CN109942815B - A kind of low dielectric constant polyimide composite resin and preparation method and application - Google Patents
A kind of low dielectric constant polyimide composite resin and preparation method and application Download PDFInfo
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Abstract
本发明公开了一种低介电常数的聚酰亚胺复合树脂及制备方法与应用，其由聚酰亚胺树脂单元与聚甲亚胺树脂单元通过共混共聚的形式组成；共聚物结构中形成网状结构，增大分子链间隙。通过聚甲亚胺树脂的引入，降低聚酰亚胺分子链的偶极矩；同时，聚合时采用含氟单体，共同降低聚酰亚胺复合树脂的介电常数。通过单体种类设计柔性的聚酰亚胺分子链段，来均衡高度刚性的聚甲亚胺分子链，使最终聚酰亚胺复合树脂中分子链段的刚性‑柔性达到一个较好的平衡点，不仅保证聚酰亚胺复合树脂有较好的机械性能，也保证聚酰亚胺复合树脂具有可控制的线性热膨胀系数，使聚酰亚胺复合树脂在挠性覆铜板、感光覆盖膜、线路板产品中有良好的应用前景。The invention discloses a polyimide composite resin with low dielectric constant, a preparation method and application, which are composed of a polyimide resin unit and a polyethylenimine resin unit in the form of blending and copolymerizing; Form a network structure and increase the gap between molecular chains. The dipole moment of the polyimide molecular chain is reduced by the introduction of the polyimide resin; at the same time, the fluorine-containing monomer is used in the polymerization to jointly reduce the dielectric constant of the polyimide composite resin. The flexible polyimide molecular segments are designed by monomer species to balance the highly rigid polyimide molecular chains, so that the rigidity-flexibility of the molecular segments in the final polyimide composite resin can reach a better balance point , not only ensures that the polyimide composite resin has good mechanical properties, but also ensures that the polyimide composite resin has a controllable linear thermal expansion coefficient, so that the polyimide composite resin can be used in flexible copper clad laminates, photosensitive cover films, circuits, etc. There are good application prospects in board products.
Description
Technical Field
The invention relates to the technical field of preparation of polyimide composite resin, in particular to polyimide composite resin obtained by blending and copolymerizing polyimide and polymethine, which has the characteristic of low dielectric constant and has good application in the fields of high-frequency high-speed circuits and electronic materials. The polyimide composite resin and the corresponding flexible copper clad laminate are suitable for flexible printed circuit boards for high-frequency transmission, insulating base materials of high-frequency electronic devices, high-fidelity signal transmission and various electronic and electrical products.
Background
Polyimide resin is a high-performance engineering plastic, and is widely applied to industrial products due to inherent heat resistance, thermal oxidation resistance, chemical stability, excellent mechanical property and thermal shock resistance, and the long-term use temperature range of-50 ℃ to 250 ℃. Polyimide has excellent insulating property, high mechanical property and strong processability, and has wide application in electronic products, particularly consumer high-end electronic products such as mobile phones, tablet computers, cameras and the like.
At present electronic product is constantly high-end, and the cell-phone is also about to promote 5G signal transmission's type, and the basic station of 5G signal will also begin to build, and this puts forward higher requirement to the inside circuit board of electronic product: on one hand, the insulating material on the circuit board needs to have lower dielectric constant and dielectric loss, so that the 5G signal is not distorted in the transmission process, and the circuit board is ensured not to generate heat when working in a 5G mode; on the other hand, the 5G signal requires the copper wire on the internal circuit board to have better transmission efficiency, and the roughness between the copper wire and the insulating substrate is as low as possible due to the skin effect of the current, which leads to the current conduction on the contact surface of the copper wire and the insulating base film layer, thereby reducing the signal transmission rate reduction and the energy loss. The current circuit board substrate mainly comprises epoxy resin, acrylic resin and polyimide resin, wherein the dielectric constant of the polyimide resin is 3.3-3.4, the dielectric loss is about 0.007, and the material is the material with the performance closest to the requirement of 5G signal transmission. Even so, the dielectric constant of the polyimide resin is high, which causes transmission loss, distortion and heat generation in the lines during 5G signal transmission.
In general, methods for lowering the dielectric constant of polyimide resins include: pore forming in the film, doping modification of fluororesin, modification of aliphatic monomer, modification of fluorine-containing monomer, and the like. The mechanical property of the film is reduced due to pore forming in the film, the insulating property is also reduced, and the possibility of electric breakdown is increased; the pore diameter of the produced pore is required to be submicron or less than 100nm, and the control to obtain the thin film with small pore diameter and uniform pore diameter distribution is difficult. Doping modification of fluororesin, and reducing the dielectric constant of the film by blending; however, the compatibility of the fluororesin and the polyimide resin is poor, and phase separation is likely to occur, resulting in a significant decrease in mechanical properties. The aliphatic monomer is modified, the charge transfer effect of a polyimide molecular chain is cut off, and the dielectric constant can be reduced; but the introduction of the fatty chain inevitably causes the reduction of heat resistance; although the heat-labile molecular chain segment can be removed by high-temperature treatment in advance to improve the subsequent heat resistance, the mechanical property of the final polyimide film is reduced, and voids in the film can also be caused to reduce the dielectric breakdown voltage of the film. The modification of the fluorine-containing monomer can obviously reduce the dielectric constant of polyimide, reduce the dipole moment of molecular chain segments through the strong electron-withdrawing capability of fluorine atoms, and increase the gaps among the molecular chain segments through the repulsion of fluorine-containing groups and other molecular chain segments, so that the fluorine-containing polyimide has a lower dielectric constant through the two capabilities. However, even so, the dielectric constant of the polyimide resin is not so low, with room for further reduction; more importantly, the fluorine-containing monomer is generally a flexible monomer, and after the fluorine-containing monomer is introduced, the rigidity of a molecular chain is reduced, the heat resistance and the dimensional stability are reduced, the degree of orientation of a molecular chain segment in a film is reduced, the thermal expansion coefficient is increased, and the fluorine-containing monomer is difficult to apply to a circuit board.
The polymethine is a high molecular material with highly oriented molecular chains and has a strong rigid structure. The main drawback of the structure is that the mechanical properties of the film in the longitudinal and transverse directions are not matched completely because the molecular chains are too rigid. Generally, a polyazomethine film prepared by a coating/melt extrusion method has molecular chains highly oriented in the longitudinal direction, excellent mechanical properties in the longitudinal direction, and brittle fracture in the transverse direction to form fibrous cleavage. However, the polyazomethines are composed of imine groups rather than imide rings on the molecular chain; the carbonyl group is not present, and thus has a lower dipole moment and a relatively reduced dielectric constant. If it is copolymerized with a polyimide having a flexible structure, the mechanical properties after film formation can be improved and the dielectric constant of the polyimide can be reduced.
The branched chain structure of the polyimide resin can bring steric hindrance to molecular chain stacking/winding, increase the space between the molecular chains and indirectly cause the occurrence of molecular chain gaps. These gaps are not only small in size but also uniformly distributed in the structure, do not affect the mechanical properties of the polyimide resin, and simultaneously exert the same function as artificially introduced holes/voids, contributing to the reduction of the dielectric constant. After the branched chain structure forms a two-dimensional network structure, the high orientation of the poly-azomethine molecular chain in one direction is improved, so that the transverse mechanical property is improved, and the transverse fibrous splitting is avoided.
Based on the reasons, the invention provides the polyimide composite resin obtained by uniformly copolymerizing polyimide and polyimide, and the dielectric constant of the polyimide composite resin is reduced by introducing a polyimide unit; the polyimide resin has a branched chain structure, so that not only is the gaps among molecular chains increased and the dielectric constant further reduced, but also the mechanical properties of the introduced polyimide resin can be improved, and the mechanical properties of the polyimide composite resin in all directions can meet the requirements of industrial products.
Disclosure of Invention
The invention aims to provide a polyimide composite resin with a low dielectric constant, a preparation method and application thereof, aiming at the defects of the prior art. By introducing a polyimide unit into the polyimide resin, the average dipole moment of a molecular chain is reduced, and the dielectric constant of the resin is reduced; by introducing the branched chain structure, not only molecular chain gaps are increased, the dielectric constant is further reduced, but also the molecular chain arrangement conditions of the polymethine unit in two different directions, namely the transverse direction and the longitudinal direction, can be improved, and certain mechanical properties in all directions are ensured. The introduction of the fluorine-containing group not only brings the effect of reducing the dielectric constant, but also increases the flexibility of the polyimide molecular chain; the flexible polyimide molecular chain unit and the high-rigidity polyimide molecular chain unit are mutually linked, so that the flexibility/rigidity of the molecular chain is in a proper range, and the processing performance, the mechanical performance and the linear thermal expansion coefficient performance are considered. Such a polyimide composite resin having a low dielectric constant property is widely used in the field of electronic information.
The purpose of the invention is realized by the following technical scheme: a polyimide composite resin with low dielectric constant is characterized in that the composite resin is composed of polyimide resin units and polyimide resin units which are linked in a copolymerization mode; the copolymer forms a network structure, the composite resin has a general formula of the following structure, and the units are mixed and copolymerized uniformly:
wherein Ar1 is a monomer represented by the following formula (I) and is selected from the group consisting of a residue of pyromellitic dianhydride, a residue of 3,3',4,4' -biphenyltetracarboxylic dianhydride, a residue of 4,4'- (hexafluoroisopropyl) bisphthalic dianhydride, a residue of 1, 4-difluoropyromellitic dianhydride, a residue of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, a residue of 2,3,3',4 '-biphenyltetracarboxylic dianhydride, a residue of 3,3',4,4 '-diphenylethertetracarboxylic dianhydride, a residue of 3,3',4,4 '-benzophenonetetracarboxylic dianhydride, a residue of 4,4' -terephthalobiphthalic anhydride, a residue of bisphenol A type diether dianhydride, a residue of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, and a residue of 2,3,6, one or more of residues of 7-tetracarboxyl-9, 9-bis (trifluoromethyl) xanthene dianhydride, residues of 1, 4-bis (trifluoromethyl) -2,3,5, 6-benzene tetracarboxylic dianhydride and residues of 1, 4-bis (3, 4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride are mixed according to any proportion;
ar2 is prepared by mixing one or more of residues of terephthalaldehyde, residues of o-phthalaldehyde, residues of m-phthalaldehyde, residues of 4, 4-biphenyldicarboxaldehyde, residues of 2, 3-naphthaldehyde and residues of 2,3,5, 6-tetrafluoroterephthalaldehyde according to any proportion;
b1 is composed of a residue of p-phenylenediamine, a residue of m-phenylenediamine, a residue of biphenyldiamine, a residue of 4,4' -diamino-2, 2' -dimethylbiphenyl, a residue of 4,4' -diamino-3, 3' -dimethylbiphenyl, a residue of 2,2' -bis (trifluoromethyl) diaminobiphenyl, a residue of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, a residue of 2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, a residue of 2, 2-bis (4-aminophenyl) hexafluoropropane, a residue of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, a residue of 2, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, a residue of 4, 2-bis [4- (3-aminophenoxy) phenyl ], A residue of 4,4' -diaminodiphenyl ether, a residue of 3,4' -diaminodiphenyl ether, a residue of 4,4' -diaminobenzophenone, a residue of 4,4' -diaminodiphenylmethane, a residue of 4,4' -diaminophenylsulfone, a residue of bis (3-amino-4-hydroxyphenyl) sulfone, one or more of a residue of 1, 3-bis (3-aminophenoxy) benzene, a residue of 1, 3-bis (4-aminophenoxy) benzene, a residue of 4,4 '-bis (4-aminophenoxy) biphenyl, a residue of 4,4' -bis (3-aminophenoxy) biphenyl, a residue of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and a residue of bis [4- (3-aminophenoxy) phenyl ] sulfone are mixed according to any proportion;
b2 is formed by mixing one or more of residues of 1,3, 5-triaminobenzene, residues of tri (2-aminoethyl) amine, residues of tri (4-aminophenyl) amine and residues of 1,3, 5-tri (4-aminophenyl) benzene according to any proportion;
m1, m2 and n1 are natural numbers, n2 is an even number, 0.5-m 1/(m1+ m2) <1, 0.8-n 1/(n1+ n2) <1, 20-m 1+ m2+ n1+ n2) < 400, and n1+ 1.5-n 2 ═ m1+ m 2.
Further, Ar1 in the formula comprises one or two of residues of pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 4,4' - (hexafluoroisopropyl) bisphthalic dianhydride, 1, 4-difluoropyromellitic dianhydride and 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, and the total amount of the residues accounts for 50-100% of the total molar amount of Ar 1;
ar2 in the general formula comprises residues of 4, 4-biphenyldicarboxaldehyde and residues of 2,3,5, 6-tetrafluoroterephthalaldehyde, and the total amount of the residues accounts for 50-100% of the total mole amount of Ar 2;
b1 in the formula comprises any one or two of residues of p-phenylenediamine, 4 '-diamino-2, 2' -dimethyl biphenyl, 2 '-bis (trifluoromethyl) diamino biphenyl, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, and the total amount of the residues accounts for 50-100% of the total molar amount of B1;
b2 in the formula comprises residues of 1,3, 5-tris (4-aminophenyl) benzene and is present in a total amount of 50-100% based on the total molar amount of B2.
Further, Ar1 in the general formula comprises one or two of residues of 1, 4-difluoropyromellitic dianhydride and residues of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, and the total amount of the residues accounts for 80-100% of the total mole amount of Ar 1;
b1 in the formula comprises any one or two of residues of 4,4' -diamino-2, 2' -dimethyl biphenyl, residues of 2,2' -bis (trifluoromethyl) diamino biphenyl and residues of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, and the total amount of the residues accounts for 80-100% of the total molar amount of B1;
a preparation method of polyimide composite resin with low dielectric constant comprises the following steps:
(1) preparing a precursor solution of the polyimide composite resin: under the nitrogen atmosphere, dissolving a mol of diamine compound and b mol of triamine compound in a strong polar solvent while stirring in a container to obtain a solution, wherein the sum of the mass percentages of the diamine compound and the triamine compound in the solution is 5-13%; then d mol of dimethyl aldehyde compound is added, the temperature of the solution is controlled to be 0-50 ℃ under the nitrogen atmosphere, and the reaction is carried out for 4-24 h; then c moles of the tetracarboxylic dianhydride compound are added into the solution for three times, and the addition amount of each time respectively accounts for 60%, 30% and 10% of the total weight of the tetracarboxylic dianhydride compound; continuously reacting for 4-48h in nitrogen atmosphere, controlling the solution temperature at 0-50 ℃, and obtaining a precursor solution of the polyimide composite resin after reaction; wherein c/(c + d) is more than or equal to 0.5 and less than 1, a/(a + b) is more than or equal to 0.8 and less than 1, and (a + b + c + d) is more than or equal to 20 and less than or equal to 400, wherein (c + d) is (a + 1.5) b which is (0.95-1.05) to 1;
wherein the tetracarboxylic dianhydride compound is selected from pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 4,4'- (hexafluoroisopropyl) bisphthalic dianhydride, 1, 4-difluoropyromellitic dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, 2,3,3',4 '-biphenyltetracarboxylic dianhydride, 3,3',4,4 '-diphenyl ether dianhydride, 3,3',4,4 '-benzophenone tetracarboxylic dianhydride, 4,4' -terephthaloylbisphthalic anhydride, bisphenol A type diether dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3,6, 7-tetracarboxyl-9, 9-bis (trifluoromethyl) xanthene dianhydride, One or more of 1, 4-bis (trifluoromethyl) -2,3,5, 6-benzene tetracarboxylic dianhydride and 1, 4-bis (3, 4-dicarboxy trifluoro phenoxy) tetrafluorobenzene dianhydride are mixed according to any proportion;
the diformaldehyde compound is formed by mixing one or more of terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, 4-phthalaldehyde, 2, 3-naphthaldehyde and 2,3,5, 6-tetrafluoro-terephthalaldehyde according to any proportion;
diamine compounds selected from the group consisting of p-phenylenediamine, m-phenylenediamine, biphenyldiamine, 4' -diamino-2, 2' -dimethylbiphenyl, 4' -diamino-3, 3' -dimethylbiphenyl, 2' -bis (trifluoromethyl) diaminobiphenyl, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, and mixtures thereof, One or more of 3,4 '-diaminodiphenyl ether, 4' -diaminobenzophenone, 4 '-diaminodiphenylmethane, 4' -diaminophenylsulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane and bis [4- (3-aminophenoxy) phenyl ] sulfone are mixed according to any proportion to form the composition;
the triamine compound is formed by mixing one or more of 1,3, 5-triaminobenzene, tri (2-aminoethyl) amine, tri (4-aminophenyl) amine and 1,3, 5-tri (4-aminophenyl) benzene according to any proportion;
the strong polar solvent is formed by mixing one or more of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and m-cresol according to any proportion;
(2) coating the precursor solution of the polyimide composite resin prepared in the step (1) on a carrier, wherein the film thickness of the dried polyimide composite resin is 10-30 mu m; then volatilizing at 80-150 ℃ to ensure that the content of the strong polar solvent is between 15-25wt percent, thus obtaining a precursor dry film layer of the polyimide composite resin;
(3) carrying out thermal curing on the carrier coated with the precursor dry film layer of the polyimide composite resin at the temperature of 280-350 ℃ in the nitrogen atmosphere; curing the precursor dry film layer of the polyimide composite resin to form an insulating film base layer;
(4) and (4) removing the insulating film base layer in the step (3) from the surface of the carrier by a water boiling method to obtain the polyimide composite resin with low dielectric constant.
Further, the tetracarboxylic dianhydride group compound comprises one or two of pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 4,4' - (hexafluoroisopropyl) bisphthalic dianhydride, 1, 4-difluoropyromellitic dianhydride and 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, and the total amount of the compounds accounts for 50-100% of the total molar amount of the tetracarboxylic dianhydride group compound; the diformaldehyde compound comprises one or two of 4, 4-biphenyldicarboxaldehyde and 2,3,5, 6-tetrafluoroterephthalaldehyde, and the total amount of the diformaldehyde compound accounts for 50-100% of the total molar amount of the diformaldehyde compound; the diamine compound comprises any one or two of p-phenylenediamine, 4 '-diamino-2, 2' -dimethyl biphenyl, 2 '-bis (trifluoromethyl) diamino biphenyl, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, and the total amount of the diamine compound accounts for 50-100% of the total mole amount of the diamine compound; the triamine compound comprises 1,3, 5-tri (4-aminophenyl) benzene, and the total amount of the triamine compound accounts for 50-100% of the total mol amount of the triamine compound.
Further, the tetracarboxylic dianhydride compound comprises one or two of 1, 4-difluoro pyromellitic dianhydride and 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, and the total amount of the tetracarboxylic dianhydride compound accounts for 80-100% of the total mole amount of the tetracarboxylic dianhydride compound; the diamine compound comprises 4,4' -diamino-2, 2' -dimethyl biphenyl, 2' -bis (trifluoromethyl) diamino biphenyl and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, and the total amount of the diamine compound accounts for 80-100% of the total mole amount of the tetracarboxylic dianhydride compound.
The application of the polyimide composite resin with the low dielectric constant is characterized in that the polyimide composite resin with the low dielectric constant is applied to prepare a single-sided flexible copper clad laminate, the single-sided flexible copper clad laminate comprises a copper foil layer and a polyimide layer positioned on the copper foil layer, and the polyimide layer can be composed of a layer of polyimide composite resin with the low dielectric constant or a multilayer structure formed by multiple polyimide composite resins with the low dielectric constants; the thickness of the copper foil layer is not more than 105 mu m, and the thickness of the polyimide composite resin layer is 5-35 mu m.
The application of the polyimide composite resin with the low dielectric constant is characterized in that the polyimide composite resin with the low dielectric constant is applied to prepare a double-sided flexible copper clad laminate, the double-sided flexible copper clad laminate comprises two copper foil layers and a polyimide layer positioned between the two copper foil layers, and the polyimide layer can be composed of a layer of polyimide composite resin with the low dielectric constant or a multilayer structure formed by multiple polyimide composite resins with low dielectric constants; the thickness of the copper foil layer is not more than 105 mu m, and the thickness of the polyimide composite resin layer is 10-70 mu m.
A positive photosensitive covering film is prepared by mixing precursor solution of polyimide composite resin with diazonaphthoquinone photosensitizer; the weight percentage of the diazonaphthoquinone sensitizer in the positive photosensitive covering film is 10-40%; the film thickness of the positive photosensitive covering film is 5-50 um; the precursor structural formula of the polyimide composite resin is shown as the following general formula:
wherein Ar1 is a monomer represented by the following formula (I) and is selected from the group consisting of a residue of pyromellitic dianhydride, a residue of 3,3',4,4' -biphenyltetracarboxylic dianhydride, a residue of 4,4'- (hexafluoroisopropyl) bisphthalic dianhydride, a residue of 1, 4-difluoropyromellitic dianhydride, a residue of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, a residue of 2,3,3',4 '-biphenyltetracarboxylic dianhydride, a residue of 3,3',4,4 '-diphenylethertetracarboxylic dianhydride, a residue of 3,3',4,4 '-benzophenonetetracarboxylic dianhydride, a residue of 4,4' -terephthalobiphthalic anhydride, a residue of bisphenol A type diether dianhydride, a residue of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, and a residue of 2,3,6, one or more of residues of 7-tetracarboxyl-9, 9-bis (trifluoromethyl) xanthene dianhydride, residues of 1, 4-bis (trifluoromethyl) -2,3,5, 6-benzene tetracarboxylic dianhydride and residues of 1, 4-bis (3, 4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride are mixed according to any proportion;
ar2 is prepared by mixing one or more of residues of terephthalaldehyde, residues of o-phthalaldehyde, residues of m-phthalaldehyde, residues of 4, 4-biphenyldicarboxaldehyde, residues of 2, 3-naphthaldehyde and residues of 2,3,5, 6-tetrafluoroterephthalaldehyde according to any proportion;
b1 is composed of a residue of p-phenylenediamine, a residue of m-phenylenediamine, a residue of biphenyldiamine, a residue of 4,4' -diamino-2, 2' -dimethylbiphenyl, a residue of 4,4' -diamino-3, 3' -dimethylbiphenyl, a residue of 2,2' -bis (trifluoromethyl) diaminobiphenyl, a residue of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, a residue of 2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, a residue of 2, 2-bis (4-aminophenyl) hexafluoropropane, a residue of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, a residue of 2, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, a residue of 4, 2-bis [4- (3-aminophenoxy) phenyl ], A residue of 4,4' -diaminodiphenyl ether, a residue of 3,4' -diaminodiphenyl ether, a residue of 4,4' -diaminobenzophenone, a residue of 4,4' -diaminodiphenylmethane, a residue of 4,4' -diaminophenylsulfone, a residue of bis (3-amino-4-hydroxyphenyl) sulfone, one or more of a residue of 1, 3-bis (3-aminophenoxy) benzene, a residue of 1, 3-bis (4-aminophenoxy) benzene, a residue of 4,4 '-bis (4-aminophenoxy) biphenyl, a residue of 4,4' -bis (3-aminophenoxy) biphenyl, a residue of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and a residue of bis [4- (3-aminophenoxy) phenyl ] sulfone are mixed according to any proportion;
b2 is formed by mixing one or more of residues of 1,3, 5-triaminobenzene, residues of tri (2-aminoethyl) amine, residues of tri (4-aminophenyl) amine and residues of 1,3, 5-tri (4-aminophenyl) benzene according to any proportion;
m1, m2 and n1 are natural numbers, n2 is an even number, 0.5-m 1/(m1+ m2) <1, 0.8-n 1/(n1+ n2) <1, 20-m 1+ m2+ n1+ n2) < 400, and n1+ 1.5-n 2 ═ m1+ m 2.
The method for preparing the positive photosensitive cover film comprises the following steps:
(1) preparing a precursor solution of the polyimide composite resin: under the nitrogen atmosphere, dissolving a mol of diamine compound and b mol of triamine compound in a strong polar solvent while stirring in a container to obtain a solution, wherein the sum of the mass percentages of the diamine compound and the triamine compound in the solution is 5-13%; then d mol of dimethyl aldehyde compound is added, the temperature of the solution is controlled to be 0-50 ℃ under the nitrogen atmosphere, and the reaction is carried out for 4-24 h; then c moles of the tetracarboxylic dianhydride compound are added into the solution for three times, and the addition amount of each time respectively accounts for 60%, 30% and 10% of the total weight of the tetracarboxylic dianhydride compound; continuously reacting for 4-48h in nitrogen atmosphere, controlling the solution temperature at 0-50 ℃, and obtaining a precursor solution of the polyimide composite resin after reaction; wherein c/(c + d) is more than or equal to 0.5 and less than 1, a/(a + b) is more than or equal to 0.8 and less than 1, and (a + b + c + d) is more than or equal to 20 and less than or equal to 400, wherein (c + d) is (a + 1.5) b which is (0.95-1.05) to 1;
wherein the tetracarboxylic dianhydride compound is selected from pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 4,4'- (hexafluoroisopropyl) bisphthalic dianhydride, 1, 4-difluoropyromellitic dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, 2,3,3',4 '-biphenyltetracarboxylic dianhydride, 3,3',4,4 '-diphenyl ether dianhydride, 3,3',4,4 '-benzophenone tetracarboxylic dianhydride, 4,4' -terephthaloylbisphthalic anhydride, bisphenol A type diether dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3,6, 7-tetracarboxyl-9, 9-bis (trifluoromethyl) xanthene dianhydride, One or more of 1, 4-bis (trifluoromethyl) -2,3,5, 6-benzene tetracarboxylic dianhydride and 1, 4-bis (3, 4-dicarboxy trifluoro phenoxy) tetrafluorobenzene dianhydride are mixed according to any proportion;
the diformaldehyde compound is formed by mixing one or more of terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, 4-phthalaldehyde, 2, 3-naphthaldehyde and 2,3,5, 6-tetrafluoro-terephthalaldehyde according to any proportion;
diamine compounds selected from the group consisting of p-phenylenediamine, m-phenylenediamine, biphenyldiamine, 4' -diamino-2, 2' -dimethylbiphenyl, 4' -diamino-3, 3' -dimethylbiphenyl, 2' -bis (trifluoromethyl) diaminobiphenyl, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, and mixtures thereof, One or more of 3,4 '-diaminodiphenyl ether, 4' -diaminobenzophenone, 4 '-diaminodiphenylmethane, 4' -diaminophenylsulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane and bis [4- (3-aminophenoxy) phenyl ] sulfone are mixed according to any proportion to form the composition;
the triamine compound is formed by mixing one or more of 1,3, 5-triaminobenzene, tri (2-aminoethyl) amine, tri (4-aminophenyl) amine and 1,3, 5-tri (4-aminophenyl) benzene according to any proportion;
the strong polar solvent is formed by mixing one or more of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and m-cresol according to any proportion;
(2) adding diazonaphthoquinone sensitizer into the precursor solution of the polyimide composite resin prepared in the step (1), so that the weight percentage of the diazonaphthoquinone sensitizer in the final positive photosensitive cover film is 10-40%; after adding, controlling the temperature of the solution to be 0-50 ℃ in the nitrogen atmosphere, and continuously stirring for 4-24h to obtain a photosensitive mixture solution;
(3) film preparation: coating the photosensitive mixture solution obtained in the step (2) on a carrier to ensure that the film thickness of the dried photosensitive mixture is 5-50 μm; and then volatilizing at 60-90 ℃ to ensure that the content of the strong polar solvent is between 2-15 wt% to obtain a photosensitive mixture film, namely the positive photosensitive covering film.
The invention has the following beneficial effects:
1. the polyimide resin unit of the invention adopts fluorine-containing monomers, thereby not only reducing the dielectric constant of the polyimide resin, but also improving the flexibility of the polyimide molecular chain.
2. The flexible molecular chain of the polyimide can improve the high rigidity of the molecular chain of the polyimide, so that the rigidity of the molecular chain of the polymer is in a reasonable range. On one hand, the directional arrangement capability of molecular chains is ensured, and the linear thermal expansion coefficient of the polyimide resin is reduced; on the other hand, the rigidity and flexibility of the poly-azomethine molecular chain are adjusted, and the mechanical property and the processing property are improved.
3. The polyimide resin unit is composed of an imine group, and has a lower dipole moment than a five-membered imide ring. The introduction of the polyimide unit reduces the dipole moment of a polyimide molecular chain and the dielectric constant of the polyimide resin.
4. Optimizing a molecular chain of the polyimide composite resin, and introducing a triamine monomer to obtain a branched molecular chain; mechanical properties in all directions are averaged after branching, and transverse fibrosis splitting caused by high rigidity of a polymethine unit is avoided; branching also increases inter-molecular chain voids, further reducing the dielectric constant to some extent.
5. The polyimide unit and the polyimide unit are copolymerized, so that the dielectric constant is reduced, the good mechanical property is ensured, and the linear thermal expansion coefficient can be regulated and controlled. The material has better application in the field of 5G circuit boards in flexible copper clad plate materials.
Detailed Description
The following representative examples are intended to illustrate the invention, but are not intended to limit the scope of the invention described herein.
The abbreviations used in the examples represent the following:
and (3) PMDA: pyromellitic dianhydride;
BPDA: 3,3',4,4' -biphenyltetracarboxylic dianhydride;
6 FDA: 4,4' - (hexafluoroisopropyl) diphthalic dianhydride;
PF2 DA: 1, 4-difluoropyromellitic dianhydride;
BFDA: 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride;
TPAL: terephthalaldehyde;
BDAL: 4, 4-biphenyldicarboxaldehyde;
NDAL: 2, 3-naphthalene dicarboxaldehyde;
TF-TPAL: 2,3,5, 6-tetrafluoroterephthalaldehyde;
p-PDA: p-phenylenediamine;
m-TB: 4,4 '-diamino-2, 2' -dimethylbiphenyl, m-tolidine;
TFMB: 2,2' -bis (trifluoromethyl) diaminobiphenyl;
6 FAP: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane;
6 FDAM: 2, 2-bis (4-aminophenyl) hexafluoropropane;
4-BDAF: 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane;
TAB: 1,3, 5-triaminobenzene;
TAPA: tris (4-aminophenyl) amine;
TAPB: 1,3, 5-tris (4-aminophenyl) benzene;
NMP: n-methyl pyrrolidone;
DNQ: diazo naphthoquinone.
[ examples 1 to 20 ]
[ polyimide composite resins A-T ] were prepared according to the raw material input in Table 1 and the following experimental procedures:
in a 100mL three-necked flask, quantitative amounts of diamine compounds and triamine compounds shown in Table 1 were dissolved in 40g of NMP under nitrogen atmosphere with stirring so that the sum of the mass percentages of the amine compounds was 5% to 13%. Then adding quantitative dimethyl aldehyde compounds shown in the table 1, controlling the temperature of the solution to be 0-50 ℃ under the nitrogen atmosphere, and reacting for 4-24 h. Then adding quantitative tetracarboxylic dianhydride compounds shown in the table 1 into the solution for three times, wherein the adding amount of each time respectively accounts for 60%, 30% and 10% of the total weight; continuously reacting for 4-48h under the nitrogen atmosphere, and controlling the solution temperature at 0-50 ℃. Finally obtaining the precursor solution of the polyimide composite resin.
The precursor solution of the polyimide composite resin was coated on a glass plate using a coater, and the film thickness of the polyimide composite resin after drying was about 10 to 30 um. Volatilizing for a certain time at 80-150 ℃ to ensure that the content of the solvent is between 15 and 25 percent, and obtaining the precursor dry film layer of the polyimide composite resin.
Thermally curing the glass plate coated with the polyimide composite resin precursor dry film layer at the temperature of 280-350 ℃ in the nitrogen atmosphere; the precursor dry film layer of the polyimide composite resin is cured to form a polyimide composite resin layer, and an insulating film base layer is formed.
And (3) removing the insulating film base layer from the glass plate by a water boiling method to obtain the polyimide composite resin film A-T with the low dielectric constant.
Comparative examples 21 to 22
Comparative [ polyimide resins U-V ] were prepared according to the raw material input amounts in table 1 and the following experimental procedure:
in a 100mL three-necked flask, a predetermined amount of the diamine compound shown in Table 1 was dissolved in 40g of NMP under nitrogen atmosphere with stirring so that the mass percentage of the amine compound was 5% to 8%. Then adding quantitative tetracarboxylic dianhydride compounds shown in the table 1 into the solution for three times, wherein the adding amount of each time respectively accounts for 60%, 30% and 10% of the total weight; the reaction was carried out for 48h under a nitrogen atmosphere, and the solution temperature was controlled at 25 ℃. Finally, a precursor solution of the polyimide resin is obtained.
The precursor solution of the polyimide resin was coated on a glass plate using a coater, and the film thickness of the polyimide resin after drying was about 10 to 30 um. Volatilizing at 150 ℃ for 10min to ensure that the content of the solvent is between 15 and 25 percent, and obtaining the precursor dry film layer of the polyimide resin.
Thermally curing the glass plate coated with the polyimide resin precursor dry film layer at 280 ℃ in a nitrogen atmosphere; the precursor dry film layer of the polyimide resin is cured to form a polyimide resin layer, forming an insulation film base layer.
And (3) taking off the insulating film base layer from the glass plate by a water boiling method to obtain the polyimide film U-V.
[ COMPARATIVE EXAMPLE 23 ]
Comparative [ polyimide composite resin W ] was prepared according to the raw material input amounts in table 1 and the following experimental procedures:
in a 100mL three-necked flask, 0.74g p-PDA and 3.28g of TFMB shown in Table 1 were dissolved in 40g of NMP under nitrogen atmosphere with stirring to give a total of 8% by mass of diamine compounds. Thereafter, 1.43g of BDAL shown in Table 1 was added, and the temperature of the solution was controlled to 0 ℃ under a nitrogen atmosphere, and the reaction was carried out for 4 hours. Then 4.55g of 6FDA shown in Table 1 is added into the solution in three times, and the adding amount of each time is respectively 60%, 30% and 10% of the total weight; the reaction was continued for 36h under nitrogen atmosphere with the solution temperature controlled at 0 ℃. Finally obtaining the precursor solution of the polyimide composite resin.
The precursor solution of the polyimide composite resin was coated on a glass plate using a coater, and the film thickness of the polyimide composite resin after drying was about 10 to 30 um. And volatilizing at 120 ℃ for 15min to ensure that the content of the solvent is 20 percent, thereby obtaining the precursor dry film layer of the polyimide composite resin.
Thermally curing the glass plate coated with the polyimide composite resin precursor dry film layer at 350 ℃ in a nitrogen atmosphere; the precursor dry film layer of the polyimide composite resin is cured to form a polyimide composite resin layer, and an insulating film base layer is formed.
And (3) taking off the insulating film base layer from the glass plate by a water boiling method to obtain the polyimide composite resin film W.
[ COMPARATIVE EXAMPLE 24 ]
[ Polyazomethine resin X ] was prepared according to the raw material input in Table 1 and the following experimental procedure:
in a 100mL three-necked flask, 1.14g p-PDA and 3.34g m-TB shown in Table 1 were dissolved in 40g of NMP under nitrogen atmosphere with stirring to give a total of 9% by mass of amine compounds. Thereafter, 5.52g of BDAL shown in Table 1 was added, and the solution was reacted for 20 hours under a nitrogen atmosphere at a controlled temperature of 20 ℃. Finally obtaining the precursor solution of the polymethine resin.
The precursor solution of the polyimide resin was coated on a glass plate using a coater, and the film thickness of the dried polyimide resin was about 10 to 30 um. And (3) volatilizing at 80 ℃ for 30min to ensure that the content of the solvent is 25 percent, thereby obtaining the precursor dry film layer of the poly-azomethine resin.
Thermally curing the glass plate coated with the polyimide resin precursor dry film layer at the temperature of 280 ℃ in the nitrogen atmosphere; the dry film layer of the precursor of the polyimide resin is cured to form a polyimide resin layer, forming an insulating film base layer.
And (3) peeling off the insulating film base layer from the glass plate by a water boiling method to obtain the polyimide resin film X.
Comparative example 25
[ Polyazomethine resin Y ] was prepared according to the raw material input in Table 1 and the following experimental procedure:
in a 100mL three-necked flask, 3.99g m-TB and 1.07g of TAPB shown in Table 1 were dissolved in 40g of NMP under nitrogen with stirring to give a total of 10% by mass of amine compounds. Thereafter, 4.94g of BDAL shown in Table 1 was added, and the temperature of the solution was controlled to 45 ℃ under a nitrogen atmosphere, and the reaction was carried out for 24 hours. Finally obtaining the precursor solution of the polymethine resin.
The precursor solution of the polyimide resin was coated on a glass plate using a coater, and the film thickness of the dried polyimide resin was about 10 to 30 um. And volatilizing at 100 ℃ for 15min to ensure that the content of the solvent is 22 percent, thereby obtaining the precursor dry film layer of the poly-azomethine resin.
Thermally curing the glass plate coated with the polyimide resin precursor dry film layer at 320 ℃ in a nitrogen atmosphere; the dry film layer of the precursor of the polyimide resin is cured to form a polyimide resin layer, forming an insulating film base layer.
And (3) peeling off the insulating film base layer from the glass plate by a water boiling method to obtain the final polyimide resin film Y.
Table 1: raw material addition amount in examples and comparative examples
The advantages of the low dielectric constant polyimide composite resin of the present invention in terms of dielectric constant, mechanical properties, thermal expansion coefficient, etc. are illustrated by comparing the properties of examples with those of comparative examples.
The polyimide composite resins A to T of examples 1 to 20 and the polyimide resins U to V, the polyimide composite resin W and the polyimide resins X to Y of comparative examples 21 to 25 were subjected to performance tests under the following specific test conditions and methods:
the dielectric constant and dielectric loss are tested on a wide-temperature wide-frequency impedance analyzer of ONTROL at NOV ℃ in Germany, and the testing frequency is from 100Hz to 1 GHz.
Tensile strength and elongation at break were measured in a universal tester by the IPC-TM-6502.4.18B method.
Coefficient of thermal expansion, measured on a Q400TMA test instrument from TA, USA.
The properties of the films obtained by the test are shown in Table 2 below.
TABLE 2 comparison of Properties of resin films obtained in examples 1 to 20 and comparative examples 21 to 25
As can be seen from Table 2, the dielectric constant of the present invention is significantly reduced after blending and copolymerizing the polyimide resin and the polyimide resin: the dielectric constant of the conventional polyimide resin (U-V sample) is 3.3 to 3.4; after blending and copolymerization of the polyimide, the dielectric constant of the polyimide composite resin is reduced to below 3, and some dielectric constants are even reduced to 2.5. This is due to the fact that, after the copolymerization of the polymethine resin, the dipole moment of the molecular chain is reduced; also benefit from the use of fluoromonomers.
In addition, the rigidity of the polyethyleneimine molecular chain was too high, and although a partial film could be obtained in the comparative example, the film was very likely to crack, and directional fiberization was observed; after the triamine compound is added into the formula, the mechanical property after film forming is improved, and the polyethyleneimine modified resin Y with the tensile strength of 110MPa can be obtained. Further, it was also found that the CTE of the polyimide modified resin Y was also small, owing to the high rigidity of its molecular chain. The triamine compound monomer is added into the polyimide composite resin, so that the effect of improving the rigidity of a molecular chain is achieved, and the mechanical property of the polyimide resin is prevented from meeting the application requirement of a product.
The addition of the triamine compound can also reduce the dielectric constant of the polyimide composite resin to a certain extent. The dielectric constant of the polyimide composite resin H, P, Q, S is substantially 2.5 or less, when the amount of the triamine compound monomer added is high. Although the fluorine-containing monomer and the polyimide resin also act together, the dielectric constants of the composite resins are obviously lower than those of other samples, which can show that the triamine compounds still contribute to the reduction of the dielectric constant.
The specific implementation mode for preparing the single-sided flexible copper-clad plate is as follows:
(1) preparing a precursor solution. Precursor solutions of polyimide composite resins were prepared according to examples 1 to 20;
(2) uniformly coating the precursor solution of the polyimide composite resin obtained in the step (1) on a copper foil with the thickness of 12-105um, and enabling the film thickness of the dried polyimide composite resin to be about 5-35 um. And (3) putting the polyimide composite resin into an oven at the temperature of 80-150 ℃, keeping the temperature for a certain time, and volatilizing to remove the solvent to ensure that the content of the solvent is between 15 and 25 percent to obtain the precursor dry film layer of the polyimide composite resin. And (3) putting the copper foil sample into a 280-plus-350-DEG C high-temperature nitrogen oven, and performing thermocuring according to a certain temperature rise program to prepare the flexible copper clad laminate substrate coated with the polyimide composite resin layer on the copper foil.
In the step (2), the copper foil can be coated with one polyimide composite resin, and can also be coated with a plurality of polyimide resins to improve other performances of the flexible copper clad laminate. When a plurality of polyimide resins are coated, a precursor solution of a first polyimide composite resin is coated and the solvent is evaporated, and then a precursor solution of a second polyimide composite resin is coated and the solvent is evaporated. The solvent volatilization conditions can be optimized by selecting the conditions listed in step (2). After the solvent is volatilized, putting the sample into a high-temperature nitrogen oven at the temperature of 280-350 ℃, performing thermal curing by a certain temperature-rising program, and performing thermal curing on the precursor dry films of the first polyimide composite resin and the second polyimide composite resin or other polyimide composite resins to obtain the flexible copper-clad plate base material coated with the polyimide composite resin layers on the copper foil.
The specific implementation mode for preparing the double-sided flexible copper-clad plate is as follows:
(1) preparing a precursor solution, which comprises the following substeps;
(1.1) preparing a precursor solution of a polyimide composite resin according to examples 1 to 20;
(1.2) preparing a precursor solution of a thermoplastic polyimide resin: under a nitrogen atmosphere, 1.00g of 1, 3-bis (3-aminophenoxy) benzene and 3.99g of 1, 3-bis (4-aminophenoxy) benzene were added to 40g of an NMP solvent and stirred until completely dissolved; then 5.02g of BPDA was added in three portions, followed by stirring for about 24 h; preparing a precursor solution of the thermoplastic polyimide resin;
(2) and preparing the pressable substrate. And (2) uniformly coating the precursor solution of the polyimide composite resin obtained in the step (1.1) on a copper foil with the thickness of 12-105um, and enabling the film thickness of the dried polyimide composite resin to be about 5-35 um. And (3) putting the polyimide composite resin into an oven at the temperature of 80-150 ℃, keeping the temperature for a certain time, and volatilizing to remove the solvent to ensure that the content of the solvent is between 15 and 25 percent to obtain the precursor dry film layer of the polyimide composite resin. Then, the precursor solution of the thermoplastic polyimide resin obtained in step (1.2) is further coated on the dry film precursor of the polyimide composite resin so that the film thickness of the thermoplastic polyimide resin after drying is about 0.5 to 3 um. Putting the mixture into an oven at the temperature of 80-150 ℃, keeping the mixture for a certain time, volatilizing to remove the solvent to ensure that the content of the solvent is between 15 and 25 percent, and forming a precursor dry film layer of the thermoplastic polyimide resin. And (3) putting the copper foil sample into a 280-350 ℃ high-temperature nitrogen oven, and performing thermosetting through a certain temperature rise procedure to prepare the pressable substrate coated with the polyimide composite resin layer and the thermoplastic polyimide resin layer on the copper foil.
(3) And (3) pressing and preparing the double-sided flexible copper-clad plate. Taking 2 laminated substrates obtained in the step (2), symmetrically laminating, and mutually contacting thermoplastic polyimide resin layers; and laminating for 10min at the temperature of 350 ℃ and under the pressure of 20Mpa to obtain the double-sided flexible copper-clad plate.
In the step (3), in addition to symmetrically attaching 2 same laminated substrates, 1 laminated substrate obtained in the step (2) and a copper foil can be attached to each other, and the thermoplastic polyimide resin layer and the other 1 copper foil are attached to each other in a contact manner; and laminating for 10min at the temperature of 350 ℃ and under the pressure of 20Mpa to obtain the double-sided flexible copper-clad plate.
Specific embodiments of the preparation of the positive photosensitive cover film are as follows:
(1) preparing a precursor solution of the polyimide composite resin according to the embodiments 1 to 20;
(2) adding diazonaphthoquinone DNQ into the precursor solution of the polyimide composite resin prepared in the step (1) to ensure that the weight percentage of DNQ in the final positive photosensitive cover film is 10-40%; after adding, controlling the temperature of the solution to be 0-50 ℃ under the nitrogen atmosphere, and continuously stirring for 4-24 h;
(3) preparing a film from the photosensitive mixture solution obtained in the step (2): coating the solution on a glass plate or other carriers to make the film thickness of the dried photosensitive mixture about 5-50 um; then volatilizing for a certain time at 60-90 ℃ to ensure that the content of the solvent is between 2-15 percent, and obtaining a photosensitive mixture film, namely the positive photosensitive covering film.
And (4) carrying out pattern exposure on the positive photosensitive covering film obtained in the step (3) through a film under the irradiation of light with a certain wavelength. Then developing in 0.1% by weight of tetramethylammonium hydroxide aqueous solution for 2-20 min. Suitable exposure energy, exposure time and development time are preferred so that areas not masked by the film are developed and removed completely, but areas protected by the film mask are left intact to obtain the desired pattern. And then, putting the cover film sample into a high-temperature nitrogen oven at the temperature of 280-350 ℃, and performing thermal curing by a certain temperature rise program to obtain a patterned cover film product required by the field of PCB/FPC.
In the above embodiments, there is no limitation on the content and formula of the polyimide composite resin of the present invention, and there is no limitation on the parameter conditions adopted when the polyimide composite resin is used to prepare the single-sided flexible copper clad laminate and the double-sided flexible copper clad laminate, and all the minor modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention are still within the scope of the technical solution of the present invention.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Claims (10)
1. A polyimide composite resin with low dielectric constant is characterized in that the composite resin is composed of polyimide resin units and polyimide resin units which are linked in a copolymerization mode; the copolymer forms a network structure, each constituent unit of the composite resin has the following molar ratio relation, and each unit is uniformly mixed and copolymerized:
wherein Ar is1Comprises a residue of pyromellitic dianhydride, a residue of 3,3',4,4' -biphenyltetracarboxylic dianhydride, a residue of 4,4' - (hexafluoroisopropyl) bisphthalic dianhydride, a residue of 1, 4-difluoropyromellitic dianhydride, and 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] dianhydride]A residue of hexafluoropropane dianhydride, a residue of 2,3,3',4' -biphenyltetracarboxylic dianhydride, a residue of 3,3',4,4' -diphenylether tetracarboxylic dianhydride, 3,3', one or more of residues of 4,4 '-benzophenone tetracarboxylic dianhydride, 4' -p-phenylenedioxy diphthalic anhydride, bisphenol A type diether dianhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 2,3,6, 7-tetracarboxyl-9, 9-bis (trifluoromethyl) xanthene dianhydride, 1, 4-bis (trifluoromethyl) -2,3,5, 6-benzene tetracarboxylic dianhydride and 1, 4-bis (3, 4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride are mixed according to any proportion;
Ar2is prepared by mixing one or more of residues of terephthalaldehyde, residues of o-phthalaldehyde, residues of m-phthalaldehyde, residues of 4, 4-biphenyldicarboxaldehyde, residues of 2, 3-naphthalenedicarboxaldehyde and residues of 2,3,5, 6-tetrafluoroterephthalaldehyde according to any proportion;
B1consisting of a residue of p-phenylenediamine, a residue of m-phenylenediamine, a residue of biphenyldiamine, a residue of 4,4' -diamino-2, 2' -dimethylbiphenyl, a residue of 4,4' -diamino-3, 3' -dimethylbiphenyl, a residue of 2,2' -bis (trifluoromethyl) diaminobiphenyl, a residue of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, a residue of 2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane]Propane residue, 2-bis (4-aminophenyl) hexafluoropropane residue, 2-bis [4- (4-aminophenoxy) phenyl group]Residue of hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl group]A residue of hexafluoropropane, a residue of 4,4 '-diaminodiphenyl ether, a residue of 3,4' -diaminodiphenyl ether, a residue of 4,4 '-diaminobenzophenone, a residue of 4,4' -diaminodiphenyl ketoneA residue of methyl ether, a residue of 4,4' -diaminophenylsulfone, a residue of bis (3-amino-4-hydroxyphenyl) sulfone, a residue of 1, 3-bis (3-aminophenoxy) benzene, a residue of 1, 3-bis (4-aminophenoxy) benzene, a residue of 4,4' -bis (4-aminophenoxy) biphenyl, a residue of 4,4' -bis (3-aminophenoxy) biphenyl, a residue of 2, 2-bis [4- (4-aminophenoxy) phenylphenyl]Residue of propane, bis [4- (3-aminophenoxy) phenyl]One or more of sulfone residues are mixed according to any proportion;
B2is formed by mixing one or more of residues of 1,3, 5-triaminobenzene, residues of tri (2-aminoethyl) amine, residues of tri (4-aminophenyl) amine and residues of 1,3, 5-tri (4-aminophenyl) benzene according to any proportion;
m1, m2, n1 are natural numbers, n2 is an even number, 0.5-m 1/(m1+ m2) <1, 0.8-n 1/(n1+ n2) <1, 20-m 1+ m2+ n1+ n2) < 400, (n1+ 1.5-n 2) ═ m1+ m 2;
wherein Ar is1、Ar2、B1And B2At least one of which is a fluorine-containing residue.
2. The low dielectric constant polyimide composite resin according to claim 1, wherein Ar in the formula1Comprises a residue of pyromellitic dianhydride, a residue of 3,3',4,4' -biphenyltetracarboxylic dianhydride, a residue of 4,4' - (hexafluoroisopropyl) bisphthalic dianhydride, a residue of 1, 4-difluoropyromellitic dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] dianhydride]One or two of residues of hexafluoropropane dianhydride, and their total amount accounts for Ar150-100% of the total molar amount of (A);
ar in the general formula2Comprises residues of 4, 4-biphenyldicarboxaldehyde and 2,3,5, 6-tetrafluoroterephthalaldehyde in total Ar250-100% of the total molar amount of (A);
b in the general formula1Including a residue of p-phenylenediamine, a residue of 4,4 '-diamino-2, 2' -dimethylbiphenyl, a residue of 2,2 '-bis (trifluoromethyl) diaminobiphenyl, a residue of 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, a residue of 2, 2-bis (4-aminophenyl) hexafluoropropane, a residue of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane) Phenyl radical]One or two of hexafluoropropane residues, and their total amount is B150-100% of the total molar amount of (A);
b in the general formula2Comprising residues of 1,3, 5-tris (4-aminophenyl) benzene, in a total amount B250-100% of the total molar amount.
3. The low dielectric constant polyimide composite resin according to claim 2, wherein Ar in the formula1Comprising a residue of 1, 4-difluoropyromellitic dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl]One or two of residues of hexafluoropropane dianhydride, and their total amount accounts for Ar180-100% of the total molar amount of (A);
b in the general formula1Including the residue of 4,4' -diamino-2, 2' -dimethylbiphenyl, the residue of 2,2' -bis (trifluoromethyl) diaminobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl]One or two of hexafluoropropane residues, and their total amount is B180-100% of the total molar amount.
4. A method for preparing the low dielectric constant polyimide composite resin according to claim 1, comprising the steps of:
(1) preparing a precursor solution of the polyimide composite resin: under the nitrogen atmosphere, dissolving a mol of diamine compound and b mol of triamine compound in a strong polar solvent while stirring in a container to obtain a solution, wherein the sum of the mass percentages of the diamine compound and the triamine compound in the solution is 5-13%; then d mol of dimethyl aldehyde compound is added, the temperature of the solution is controlled to be 0-50 ℃ under the nitrogen atmosphere, and the reaction is carried out for 4-24 h; then c moles of the tetracarboxylic dianhydride compound are added into the solution for three times, and the addition amount of each time respectively accounts for 60%, 30% and 10% of the total weight of the tetracarboxylic dianhydride compound; continuously reacting for 4-48h in nitrogen atmosphere, controlling the solution temperature at 0-50 ℃, and obtaining a precursor solution of the polyimide composite resin after reaction; wherein c/(c + d) is more than or equal to 0.5 and less than 1, a/(a + b) is more than or equal to 0.8 and less than 1, and (a + b + c + d) is more than or equal to 20 and less than or equal to 400, wherein (c + d) is (a + 1.5) b which is (0.95-1.05) to 1;
wherein the tetracarboxylic dianhydride compound is selected from pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 4,4'- (hexafluoroisopropyl) bisphthalic dianhydride, 1, 4-difluoropyromellitic dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, 2,3,3',4 '-biphenyltetracarboxylic dianhydride, 3,3',4,4 '-diphenyl ether dianhydride, 3,3',4,4 '-benzophenone tetracarboxylic dianhydride, 4,4' -terephthaloylbisphthalic anhydride, bisphenol A type diether dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3,6, 7-tetracarboxyl-9, 9-bis (trifluoromethyl) xanthene dianhydride, One or more of 1, 4-bis (trifluoromethyl) -2,3,5, 6-benzene tetracarboxylic dianhydride and 1, 4-bis (3, 4-dicarboxy trifluoro phenoxy) tetrafluorobenzene dianhydride are mixed according to any proportion;
the diformaldehyde compound is formed by mixing one or more of terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, 4-phthalaldehyde, 2, 3-naphthaldehyde and 2,3,5, 6-tetrafluoro-terephthalaldehyde according to any proportion;
diamine compounds selected from the group consisting of p-phenylenediamine, m-phenylenediamine, biphenyldiamine, 4' -diamino-2, 2' -dimethylbiphenyl, 4' -diamino-3, 3' -dimethylbiphenyl, 2' -bis (trifluoromethyl) diaminobiphenyl, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, and mixtures thereof, One or more of 3,4 '-diaminodiphenyl ether, 4' -diaminobenzophenone, 4 '-diaminodiphenylmethane, 4' -diaminophenylsulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane and bis [4- (3-aminophenoxy) phenyl ] sulfone are mixed according to any proportion to form the composition;
the triamine compound is formed by mixing one or more of 1,3, 5-triaminobenzene, tri (2-aminoethyl) amine, tri (4-aminophenyl) amine and 1,3, 5-tri (4-aminophenyl) benzene according to any proportion;
the strong polar solvent is formed by mixing one or more of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and m-cresol according to any proportion;
(2) coating the precursor solution of the polyimide composite resin prepared in the step (1) on a carrier, wherein the film thickness of the dried polyimide composite resin is 10-30 mu m; then volatilizing at 80-150 ℃ to ensure that the content of the strong polar solvent is between 15-25wt percent, thus obtaining a precursor dry film layer of the polyimide composite resin;
(3) carrying out thermal curing on the carrier coated with the precursor dry film layer of the polyimide composite resin at the temperature of 280-350 ℃ in the nitrogen atmosphere; curing the precursor dry film layer of the polyimide composite resin to form an insulating film base layer;
(4) and (4) removing the insulating film base layer in the step (3) from the surface of the carrier by a water boiling method to obtain the polyimide composite resin with low dielectric constant.
5. The method for preparing a low dielectric constant polyimide composite resin according to claim 4, wherein the tetracarboxylic dianhydride-based compound comprises one or two of pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 4,4' - (hexafluoroisopropyl) bisphthalic dianhydride, 1, 4-difluoropyromellitic dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, and the total amount thereof is 50 to 100% of the total molar amount of the tetracarboxylic dianhydride-based compound; the diformaldehyde compound comprises one or two of 4, 4-biphenyldicarboxaldehyde and 2,3,5, 6-tetrafluoroterephthalaldehyde, and the total amount of the diformaldehyde compound accounts for 50-100% of the total molar amount of the diformaldehyde compound; the diamine compound comprises any one or two of p-phenylenediamine, 4 '-diamino-2, 2' -dimethyl biphenyl, 2 '-bis (trifluoromethyl) diamino biphenyl, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, and the total amount of the diamine compound accounts for 50-100% of the total mole amount of the diamine compound; the triamine compound comprises 1,3, 5-tri (4-aminophenyl) benzene, and the total amount of the triamine compound accounts for 50-100% of the total mol amount of the triamine compound.
6. The method for preparing a low dielectric constant polyimide composite resin according to claim 4, wherein the tetracarboxylic dianhydride-based compound comprises one or two of 1, 4-difluoropyromellitic dianhydride and 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride in a total amount of 80 to 100% by mole based on the tetracarboxylic dianhydride-based compound; the diamine compound comprises 4,4' -diamino-2, 2' -dimethyl biphenyl, 2' -bis (trifluoromethyl) diamino biphenyl and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, and the total amount of the diamine compound accounts for 80-100% of the total mole amount of the tetracarboxylic dianhydride compound.
7. The application of the polyimide composite resin with low dielectric constant of claim 1, which is characterized in that the polyimide composite resin with low dielectric constant is applied to prepare a single-sided flexible copper clad laminate, the single-sided flexible copper clad laminate comprises a copper foil layer and a polyimide layer positioned on the copper foil layer, and the polyimide layer consists of a layer of polyimide composite resin with low dielectric constant or a multilayer structure formed by a plurality of polyimide composite resins with low dielectric constant; the thickness of the copper foil layer is not more than 105 mu m, and the thickness of the polyimide composite resin layer is 5-35 mu m.
8. The application of the low dielectric constant polyimide composite resin as claimed in claim 1, wherein the low dielectric constant polyimide composite resin is used to prepare a double-sided flexible copper clad laminate, the double-sided flexible copper clad laminate comprises two copper foil layers and a polyimide layer positioned between the two copper foil layers, and the polyimide layer is composed of a layer of low dielectric constant polyimide composite resin or a multi-layer structure formed by a plurality of low dielectric constant polyimide composite resins; the thickness of the copper foil layer is not more than 105 mu m, and the thickness of the polyimide composite resin layer is 10-70 mu m.
9. A positive photosensitive covering film is characterized in that the positive photosensitive covering film is obtained by mixing a precursor solution of polyimide composite resin with a diazonaphthoquinone photosensitizer; the weight percentage of the diazonaphthoquinone sensitizer in the positive photosensitive covering film is 10-40%; the film thickness of the positive photosensitive covering film is 5-50 um; the precursor of the polyimide composite resin has the following molar ratio relationship:
wherein Ar is1Comprises a residue of pyromellitic dianhydride, a residue of 3,3',4,4' -biphenyltetracarboxylic dianhydride, a residue of 4,4' - (hexafluoroisopropyl) bisphthalic dianhydride, a residue of 1, 4-difluoropyromellitic dianhydride, and 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] dianhydride]A residue of hexafluoropropane dianhydride, a residue of 2,3,3',4' -biphenyltetracarboxylic dianhydride, a residue of 3,3',4,4' -diphenylether tetracarboxylic dianhydride, 3,3', one or more of residues of 4,4 '-benzophenone tetracarboxylic dianhydride, 4' -p-phenylenedioxy diphthalic anhydride, bisphenol A type diether dianhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 2,3,6, 7-tetracarboxyl-9, 9-bis (trifluoromethyl) xanthene dianhydride, 1, 4-bis (trifluoromethyl) -2,3,5, 6-benzene tetracarboxylic dianhydride and 1, 4-bis (3, 4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride are mixed according to any proportion;
Ar2is prepared by mixing one or more of residues of terephthalaldehyde, residues of o-phthalaldehyde, residues of m-phthalaldehyde, residues of 4, 4-biphenyldicarboxaldehyde, residues of 2, 3-naphthalenedicarboxaldehyde and residues of 2,3,5, 6-tetrafluoroterephthalaldehyde according to any proportion;
B1consisting of a residue of p-phenylenediamine, a residue of m-phenylenediamine, a residue of biphenyldiamine, a residue of 4,4' -diamino-2, 2' -dimethylbiphenyl, a residue of 4,4' -diamino-3, 3' -dimethylbiphenyl, a residue of 2,2' -bis (trifluoromethyl) diaminobiphenyl, a residue of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and a residue of 2, 2-bis [4- (2-trifluoromethyl) hexafluoropropane-4-aminophenoxy) phenyl]Propane residue, 2-bis (4-aminophenyl) hexafluoropropane residue, 2-bis [4- (4-aminophenoxy) phenyl group]Residue of hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl group]A residue of hexafluoropropane, a residue of 4,4' -diaminodiphenyl ether, a residue of 3,4' -diaminodiphenyl ether, a residue of 4,4' -diaminobenzophenone, a residue of 4,4' -diaminodiphenylmethane, a residue of 4,4' -diaminophenylsulfone, a residue of bis (3-amino-4-hydroxyphenyl) sulfone, a residue of 1, 3-bis (3-aminophenoxy) benzene, a residue of 1, 3-bis (4-aminophenoxy) benzene, a residue of 4,4' -bis (4-aminophenoxy) biphenyl, a residue of 4,4' -bis (3-aminophenoxy) biphenyl, a residue of 2, 2-bis [4- (4-aminophenoxy) phenylphenylbiphenyl]Residue of propane, bis [4- (3-aminophenoxy) phenyl]One or more of sulfone residues are mixed according to any proportion;
B2is formed by mixing one or more of residues of 1,3, 5-triaminobenzene, residues of tri (2-aminoethyl) amine, residues of tri (4-aminophenyl) amine and residues of 1,3, 5-tri (4-aminophenyl) benzene according to any proportion;
m1, m2, n1 are natural numbers, n2 is an even number, 0.5-m 1/(m1+ m2) <1, 0.8-n 1/(n1+ n2) <1, 20-m 1+ m2+ n1+ n2) < 400, (n1+ 1.5-n 2) ═ m1+ m 2;
wherein Ar is1、Ar2、B1And B2At least one of which is a fluorine-containing residue.
10. The method for producing the positive photosensitive coverlay of claim 9, comprising the steps of:
(i) preparing a precursor solution of the polyimide composite resin: under the nitrogen atmosphere, dissolving a mol of diamine compound and b mol of triamine compound in a strong polar solvent while stirring in a container to obtain a solution, wherein the sum of the mass percentages of the diamine compound and the triamine compound in the solution is 5-13%; then d mol of dimethyl aldehyde compound is added, the temperature of the solution is controlled to be 0-50 ℃ under the nitrogen atmosphere, and the reaction is carried out for 4-24 h; then c moles of the tetracarboxylic dianhydride compound are added into the solution for three times, and the addition amount of each time respectively accounts for 60%, 30% and 10% of the total weight of the tetracarboxylic dianhydride compound; continuously reacting for 4-48h in nitrogen atmosphere, controlling the solution temperature at 0-50 ℃, and obtaining a precursor solution of the polyimide composite resin after reaction; wherein c/(c + d) is more than or equal to 0.5 and less than 1, a/(a + b) is more than or equal to 0.8 and less than 1, and (a + b + c + d) is more than or equal to 20 and less than or equal to 400, wherein (c + d) is (a + 1.5) b which is (0.95-1.05) to 1;
wherein the tetracarboxylic dianhydride compound is selected from pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 4,4'- (hexafluoroisopropyl) bisphthalic dianhydride, 1, 4-difluoropyromellitic dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, 2,3,3',4 '-biphenyltetracarboxylic dianhydride, 3,3',4,4 '-diphenyl ether dianhydride, 3,3',4,4 '-benzophenone tetracarboxylic dianhydride, 4,4' -terephthaloylbisphthalic anhydride, bisphenol A type diether dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3,6, 7-tetracarboxyl-9, 9-bis (trifluoromethyl) xanthene dianhydride, One or more of 1, 4-bis (trifluoromethyl) -2,3,5, 6-benzene tetracarboxylic dianhydride and 1, 4-bis (3, 4-dicarboxy trifluoro phenoxy) tetrafluorobenzene dianhydride are mixed according to any proportion;
the diformaldehyde compound is formed by mixing one or more of terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, 4-phthalaldehyde, 2, 3-naphthaldehyde and 2,3,5, 6-tetrafluoro-terephthalaldehyde according to any proportion;
diamine compounds selected from the group consisting of p-phenylenediamine, m-phenylenediamine, biphenyldiamine, 4' -diamino-2, 2' -dimethylbiphenyl, 4' -diamino-3, 3' -dimethylbiphenyl, 2' -bis (trifluoromethyl) diaminobiphenyl, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, and mixtures thereof, One or more of 3,4 '-diaminodiphenyl ether, 4' -diaminobenzophenone, 4 '-diaminodiphenylmethane, 4' -diaminophenylsulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane and bis [4- (3-aminophenoxy) phenyl ] sulfone are mixed according to any proportion to form the composition;
the triamine compound is formed by mixing one or more of 1,3, 5-triaminobenzene, tri (2-aminoethyl) amine, tri (4-aminophenyl) amine and 1,3, 5-tri (4-aminophenyl) benzene according to any proportion;
the strong polar solvent is formed by mixing one or more of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and m-cresol according to any proportion;
(ii) (ii) adding diazonaphthoquinone sensitizer into the precursor solution of the polyimide composite resin prepared in the step (i), so that the weight percentage of the diazonaphthoquinone sensitizer in the final positive photosensitive cover film is 10-40%; after adding, controlling the temperature of the solution to be 0-50 ℃ in the nitrogen atmosphere, and continuously stirring for 4-24h to obtain a photosensitive mixture solution;
(iii) film preparation: (iii) coating the photosensitive mixture solution obtained in step (ii) on a carrier so that the film thickness of the photosensitive mixture after drying is 5-50 μm; and then volatilizing at 60-90 ℃ to ensure that the content of the strong polar solvent is between 2-15 wt% to obtain a photosensitive mixture film, namely the positive photosensitive covering film.
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| CN111138695A (en) * | 2019-12-24 | 2020-05-12 | 深圳先进电子材料国际创新研究院 | Polyimide film and preparation method thereof |
| CN113347783B (en) * | 2020-03-02 | 2023-02-28 | 广东生益科技股份有限公司 | Adhesive-free single-sided board, preparation method thereof and adhesive-free double-sided board comprising same |
| CN111876085B (en) * | 2020-07-10 | 2022-09-27 | 东莞东阳光科研发有限公司 | Composite bonding sheet, flexible metal laminated board and preparation method thereof |
| CN111880371B (en) * | 2020-08-13 | 2022-05-03 | 常州华睿芯材科技有限公司 | Photoresist and method for patterning imine material |
| CN113563585B (en) * | 2021-07-29 | 2022-06-17 | 上海八亿时空先进材料有限公司 | Polyimide and application thereof in metal laminated plate |
| CN114230791B (en) * | 2021-12-29 | 2023-10-24 | 山东华夏神舟新材料有限公司 | Intrinsic low-dielectric fluorine-containing polyimide film and preparation method thereof |
| CN114854012B (en) * | 2022-06-20 | 2024-10-11 | 杭州福斯特应用材料股份有限公司 | Polyimide resin, polyimide film and preparation method thereof, copper clad plate |
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