CN110591581B - Coating covering film and preparation method and application thereof - Google Patents
Coating covering film and preparation method and application thereof Download PDFInfo
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- CN110591581B CN110591581B CN201910877354.7A CN201910877354A CN110591581B CN 110591581 B CN110591581 B CN 110591581B CN 201910877354 A CN201910877354 A CN 201910877354A CN 110591581 B CN110591581 B CN 110591581B
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2463/00—Presence of epoxy resin
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
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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
Abstract
The invention provides a coating covering film and a preparation method and application thereof, wherein the coating covering film comprises a polyimide film and release paper arranged on one side of the polyimide film, and an adhesive is arranged between the polyimide film and the release paper; the coating covering film further comprises a protective coating arranged on the other side of the polyimide film. The coating covering film provided by the invention has excellent flexibility and thermal aging resistance, and after desmear and plasma processing, the mechanical property, folding resistance and reliability of the coating covering film are not reduced, and the processing requirement and performance requirement of a soft-hard combined board on the covering film can be met.
Description
Technical Field
The invention belongs to the technical field of covering films, and relates to a coating covering film, and a preparation method and application thereof.
Background
The electronic product has the advantages of reducing the assembly size and weight of the electronic product, avoiding online errors, increasing the assembly flexibility, improving the reliability and realizing three-dimensional installation under different assembly conditions, and is a necessary requirement for the increasingly-developed electronic products. The birth and development of a rigid circuit board (PCB) and a flexible circuit board (FPC) urge a new product of a soft-hard combined board; the soft and hard combined board is a circuit board with FPC and PCB characteristics formed by combining a soft circuit board and a rigid circuit board together according to relevant process requirements through processes such as pressing and the like. The rigid-flex circuit board integrates the advantages of the flexible circuit board and the rigid circuit board, can realize three-dimensional installation and effectively utilize the installation space. The appearance of the rigid-flex board provides a new connection mode for interconnection between electronic components, and the rigid-flex board just meets the trend along with the development of electronic information technology and the trend of lightness, thinness, shortness and multifunctionality of people's requirements on electronic equipment.
However, the hard-soft combined board has high technical threshold and complicated process, and the process flow thereof must go through the high-strength desmear and plasma treatment processes, wherein the desmear process of the circuit board factory mostly adopts the high-strength alkaline potassium permanganate solution for treatment, and the plasma inevitably damages organic materials. The common covering film adopts a polyimide film (PI film) as a base film, the polyimide is usually not alkali-resistant, and the PI film is easy to bite after desmear and plasma processes, so that the mechanical property, folding resistance and reliability of the covering film are reduced. At present, many manufacturers in the industry slow down the influence of PI film biting on the performance of a covering film in desmear and plasma procedures by increasing the thickness of a PI film, but the mode does not meet the development requirements of lightness, thinness and smallness of electronic products, and the whole covering film is hardened, and the cost of the covering film is greatly increased.
CN102083271A discloses a cover film for printed circuit board, which includes a core layer, a black composite material layer with low refractive index and an adhesive layer for adhering the cover film to the printed circuit board, the core layer is fixedly sandwiched between the composite material layer and the adhesive layer, the composite material layer is formed by mixing resin, black substance and inorganic filler, the composite material layer has low refractive index and black color, the cover film provided by the patent has good folding resistance and is suitable for flexible printed circuit boards, but the patent does not study on the reduction of PI film bite in desmear and plasma procedures. CN102143645A discloses a coverlay film and a printed circuit board having the coverlay film, wherein the coverlay film comprises a base material having a protective effect and an electrical insulating effect and an adhesive layer for adhering the coverlay film to a copper foil substrate, the base material has a first surface and a second surface opposite to each other, the adhesive layer contains a silicon-containing additive, and the adhesive layer is fixedly covered on the first surface of the base material.
Therefore, a new cover film needs to be developed to meet the processing requirements and performance requirements of the rigid-flex board on the cover film.
Disclosure of Invention
The invention aims to provide a coating covering film and a preparation method and application thereof; the coating covering film provided by the invention has excellent flexibility and thermal aging resistance, and after desmear and plasma processing, the mechanical property, folding resistance and reliability of the coating covering film are not reduced, and the processing requirement and performance requirement of a soft-hard combined board on the covering film can be met.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a coating covering film, which comprises a polyimide film and release paper arranged on one side of the polyimide film, wherein an adhesive is arranged between the polyimide film and the release paper;
the coating covering film further comprises a protective coating arranged on the other side of the polyimide film.
According to the invention, the protective coating is arranged on one side of the polyimide film, and the protective coating is removed without damaging the polyimide film after being treated by desmear and plasma procedures, so that the coating covering film provided by the invention can ensure that the mechanical property, folding resistance and the like of the covering film are not reduced after being treated by desmear and plasma procedures.
In the present invention, the protective coating is any one of a polyester coating, a polyurethane coating, or an epoxy coating.
The polyester composition used for the polyester coating layer may be any of those in the prior art, which is required to include 100 parts by weight of a polyester resin selected from VYLON 600, GK140, GK150, manufactured by toyobo co., japan, and 5 to 10 parts by weight of a curing agent; l411, L411-03 and the like which win and create production; the curing agent is any one or combination of at least two of anhydride curing agent or isocyanate curing agent, preferably, the anhydride curing agent is one or combination of at least two of tetrahydrophthalic anhydride, hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride, the isocyanate curing agent is not suitable for aromatic isocyanate curing agent, and any one or combination of two of aliphatic isocyanate curing agent and alicyclic isocyanate curing agent is selected; the aliphatic isocyanate curing agent is any one or a mixture of at least two of hexamethylene diisocyanate dimer, trimer or adduct; the alicyclic isocyanate curing agent is any one or a mixture of at least two of isophorone diisocyanate dimer, trimer or addition product. The aliphatic isocyanate curing agent or the alicyclic isocyanate curing agent is selected, so that yellowing and aging of the coating in the high-temperature multiple pressing process can be effectively avoided.
The polyurethane composition used for the polyurethane coating can be any polyurethane composition in the prior art, wherein 100 parts by weight of polyurethane resin and 8-15 parts by weight of curing agent are required, and the 8-15 parts by weight can be 10 parts by weight, 11 parts by weight, 13 parts by weight and the like; the polyurethane resin can be selected from UR-3500 and SD-5000 manufactured by Toyo Boseki Kabushiki Kaisha of Japan; the curing agent is multifunctional epoxy resin, and can be selected from ERISYS GA-240 of CVC company in America and NPPN-431A70 of south Asia company. The multifunctional epoxy resin is selected as the curing agent, so that on one hand, the heat resistance of the coating can be improved to make up for the defect of insufficient heat resistance of the polyurethane resin, and on the other hand, the multifunctional epoxy resin is used as the curing agent, so that the crosslinking density can be improved, and the resistance of the coating to desmear and plasma biting can be improved.
The epoxy resin composition used for the epoxy resin coating can be any epoxy resin composition in the prior art, wherein 100 parts by weight of epoxy resin and 20-30 parts by weight of curing agent are required, and the 20-30 parts by weight can be 22 parts by weight, 25 parts by weight, 28 parts by weight and the like; the cured coating has better flexibility and can improve the adhesion with the PI film by generally adopting flexible epoxy resin and flexible curing agent, and particularly, the epoxy resin can be selected from one of HyPox UA10 produced by CVC in the United states and NPER-133L produced by south Asia company; the curing agent is amine curing agent, and can be selected from Versamid 125 of Gabriel company and Baxxodur EC301 of BASF company.
The resin composition of the present invention is prepared by dissolving the components in a solvent, wherein the solvent may be any one or a combination of at least two of butanone, acetone, cyclohexanone, toluene or N, N' -dimethylformamide.
Because the processing procedure of the rigid-flex board needs a plurality of high-temperature pressing procedures, the protective coating selected by the invention has good thermal aging resistance, and the corrosion resistance of the protective coating selected by the invention is moderate, if the corrosion resistance is too good, the protective coating cannot be effectively removed when the desmear procedure is carried out, so that the whole covering film becomes thick, and the folding resistance and the flexing resistance become poor; if the corrosion resistance is too poor, the PI film bites during desmear and plasma processes, resulting in a thinner coating film and a lower performance. Thus, the polyester coating, polyurethane coating, or epoxy coating selected in the present invention has moderate corrosion resistance.
In the present invention, the thickness of the protective coating is 3-5 μm, such as 3.5 μm, 4 μm, 4.5 μm, and the like.
If the thickness of the protective coating is thicker, the protective coating on the surface of the covering film is left in a large area after being treated by desmear and plasma procedures, so that the integral thickness of the covering film is increased, and the folding resistance of the obtained soft and hard combined board is reduced; if the thickness of the protective coating is small, the polyimide film is difficult to protect after desmear and plasma processes.
In the present invention, it is desirable that the protective coating be completely removed without damaging the polyimide film, and in the actual process, the protective coating may remain on the polyimide film in a very small area with a very small amount without affecting the properties of the polyimide, and it is considered that the protective coating has been removed as much as possible.
Preferably, the protective coating has a visible light transmission of 85% or more, such as 87%, 89%, 90%, 91%, 92%, 95%, and the like.
Preferably, the protective coating has a haze of 4% or less, e.g., 1%, 2%, 3%, 4%, etc.
In order not to affect the apparent morphology of the cover film, the visible light transmission and haze of the protective coating should be moderate.
Preferably, the glass transition temperature of the protective coating is 20-50 ℃, such as 22 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and the like.
If the glass transition temperature is too high, the cover film will be hard; if the glass transition temperature is too low, the surface of the protective coating tends to be sticky, which affects the handling properties.
In the present invention, the thickness of the polyimide film is 10 to 50 μm, for example, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or the like.
In the present invention, the thickness of the adhesive is 15 to 50 μm, for example, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, etc.
In the invention, the adhesive is a modified epoxy resin adhesive.
In a second aspect, the present invention provides a method for preparing a coating overlay film according to the first aspect, the method comprising the steps of:
(1) coating a resin composition solution of a protective coating on one side of a polyimide film, drying and curing to obtain a protective coating-polyimide film;
(2) and coating an adhesive on the other side of the obtained polyimide film, drying, and then compounding with release paper to obtain the coating covering film.
In the present invention, the polyimide film is subjected to corona treatment before the coating in step (1).
In the present invention, the solid content of the resin composition solution is 40 to 50% by weight, for example, 42%, 45%, 47%, 48%, 49% by weight, and the like.
In a third aspect, the present invention provides a use of the coating overlay film according to the first aspect in a rigid-flex board.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the protective coating is arranged on one side of the polyimide film, and is removed without damaging the polyimide film after being treated by desmear and plasma procedures, so that the coating covering film provided by the invention can ensure that the mechanical property, folding resistance and the like of the covering film are not reduced after being treated by desmear and plasma procedures;
(2) if the thickness of the protective coating is thicker, the protective coating on the surface of the covering film is left in a large area after being treated by desmear and plasma procedures, so that the integral thickness of the covering film is increased, and the folding resistance of the obtained soft and hard combined board is reduced; if the thickness of the protective coating is thinner, the polyimide film is difficult to protect after desmear and plasma processing;
(3) the coating film provided by the invention is treated by desmear and plasma procedures, the mechanical property, folding resistance and reliability of the coating film are not reduced, and the coating film has excellent aging resistance, wherein the heat resistance is more than 280 ℃, the tensile strength is more than 93MPa, and the folding resistance is more than 142 times.
Drawings
Fig. 1 is a schematic structural diagram of a coating covering film provided in example 1 of the present invention.
Wherein, 1-release paper; 2-an adhesive; 3-a polyimide film; 4-protective coating.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The modified epoxy adhesive is an adhesive for SF305C type covering films produced by health and technology; the polyimide film can be one of HN type PI film of DuPont and TH type PI film of Taiwan Damai; the release paper can be Taibo PEK type release paper.
Example 1
A coating covering film is composed of release paper 1, an adhesive 2, a polyimide film 3 and a protective coating 4 which are sequentially arranged.
Wherein the adhesive is a modified epoxy adhesive with the thickness of 15 μm, and the polyimide film is a Taiwan Damai TH type PI film with the thickness of 12.5 μm; the protective coating is a polyester coating with a thickness of 3 μm.
The preparation method comprises the following steps:
(1) stirring and dissolving 100 parts by weight of VYLON 600 and 5 parts by weight of tetrahydrophthalic anhydride by using butanone, uniformly mixing, and controlling the solid content to be 40 wt% to obtain a polyester composition solution;
(2) carrying out corona treatment on a PI film with the thickness of 12.5 microns, then coating a polyester composition solution on the PI film subjected to corona treatment, drying at 160 ℃ for 3 minutes, and curing at 120 ℃ for 2 hours to obtain a protective coating-polyimide film;
(3) and coating a 15-micron modified epoxy adhesive on the other side of the obtained PI film, drying at 160 ℃ for 3 minutes, and compounding with release paper at 70 ℃ to obtain a coating covering film.
Example 2
A coating covering film is composed of release paper, an adhesive, a polyimide film and a protective coating which are sequentially arranged.
Wherein the adhesive is a modified epoxy adhesive with the thickness of 15 μm, and the polyimide film is a Taiwan Damai TH type PI film with the thickness of 12.5 μm; the protective coating is a polyester coating with a thickness of 4 μm.
The preparation method comprises the following steps:
(1) stirring and dissolving 100 parts by weight of GK140 and 7 parts by weight of hexahydrophthalic anhydride by using acetone, uniformly mixing, and controlling the solid content to be 40 wt% to obtain a polyester composition solution;
(2) carrying out corona treatment on a PI film with the thickness of 12.5 microns, then coating a polyester composition solution on the PI film subjected to corona treatment, drying at 160 ℃ for 3 minutes, and curing at 120 ℃ for 2 hours to obtain a protective coating-polyimide film;
(3) and coating a 15-micron modified epoxy adhesive on the other side of the obtained PI film, drying at 160 ℃ for 3 minutes, and compounding with release paper at 70 ℃ to obtain a coating covering film.
Example 3
A coating covering film is composed of release paper, an adhesive, a polyimide film and a protective coating which are sequentially arranged.
Wherein the adhesive is a modified epoxy adhesive with the thickness of 15 μm, and the polyimide film is a Taiwan Damai TH type PI film with the thickness of 12.5 μm; the protective coating is a polyester coating with a thickness of 5 μm.
The preparation method comprises the following steps:
(1) stirring and dissolving 100 parts by weight of L411-03 and 7 parts by weight of methylhexahydrophthalic anhydride by using acetone, uniformly mixing, and controlling the solid content to be 45 wt% to obtain a polyester composition solution;
(2) carrying out corona treatment on a PI film with the thickness of 12.5 microns, then coating a polyester composition solution on the PI film subjected to corona treatment, drying at 160 ℃ for 3 minutes, and curing at 120 ℃ for 2 hours to obtain a protective coating-polyimide film;
(3) and coating a 15-micron modified epoxy adhesive on the other side of the obtained PI film, drying at 160 ℃ for 3 minutes, and compounding with release paper at 70 ℃ to obtain a coating covering film.
Examples 4 to 5
The difference from example 1 is that the thickness of the final protective coating layer was controlled to be 2 μm (example 4) and 6 μm (example 5) by controlling the coating amount of the polyester composition.
Example 6
A coating covering film is composed of release paper, an adhesive, a polyimide film and a protective coating which are sequentially arranged.
Wherein the adhesive is a modified epoxy adhesive with the thickness of 15 μm, and the polyimide film is a Taiwan Damai TH type PI film with the thickness of 12.5 μm; the protective coating is a polyester coating with a thickness of 4 μm.
The preparation method comprises the following steps:
(1) stirring and dissolving an adduct of 100 parts by weight of L411 and 10 parts by weight of hexamethyldiisocyanate with acetone, uniformly mixing, and controlling the solid content to be 45 wt% to obtain a polyester composition solution;
(2) carrying out corona treatment on a PI film with the thickness of 12.5 microns, then coating a polyester composition solution on the PI film subjected to corona treatment, drying at 160 ℃ for 3 minutes, and curing at 120 ℃ for 2 hours to obtain a protective coating-polyimide film;
(3) and coating a 15-micron modified epoxy adhesive on the other side of the obtained PI film, drying at 160 ℃ for 3 minutes, and compounding with release paper at 70 ℃ to obtain a coating covering film.
Examples 7 to 8
The difference from example 1 is that in this example, the polyester composition is replaced with a polyurethane composition, specifically as follows:
100 parts by weight of SD-5000 and 9 parts by weight of ERISYS GA-240 were dissolved in toluene with stirring, and mixed uniformly to control the solid content to 45% by weight, to obtain a polyurethane composition (example 7).
100 parts by weight of UR-3500 and 15 parts by weight of NPPN-431A70 were dissolved in N, N' -dimethylformamide with stirring and mixed uniformly to control the solid content to 50% by weight, to obtain a polyurethane composition (example 8).
Examples 9 to 10
The difference from example 1 is that in this example, the polyester composition is replaced with an epoxy resin composition, specifically as follows:
100 parts by weight of HyPox UA10 and 20 parts by weight of Versamid 125 were dissolved with stirring in acetone, and mixed uniformly so as to control the solid content to 45% by weight, to obtain an epoxy resin composition (example 9).
100 parts by weight of NPER-133L and 30 parts by weight of Baxxodur EC301 were dissolved with cyclohexanone while stirring, and mixed uniformly so as to control the solid content to 48% by weight, to obtain an epoxy resin composition (example 10).
Example 11
A coating covering film is composed of release paper, an adhesive, a polyimide film and a protective coating which are sequentially arranged.
Wherein the adhesive is a modified epoxy adhesive with the thickness of 25 μm, and the polyimide film is an American DuPont HN type PI film with the thickness of 25 μm; the protective coating is a polyurethane coating with a thickness of 4 μm.
The preparation method comprises the following steps:
(1) dissolving 100 parts by weight of UR-3500 and 15 parts by weight of ERISYS GA-240 in toluene under stirring, and uniformly mixing, wherein the solid content is controlled to be 45 wt%, so as to obtain a polyurethane composition;
(2) carrying out corona treatment on a PI film with the thickness of 25 microns, then coating a polyester composition solution on the PI film subjected to corona treatment, drying at 120 ℃ for 3 minutes, and curing at 150 ℃ for 1 hour to obtain a protective coating-polyimide film;
(3) and coating a 25-micron modified epoxy adhesive on the other side of the obtained PI film, drying at 160 ℃ for 3 minutes, and compounding with release paper at 70 ℃ to obtain a coating covering film.
Example 12
A coating covering film is composed of release paper, an adhesive, a polyimide film and a protective coating which are sequentially arranged.
Wherein the adhesive is a modified epoxy adhesive with the thickness of 50 μm, and the polyimide film is a Taiwan Damai TH type PI film with the thickness of 50 μm; the protective coating is a polyurethane coating with a thickness of 5 μm.
The preparation method comprises the following steps:
(1) stirring and dissolving 100 parts by weight of SD-5000 and 13 parts by weight of NPPN-431A70 by using N, N' -dimethylformamide, and uniformly mixing to control the solid content to be 50 wt% so as to obtain a polyurethane composition;
(2) carrying out corona treatment on a PI film with the thickness of 50 micrometers, then coating a polyurethane composition solution on the PI film subjected to corona treatment, drying for 3 minutes at 160 ℃, and curing for 1 hour at 160 ℃ to obtain a protective coating-polyimide film;
(3) and coating a 50-micron modified epoxy adhesive on the other side of the obtained PI film, drying at 160 ℃ for 3 minutes, and compounding with release paper at 70 ℃ to obtain a coating covering film.
Example 13
The difference from example 11 is that the cover film protective coating in this example is a silicone coating.
The preparation method comprises the following steps:
(1) stirring and dissolving 100 parts by weight of hydroxyl-terminated silicone oil and 5 parts by weight of ethyl orthosilicate by using toluene, uniformly mixing, and controlling the solid content to be 45 wt% to obtain an organic silicon composition;
(2) carrying out corona treatment on a PI film with the thickness of 25 microns, then coating an organic silicon composition solution on the PI film subjected to corona treatment, drying at 120 ℃ for 3 minutes, and curing at 150 ℃ for 1 hour to obtain a protective coating-polyimide film;
(3) and coating a 25-micron modified epoxy adhesive on the other side of the obtained PI film, drying at 160 ℃ for 3 minutes, and compounding with release paper at 70 ℃ to obtain a coating covering film.
Example 14
The difference from example 12 is that the cover film protective coating in this example is a polyacrylate coating.
The preparation method comprises the following steps:
(1) stirring and dissolving 100 parts by weight of polyacrylate resin and 8 parts by weight of hexamethylene diisocyanate adduct by using butanone, uniformly mixing, and controlling the solid content to be 50 wt% to obtain a polyacrylate composition;
(2) carrying out corona treatment on a 50-micron PI film, then coating a polyacrylate composition solution on the PI film subjected to corona treatment, drying at 160 ℃ for 3 minutes, and curing at 160 ℃ for 1 hour to obtain a protective coating-polyimide film;
(3) and coating a 50-micron modified epoxy adhesive on the other side of the obtained PI film, drying at 160 ℃ for 3 minutes, and compounding with release paper at 70 ℃ to obtain a coating covering film.
Comparative example 1
The difference from example 10 is that the cover film in this comparative example does not include a protective coating.
Performance testing
The samples provided in examples 1-14 and comparative example 1 were tested for performance by the following method:
(1) thickness: tearing off release paper from the cover film samples prepared in the embodiment and the comparative example, oppositely pressing the cover film samples, mutually adhering the modified epoxy glue layers, curing the protective coating on the outer side at 160 ℃ for 1 hour, sequentially performing desmear and plasma procedure treatment, measuring the total thickness by a ten-thousandth micrometer, and calculating the thickness of a single-layer cover film;
(2) heat resistance: tearing off release paper from a cover film sample prepared in the embodiment and the comparative example, pressing the release paper with two sides of a copper foil, curing a protective coating on the outer side at 160 ℃ for 1 hour, sequentially performing desmear and plasma procedures, testing the ultimate dip-soldering temperature, namely, respectively soaking the cover film sample in tin furnaces at different temperatures for 20 seconds, taking out the cover film sample, observing the cover film sample, and detecting whether layering and foaming exist; the test temperature starts from 280 ℃, the test is carried out by taking 10 ℃ as a step for gradual temperature rise, and the previous temperature when layered foaming occurs is the ultimate dip-soldering temperature;
(3) tensile strength: tearing off release paper from the cover film samples prepared in the examples and the comparative examples, pressing the cover film samples against the modified epoxy glue layers, adhering the modified epoxy glue layers with each other, curing the protective coating layer at 160 ℃ for 1 hour, sequentially performing desmear and plasma procedures, and testing by using a universal material testing machine according to ASTM D-882;
(4) folding endurance: the coverlay film samples of examples and comparative examples were peeled off release paper and laminated on both sides of the wiring, the protective coating was on the outside, and after curing at 160 ℃ for 1 hour, the test was carried out after treatment in the order of desmear and plasma, according to JIS C-6471 under the test conditions of 0.5 kg/0.8R.
The test results are shown in table 1:
TABLE 1
The protective coating thickness of examples 1-3 and 6-12 is 3-5 μm, and in the optimum range of the present invention, the coating is completely removed after desmear and plasma treatment, and the PI film can be effectively protected, so that the mechanical properties, folding endurance and heat resistance are not reduced, the heat resistance is above 350 ℃, the tensile strength is above 174MPa, and the folding endurance is above 385 times. The thicknesses of the protective coatings of the embodiments 4-5 are respectively 2 μm and 6 μm, which are not in the optimal range of the invention, and the protective coating of the embodiment 4 can not effectively protect the PI film after being processed by desmear and plasma procedures, so that the PI film is bitten and the total thickness is reduced; the protective coating of example 5 was too thick and could not be completely removed after desmear and plasma treatments, resulting in an increase in overall thickness, and therefore, the mechanical properties, folding resistance and heat resistance of both were superior to those of comparative example 1 (after treatment), but not as good as examples 1-3 and examples 6-12. Example 13 employs a silicone coating, which has excellent corrosion resistance, and after desmear and plasma treatment, the coating cannot be completely removed, thereby affecting mechanical properties and folding endurance; example 14, which uses a polyacrylate coating, has poor corrosion resistance and does not effectively protect the PI film after desmear and plasma treatments, resulting in reduced mechanical properties, heat resistance and folding endurance.
As can be seen from the comparative example performance test, comparative example 1 has no protective coating, and the mechanical properties, heat resistance and folding resistance thereof are greatly reduced after desmear and plasma treatment.
Therefore, only by selecting the optimal coating resin composition and thickness range of the invention, the coating film with excellent performance can be obtained, and the application requirements of the rigid-flexible printed circuit board can be met.
The applicant states that the present invention is illustrated by the above examples of the coating overlay film of the present invention and the method of preparation and use thereof, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (11)
1. The coating covering film is characterized by comprising a polyimide film and release paper arranged on one side of the polyimide film, wherein an adhesive is arranged between the polyimide film and the release paper;
the coating covering film further comprises a protective coating arranged on the other side of the polyimide film;
the protective coating is any one of a polyester coating, a polyurethane coating or an epoxy coating;
the polyester composition used for the polyester coating comprises 100 parts by weight of polyester resin and 5-10 parts by weight of curing agent;
the polyester resin comprises any one or a combination of at least two of VYLON 600, GK140 and GK150 produced by Toyo Boseki Co., Ltd, L411 produced by winning creation and L411-03 produced by winning creation;
the 5-10 parts by weight of curing agent comprises an anhydride curing agent and/or an isocyanate curing agent;
the isocyanate curing agent comprises an aliphatic isocyanate curing agent and/or an alicyclic isocyanate curing agent;
the polyurethane composition used for the polyurethane coating comprises 100 parts by weight of polyurethane resin and 8-15 parts by weight of curing agent;
the polyurethane resin includes UR-3500 and/or SD-5000 manufactured by Toyo Boseki Kabushiki Kaisha of Japan;
8-15 parts by weight of a curing agent is multifunctional epoxy resin;
the epoxy resin composition used for the epoxy coating comprises 100 parts by weight of epoxy resin and 20-30 parts by weight of curing agent;
the epoxy resin comprises HyPox UA10 produced by CVC in the United states and/or NPER-133L produced by south Asia company;
the 20-30 parts by weight of curing agent is amine curing agent;
the thickness of the protective coating is 3-5 μm.
2. The coating coverfilm of claim 1, wherein the protective coating has a visible light transmission of 85% or more.
3. The coated coverfilm of claim 1, wherein the protective coating has a haze of 4% or less.
4. The coating coverfilm of claim 1, wherein the glass transition temperature of the protective coating is 20-50 ℃.
5. The coating coverfilm of claim 1, wherein the polyimide film has a thickness of 10-50 μ ι η.
6. The coated coverfilm of claim 1, wherein the adhesive has a thickness of 15-50 μ ι η.
7. The coating coverfilm of claim 1, wherein the adhesive is a modified epoxy adhesive.
8. Method for the preparation of the coating mulch film according to any one of the claims 1-7 characterized in that the preparation method comprises the steps of:
(1) coating a resin composition solution of a protective coating on one side of a polyimide film, drying and curing to obtain a protective coating-polyimide film;
(2) and coating an adhesive on the other side of the obtained polyimide film, drying, and then compounding with release paper to obtain the coating covering film.
9. The production method according to claim 8, wherein the polyimide film is subjected to corona treatment before the coating in step (1).
10. The production method according to claim 8, wherein the solid content of the resin composition solution is 40 to 50 wt%.
11. Use of a coating overlay film according to any of claims 1-7 in a rigid-flex board.
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| CN113881362A (en) * | 2021-11-02 | 2022-01-04 | 芜湖徽氏新材料科技有限公司 | Low surface energy adhesive tape for lithium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201721100U (en) * | 2010-07-16 | 2011-01-26 | 广东生益科技股份有限公司 | Black covering film |
| CN108368412A (en) * | 2016-03-15 | 2018-08-03 | 东洋纺株式会社 | Use the adhesive composition of polyamide-imide resin |
| CN108659724A (en) * | 2018-06-11 | 2018-10-16 | 滁州德泰电子科技有限公司 | A kind of covering membrane preparation method of high-radiation super-thin PI films and adhesive |
| JP2019102503A (en) * | 2017-11-28 | 2019-06-24 | 藤森工業株式会社 | Coverlay film and electronic apparatus using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102083271B (en) * | 2009-11-26 | 2015-06-03 | 昆山雅森电子材料科技有限公司 | Cover membrane for printed circuit board |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201721100U (en) * | 2010-07-16 | 2011-01-26 | 广东生益科技股份有限公司 | Black covering film |
| CN108368412A (en) * | 2016-03-15 | 2018-08-03 | 东洋纺株式会社 | Use the adhesive composition of polyamide-imide resin |
| JP2019102503A (en) * | 2017-11-28 | 2019-06-24 | 藤森工業株式会社 | Coverlay film and electronic apparatus using the same |
| CN108659724A (en) * | 2018-06-11 | 2018-10-16 | 滁州德泰电子科技有限公司 | A kind of covering membrane preparation method of high-radiation super-thin PI films and adhesive |
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