CN109503836A - The preparation method of polyamic acid resin and the preparation method of double-faced flexible copper-clad plate - Google Patents
The preparation method of polyamic acid resin and the preparation method of double-faced flexible copper-clad plate Download PDFInfo
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- CN109503836A CN109503836A CN201811141350.4A CN201811141350A CN109503836A CN 109503836 A CN109503836 A CN 109503836A CN 201811141350 A CN201811141350 A CN 201811141350A CN 109503836 A CN109503836 A CN 109503836A
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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
-
- 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
- B32B15/088—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 comprising polyamides
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
-
- 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
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber 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
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
-
- 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
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
Abstract
The invention discloses the preparation method of polyamic acid resin resin and the preparation methods of double-faced flexible copper-clad plate; polyamic acid resin is the preparation method is as follows: under nitrogen protection; aromatic diamine monomer is dissolved in aprotic polar solvent; in 25 DEG C~50 DEG C stirring and dissolvings, the aromatic diamine monomer solution that mass concentration is 6%~9% is obtained；After aromatic diamine monomer solution is cooled to 0 DEG C~25 DEG C, aromatic diacid anhydride monomer is added, the aromatic diamine monomer and the molar ratio of aromatic diacid anhydride monomer are 1:0.95~1:1.05, defoaming is stood after polymerization reaction 6~10 hours, up to polyamic acid resin, and disclose the preparation method that double-faced flexible copper-clad plate is prepared using this polyamic acid resin.The reaction of polyamic acid resin preparation of the present invention is simply controllable, and polyamic acid resin has excellent heat resistance, endurance；The double-faced flexible copper-clad plate being prepared is heat-resist, and dimensional stability is strong, and endurance can be excellent, and the performances such as peel strength, elongation are excellent.
Description
Technical field
The present invention relates to technical field of electronic materials, the preparation method and double-faced flexible of specially a kind of polyamic acid resin
The preparation method of copper-clad plate.
Background technique
Flexible printed wiring board, abbreviation soft board have many advantages, such as soft, light, thin and deflection, quickly walk in electronic product
To under light, thin, short, small trend, it has been widely used in the electricity such as laptop, digital camera, mobile phone, night crystal display at present
Subdomains.
Traditional soft plate material mainly with polyimide film, bonding agent, copper foil three-decker based on, bonding agent is with asphalt mixtures modified by epoxy resin
Based on rouge and acrylic compounds, the soft board material of this structure is had the following deficiencies:
1, poor heat resistance: long-term use temperature is limited in 100 DEG C~200 DEG C, and when temperature is greater than 120 DEG C, three layers have glue soft board base
The tear strength of plate is because bonding agent deteriorates so that tear strength acutely declines, and generally when doing SMT welding on soft board, temperature is most
More than 300 DEG C, in addition bonding processes temperature is also up to 20 DEG C in Rigid Flex production, for three layers of soft board substrate and uncomfortable
It is limited using field for high temperature process；
2, the size changing rate of glue soft board is affected by temperature very greatly for three layers, dimensional stability is poor；
3, endurance is poor: three layers have glue soft board substrate because the chemical resistance of bonding agent is bad, and tear strength increases with the time
It grows and declines to a great extent.
In recent years, manufacture double-faced flexible copper-clad plate mainly has following two methods:
(1) sputtering method/galvanoplastic: using polyimide film as substrate, one layer of metal is plated in polyimide film using vacuum splashing and plating
After layer, then with galvanoplastic, increase copper thickness.But sputtering method for and its require it is very high, the yield of product is very low, and machine at
This is very high, and no glue flexible double-sided flexible copper-clad plate peel strength produced is very low (0.3~0.5Kgf/cm), and copper foil is easy to
It falls off from substrate.
(2) it presses method: using the thermoplasticity of TPI at high temperature, PI and copper foil press no glue flexibility is made covers
Copper sheet, this method to machine require it is very high, prepared by the dimensional stability without glue double-faced flexible copper-clad plate it is poor, peel strength
It is lower.
By the above as it can be seen that the poor heat resistance of bonding agent used by preparing, weak endurance is limitation soft printing electricity
The key factor of road plate application field, so as to cause current double-faced flexible copper-clad plate and preparation there are problems that it is main there are three: one,
Dimensional stability is poor；Two, peel strength is lower；Three, complex process, preparation cost are high.It therefore is expansion flexible printer circuit
The application range of plate, the above problem in the urgent need to address.
Summary of the invention
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, on the one hand provide one kind
The preparation method of polyamic acid resin, reaction is simple and controllable, the polyamic acid resin being prepared have excellent heat resistance,
Endurance；On the other hand a kind of double-faced flexible copper-clad plate being prepared based on polyamic acid resin is provided, with existing soft print
For printed circuit board compared to heat-resist, dimensional stability is strong, and endurance can be excellent, and peel strength, elongation, tensile strength and heat
The performances such as the coefficient of expansion are excellent.
According to invention in a first aspect, a kind of preparation method of polyamic acid resin, the polyamic acid resin is by as follows
Method is prepared: under nitrogen protection, aromatic diamine monomer being dissolved in aprotic polar solvent, is stirred at 25 DEG C~50 DEG C
Dissolution is mixed, the aromatic diamine monomer solution that mass concentration is 6%~9% is obtained；Aromatic diamine monomer solution is cooled to 0 DEG C
After~25 DEG C, aromatic diacid anhydride monomer is added, the aromatic diamine monomer and the molar ratio of aromatic diacid anhydride monomer are
1:0.95~1:1.05 stands defoaming to get polyamic acid resin after polymerization reaction 6~10 hours.It is anti-that the present invention carries out chemistry
Also aromatic diamine monomer and aromatic diacid anhydride monomer can be pre-processed respectively before answering, since aromatic diamine is put for a long time
It sets easy to oxidize in air, is purified by sublimation purification method, remove oxide, while aromatic diacid acid anhydride is placed in 170
DEG C drying in oven 5 hours, extra moisture is removed, excess moisture is avoided, synthetic resin is caused to hydrolyze.The present invention selects fragrance
Race's diamine monomer and aromatic diacid anhydride monomer are opened and a kind of prepare the new of polyamic acid resin as polymerization reaction starting material
Method, and reaction has the characteristics that simple, controllable, the polyamic acid resin that polymerization reaction obtains is with excellent heat resistance and resistance to
The property changed.Accelerate aromatic diamine monomer to dissolve in aprotic polar solvent under the conditions of 25 DEG C~50 DEG C, aromatic series two is added
Aromatic diamine monomer solution is cooled down before anhydride monomers, controls the intensity of polymerization reaction, makes reaction that there is controllability.
Further, the polymeric reaction condition is ice-water bath, and speed of agitator is 100~250 revs/min.Pass through ice water
Bath control polymerization reaction intensity is uniformly mixed aromatic diamine monomer and aromatic diacid anhydride monomer to sufficiently by stirring
Reaction, mixing speed are lower than 100 revs/min, then are easy to appear the biggish polymer/solid of volume, and mixing speed is higher than 250 revs/min
Clock then causes reactant to splash out.
Further, the aromatic diamine monomer is p-phenylenediamine, 4,4'- diaminodiphenyl ether, the bis- [4- (4- of 2,2-
Amino-benzene oxygen) phenyl] propane, bis- (4- amino-benzene oxygen) benzene of 1,3-, one in bis- (4- amino-benzene oxygen) diphenyl sulphone (DPS)s of 4,4'-
Kind is a variety of.Said components preferred reagent purity grade is electron level, and the resin being synthetically prepared has good high temperature resistant
Property, and common sale in the market, it is easy to obtain.
Further, the aromatic diacid anhydride monomer be pyromellitic dianhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides,
3,3', 4,4'- benzophenone tetracarboxylic dianhydrides, 4,4- oxygen double phthalic anhydrides, diphenyl sulphone (DPS) -3,3`, 4,4`- tetracarboxylic dianhydrides
One of or it is a variety of.Said components preferred reagent purity grade is electron level, and the poly- of generation is polymerize with aromatic diamine monomer
Amide acid resin has excellent heat resistance and endurance.
Further, the aprotic polar solvent is N-Methyl pyrrolidone, dimethyl acetamide, dimethylformamide
One of.Aprotic polar solvent has very strong solvability, can be completely dissolved the aromatic diamine monomer and virtue of addition
Fragrant race's dianhydride monomer.
Further, the adding manner of the aromatic diacid anhydride monomer be first be added the total anhydride molar ratio of Zhan be 30%~
After 80%, stirring 1~2 hour, surplus is added and is stirred for 5~8 hours.Aromatic diacid anhydride monomer is distributed and is added, it is ensured that
The aromatic diacid anhydride monomer being added sufficiently is reacted with aromatic diamine monomer, and being all added at one time can be because reacting excessively
Fierce and gel, does not meet production requirement, leads to material scrap.
The preparation method reaction of above-mentioned polyamic acid resin is simple and controllable, and the polyamic acid resin being prepared has excellent
Different heat resistance, endurance.
Another invention of the present invention provides a kind of preparation method of double-faced flexible copper-clad plate, the double-faced flexible copper-clad plate base
It is prepared in the described in any item polyamic acid resins of the claims 1 to 6, preparation method is as follows:
Step 1, synthesized polyamic acid resin is coated on PI film, the temperature range in baking oven at 140 DEG C~170 DEG C is pre-
Baking removes solvent, and polyamic acid resin layer is formed on PI film；It is gone out the solvent in polyamic acid resin by prebake conditions,
So that it is formed by curing polyamic acid resin layer in PI film upper half, guarantees that it does not allow with good viscosity, and in following process
It is easily-deformable；
Step 2, under nitrogen, the PI film after step 1 processing is pressed with copper foil in 350 DEG C~380 DEG C temperature ranges, i.e.,
Obtain single side force fit plate；Press copper foil closely with PI film by polyamic acid resin layer under the high temperature conditions, this operating procedure needs
It to carry out under a nitrogen atmosphere, by nitrogen protection polyamic acid resin, avoid aoxidizing under hot conditions；
Step 3, the single side force fit plate that step 2 is prepared is placed in the high-temperature oxidation-free baking oven under nitrogen protection from 80 DEG C of ladders
Degree is warming up to 320 DEG C~350 DEG C, makes the polyamic acid resin layer imidizate completely to get single-side coated copper plate；Pass through gradient
Heating heating is polyamic acid resin imidizate, and imide group cellular construction is contained in main chain, improves polyamic acid tree
The heat-resistant stable of rouge；
Step 4, synthesized polyamic acid resin is coated on the PI film another side for the single-side coated copper plate that step 3 is prepared,
In 140 DEG C~170 DEG C of temperature range prebake conditions in baking oven, solvent is removed, forms polyamic acid resin layer on PI film；
Step 5, under nitrogen, the PI film after step 4 processing is pressed with copper foil in 350 DEG C~380 DEG C temperature ranges, i.e.,
Obtain two-sided force fit plate；
Step 6, the single side force fit plate that step 5 is prepared is placed in the high-temperature oxidation-free baking oven under nitrogen protection from 80 DEG C of ladders
Degree is warming up to 320 DEG C~350 DEG C, makes the polyamic acid resin layer imidizate completely to get double-faced flexible copper-clad plate.
Double-faced flexible copper-clad plate of the invention is prepared based on above-mentioned polyamic acid resin, with polyamic acid resin
Make PI film as binder and copper foil is compound that double-faced flexible copper-clad plate is prepared, due to using with superior heat resistance performance and resistance to
The polyamic acid resin for changing performance replaces the bonding agent of poor heat resistance, makes the heat resistance of double-faced flexible copper-clad plate being prepared
Quite excellent, long-term use temperature uses its tear strength up to 300 DEG C or more under hot conditions or for a long time for a long time
Change it is also minimum, and due to polyamic acid resin influenced by temperature change it is small, to be prepared with polyamic acid resin double
Face flexible copper-clad plate also has good dimensional stability, heated under the conditions of 150 DEG C 30 minutes change in size 0.05% it
It is interior, fine rule road is made and has quite big help.And the preparation manipulation of this double-faced flexible copper-clad plate mainly includes coating, goes
Solvent, pressing, imidizate, preparation process is simple, can be completed using conventional equipment, reduces the investment of production equipment, reduces
Production cost.
Further, the prebake conditions time is 5~10 minutes.Prebake conditions are mainly for by dry out solvent, overlong time
Production efficiency is reduced, the time is too short to cause solvent not dried completely, then polyamic acid resin layer is easy to deform during the pressing process.
Further, the PI film thickness is 12.5 μm, and the copper thickness is 17~19 μm, the polyamic acid resin
Layer is with a thickness of 6~7 μm.PI film routinely selects 12.5 μm, and controls the polyamic acid resin thickness for being coated on PI film upper and lower surface
Degree is 6~7 μm, makes overall thickness control in 24.5~26.5 μ ms, and selecting copper thickness is 17~19 μm, guarantees preparation
The pliability of obtained double-faced flexible copper-clad plate reduces base material thickness.
Further, the gradient increased temperature is 80 ± 5 DEG C 30 minutes dry, 120 ± 5 DEG C drying 60 minutes, respectively at
Distinguish at 160 ± 5 DEG C, 200 ± 5 DEG C, 250 ± 5 DEG C 30 minutes, it is then 20 minutes dry in 300 ± 5 DEG C, then at 320 DEG C~
350 DEG C drying 60 minutes.Keep polyamic acid resin layer imidizate complete by gradient increased temperature, it is strong to form endurance, heat resistance
Adhesive layer, improve double-faced flexible copper-clad plate heat resistance and endurance.
Double-faced flexible copper-clad plate is prepared using the heat resistance and endurance of polyamic acid resin in the present invention, due to not having
The bonding agent of poor heat resistance, so heat resistance is quite excellent, and long-term use temperature is up to 300 DEG C or more, long-time high temperature
Under the conditions of, the tear strength variation of double-faced flexible copper-clad plate is small, does not need using bonding agent to extend its service life and expand
Big application range, especially suitable for meeting the pb-free solder of environmental requirement.Simultaneously as using polyamide between PI film and copper foil
Acid resin is not easy to deform under the high temperature conditions as bonding agent, is improved the dimensional stability of double-faced flexible copper-clad plate, is made it
It is low to press equipment requirement, production equipment cost is reduced, and good dimensional stability has phase for fine rule road processing procedure
It is helped when big, the electronic product of high-order such as LCD, plasm TV, COF substrate etc. all emphasize graph thinning, high density, high ruler now
Very little stable, high temperature resistant and reliability, so under the trend development that information electronic product gradually moves towards light and short, no glue soft board
The mainstream in market will be become.And the excellent endurance of polyamic acid resin keeps the endurance of double-faced flexible copper-clad plate quite excellent,
Tear strength is without substantially changeing under long-time.And to prepare base material thickness used when double-faced flexible copper-clad plate thin and poly- by the present invention
Amic acid resin layer coating thickness is thin, guarantees that finished product integral thickness is small, meets requirement of the market to flexible printed wiring board specification.
And the double-faced flexible copper-clad plate being prepared polyamic acid resin layer after overetch keeps smooth, elongation >=35%,
Tensile strength >=250MPa has stronger peel strength, peel strength >=1.3kgf/cm.
Detailed description of the invention
Fig. 1 is the folding strength of the preparation method of polyamic acid resin of the present invention and the preparation method of double-faced flexible copper-clad plate
The line pattern of testing two-sided flexible copper-clad plate.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, below with reference to embodiment to this hair
It is bright to be described in further detail.
Embodiment 1
A kind of preparation method of polyamic acid resin, the polyamic acid resin are prepared as follows to obtain:
(1) in the three neck vessel of logical nitrogen, 1095 grams of N-Methyl pyrrolidones is added, adds 43.5 grams and (is equivalent to 0.40
Mole) p-phenylenediamine and bis- (4- amino-benzene oxygen) benzene of 29.0 grams of (being equivalent to 0.10 mole) 1,3-, the stirring and dissolving at 50 DEG C
To be completely dissolved to get mass concentration be 6.6% aromatic diamine solution；
(2) after the aromatic diamine solution of step 1 being cooled to 10 DEG C, 119.2 grams of (being equivalent to 0.405 mole) 3,3' are added,
4,4'- bibenzene tetracarboxylic dianhydride, 31.0 grams of addition (is equivalent to 0.10 to rub after stirring 2 hours with 100 revs/min of revolving speed
You) the double phthalic anhydrides of 4,4- oxygen, are continued to be stirred 8 hours with 100 revs/min of revolving speed, obtain polyamic acid resin；
(3) polyamic acid resin that step 2 is prepared stands defoaming, and measuring solid content is 15.3%, and viscosity is
18300CPS。
A kind of preparation method of double-faced flexible copper-clad plate, the double-faced flexible copper-clad plate are prepared as follows to obtain:
(1) it is coated with above-mentioned polyamic acid resin using automatic coating machine on the Du Pont 50EN type PI film with a thickness of 12.5 μm, it is thick
Degree is 7 μm, is placed in baking oven and toasts 10 minutes for 160 DEG C, removes solvent；
(2) under a nitrogen, by the PI film after step 1 processing and with a thickness of 18 μm of copper foils (model: (day mine) JE BHY-22BT
Type 1/2oz RA Copper) under nitrogen protection 360 DEG C pressing to get single side force fit plate；
(3) 30 minutes dry with 80 DEG C in the high-temperature oxidation-free baking oven under nitrogen protection, 120 DEG C drying 60 minutes, in
It is 30 minutes dry at 160 DEG C, 200 DEG C, 250 DEG C, it is then 20 minutes dry in 300 DEG C, then at 330 DEG C of dry 60 minute minutes
Gradient increased temperature is carried out, the single side force fit plate imidizate that step 2 is prepared is complete；
(4) polyamic acid resin synthesized by being coated on the single side force fit plate after step 3 imidizate, coating thickness 7um,
160 DEG C of baking 10 minutes in baking oven remove solvent；
(5) under a nitrogen, by the PI film and 18 μm of copper foil (models: (day mine) JE BHY-22BT type 1/2oz after step 4 processing
RA Copper) under nitrogen protection 360 DEG C pressing to get two-sided force fit plate；
(6) 30 minutes dry with 80 DEG C in the high-temperature oxidation-free baking oven under nitrogen protection, 1205 DEG C drying 60 minutes, in
It is 30 minutes dry at 160 DEG C, 200 DEG C, 250 DEG C, it is then 20 minutes dry in 300 DEG C, it is carried out within dry 60 minutes then at 330 DEG C
Gradient increased temperature keeps two-sided force fit plate imidizate complete, obtains double-faced flexible copper-clad plate.
Embodiment 2
A kind of preparation method of polyamic acid resin, the polyamic acid resin are prepared as follows to obtain:
(1) in the three neck vessel of logical nitrogen, 1530 grams of dimethyl acetamides is added, adds 60.5 grams and (is equivalent to 0.03 to rub
You) 4,4'- diaminodiphenyl ether and bis- (4- amino-benzene oxygen) diphenyl sulphone (DPS)s of 86.5 grams of (being equivalent to 0.20 mole) 4,4'-, in 40
At DEG C stirring and dissolving to be completely dissolved to get mass concentration be 9.0% aromatic diamine solution；
(2) after the aromatic diamine solution of step 1 being cooled to 0 DEG C, 43.5 grams (being equivalent to 0.20 mole) benzene tetramethyl is added
107.5 grams of (being equivalent to 0.30 mole) diphenyl sulphone (DPS)s -3,3` are added after stirring 2 hours with 150 revs/min of revolving speed in acid anhydrides,
4,4`- tetracarboxylic dianhydrides are continued to be stirred 7 hours with 150 revs/min of revolving speed, obtain polyamic acid resin；
(3) polyamic acid resin that step 2 is prepared stands defoaming, and measuring solid content is 15.2%, and viscosity is
12700CPS。
A kind of preparation method of double-faced flexible copper-clad plate, the double-faced flexible copper-clad plate are prepared as follows to obtain:
(1) it is coated with above-mentioned polyamic acid resin using automatic coating machine on the Du Pont 50EN type PI film with a thickness of 12.5 μm, it is thick
Degree is 7 μm, is placed in baking oven and toasts 10 minutes for 170 DEG C, removes solvent；
(2) under a nitrogen, by the PI film after step 1 processing and with a thickness of 17 μm of copper foils (model: (day mine) JE JTCS type 1/
2oz ED Copper) under nitrogen protection 380 DEG C pressing to get single side force fit plate；
(3) 30 minutes dry with 85 DEG C in the high-temperature oxidation-free baking oven under nitrogen protection, 125 DEG C drying 60 minutes, in
It is 30 minutes dry at 165 DEG C, 205 DEG C, 255 DEG C, it is then 20 minutes dry in 305 DEG C, then at 340 DEG C of dry 60 minute minutes
Gradient increased temperature is carried out, the single side force fit plate imidizate that step 2 is prepared is complete；
(4) polyamic acid resin synthesized by being coated on the single side force fit plate after step 3 imidizate, coating thickness 6um,
170 DEG C of baking 10 minutes in baking oven remove solvent；
(5) under a nitrogen, by the PI film after step 4 processing and with a thickness of 17 μm of copper foils (model: (day mine) JE JTCS type 1/
2oz ED Copper) under nitrogen protection 380 DEG C pressing to get two-sided force fit plate；
(6) 30 minutes dry with 85 DEG C in the high-temperature oxidation-free baking oven under nitrogen protection, 125 DEG C drying 60 minutes, in 165
DEG C, 205 DEG C, it is 30 minutes dry at 255 DEG C, it is then 20 minutes dry in 305 DEG C, then at 340 DEG C of dry 60 minute minute progress
Gradient increased temperature keeps two-sided force fit plate imidizate complete, obtains double-faced flexible copper-clad plate.
Embodiment 3
A kind of preparation method of polyamic acid resin, the polyamic acid resin are prepared as follows to obtain:
(1) in the three neck vessel of logical nitrogen, 1080 grams of dimethyl acetamides is added, adds 30.5 grams and (is equivalent to 0.15 to rub
You) 4,4'- diaminodiphenyl ether and 38.0 grams of (being equivalent to 0.35 mole) p-phenylenediamine, stirring and dissolving is to complete at 50 DEG C
Dissolve the aromatic diamine solution for being 6.3% to get mass concentration；
(2) after the aromatic diamine solution of step 1 being cooled to 20 DEG C, 27.5 grams (being equivalent to 0.125 mole) benzene four is added
99.0 grams of (being equivalent to 0.35 mole) 3,3', 4,4'- are added after stirring 1.5 hours with 250 revs/min of revolving speed in formic anhydride
Bibenzene tetracarboxylic dianhydride is continued to be stirred 6 hours with 250 revs/min of revolving speed, obtains polyamic acid resin；
(3) polyamic acid resin that step 2 is prepared stands defoaming, and measuring solid content is 15.8%, and viscosity is
15300CPS。
A kind of preparation method of double-faced flexible copper-clad plate, the double-faced flexible copper-clad plate are prepared as follows to obtain:
(1) it is coated with above-mentioned polyamic acid resin using automatic coating machine on the Du Pont 50ENS type PI film with a thickness of 12.5 μm, it is thick
Degree is 6 μm, is placed in baking oven and toasts 5 minutes for 160 DEG C, removes solvent；
(2) under a nitrogen, by the PI film after step 1 processing and with a thickness of 19 μm of copper foils (model: Feitian CF-T9FB-HTE type
1/2oz ED Copper) under nitrogen protection 370 DEG C pressing to get single side force fit plate；
(3) 30 minutes dry with 75 DEG C in the high-temperature oxidation-free baking oven under nitrogen protection, 115 DEG C drying 60 minutes, in
It is 30 minutes dry at 155 DEG C, 195 DEG C, 245 DEG C, it is then 20 minutes dry in 295 DEG C, then at 350 DEG C of dry 60 minute minutes
Gradient increased temperature is carried out, the single side force fit plate imidizate that step 2 is prepared is complete；
(4) synthesized polyamic acid resin is coated on the single side force fit plate after step 3 imidizate, coating thickness is 6 μm,
160 DEG C of baking 5 minutes in baking oven remove solvent；
(5) under a nitrogen, by the PI film after step 4 processing and with a thickness of 19 μm of copper foils (model: Feitian CF-T9FB-HTE type
1/2oz ED Copper) under nitrogen protection 370 DEG C pressing to get two-sided force fit plate；
(6) 30 minutes dry with 75 DEG C in the high-temperature oxidation-free baking oven under nitrogen protection, 115 DEG C drying 60 minutes, in 155
DEG C, 195 DEG C, it is 30 minutes dry at 245 DEG C, it is then 20 minutes dry in 295 DEG C, then at 350 DEG C of dry 60 minute minute progress
Gradient increased temperature keeps two-sided force fit plate imidizate complete, obtains double-faced flexible copper-clad plate.
Embodiment 4
A kind of preparation method of polyamic acid resin, the polyamic acid resin are prepared as follows to obtain:
(1) in the three neck vessel of logical nitrogen, 1635 grams of dimethylformamides is added, adds 60.5 grams and (is equivalent to 0.30 to rub
You) 4,4'- diaminodiphenyl ether and bis- [4- (4- amino-benzene oxygen) phenyl] propane of 82.0 grams of (being equivalent to 0.35 mole) 2,2-,
At 40 DEG C stirring and dissolving to be completely dissolved to get mass concentration be 8.7% aromatic diamine solution；
(2) after the aromatic diamine solution of step 1 being cooled to 10 DEG C, 48.5 grams of (being equivalent to 0.15 mole) 3,3', 4 are added,
103.0 grams of (being equivalent to 0.35 mole) 3,3', 4,4'- biphenyl is added after stirring 2 hours in 4'- benzophenone tetracarboxylic dianhydride
Tetracarboxylic acid dianhydride continues stirring 7 hours, obtains polyamic acid resin；
(3) polyamic acid resin that step 2 is prepared stands defoaming, and measuring solid content is 14.5%, and viscosity is
12200CPS。
A kind of preparation method of double-faced flexible copper-clad plate, the double-faced flexible copper-clad plate are prepared as follows to obtain:
(1) it is coated with above-mentioned polyamic acid resin using automatic coating machine on the Du Pont 50ENS type PI film with a thickness of 12.5 μm, it is thick
Degree is 6 μm, is placed in baking oven and toasts 5 minutes for 170 DEG C, removes solvent；
(2) under a nitrogen, by the PI film after step 1 processing and with a thickness of 18 μm of copper foils (model: three well 3EC-M3S-HTE types
1/2oz ED Copper) under nitrogen protection 360 DEG C pressing to get single side force fit plate；
(3) 30 minutes dry with 80 DEG C in the high-temperature oxidation-free baking oven under nitrogen protection, 120 DEG C drying 60 minutes, in
It is 30 minutes dry at 160 DEG C, 200 DEG C, 250 DEG C, it is then 20 minutes dry in 300 DEG C, then at 350 DEG C of dry 60 minute minutes
Gradient increased temperature is carried out, the single side force fit plate imidizate that step 2 is prepared is complete；
(4) synthesized polyamic acid resin is coated on the single side force fit plate after step 3 imidizate, coating thickness is 6 μm,
170 DEG C of baking 5 minutes in baking oven remove solvent；
(5) under a nitrogen, by the PI film after step 4 processing and with a thickness of 18 μm of copper foils (model: three well 3EC-M3S-HTE types
1/2oz ED Copper) under nitrogen protection 370 DEG C pressing to get two-sided force fit plate；
(6) 30 minutes dry with 80 DEG C in the high-temperature oxidation-free baking oven under nitrogen protection, 120 DEG C drying 60 minutes, in 160
DEG C, 200 DEG C, it is 30 minutes dry at 250 DEG C, it is then 20 minutes dry in 300 DEG C, then at 350 DEG C of dry 60 minute minute progress
Gradient increased temperature keeps two-sided force fit plate imidizate complete, obtains double-faced flexible copper-clad plate.
The double-faced flexible copper-clad plate that above-described embodiment 1 to embodiment 4 is prepared is tested for the property respectively, test condition
It is as follows:
1, it thickness: is tested using Japan NIKON MS-4G type altimeter, is accurate to 0.1um:
2, peel strength: using Japanese Shimadzu AG-1 type tensilon test
Establishing criteria: IPC-TM-650, Method 2.4.9
Tensile speed: 50mm/min
Test piece width: 3.175mm
Test piece measuring distance: 70mm
The test of an angle of 90 degrees idler wheel
3, tensile strength and elongation: using Japanese Shimadzu AG-1 type tensilon
Establishing criteria: 882 method A of ASTM D
Test method:
1) longitudinal direction MD (transverse direction), TD(is cut respectively) each 5 of direction, the wide 15mm of sample × long 210mm
2) MD and the test piece of the direction TD are respectively in pulling force aircraft measurements tensile strength and elongation
3) up and down between fixture between be divided into 100mm;Tensile speed: 200mm/min
4) calculation formula:
5) elongation directly reads display data
4, glass transition temperature (Tg)
Using U.S. TA company Q800 type DMA instrument test；
Test condition: 50-400 DEG C, under 99.9999% high pure nitrogen, 3 DEG C/min of heating rate
5, thermal expansion coefficient (CTE)
Using U.S. TA company Q400 type TMA instrument test,
Test condition: 50-300 DEG C, heating rate 10 DEG C/min, 100-200 DEG C of value range
6, soldering heat resistance
It is tested using Taiwan " Yong Li Science and Technology Ltd. " YSC type tin furnace
Establishing criteria: IPC-TM-650, Method 2.4.13
Test condition: tin furnace is immersed in test piece after 105 DEG C of baking 1h, observes its variation
7, it dimensional stability: is tested using U.S. OPTEK 712J type Quadratic Finite Element coordinatograph
Establishing criteria: IPC-TM-650 2.2.4 Method C
8, folding strength: testing using Taiwan is great up to HT-8636A type folding machine,
Establishing criteria: JISC-6471
Test condition:
1) test test piece respectively makes 5 in the direction MD and TD.
2) test test piece length is 16.3cm, and route width is 1mm, and trace clearance 1mm, line pattern is as shown in Fig. 1,
Test piece is to expose, develop, etching mode makes.
3) the lower fixture for selecting radius of curvature R=0.38mm or 0.80mm, the mark point of folding stayed mast is pressed onto "
0.5 " position measurement of kg.
9, sheet resistance and volume resistance:
Instrument: megger: HP4339B High Resistance Meter.
Resistance value tester: HP16008B Resistivity Cell.
Establishing criteria: IPC-TM-650, Method 2.5.17
Test method: toasting 10min in 105 DEG C of baking ovens for the PI film test piece of 10cm X 10cm,
Test piece after baking is placed in in 23 DEG C and 65 ﹪ RH of drying box re-test after 96 ± 2hr
10, dielectric constant:
Instrument: Agilent 4339B-ATO-13248 type megger
Constant temperature and humidity machine: lift QA-TG-50/HD-43 type
Establishing criteria: IPC-TM-650, Method 2.5.5.3
Test method: the PI film test piece of the 3cm × 3cm etched is placed in the constant temperature and humidity machine of 23oC and 50% RH and is handled
After for 24 hours, adjustment megger frequency is that 1MHz is measured again.
11, water absorption rate:
Instrument: Mei Tele AB204-S type micro-analytical balance
Testing standard: IPC-TM-650, Method 2.6.2
Test method: 1) taking specimen size is 5cm × 5cm, and copper foil is fully etched,
2) after drying the PI film test piece flushing after etching, dry 1h is placed in 105oC baking oven,
3) it takes out test piece and is put into drier, cool down 10min,
4) test piece weighing W1, need to be accurate to 0.1mg,
5) test piece for finishing weighing is totally immersed into 23 DEG C of distilled water or pure water, 24 ± 0.5h,
6) after with blotting paper wiped clean, weigh W2 at once, need to be accurate to 0.1mg,
7) water absorption rate=(W2-W1)/W1 × 100%
12, anti-flammability:
Instrument: Bunsen burner
Testing standard: VTM-0 grades of UL94
13, the solid content of resin:
Instrument: Mei Tele-support benefit HG53 type moisture determination instrument
Test condition: weighing 2 ± 0.1 grams of resin, in 160 DEG C or 190 DEG C, until to reading after constant mass 1 minute
14, the viscosity of polyamic acid resin:
Instrument: BROOKFIELD LVDV-I+ type rotational viscometer
Test condition: the test after constant temperature 30 minutes or more in 25 DEG C of water-bath
The test performance for the double-faced flexible copper-clad plate that above embodiments are prepared is as shown in table 1.
The performance test of 1 double-faced flexible copper-clad plate of table
By above-mentioned the performance test results as it can be seen that the double-faced flexible copper-clad plate integral thickness that embodiment 1 to embodiment 4 is prepared
Thin, elongation is all larger than 35%, has good elongation, and tensile strength is all larger than 250MPa, has stronger removing strong
Degree, peel strength is all larger than 1.3kgf/cm, and glass transition temperature reaches 320 DEG C or more, and satisfaction is SMT on soft board
The temperature requirement of welding expands its use scope, and dimensional stability is strong, is not easy to deform displacement during the preparation process, improves system
Standby obtained product yield；And has lower sheet resistance and volume resistance, reduce insulation rate, improve what it was prepared
Route power effect；With folding strength, good flexibility is made it have, while water absorption rate is low, it is not easy to lead to polyamide
Acid resin layer oxygenolysis improves endurance energy, guarantees there is stronger resistance to tear energy for a long time.
Above-mentioned is presently preferred embodiments of the present invention, is not intended to limit the present invention in any form；All industry
Those of ordinary skill can implement the present invention by the above and swimmingly；But all those skilled in the art exist
Do not depart within the scope of technical solution of the present invention, a little change for being made using disclosed above technology contents, modification with
The equivalent variations of differentiation is equivalent embodiment of the invention；Meanwhile all substantial technologicals according to the present invention are to above embodiments
The variation, modification and evolution etc. of made any equivalent variations, within the protection scope for still falling within technical solution of the present invention.
Claims (10)
1. a kind of preparation method of polyamic acid resin, which is characterized in that the polyamic acid resin is prepared as follows
It arrives: under nitrogen protection, aromatic diamine monomer being dissolved in aprotic polar solvent, in 25 DEG C~50 DEG C stirring and dissolvings, obtain
The aromatic diamine monomer solution for being 6%~9% to mass concentration；After aromatic diamine monomer solution is cooled to 0 DEG C~25 DEG C,
Aromatic diacid anhydride monomer is added, the aromatic diamine monomer and the molar ratio of aromatic diacid anhydride monomer are 1:0.95~1:
Defoaming is stood after 1.05, polymerization reaction 6~10 hours to get polyamic acid resin.
2. the preparation method of polyamic acid resin according to claim 1, which is characterized in that the polymeric reaction condition is
Ice-water bath, speed of agitator are 100~250 revs/min.
3. the preparation method of polyamic acid resin according to claim 2, which is characterized in that the aromatic diamine monomer
For p-phenylenediamine, 4,4'- diaminodiphenyl ether, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane, bis- (the 4- aminobenzenes of 1,3-
Oxygroup) benzene, one of bis- (4- amino-benzene oxygen) diphenyl sulphone (DPS)s of 4,4'- or a variety of.
4. the preparation method of polyamic acid resin according to claim 3, which is characterized in that the aromatic diacid acid anhydride list
Body is pyromellitic dianhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride, 4,4- oxygen
Double phthalic anhydrides, diphenyl sulphone (DPS) -3,3`, one of 4,4`- tetracarboxylic dianhydrides or a variety of.
5. the preparation method of polyamic acid resin according to claim 4, which is characterized in that the aprotic polar solvent
For one of N-Methyl pyrrolidone, dimethyl acetamide, dimethylformamide.
6. the preparation method of polyamic acid resin according to claim 5, which is characterized in that the aromatic diacid acid anhydride list
The adding manner of body is that first the addition total anhydride molar ratio of Zhan is 30%~80%, after stirring 1~2 hour, surplus is added and is stirred for 5
~8 hours.
7. a kind of preparation method of double-faced flexible copper-clad plate, which is characterized in that the double-faced flexible copper-clad plate is based on aforesaid right
It is required that 1 to 6 described in any item polyamic acid resins are prepared, preparation method is as follows:
Step 1, synthesized polyamic acid resin is coated on PI film, the temperature range in baking oven at 140 DEG C~170 DEG C is pre-
Baking removes solvent, and polyamic acid resin layer is formed on PI film；
Step 2, under nitrogen, the PI film after step 1 processing is pressed with copper foil in 350 DEG C~380 DEG C temperature ranges, i.e.,
Obtain single side force fit plate；
Step 3, the single side force fit plate that step 2 is prepared is placed in the high-temperature oxidation-free baking oven under nitrogen protection from 80 DEG C of ladders
Degree is warming up to 320 DEG C~350 DEG C, makes the polyamic acid resin layer imidizate completely to get single-side coated copper plate；
Step 4, synthesized polyamic acid resin is coated on the PI film another side for the single-side coated copper plate that step 3 is prepared,
In 140 DEG C~170 DEG C of temperature range prebake conditions in baking oven, solvent is removed, forms polyamic acid resin layer on PI film；
Step 5, under nitrogen, the PI film after step 4 processing is pressed with copper foil in 350 DEG C~380 DEG C temperature ranges, i.e.,
Obtain two-sided force fit plate；
Step 6, the single side force fit plate that step 5 is prepared is placed in the high-temperature oxidation-free baking oven under nitrogen protection from 80 DEG C of ladders
Degree is warming up to 320 DEG C~350 DEG C, makes the polyamic acid resin layer imidizate completely to get double-faced flexible copper-clad plate.
8. the preparation method of double-faced flexible copper-clad plate according to claim 7, which is characterized in that the prebake conditions time is
5~10 minutes.
9. the preparation method of double-faced flexible copper-clad plate according to claim 8, which is characterized in that the PI film thickness is
12.5 μm, the copper thickness is 17~19 μm, and the polyamic acid resin layer is with a thickness of 6~7 μm.
10. the preparation method of double-faced flexible copper-clad plate according to claim 9, which is characterized in that the gradient increased temperature is
80 ± 5 DEG C drying 30 minutes, 120 ± 5 DEG C drying 60 minutes, respectively at 160 ± 5 DEG C, 200 ± 5 DEG C, 250 ± 5 DEG C do
It is dry 30 minutes, then 20 minutes dry in 300 ± 5 DEG C, then at 320 DEG C~350 DEG C drying 60 minutes.
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