CN106515130A - Polyimide with low water absorption rate and adhesive-free board prepared by using polyimide and preparation method of adhesive-free board - Google Patents
Polyimide with low water absorption rate and adhesive-free board prepared by using polyimide and preparation method of adhesive-free board Download PDFInfo
- Publication number
- CN106515130A CN106515130A CN201611225464.8A CN201611225464A CN106515130A CN 106515130 A CN106515130 A CN 106515130A CN 201611225464 A CN201611225464 A CN 201611225464A CN 106515130 A CN106515130 A CN 106515130A
- Authority
- CN
- China
- Prior art keywords
- water absorption
- low water
- tpi
- polyimides
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- 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
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/552—Fatigue strength
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of printed circuit boards, in particular to polyimide with the low water absorption rate, and an adhesive-free board prepared by using the polyimide and a preparation method of the adhesive-free board. A fluorine-containing thermoplastic polyimide precursor is synthesized and then coated on copper foil to be subjected to thermal imidization to obtain a polyimide layer with the low water absorption rate, the polyimide layer and the copper foil form a single sided board, and then the single sided board and a TPI composite film are subjected to high temperature lamination to prepare the adhesive-free double-sided board with a relatively low water absorption rate. The prepared adhesive-free double-sided board is good in heat resistance and aging resistance and low in water absorption, the bond strength of the copper foil is good, and at the same time, the dielectric constant of the adhesive-free double-sided board is reduced.
Description
Technical field
The present invention relates to printed substrate technical field, more particularly to a kind of polyimides of low water absorption and its preparation
Without offset plate material, and the preparation method without offset plate material.
Background technology
As the development of science and technology and the overall of technical merit are improved, increasing electronic equipment tends to slimming, high collection
Develop into degree direction, therefore the consumption of flexibility coat copper plate rises year by year, simultaneously because with better function, integrated level is more preferably, to base material
Thermostability, stability, reliability put forward higher requirement.For having compared offset plate material, without offset plate material due to using high-strength
The polyimide material of Gao Mo, excellent heat resistance and electric property and obtaining in recent years quickly development.In recent years, due to scratching
The raising of property plate integrated level, in order to improve the integrated level of electronic device, the use without glue double sided timber is more and more.It is two-sided without glue
There is Copper Foil because of its both sides in plate, therefore be more easy to meet the demand of Flexible PCB manufacturer.
There is two kinds of Thermocurable polyimide and TPI simultaneously without in offset plate material at present.Thermosetting polyamides is sub-
Amine provides excellent mechanical property, hot property and dimensional stability, and TPI plays a part of bonding, is similar to
In adhesive.At present, the main flow structure without offset plate material of commercialization has following two：Cu/TPI/PI/TPI/Cu and Cu/PI/
TPI/PI/Cu.But, no matter which kind of structure, due to the water absorption rate of PI itself higher (1.5-3%), therefore in moist environment
Under, because thin film absorbs water, cause its dielectric loss to significantly increase.The sheet material for being currently employed for high-frequency high-speed is all based on greatly LCP materials,
Although the dielectric constant of LCP is 2.9, its water absorption rate is very low, therefore possesses very high stability.Low water absorption is poly- at present
Imido preparation method is primarily introduced into fluorine element, either on main chain introduces or adds as filler, in certain journey
The overall water absorption rate of material can be reduced on degree.But the addition of filler can largely reduce the mechanical performance of material,
Therefore become the focus of research using fluorine-containing monomer.There are addition fluorine-based resin particles in documents CN105599389 in heat
Inside thermosetting resin, but granule easily produces migration and disperses uneven problem, and the fluoro resin heat of documents
Solidity polyimide resin layer is placed on centre, and both sides are completely cut off, and our scheme is to prepare fluorine-containing thermoplastic poly
Imide solution and surface layer is placed on, can preferably prevent moisture from penetrating into.
Based on considerations above, this patent carries out high-temperature high-pressure by preparing fluorine-containing TPI with TPI composite membranes
Closing, barrier layer being introduced on the top layer of TPI composite membranes, the structure can significantly reduce the water absorption rate of material, meanwhile, Jie can be improved
Electrical property.
The content of the invention
An object of the present invention is to provide a kind of polyimides of low water absorption；The second object of the present invention is to carry
For a kind of polyimides preparation using above-mentioned low water absorption without offset plate material；The third object of the present invention is to provide in one kind
State the preparation method without offset plate material.There is relatively low water absorption rate by prepared by the polyimides of low water absorption without offset plate material, meanwhile,
With good dielectric properties.
For realizing the purpose, the present invention provides a kind of polyimides of low water absorption, the polyimides of the low water absorption
It is obtained Jing after imidization by fluorine-containing TPI presoma, the fluorine-containing TPI presoma is by diamidogen list
Body is polymerized with dianhydride monomer, and at least one of the diamine monomer and described dianhydride monomer contain fluorine.
It is preferred that the imidization includes hot imidization or chemical imidization.
It is preferred that the temperature of the hot imidization is 280 DEG C～340 DEG C.For example, 285 DEG C, 290 DEG C, 300 DEG C, 310
DEG C, 320 DEG C, 330 DEG C, 335 DEG C or 339 DEG C.
It is preferred that the chemical imidization adopts dehydrant/accelerator system, wherein, dehydrant is acetic anhydride, accelerator
For at least one in pyridine, triethylamine, isoquinolin.
It is preferred that the fluorine-containing TPI presoma also include solvent, the solvent be N, N- dimethyl methyls
In amide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, N-Methyl pyrrolidone any one or at least two mixing
Thing.
It is preferred that the diamine monomer is：(bis- Trifluoromethyl-biphenyl ammonia of 2,2-),(bis- Trifluoromethyl-biphenyl ether diaminos of 2,2-),
(4,4 '-bis- (amino-benzene oxygens)
Diphenyl ether),(double [the 4- (4- amino-benzene oxygens) of 2,2-
Phenyl] propane),(double [3 (4) amino-benzene oxygen] benzene of 1,3-),In (double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa of 2,2-) at least one
Kind.
It is preferred that the dianhydride monomer is：(3,3 ', 4,4 '-diphenyl ether dianhydride),(hexafluorodianhydride (6FDA)),(3,3 ', 4,4 '-biphenyl two
Acid anhydride),At least one in (2,2 ', 3,3 '-biphenyl dianhydride).
The present invention also provide a kind of low water absorption without offset plate material, including a Copper Foil, TPI composite membranes and located at described
The polyimides of the low water absorption as above between Copper Foil and the TPI composite membranes.
It is preferred that the thickness of the polyimides of the low water absorption is 2～10 μm, most preferably 3～6 μm.
It is preferred that the thickness of the TPI composite membranes is 12.5～50 μm.For example,：12.5μm、20μm、25μm、50μm.
The present invention also provides a kind of method without offset plate material for preparing low water absorption as above, the preparation method bag
Include：
(1) the fluorine-containing TPI presoma is applied on a Copper Foil hair side, is dried and hot imidization institute
State the polyimide layer that fluorine-containing TPI presoma obtains low water absorption, the polyimide layer of the low water absorption with
The Copper Foil constitutes a single sided board；And
(2) single sided board and TPI composite membranes are carried out into high temperature roll-in, obtain the low water absorption without offset plate material.
The present invention provides the method without offset plate material that another kind prepares low water absorption as above, the preparation method bag
Include：
(1) the fluorine-containing TPI presoma is carried out into chemical imidization, is then applied to a Copper Foil
On hair side, the polyimide layer of low water absorption, the polyimide layer of the low water absorption and the Copper Foil group are obtained after drying
Into a single sided board；And
(2) single sided board and TPI composite membranes are carried out into high temperature roll-in, obtain the low water absorption without offset plate material.
It is preferred that the single sided board is 380 DEG C of 350 DEG C of ￣ with the temperature of the TPI composite membranes high temperature roll-in.
Prior art is compared, and the present invention has the advantages that：
It is obtained that there is good thermostability, resistance to ag(e)ing, low water absorption without glue dual platen, possess good gluing to Copper Foil
Knotting strength, while reduce the dielectric constant without glue dual platen.Specifically, this patent is related to without offset plate material, using fluorine-containing low suction
The polyimides of water rate are not only largely reduced without the overall water absorption rate of offset plate material as Rotating fields are intercepted, while reducing
Its dielectric constant.As the polyimides of fluorine-containing low water absorption are one-component, if it is not fluorine-containing in polyimides
Material, compares by way of adding fluorine-containing filler, and the mechanical performance of the polyimides of the low water absorption of the present invention is maintained,
Its water absorption rate is greatly improved simultaneously, the light transmission without offset plate material therefore does not affect follow-up PCB with commonly without offset plate material indifference
Processing procedure.The polyimides of the low water absorption possess excellent adhesion with Copper Foil.
In addition, the present invention can use chemical imidization method, by preparing fluorine-containing TPI presoma, Ran Houjin
The gentle chemical imidization of row obtains soluble fluorine-containing TPI, and being coated directly onto on Copper Foil carries out desolventizing
The polyimides of low water absorption are obtained after process, then can be pressed with TPI composite membranes, therefore production technology is easy.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
The raw material and brief expression way for synthesizing the polyimides of low water absorption in the present invention is described below：
NMP：Polar solvent, N-Methyl pyrrolidone；
DMAc:Polar solvent, N,N-dimethylacetamide；
TFMB：(molecular weight is 320.23, CASNo to 2,2- bis- trifluoromethyl-biphenyl amine：341-58-2)；
6FODA：(molecular weight is 336.23, CAS No to 2,2- bis- trifluoromethyl-biphenyl ether diamines：344-48-9)；
BAPP：(molecular weight is 410.51, CAS No to propane to 2,2- double [4- (4- amino-benzene oxygens) phenyl]：13080-86-
9)；
TPE-R：1,3- double (3- amino-benzene oxygens) benzene (molecular weight 292.33, CAS No：10526-07-5)；
HFBAPP：(molecular weight is 518.45, CAS No to HFC-236fa to 2,2- double [4- (4- amino-benzene oxygens) phenyl]：
69563-88-8)；
BPDA：(molecular weight is 294.22, CAS No to biphenyl dianhydride：2420-87-3)；
6FDA：(molecular weight is 444.24, CAS No to hexafluorodianhydride (6FDA)：1107-00-2).
A kind of method without offset plate material for preparing low water absorption, the preparation method include：
(1) the fluorine-containing TPI presoma is applied on a Copper Foil hair side, is dried and hot imidization institute
State the polyimide layer that fluorine-containing TPI presoma obtains low water absorption, the polyimide layer of the low water absorption with
The Copper Foil constitutes a single sided board；And
(2) single sided board and TPI composite membranes are carried out into high temperature roll-in, obtain the low water absorption without offset plate material.
Another kind prepares the method without offset plate material of low water absorption, and the preparation method includes：
(1) the fluorine-containing TPI presoma is carried out into chemical imidization, is then applied to a Copper Foil
On hair side, the polyimide layer of low water absorption, the polyimide layer of the low water absorption and the Copper Foil group are obtained after drying
Into a single sided board；And
(2) single sided board and TPI composite membranes are carried out into high temperature roll-in, obtain the low water absorption without offset plate material.
Specifically, synthesize 2,2-, bis- Trifluoromethyl-biphenyl ammonia, 2,2- bis- or three during the fluorine-containing thermoplastic diamine monomer is
Methyl fluoride-Biphenyl Ether diamino, double [4- (4- amino-benzene oxygens) phenyl] propane of 2,2-, double [3 (4) amino-benzene oxygen] benzene of 1,3-
In at least one.
It is preferred that the synthesis fluorine-containing thermoplastic dianhydride monomer is 3,3 ', 4,4 '-BPDA, 3,3 ', 4,
At least one in 4 '-oxydiphthalic, hexafluorodianhydride (6FDA), 2,2 ', 3,3 '-BPDA.
Prepare without offset plate material, prepare fluorine-containing TPI presoma, the concrete side of one of which first
Method is as follows.
Synthesis example 1
Polar solvent NMP (N-Methyl pyrrolidone) and DMAc (N, N- dimethylacetamides is added in the there-necked flask of 1L
Amine) common 410g, the 6FODA and 12.32gBAPP of TFMB, 13.45g of 9.62g is weighed, above-mentioned polar solvent NMP is dissolved in
With obtain solution in DMAc, the solution is cooled down in a water bath, the BPDA and 13.33g of 20.59g is added under nitrogen flowing
6FDA, controlling reaction temperature are 15-20 DEG C, persistently stir 12-24 hours, are reacted, prepare fluorine-containing thermoplasticity polyamides
Imines presoma, solid content therein are 15%.
Synthesis example 2
Polar solvent NMP (N-Methyl pyrrolidone) and DMAc (N, N- dimethylacetamides is added in the there-necked flask of 1L
Amine) common 400g, the 6FODA and 5.85gTPER of TFMB, 16.81g of 9.62g is weighed, above-mentioned polar solvent NMP is dissolved in
With obtain solution in DMAc, the solution is cooled down in a water bath, the BPDA and 13.33g of 20.59g is added under nitrogen flowing
6FDA, controlling reaction temperature are 15-20 DEG C, persistently stir 12-24 hours, are reacted, prepare fluorine-containing thermoplasticity polyamides
Imines presoma, solid content therein are 15%.
Synthesis example 3
Polar solvent NMP (N-Methyl pyrrolidone) and DMAc (N, N- dimethylacetamides is added in the there-necked flask of 1L
Amine) common 410g, the 6FODA and 16.42gBAPP of TFMB, 13.45g of 6.41g is weighed, above-mentioned polar solvent NMP is dissolved in
With obtain solution in DMAc, the solution is cooled down in a water bath, the BPDA and 13.33g of 20.59g is added under nitrogen flowing
6FDA, controlling reaction temperature are 15-20 DEG C, persistently stir 12-24 hours, are reacted, prepare fluorine-containing thermoplasticity polyamides
Imines presoma, solid content therein are 15%；
Subsequent chemical imidization：Fluorine-containing thermoplasticity obtained above is added after taking acetic anhydride 80ml, triethylamine 40ml mixing
In polyimide precursor, stirring reaction 24h under room temperature.
Synthesis example 4
Polar solvent NMP (N-Methyl pyrrolidone) and DMAc (N, N- dimethylacetamides is added in the there-necked flask of 1L
Amine) common 421g, the 6FODA and 20.74gHFBAPP of TFMB, 10.09g of 9.61g is weighed, above-mentioned polar solvent is dissolved in
Solution is obtained in NMP and DMAc, the solution is cooled down in a water bath, add the BPDA and 13.33g of 20.59g under nitrogen flowing
6FDA, controlling reaction temperature are 15-20 DEG C, persistently stir 12-24 hours, are reacted, prepare fluorine-containing thermoplasticity polyamides
Imines presoma, solid content therein are 15%.
Synthesis example 5
Polar solvent NMP (N-Methyl pyrrolidone) and DMAc (N, N- dimethylacetamides is added in the there-necked flask of 1L
Amine) common 440g, the 6FODA and 20.74gHFBAPP of TFMB, 10.09g of 9.61g is weighed, above-mentioned polar solvent is dissolved in
Solution is obtained in NMP and DMAc, the solution is cooled down in a water bath, add the BPDA and 22.21g of 14.71g under nitrogen flowing
6FDA, controlling reaction temperature are 15-20 DEG C, persistently stir 12-24 hours, are reacted, prepare fluorine-containing thermoplasticity polyamides
Imines presoma, solid content therein are 15%.
Synthesis example 6
Polar solvent NMP (N-Methyl pyrrolidone) and DMAc (N, N- dimethylacetamides is added in the there-necked flask of 1L
Amine) common 460g, the 6FODA and 20.74gHFBAPP of TFMB, 10.09g of 9.61g is weighed, above-mentioned polar solvent is dissolved in
Solution is obtained in NMP and DMAc, the solution is cooled down in a water bath, add the BPDA and 35.54g of 5.88g under nitrogen flowing
6FDA, controlling reaction temperature are 15-20 DEG C, persistently stir 12-24 hours, are reacted, prepare fluorine-containing thermoplasticity polyamides
Imines presoma, solid content therein are 15%.
Finally enter to be about to prepared fluorine-containing TPI presoma to be applied to without offset plate material, concrete manufacture method
It is as follows.
Embodiment 1
First, by obtained fluorine-containing TPI presoma (synthesis example 1) in previous step, being coated on thickness is
On 12 μm of Copper Foil hair side, coating layer thickness is 5 μm, 160 DEG C of hot air dryings 5 minutes；Temperature programming, 300 DEG C of imidizations obtain list
Panel.
Then, by the single sided board of the polyimide layer containing low water absorption obtained above and 25 microns of TPI composite membranes patches
Close, on high temperature press with 360 DEG C at a temperature of pressed, obtain without offset plate material.
Embodiment 2
First, by obtained fluorine-containing TPI solution (synthesis example 2) in previous step, thickness is coated on for 12
μm Copper Foil hair side on, coating layer thickness is 5 μm, 160 DEG C of hot air dryings 5 minutes；Temperature programming, 300 DEG C of imidizations obtain one side
Plate.Then, the single sided board of the polyimide layer containing low water absorption obtained above is fitted with 25 microns of TPI composite membranes,
To be pressed at a temperature of 360 DEG C on high temperature press, obtain without offset plate material.
Embodiment 3
First, by obtained fluorine-containing TPI solution (synthesis example 3) in previous step, thickness is coated on for 12
μm Copper Foil hair side on, coating layer thickness is 2 μm, 160 DEG C of hot air dryings 5 minutes；Obtain single sided board.
Then, by the single sided board of the polyimide layer containing low water absorption obtained above and 25 microns of TPI composite membranes patches
Close, on high temperature press with 360 DEG C at a temperature of pressed, obtain without offset plate material.
Embodiment 4
First, by obtained fluorine-containing TPI presoma (synthesis example 4) in previous step, being coated on thickness is
On 12 μm of Copper Foil hair side, coating layer thickness is 5 μm, 160 DEG C of hot air dryings 5 minutes；Temperature programming, 330 DEG C of imidizations obtain list
Panel.
Then, by the single sided board of the polyimide layer containing low water absorption obtained above and 25 microns of TPI composite membranes patches
Close, on high temperature press with 360 DEG C at a temperature of pressed, obtain without offset plate material.
Embodiment 5
First, by obtained fluorine-containing TPI presoma (synthesis example 5) in previous step, being coated on thickness is
On 12 μm of Copper Foil hair side, coating layer thickness is 5 μm, 160 DEG C of hot air dryings 5 minutes；Temperature programming, 310 DEG C of imidizations obtain list
Panel.
Then, by the single sided board of the polyimide layer containing low water absorption obtained above and 25 microns of TPI composite membranes patches
Close, on high temperature press with 360 DEG C at a temperature of pressed, obtain without offset plate material.
Embodiment 6
First, by obtained fluorine-containing TPI presoma (synthesis example 6) in previous step, being coated on thickness is
On 12 μm of Copper Foil hair side, coating layer thickness is 5 μm, 160 DEG C of hot air dryings 5 minutes；Temperature programming, 290 DEG C of imidizations obtain list
Panel.
Then, by the single sided board of the polyimide layer containing low water absorption obtained above and 25 microns of TPI composite membranes patches
Close, on high temperature press with 360 DEG C at a temperature of pressed, obtain without offset plate material.
Embodiment 7
First, by obtained fluorine-containing TPI presoma (synthesis example 6) in previous step, being coated on thickness is
On 12 μm of Copper Foil hair side, coating layer thickness is 3 μm, 160 DEG C of hot air dryings 5 minutes；Temperature programming, 300 DEG C of imidizations obtain list
Panel.
Then, by the single sided board of the polyimide layer containing low water absorption obtained above and 12 microns of TPI composite membranes patches
Close, on high temperature press with 360 DEG C at a temperature of pressed, obtain without offset plate material.
Comparative example 1
25 microns of TPI composite membranes Copper Foil directly with 12 microns is taken, is pressed at 360 degrees Celsius.
Obtained double side flexible copper coated board in above-described embodiment and comparative example is detected into that its properties data is as follows
Shown in table.
Wherein, in table, the method for testing of each performance test is as follows：
Heat decomposition temperature (Td5%)：Adopt thermogravimetric analyzer (TGA) with the speed of 10 DEG C/min by room temperature to 800
DEG C, weight change is observed, 5% weight is obtained and is reduced temperature；
Dimensional stability is pressed：IPC-TM-650 methods 2.2.4 are tested, and wherein "+" represents expansion, and "-" represents contraction；
Thermal coefficient of expansion：Using thermomechanical analyzer (TMA), it is warmed up in TMA to the polyimides sample tested
250 DEG C, after being kept for 10 minutes at such a temperature, with the rate of temperature fall of 5 DEG C/min, obtain the thermal expansion between 240 DEG C to 100 DEG C
Coefficient；
Hydroscopicity (RMA)：By the polyimide film of 40cm × 20cm each 3, after being dried 2 hours at 120 DEG C 23 DEG C/
Stand more than or equal to 24 hours in the thermostatic constant wet chamber of 50%RH, obtained by the weight change before and after which as the following formula：
RMA (%)=[weight after (weight after weight-drying after moisture absorption)/drying] × 100%；
Anti-flammability：Tested with reference to UL94 standards；
Peel strength：Peel strength：Test according to IPC-TM-650 2.4.9 methods, 90 ° of peel angle, " T " represents copper
Paper tinsel is separated with polyimides；" M " represents that TPI is separated with low dielectric polyimide layer.
Dielectric constant：Agilent vector network analyzer N52230A, SPDR methods 1.1GHz.
Can learn from following table, it is obtained that there is good thermostability, resistance to ag(e)ing, low water absorption without glue dual platen, it is right
Copper Foil possesses good adhesion strength, while reducing the dielectric constant without glue dual platen.Specifically, this patent is related to without offset plate
Material, using the polyimides of fluorine-containing low water absorption as Rotating fields are intercepted, not only largely reduces without offset plate material entirety
Water absorption rate, while reducing its dielectric constant.As the polyimides of fluorine-containing low water absorption are one-component, it is not poly-
If fluorine-containing material in acid imide, compares by way of adding fluorine-containing filler, the polyimides of the low water absorption of the present invention
Mechanical performance is maintained, while greatly improve its water absorption rate, the light transmission without offset plate material with commonly without offset plate material indifference,
Therefore the processing procedure of follow-up PCB is not affected.The polyimides of the low water absorption possess excellent adhesion with Copper Foil.
In addition, the present invention can use chemical imidization method, by preparing fluorine-containing TPI presoma, Ran Houjin
The gentle chemical imidization of row obtains soluble fluorine-containing TPI, and being coated directly onto on Copper Foil carries out desolventizing
The polyimides of low water absorption are obtained after process, then can be pressed with TPI composite membranes, therefore production technology is easy.
More than, only presently preferred embodiments of the present invention, for the person of ordinary skill of the art, can be according to this
Bright technical scheme and technology design make other various corresponding changes and deformation, and all these changes and deformation should all belong to
In the scope of the claims in the present invention.
The present invention illustrates the method detailed of the present invention by above-described embodiment, but the invention is not limited in above-mentioned detailed
Method, that is, do not mean that the present invention has to rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should
Understand, any improvement in the present invention, addition, the concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention
Selection etc., all fall within protection scope of the present invention and it is open within the scope of.
Claims (13)
1. a kind of polyimides of low water absorption, it is characterised in that the polyimides of the low water absorption are by fluorine-containing thermoplastic poly
Acid imide presoma is obtained Jing after imidization, and the fluorine-containing TPI presoma is gathered with dianhydride monomer by diamine monomer
Conjunction is formed, and at least one of the diamine monomer and described dianhydride monomer contain fluorine.
2. polyimides of low water absorption as claimed in claim 1, it is characterised in that the imidization include hot imidization or
Chemical imidization.
3. polyimides of low water absorption as claimed in claim 2, it is characterised in that the temperature of the hot imidization is 280
DEG C～340 DEG C.
4. polyimides of low water absorption as claimed in claim 2, it is characterised in that the chemical imidization is using dehydration
Agent/accelerator system, wherein, dehydrant is acetic anhydride, and accelerator is pyridine, triethylamine, at least one in isoquinolin.
5. polyimides of low water absorption as claimed in claim 1, it is characterised in that before the fluorine-containing TPI
Driving body also includes solvent, and the solvent is DMF, N,N-dimethylacetamide, dimethyl sulfoxide, N- methyl
In ketopyrrolidine any one or at least two mixture.
6. polyimides of low water absorption as claimed in claim 1, it is characterised in that the diamine monomer is： In at least one.
7. polyimides of low water absorption as claimed in claim 1, it is characterised in that the dianhydride monomer is： In at least one.
8. a kind of low water absorption without offset plate material, including a Copper Foil, TPI composite membranes and be located at the Copper Foil and the TPI
The polyimides of the low water absorption as described in any one of claim 1～7 between composite membrane.
9. low water absorption as claimed in claim 8 without offset plate material, it is characterised in that the polyimides of the low water absorption
Thickness is 2～10 μm.
10. low water absorption as claimed in claim 8 without offset plate material, it is characterised in that the thickness of the TPI composite membranes is
12.5～50 μm.
A kind of 11. methods without offset plate material for preparing the low water absorption as described in any one of claim 8～10, its feature exist
In the preparation method includes：
(1) the fluorine-containing TPI presoma is applied on a Copper Foil hair side, is contained described in drying hot imidization
Fluorine TPI presoma obtains the polyimide layer of low water absorption, the polyimide layer of the low water absorption with it is described
Copper Foil constitutes a single sided board；And
(2) single sided board and TPI composite membranes are carried out into high temperature roll-in, obtain the low water absorption without offset plate material.
A kind of 12. methods without offset plate material for preparing the low water absorption as described in any one of claim 8～10, its feature exist
In the preparation method includes：
(1) the fluorine-containing TPI presoma is carried out into chemical imidization, is then applied to a Copper Foil hair side
On, the polyimide layer of low water absorption, the polyimide layer of the low water absorption and Copper Foil composition one is obtained after drying
Single sided board；And
(2) single sided board and TPI composite membranes are carried out into high temperature roll-in, obtain the low water absorption without offset plate material.
13. preparation methoies as claimed in claim 11, it is characterised in that the single sided board and the TPI composite membranes high-temperature roller
The temperature of pressure is 350 DEG C～380 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611225464.8A CN106515130B (en) | 2016-12-27 | 2016-12-27 | The polyimides of low water absorption a kind of and its preparation without offset plate material and the preparation method without offset plate material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611225464.8A CN106515130B (en) | 2016-12-27 | 2016-12-27 | The polyimides of low water absorption a kind of and its preparation without offset plate material and the preparation method without offset plate material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106515130A true CN106515130A (en) | 2017-03-22 |
| CN106515130B CN106515130B (en) | 2019-04-30 |
Family
ID=58338927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611225464.8A Active CN106515130B (en) | 2016-12-27 | 2016-12-27 | The polyimides of low water absorption a kind of and its preparation without offset plate material and the preparation method without offset plate material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106515130B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796867A (en) * | 2019-01-29 | 2019-05-24 | 法尔泰氪(苏州)安全科技有限公司 | A kind of preparation method of high temperature resistant type high-molecular coating |
| CN110582168A (en) * | 2019-11-08 | 2019-12-17 | 南京中鸿润宁新材料科技有限公司 | Low dielectric polyimide circuit board |
| CN110744890A (en) * | 2019-10-30 | 2020-02-04 | 深圳市弘海电子材料技术有限公司 | Fluorine polyimide high-frequency adhesive-free flexible copper clad laminate and manufacturing method thereof |
| WO2021082164A1 (en) * | 2019-10-30 | 2021-05-06 | 深圳市弘海电子材料技术有限公司 | High-frequency, low-loss, adhesive-free flexible copper clad laminate and manufacturing method thereof |
| CN113347783A (en) * | 2020-03-02 | 2021-09-03 | 广东生益科技股份有限公司 | Adhesive-free single-sided board, preparation method thereof and adhesive-free double-sided board comprising same |
| CN113619224A (en) * | 2021-07-23 | 2021-11-09 | 中山新高电子材料股份有限公司 | Low-water-absorption flexible fluorine copper-clad plate and preparation method thereof |
| WO2024070802A1 (en) * | 2022-09-27 | 2024-04-04 | 東レ株式会社 | Resin composition, cured product, and organic el display device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060115670A1 (en) * | 2002-12-13 | 2006-06-01 | Shigeru Tanaka | Thermoplastic polyimide resin film, multilayer body and method for manufacturing printed wiring board composed of same |
| CN101062980A (en) * | 2006-04-28 | 2007-10-31 | 中国科学院化学研究所 | Fluorine-containing thermoplastic polyimide polymer and preparation method thereof |
| CN102199290A (en) * | 2011-04-12 | 2011-09-28 | 中国科学院化学研究所 | Thermoplastic polyimide adhesive film as well as preparation method and application thereof |
| CN104744938A (en) * | 2013-12-27 | 2015-07-01 | 新日铁住金化学株式会社 | Polyamic acid composition, polymide, resin film and metal-clad laminate |
| CN105367794A (en) * | 2014-08-21 | 2016-03-02 | 台虹科技股份有限公司 | Soluble thermoplastic polyimide composition and laminate made therefrom |
-
2016
- 2016-12-27 CN CN201611225464.8A patent/CN106515130B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060115670A1 (en) * | 2002-12-13 | 2006-06-01 | Shigeru Tanaka | Thermoplastic polyimide resin film, multilayer body and method for manufacturing printed wiring board composed of same |
| CN101062980A (en) * | 2006-04-28 | 2007-10-31 | 中国科学院化学研究所 | Fluorine-containing thermoplastic polyimide polymer and preparation method thereof |
| CN102199290A (en) * | 2011-04-12 | 2011-09-28 | 中国科学院化学研究所 | Thermoplastic polyimide adhesive film as well as preparation method and application thereof |
| CN104744938A (en) * | 2013-12-27 | 2015-07-01 | 新日铁住金化学株式会社 | Polyamic acid composition, polymide, resin film and metal-clad laminate |
| CN105367794A (en) * | 2014-08-21 | 2016-03-02 | 台虹科技股份有限公司 | Soluble thermoplastic polyimide composition and laminate made therefrom |
Non-Patent Citations (1)
| Title |
|---|
| 吴培熙等: "《塑料制品生产工艺手册》", 31 October 2004, 化学工业出版社 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796867A (en) * | 2019-01-29 | 2019-05-24 | 法尔泰氪(苏州)安全科技有限公司 | A kind of preparation method of high temperature resistant type high-molecular coating |
| CN110744890A (en) * | 2019-10-30 | 2020-02-04 | 深圳市弘海电子材料技术有限公司 | Fluorine polyimide high-frequency adhesive-free flexible copper clad laminate and manufacturing method thereof |
| WO2021082164A1 (en) * | 2019-10-30 | 2021-05-06 | 深圳市弘海电子材料技术有限公司 | High-frequency, low-loss, adhesive-free flexible copper clad laminate and manufacturing method thereof |
| CN110582168A (en) * | 2019-11-08 | 2019-12-17 | 南京中鸿润宁新材料科技有限公司 | Low dielectric polyimide circuit board |
| CN110582168B (en) * | 2019-11-08 | 2020-03-06 | 南京中鸿润宁新材料科技有限公司 | Low dielectric polyimide circuit board |
| WO2021088353A1 (en) * | 2019-11-08 | 2021-05-14 | 南京中鸿润宁新材料科技有限公司 | Low-dielectric polyimide circuit board |
| CN113347783A (en) * | 2020-03-02 | 2021-09-03 | 广东生益科技股份有限公司 | Adhesive-free single-sided board, preparation method thereof and adhesive-free double-sided board comprising same |
| CN113347783B (en) * | 2020-03-02 | 2023-02-28 | 广东生益科技股份有限公司 | Adhesive-free single-sided board, preparation method thereof and adhesive-free double-sided board comprising same |
| CN113619224A (en) * | 2021-07-23 | 2021-11-09 | 中山新高电子材料股份有限公司 | Low-water-absorption flexible fluorine copper-clad plate and preparation method thereof |
| CN113619224B (en) * | 2021-07-23 | 2024-02-02 | 中山新高电子材料股份有限公司 | Low-water-absorption fluorine material flexible copper-clad plate and preparation method thereof |
| WO2024070802A1 (en) * | 2022-09-27 | 2024-04-04 | 東レ株式会社 | Resin composition, cured product, and organic el display device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106515130B (en) | 2019-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106515130B (en) | The polyimides of low water absorption a kind of and its preparation without offset plate material and the preparation method without offset plate material | |
| TWI716524B (en) | Copper clad laminate and printed circuit board | |
| US6320019B1 (en) | Method for the preparation of polyamic acid and polyimide | |
| CN105500828B (en) | A kind of two layers of method double side flexible copper coated board | |
| CN101516616B (en) | Laminate of heat resistant film and metal foil, and method for production thereof | |
| CN108138013A (en) | Temporary adhesion laminate film uses the substrate processome of temporary adhesion laminate film and the manufacturing method of multilayer board processome and the manufacturing method using their semiconductor devices | |
| US5728473A (en) | Adhesive polyimide siloxane composition employable for combining electronic parts | |
| TW202012501A (en) | Resin film, cover film, circuit substrate, resin-attached copper foil, metal-clad laminate, multilayer circuit substrate, polyimide and adhesive resin composition capable of addressing the tendency of higher frequency for electronic equipment | |
| CN106810692B (en) | Preparation method of polyamic acid solution and polyimide film | |
| CN105538827B (en) | A kind of two layers of method double side flexible copper coated board and preparation method thereof | |
| CN100494281C (en) | Modified maleimide end-sealed type polyimide resin composition and application thereof | |
| CN105367794B (en) | Soluble thermoplastic polyimide composition and laminate made therefrom | |
| CN101608019A (en) | A kind of preparation method of maleimide end-sealed type polyimide resin | |
| JP2022099778A (en) | Polyimide composition, resin film, laminate, cover lay film, copper foil with resin, metal-clad laminate, and circuit board | |
| CN106800908B (en) | Thermoplastic polyimide adhesive for two-layer flexible copper clad laminate and preparation method and application thereof | |
| JP2952868B2 (en) | Heat resistant adhesive | |
| JP5547874B2 (en) | Polyimide resin | |
| CN102532543B (en) | Copolymerization hot-sealing polyimide and preparation method and application thereof | |
| US20230173791A1 (en) | Low-dielectric constant, low-dissipation factor laminates including aerogel layers | |
| US20080114148A1 (en) | Manufacturing method for polyimide resin containing a norbornene group | |
| CN105398136B (en) | A kind of two layers of method double side flexible copper coated board | |
| CN107266683A (en) | A kind of thermoplastic polyimide film and prepared therefrom without glue flexible copper-clad plate | |
| JP4780548B2 (en) | Polyimide film, method for producing the same, and flexible circuit board | |
| CN103101282B (en) | A kind of preparation method of high-adhesiveness glue-free flexible copper-clad plate | |
| JP2008238788A (en) | Laminated polyimide film, its manufacturing process, and flexible circuit board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |