CN108045025A - A kind of two layers of gum-free double side flexible copper coated board and preparation method thereof - Google Patents
A kind of two layers of gum-free double side flexible copper coated board and preparation method thereof Download PDFInfo
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- CN108045025A CN108045025A CN201810015594.1A CN201810015594A CN108045025A CN 108045025 A CN108045025 A CN 108045025A CN 201810015594 A CN201810015594 A CN 201810015594A CN 108045025 A CN108045025 A CN 108045025A
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- pbat
- pla
- kapton
- copper foil
- double side
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010949 copper Substances 0.000 title claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 64
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 claims abstract description 40
- 239000011889 copper foil Substances 0.000 claims abstract description 39
- 238000010030 laminating Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003475 lamination Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 9
- 238000007711 solidification Methods 0.000 claims description 8
- 230000008023 solidification Effects 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 29
- 229920006259 thermoplastic polyimide Polymers 0.000 abstract description 21
- 239000009719 polyimide resin Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 13
- 238000003825 pressing Methods 0.000 abstract description 7
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 abstract description 2
- 239000012815 thermoplastic material Substances 0.000 abstract description 2
- 239000004626 polylactic acid Substances 0.000 description 28
- 229920006381 polylactic acid film Polymers 0.000 description 16
- 229920001721 polyimide Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 239000004952 Polyamide Substances 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- 239000003292 glue Substances 0.000 description 8
- 229920001169 thermoplastic Polymers 0.000 description 7
- 239000004416 thermosoftening plastic Substances 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- PMTMAFAPLCGXGK-JMTMCXQRSA-N (15Z)-12-oxophyto-10,15-dienoic acid Chemical compound CC\C=C/C[C@H]1[C@@H](CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-JMTMCXQRSA-N 0.000 description 1
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- PMTMAFAPLCGXGK-UHFFFAOYSA-N OPDA Natural products CCC=CCC1C(CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-UHFFFAOYSA-N 0.000 description 1
- 101100028078 Oryza sativa subsp. japonica OPR1 gene Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- -1 alcohol ester Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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
- B32B15/09—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 polyesters
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
Landscapes
- Laminated Bodies (AREA)
Abstract
The present invention relates to a kind of two layers of gum-free double side flexible copper coated boards and preparation method thereof, including upper and lower two copper foil layer and the insulating layer being located between two copper foil layers, the PBAT/PLA laminated films of insulating layer both sides including intermediate Kapton and above and below Kapton.The existing good ductility of PBAT and PLA and elongation at break that the present invention uses, also there is preferable heat resistance and impact resistance, flexible group is not contained in its strand and free volume is small, it is not hygroscopic, and PBAT and PLA are also thermoplastic material in itself, the bonding between insulating layer and copper foil can be equally realized under its high temperature after melting pressing, thermoplastic polyimide resin (TPI), which is substituted, using it perfectly solves TPI poor heat resistances afterwards, the problems such as hygroscopic, therefore, gum-free double side flexible copper coated board provided by the invention is provided with high peel strength and dimensional stability simultaneously, solve the problems of existing two layers of method double side flexible copper coated board.
Description
Technical field
The present invention relates to a kind of copper-clad plate and preparation method thereof more particularly to a kind of gum-free double side flexible copper coated board and its
Preparation method belongs to copper-clad plate technical field.
Background technology
In recent years, with digital camera, DV, automobile navigation instrument, computer fittings and other electronic products
High performance, miniaturization, lightness and high-end electronic product, such as the appearance of tablet computer, smart mobile phone, electricity therein
Sub-line road is also constantly towards the trend development of " light, thin, short, small ".The rigid copper-clad plate that tradition uses, does not possess pliability, raw
Assembling can not be bent by producing obtained electronic circuit, bulky, can not meet actual demand.Densification, multiple stratification, height
The double side flexible copper coated board of heat resistance, high-dimensional stability is gradually replacing these rigid copper-clad plates, becomes the market mainstream.
The manufacturing method of traditional double side flexible copper coated board, which is three layers, glue-type, and thickness is generally 24.5~110 μm, nothing
Method meets the demands such as copper-clad plate slimming, pliability, and the adhesive for having used heat resistance not high in producing, and can not meet resistance to
The performances such as hot, soldering stability, applied at elevated temperature are easily layered blistering, therefore, people consider extensively without using epoxy resin or
Acrylic tackifier only uses polyimide material to do the two of insulating layer layers of gum-free double side flexible copper coated board.
Known polyimide material is divided into non-thermal plasticity polyimide resin (PI) and thermoplastic polyimide resin
(TPI) two kinds, for both polyimide resins due to the difference of monomer structure, performance has apparent difference, non-thermoplastic
Property polyimide resin (PI) coefficient of thermal expansion than relatively low, apply in copper-clad plate, copper-clad plate made to have the good size steady
Qualitative and high-fire resistance, but its peel strength with copper foil is than relatively low, it is difficult to it is used alone；Thermoplastic polyimide resin
(TPI) heat resistance is not so good as non-thermal plasticity polyimide resin, but coefficient of thermal expansion is very high, the dimensional stability of copper-clad plate of support
It shrinks excessive, but pressing can be melted at high temperature, realize the heat pressure adhesive between resin bed and copper foil, it is therefore, existing
Two kinds of thermoplastic polyimide and non-thermal plasticity polyimides are existed simultaneously in two layers of method double side flexible copper coated board, wherein, it is non-thermal
Plastic polyimide resin provides excellent dimensional stability rather than thermoplastic polyimide resin plays cementation, with
Phase obtains good dimensional stability and high-peeling strength simultaneously.
At present, there are two types of the mainstream structures of two layers of method double side flexible copper coated board of commercialization, Cu/TPI/PI/TPI/Cu and
Cu/PI/TPI/PI/Cu, the existing higher peel strength of double side flexible copper coated board of former structure have the good size steady again
Qualitative, but its problem is that the TPI heat resistances of outer layer are poor, when running into burning, TPI layers are easy to decompose, cause this two
The anti-flammability of layer method double side flexible copper coated board is poor, simultaneously because TPI is in itself containing more flexible group and with larger
Free volume, be easy to absorb water, under the repeatedly damp and hot impact of the following process of pcb board, it is easy to cause plate bursting, it is latter
Although kind of structure avoids to a certain extent to be influenced caused by the deficiency of TPI, it is difficult to avoid TPI performances completely not
Problem caused by foot, and the structure is higher to the formula of TPI and PI, manufacturing process technological requirement, adds production difficulty.
The content of the invention
It is two-sided to provide a kind of two layers of gum-free for deficiency existing for the double side flexible copper coated board of existing two layers of method by the present invention
Flexibility coat copper plate and preparation method thereof.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of two layers of gum-free double side flexible copper coated board including upper and lower two copper foil layer and are located in exhausted between two copper foil layers
Edge layer, the insulating layer includes intermediate Kapton and the PBAT/PLA of both sides is compound above and below Kapton
Film.
Further, the thickness of the insulating layer is 18~65 μm.
Further, the copper foil is one kind in rolled copper foil or electrolytic copper foil.
The advantageous effect of double side flexible copper coated board provided by the invention is：
Present invention employs tetramethylene adipate and the copolymer of mutual-phenenyl two acid bromide two alcohol ester (PBAT) and polylactic acid
(PLA) as the material for carrying out heat pressure adhesive in insulating layer with copper foil, the existing good ductility of PBAT, PLA and extension at break
Rate, it may have preferable heat resistance and impact resistance do not contain flexible group in strand and free volume are small, be not easy to inhale
Water, and PBAT and PLA be in itself also for thermoplastic material, can equally be realized after melting pressing under high temperature insulating layer and copper foil it
Between bonding, using its substitute thermoplastic polyimide resin (TPI) perfectly solve TPI poor heat resistances, hygroscopic etc. afterwards
Problem, therefore, double side flexible copper coated board provided by the invention are provided with high peel strength and dimensional stability simultaneously, solve
The problems of existing two layers of method double side flexible copper coated board.
The preparation method of above-mentioned double side flexible copper coated board is also claimed in the present invention, includes the following steps：
1) agitating and heating is dried after PBAT is mixed with PLA raw materials, and is delivered to the storage bin of laminating machine；
2) raw material in storage bin heats propulsion after entering the screw rod of laminating machine, is divided into laminating machine along screw rod direction multiple
Bringing-up section, the temperature of each bringing-up section gradually rises along screw rod direction reaches leaching after the fusing point of arrival PBAT, material melts
The film head of film machine, control laminating machine the mixed material lamination of PBAT and PLA is coated on Kapton, postcooling
Make the PBAT/PLA laminated films of molten condition that can be quickly cooled down solidification after being coated on Kapton, obtain single side and drape over one's shoulders
Cover the Kapton of PBAT/PLA laminated films；
3) using the Kapton of the single side coating PBAT/PLA laminated films of gained in step 2) as base material, then secondary control
PBAT and PLA laminations are coated on the another side of Kapton by laminating machine processed, postcooling make the PBAT/ of molten condition
PLA laminated films can be quickly cooled down solidification after being coated on Kapton, obtain two-sided coating PBAT/PLA THIN COMPOSITEs
The Kapton of film, i.e. insulating layer；
4) last layer copper foil is respectively covered on the two sides of insulating layer, hot pressing is carried out at 350~400 DEG C through vacuum pressing-combining machine,
So that the melting of PBAT/PLA laminated films is bonded with copper foil, so as to which double side flexible copper coated board be made.
Further, the weight ratio of both PBAT and PLA raw materials is (3~5) in step 1)：1.
Further, the pressure of vacuum pressing-combining machine described in step 4) is 10~15MPa, and the time of hot pressing is 60~90s.
Further, the range of number-average molecular weight of the PBAT is 1~1,000,000, and the number-average molecular weight of the PLA is 1~100
Ten thousand.
Further, multiple bringing-up sections described in step 2) are 6 bringing-up sections, and the heating temperatures of 6 bringing-up sections is from 150
DEG C increased with 30~40 DEG C incremented by successively, 60~70 DEG C, 10~20 DEG C, 10~20 DEG C, 10~20 DEG C of rule.
The advantageous effect of preparation method provided by the invention is：
1) preparation method of the invention the method for hot pressing after insulating layer is made using lamination in situ, copper-clad plate is made so that
Bond strength between Kapton and PBAT/PLA films, between PBAT/PLA films and copper foil reaches maximum so that made
The copper foil obtained has highest peel strength and dimensional stability；
2) its thickness of the copper-clad plate obtained by preparation method using the present invention is much lower with respect to conventional method, insulating layer
Thickness can meet the application demand of high-end electronic product substantially below 65 μm；
3) preparation method of the invention cleverly make use of laminating machine to carry out the process instead of chemical synthesis and coating,
Chemical reagent and artificial use are greatly reduced, is greatly improved work efficiency.
Specific embodiment
The principle of the present invention and feature are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
Embodiment 1：
A kind of two layers of gum-free double side flexible copper coated board including upper and lower two copper foil layer and are located in exhausted between two copper foil layers
Edge layer, the insulating layer includes intermediate Kapton and the PBAT/PLA of both sides is thin above and below Kapton
Film.
Wherein, the copper foil is rolled copper foil, and thickness is 12~35 μm, and the thickness of Kapton is 6~25 μm,
The thickness of PBAT/PLA films is 6~20 μm, and the weight ratio of both PBAT and PLA are 3：1, PBAT number-average molecular weight for 1~
The number-average molecular weight of 600000, PLA are 50~1,000,000.
The preparation method of above-mentioned double side flexible copper coated board is as follows：
1) PBAT and PLA raw materials agitating and heating is dried, and is delivered to the storage bin of laminating machine；
2) raw material in storage bin heats propulsion after entering the screw rod of laminating machine, and laminating machine is interior to be divided into 6 along screw rod direction
Bringing-up section, the heating temperatures of 6 bringing-up sections are increased from 150 DEG C with 40 DEG C incremented by successively, 60 DEG C, 10 DEG C, 20 DEG C, 20 DEG C of rule
Until reaching the film head of laminating machine after the fusing point of arrival PBAT, PBAT and PLA meltings, laminating machine is controlled by PBAT and PLA laminations
Be coated on Kapton, postcooling make the PBAT/PLA films of molten condition be coated on Kapton after energy
Solidification is enough quickly cooled down, obtains the Kapton of single side coating PBAT/PLA films；
3) using the Kapton of the single side coating PBAT/PLA films of gained in step 2) as base material, lamination is controlled again
PBAT and PLA laminations are coated on the another side of Kapton by machine, postcooling drape over one's shoulders the PBAT/PLA films of molten condition
Solidification can be quickly cooled down after overlaying on Kapton, obtains the Kapton of two-sided coating PBAT/PLA films, i.e.,
Insulating layer；
4) last layer copper foil is respectively covered on the two sides of insulating layer, hot pressing, vacuum pressure is carried out at 350 DEG C through vacuum pressing-combining machine
The pressure of conjunction machine is 15MPa, and the time of hot pressing is 60s so that PBAT/PLA films are melted to be bonded with copper foil, two-sided so as to be made
Flexibility coat copper plate.
Embodiment 2：
A kind of two layers of gum-free double side flexible copper coated board including upper and lower two copper foil layer and are located in exhausted between two copper foil layers
Edge layer, the insulating layer includes intermediate Kapton and the PBAT/PLA of both sides is thin above and below Kapton
Film.
Wherein, the copper foil is electrolytic copper foil, and thickness is 12~70 μm, and the thickness of Kapton is 6~25 μm,
The thickness of PBAT/PLA films is 6~20 μm, and the weight ratio of both PBAT and PLA are 5：1, PBAT number-average molecular weight for 60~
The number-average molecular weight of 1000000, PLA are 1~500,000.
The preparation method of above-mentioned double side flexible copper coated board is as follows：
1) PBAT and PLA raw materials agitating and heating is dried, and is delivered to the storage bin of laminating machine；
2) raw material in storage bin heats propulsion after entering the screw rod of laminating machine, and laminating machine is interior to be divided into 6 along screw rod direction
Bringing-up section, the heating temperatures of 6 bringing-up sections are increased from 150 DEG C with 30 DEG C incremented by successively, 70 DEG C, 20 DEG C, 10 DEG C, 10 DEG C of rule
Until reaching the film head of laminating machine after the fusing point of arrival PBAT, PBAT and PLA meltings, control laminating machine drapes over one's shoulders PBAT/PLA laminations
Overlay on Kapton, postcooling make the PBAT/PLA films of molten condition can after being coated on Kapton
Solidification is quickly cooled down, obtains the Kapton of single side coating PBAT/PLA films；
3) using the Kapton of the single side coating PBAT/PLA films of gained in step 2) as base material, lamination is controlled again
PBAT and PLA laminations are coated on the another side of Kapton by machine, postcooling drape over one's shoulders the PBAT/PLA films of molten condition
Solidification can be quickly cooled down after overlaying on Kapton, obtains the Kapton of two-sided coating PBAT/PLA films, i.e.,
Insulating layer；
4) last layer copper foil is respectively covered on the two sides of insulating layer, hot pressing, vacuum pressure is carried out at 400 DEG C through vacuum pressing-combining machine
The pressure of conjunction machine is 15MPa, and the time of hot pressing is 90s so that PBAT/PLA films are melted to be bonded with copper foil, two-sided so as to be made
Flexibility coat copper plate.
Comparative example 1：
1) rolled copper foil that thickness is 12~35 μm, polyamide thermoplastic acid resin glue and thermosetting polyamide acid are prepared
Resin adhesive liquid；
2) thermosetting polyamide acid resin glue-coating is obtained into double-deck knot in the surface of copper foil through 120 DEG C of drying of baking oven
The single sided board of structure in single sided board surface drying layer surface coating thermoplastic polyamic acid resin glue, is dried after 120 DEG C, using
Imidization obtains the single sided board of three-decker；
3) single sided board of two pieces of three-deckers is obtained into the dual platen of five-layer structure through 350~400 DEG C of pressings of pressing machine.
Comparative example 2：
1) electrolytic copper foil that thickness is 12~70 μm, polyamide thermoplastic acid resin glue and thermosetting polyamide acid are prepared
Resin adhesive liquid；
2) polyamide thermoplastic acid resin glue-coating is obtained into double-deck knot in the surface of copper foil through 120 DEG C of drying of baking oven
The single sided board of structure is coated with thermosetting property polyamic acid resin glue in single sided board surface drying layer surface, is dried after 120 DEG C, using
Imidization obtains the single sided board of three-decker；
3) single sided board of two pieces of three-deckers is obtained into the dual platen of five-layer structure through 350~400 DEG C of pressings of pressing machine.
The preparation method of thermosetting polyamide acid resin glue is as follows：
NMP (N-Methyl pyrrolidone) and DMAc (DMAC N,N' dimethyl acetamide) is added in the three-necked flask of 1L altogether
360g weighs the PDA of the ODA and 16.006g of 6.50g, is dissolved in above-mentioned polar solvent NMP and DMAc and obtains solution, then will
The solution cools down in a water bath, adds in the BPDA (bibenzene tetracarboxylic dianhydride) of 52.665g under nitrogen flowing, and controlling reaction temperature is
It 15~20 DEG C, is reacted when persistently stirring 8 is small, thermosetting polyamide acid resin glue, solid content 15% is prepared.
The preparation method of polyamide thermoplastic acid resin glue is as follows：
NMP (N-Methyl pyrrolidone) and DMAc (DMAC N,N' dimethyl acetamide) is added in the three-necked flask of 1L altogether
460g weighs the BAPP of the BAPS and 32.841g of 8.654g, is dissolved in above-mentioned polar solvent NMP and DMAc and obtains solution, then
The solution is cooled down in a water bath, adds in the BPDA (bibenzene tetracarboxylic dianhydride) and 18.631g of 11.697g under nitrogen flowing
OPDA (3,3', 4,4'- diphenyl ether dianhydride), controlling reaction temperature are 15~20 DEG C, are reacted, prepared when persistently stirring 8 is small
Obtain polyamide thermoplastic acid resin glue, solid content 14%.
In order to verify the technique effect of double side flexible copper coated board provided by the invention, we are by embodiment 1,2 and of embodiment
The copper-clad plate of comparative example 1,2 gained of comparative example carries out the test of properties, and concrete outcome is as shown in table 1：
Glass transition temperature is tested：Using dynamic thermomechanical analysis apparatus (DMA2980, TA companies of the U.S.)；Assign 1Hz's
Vibration frequency, in a nitrogen atmosphere with the heating rate of 3 DEG C/min from room temperature to 400 DEG C, in dielectric loss angle tangent
Glass transition temperature is obtained at maximum survey；
Heat decomposition temperature (Td 5%):Use thermogravimetric analyzer (TGA) with the rate of 10 DEG C/min by room temperature to 800
DEG C, weight change is observed, 5% weight is obtained and reduces temperature；
Crimpness test method：Material is cut into the size of 250mm × 250mm, on the table, four sides of measurement crimp for tiling
The average value of height；
Thermal stress：Plate is placed in 340 DEG C of tin stoves after handling 10 seconds and taken out, observation plate performance situation；
Coefficient of thermal expansion：Using thermomechanical analyzer (TMA), the polyimides sample to test is warming up in TMA
It 250 DEG C, keeps after ten minutes, with the rate of temperature fall of 5 DEG C/min, the thermal expansion between 240 DEG C to 100 DEG C being obtained at such a temperature
Coefficient；
Dimensional stability：It is tested according to the method for IPC-TM-650-2.4.4；
Peel strength：It is tested according to the method for IPC-TM-650-2.4.8；
Anti-flammability：It is tested with reference to UL94 standards.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modifications, equivalent replacements and improvements are made should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of two layers of gum-free double side flexible copper coated board, which is characterized in that including upper and lower two copper foil layer and be located in two copper foils
Insulating layer between layer, the insulating layer include intermediate Kapton and the both sides above and below Kapton
PBAT/PLA laminated films.
2. double side flexible copper coated board according to claim 1, which is characterized in that the thickness of the insulating layer is 18~65 μ
m。
3. double side flexible copper coated board according to claim 1 or 2, which is characterized in that the copper foil is rolled copper foil or electricity
Solve one kind in copper foil.
4. a kind of preparation method of two layers of gum-free double side flexible copper coated board, which is characterized in that include the following steps：
1) agitating and heating is dried after PBAT is mixed with PLA raw materials, and is delivered to the storage bin of laminating machine；
2) raw material in storage bin heats propulsion after entering the screw rod of laminating machine, and laminating machine is interior to be divided into multiple heating along screw rod direction
Section, the temperature of each bringing-up section gradually rises along screw rod direction reaches laminating machine after the fusing point of arrival PBAT, material melts
Film head, control laminating machine the mixed material lamination of PBAT and PLA is coated on Kapton, postcooling make to melt
Melt state PBAT/PLA laminated films be coated on Kapton after can be quickly cooled down solidification, obtain single side coating
The Kapton of PBAT/PLA laminated films；
3) using the Kapton of the single side coating PBAT/PLA laminated films of gained in step 2) as base material, control leaching again
PBAT and PLA laminations are coated on the another side of Kapton by film machine, postcooling answer the PBAT/PLA of molten condition
Solidification can be quickly cooled down by closing after film is coated on Kapton, obtain the poly- of two-sided coating PBAT/PLA laminated films
Imide membrane, i.e. insulating layer；
4) last layer copper foil is respectively covered on the two sides of insulating layer, hot pressing is carried out at 350~400 DEG C through vacuum pressing-combining machine so that
PBAT/PLA laminated films are melted to be bonded with copper foil, so as to which double side flexible copper coated board be made.
5. preparation method according to claim 4, which is characterized in that the weight of both PBAT and PLA raw materials in step 1)
Than for (3~5)：1.
6. preparation method according to claim 4 or 5, which is characterized in that the pressure of vacuum pressing-combining machine described in step 4)
For 10~15MPa, the time of hot pressing is 60~90s.
7. preparation method according to claim 6, which is characterized in that the range of number-average molecular weight of the PBAT is 1~100
The number-average molecular weight of ten thousand, the PLA are 1~1,000,000.
8. preparation method according to claim 6, which is characterized in that multiple bringing-up sections described in step 2) are 6 heating
Section, the heating temperatures of 6 bringing-up sections from 150 DEG C with 30~40 DEG C incremented by successively, 60~70 DEG C, 10~20 DEG C, 10~20
DEG C, 10~20 DEG C of rule increases.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109094142A (en) * | 2018-08-30 | 2018-12-28 | 招远春鹏电子科技有限公司 | A kind of preparation method of paper-based copper-coated board |
| CN109228561A (en) * | 2018-08-30 | 2019-01-18 | 招远春鹏电子科技有限公司 | A kind of preparation method of paper-based copper-coated board |
| CN113386416A (en) * | 2021-07-08 | 2021-09-14 | 江西柔顺科技有限公司 | Heat-conducting double-sided copper-clad plate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465212A (en) * | 2000-09-07 | 2003-12-31 | 奥克-三井有限公司 | Manufacturing fire retardant circuit boards without the use of fire retardant resin additives |
| CN202986235U (en) * | 2012-12-10 | 2013-06-12 | 广东生益科技股份有限公司 | A double-sided flexible copper clad laminate |
-
2018
- 2018-01-08 CN CN201810015594.1A patent/CN108045025A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465212A (en) * | 2000-09-07 | 2003-12-31 | 奥克-三井有限公司 | Manufacturing fire retardant circuit boards without the use of fire retardant resin additives |
| CN202986235U (en) * | 2012-12-10 | 2013-06-12 | 广东生益科技股份有限公司 | A double-sided flexible copper clad laminate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109094142A (en) * | 2018-08-30 | 2018-12-28 | 招远春鹏电子科技有限公司 | A kind of preparation method of paper-based copper-coated board |
| CN109228561A (en) * | 2018-08-30 | 2019-01-18 | 招远春鹏电子科技有限公司 | A kind of preparation method of paper-based copper-coated board |
| CN113386416A (en) * | 2021-07-08 | 2021-09-14 | 江西柔顺科技有限公司 | Heat-conducting double-sided copper-clad plate and preparation method thereof |
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