CN108314782A - The polyimide film and circuit board of resin combination and the application resin combination - Google Patents
The polyimide film and circuit board of resin combination and the application resin combination Download PDFInfo
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- CN108314782A CN108314782A CN201710032496.4A CN201710032496A CN108314782A CN 108314782 A CN108314782 A CN 108314782A CN 201710032496 A CN201710032496 A CN 201710032496A CN 108314782 A CN108314782 A CN 108314782A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
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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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
A kind of resin combination, the resin combination contain modified polyimide high-molecular compound, epoxy resin and solvent, and the chemical structural formula of the modified polyimide high-molecular compound is
Description
Technical field
The present invention relates to a kind of resin combination, using the polyimide film and circuit board of the resin combination.
Background technology
In the big data epoch, the information processing of electronic product is constantly towards the side of signal transmission high frequency and high-speed digitization
To development.There is good signal transmission quality simultaneously under conditions of high frequency signal transmission to ensure electronic product, need
It is in impedance matching condition between transmission line and its electronic component connected in the copper-foil conducting electricity of flexible PCB, avoids making
Phenomena such as at signal reflex, scattering, decaying and delay.Jie of the material for the glue-line being in contact with conducting wire in flexible PCB
Electric constant and dielectric loss factor are to influence a key factor of high-frequency transmission impedance matching.It is used for flexible printing in the prior art
Polyimide film in circuit board is generally prepared using two ammoniac compounds with diacid compound anhydride, and Yin Qinei includes
Polar functional group so that the dielectric constant of the film layer is often higher than 3.0, and flexible PCB is caused to be unable to reach high-frequency signal biography
Defeated impedance matching affects the high frequency and high-speed digitization of signal transmission.
Invention content
In view of this, it is necessary to provide a kind of low-k and heat-resist resin combinations.
A kind of polyimide film using the resin combination is provided in addition, there is a need to.
In addition, there is a need to circuit board made from a kind of application resin combination of offer.
A kind of resin combination, the resin combination contain modified polyimide high-molecular compound, epoxy resin and molten
The chemical structural formula of agent, the modified polyimide high-molecular compound is
The wherein described Ar ' groups are selected from phenyl, and (chemical structural formula is：), (chemical structural formula is diphenyl ether group：), (chemical structural formula is biphenyl group：), hexichol hexafluoro isopropyl groups (chemistry knot
Structure formula is：), (chemical structural formula is benzophenone group：) and (change of diphenyl sulphone (DPS) group
Learning structural formula is：At least one of), in the resin combination, the modified polyimide macromolecule
The content of compound is 100 parts by weight, the molar ratio of the epoxy resin and the modified polyether high-molecular compound is 0.1~
1。
Further, the epoxy resin is respectively selected from chemical constitutionAnd
At least one of resin.
Further, the resin combination further includes porous material, in the resin combination, described hole material
Content is 0.1~10 parts by weight.
Further, the solvent is n,N-dimethylacetamide.
A kind of polyimide film using the resin combination, the polyimide film is by above-mentioned resin combination through pre-
After baking again elevated cure be made, between the modified polyimide high-molecular compound in the resin combination by with asphalt mixtures modified by epoxy resin
Fat reacts to form chemical crosslinking network structure.
Circuit board made from a kind of application resin combination comprising circuit board and be incorporated into the circuit board extremely
The polyimide film on a few surface, the polyimide film by above-mentioned resin combination through elevated cure is made again after prebake conditions,
Between modified polyimide high-molecular compound in the resin combination chemical crosslinking net is formed by being reacted with epoxy resin
Network structure.
A method of preparing polyimide film using resin combination as described above comprising following steps：By institute
It states resin combination and carries out elevated cure again after prebake conditions.
Further, it after the resin combination toasts 30 minutes at a temperature of 140 degrees Celsius, then is taken the photograph successively 180
Family name's degree, 200 set degree Celsius and 220 degrees Celsius at a temperature of cure respectively 2 hours the polyimide film be made.
The resin combination of the present invention, it is poly- due to containing the modification in polyimide film made from the resin combination
Acid imide high-molecular compound is linked with acrylate group on the branch of the modified polyimide high-molecular compound, institute
It states acrylate group to react with the epoxy resin during subsequent cure so that in the polyimide film cured not
Have secondary alcohol polar group, reduces the dielectric constant of the polyimide film.And the resin combination is in heating shape
During at polyimide film, between the modified polyimide high-molecular compound by thereon it is acrylate-based with it is described
Epoxy resin reacts and is bonded together, and forms chemical crosslinking network structure, can further increase the resin combination
The crosslink density of object so that the network structure of the chemical crosslinking in the polyimide film in subsequent conventional circuit board
The processing procedures such as scolding tin in will not fail, improve the heat-resisting of the polyimide film of circuit board made from the resin combination
Property.In addition, due to being connected to the miscellaneous -10- phospho hetero phenanthrenes-of 9,10- dihydro-9-oxies among the modified polyimide high-molecular compound
10- oxide groups, so that polyimide film obtained has excellent flame retardancy.
Specific implementation mode
The resin combination of better embodiment of the present invention is mainly used for the base of circuit board (such as rigid-flex combined board)
In material, glue-line or cover film.The resin combination contains modified polyimide high-molecular compound, epoxy resin and solvent.
In the resin combination, the content of the modified polyimide high-molecular compound is 100 parts by weight, the epoxy resin with
The molar ratio of the modified polyimide high-molecular compound is 0.1~1.
The chemical structural formula of the modified polyimide high-molecular compound is
Wherein Ar ' groups can be selected from but be not limited only to phenyl (chemical structural formula be：), diphenyl ether group (chemical structural formula
For：), (chemical structural formula is biphenyl group：), hexichol hexafluoro isopropyl groups (change
Learning structural formula is：), (chemical structural formula is benzophenone group：) and diphenyl sulfone
(chemical structural formula is for group：At least one of).In present embodiment, the modified polyimide high score
The polymerization degree n of sub- compound is 1~50.
In the present embodiment, the modified polyimide high-molecular compound is prepared by following step：
1)、
2)、
3)、
The epoxy resin can be selected from but be not limited only to chemical constitutionAnd
At least one of resin.
In present embodiment, the solvent is n,N-dimethylacetamide (DMAc).In other embodiments, described molten
Agent can also be the organic solvent of other dissolving ethers high-molecular compounds commonly used in the art and epoxy resin.
In present embodiment, the resin combination may also include porous material.In present embodiment, described hole material
It can be selected from the molecular sieve of the model MCM-41 of Tianjin Nan Hua catalyst Co., Ltd production.It is described in the resin combination
The content of porous material is 0.1~10 parts by weight.
It is prepared by the resin combination：By modified polyimide high-molecular compound, the epoxy resin of the modification
And solvent is added according to scheduled ratio in reaction bulb, is mixed, makes the modified polyimide high-molecular compound, epoxy
Resin and solvent are sufficiently mixed dissolving, obtain the resin combination.
One kind polyimide film made from above-mentioned resin combination.The polyimide film is by by the resin combination
Elevated cure is made object again after prebake conditions.In present embodiment, the resin combination toasts at a temperature of 140 degrees Celsius
After 30 minutes, then set degree Celsius and 220 degrees Celsius of at a temperature ofs cure 2 hours obtained institutes respectively 180 degrees Celsius, 200 successively
State polyimide film.
One kind circuit board made from above-mentioned resin combination comprising an at least circuit board and be incorporated into the circuit
The polyimide film on a substrate at least surface.The polyimide film by the resin combination by being coated on the circuit base
An at least surface for plate, elevated cure is made again after prebake conditions.In present embodiment, the tree being coated in circuit board
After oil/fat composition toasts 30 minutes at a temperature of 140 degrees Celsius, then set degree Celsius 180 degrees Celsius, 200 successively and 220 take the photograph
Cure respectively at a temperature of family name's degree 2 hours and the polyimide film is made.
Due to containing the modified polyimide high-molecular compound in polyimide film made from the resin combination,
Acrylate group is linked on the branch of the modified polyimide high-molecular compound, the acrylate group is follow-up
It is reacted with the epoxy resin in solidification process so that do not have secondary alcohol polar group in the polyimide film cured,
Reduce the dielectric constant of the polyimide film.And the resin combination is in the process for being thermally formed polyimide film
In, between the modified polyimide high-molecular compound by the acrylate-based and epoxy resin thereon reacts
It is bonded together, forms chemical crosslinking network structure, the crosslink density of the resin combination can be further increased to make
The network structure for obtaining the chemical crosslinking in the polyimide film will not in the processing procedures such as the scolding tin of subsequent conventional circuit board
Failure, improves the heat resistance of the polyimide film of circuit board made from the resin combination.In addition, due to the modification
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group is connected among polyimides high-molecular compound, so that
Polyimide film obtained has excellent flame retardancy.And due to containing porous material in resin combination so that be formed by curing
Polyimide film in band hole, enter convenient for air, and then further reduced the dielectric constant of the polyimide film.
The present invention is specifically described below by Examples and Comparative Examples.
Embodiment 1
Sequentially added in the first reaction bulb DOPO, 3.0g para aminoacetophenone of 4.8g, 4.8g o-aminophenols,
0.19g p-methyl benzenesulfonic acids and 10g dimethyl sulfoxide (DMSO)s and stirring and dissolving, are then heated in nitrogen atmosphere under 100 degrees Celsius
Preparing chemical structural formula within 12 hours isThe first product.
The N- methyl of the first products of 1.0g, the pyromellitic acid anhydride of 0.7g, 6.8g are sequentially added in the second reaction bulb
Pyrrolidones and 3.4g diformazan benzo stirring and dissolvings are then heated 20 hours under 140 degrees Celsius in nitrogen atmosphere and are returned
Stream water removal prepares chemical structural formula and isThe second product.
Sequentially added in third reaction bulb the second products of 10g, the 2- methacrylic anhydrides of 3.5g, 0.1g sodium acetates and
The n,N-dimethylacetamide and stirring and dissolving of 100g, is then heated 12 hours in nitrogen atmosphere at a temperature of 80 degrees Celsius
Preparing chemical structural formula isModified polyimide macromolecule chemical combination
Object (I).
100g modified polyimides high-molecular compound (I) and the modified polyamides are sequentially added in the 4th reaction bulb
The chemical structural formula that the molar ratio of imines high-molecular compound (I) is 1 isEpoxy resin
And the n,N-dimethylacetamide of 100g, stirring and dissolving configure and complete resin combination.The viscosity of the resin combination is
50000cps。
Embodiment 2
The pyromellitic acid anhydride of the 0.7g in embodiment 1 is replaced with to the double phthalic acids of 4,4 '-oxygen of 0.7g
The acid anhydride and constant chemical structural formula for preparing of other conditions isModified polyimide
High-molecular compound (II).
100g modified polyimides high-molecular compound (II) and the modified polyimide are sequentially added in reaction bulb
The chemical structural formula that the molar ratio of high-molecular compound (II) is 1 is
Epoxy resin and 100g n,N-dimethylacetamide, stirring and dissolving i.e. configure complete resin combination.The resin combination
The viscosity of object is 40000cps.
Embodiment 3
The pyromellitic acid anhydride of the 0.7g in embodiment 1 is replaced with to 3,4,3 ', the 4 '-bibenzene tetracarboxylics of 0.7g
The dianhydride and constant chemical structural formula for preparing of other conditions isModification it is poly-
Acid imide high-molecular compound (III).
100g modified polyimides high-molecular compound (III) is sequentially added in reaction bulb and the modified polyamides is sub-
The chemical structural formula that the molar ratio of amine high-molecular compound (III) is 1 isEpoxy resin and
The n,N-dimethylacetamide of 100g, stirring and dissolving configure and complete resin combination.The viscosity of the resin combination is
48000cps。
Embodiment 4
The pyromellitic acid anhydride of the 0.7g in embodiment 1 is replaced with to 4,4 '-(the hexafluoro isopropyl alkene) two of 0.7g
The anhydride phthalic acid and constant chemical structural formula for preparing of other conditions is
Modified polyimide high-molecular compound (IV).
100g modified polyimides high-molecular compound (IV) and the modified polyimide are sequentially added in reaction bulb
The chemical structural formula that the molar ratio of high-molecular compound (IV) is 1 isEpoxy resin and
The n,N-dimethylacetamide of 100g, stirring and dissolving configure and complete resin combination.The viscosity of the resin combination is
23000cps。
Embodiment 5
The pyromellitic acid anhydride of the 0.7g in embodiment 1 is replaced with to 3,3 ', the 4,4 '-benzophenone four of 0.7g
The formic acid dianhydride and constant chemical structural formula for preparing of other conditions is's
Modified polyimide high-molecular compound (V).
100g modified polyimides high-molecular compound (V) and the modified polyimide are sequentially added in reaction bulb
The chemical structural formula that the molar ratio of high-molecular compound (V) is 1 isEpoxy resin and
The n,N-dimethylacetamide of 100g, stirring and dissolving configure and complete resin combination.The viscosity of the resin combination is
50000cps。
Embodiment 6
The pyromellitic acid anhydride of the 0.7g in embodiment 1 is replaced with to 3,3 ', the 4,4 '-diphenyl sulfones four of 0.7g
The carboxylic diacid acid anhydride and constant chemical structural formula for preparing of other conditions is
Modified polyimide high-molecular compound (VI).
100g modified polyimides high-molecular compound (VI) and the modified polyimide are sequentially added in reaction bulb
The chemical structural formula that the molar ratio of high-molecular compound (VI) is 1 is's
The n,N-dimethylacetamide of epoxy resin and 100g, stirring and dissolving configure and complete resin combination.The resin combination
Viscosity be 40000cps.
Embodiment 7
Modified polyether high-molecular compound (III) and the modified polyamides in 100g embodiments 3 are sequentially added in reaction bulb
The chemical structural formula that the molar ratio of imines high-molecular compound (III) is 1 is
Epoxy resin, the Tianjin 0.5g Nan Hua catalyst Co., Ltd production model MCM-41 molecular sieve and 100g N, N- bis-
Methylacetamide is uniformly mixed i.e. configuration and completes resin combination.The viscosity of the resin combination is 48000cps.
Comparative example 1
The p-phenylenediamine of 70g, 3,4,3 ', the 4 '-bibenzene tetracarboxylic dianhydrides of 30g and 100g are sequentially added in reaction bulb
N,N-dimethylacetamide, stirring and dissolving configure and complete resin combination.The viscosity of the resin combination is 40000cps.
Comparative example 2
3,4,3 ', the 4 '-connection of p-phenylenediamine, 30g through 2- methacrylic acid anhydride modifications of 70g are sequentially added in reaction bulb
The n,N-dimethylacetamide of pyromellitic dianhydride and 100g, stirring and dissolving configure and complete resin combination.The resin group
The viscosity for closing object is 20561cps.
Comparative example 3
Sequentially added in reaction bulb the p-phenylenediamine of 70g, 3,4,3 ', the 4 '-bibenzene tetracarboxylic dianhydrides of 30g, 0.5g days
The molecular sieve of the model MCM-41 of Jin Nanization catalyst Co., Ltd production and the n,N-dimethylacetamide of 100g, stirring are mixed
It closes uniformly to configure and completes resin combination.The viscosity of the resin combination is 25656cps.
10 kinds of resin combinations prepared by Examples 1 to 7 and comparative example 1~3 are respectively coated on the one of 10 copper foils
Surface forms 10 kinds of circuit boards, and 7 kinds of resin combinations prepared by the Examples 1 to 7 by copper foil surface are under 140 degrees Celsius
Prebake conditions cure 2 hours under 180 degrees Celsius, 200 degrees Celsius and 220 degrees Celsius respectively successively after 30 minutes is respectively formed 7 kinds
Polyimide film, 3 kinds of resin combinations prepared by the comparative example 1~3 by copper foil surface divide in 140 degrees Celsius of lower prebake conditions 30
Cure 1 hour under 350 degrees Celsius after clock and is respectively formed 3 kinds of polyimide films.
3 kinds of polyamides that the 7 kinds of polyimide films and comparative example 1~3 be correspondingly formed to above-described embodiment 1~7 are correspondingly formed
The dielectric constant D of imines filmkWith dielectric absorption DfIt is tested respectively.Copper-stripping strength test is carried out to above-mentioned 10 kinds of circuit boards
And drift tin heat resistance test.Testing result please refers to the performance detection data of table 1.Wherein, if drift tin heat resistance test condition is big
When equal to 320 DEG C, 10sec, glue-line do not generate blistering, stripping phenomena such as, then float tin heat resistance test result be " passing through ", table
Bright circuit board reaches the requirement of heat resistance.
Measured value of the table 1 about the related data of above-mentioned each circuit board mesoglea
3 kinds of glue-lines that resin combination compared to comparative example 1-3 it can be seen from table one is respectively formed, the present invention are real
Applying 7 kinds of glue-lines that the resin combination of example 1~7 is respectively formed has lower dielectric constant Dk.In addition, the embodiment of the present invention 1
4 kinds of glue-lines that~7 resin combination is respectively formed have good heat resistance.
Due to containing the modified polyimide high-molecular compound in polyimide film made from the resin combination,
Acrylate group is linked on the branch of the modified polyimide high-molecular compound, the acrylate group is follow-up
It is reacted with the epoxy resin in solidification process so that do not have secondary alcohol polar group in the polyimide film cured,
Reduce the dielectric constant of the polyimide film.And the resin combination is in the process for being thermally formed polyimide film
In, between the modified polyimide high-molecular compound by the acrylate-based and epoxy resin thereon reacts
It is bonded together, forms chemical crosslinking network structure, the crosslink density of the resin combination can be further increased to make
The network structure for obtaining the chemical crosslinking in the polyimide film will not in the processing procedures such as the scolding tin of subsequent conventional circuit board
Failure, improves the heat resistance of the polyimide film of circuit board made from the resin combination.In addition, due to the modification
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group is connected among polyimides high-molecular compound, so that
Polyimide film obtained has excellent flame retardancy.And due to containing porous material in resin combination so that be formed by curing
Polyimide film in band hole, enter convenient for air, and then further reduced the dielectric constant of the polyimide film.
In addition, for those of ordinary skill in the art, can be made with technique according to the invention design other each
It is kind corresponding to change and deformation, and all these changes and deformation should all belong to the protection domain of the claims in the present invention.
Claims (8)
1. a kind of resin combination, it is characterised in that：The resin combination contains modified polyimide high-molecular compound, asphalt mixtures modified by epoxy resin
The chemical structural formula of fat and solvent, the modified polyimide high-molecular compound is
The wherein described Ar ' groups are selected from phenyl, and (chemical structural formula is：), (chemical structural formula is diphenyl ether group：), (chemical structural formula is biphenyl group：), hexichol hexafluoro isopropyl groups (chemistry knot
Structure formula is：), (chemical structural formula is benzophenone group：) and (change of diphenyl sulphone (DPS) group
Learning structural formula is：At least one of), in the resin combination, the modified polyimide macromolecule
The content of compound is 100 parts by weight, the molar ratio of the epoxy resin and the modified polyether high-molecular compound is 0.1~
1。
2. resin combination as described in claim 1, it is characterised in that：The epoxy resin is respectively selected from chemical constitution And's
At least one of resin.
3. resin combination as described in claim 1, it is characterised in that：The resin combination further includes porous material, institute
It states in resin combination, the content of described hole material is 0.1~10 parts by weight.
4. resin combination as described in claim 1, it is characterised in that：The solvent is DMAC N,N' dimethyl acetamide.
5. a kind of polyimide film, it is characterised in that：The polyimide film is by as described in Claims 1 to 4 any one
Elevated cure is made resin combination again after prebake conditions, the modified polyimide high-molecular compound in the resin combination
Between by being reacted with epoxy resin to form chemical crosslinking network structure.
6. a kind of circuit board comprising circuit board and the polyimide film for being incorporated into a circuit board at least surface,
It is characterized in that：The polyimide film is heated up by the resin combination described in Claims 1 to 4 any one after prebake conditions again
Solidification is made, by reacting to be formed with epoxy resin between the modified polyimide high-molecular compound in the resin combination
Learn cross-linked network structure.
7. a kind of method that resin combination using as described in Claims 1 to 4 any one prepares polyimide film, packet
Include following steps：It will be made in elevated cure after resin combination progress prebake conditions.
8. preparation method as claimed in claim 7, it is characterised in that：The resin combination is at a temperature of 140 degrees Celsius
After baking 30 minutes, then set degree Celsius and 220 degrees Celsius of at a temperature ofs cure 2 hours and make respectively 180 degrees Celsius, 200 successively
Obtain the polyimide film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032496.4A CN108314782A (en) | 2017-01-16 | 2017-01-16 | The polyimide film and circuit board of resin combination and the application resin combination |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032496.4A CN108314782A (en) | 2017-01-16 | 2017-01-16 | The polyimide film and circuit board of resin combination and the application resin combination |
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| Publication Number | Publication Date |
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| CN108314782A true CN108314782A (en) | 2018-07-24 |
Family
ID=62892028
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710032496.4A Pending CN108314782A (en) | 2017-01-16 | 2017-01-16 | The polyimide film and circuit board of resin combination and the application resin combination |
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| Country | Link |
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| CN (1) | CN108314782A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111298303A (en) * | 2020-03-09 | 2020-06-19 | 成都石墨烯应用产业技术研究院有限公司 | Graphene physiotherapy assembly and application thereof |
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Application publication date: 20180724 |