CN110857332B - Polymer resin, polymer resin composition and copper-clad plate - Google Patents

Polymer resin, polymer resin composition and copper-clad plate Download PDF

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CN110857332B
CN110857332B CN201810962530.2A CN201810962530A CN110857332B CN 110857332 B CN110857332 B CN 110857332B CN 201810962530 A CN201810962530 A CN 201810962530A CN 110857332 B CN110857332 B CN 110857332B
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polymer resin
formula
chemical structural
structural formula
resin composition
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CN110857332A (en
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向首睿
黄楠昆
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Zhen Ding Technology Co Ltd
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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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • 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
    • B32B2457/00—Electrical equipment

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  • Polymers & Plastics (AREA)
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  • Fluid Mechanics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention relates to a high molecular resin, which comprises a copolymerization high polymer formed by repeating units shown in a formula I and a formula II; wherein, the chemical structural formula of formula I is:
Figure DDA0001774133660000011
the chemical structural formula of formula II is:
Figure DDA0001774133660000012
X 1 is a straight carbon chain diol dicarboxylate group, X 2 Is a cyclic carbon chain diol dicarboxylate group; y is 1 、Y 2 All include a phenyl ester group. The invention also relates to a high molecular resin composition and a copper-clad plate.

Description

Polymer resin, polymer resin composition and copper-clad plate
Technical Field
The invention relates to a high molecular resin, a high molecular resin composition and a copper-clad plate.
Background
In the big data age, information processing of electronic products is continuously developing towards high frequency and high speed digitization of signal transmission. In order to ensure that the electronic product has good signal transmission quality under the condition of high-frequency signal transmission, it is necessary that the transmission line in the conductive copper foil of the flexible circuit board and the electronic element connected with the transmission line are in an impedance matching state, so as to avoid the phenomena of signal reflection, scattering, attenuation, delay and the like. The dielectric constant and dielectric dissipation factor of the material of the adhesive layer in contact with the conductive circuit in the flexible circuit board are important factors influencing the impedance matching of high-frequency transmission. In the prior art, high-frequency material polyphenylene oxide resin is often added into an adhesive layer, so that the adhesive layer has a low dielectric constant and a low dielectric dissipation factor. However, the structure of polyphenylene ether resin is too rigid, and excessive addition of a brittle risk is not suitable for application as a flexible board high-frequency substrate.
Disclosure of Invention
In view of the above, it is desirable to provide a polymer resin composition, a polymer resin composition and a copper-clad plate with low dielectric constant suitable for the application of a flexible printed circuit board as a high-frequency substrate.
A high molecular resin comprises a copolymerized high polymer formed by repeating units shown in formula I and formula II; wherein, the chemical structural formula of formula I is:
Figure BDA0001774133650000011
the chemical structural formula of formula II is:
Figure BDA0001774133650000012
x1 is a straight carbon chain diol carbamate group, and X2 is a ring carbon chain diol carbamate group; y1 and Y2 both comprise a phenyl ester group.
Further, the polymer resin has a molar fraction of the repeating unit of formula I of 10% to 95%.
Further, in the polymer resin, X in the repeating unit of formula I 1 With X in the recurring unit of formula II 2 The molar ratio of (A) is 0.11 to 19.
Further, X 1 Has the chemical structural formula of
Figure BDA0001774133650000021
(R is a carbon chain containing 6 to 12 carbon atoms) or
Figure BDA0001774133650000022
At least one of (1).
Further, X 2 Has a chemical structural formula of
Figure BDA0001774133650000023
Figure BDA0001774133650000024
At least one of (a).
Further, Y 1 Has the chemical structural formula of
Figure BDA0001774133650000025
Figure BDA0001774133650000026
Figure BDA0001774133650000027
At least one of, Y 2 Has the chemical structural formula of
Figure BDA0001774133650000028
Figure BDA0001774133650000029
At least one of, Y 1 And Y 2 The same is true.
Further, Y 1 Has the chemical structural formula of
Figure BDA0001774133650000031
Figure BDA0001774133650000032
Figure BDA0001774133650000033
At least one of (a), Y 2 Has a chemical structural formula of
Figure BDA0001774133650000034
Figure BDA0001774133650000035
At least one of (a), Y 1 And Y 2 Are not the same.
Further, the polymer resin is generated by performing high-temperature ring-closing reaction on at least one dianhydride monomer with a straight carbon chain diol diester group, at least one dianhydride monomer with a cyclic carbon chain diol diester group and at least one diamine monomer with a phenyl ester group through polymer copolymerization.
Further, theThe chemical structural formula of the dianhydride monomer with the straight carbon chain dihydric alcohol diformate group is shown in the specification
Figure BDA0001774133650000036
(R is a carbon chain containing 6 to 12 carbon atoms) or
Figure BDA0001774133650000037
Further, the chemical structural formula of the dianhydride monomer with the cyclic carbon chain diol diformate group is shown in the specification
Figure BDA0001774133650000041
Figure BDA0001774133650000042
At least one of (1).
Further, the chemical structural formula of the diamine monomer with the phenyl ester group is shown in the specification
Figure BDA0001774133650000043
Figure BDA0001774133650000044
At least one of (a).
A polymer resin composition, comprising the polymer resin, an inorganic powder and a solvent, wherein the weight ratio of the inorganic powder to the polymer resin composition is 0.5-20, and the weight ratio of the solvent to the polymer resin composition is 60-90.
The copper-clad plate comprises the high polymer resin composition and a copper foil layer, wherein the high polymer resin composition is formed on the copper foil layer.
The polymer resin and the polymer resin composition provided by the invention have lower dielectric constant D k The copper-clad laminate has better heat resistance and copper peel strength, and is suitable for the pressing application requirement of the manufacturing process of the flexible circuit board.
Detailed Description
In order to further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed descriptions of the structures, features, effects and preparation methods of the polymer resin and the polymer resin composition provided by the present invention are provided in the following embodiments.
The present invention provides a polymer resin composition, which has thermal plasticity or solubility and can be used in a substrate, an adhesive layer or a cover film of a circuit board (such as a flex-rigid board or a flexible circuit board).
The polymer resin composition comprises polymer resin, inorganic powder and a solvent. Wherein the weight ratio of the inorganic powder to the polymer resin composition is 0.5-20, and the weight ratio of the solvent to the polymer resin composition is 60-90.
Wherein, the polymer resin comprises a formula I (chemical structural formula is:
Figure BDA0001774133650000051
) And formula II (chemical structural formula:
Figure BDA0001774133650000052
) A copolymer polymer composed of repeating units; wherein, X 1 Is a straight carbon chain diol carbamate group, and X2 is a ring carbon chain diol carbamate group; y is 1 、Y 2 All include a phenyl ester group.
Wherein Y1 and Y2 may be the same or different.
Wherein the molar fraction of the repeating unit of formula I in the polymer resin is 10 to 95%.
Wherein, in the polymer resin, X in the repeating unit of formula I 1 With X in the repeat unit of formula II 2 The molar ratio of (A) is 0.11 to 19.
In this embodiment, X 1 May be selected from, but is not limited to
Figure BDA0001774133650000053
(R isA carbon chain containing 6 to 12 carbon atoms) or
Figure BDA0001774133650000054
In this embodiment, X 2 May be selected from, but is not limited to
Figure BDA0001774133650000055
At least one of (1).
Wherein, Y 1 May be selected from, but is not limited to
Figure BDA0001774133650000061
Figure BDA0001774133650000062
Figure BDA0001774133650000063
At least one of (1).
Wherein Y is 2 May be selected from, but is not limited to
Figure BDA0001774133650000064
Figure BDA0001774133650000065
Figure BDA0001774133650000066
At least one of (a).
The polymer resin is prepared from at least one dianhydride monomer with a straight carbon chain dihydric alcohol diformate group, at least one dianhydride monomer with a cyclic carbon chain dihydric alcohol diformate group and at least one diamine monomer with a phenyl ester group through high-temperature ring-closing reaction of polymer copolymerization.
In this embodiment, the chemical structural formula of the dianhydride monomer with the straight carbon chain diol dicarboxylate group can be selected from, but is not limited to
Figure BDA0001774133650000067
(R is a carbon chain containing 6 to 12 carbon atoms) or
Figure BDA0001774133650000068
In this embodiment, the chemical structural formula of the dianhydride monomer with the cyclic carbon chain diol dicarboxylate group can be selected from, but is not limited to
Figure BDA0001774133650000071
In this embodiment, the chemical structure of the diamine monomer with a phenyl ester group can be selected from, but not limited to
Figure BDA0001774133650000072
Figure BDA0001774133650000073
Wherein, the inorganic powder can be selected from but not limited to silica, calcium carbonate, talcum powder, calcined kaolin and the like.
The silica may be molten silica, non-molten silica, porous silica or hollow silica.
Preferably, the inorganic powder may be selected from, but not limited to, nano hollow silica, solar chemical nano hollow silica, granddex nano hollow silica of the Niger iron mining company.
Wherein the solvent is selected from but not limited to those with the chemical structural formula
Figure BDA0001774133650000074
1,3-Dimethyl-2-imidazolidinone (1, 3-Dimethyl-2-imidazolidinone; DMI) having a chemical structural formula
Figure BDA0001774133650000075
The N-methyl-2-pyrrolidone (NMP) has a chemical structural formula
Figure BDA0001774133650000081
The gamma-butyrolactone (GBL) has a chemical structural formula
Figure BDA0001774133650000082
N, N-Dimethylacetamide (DMAC) with a chemical structural formula
Figure BDA0001774133650000083
Xylene (Xylene) with the chemical structural formula
Figure BDA0001774133650000084
Toluene (Toluene) or the chemical structural formula is
Figure BDA0001774133650000085
And (3) at least one of cyclohexanone (cyclohexone).
Wherein, the reaction mechanism for preparing the high polymer resin by the dianhydride monomer and the diamine monomer is as follows:
Figure BDA0001774133650000086
the invention also relates to a copper-clad plate which comprises the high polymer resin composition and a copper foil layer, wherein the high polymer resin composition is formed on the copper foil layer.
The copper-clad plate can be a double-sided copper-clad plate or a single-sided copper-clad plate. The polymer resin composition may be formed directly on the copper foil layer or indirectly on the copper foil layer, for example: an insulating substrate layer or an insulating substrate layer and a glue layer are also formed between the copper foil layer and the polymer resin composition.
The present invention will be specifically described below with reference to examples and comparative examples.
Example 1
Firstly, 120g of a compound represented by the following chemical formula
Figure BDA0001774133650000087
Adding the N-methyl-2-pyrrolidone into a reaction bottle, and adding 3g of inorganic SiO 2 Uniformly stirring and dissolving the powder, and then adding 10.23g of the powder with the chemical structural formula shown in the specification
Figure BDA0001774133650000091
4-aminobenzoic acid-4-aminophenyl ester, stirring thoroughly to dissolve, then adding 6.5g of a compound having a chemical structural formula
Figure BDA0001774133650000092
(R is a carbon chain containing 6-12 carbon atoms) for 2 hours, and adding 13.25g of dianhydride monomer with the chemical structural formula
Figure BDA0001774133650000093
Stirring the dianhydride monomer for 4 hours to obtain the thermoplastic polymer resin composition. Defoaming the polymer resin composition, coating the polymer resin composition on a copper foil substrate, introducing nitrogen, and baking in two stages, wherein the first stage temperature is 210 ℃, the heating rate is 1.6 ℃ per minute, so as to remove residual solvent, and keeping the temperature for half an hour; and then heating to the second stage temperature of 350 ℃, wherein the heating rate is 1 ℃ per minute, and dehydrating and cyclizing the polymer resin composition at 350 ℃ to generate a polymer film. Then cooling and cooling to obtain a single-sided flexible copper foil substrate; further, the single-sided flexible copper foil substrate is thermally pressed to form a double-sided flexible copper foil substrate. The hot pressing temperature is: 280 ℃, hot pressure: 30 kgf/mm, hot pressing time: for 60 minutes.
Example 2
Firstly, 120g of a compound represented by the following chemical formula
Figure BDA0001774133650000094
Adding the N-methyl-2-pyrrolidone into a reaction bottle, and adding 3g of inorganic SiO 2 Uniformly stirring and dissolving the powder, and then adding 10.39g of the powder with a chemical structural formula shown in the specification
Figure BDA0001774133650000095
4-aminobenzoic acid-4-aminophenyl ester is fully stirred and dissolved, and 11.36g of the compound with the chemical structural formula
Figure BDA0001774133650000096
(R is a carbon chain containing 6-12 carbon atoms) for 2 hours, and then 10.39g of dianhydride monomer with the chemical structural formula
Figure BDA0001774133650000101
Stirring the dianhydride monomer for 4 hours to obtain the thermoplastic polymer resin composition. Defoaming the polymer resin composition, coating the polymer resin composition on a copper foil substrate, introducing nitrogen, and baking in two stages, wherein the first stage temperature is 210 ℃, the heating rate is 1.6 ℃ per minute, so as to remove residual solvent, and keeping the temperature for half an hour; and then heating to the second-stage temperature of 350 ℃, wherein the heating rate is 1 ℃ per minute, and dehydrating and cyclizing the polymer resin composition at 350 ℃ to generate the polymer film. Then cooling and cooling to obtain a single-sided flexible copper foil substrate; further, the single-sided flexible copper foil substrate is thermally pressed to form a double-sided flexible copper foil substrate. The hot pressing temperature is: 280 ℃, the hot pressure is: 30 kg force/mm, hot pressing time: for 60 minutes.
Example 3
Firstly, 120g of a compound of the formula
Figure BDA0001774133650000102
Adding the N-methyl-2-pyrrolidone into a reaction bottle, and adding 3g of inorganic SiO 2 Uniformly stirring and dissolving the powder, and then adding 4.69g of a chemical structural formula
Figure BDA0001774133650000103
4-aminobenzoic acid-4-aminophenyl ester and 7.16g of a chemical mechanism having the formula
Figure BDA0001774133650000104
The 1, 4-bis (4-aminobenzoyloxy) benzene is fully stirred and dissolved, and then 5.99g of the mixture is added
Figure BDA0001774133650000105
(R is a carbon chain containing 6-12 carbon atoms) for 2 hours, and then adding 12.16g of dianhydride monomer with the chemical structural formula
Figure BDA0001774133650000106
Stirring for 4 hours to obtain the thermoplastic polymer resin composition. Defoaming the polymer resin composition, coating the polymer resin composition on a copper foil substrate, introducing nitrogen, and baking in two stages, wherein the first stage temperature is 210 ℃, the heating rate is 1.6 ℃ per minute, so as to remove residual solvent, and keeping the temperature for half an hour; and then heating to the second stage temperature of 350 ℃, wherein the heating rate is 1 ℃ per minute, and dehydrating and cyclizing the polymer resin composition at 350 ℃ to generate a polymer film. Then cooling and cooling to obtain a single-sided flexible copper foil substrate; further, the single-sided flexible copper foil substrate is thermally pressed to form a double-sided flexible copper foil substrate. The hot pressing temperature is: 280 ℃, the hot pressure is: 30 kgf/mm, hot pressing time: for 60 minutes.
Example 4
Firstly, 120g of a compound represented by the following chemical formula
Figure BDA0001774133650000111
Adding the N-methyl-2-pyrrolidone into a reaction bottle, and adding 3g of inorganic SiO 2 Uniformly stirring and dissolving the powder, and then adding 6.58g of a chemical structural formula
Figure BDA0001774133650000112
1, 4-bis (4-aminobenzoyloxy) benzene and 6.76g of a compound having a chemical formula of
Figure BDA0001774133650000113
The bis- (4-aminophenyl) -1, 4-estercyclohexane was thoroughly stirred and dissolved, and 5.5g of a compound having the chemical formula
Figure BDA0001774133650000114
(R is a carbon chain containing 6-12 carbon atoms) dicarboxylic anhydrideStirring the monomer for 2 hours, and adding 11.16g of a mixture with a chemical structural formula
Figure BDA0001774133650000115
Stirring the dianhydride monomer for 4 hours to obtain the thermoplastic polymer resin composition. Defoaming the polymer resin composition, coating the polymer resin composition on a copper foil substrate, introducing nitrogen, and baking in two stages, wherein the first stage temperature is 210 ℃, the heating rate is 1.6 ℃ per minute, so as to remove residual solvent, and keeping the temperature for half an hour; and then heating to the second-stage temperature of 350 ℃, wherein the heating rate is 1 ℃ per minute, and dehydrating and cyclizing the polymer resin composition at 350 ℃ to generate the polymer film. Then cooling and cooling to obtain a single-sided flexible copper foil substrate; further, the single-sided flexible copper foil substrate is thermally pressed to form a double-sided flexible copper foil substrate. The hot pressing temperature is: 280 ℃, the hot pressure is: 30 kgf/mm, hot pressing time: for 60 minutes.
Example 5
Firstly, 120g of a compound represented by the following chemical formula
Figure BDA0001774133650000121
Adding the N-methyl-2-pyrrolidone into a reaction bottle, and adding 3g of inorganic SiO 2 Uniformly stirring and dissolving the powder, and then adding 4.66g of a chemical structural formula
Figure BDA0001774133650000122
4-aminobenzoic acid-4-aminophenyl ester and 7.32g of a compound having a chemical structural formula of
Figure BDA0001774133650000123
The bis- (4-aminophenyl) -1, 4-estercyclohexane was thoroughly stirred and dissolved, and 5.95g of a compound having the chemical formula
Figure BDA0001774133650000124
(R is a carbon chain containing 6-12 carbon atoms) for 2 hours, and adding 12.07g of dianhydride monomer with the chemical structural formula
Figure BDA0001774133650000125
Stirring the dianhydride monomer for 4 hours to obtain the thermoplastic polymer resin composition. Defoaming the polymer resin composition, coating the polymer resin composition on a copper foil substrate, introducing nitrogen, and baking in two stages, wherein the first stage temperature is 210 ℃, the heating rate is 1.6 ℃ per minute, so as to remove residual solvent, and keeping the temperature for half an hour; and then heating to the second stage temperature of 350 ℃, wherein the heating rate is 1 ℃ per minute, and dehydrating and cyclizing the polymer resin composition at 350 ℃ to generate a polymer film. Then cooling and cooling to obtain a single-sided flexible copper foil substrate; further, the single-sided flexible copper foil substrate is thermally pressed to form a double-sided flexible copper foil substrate. The hot pressing temperature is: 280 ℃, the hot pressure is: 30 kgf/mm, hot pressing time: for 60 minutes.
Comparative example 1
Laminating a commercially available polyimide film on a copper foil substrate to form a single-sided flexible copper foil substrate; further, the single-sided flexible copper foil substrate is thermally pressed to form a double-sided flexible copper foil substrate. The hot pressing temperature is: 280 ℃, the hot pressure is: 30 kgf/mm, hot pressing time: for 60 minutes.
Comparative example 2
Pressing a commercially available epoxy adhesive film on the copper foil substrate to form a single-sided flexible copper foil substrate; further, the single-sided flexible copper foil substrate is thermally pressed to form a double-sided flexible copper foil substrate. The hot pressing temperature is: 280 ℃, the hot pressure is: 30 kgf/mm, hot pressing time: for 60 minutes.
Dielectric constant D of Polymer films 1 to 5 formed in examples 1 to 5 and polyimide films and epoxy adhesive films formed in comparative examples 1 to 2 k And dielectric loss D f The five polymer films, a polyimide film and an epoxy adhesive film were tested separately, and the copper peel strength test and the floating tin heat resistance test were performed.
The test results refer to the performance test data in table 1. If the adhesive layer does not generate phenomena such as foaming and stripping when the temperature of the tin bleaching heat resistance test condition is more than or equal to 300 ℃ and 10 seconds, the tin bleaching heat resistance test result is 'pass', which indicates that the circuit board meets the heat resistance requirement.
TABLE 1 measured values of data relating to the adhesive layers in the above-mentioned respective circuit boards
Figure BDA0001774133650000131
As can be seen from the foregoing Table I, the 5 polymer films formed from the polymer resin compositions of examples 1 to 5 of the present invention have lower dielectric constants D than the polyimide film and the epoxy resin film of comparative examples 1 to 2 k And the copper alloy has better heat resistance and copper peeling strength when heated.
The polymer resin composition and the polymer film provided by the invention are formed by high-temperature ring-closing of a monomer with long carbon chain ester-based dianhydride and a monomer with ester-based diamine through polymer copolymerization, the glass transition temperature Tg (designed within the range of 250-350 ℃) of the polymer resin composition is controlled through molecular design, the polymer is molten and flows, a low-dielectric flexible copper foil substrate can be formed through hot pressing, and the low-dielectric flexible copper foil substrate has a low dielectric constant D k The copper-clad laminate has better heat resistance and copper peel strength, and is suitable for the pressing application requirement of the manufacturing process of the flexible circuit board.
Although the present invention has been described with reference to the above preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (11)

1. A polymer resin, which is characterized in that the polymer resin comprises a copolymerized polymer composed of repeating units of formula I and formula II(ii) a Wherein, the chemical structural formula of formula I is:
Figure FDA0003732336980000011
the chemical structural formula of formula II is:
Figure FDA0003732336980000012
X 1 is a straight carbon chain diol dicarboxylate group, X 1 Has the chemical structural formula of
Figure FDA0003732336980000013
Wherein R is a carbon chain containing 6-12 carbon atoms; x 2 Is a cyclic carbon chain diol dicarboxylate group, X 2 Has the chemical structural formula of
Figure FDA0003732336980000014
Figure FDA0003732336980000015
At least one of; y is 1 、Y 2 All include a phenyl ester group.
2. The polymer resin according to claim 1, wherein the molar fraction of the recurring unit of formula I in the polymer resin is from 10% to 95%.
3. The polymer resin according to claim 1, wherein X in the repeating unit of formula I is X 1 With X in the recurring unit of formula II 2 The molar ratio of (A) is 0.11 to 19.
4. The polymer resin according to claim 1, wherein Y is Y 1 Has the chemical structural formula of
Figure FDA0003732336980000021
Figure FDA0003732336980000022
At least one of (a), Y 2 Has a chemical structural formula of
Figure FDA0003732336980000023
Figure FDA0003732336980000024
Figure FDA0003732336980000025
At least one of (a), Y 1 And Y 2 The same is true.
5. The polymer resin according to claim 1, wherein Y is 1 Has the chemical structural formula of
Figure FDA0003732336980000026
Figure FDA0003732336980000027
At least one of, Y 2 Has the chemical structural formula of
Figure FDA0003732336980000028
Figure FDA0003732336980000029
Figure FDA0003732336980000031
At least one of (a), Y 1 And Y 2 Are not the same.
6. The polymeric resin of claim 1, wherein the polymeric resin is formed by a high temperature ring closure reaction of at least one dianhydride monomer with a straight carbon chain diol carbamate group, at least one dianhydride monomer with a cyclic carbon chain diol carbamate group, and at least one diamine monomer with a phenyl ester group through a polymer copolymerization.
7. The polymeric resin of claim 6, wherein the dianhydride monomer with a straight carbon chain diol dicarboxylate group has the chemical formula
Figure FDA0003732336980000032
R is a carbon chain containing 6-12 carbon atoms.
8. A polymeric resin according to claim 6, wherein the dianhydride monomer having a cyclic carbon chain diol dicarboxylate group has the chemical formula
Figure FDA0003732336980000033
Figure FDA0003732336980000034
At least one of (a).
9. The polymeric resin of claim 6, wherein the phenylene group-containing diamine monomer has the chemical formula
Figure FDA0003732336980000035
Figure FDA0003732336980000041
Figure FDA0003732336980000042
At least one of (a).
10. A polymer resin composition comprising the polymer resin according to any one of claims 1 to 9, an inorganic powder, and a solvent, wherein the weight ratio of the inorganic powder to the polymer resin composition is 0.5 to 20, and the weight ratio of the solvent to the polymer resin composition is 60 to 90.
11. A copper-clad plate comprising the polymeric resin composition of claim 10 and a copper foil layer, wherein the polymeric resin composition is formed on the copper foil layer.
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