TWI758618B - 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

Polyimide composition, polyimide copper clad laminate and circuit board

The invention relates to a polyamide acid composition, a polyimide copper clad plate prepared by cyclization of the polyamide acid composition, and a circuit board prepared by using the polyimide copper clad plate.

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. Wherein, the copper clad laminate includes copper foil, polyimide film, and an adhesive layer located between the copper foil and the polyimide film for bonding the copper foil and the polyimide film together.

During the production process of the circuit board, part of the copper foil bound to the surface of the polyimide film will be etched away, so that the polyimide film in this area will be exposed without being bound to the copper foil. The uncoated polyimide film was seen through a CCD camera for precise component positioning. Thus, the copper-unbonded polyimide film is required to have excellent light transmittance.

In order to make the polyimide film after removing the copper foil to have higher transmittance, a polyimide film can be formed on the surface of the copper foil with low surface roughness, which can ensure that the polyimide film is removed after the copper foil is removed. The surface roughness of the imine film is lower and the light transmittance is higher.

However, the bonding force between the existing polyimide film and the copper foil with low surface roughness is relatively low. Low.

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

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

In addition, it is also necessary to provide a circuit board prepared by using the polyimide copper clad laminate.

中的至少一種；其中，R及R'為氨基，X及Y為-CH=CH-、-C≡C-、-CH=N-、-CH=N-及-COO-中的至少一種；所述二胺單體的所述柔軟結構是指長鏈飽和脂肪烴基或長鏈不飽和脂肪烴基或醚基，長鏈是指四碳或四碳以上之碳氫直鏈結構。 A polyamide acid composition is formed by polymerizing a dianhydride monomer and a diamine monomer, and the molar ratio of the dianhydride monomer and the diamine monomer ranges from 0.9 to 1.1; the diamine The monomers include diamine monomers containing liquid crystal units, diamine monomers containing soft structures and diamine monomers containing nitrogen heterocycles; in the diamine monomers, the diamine monomers containing nitrogen heterocycles The molar percentage of the body is 3%~8%, and the sum of the molar percentages of the diamine monomer containing the liquid crystal unit and the diamine monomer containing the soft structure is 92%~97%; The structural formula of the unit of the diamine monomer is

At least one in; wherein, R and R ' are amino, X and Y are at least one of -CH=CH-, -C≡C-, -CH=N-, -CH=N- and -COO-; The soft structure of the diamine monomer refers to a long-chain saturated aliphatic hydrocarbon group or a long-chain unsaturated aliphatic hydrocarbon group or an ether group, and the long chain refers to a straight chain structure of hydrocarbons with four carbons or more.

、

、

中的至少一種；其中，R及R'為酸酐，X及Y為-CH=CH-、-C≡C-、-CH=N-、-CH=N-及-COO-中的至少一種；所述二酸酐單體的柔軟結構中包含有-O-、-CH₃CCH₃-、-CF₃CCF₃-、-SO₂-、-C=O-基團中的至少一種。 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; the structural formula of the dianhydride monomer containing a liquid crystal unit is:

,

,

At least one in; wherein, R and R ' are acid anhydrides, and X and Y are at least one of -CH=CH-, -C≡C-, -CH=N-, -CH=N- and -COO-; The soft structure of the dianhydride monomer includes at least one of -O-, -CH ₃ CCH ₃ -, -CF ₃ CCF ₃ -, -SO ₂ -, and -C=O- groups.

Further, in the diamine monomer containing a liquid crystal unit and the diamine monomer containing a soft structure, the percentage of the diamine monomer containing a liquid crystal unit is 30-70%, and the The percentage of diamine monomer with soft structure is 30~70%, and the sum of the two is 100%.

,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 monomers containing liquid crystal units are 3,3',4,4'-biphenyltetracarboxylic dianhydride, p-phenylbis(trimellitate) 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 described p-phenylene bis (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 the liquid crystal unit is at least p-aminophenyl p-aminobenzoate, 1,4-bis(4-aminophenoxy)benzene and di-p-aminophenyl terephthalate. A kind of; Wherein, the structural formula of described p-aminobenzoic acid p-aminophenyl ester is:

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

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

,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 the 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-diphenyltetracarboxylic dianhydride, hexafluorodianhydride and bisphenol A type diether dianhydride; wherein, the The structural formula of 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: is

, the structural formula of the 3,3,4,4-diphenyltetracarboxylic acid dianhydride is: the structural formula of the hexafluorodianhydride is:

, the structural formula of described 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, commercially available industrial product numbers are D230 and D400 and the structure is

The diamine, commercially available industrial product number is DA-C6 and the structure is

The diamine, the structural formula is

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

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

, the structural formula of described 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-(4-aminophenyl)-5-aminobenzimidazole , at least one of 5-bis(4-aminophenyl) pyrimidines: wherein, the structural formula of the 3,5-diamino-1,2,4-triazole is:

, the structural formula of described 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 coated on the copper foil by the above-mentioned polyimide composition. The surface is 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 combined on at least one surface of the polyimide film, The circuit substrate is made of a copper clad laminate, the copper clad laminate includes 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 The polyimide film is formed by cyclization after coating the above-mentioned polyimide composition on the surface of the copper foil.

The polyamic acid composition provided by the present invention is formed by polymerizing a dianhydride monomer and a diamine monomer, and the dianhydride monomer includes a dianhydride monomer containing a liquid crystal unit or a dianhydride monomer containing a soft structure. At least one of the diamine monomers, the diamine monomers include a liquid crystal unit-containing diamine monomer, a soft structure-containing diamine monomer, and a nitrogen heterocycle-containing diamine monomer; 1) the nitrogen heterocycle-containing diamine monomer The nitrogen atom on the nitrogen heterocyclic ring 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 units in the polymer structure to form crystals. The effect of hardness reduces the bonding strength of polyimide and copper foil; 2) Under high temperature conditions, the dianhydride monomer or diamine monomer containing liquid crystal units can make the liquid crystal in the polymer structure of polyimide The units are closely arranged to form crystals, which reduces the mobility of the polyimide polymer structure under the high-frequency electric field, thereby reducing the dielectric loss; 3) 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 polyimide, so that it can match the copper foil, thereby avoiding the warpage of the copper clad laminate.

100: Polyimide copper clad laminate

10: Copper foil

20: Polyimide film

200: circuit board

201: circuit substrate

2011: Conductive circuit layers

202: Overlay

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

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

Please refer to FIG. 1 , a preferred embodiment of the present invention provides a polyimide composition, which is mainly used for making the polyimide film 20 in the polyimide copper clad laminate 100 combined with the surface of the copper foil 10 .

The polyamic acid composition is mainly formed by polymerizing dianhydride monomers and diamine monomers.

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.

Preferably, the soft structure of the dianhydride monomer 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. Wherein, the soft structure of the diamine monomer refers to a long-chain saturated aliphatic hydrocarbon group, a long-chain unsaturated aliphatic hydrocarbon group, an ether group, or the like. Among them, the definition of long chain refers to the straight chain structure of four carbons or more hydrocarbons. Preferably, the soft structure of the diamine monomer contains at least one of -O-, -CH ₃ CCH ₃ -, -CF ₃ CCF ₃ -, -SO ₂ -, -C=O- and other groups .

The nitrogen atom on the nitrogen heterocycle in the nitrogen heterocycle-containing diamine monomer can coordinate with copper, thereby improving the bonding strength between the polyimide and the copper foil, improving the liquid crystal unit in the polymer structure. The rigidity effect caused by the close arrangement of crystals reduces the bonding strength of the polyimide to the copper foil.

Under high temperature conditions, the dianhydride monomer or diamine monomer containing liquid crystal units can make the liquid crystal units in the polymer structure of polyimide closely arranged to form crystals, which reduces the problem of polyimide under high-frequency electric field. Mobility of the amine polymer structure, thereby reducing dielectric losses.

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

Wherein, the use range of the molar ratio of the dianhydride monomer to the diamine monomer is 0.9 to 1.1. Polyimide is formed by the condensation polymerization of 1:1 dianhydride monomer and diamine monomer. When the condensation polymerization is carried out under the condition that the two quantities are not equal, the average molecular weight of the resulting polymer will be too low. In addition, the molecular weight distribution will be too broad. If the polymer in this case is further processed into materials for industrial use, the physicochemical properties or mechanical properties of the materials themselves will not meet the industrial specifications.

Wherein, the sum of the molar percentages of the liquid crystal unit-containing diamine monomer and the soft structure-containing diamine monomer in the diamine monomer is 92% to 97%. Wherein, in the diamine monomer containing a liquid crystal unit and the diamine monomer containing a flexible structure, the liquid crystal unit containing The percentage of the diamine 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%. Among them, the difference in the content range will indirectly or directly affect the change of the dielectric loss and the CTE value of the material due to the amount of the liquid crystal unit or the soft unit of the polymer.

Wherein, in the diamine monomer, the molar percentage of the diamine monomer containing a nitrogen heterocycle is 3% to 8%. In the content range, the polyimide film prepared from the polyimide composition can have strong peeling strength and better light transmittance. Experiments show that when the molar amount of the nitrogen heterocycle-containing diamine monomer is greater than the range of 3% to 8%, the peel strength of the obtained polyimide film is not greatly improved, but due to the nitrogen content. Heterocyclic diamine monomers have a large charge transfer effect when absorbing light, resulting in a significant decrease in light transmittance.

中的至少一種；其中，R及R'為酸酐，X及Y為-CH=CH-、-C≡C-、-CH=N-、-CH=N-及-COO-中的至少一種。 Wherein, the structural formula of the dianhydride monomer containing liquid crystal unit is:

At least one of ; wherein, R and R ' are acid anhydrides, 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 unit is preferably an aromatic tetracarboxylic dianhydride. Wherein, the dianhydride monomer containing liquid crystal unit may 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-carboxylate ethyl ester)(cyclohexane-1,4-diylbis(methylene)bis (1,3-dioxo-1,3-dihy-droisobenzofuran-5-carboxylate), at least one of 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 described p-phenylene bis (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:

、

中的至少一種；其中，R及R'為氨基，X及Y為-CH=CH-、-C≡C-、-CH=N-、-CH=N-及-COO-中的至少一種。 The structural formula of the diamine monomer containing the liquid crystal unit is:

,

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

Specifically, the diamine monomer containing the liquid crystal unit may be, but not limited to, p-aminophenyl p-aminobenzoic acid (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 described p-aminobenzoic acid p-aminophenyl ester is:

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

, the structural formula of described 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 can be, but is not limited to, 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 tetracarboxylic dianhydride (Benzophenone-3,3 ' ,4,4 ' -tetracarboxylic dianhydride, BTDA; CAS: 2421-28-5), 3,3,4,4-diphenyltetracarboxylic acid Dianhydride (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 described 4,4'-oxygen diphthalic 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: is

, the structural formula of the 3,3,4,4-diphenyltetracarboxylic acid dianhydride is:

, the structural formula of the hexafluorodianhydride is:

, the structural formula of described 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, an aliphatic diamine, or the like. Specifically, the diamine monomer containing a soft structure can be, but is not limited to, 4,4'-diaminodiphenyl ether (4,4'-Oxydianiline, ODA; CAS: 101-80-4), 4,4'-Oxydianiline, ODA; CAS: 101-80-4 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, commercially available industrial product number is DA-C6 and the structure is

The diamine, the structural formula is

at least one of hexamethylenediamine.

,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 described 4,4'-diaminodiphenyl ether is:

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

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

Wherein, the diamine monomer containing nitrogen heterocycle may 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 described 2-(4-aminophenyl)-5-aminobenzimidazole is:

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

.

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

Please refer to FIGS. 1 to 2 in conjunction with a polyimide copper clad laminate 100 for manufacturing 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 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 above-mentioned polyimide composition on the surface of the copper foil 10 and cyclizing at a high temperature.

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

Because the polyamic acid composition includes a nitrogen heterocyclic ring-containing diamine monomer, the nitrogen atom on the nitrogen heterocyclic ring in the nitrogen heterocyclic ring-containing diamine monomer can coordinate with the copper foil 10 Therefore, the polyimide film 20 and the copper foil 10 have 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 film 20 can be made flat. The imine film 20 has high light transmittance.

Wherein, the copper foil 10 of the polyimide copper clad laminate 100 is directly combined with the polyimide film 20 , and no glue is provided between the copper foil 10 and the polyimide film 20 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: providing a copper foil 10, and the surface roughness of the copper foil 10 is between 0.12um and 2.1um.

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

In the high temperature cyclization, the polyimide composition on the surface of the copper foil 10 is dehydrated at a high temperature to close the loop to obtain the polyimide film 20 bonded to the surface of the copper foil 10 , that is, the copper clad laminate 100 is prepared. Wherein, the temperature range of the high-temperature cyclization is approximately 300-400°C.

The present invention also provides a polyimide film 20, the polyimide film 20 is formed by coating the polyimide composition on the surface of a substrate and then cyclizing at high temperature. Wherein, the base material can be a base material conventionally used for preparing polyimide film, such as release film, metal foil, resin, etc. 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 bound to the surface of the substrate.

Referring to FIG. 2 , a circuit board 200 is applied to electronic devices (not shown) such as computers, electronic 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 polyamide composition of the present invention will be further described below through specific examples.

Example 1

Add NMP (203.37g), APAB (0.068mol, 15.52g), ODA (0.027mol, 5.41g), DTZ (0.005mol, 0.50g) to a 500mL reaction flask, stir at high speed until dissolved, then add BPDA (0.1 mol, 29.42 g) in an anhydrous nitrogen environment, stirring and reacting at a condition lower than room temperature for 48 hours, that is, the configuration of the polyamide acid composition is completed.

Example 2

NMP (205.77g), APAB (0.078mol, 17.80g), ODA (0.017mol, 3.40g), DTZ (0.005mol, 0.50g) were added to the 500mL reaction flask, and ODPA was added after high-speed stirring until dissolved. (0.02mol, 6.20g), BPDA (0.08mol, 23.54g) in anhydrous nitrogen environment, stirring and reacting under the condition of room temperature for 48 hours, that is, the configuration of the polyamide acid composition is completed.

Example 3

NMP (250.75g), APAB (0.045mol, 10.27g), ODA (0.060mol, 12.01g), DTZ (0.005mol, 0.50g) were added to the 500mL reaction flask, and ODPA was added after high-speed stirring until dissolved. (0.04mol, 12.41g), TAHQ (0.06mol, 27.50g) in an anhydrous nitrogen environment, stirring and reacting under the condition of room temperature for 48 hours, that is, the configuration of the polyamide acid composition is completed.

Example 4

Add NMP (211.68g), APAB (0.085mol, 19.40g), ODA (0.010mol, 2.00g), DTZ (0.005mol, 0.50g) to a 500mL reaction flask, stir at high speed until dissolved, then add ODPA (0.1 mol, 31.02 g) in an anhydrous nitrogen environment, stirring and reacting at a condition lower than room temperature for 48 hours, that is, the configuration of the polyamide acid composition is completed.

Comparative Example 1

Add NMP (170.66g), PDA (0.068mol, 7.34g), ODA (0.027mol, 5.41g), DTZ (0.005mol, 0.50g) to the 500mL reaction flask, stir at high speed until dissolved, then add BPDA (0.1 mol, 29.42 g) in an anhydrous nitrogen environment, stirring and reacting at a condition lower than room temperature for 48 hours, that is, the configuration of the polyamide acid composition is completed.

Comparative Example 2

Add NMP (205.61g), APAB (0.070mol, 15.98g), ODA (0.030mol, 6.01g) to a 500mL reaction flask, stir at high speed until dissolved, then add BPDA (0.1mol, 29.42g) in anhydrous Under a nitrogen atmosphere, the reaction is stirred for 48 hours at a condition lower than room temperature, that is, the configuration of the polyamide acid composition is completed.

Comparative Example 3

Add NMP (263.41g) and ODA (0.1mol, 20.02g) to a 500mL reaction flask, stir at a high speed to dissolve, then add TAHQ (0.1mol, 45.83g) in an anhydrous nitrogen environment, at a temperature lower than room temperature Condition stirring reaction for 48 hours, that is, the configuration of the polyamide acid composition is completed.

Comparative Example 4

Add NMP (208.98g) and APAB (0.1mol, 22.83g) to a 500mL reaction flask, stir at a high speed to dissolve, and then add BPDA (0.1mol, 29.42g) under anhydrous nitrogen atmosphere, at a temperature lower than room temperature Condition stirring reaction for 48 hours, that is, the configuration of the polyamide acid composition is completed.

The polyamic acid compositions prepared in the above-mentioned Examples 1 to 4 and Comparative Examples 1 to 4 were respectively coated on the surface of the copper foil 10, and the copper foils 10 coated with the polyamic acid composition were placed at a high temperature. Under the environment, the polyimide composition is cyclized and polymerized at high temperature to form the polyimide film 20 bonded to the surface of the copper foil 10 , so as to obtain the copper clad laminate 100 .

The CCL 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). The test results are shown in Table 1. Among them, 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.

As can be seen from the above table, Examples 1 to 4 are monomers containing liquid crystal cells and diamine monomers containing nitrogen heterocycles introduced in the present invention, which still maintain good peel strength with copper foil and can reduce the dielectric loss Df value. 0.004~0.006, and Comparative Example 1 has a dielectric loss Df value of 0.014 because of the polyamide acid composition that does not contain a liquid crystal cell monomer. Although the comparative examples 2-4 contained the monomer of a liquid crystal cell, since the diamine monomer containing a nitrogen heterocyclic ring was lacking, the peeling strength with copper foil fell very low. In Comparative Example 3, the monomer containing the liquid crystal unit is only matched with the soft monomer, and the CTE value is too high, which will cause the copper clad laminate to warp. In Comparative Example 4, the monomer containing the liquid crystal unit is not matched with the soft monomer, the CTE value is low, and the copper clad laminate is also warped.

The polyamic acid composition provided by the present invention is formed by polymerizing a dianhydride monomer and a diamine monomer, and the dianhydride monomer includes a dianhydride monomer containing a liquid crystal unit or a dianhydride monomer containing a soft structure. At least one of the diamine monomers, the diamine monomers include a liquid crystal unit-containing diamine monomer, a soft structure-containing diamine monomer, and a nitrogen heterocycle-containing diamine monomer; 1) the nitrogen heterocycle-containing diamine monomer The nitrogen atom on the nitrogen heterocyclic ring 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 units in the polymer structure to form crystals. The effect of hardness reduces the bonding strength of polyimide and copper foil; 2) Under high temperature conditions, the dianhydride monomer or diamine monomer containing liquid crystal units can make the liquid crystal in the polymer structure of polyimide The units are closely arranged to form crystals, which reduces the mobility of the polyimide polymer structure under the high-frequency electric field, thereby reducing the dielectric loss; 3) 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 polyimide, so that it can 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 deformations can be made according to the technical concept of the present invention, and all these changes and deformations should belong to the protection scope of the invention application patent scope of the present invention.

20: Polyimide film

200: circuit board

201: circuit substrate

2011: Conductive circuit layers

202: Overlay

Claims (9)

A polyamide acid composition, which is formed by polymerizing a dianhydride monomer and a diamine monomer, and the molar ratio of the dianhydride monomer and the diamine monomer ranges from 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; in the diamine monomers, the diamine monomers containing nitrogen heterocycles The molar percentage of the amine monomer is 3% to 8%, and the sum of the molar percentages of the diamine monomer containing the liquid crystal unit and the diamine monomer containing the soft structure is 92% to 97%; the The structural formula of the diamine monomer containing the liquid crystal unit is

At least one in; wherein, R and R ' are amino, X and Y are at least one of -CH=CH-, -C≡C-, -CH=N-, -CH=N- and -COO-; The soft structure of the diamine monomer refers to a long-chain saturated aliphatic hydrocarbon group or a long-chain unsaturated aliphatic hydrocarbon group or an ether group, and the long chain refers to a straight chain structure of hydrocarbons with four carbons or more; In the diamine monomer of the liquid crystal unit and the diamine monomer containing the soft structure, the percentage of the diamine monomer containing the liquid crystal unit is 30-70%, and the diamine monomer containing the soft structure The percentage is 30~70%, and the sum of the two is 100%. The polyamic acid composition according to claim 1, wherein the dianhydride monomer comprises at least one of a dianhydride monomer containing a liquid crystal unit or a dianhydride monomer containing a soft structure; the dianhydride monomer containing a liquid crystal unit The structural formula of the dianhydride monomer is

,

At least one in; wherein, R and R ' are acid anhydrides, and X and Y are at least one of -CH=CH-, -C≡C-, -CH=N-, -CH=N- and -COO-; The soft structure of the dianhydride monomer includes at least one of -O-, -CH ₃ CCH ₃ -, -CF ₃ CCF ₃ -, -SO ₂ -, and -C=O- groups. The polyamic acid composition according to claim 2, wherein the dianhydride monomer containing liquid crystal cells is 3,3',4,4'-biphenyltetracarboxylic dianhydride, p-phenylenedi( Trimellitic acid anhydride and cyclohexane-1,4-diylbis(methylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) At least one of ethyl esters), wherein the structural formula of the 3,3',4,4'-biphenyltetracarboxylic dianhydride is

, the structural formula of described p-phenylene bis (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 polyamic acid composition according to claim 1, wherein the diamine monomer containing liquid crystal cells is p-aminophenyl p-aminobenzoate, 1,4-bis(4-aminophenoxy)benzene And at least one in di-p-aminophenyl terephthalate; Wherein, the structural formula of described p-aminobenzoic acid p-aminophenyl is:

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

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

. The polyamic acid composition according to claim 2, wherein the dianhydride monomer containing a soft structure is 4,4'-oxybisphthalic anhydride, 2,3,3',4'- Diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenyltetracarboxylic dianhydride, hexafluorodianhydride and Bisphenol A type diether dianhydride; 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: is

, the structural formula of the 3,3,4,4-diphenyltetracarboxylic dianhydride is:

, the structural formula of the hexafluorodianhydride is:

, the structural formula of described bisphenol A diether dianhydride is

The polyamic acid composition according to claim 1, wherein the diamine monomer containing a soft structure is 4,4'-diaminodiphenyl ether, 4,4'-bis(4-aminophenoxy base) 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, commercially available industrial product numbers are D230 and D400 and the structure is

The diamine, commercially available industrial product number is DA-C6 and the structure is

The diamine, the structural formula is

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

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

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

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

, the structural formula of described 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 made of any one of claims 1 to 2 and 7 The polyamide composition is formed by cyclization after coating on the surface of the copper foil. 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 combined 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 copper foil and a polyimide film bonded to the surface of the copper foil, and the conductive circuit layer passes through the copper foil. Patterning is performed, wherein the polyimide film is formed by cyclization after coating the surface of the copper foil with the polyimide composition according to any one of claims 1 to 2 and 7.

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