CN109337072A - A kind of polymeric composition, copper-clad plate and the circuit board of low DK and DF - Google Patents
A kind of polymeric composition, copper-clad plate and the circuit board of low DK and DF Download PDFInfo
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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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
- H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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Abstract
The invention discloses the polymeric compositions of low DK and DF a kind of, are made of the component of following parts by weight: 20~60 parts of the dicarboxylic anhydride containing ester groups, 100~180 parts of 1~25 part of diamine monomer, the solvent containing pyrimidine group.The invention also discloses a kind of copper-clad plates of the polymeric composition preparation of low DK and DF, including copper foil and it is attached to the polyimide layer of copper foil surface, the polyimide layer is to be coated on copper foil surface by the polymeric composition of the low DK and DF to be formed by heating high temperature cyclization.The polymeric composition of low DK and DF of the invention solve the problems, such as that DK and DF are excessively high, provide the laminate for wiring board with polyimide layer, and the copper foil of the polyimide layer and low roughness can get the characteristic of low DK and DF, high-transmission when arranging in pairs or groups.
Description
Technical field
The invention belongs to technical field of electronic materials, specifically, being related to the polymeric composition of low DK and DF a kind of, covering
Copper sheet and circuit board.
Background technique
The industrial technology of PCB is regardless of soft board and hardboard sent out toward the method for high frequency, high speed and high density structure dress at present
Exhibition, corresponding product is light, it is thin, can carry, the development trend of multifunction, can be increasingly for the demand of material and preparation method
Harsh, in addition the brought data transmission of money/communication actionization flourishes, the development trend of high band (~GHZ) is a kind of aobvious
It learns, most important one material property demand is exactly LOW DK/DF and high-fire resistance, peel strength.
Product are light, it is thin, can carry, the development trend of multifunction, can be increasingly for the demand of material and preparation method
Harsh, in addition the brought data transmission of money/communication actionization flourishes, the development trend of high band (~GHZ) is a kind of aobvious
It learns, most important one material property demand is exactly LOW DK/DF and high-fire resistance, peel strength.
In the prior art, polyamic acid (PAA) is generally synthesized with diamines and dicarboxylic anhydride, through using high temperature cyclization method into
Row dehydration synthesizes polyimides (PI).But because the Moore polarizability height of atomic group makes DK≤3.0, structural arrangement is not tight
So that Df≤0.008, therefore to reduce Dk and Df needs importing esters functional group and storehouse in structure close on molecular structure, such as
Shown in lower.
Summary of the invention
In order to solve the problems, such as that DK is excessively high with DF, the first purpose of the invention is to provide the macromolecules of low DK and DF a kind of
Composition.
It is a further object to provide a kind of copper-clad plates of the polymeric composition preparation of low DK and DF.
It is also another object of the present invention to provide one kind circuit boards made of the copper-clad plate.
To achieve the goals above, The technical solution adopted by the invention is as follows:
The first aspect of the invention provides the polymeric composition of low DK and DF a kind of, is by the group of following parts by weight
Divide and be made:
20~60 parts of dicarboxylic anhydride containing ester groups；
1~25 part of diamine monomer containing pyrimidine group；
100~180 parts of solvent.
The dicarboxylic anhydride containing ester groups is aromatic tetracarboxylic dianhydride, the preferably bis- trihemellitic acids of p-phenylene-
Ester dianhydride (TAHQ), 3,3', 4,4'- biphenyltetracarboxylic dianhydrides (BPDA), Bisphenol A Type Diether Dianhydride (BPADA), specific structure is such as
Shown in lower:
The diamine monomer containing pyrimidine group is aromatic diamine, preferably 3,5- diaminostilbene, 2,4- triazoles
(DTZ), 1,4- phenylene bis- (4-aminobenzoic acid ester) (ABHQ), two p-aminophenyl ester (BPTP) of terephthalic acid (TPA), to amino
Benzoic acid p-aminophenyl ester (APAB), 4,4 '-diaminodiphenyl ethers (ODA), bis- (4- aminophenyl) terephthalates
(BPBT), specific structure is as follows:
The diamine monomer containing pyrimidine group is 3,5- diaminostilbene, 2,4- triazole (DTZ), p-aminobenzoic acid
The mixture of p-aminophenyl ester (APAB), 4,4 '-diaminodiphenyl ethers (ODA).
The solvent is N-Methyl pyrrolidone (NMP), DMAC N,N' dimethyl acetamide, butyrolactone, N.N- dimethyl formyl
Amine, dimethyl sulfoxide.
The solid content of the polymeric composition of the low DK and DF is 30wt% (low DK and DF polyamic acid solution), is glued
Degree is 30000~60000CPs.
The second aspect of the invention provides a kind of preparation method of the polymeric composition of low DK and DF, including
Following steps:
The dicarboxylic anhydride containing ester groups, the diamine monomer containing pyrimidine group are dissolved in solvent by the proportion, stirred
Mix the polymeric composition that dissolution obtains the low DK and DF.
The third aspect of the invention provides a kind of copper-clad plate of the polymeric composition preparation of low DK and DF, packet
It includes copper foil and is attached to the polyimide layer of copper foil surface, the polyimide layer is by the polymeric composition of the low DK and DF
Copper foil surface is coated on to be formed by heating high temperature cyclization.
The polyimide layer with a thickness of 9-50um.
The copper foil with a thickness of 12-18um.
The fourth aspect of the invention provides a kind of copper-clad plate of the polymeric composition preparation of low DK and DF
Preparation method, comprising the following steps:
It by the polymeric composition of the low DK and DF via coating process, is coated on copper foil, through overbaking, curing shape
At the polyimide layer of low DK and DF, copper-clad plate is obtained.
Described BHFX-92F-HA-V2-12 μm of copper foil model, RZ=0.45 (day mine).
The condition of the baking is 140 DEG C, keeps the temperature 15min, is then down to room temperature.
The condition of the curing is at room temperature, to be warming up to 150 DEG C through 15min, keep the temperature 5min, be warming up to 200 through 10min
DEG C, 5min is kept the temperature, 250 DEG C is warming up to through 10min, keeps the temperature 5min, 300 DEG C is warming up to through 10min, 30min is kept the temperature, through 10min
350 DEG C are warming up to, 30min is kept the temperature, is then down to room temperature through 60min.
The principle of the present invention part is as follows:
The method for reducing dielectric constant:
Claslius-Mosotti equation:
Wherein Pm: the Moore polarizability of atomic group, Vm: the Moore volume of atomic group.
Pm can be reduced by introducing esters functional group, coplanar increase Vm that macoradical destroys phenyl ring can also be introduced.
Therefore the method for reducing dielectric constant mainly has introduction esters functional group, close structure arrangement, blending low Df material.
General PI is because of structurally flexible (CH2,-O- etc.) structure is easy rotation, be easy to produce gap in storehouse, lead to storehouse not
Dk and Df is closely made to increase, therefore the structure that ester-introduced class formation (C=CO) makes with introducing macoradical in structure is not easy to rotate,
Close structure causes Dk and Df to decline after storehouse again.
The storehouse gap of the prior art is as follows:
Dk=3.2
Df=0.008.
The storehouse of the application is close, specific as follows:
For conductor copper foil, path is shorter when the more smooth electric current of conductive surface flows through, the more coarse electric current of conductive surface
Path is longer when flowing through, as shown in Figure 1, Fig. 1 is schematic diagram when conductor copper foil surface current flows through.Selection has low roughness
Copper foil can have the characteristic of excellent LOW DK and DF, but when copper foil roughness is lower, will cause polyimide layer and copper
The low defect of tackness between foil.Therefore the composition to copper Bonding strength can be promoted on Molecular Design.In the composition
Using the diamine monomer containing pyrimidine group, wherein pyrimidine group can will enhance polyimides and copper foil with the coordination of copper
Bond strength.As shown in Fig. 2, the material that Fig. 2 is the prior art and the application is attached to the schematic diagram on copper foil.In the prior art
Peel strength be 0.5kgf/cm, the application and copper generate coordination, peel strength 0.9kgf/cm.
The fifth aspect of the invention provides a kind of circuit board made of the copper-clad plate.
Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effects:
The polymeric composition of low DK and DF of the invention solve the problems, such as that DK and DF are excessively high, provide with polyimides
The laminate for wiring board of layer, copper-clad plate can be fabricated to the laminate of wiring board, the polyimide layer after being made
It can get the characteristic of low DK and DF, high-transmission when arranging in pairs or groups with the copper foil of low roughness.
Polymeric composition, that is, polyamic acid solution of low DK and DF of the invention are the combination that one kind can reduce DK and DF
Object simultaneously has excellent heat resistance.The dicarboxylic anhydride containing ester groups and the diamine monomer containing pyrimidine group are used in the composition,
Wherein the collocation effect of LOW DK&DF glue and copper can effectively be fabricated to high frequency.The composition solid part is 30%, and viscosity is
30000~60000CPs can be coated on copper foil via coating process, carry out sub- amidation via heat treatment to form LOW
DK and DF polyimide polymer, the LOW DK and DF polyimide polymer can generate heat resistance in copper foil surface
LOW DK and DF polyimide layer, as high frequency is without products such as glue system substrate of flexible circuit board (2L-FCCL).Copper foil base material
(FCCL) be divided into two major classes: tradition has then three layers of flexible board substrate of dosage form (3L FCCL) and novel nothing then two layers of soft board of dosage form
Substrate (2L FCCL) two major classes.The application belongs to without then two layers of flexible board substrate (2L FCCL of dosage form.
Relatively low general high frequency copper foil copper-clad plate pulling force is 0.5-0.7kgf/cm, is added 3,5- diaminostilbene in the application, 2,
4- triazole DTZ promotes pulling force；The electrical property of general copper foil copper-clad plate is higher (DF=0.008), and C=OO structure is added in the application
DF (DF=0.003) can be effectively reduced, therefore, the application is added DTZ and introduces C=OO structure can promote pulling force and drop simultaneously
Low DF.
Detailed description of the invention
Fig. 1 is schematic diagram when conductor copper foil surface current flows through.
Fig. 2 is the schematic diagram that the material of the prior art and the application are attached on copper foil.
Fig. 3 is the preparation technology flow chart of copper-clad plate of the invention.
Fig. 4 is cooking conditions schematic diagram.
Fig. 5 is the preparation technology flow chart of the copper-clad plate of the embodiment of the present invention.
Fig. 6 is the preparation technology flow chart of the copper-clad plate of comparative example.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Agents useful for same of the embodiment of the present invention is as follows:
Diamines: the diamine monomer in the present invention can be aromatic diamine, can be following monomer, but not limited to this；In
Text: 3,5- diaminostilbenes, 2,4- triazoles, English: 1,2,4-Triazole-3,5-diamine, abbreviation: DTZ, CAS:1455-
77-2.Chinese: Isosorbide-5-Nitrae-phenylene is bis- (4-aminobenzoic acid ester), English: Isosorbide-5-Nitrae-phenylene bis (4-
Aminobenzoate) or Isosorbide-5-Nitrae-Bis (4-aminobenzo-yloxy) benzene, abbreviation: ABHQ, CAS:22095-98-3.
Chinese: two p-aminophenyl ester of terephthalic acid (TPA), English: Bis (4-aminophenyl) terephthalate, abbreviation: BPTP,
CAS:16926-73-1.Chinese: p-aminobenzoic acid p-aminophenyl ester, English: 4-Aminophenyl-4-
Aminobenzoate, abbreviation: APAB, CAS:20610-77-9.Chinese: 4,4 '-diaminodiphenyl ethers, English: 4,4'-
Oxybisbenzenamine, abbreviation: ODA.Chinese: bis- (4- aminophenyl) terephthalates, English: bis (4-
Aminophenyl) terephthalate, abbreviation: BPBT.
Dicarboxylic anhydride: dianhydride monomer in the present invention can be aromatic tetracarboxylic dianhydride, be exemplified below, but not as
Limit；Chinese: the bis- tritrimellitate dianhydrides of p-phenylene-, English: p-phenylenebis (trimellitate
Anhydride), abridge: TAHQ, CAS:2770-49-2.Chinese: 3,3', 4,4'- biphenyltetracarboxylic dianhydrides, English: 3,3 ', 4,
4 '-Biphenyltetracarboxylic dianhydride, abbreviation: BPDA, CAS:2420-87-3.Chinese: bisphenol A-type two
Ether dianhydride, English: 4,4'- (4,4'-ISOPROPYLIDENEDIPHENOXY) BIS (PHTHALIC ANHYDRIDE), abbreviation:
BPADA, CAS:38103-06-9.
Examples 1 to 4
Raw material used by Examples 1 to 4 is as shown in table 1, a kind of preparation of the polymeric composition of the low DK and DF
Method, comprising the following steps: add NMP, APAB, ODA, DTZ after high-speed stirred to after dissolving by proportion described in table 1
BPDA is stirred to react 12 hours, obtains the polymeric composition of the low DK and DF.
A kind of preparation method of the copper-clad plate of the polymeric composition preparation of the low DK and DF, comprising the following steps:
By the polymeric composition of the low DK and DF via coating process, be coated on copper foil (copper foil is Cu:
BHFX-92F-HA-V2-12 μm, RZ=0.45 (day mine)) on, the polyimide layer of low DK and DF are formed through overbaking, curing,
Copper-clad plate is obtained, specific Fig. 3 is the preparation technology flow chart of copper-clad plate of the invention as shown in Figure 3 and Figure 5, and Fig. 5 is the present invention
The preparation technology flow chart of the copper-clad plate of embodiment.
The condition of the baking is 140 DEG C, keeps the temperature 15min, is then down to room temperature；The condition of the curing is (specific such as Fig. 4
Shown, Fig. 4 is cooking conditions schematic diagram.) it is at room temperature, to be warming up to 150 DEG C through 15min, keep the temperature 5min, be warming up to through 10min
200 DEG C, 5min is kept the temperature, 250 DEG C is warming up to through 10min, keeps the temperature 5min, is warming up to 300 DEG C through 10min, keeps the temperature 30min, warp
10min is warming up to 350 DEG C, keeps the temperature 30min, is then down to room temperature through 60min.
The copper-clad plate includes copper foil and the polyimide layer for being attached to copper foil surface, and the polyimide layer is by described low
The polymeric composition of DK and DF is coated on copper foil surface and is formed by heating high temperature cyclization.The polyimide layer with a thickness of
9-50um, the copper foil with a thickness of 12-18um.Test DK and DF is carried out to the copper-clad plate of preparation, then carries out test removing
Intensity, finally carries out drift tin test, and drift tin test continues 10sec in 340 DEG C of conditions of temperature, indicates to pass through.According to upper in table 1
State test result, it may be said that bright copper-clad plate performance of the invention is good compared with comparative example.
Table 1
* curable type part 30%, viscosity 30000-60000CPs.
Diamines dosage is total up to 21.21g in embodiment 1, and diamines dosage is total up to 21.49g in embodiment 2, in embodiment 3
Diamines dosage is total up to 21.76g, and diamines dosage is total up to 22.04g in embodiment 4.
Embodiment 5~8
Raw material used by embodiment 5~8 is as shown in table 2, a kind of preparation of the polymeric composition of the low DK and DF
Method, comprising the following steps: add NMP, APAB, ODA, DTZ after high-speed stirred to after dissolving by proportion described in table 2
BPADA is stirred to react 12 hours, obtains the polymeric composition of the low DK and DF.
A kind of preparation method of the copper-clad plate of the polymeric composition preparation of the low DK and DF, comprising the following steps:
By the polymeric composition of the low DK and DF via coating process, be coated on copper foil (copper foil is Cu:
BHFX-92F-HA-V2-12 μm, RZ=0.45 (day mine)) on, the polyimide layer of low DK and DF are formed through overbaking, curing,
Obtain copper-clad plate；The condition of the baking is 140 DEG C, keeps the temperature 15min, is then down to room temperature；The condition of the curing is room temperature
Under, 150 DEG C are warming up to through 15min, keeps the temperature 5min, 200 DEG C is warming up to through 10min, keeps the temperature 5min, be warming up to 250 through 10min
DEG C, 5min is kept the temperature, 300 DEG C is warming up to through 10min, keeps the temperature 30min, 350 DEG C is warming up to through 10min, keeps the temperature 30min, then pass through
60min is down to room temperature.
The copper-clad plate includes copper foil and the polyimide layer for being attached to copper foil surface, and the polyimide layer is by described low
The polymeric composition of DK and DF is coated on copper foil surface and is formed by heating high temperature cyclization.The polyimide layer with a thickness of
9-50um, the copper foil with a thickness of 12-18um.Test DK and DF is carried out to the copper-clad plate of preparation, then carries out test removing
Intensity finally carries out drift tin test.According to the above-mentioned test result in table 2, it may be said that bright copper-clad plate performance of the invention compared with than
It is good compared with example.
Table 2
* 30% viscosity 30000-60000CPs of curable type part.
Diamines dosage is total up to 21.21g in embodiment 5, and diamines dosage is total up to 21.49g in embodiment 6, in embodiment 7
Diamines dosage is total up to 21.76g, and diamines dosage is total up to 22.04g in embodiment 8.
Embodiment 9~12
Raw material used by embodiment 9~12 is as shown in table 3, a kind of preparation of the polymeric composition of the low DK and DF
Method, comprising the following steps: add NMP, APAB, ODA, DTZ after high-speed stirred to after dissolving by proportion described in table 3
TAHQ is stirred to react 12 hours, obtains the polymeric composition of the low DK and DF.
A kind of preparation method of the copper-clad plate of the polymeric composition preparation of the low DK and DF, comprising the following steps:
By the polymeric composition of the low DK and DF via coating process, be coated on copper foil (copper foil is Cu:
BHFX-92F-HA-V2-12 μm, RZ=0.45 (day mine)) on, the polyimide layer of low DK and DF are formed through overbaking, curing,
Obtain copper-clad plate；The condition of the baking is 140 DEG C, keeps the temperature 15min, is then down to room temperature；The condition of the curing is room temperature
Under, 150 DEG C are warming up to through 15min, keeps the temperature 5min, 200 DEG C is warming up to through 10min, keeps the temperature 5min, be warming up to 250 through 10min
DEG C, 5min is kept the temperature, 300 DEG C is warming up to through 10min, keeps the temperature 30min, 350 DEG C is warming up to through 10min, keeps the temperature 30min, then pass through
60min is down to room temperature.
The copper-clad plate includes copper foil and the polyimide layer for being attached to copper foil surface, and the polyimide layer is by described low
The polymeric composition of DK and DF is coated on copper foil surface and is formed by heating high temperature cyclization.The polyimide layer with a thickness of
9-50um, the copper foil with a thickness of 12-18um.Test DK and DF is carried out to the copper-clad plate of preparation, then carries out test removing
Intensity finally carries out drift tin test.According to the above-mentioned test result in table 3, it may be said that bright copper-clad plate performance of the invention compared with than
It is good compared with example.
Table 3
* 30% viscosity 30000-60000CPs of curable type part.
Diamines dosage is total up to 21.21g in embodiment 9, and diamines dosage is total up to 21.49g, embodiment 11 in embodiment 10
Middle diamines dosage is total up to 21.76g, and diamines dosage is total up to 22.04g in embodiment 12.
Comparative example 1 and 2
Comparative example 1 and comparative example 2 are specific as shown in table 4 and Fig. 6.Fig. 6 is the preparation process flow of the copper-clad plate of comparative example
Figure.Coating of liquid crystalline polymer (LCP) on copper foil, then toasts 20min under the conditions of at a temperature of 90 °C, is then in temperature
180min is made annealing treatment under conditions of 300 DEG C, obtains product.
Table 4
| Comparative example 1 | Comparative example 2 | |
| Manufacturer | Taiflex (2LP) is general | Azotek (LDS) high frequency |
| Model | 2LP | LDS |
| DK(10GHz) | 3.2 | 2.8 |
| DF(10GHz) | 0.008 | 0.004 |
| Peel strength (Kgf/cm) | 0.85 | 0.55 |
| Float tin test | 320℃10sec PASS | 340℃10sec PASS |
Circuit board is made in copper-clad plate prepared by embodiment 1~12.
Comparative example 3~5
Raw material used by comparative example 3~5 is as shown in table 1~3, comprising the following steps: will by matching described in table 1~3
NMP, PDA, ODA high-speed stirred add dicarboxylic anhydride BPDA or BPADA or TAHQ, are stirred to react 12 hours to dissolving, and obtain high
Molecular composition.
The preparation method of copper-clad plate prepared by the polymeric composition, comprising the following steps:
By the polymeric composition via coating process, being coated on copper foil, (copper foil is Cu:BHFX-92F-HA-
V2-12 μm, RZ=0.45 (day mine)) on, polyimide layer is formed through overbaking, curing, obtains copper-clad plate；The item of the baking
Part is 140 DEG C, keeps the temperature 15min, is then down to room temperature；The condition of the curing is at room temperature, to be warming up to 150 DEG C through 15min, protect
Warm 5min, is warming up to 200 DEG C through 10min, keeps the temperature 5min, is warming up to 250 DEG C through 10min, keeps the temperature 5min, be warming up to through 10min
300 DEG C, 30min is kept the temperature, 350 DEG C is warming up to through 10min, keeps the temperature 30min, be then down to room temperature through 60min.
The copper-clad plate includes copper foil and the polyimide layer for being attached to copper foil surface, and the polyimide layer is by the height
Molecular composition is coated on copper foil surface and is formed by heating high temperature cyclization.The polyimide layer with a thickness of 9-50um, institute
State copper foil with a thickness of 12-18um.Test DK and DF is carried out to the copper-clad plate of preparation, then carries out test peel strength, finally
Carry out drift tin test.
Diamines selects ODA+DTZ+APAB in Examples 1 to 4, and diamines selects ODA+PDA, other components one in comparative example 3
Sample, manufactured copper-clad plate find that DK is respectively 2.89,2.86,2.86,2.82 in Examples 1 to 4 by performance test, compare
DK is 3.2 in example 3, and discovery embodiment is reduced compared with the DK value of comparative example；In Examples 1 to 4 DF be respectively 0.0038,0.0036,
0.0035,0.0035, DF is 0.008 in comparative example 3, and discovery embodiment is reduced compared with the DK value of comparative example；In conclusion by choosing
DK and DF can be effectively reduced with diamines used in the embodiment of the present invention.
Diamines selects ODA+DTZ+APAB in embodiment 5~8, and diamines selects ODA+PDA, other components one in comparative example 4
Sample, manufactured copper-clad plate find that DK is respectively 2.89,2.86,2.86,2.82 in embodiment 5~8 by performance test, compare
DK is 3.1 in example 4, and discovery embodiment is reduced compared with the DK value of comparative example；In embodiment 5~8 DF be respectively 0.0038,0.0036,
0.0035,0.0035, DF is 0.008 in comparative example 4, and discovery embodiment is reduced compared with the DK value of comparative example；In conclusion by choosing
DK and DF can be effectively reduced with diamines used in the embodiment of the present invention.
Diamines selects ODA+DTZ+APAB in embodiment 9~12, and diamines selects ODA+PDA, other components one in comparative example 5
Sample, manufactured copper-clad plate find that DK is respectively 3.14,3.18,3.23,3.27 in embodiment 9~12 by performance test, compare
DK is 3.3 in example 5, and discovery embodiment is reduced compared with the DK value of comparative example；In embodiment 9~12 DF be respectively 0.0034,0.0028,
0.0028,0.0022, DF is 0.006 in comparative example 5, and discovery embodiment is reduced compared with the DK value of comparative example；In conclusion by choosing
DK and DF can be effectively reduced with diamines used in the embodiment of the present invention.
In conclusion introducing APAB in an embodiment of the present invention, C=OO functional group is added in structure can be effectively reduced DF
(reducing about 1/2), and comparative example declines compared with the pulling force of embodiment, therefore DTZ need to be added and promote value of thrust.
Comparative example 6~8
Raw material used by comparative example 6~8 is as shown in table 5, comprising the following steps: by proportion described in table 5 by NMP,
PDA, ODA, DTZ high-speed stirred add dicarboxylic anhydride BPDA or BPADA or TAHQ, are stirred to react 12 hours to dissolving, and obtain high
Molecular composition.
The polymeric composition is prepared into the preparation method of copper-clad plate, comprising the following steps:
By the polymeric composition via coating process, being coated on copper foil, (copper foil is Cu:BHFX-92F-HA-
V2-12 μm, RZ=0.45 (day mine)) on, polyimide layer is formed through overbaking, curing, obtains copper-clad plate；The item of the baking
Part is 140 DEG C, keeps the temperature 15min, is then down to room temperature；The condition of the curing is at room temperature, to be warming up to 150 DEG C through 15min, protect
Warm 5min, is warming up to 200 DEG C through 10min, keeps the temperature 5min, is warming up to 250 DEG C through 10min, keeps the temperature 5min, be warming up to through 10min
300 DEG C, 30min is kept the temperature, 350 DEG C is warming up to through 10min, keeps the temperature 30min, be then down to room temperature through 60min.
The copper-clad plate includes copper foil and the polyimide layer for being attached to copper foil surface, and the polyimide layer is by the height
Molecular composition is coated on copper foil surface and is formed by heating high temperature cyclization.The polyimide layer with a thickness of 9-50um, institute
State copper foil with a thickness of 12-18um.Test DK and DF is carried out to the copper-clad plate of preparation, then carries out test peel strength, finally
Carry out drift tin test.
Table 5
Embodiment 13~15
Raw material used by embodiment 13~15 is as shown in table 6, a kind of system of the polymeric composition of the low DK and DF
Preparation Method, comprising the following steps: by proportion described in table 6 by NMP, APAB, ODA, DTZ, after high-speed stirred to after dissolving, then plus
Enter dicarboxylic anhydride to be stirred to react 12 hours, obtains the polymeric composition of the low DK and DF.
A kind of preparation method of the copper-clad plate of the polymeric composition preparation of the low DK and DF, comprising the following steps:
By the polymeric composition of the low DK and DF via coating process, be coated on copper foil (copper foil is Cu:
BHFX-92F-HA-V2-12 μm, RZ=0.45 (day mine)) on, the polyimide layer of low DK and DF are formed through overbaking, curing,
Obtain copper-clad plate；The condition of the baking is 140 DEG C, keeps the temperature 15min, is then down to room temperature；The condition of the curing is room temperature
Under, 150 DEG C are warming up to through 15min, keeps the temperature 5min, 200 DEG C is warming up to through 10min, keeps the temperature 5min, be warming up to 250 through 10min
DEG C, 5min is kept the temperature, 300 DEG C is warming up to through 10min, keeps the temperature 30min, 350 DEG C is warming up to through 10min, keeps the temperature 30min, then pass through
60min is down to room temperature.
The copper-clad plate includes copper foil and the polyimide layer for being attached to copper foil surface, and the polyimide layer is by described low
The polymeric composition of DK and DF is coated on copper foil surface and is formed by heating high temperature cyclization.The polyimide layer with a thickness of
9-50um, the copper foil with a thickness of 12-18um.Test DK and DF is carried out to the copper-clad plate of preparation, then carries out test removing
Intensity finally carries out drift tin test.According to the above-mentioned test result in table 6, it may be said that bright copper-clad plate performance of the invention compared with than
It is good compared with example.
Table 6
Diamines selects ODA+DTZ+APAB in embodiment 13, and diamines selects ODA+DTZ+PDA, other components in comparative example 6
Equally, manufactured copper-clad plate is found by performance test, and DK is 3.2 in embodiment 13, and DK is 3 in comparative example 6, and discovery will be implemented
Diamines APAB is changed to the PDA in comparative example 6 in example 13, and other diamines are constant, and embodiment is increased compared with the DK value of comparative example；Embodiment
DF is 0.0043 in 13, and DF is 0.01 in comparative example 6, and diamines APAB in embodiment 13 is changed to the PDA in comparative example 6 by discovery,
Other diamines are constant, and embodiment is reduced compared with the DF value of comparative example；In conclusion by selecting diamines used in the embodiment of the present invention
DF can be effectively reduced, DK value increases.It can also be seen that thermogravimetric weight loss temperature of the embodiment compared with comparative example from table 5 and table 6
It improves (heat resistance increase).
Diamines selects ODA+DTZ+APAB in embodiment 14, and diamines selects ODA+DTZ+PDA, other components in comparative example 7
Equally, manufactured copper-clad plate is found by performance test, and DK is 3.2 in embodiment 14, and DK is 3.1 in comparative example 7, and discovery will be real
It applies diamines APAB in example 14 and is changed to the PDA in comparative example 7, other diamines are constant, and embodiment is increased compared with the DK value of comparative example；Implement
DF is 0.0044 in example 14, and DF is 0.009 in comparative example 7, and diamines APAB in embodiment 14 is changed in comparative example 7 by discovery
PDA, other diamines are constant, and embodiment is reduced compared with the DF value of comparative example；In conclusion used in the embodiment of the present invention by selecting
Diamines can effectively reduce DF, and DK value increases.It can also be seen that thermogravimetric weight loss of the embodiment compared with comparative example from table 5 and table 6
Temperature improves (heat resistance increase).
Diamines selects ODA+DTZ+APAB in embodiment 15, and diamines selects ODA+DTZ+PDA, other components in comparative example 8
Equally, manufactured copper-clad plate is found by performance test, and DK is 3.4 in embodiment 15, and DK is 3.2 in comparative example 8, and discovery will be real
It applies diamines APAB in example 15 and is changed to the PDA in comparative example 8, other diamines are constant, and embodiment is increased compared with the DK value of comparative example；Implement
DF is 0.0035 in example 15, and DF is 0.007 in comparative example 8, and diamines APAB in embodiment 15 is changed in comparative example 8 by discovery
PDA, other diamines are constant, and embodiment is reduced compared with the DF value of comparative example；In conclusion used in the embodiment of the present invention by selecting
Diamines can effectively reduce DF, and DK value increases.
In conclusion the PDA in comparative example is changed to APAB, due to introducing C=OO structure, DF can be effectively reduced
Value.In the embodiment of the present invention be added APAB (functional group C=OO) structure stack can be allowed close, the value of DF is effectively reduced, from than
It can be clearly visible DF drop by half compared with example, but because the too close storehouse of structure causes steel that pulling force is made to decline (comparative example 3-5) firmly,
The N in structure is enabled to generate coordination with copper to promote pulling force so DTZ is added in structure.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of polymeric composition of low DK and DF, it is characterised in that: be made of the component of following parts by weight:
20~60 parts of dicarboxylic anhydride containing ester groups；
1~25 part of diamine monomer containing pyrimidine group；
100~180 parts of solvent.
2. the polymeric composition of low DK and DF according to claim 1, it is characterised in that: described containing ester groups
Dicarboxylic anhydride is aromatic tetracarboxylic dianhydride, preferably the bis- tritrimellitate dianhydrides of p-phenylene-, 3,3', 4,4'- biphenyl tetracarboxylic acids
Acid dianhydride, Bisphenol A Type Diether Dianhydride.
3. the polymeric composition of low DK and DF according to claim 1, it is characterised in that: described containing pyrimidine group
Diamine monomer is aromatic diamine, preferably 3,5- diaminostilbene, 2,4- triazoles, the bis- (4-aminobenzoic acid of Isosorbide-5-Nitrae-phenylene
Ester), two p-aminophenyl ester of terephthalic acid (TPA), p-aminobenzoic acid p-aminophenyl ester, 4,4 '-diaminodiphenyl ethers, bis- (4- amino
Phenyl) terephthalate.
4. the polymeric composition of low DK and DF according to claim 3, it is characterised in that: the solvent is N- methyl pyrrole
Pyrrolidone, DMAC N,N' dimethyl acetamide, butyrolactone, N.N- dimethylformamide, dimethyl sulfoxide；
The diamine monomer containing pyrimidine group is 3,5- diaminostilbene, 2,4- triazole, p-aminobenzoic acid p-aminophenyl
The mixture of ester, 4,4 '-diaminodiphenyl ethers；
The solid content of the polymeric composition of the low DK and DF is 30wt%, and viscosity is 30000~60000CPs.
5. copper-clad plate prepared by the polymeric composition of described in any item low DK and DF of Claims 1-4 a kind of, feature exist
In: including copper foil and it is attached to the polyimide layer of copper foil surface, the polyimide layer is by the macromolecule of the low DK and DF
Composition is coated on copper foil surface and is formed by heating high temperature cyclization.
6. copper-clad plate prepared by the polymeric composition of low DK and DF according to claim 5, it is characterised in that: described poly-
Imide layer with a thickness of 9-50um；
The copper foil with a thickness of 12-18um.
7. a kind of preparation method of the copper-clad plate of the polymeric composition preparation of low DK and DF described in claim 5 or 6, special
Sign is: the following steps are included:
It by the polymeric composition of the low DK and DF via coating process, is coated on copper foil, is formed through overbaking, curing low
The polyimide layer of DK and DF obtains copper-clad plate.
8. the preparation method of copper-clad plate prepared by the polymeric composition of low DK and DF according to claim 7, feature
It is: described BHFX-92F-HA-V2-12 μm of copper foil model, RZ=0.45；
The condition of the baking is 140 DEG C, keeps the temperature 15min, is then down to room temperature.
9. the preparation method of copper-clad plate prepared by the polymeric composition of low DK and DF according to claim 7, feature
Be: the condition of the curing is at room temperature, to be warming up to 150 DEG C through 15min, keep the temperature 5min, is warming up to 200 DEG C through 10min, protects
Warm 5min, is warming up to 250 DEG C through 10min, keeps the temperature 5min, is warming up to 300 DEG C through 10min, keeps the temperature 30min, be warming up to through 10min
350 DEG C, 30min is kept the temperature, is then down to room temperature through 60min.
10. made of a kind of copper-clad plate prepared by the polymeric composition the described in any item low DK and DF of Claims 1-4
Circuit board.
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| CN112239539A (en) * | 2019-07-16 | 2021-01-19 | 臻鼎科技股份有限公司 | Polyamide acid composition, polyimide copper-clad plate and circuit board |
| WO2021251120A1 (en) * | 2020-06-09 | 2021-12-16 | 日東電工株式会社 | Polyimide film and metal-lined layered sheet |
| EP4079790A1 (en) * | 2021-04-19 | 2022-10-26 | Nitto Denko Corporation | Porous polyimide film |
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