TW202104434A - Polyaminic acid composition, polyamidite copper clad laminate, and circuit board - Google Patents

Abstract

A polyaminic acid composition obtained by polymerizing a dianhydride monomer and a diamine monomer. A molar ratio of the dianhydride monomer to the diamine monomer is in a range of 0.9 to 1.1. The diamine monomer includes a diamine monomer containing a liquid crystal unit, a diamine monomer containing a soft structure, and a diamine monomer containing a nitrogen heterocycle. A molar percentage of the diamine monomer containing a nitrogen heterocycle in the diamine monomer is 3% to 8%, the sum of a molar percentage of the diamine monomer containing a liquid crystal unit and the diamine monomer containing a soft structure is 92% to 97%. The invention also provides a polyamidite copper clad laminate obtained by cyclizing the polyamic acid composition and a circuit board manufactured by the polyamidene copper clad laminate.

Description

Polyamide acid composition, polyimide copper clad laminate and circuit board

The invention relates to a polyimide composition, a polyimide copper clad laminate prepared by cyclizing the polyimide composition, and a circuit board prepared by using the polyimide copper clad laminate.

In recent years, printed circuit boards have been widely used in various electronic products. At present, printed circuit boards are generally made of copper clad laminates as substrates. Among them, the copper clad laminate includes copper foil, a polyimide film, and an adhesive layer between the copper foil and the polyimide film for bonding the copper foil and the polyimide film together.

During the circuit board manufacturing process, part of the copper foil bonded to the surface of the polyimide film will be etched away, so that the polyimide film in this area is exposed without bonding the copper foil. It will be exposed during the circuit board installation and other manufacturing processes. A CCD camera was used to see through the polyimide film without copper foil to accurately position the element. Therefore, the polyimide film without copper foil is required to have excellent light transmittance.

In order to make the polyimide film after removing the copper foil have higher light transmittance, the polyimide film can be coated on the surface of the copper foil with lower surface roughness to ensure that the polyimide film is removed after the copper foil is removed. The surface roughness of the imine film is low and it has a high transmittance. However, the existing polyimide film has a low bonding force with a copper foil with a low surface roughness. When a copper foil with a low surface roughness is used to make a copper clad laminate, the bonding force between the copper foil and the polyimide film is relatively low. low.

In view of this, it is necessary to provide a new type of polyimide composition for making polyimide films to solve the above problems.

In addition, it is also necessary to provide a polyimide copper clad laminate prepared by cyclization of the polyimide composition.

In addition, it is also necessary to provide a circuit board made of the polyimide copper clad laminate.

A polyamide acid composition formed by polymerizing dianhydride monomer and diamine monomer, and the molar ratio of the dianhydride monomer to the diamine monomer is in the range of 0.9 to 1.1; the diamine Monomers include diamine monomers containing liquid crystal units, diamine monomers containing soft structures, and diamine monomers containing nitrogen heterocycles; among the diamine monomers, the diamine monomers containing nitrogen heterocycles The mole percentage of the body is 3%-8%, and the sum of the mole percentages of the diamine monomer containing the liquid crystal cell and the diamine monomer containing the soft structure is 92%-97%.

Further, the dianhydride monomer includes at least one of a dianhydride monomer containing a liquid crystal unit or a dianhydride monomer containing a soft structure.

Further, in the diamine monomer containing liquid crystal cells and the diamine monomer containing soft structure, the percentage of the diamine monomer containing liquid crystal cells is 30 to 70%, and the diamine monomer containing liquid crystal cells accounts for 30 to 70%. The percentage of diamine monomer with soft structure is 30~70%, and the sum of the two is 100%.

Further, the soft structure includes a long-chain saturated aliphatic hydrocarbon group, a long-chain unsaturated aliphatic hydrocarbon group or an ether group, and the long chain refers to a hydrocarbon straight-chain structure with four carbons or more.

、

、

、

、

、

中的至少一種；其中，R及R′為烴基，X及Y為-CH=CH-、-C ≡C-、-CH=N-、-CH=N-及-COO-中的至少一種。Further, the liquid crystal cell is

,

,

,

,

,

At least one of; wherein R and R'are hydrocarbon groups, and X and Y are at least one of -CH=CH-, -C ≡C-, -CH=N-, -CH=N- and -COO-.

，所述對苯基二(偏苯三酸酯)二酸酐的結構式為

，所述環己烷-1,4-二基雙(亞甲基)雙(1,3-二氧代-1,3-二氫異苯並呋喃-5-羧酸乙酯)的結構式為：

。Further, the dianhydride monomer containing liquid crystal cells is 3,3',4,4'-biphenyltetracarboxylic dianhydride, p-phenylbis(trimellitic acid ester) dianhydride and cyclohexane- At least one of 1,4-diylbis(methylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid ethyl ester), wherein the 3 The structural formula of ,3',4,4'-biphenyltetracarboxylic dianhydride is

, The structural formula of the p-phenylbis(trimellitic acid ester) dianhydride is

, The structural formula of the cyclohexane-1,4-diylbis(methylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid ethyl ester) for:

.

，所述1,4-雙(4-氨基苯氧基)苯的結構式為：

，所述對苯二甲酸二對氨基苯酯的結構式為：

。Further, the diamine monomer containing liquid crystal units is at least one of p-aminophenyl p-aminobenzoate, 1,4-bis(4-aminophenoxy)benzene, and di-p-aminophenyl terephthalate. One; wherein the structural formula of the p-aminophenyl p-aminobenzoate is:

, The structural formula of the 1,4-bis(4-aminophenoxy)benzene is:

, The structural formula of the di-p-aminophenyl terephthalate is:

.

的二胺、市售工業品號為DA-C6且結構為

的二胺、結構式為

的己二胺中的至少一種；其中，所述4,4'-氧雙鄰苯二甲酸酐的結構式為：

，所述2,3,3',4'-二苯醚四甲酸二酐的結構式為：

，所述3,3',4,4'-二苯甲酮四甲酸二酐的結構式：為

，所述3,3,4,4-二苯基碸四羧酸二酸酐的結構式為：，所述六氟二酐的結構式為：

，所述雙酚A型二醚二酐的結構式為

。Further, the dianhydride monomer containing a soft structure is 4,4'-oxydiphthalic anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenyl tetracarboxylic dianhydride, hexafluoro dianhydride and bisphenol A type diether dianhydride, commercial products The numbers are D230 and D400 and the structure is

The diamine, the commercial product number is DA-C6 and the structure is

The diamine, the structural formula is

At least one of the hexamethylene diamine; wherein the structural formula of the 4,4'-oxydiphthalic anhydride is:

, The structural formula of the 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride is:

, The structural formula of the 3,3',4,4'-benzophenone tetracarboxylic dianhydride:

, The structural formula of the 3,3,4,4-diphenyl tetracarboxylic dianhydride is: and the structural formula of the hexafluorodianhydride is:

, The structural formula of the bisphenol A diether dianhydride is

.

的二胺、市售工業品號為DA-C6且結構為

的二胺、結構式為

的己二胺中的至少一種；其中，所述4,4'-二氨基二苯醚的結構式為：

，所述4,4'-二(4-氨基苯氧基)聯苯的結構式為：

，所述2,2'-雙[4-(4-氨基苯氧基苯基)]丙烷的結構式為：

，所述2,2-雙[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷的結構式為：

，所述1,3-雙(4'-氨基苯氧基)苯的結構式為：

，所述1,3-雙(3-氨基苯氧基)苯的結構式為：

。Further, the diamine monomer containing a soft structure is 4,4'-diaminodiphenyl ether, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-bis[4 -(4-Aminophenoxyphenyl)]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis(4'-aminophenoxy)benzene and 1,3-bis(3-aminophenoxy)benzene, the commercial product numbers are D230 and D400 and the structure is

The diamine, the commercial product number is DA-C6 and the structure is

The diamine, the structural formula is

At least one of the hexamethylene diamine; wherein the structural formula of the 4,4'-diaminodiphenyl ether is:

, The structural formula of the 4,4'-bis(4-aminophenoxy)biphenyl is:

, The structural formula of the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is:

, The structural formula of the 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane is:

, The structural formula of the 1,3-bis(4'-aminophenoxy)benzene is:

, The structural formula of the 1,3-bis(3-aminophenoxy)benzene is:

.

、所述2-(4-氨基苯基)-5-氨基苯並咪唑的結構式為：

，所述2,5-雙(4-氨基苯基)嘧啶的結構式為：

。Further, the diamine monomer containing nitrogen heterocycle is 3,5-diamino-1,2,4-triazole, 2-(4-aminophenyl)-5-aminobenzimidazole and 2 At least one of ,5-bis(4-aminophenyl)pyrimidine; wherein the structural formula of the 3,5-diamino-1,2,4-triazole is:

, The structural formula of the 2-(4-aminophenyl)-5-aminobenzimidazole is:

, The structural formula of the 2,5-bis(4-aminophenyl)pyrimidine is:

.

A polyimide copper clad laminate comprising copper foil and a polyimide film bonded to the surface of the copper foil, the polyimide film being coated on the copper foil by the polyimide composition described above The surface is formed after cyclization.

A circuit board comprising a circuit substrate and a cover film covering at least one surface of the circuit substrate, the circuit substrate comprising a polyimide film and a conductive circuit layer bonded on at least one surface of the polyimide film, The circuit substrate is made of a copper clad laminate. The copper clad laminate includes a copper foil and a polyimide film bonded to the surface of the copper foil. The conductive circuit layer is formed by patterning the copper foil. The polyimide film is formed by coating the above-mentioned polyimide acid composition on the surface of the copper foil and then cyclizing it.

The polyamide acid composition provided by the present invention is formed by polymerizing dianhydride monomers and diamine monomers, and the dianhydride monomers include dianhydride monomers containing liquid crystal units or dianhydride monomers containing soft structures. At least one of the diamine monomers includes a diamine monomer containing a liquid crystal unit, a diamine monomer containing a soft structure, and a diamine monomer containing a nitrogen heterocycle; 1) the diamine monomer containing a nitrogen heterocycle The nitrogen atom on the nitrogen heterocycle in the amine monomer can coordinate with copper, which can improve the bonding strength of polyimide and copper foil, and improve the rigidity caused by the close arrangement of liquid crystal cells in the polymer structure to form crystals. The effect of rigidity reduces the bonding strength of polyimide and copper foil; 2) Under high temperature conditions, the dianhydride monomer or diamine monomer containing liquid crystal unit can make the liquid crystal in the polymer structure of polyimide The units are tightly arranged to form crystals, which reduces the mobility of the polyimide polymer structure under high-frequency electric fields, thereby reducing dielectric loss; 3) The dianhydride monomer or diamine monomer containing a soft structure can Adjust the rigidity caused by the close arrangement of the liquid crystal cells in the polymer structure to form crystals, and adjust the coefficient of thermal expansion (CTE) of the polyimide to match the copper foil, thereby avoiding the warpage of the copper clad laminate.

1 in conjunction with FIG. 1, a preferred embodiment of the present invention provides a polyimide composition, which is mainly used to make the polyimide film 20 bonded to the surface of the copper foil 10 in the polyimide copper clad laminate 100.

The polyamide acid composition is mainly formed by polymerizing dianhydride monomer and diamine monomer.

Wherein, the dianhydride monomer includes at least one of a dianhydride monomer containing a liquid crystal unit or a dianhydride monomer containing a soft structure. Among them, the soft structure refers to the soft structure refers to long-chain saturated aliphatic hydrocarbon groups or long-chain unsaturated aliphatic hydrocarbon groups or ether groups. Among them, the definition of long chain refers to a straight chain structure of hydrocarbons with four carbons or more.

Preferably, the soft structure contains at least one of -O-, -CH ₃ CCH _3- , -CF ₃ CCF _3- , -SO _2- , -C=O- and other groups.

Wherein, the diamine monomer includes a diamine monomer containing a liquid crystal unit, a diamine monomer containing a soft structure, and a diamine monomer containing a nitrogen heterocycle. Among them, the soft structure refers to the soft structure refers to long-chain saturated aliphatic hydrocarbon groups or long-chain unsaturated aliphatic hydrocarbon groups or ether groups. Among them, the definition of long chain refers to a straight chain structure of hydrocarbons with four carbons or more. Preferably, the soft structure contains at least one of -O-, -CH ₃ CCH _3- , -CF ₃ CCF _3- , -SO _2- , -C=O- and other groups.

The nitrogen atoms on the nitrogen heterocycles in the diamine monomers containing nitrogen heterocycles can coordinate with copper, which can increase the bonding strength between polyimine and copper foil, and improve the liquid crystal unit in the polymer structure. The rigidity caused by the close arrangement of crystals reduces the bonding strength of polyimide and copper foil.

Under high temperature conditions, the dianhydride monomers or diamine monomers containing liquid crystal cells can make the liquid crystal cells in the polymer structure of polyimide tightly arranged, form crystals, and reduce the amount of polyimide in the high-frequency electric field. The mobility of the amine polymer structure reduces the dielectric loss.

The dianhydride monomer or diamine monomer containing a soft structure can adjust the rigidity caused by the close arrangement of liquid crystal cells in the polymer structure to form crystals, and adjust the coefficient of thermal expansion (CTE) of the polyimide to make it It can be matched with copper foil to avoid warping of copper clad laminate.

Wherein, the use range of the molar ratio of the dianhydride monomer to the diamine monomer is 0.9-1.1. Polyimide is produced by the condensation polymerization reaction of 1:1 dianhydride monomer and diamine monomer. When the condensation polymerization reaction is carried out under conditions where the two amounts are not equal, the average molecular weight of the resulting polymer will be too low. In addition, the molecular weight distribution will be too wide. If the polymer in this case is further processed into materials for industrial use, the physical and chemical properties or mechanical properties of the material itself will not be able to meet the industrial specifications.

Wherein, the sum of the mole percentages of the diamine monomer containing the liquid crystal unit and the diamine monomer containing the soft structure in the diamine monomer is 92%-97%. Wherein, in the diamine monomer containing the liquid crystal cell and the diamine monomer containing the soft structure, the percentage of the diamine monomer containing the liquid crystal cell is 30 to 70%, and the diamine monomer containing the soft structure The percentage of the structure of the diamine monomer is 30~70%, and the sum of the two is 100%. Among them, the difference in the content range will indirectly or directly affect the change of the material's dielectric loss and the CTE value due to the amount of polymer liquid crystal cells or flexible cells.

Wherein, in the diamine monomer, the mole percentage of the diamine monomer containing the nitrogen heterocycle is 3% to 8%. According to the content range, the polyimide film prepared from the polyamide acid composition has strong peel strength and good light transmittance. Experiments have shown that when the molar amount of the diamine monomer containing the nitrogen heterocycle is greater than 3% to 8%, the peel strength of the polyimide film is not greatly improved, but it contains nitrogen. The heterocyclic diamine monomer has a greater charge transfer effect when it absorbs light, which leads to a significant decrease in light transmittance.

、

、

、

、

、

中的至少一種；其中，R及R′為烴基，X及Y為-CH=CH-、-C ≡C-、-CH=N-、-CH=N-及-COO-中的至少一種。Wherein, the liquid crystal cell is

,

,

,

,

,

At least one of; wherein R and R'are hydrocarbon groups, and X and Y are at least one of -CH=CH-, -C ≡C-, -CH=N-, -CH=N- and -COO-.

Specifically, the dianhydride monomer containing a liquid crystal cell is preferably an aromatic tetracarboxylic dianhydride. Wherein, the dianhydride monomer containing liquid crystal cells can be, but not limited to, 3,3',4,4'-Biphenyltetracarboxylic dianhydride (3,3',4,4'-Biphenyltetracarboxylic dianhydride, BPDA ; CAS: 2420-87-3), p-Phenylene bis(trimellitate) dianhydride (TAHQ; CAS: 2770-49-2) and cyclohexane-1, 4-diylbis(methylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid ethyl ester)(cyclohexane-1,4-diylbis(methylene)bis (1,3-dioxo-1,3-dihy-droisobenzofuran-5-carboxylate), TA-CHDM).

，所述對苯基二(偏苯三酸酯)二酸酐的結構式為

，所述環己烷-1,4-二基雙(亞甲基)雙(1,3-二氧代-1,3-二氫異苯並呋喃-5-羧酸乙酯)的結構式為：

。Wherein, the structural formula of the 3,3',4,4'-biphenyltetracarboxylic dianhydride is

, The structural formula of the p-phenylbis(trimellitic acid ester) dianhydride is

, The structural formula of the cyclohexane-1,4-diylbis(methylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid ethyl ester) for:

.

Specifically, the diamine monomer containing liquid crystal cells may be, but not limited to, 4-Aminobenzoic acid 4-aminophenyl ester (APAB; CAS: 20610-77-9), 1, 4-bis(4-aminophenoxy)benzene (1,4-Bis(4-aminobenzo-yloxy)benzene, ABHQ; CAS:22095-98-3) and di-p-aminophenyl terephthalate (1, At least one of 4-Benzenedicarboxylic acid bis(4-aMinophenyl) ester, BPTP; CAS: 16926-73-1).

，所述1,4-雙(4-氨基苯氧基)苯的結構式為：

，所述對苯二甲酸二對氨基苯酯的結構式為：

。Wherein, the structural formula of the p-aminophenyl p-aminobenzoate is:

, The structural formula of the 1,4-bis(4-aminophenoxy)benzene is:

, The structural formula of the di-p-aminophenyl terephthalate is:

.

Among them, the dianhydride monomer containing a soft structure is preferably an aromatic tetracarboxylic dianhydride. Specifically, the dianhydride monomer containing a soft structure may be, but not limited to, 4,4'-oxydiphthalic anhydride (4,4'-Oxydiphthalic anhydride, ODPA; CAS: 1823-59-2) , 2,3,3',4'-Diphenyl ether tetracarboxylic dianhydride (3,4'-Oxydiphthalic Anhydride, A-ODPA; CAS: 50662-95-8), 3,3',4,4'- Benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA; CAS: 2421-28-5), 3,3,4,4-diphenyl tetracarboxylic acid Diacid anhydride (3,3',4,4'-Diphenylsulfonetetracarboxylic Dianhydride, DSDA; CAS: 2540-99-0), hexafluorodianhydride (4,4'-(Hexafluoroisopropylidene) diphthalic anhydride, 6FDA; CAS: 1107-00) -2) and at least one of bisphenol A type diether dianhydride (4,4'-(4,4'-isopropylidenediphenoxy)bis-(phthalic anhydride), BPADA; CAS: 38103-06-9).

，所述2,3,3',4'-二苯醚四甲酸二酐的結構式為：

，所述3,3',4,4'-二苯甲酮四甲酸二酐的結構式：為

，所述3,3,4,4-二苯基碸四羧酸二酸酐的結構式為：

，所述六氟二酐的結構式為：

，所述雙酚A型二醚二酐的結構式為

。Wherein, the structural formula of the 4,4'-oxydiphthalic anhydride is:

, The structural formula of the 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride is:

, The structural formula of the 3,3',4,4'-benzophenone tetracarboxylic dianhydride:

, The structural formula of the 3,3,4,4-diphenyl tetracarboxylic dianhydride is:

, The structural formula of the hexafluorodianhydride is:

, The structural formula of the bisphenol A diether dianhydride is

.

的二胺、市售工業品號為DA-C6且結構為

的二胺、結構式為

的己二胺中的至少一種。Wherein, the diamine monomer containing a soft structure is an aromatic diamine or an aliphatic diamine or the like. Specifically, the diamine monomer containing a soft structure may be, but is not limited to, 4,4'-diaminodiphenyl ether (4,4'-Oxydianiline, ODA; CAS: 101-80-4), 4, 4'-Bis(4-aminophenoxy)biphenyl (4,4'-Bis(4-aminophenoxy)biphenyl, BAPB; CAS: 13080-85-8), 2,2'-bis[4-(4 -Aminophenoxyphenyl)]propane (4,4'-(4,4'-Isopropylidenediphenyl-1,1'-diyldioxy)dianiline, m-BAPP; CAS: 13080-86-9), 2,2- Bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, HFBAPP ;CAS: 69563-88-8), 1,3-bis(4'-aminophenoxy)benzene (4,4'-(1,3-Phenylenedioxy)dianiline, TPE-R; CAS: 2479-46- 1) And 1,3-Bis(3-aminophenoxy)benzene (1,3-Bis(3-aminophenoxy)benzene, TPE-M; CAS: 10526-07-5), the commercial product number is D230 And D400 and the structure is

The diamine, the commercial product number is DA-C6 and the structure is

The diamine, the structural formula is

At least one of the hexamethylene diamine.

，所述4,4'-二(4-氨基苯氧基)聯苯的結構式為：

，所述2,2'-雙[4-(4-氨基苯氧基苯基)]丙烷的結構式為：

，所述2,2-雙[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷的結構式為：

，所述1,3-雙(4'-氨基苯氧基)苯的結構式為：

，所述1,3-雙(3-氨基苯氧基)苯的結構式為：

。Wherein, the structural formula of the 4,4'-diaminodiphenyl ether is:

, The structural formula of the 4,4'-bis(4-aminophenoxy)biphenyl is:

, The structural formula of the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is:

, The structural formula of the 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane is:

, The structural formula of the 1,3-bis(4'-aminophenoxy)benzene is:

, The structural formula of the 1,3-bis(3-aminophenoxy)benzene is:

.

Wherein, the diamine monomer containing nitrogen heterocycle can be but not limited to 3,5-diamino-1,2,4-triazole (1,2,4-Triazole-3,5-diamine, DTZ; CAS: 1455-77-2), 2-(4-aminophenyl)-5-aminobenzimidazole (2-(4-Aminophenyl)-1H-benzimidazol-5-amine, APBIA; CAS: 7621- 86-5) and at least one of 2,5-bis(4-aminophenyl)pyrimidine (4,4'-pyrimidine-2,5-diyldianiline, PRM; CAS: 102570-64-9).

、所述2-(4-氨基苯基)-5-氨基苯並咪唑的結構式為：

，所述2,5-雙(4-氨基苯基)嘧啶的結構式為：

。Wherein, the structural formula of the 3,5-diamino-1,2,4-triazole is:

, The structural formula of the 2-(4-aminophenyl)-5-aminobenzimidazole is:

, The structural formula of the 2,5-bis(4-aminophenyl)pyrimidine is:

.

The preparation method of the polyamide acid composition can be: adding a diamine monomer containing a liquid crystal unit, a diamine monomer containing a soft structure, and a diamine monomer containing a nitrogen heterocycle into a reaction flask with a solvent; High-speed stirring makes the diamine monomer containing the liquid crystal unit, the diamine monomer containing the soft structure and the diamine monomer containing the nitrogen heterocycle completely dissolved in the solvent; then, the dianhydride monomer containing the liquid crystal unit or the diamine monomer containing the soft At least one of the dianhydride monomers of the structure is added into the reaction flask, and the reaction is stirred for a period of time to obtain the polyamide acid composition. Among them, the solvent is preferably a bipolar aprotic solvent. The bipolar aprotic solvent may be dimethylformamide (DMF), dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethylsulfene (DMSO), and the like. The addition amount of the solvent can be changed as needed, as long as the diamine monomer containing liquid crystal unit, the diamine monomer containing soft structure, the diamine monomer containing nitrogen heterocycle, and the dianhydride containing liquid crystal unit The monomer and/or the dianhydride monomer with a soft structure can be completely dissolved. The rotational speed of the high-speed stirring may be about 1400 rpm (revolutions per minute).

Please refer to FIGS. 1 and 2 in combination, a polyimide copper clad laminate 100 used to make a circuit board 200. The polyimide copper clad laminate 100 includes a copper foil 10 and a polyimide film 20 bonded to a surface of the copper foil 10. The surface of the copper foil 10 has relatively low roughness. Wherein, the surface roughness of the copper foil 10 is between 0.12um and 2.1um. The polyimide film 20 is formed by coating the polyimide acid composition on the surface of the copper foil 10 and then undergoing high-temperature cyclization.

。Wherein, the principle of forming the polyimide film 20 from the polyimide composition through high temperature cyclization is as follows:

.

Since the polyamide acid composition includes a diamine monomer containing a nitrogen heterocycle, the nitrogen atom on the nitrogen heterocycle in the diamine monomer containing a nitrogen heterocycle can coordinate with the copper foil 10 Therefore, the polyimide film 20 and the copper foil 10 have a strong bonding force. In this way, the copper foil 10 with lower surface roughness can be used to make the polyimide copper clad laminate 100, so that the surface of the polyimide film 20 formed on the surface of the copper foil 10 can be relatively flat, so that the polyimide The imine film 20 has high light transmittance.

Wherein, the copper foil 10 of the polyimide copper clad laminate 100 and the polyimide film 20 are directly bonded together, and no glue is provided between the copper foil 10 and the polyimide film 20 Adhesive layer, in this way, the light transmittance of the polyimide film 20 can be further improved, and the cost can be saved.

A manufacturing method of the above-mentioned polyimide copper clad laminate 100:

A copper foil 10 is provided, and the surface roughness of the copper foil 10 is between 0.12um and 2.1um.

A polyamide composition is provided, and the polyamide composition is coated on the surface of the copper foil 10.

High-temperature cyclization is performed to dehydrate the polyamide acid composition on the surface of the copper foil 10 at a high temperature to close the loop to obtain the polyimide film 20 bonded to the surface of the copper foil 10, and thus the copper-clad laminate 100 is obtained. Wherein, the temperature range of the high-temperature cyclization is approximately 300-400°C.

The present invention also provides a polyimide film 20, which is formed by coating the polyimide acid composition on the surface of a substrate and then undergoing high-temperature cyclization. Wherein, the substrate may be a release film, metal foil, resin, etc., which are conventionally used for preparing polyimide films. In the high-temperature cyclization process, the polyimide composition will be dehydrated at high temperature to close the ring, thereby obtaining the polyimide film 20 bonded to the surface of the substrate.

Please refer to FIG. 2, a circuit board 200 applied to electronic devices (not shown) such as computers, e-readers, tablet computers, and smart watches. The circuit board 200 includes a circuit substrate 201 and a cover film 202 covering at least one surface of the circuit substrate 201. The circuit substrate 201 includes the polyimide film 20 and a conductive circuit layer 2011 bonded to at least one surface of the polyimide film 20. The conductive circuit layer 2011 is formed by patterning the copper foil 10 of the polyimide copper clad laminate 100. The cover film 202 is bonded to the surface of the conductive circuit layer 2011 away from the polyimide film 20.

The following further describes the polyamide acid composition of the present invention through specific examples.

Example 1

Add NMP (203.37 g), APAB (0.068mol, 15.52g), ODA (0.027mol, 5.41g), and DTZ (0.005mol, 0.50g) into a 500mL reaction flask. After stirring at high speed to dissolve, add BPDA (0.1mol, 29.42g) Under anhydrous nitrogen environment, the reaction is stirred for 48 hours under the condition of lower than room temperature, and the polyamide acid composition is configured.

Example 2

Add NMP (205.77 g), APAB (0.078mol, 17.80g), ODA (0.017mol, 3.40g), DTZ (0.005mol, 0.50g) into a 500mL reaction flask, and then add ODPA after stirring at high speed to dissolve (0.02mol, 6.20g), BPDA (0.08mol, 23.54g) in anhydrous nitrogen environment, under the conditions of lower than room temperature, stirring and reacting for 48 hours, that is, the polyamide acid composition is configured.

Example 3

Add NMP (250.75 g), APAB (0.045mol, 10.27g), ODA (0.060mol, 12.01g), and DTZ (0.005mol, 0.50g) into a 500mL reaction flask. After stirring at high speed to dissolve, add ODPA (0.04mol, 12.41g), TAHQ (0.06mol, 27.50g) in an anhydrous nitrogen environment, stirred and reacted at a condition below room temperature for 48 hours, and the polyamide acid composition was configured.

Example 4

Add NMP (211.68 g), APAB (0.085mol, 19.40g), ODA (0.010mol, 2.00g), DTZ (0.005mol, 0.50g) into a 500mL reaction flask, and then add ODPA after stirring at high speed to dissolve (0.1mol, 31.02g) In an anhydrous nitrogen environment, the reaction is stirred for 48 hours at a temperature lower than room temperature, and the polyamide acid composition is configured.

Comparative example 1

Add NMP (170.66 g), PDA (0.068mol, 7.34g), ODA (0.027mol, 5.41g), and DTZ (0.005mol, 0.50g) into a 500mL reaction flask, and then add BPDA after stirring at high speed to dissolve. (0.1mol, 29.42g) In an anhydrous nitrogen environment, the reaction is stirred for 48 hours at a temperature lower than room temperature, and the polyamide acid composition is configured.

Comparative example 2

Add NMP (205.61 g), APAB (0.070mol, 15.98g), and ODA (0.030mol, 6.01g) into a 500mL reaction flask. After stirring at high speed to dissolve, add BPDA (0.1mol, 29.42g) to anhydrous Under a nitrogen environment, the reaction is stirred for 48 hours at a temperature lower than room temperature, and the polyamide acid composition is configured.

Comparative example 3

Add NMP (263.41g) and ODA (0.1mol, 20.02g) into a 500mL reaction flask. After stirring at high speed to dissolve, add TAHQ (0.1mol, 45.83g) in anhydrous nitrogen environment, below room temperature The conditions are stirred and reacted for 48 hours to complete the configuration of the polyamide acid composition.

Comparative example 4

Add NMP (208.98 g) and APAB (0.1mol, 22.83g) to a 500mL reaction flask, and stir at high speed to dissolve, then add BPDA (0.1mol, 29.42g) in anhydrous nitrogen environment, below room temperature The conditions are stirred and reacted for 48 hours to complete the configuration of the polyamide acid composition.

The polyamide acid compositions prepared in the foregoing Examples 1 to 4 and Comparative Examples 1 to 4 were respectively coated on the surface of the copper foil 10, and the copper foil 10 coated with the polyamide composition was placed at a high temperature. Under the environment, the polyimide composition is cyclized and polymerized at a high temperature to form the polyimide film 20 bonded to the surface of the copper foil 10, and the copper clad laminate 100 is produced.

The copper clad laminate 100 is subjected to peel strength test, tin bleaching test, coefficient of thermal expansion (CTE) test, thermogravimetric test (Tg), dielectric constant (Dk) and dielectric loss (Df), respectively. The test results are shown in Table 1. Wherein, in the tin bleaching test, if the tin bleaching test lasts for 10 sec at a temperature of 288° C. and the tin does not fall off, the result of the tin bleaching test is "passed", indicating that the copper clad laminate 100 meets the requirements of the tin bleaching test.

Table 1: Peeling strength, bleaching properties, thermal expansion coefficient, thermogravimetry and dielectric properties of polyimide film of copper clad laminates prepared from the polyamide acid compositions of Examples 1 to 4 and Comparative Examples 1 to 4 Constant and dielectric loss test results Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 ingredient APAB 0.068 0.078 0.045 0.085 0.07 0.1 PDA 0.068 ODA 0.027 0.017 0.060 0.010 0.027 0.03 0.1 DTZ 0.005 0.005 0.005 0.005 0.005 TAHQ 0.06 0.1 BPDA 0.1 0.08 0.1 0.1 0.1 ODPA 0.02 0.04 0.1 Peel strength (kgf/cm) 0.84 0.95 0.93 0.91 1.07 0.19 0.24 0.01 Floating tin test (288℃/10sec) by by by by by by by by Tg (℃) 335 320 325 345 327 335 340 >400 CTE (ppm/℃) 14.3 16.7 23.2 35.3 18.4 15 51.2 3.4 Dk (10GHz) 3.14 3.12 3.19 3.23 3.13 3.14 3.16 3.28 Df (10GHz) 0.005 0.004 0.005 0.006 0.014 0.005 0.004 0.002

As can be seen from the above table, Examples 1 to 4 are the introduction of a monomer containing a liquid crystal cell and a diamine monomer containing a nitrogen-containing heterocyclic ring in the present invention, which still maintains good peel strength with copper foil and can reduce the dielectric loss Df value 0.004 to 0.006, and Comparative Example 1 has a dielectric loss Df value of 0.014 because of the polyamide acid composition containing no liquid crystal cell monomer. Although Comparative Examples 2 to 4 contained monomers of liquid crystal cells, they lacked a diamine monomer containing a nitrogen-containing heterocyclic ring, so the peel strength from the copper foil was very low. In Comparative Example 3, the monomer containing the liquid crystal cell is only matched with a soft monomer, and the CTE value is too large, causing the copper clad laminate to warp. In Comparative Example 4, the liquid crystal cell-containing monomer is not matched with a soft monomer, and the CTE value is low, which will also cause the copper clad laminate to warp.

The polyamide acid composition provided by the present invention is formed by polymerizing dianhydride monomers and diamine monomers, and the dianhydride monomers include dianhydride monomers containing liquid crystal units or dianhydride monomers containing soft structures. At least one of the diamine monomers includes a diamine monomer containing a liquid crystal unit, a diamine monomer containing a soft structure, and a diamine monomer containing a nitrogen heterocycle; 1) the diamine monomer containing a nitrogen heterocycle The nitrogen atom on the nitrogen heterocycle in the amine monomer can coordinate with copper, which can improve the bonding strength of polyimide and copper foil, and improve the rigidity caused by the close arrangement of liquid crystal cells in the polymer structure to form crystals. The effect of rigidity reduces the bonding strength of polyimide and copper foil; 2) Under high temperature conditions, the dianhydride monomer or diamine monomer containing liquid crystal unit can make the liquid crystal in the polymer structure of polyimide The units are tightly arranged to form crystals, which reduces the mobility of the polyimide polymer structure under high-frequency electric fields, thereby reducing dielectric loss; 3) The dianhydride monomer or diamine monomer containing a soft structure can Adjust the rigidity caused by the close arrangement of the liquid crystal cells in the polymer structure to form crystals, and adjust the coefficient of thermal expansion (CTE) of the polyimide to match the copper foil, thereby avoiding the warpage of the copper clad laminate.

In addition, for those of ordinary skill in the art, various other corresponding changes and modifications can be made according to the technical concept of the present invention, and all these changes and modifications should fall within the protection scope of the patent application of the present invention.

100: Polyimide copper clad laminate 10: Copper foil 20: Polyimide film 200: circuit board 201: Circuit board 2011: Conductive circuit layer 202: Cover film

Fig. 1 is a schematic cross-sectional view of a copper clad laminate according to a preferred embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view of a circuit board according to a preferred embodiment of the present invention.

20: Polyimide film

200: circuit board

201: Circuit board

2011: Conductive circuit layer

202: Cover film

Claims (12)

A polyamide acid composition is formed by polymerizing dianhydride monomer and diamine monomer, and the molar ratio of the dianhydride monomer to the diamine monomer is in the range of 0.9 to 1.1; wherein, the Diamine monomers include diamine monomers containing liquid crystal units, diamine monomers containing soft structures, and diamine monomers containing nitrogen heterocycles; among the diamine monomers, the diamine monomers containing nitrogen heterocycles The mole percentage of the amine monomer is 3%-8%, and the sum of the mole percentages of the diamine monomer containing the liquid crystal unit and the diamine monomer containing the soft structure is 92%-97%. The polyamide acid composition according to claim 1, wherein the dianhydride monomer includes at least one of a dianhydride monomer containing a liquid crystal unit or a dianhydride monomer containing a soft structure. The polyamide acid composition according to claim 1, wherein in the diamine monomer containing liquid crystal cells and the diamine monomer containing soft structure, the diamine containing liquid crystal cells The percentage of the monomer is 30-70%, the percentage of the diamine monomer containing the soft structure is 30-70%, and the sum of the two is 100%. The polyamide acid composition according to claim 1 or 2, wherein the soft structure includes a long-chain saturated aliphatic hydrocarbon group, a long-chain unsaturated aliphatic hydrocarbon group or an ether group, and the long chain refers to four carbon or Hydrocarbon straight chain structure with more than four carbons. The polyamide acid composition according to any one of claims 1-3, wherein the liquid crystal cell is

,

,

,

,

,

At least one of; wherein R and R'are hydrocarbon groups, and X and Y are at least one of -CH=CH-, -C ≡C-, -CH=N-, -CH=N- and -COO-. The polyamide acid composition according to claim 5, wherein the dianhydride monomer containing liquid crystal cells is 3,3',4,4'-biphenyltetracarboxylic dianhydride, p-phenylene Bis(trimellitic acid ester) dianhydride and cyclohexane-1,4-diylbis(methylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5- At least one of ethyl carboxylate), wherein the structural formula of the 3,3',4,4'-biphenyltetracarboxylic dianhydride is

, The structural formula of the p-phenylbis(trimellitic acid ester) dianhydride is

, The structural formula of the cyclohexane-1,4-diylbis(methylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid ethyl ester) for:

. The polyamide acid composition according to claim 5, wherein the diamine monomer containing a liquid crystal unit is p-aminophenyl p-aminobenzoate, 1,4-bis(4-aminophenoxy) ) At least one of benzene and di-p-aminophenyl terephthalate; wherein the structural formula of the p-aminophenyl p-aminobenzoate is:

, The structural formula of the 1,4-bis(4-aminophenoxy)benzene is:

, The structural formula of the di-p-aminophenyl terephthalate is:

. The polyamide acid composition according to claim 1 or 2, wherein the dianhydride monomer containing a soft structure is 4,4'-oxydiphthalic anhydride, 2,3,3',4'-Diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenyl tetracarboxylic dianhydride, hexa Fluorinated dianhydride and bisphenol A type diether dianhydride, commercially available industrial product numbers are D230 and D400, and the structure is

The diamine, the commercial product number is DA-C6 and the structure is

The diamine, the structural formula is

At least one of the hexamethylene diamine; wherein the structural formula of the 4,4'-oxydiphthalic anhydride is:

, The structural formula of the 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride is:

, The structural formula of the 3,3',4,4'-benzophenone tetracarboxylic dianhydride:

, The structural formula of the 3,3,4,4-diphenyl tetracarboxylic dianhydride is:

, The structural formula of the hexafluorodianhydride is:

, The structural formula of the bisphenol A diether dianhydride is

. The polyamide acid composition according to claim 1 or 3, wherein the diamine monomer containing a soft structure is 4,4'-diaminodiphenyl ether, 4,4'-bis(4 -Aminophenoxy)biphenyl, 2,2'-bis[4-(4-aminophenoxyphenyl)]propane, 2,2-bis[4-(4-aminophenoxy)phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis(4'-aminophenoxy)benzene and 1,3-bis(3-aminophenoxy)benzene at least One; wherein the structural formula of the 4,4'-diaminodiphenyl ether is:

, The structural formula of the 4,4'-bis(4-aminophenoxy)biphenyl is:

, The structural formula of the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is:

, The structural formula of the 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane is:

, The structural formula of the 1,3-bis(4'-aminophenoxy)benzene is:

, The structural formula of the 1,3-bis(3-aminophenoxy)benzene is:

. The polyamide acid composition according to claim 1, wherein the diamine monomer containing a nitrogen heterocycle is 3,5-diamino-1,2,4-triazole, 2-( At least one of 4-aminophenyl)-5-aminobenzimidazole and 2,5-bis(4-aminophenyl)pyrimidine; wherein the 3,5-diamino-1,2,4-tri The structural formula of azole:

, The structural formula of the 2-(4-aminophenyl)-5-aminobenzimidazole is:

, The structural formula of the 2,5-bis(4-aminophenyl)pyrimidine is:

. A polyimide copper clad laminate, comprising copper foil and a polyimide film bonded to the surface of the copper foil, wherein the polyimide film is composed of any one of claims 1-3 and 10 The polyamide acid composition is coated on the surface of the copper foil and then formed by cyclization. A circuit board comprising a circuit substrate and a cover film covering at least one surface of the circuit substrate, the circuit substrate comprising a polyimide film and a conductive circuit layer bonded on at least one surface of the polyimide film, The circuit substrate is made of a polyimide copper clad laminate, the polyimide copper clad laminate includes a copper foil and a polyimide film bonded to the surface of the copper foil, and the conductive circuit layer passes through the copper foil The patterning is performed, wherein the polyimide film is formed by coating the polyimide composition according to any one of claims 1 to 3 and 10 on the surface of the copper foil and then cyclizing.

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