aminophenoxy) bezene (tper)), 1, 4-bis (4-aminophenoxy) benzene (1, 4-aminophenoxy) bezene (tpeq)), 4 '-diamino-2, 2' -dimethyl-1, 1 '-biphenyl (2, 2' -dimethyll [1, 1 '-dienyl ] -4, 4' -diamine (m-HG-1)), TB, 3-Bis (3-aminophenoxy) benzene (1, 3 ' -Bis (3-aminophenoxy) bezene (APBN)), 3, 5-Diaminobenzotrifluoride (DABTF)), 2 ' -Bis [4- (4-aminophenoxy phenyl) ] propane (2, 2 ' -Bis [4- (4-aminophenoxy) phenyl ] propane (BAPP)), 6-amino-2- (4-aminophenyl) -benzoxazole (6-amino-2- (4-aminophenyl) benzoxazole (6PBOA)), 5-amino-2- (4-aminophenyl) -benzoxazole (5-amino-2- (4-aminophenoxy) benzoxazole (5PBOA)), and the like, which can be used alone or in combination.
In examples, the dianhydride monomer may be 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA), 2-Bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), pyromellitic dianhydride (pmda), 4, 4 '- (hexafluoroisopropenyl) diphthalic anhydride (2, 2' -Bis- (3, 4-dicarboxyphenoxy) phenyl) phthalic anhydride (6FDA), diphenylether tetracarboxylic dianhydride (4, 4-oxophthalic anhydride (pda pa)), phenylketotetracarboxylic dianhydride (benzophenone tetracarboxylic dianhydride), 3 ', 4' -biphenyltetracarboxylic dianhydride (BPDA), 3 ', 4' -biphenyltetracarboxylic dianhydride (3 ', 4, 4' -dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), etc., can be used alone or in combination.
In some embodiments, the monomers of the first polyimide film 10 include the following: the diamine can be 4, 4 ' -diaminodiphenyl ether (4, 4 ' -ODA), p-phenylenediamine (p-PDA), 2 ' -bis (trifluoromethyl) benzidine (TFMB), either alone or in combination; the dianhydride may be pyromellitic dianhydride (PMDA), 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), and may be used alone or in combination.
In embodiments, the first polyimide film 10 may use the same, partially the same, or different monomers as the second polyimide film 12. In some embodiments, the diamine used in the second polyimide film 12 may be 4, 4 ' -diaminodiphenyl ether (4, 4 ' -ODA), p-phenylenediamine (p-PDA), 2 ' -bis (trifluoromethyl) benzidine (TFMB), either alone or in combination; and the dianhydride may be pyromellitic dianhydride (PMDA), 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), and may be used alone or in combination.
Example 1
Firstly, adding a needed diamine ODA monomer into a DMAc solvent, stirring and waiting for the diamine ODA monomer to be dissolved, then slowly adding a dianhydride PMDA monomer into the solution to increase the viscosity to 160,000cps, and finally controlling the solid content to be about 18 percent, wherein the formula is the formula of the first polyimide film; and the diamine monomers of the formula of the second polyimide film are ODA and PDA respectively, and the proportion of the ODA to the PDA is 80: 20, the dianhydride monomers are all made up of PMDA.
Example 2
In this embodiment, a needed diamine ODA monomer is added into a DMAc solvent to be stirred and dissolved, a dianhydride PMDA monomer is slowly added, the viscosity of the solution is continuously increased after the PMDA is added, when the viscosity is increased to about 160,000cps, the solid content of the solution is finally controlled to be about 18%, the solution is the formula of a first polyimide film, diamine monomers of a formula of a second polyimide film are respectively ODA and PDA, the ratio of the diamine monomers to the PDA is 70: 30, and the dianhydride monomers are all composed of PMDA.
Example 3
The first polyimide film 10 of this example was formulated with ODA and PMDA, and the polymerization process was as in the previous examples, while the second polyimide film was formulated with diamine monomers and dianhydride monomers, TFMB and 6FDA, respectively.
Comparative example
The formulation of the first polyimide film 10 of the comparative example was composed of ODA and PMDA as in the example, while the diamine monomers of the formulation of the second polyimide film were ODA and PDA, respectively, in a ratio of 85: 15, and the dianhydride monomer was composed of PMDA.
The results of the tests of the examples and comparative examples show that when the difference in thermal expansion coefficient between the two polyimide films is greater than 9 μm/m.DEG C, the adhesiveness of the two polyimide films can be reduced and the two polyimide films can be peeled from each other. Therefore, under the reference of the polyimide films with the same thickness, whether the products can be peeled or not can be controlled through the difference of the thermal expansion coefficients of the two layers of polyimide films, and the peelability can ensure that the process of the polyimide films is easier to control in subsequent processes such as gluing and the like, so that the product percent of pass is improved.
The results of the evaluation of the releasability of the diamine monomer ratio of the first polyimide film and the second polyimide film show that the difference in Coefficient of Thermal Expansion (CTE) between the two layers can be controlled to be 9 μm/m.DEG or more by changing the diamine monomer, and the releasability can be achieved.
TABLE I evaluation of the peeling Capacity of the first polyimide film and the second polyimide film
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A strippable thin polyimide composite film comprising:
a first polyimide film having first and second surfaces; and
and the second polyimide film is attached to the first surface of the first polyimide film, wherein the difference between the thermal expansion coefficients of the first polyimide film and the second polyimide film is larger than 9 mu m/m DEG C, so that the first polyimide film and the second polyimide film can be peeled from each other.
2. The peelable thin polyimide composite film according to claim 1, wherein the first polyimide film is obtained by reacting a diamine selected from the group consisting of 4, 4 ' -diaminodiphenyl ether (ODA) and p-Phenylenediamine (PDA) with a dianhydride selected from the group consisting of pyromellitic dianhydride (PMDA) and 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride (BPDA).
3. The peelable thin polyimide composite film according to claim 1, wherein the second polyimide film is obtained by reacting a diamine selected from the group consisting of 4, 4 ' -diaminodiphenyl ether (ODA) and p-Phenylenediamine (PDA) with a dianhydride selected from the group consisting of pyromellitic dianhydride (PMDA) and 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride (BPDA).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811214312.7A CN111070832A (en) | 2018-10-18 | 2018-10-18 | Strippable polyimide composite film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811214312.7A CN111070832A (en) | 2018-10-18 | 2018-10-18 | Strippable polyimide composite film |
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| CN111070832A true CN111070832A (en) | 2020-04-28 |
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| CN201811214312.7A Pending CN111070832A (en) | 2018-10-18 | 2018-10-18 | Strippable polyimide composite film |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104015466A (en) * | 2013-02-28 | 2014-09-03 | 新日铁住金化学株式会社 | Manufacturing method for laminated component |
| CN106541652A (en) * | 2015-09-23 | 2017-03-29 | 新日铁住金化学株式会社 | Polyimides laminate structure and its manufacture method and display device and touch screen |
| CN107263984A (en) * | 2016-03-31 | 2017-10-20 | 新日铁住金化学株式会社 | Polyimide resin layer stack and its manufacture method and the polyimide film with functional layer |
| CN108136755A (en) * | 2015-10-15 | 2018-06-08 | 新日铁住金化学株式会社 | Polyimides laminated body and its manufacturing method |
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2018
- 2018-10-18 CN CN201811214312.7A patent/CN111070832A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104015466A (en) * | 2013-02-28 | 2014-09-03 | 新日铁住金化学株式会社 | Manufacturing method for laminated component |
| CN106541652A (en) * | 2015-09-23 | 2017-03-29 | 新日铁住金化学株式会社 | Polyimides laminate structure and its manufacture method and display device and touch screen |
| CN108136755A (en) * | 2015-10-15 | 2018-06-08 | 新日铁住金化学株式会社 | Polyimides laminated body and its manufacturing method |
| CN107263984A (en) * | 2016-03-31 | 2017-10-20 | 新日铁住金化学株式会社 | Polyimide resin layer stack and its manufacture method and the polyimide film with functional layer |
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Application publication date: 20200428 |