CN104149472B - The preparation method of a kind of dimensional stability non-gel flexible copper-clad plate - Google Patents
The preparation method of a kind of dimensional stability non-gel flexible copper-clad plate Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of dimensional stability non-gel flexible copper-clad plate, comprise the following steps: to dissolve rigidity diamine monomer with aprotic polar solvent, add bibenzene tetracarboxylic dianhydride BPDA after dissolving, the obtained mass fraction of more than low-temp reaction 8h is the solution of 8 ~ 12%; Butyl titanate-acetylacetone,2,4-pentanedione solution is dripped, Keep agitation 2h in solution; Slowly add the suspension that benzophenone tetracarboxylic dianhydride BTDA is dissolved in aprotic polar solvent formation, obtained polyimide precursor solution; The matsurface of Copper Foil applies obtained polyimide precursor PAA solution, and ladder-elevating temperature obtains polyimides PI film.Glue-free flexible copper-clad plate obtained in the present invention has lower thermal coefficient of expansion and higher force performance, and have the heat resistance of excellence, good dimensional stability and preferably mechanical strength, crimpiness is little, folding resistance is high, dielectric constant and water absorption rate low.
Description
Technical field
The present invention relates to a kind of preparation method of copper-clad plate, refer to the preparation method of a kind of dimensional stability non-gel flexible copper-clad plate particularly.
Background technology
Along with the fast development of modern electronics industry, people it is also proposed higher requirement to the outward appearance of electronic product and performance, and short, little, light, thin and excellent performance also becomes first-selected.And flexibility coat copper plate (FPC) industry is in order to meet this requirement, also start to occur that thickness is thinner, the better glue-free flexible copper-clad plate base material of performance.As in the patents such as CN101121819, CN101157077 the preparation method that introduces, this common glue-free flexible copper-clad plate is prepared at copper foil surface coating individual layer polyimid-base resin, due to the restriction of the performance of individual layer polyimides own, the premium quality product that dimensionally stable is good cannot be obtained.
So people begin one's study to adopt have the monomer of rigid structure and inorganic nano-filler to improve the low-expansion coefficient of polyimides, reach the object improving flexibility coat copper plate performance.CN101407590B prepares Nano-meter SiO_2
2colloid is blended into prepare in polyimide precursor (PAA) solution prepares a kind of low-expansion polyimides (PI).This theoretical method is good, but in full-bodied PAA solution, is difficult to the ready-made Nano-meter SiO_2 of dispersion
2colloid, causes a large amount of reunions of nano particle, and form microfissure in PI film, causes PI layer mechanical properties decrease.Nano particle can not be given full play to the low-expansion effect of reduction PI film simultaneously.
Summary of the invention
Object of the present invention is exactly the deficiency that will solve above-mentioned background technology, provides the preparation method of the dimensional stability non-gel flexible copper-clad plate of a kind of low-expansion coefficient, strong mechanical performance.
Technical scheme of the present invention is: the preparation method of a kind of dimensional stability non-gel flexible copper-clad plate, is characterized in that: the method comprises the following steps:
A. rigidity diamine monomer is dissolved with aprotic polar solvent, rigidity dianhydride monomer bibenzene tetracarboxylic dianhydride BPDA is added after dissolving, the mol ratio controlling bibenzene tetracarboxylic dianhydride BPDA and rigidity diamines is 0.8 ~ 0.9:1, obtaining mass fraction at 5 ~ 10 DEG C of more than low-temp reaction 8h is the solution of 8 ~ 12%, continues at the uniform velocity to stir in course of reaction;
B. in solution, butyl titanate-acetylacetone,2,4-pentanedione solution is dripped, Keep agitation 2h;
C. the suspension that another kind of rigidity dianhydride monomer benzophenone tetracarboxylic dianhydride BTDA is dissolved in aprotic polar solvent formation is added, controlling to add the integral molar quantity of two kinds of rigidity dianhydride monomers in rear solution with the mole ratio of rigidity diamine monomer is 1 ~ 1.05:1, stops after viscosity reaches 40000 ~ 60000mPas;
D. obtained in coating step c on the matsurface of Copper Foil polyimide precursor solution, toasts 2 ~ 4h in the baking oven of 80 ~ 120 DEG C; Start to be filled with N in baking oven
2, when oxygen content in baking oven lower than 0.1% time, after being progressively warmed up to 150 ~ 180 DEG C keep baking 2h; Then baking 1h is kept after being warmed up to 250 ~ 270 DEG C; Baking 2h is kept after being again warmed up to 310 ~ 330 DEG C; After finally reducing the temperature to 150 DEG C with 1 DEG C/min speed, room temperature is down in cooling naturally, forms polyimides (PI) film.
Preferably, described rigidity diamine monomer is mixed by two (phenylamino) the ether ODA and Isosorbide-5-Nitrae-diaminobenzene PDA of 4,4'-, and wherein 4,4'-two (phenylamino) ether ODA mole amounts are 0.7 ~ 0.8:1 with rigidity diamines integral molar quantity ratio.
Preferably, rigidity diamines is two (phenylamino) the ether ODA and 1 of 4,4'-, two (3-amino-benzene oxygen) benzene 1 of 3-, 3-BAB mixes, and wherein 4,4'-two (phenylamino) ether ODA moles are 0.7 ~ 0.8:1 with rigidity diamines integral molar quantity ratio.
Preferably, aprotic polar solvent is the one in DMF DMF, dimethylacetylamide DMAc.
Preferably, copper thickness is 18 μm or 13 μm.
Preferably, in step b butyl titanate add quality account for add in step a rigidity diamines, add 8.7 ~ 22.4% of the quality summation of benzophenone tetracarboxylic dianhydride BTDA in bibenzene tetracarboxylic dianhydride BPDA, step c.To ensure the nano-TiO of hydrolysis
2weight account for rigidity diamines in solution, rigidity dianhydride gross weight 2 ~ 5%, i.e. nano-TiO
2in PI, mass percent is about 2 ~ 5%.
Preferably, in described butyl titanate-acetylacetone,2,4-pentanedione solution, butyl titanate and acetylacetone,2,4-pentanedione mol ratio are 1:4.
The mol ratio of starting stage rigidity dianhydride bibenzene tetracarboxylic dianhydride BPDA of the present invention and rigidity diamines is 0.8 ~ 0.9:1, polyimide precursor (PAA) solution viscosity synthesized because diamines is excessive is lower and in alkalescent, dispersion and the butyl titanate of being convenient to nanoparticle are hydrolyzed; Adopt dropping method to be slowly added drop-wise in PAA solution by butyl titanate-acetylacetone,2,4-pentanedione solution, make butyl titanate be hydrolyzed into nano-TiO
2, and evenly spreading in PAA solution, adding of inorganic material makes the PI of preparation have lower thermal coefficient of expansion; Adopt and add the good benzophenone tetracarboxylic dianhydride BTDA of suspended dispersed to regulate the viscosity of PAA, increase the molecular weight of PAA, thus maintain the mechanical property of polyimides (PI) film.Preparing in glue-free flexible copper-clad plate process the N adopting ladder-elevating temperature, slow cooling and anti-Copper Foil to be oxidized
2safeguard measure, can impel PAA high temperature cyclization to aggregate into PI, and keeps the planarization of glue-free flexible copper-clad plate and prevent the oxidation of copper foil layer.Thus obtain dimensionally stable and the better glue-free flexible copper-clad plate of mechanical property.
In the present invention, glue-free flexible copper-clad plate has lower thermal coefficient of expansion and higher force performance, and have excellent heat resistance, good dimensional stability and preferably mechanical strength, crimpiness is little, folding resistance is high, has comparatively low-k and water absorption rate simultaneously.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
Accurately take dried 4,4'-diaminodiphenyl ether (ODA) 0.04mol (8.01g), 1,4-diaminobenzene (PDA) 0.01mol (1.08g), join in the 500ml there-necked flask of clean dried, add people 210gDMAc solution, after two amine solvents, add bibenzene tetracarboxylic dianhydride (BPDA) 0.045mol (13.24g), be about the PAA solution of 10% at the obtained percent concentration of 5 ~ 10 DEG C of more than low-temp reaction 8h.At the uniform velocity make a gesture of measuring the butyl titanate-acetylacetone,2,4-pentanedione solution 4.529g into 1:4 to the dropping mole of PAA solution in whipping process, wherein butyl titanate is 0.006mol, to ensure nano-TiO
2in PI, mass percent is about 2%, keeps the transparency of PAA solution in dropping process.Keep agitation 2h after completing dropping, start slowly to add the suspension that benzophenone tetracarboxylic dianhydride (BTDA) 0.005mol (1.611g) is dissolved in DMAc, and the viscosity of sampling and testing PAA, after viscosity reaches 40000 ~ 60000mPas, be namely prepared into high viscosity containing nano-TiO
2and rigid structure polyimide precursor PAA.
The matsurface of 18 μm of thick electrolytic copper foils applies the PAA of above-mentioned preparation, ensures that the thickness of PI is 13 μm after film forming, after toasting the preliminary solvent flashing of 2 ~ 4h, starts to be filled with N in baking oven in the baking oven of 80 DEG C
2, when oxygen content in tail gas lower than 0.1% time, after being progressively warmed up to 150 DEG C keep baking 2h, after being then warmed up to 250 DEG C keep baking 1h, after being again warmed up to 310 DEG C keep baking 2h.After finally reducing the temperature to 150 DEG C with 1 DEG C/min speed, Temperature fall is to room temperature.So just prepare the copper-clad plate of a kind of dimensional stability non-gel flexible.
Embodiment 2
Accurately take dried 4,4'-diaminodiphenyl ether (ODA) 0.04mol (8.01g), 1,4-diaminobenzene (PDA) 0.01mol (1.08g), join in the 500ml there-necked flask of clean dried, add people 210gDMAc solution, after two amine solvents, add bibenzene tetracarboxylic dianhydride (BPDA) 0.04mol (11.77g), be about the PAA solution of 10% at the obtained percent concentration of 5 ~ 10 DEG C of more than low-temp reaction 8h.At the uniform velocity make a gesture of measuring the butyl titanate-acetylacetone,2,4-pentanedione solution 12.143g into 1:4 to the dropping mole of PAA solution in whipping process, wherein butyl titanate is 0.016mol, to ensure nano-TiO
2in PI, mass percent is about 5%, keeps the transparency of PAA solution in dropping process.Keep agitation 2h after completing dropping, start the DMAc suspension slowly adding benzophenone tetracarboxylic dianhydride (BTDA) 0.0125mol (4.028g), and the viscosity of sampling and testing PAA, after viscosity reaches 40000 ~ 60000mPas, be namely prepared into high viscosity containing nano TiO 2 and rigid structure polyimide precursor PAA.
The matsurface of 18 μm of thick electrolytic copper foils applies the PAA of above-mentioned preparation, ensures that the thickness of PI is 13 μm after film forming, after toasting the preliminary solvent flashing of 2 ~ 4h, starts to be filled with N in baking oven in the baking oven of 120 DEG C
2, when oxygen content in tail gas lower than 0.1% time, after being progressively warmed up to 180 DEG C keep baking 2h, after being then warmed up to 250 ~ 270 DEG C keep baking 1h, after being again warmed up to 330 DEG C keep baking 2h.After finally reducing the temperature to 150 DEG C with 1 DEG C/min speed, Temperature fall is to room temperature.So just prepare the copper-clad plate of a kind of dimensional stability non-gel flexible.
Embodiment 3
Accurately take dried 4,4'-diaminodiphenyl ether (ODA) 0.04mol (8.01g), 1,4-diaminobenzene (PDA) 0.01mol (1.08g), join in the 500ml there-necked flask of clean dried, add people 210gDMAc solution, after two amine solvents, add bibenzene tetracarboxylic dianhydride (BPDA) 0.044mol (12.95g), be about the PAA solution of 10% at the obtained percent concentration of 5 ~ 10 DEG C of more than low-temp reaction 8h.At the uniform velocity make a gesture of measuring the butyl titanate-acetylacetone,2,4-pentanedione solution 8.28g into 1:4 to the dropping mole of PAA solution in whipping process, wherein butyl titanate is 0.011mol, to ensure nano-TiO
2in PI, mass percent is about 3.5%, keeps the transparency of PAA solution in dropping process.Keep agitation 2h after completing dropping, start the DMAc suspension slowly adding benzophenone tetracarboxylic dianhydride (BTDA) 0.008mol (2.578g), and the viscosity of sampling and testing PAA, after viscosity reaches 40000 ~ 60000mPas, be namely prepared into high viscosity containing nano-TiO
2and rigid structure polyimide precursor PAA.
The matsurface of 18 μm of thick electrolytic copper foils applies the PAA of above-mentioned preparation, ensures that the thickness of PI is 13 μm after film forming, after toasting the preliminary solvent flashing of 2 ~ 4h, starts to be filled with N in baking oven in the baking oven of 100 DEG C
2, when oxygen content in tail gas lower than 0.1% time, after being progressively warmed up to 170 DEG C keep baking 2h, after being then warmed up to 270 DEG C keep baking 1h, after being again warmed up to 315 DEG C keep baking 2h.After finally reducing the temperature to 150 DEG C with 1 DEG C/min speed, Temperature fall is to room temperature.So just prepare the copper-clad plate of a kind of dimensional stability non-gel flexible.
Embodiment 4
Accurately take dried 4,4'-diaminodiphenyl ether (ODA) 0.04mol (8.01g), 1, two (3-amino-benzene oxygen) benzene 1 of 3-, 3-BAB0.01mol (2.92g), join in the 500ml there-necked flask of clean dried, add people 210gDMAc solution, after two amine solvents, add bibenzene tetracarboxylic dianhydride (BPDA) 0.045mol (13.24g), be about the PAA solution of 10% at the obtained percent concentration of 5 ~ 10 DEG C of more than low-temp reaction 8h.At the uniform velocity make a gesture of measuring the butyl titanate-acetylacetone,2,4-pentanedione solution 7.39g into 1:4 to the dropping mole of PAA solution in whipping process, wherein butyl titanate is 0.01mol, to ensure nano-TiO
2in PI, mass percent is about 3%, keeps the transparency of PAA solution in dropping process.Keep agitation 2h after completing dropping, start the DMAc suspension slowly adding benzophenone tetracarboxylic dianhydride (BTDA) 0.005mol (1.611g), and the viscosity of sampling and testing PAA, after viscosity reaches 40000 ~ 60000mPas, be namely prepared into high viscosity containing nano-TiO
2and rigid structure polyimide precursor PAA.
The matsurface of 13 μm of thick electrolytic copper foils applies the PAA of above-mentioned preparation, ensures that the thickness of PI is 13 μm after film forming, after toasting the preliminary solvent flashing of 2 ~ 4h, starts to be filled with N in baking oven in the baking oven of 100 DEG C
2, when oxygen content in tail gas lower than 0.1% time, after being progressively warmed up to 170 DEG C keep baking 2h, after being then warmed up to 270 DEG C keep baking 1h, after being again warmed up to 315 DEG C keep baking 2h.After finally reducing the temperature to 150 DEG C with 1 DEG C/min speed, Temperature fall is to room temperature.So just prepare the copper-clad plate of a kind of dimensional stability non-gel flexible.
Embodiment 5
Accurately take dried 4,4'-diaminodiphenyl ether (ODA) 0.035mol (7.01g), 1, two (3-amino-benzene oxygen) benzene 1 of 3-, 3-BAB0.015mol (4.38g), join in the 500ml there-necked flask of clean dried, add people 210gDMAc solution, after two amine solvents, add bibenzene tetracarboxylic dianhydride (BPDA) 0.045mol (13.24g), be about the PAA solution of 10% at the obtained percent concentration of 5 ~ 10 DEG C of more than low-temp reaction 8h.At the uniform velocity make a gesture of measuring the butyl titanate-acetylacetone,2,4-pentanedione solution 10.136g into 1:4 to the dropping mole of PAA solution in whipping process, wherein butyl titanate is 0.014mol, to ensure nano-TiO
2in PI, mass percent is about 4%, keeps the transparency of PAA solution in dropping process.Keep agitation 2h after completing dropping, start the DMAc suspension slowly adding benzophenone tetracarboxylic dianhydride (BTDA) 0.005mol (1.611g), and the viscosity of sampling and testing PAA, after viscosity reaches 40000 ~ 60000mPas, be namely prepared into high viscosity containing nano-TiO
2and rigid structure polyimide precursor PAA.
The matsurface of 13 μm of thick electrolytic copper foils applies the PAA of above-mentioned preparation, ensures that the thickness of PI is 13 μm after film forming, after toasting the preliminary solvent flashing of 2 ~ 4h, starts to be filled with N in baking oven in the baking oven of 115 DEG C
2, when oxygen content in tail gas lower than 0.1% time, after being progressively warmed up to 150 ~ 180 DEG C keep baking 2h, after being then warmed up to 265 DEG C keep baking 1h, after being again warmed up to 330 DEG C keep baking 2h.After finally reducing the temperature to 150 DEG C with 1 DEG C/min speed, Temperature fall is to room temperature.So just prepare the copper-clad plate of a kind of dimensional stability non-gel flexible.
The performance of the glue-free flexible copper-clad plate prepared in above-described embodiment 1-5 is as shown in table 1.
Performance test methods:
(1) thermal coefficient of expansion: according to TMA method of testing.
(2) anti-flammability: according to UL94 method of testing.
(3) dimensional stability: according to IPC-TM-650, NO.2.2.4 method of testing.
(4) resistance to tin-welding: according to IPC-TM-650, NO.2.4.13 method of testing.
(5) bending resistance folding endurance: according to JIS6471, (0.8R, 0.5kg) method of testing.
(6) sheet resistance: according to IPC-TM-650, NO.2.5.17 method of testing.
(7) volume resistance: according to IPC-TM-650, NO.2.5.17 method of testing.
(8) water absorption rate: according to IPC-TM-650, NO.2.6.2 method of testing.
(9) dielectric constant: according to IPC-TM-650, NO.2.5.5.3 method of testing.
(10) tensile strength: according to IPC-TM-650, NO.2.4.19 method of testing.
(11) peel strength: according to IPC-TM-650, NO.2.4.9 method of testing.
Claims (5)
1. a preparation method for dimensional stability non-gel flexible copper-clad plate, is characterized in that: the method comprises the following steps:
A. rigidity diamine monomer is dissolved with aprotic polar solvent dimethylacetylamide DMAc, rigidity dianhydride monomer bibenzene tetracarboxylic dianhydride BPDA is added after dissolving, the mol ratio controlling bibenzene tetracarboxylic dianhydride BPDA and rigidity diamines is 0.8 ~ 0.9:1, obtaining mass fraction at 5 ~ 10 DEG C of more than low-temp reaction 8h is the solution of 10%, continues at the uniform velocity to stir in course of reaction;
B. in solution, drip butyl titanate-acetylacetone,2,4-pentanedione solution, Keep agitation 2h, in described butyl titanate-acetylacetone,2,4-pentanedione solution, butyl titanate and acetylacetone,2,4-pentanedione mol ratio are 1:4;
C. the suspension that another kind of rigidity dianhydride monomer benzophenone tetracarboxylic dianhydride BTDA is dissolved in aprotic polar solvent dimethylacetylamide DMAc formation is added, the mol ratio controlling the integral molar quantity and rigidity diamine monomer adding two kinds of rigidity dianhydride monomers in rear solution is 1 ~ 1.05:1, stop after viscosity reaches 40000 ~ 60000mPas, obtain polyimide precursor solution, the TiO that in step b, butyl titanate hydrolysis produces
2account for rigidity diamines in polyimide precursor solution, rigidity dianhydride gross weight 2 ~ 5%;
D. obtained in coating step c on the matsurface of Copper Foil polyimide precursor solution, toasts 2 ~ 4h in the baking oven of 80 ~ 120 DEG C; Start to be filled with N in baking oven
2, when oxygen content in baking oven lower than 0.1% time, after being progressively warmed up to 150 ~ 180 DEG C keep baking 2h; Then baking 1h is kept after being warmed up to 250 ~ 270 DEG C; Baking 2h is kept after being again warmed up to 310 ~ 330 DEG C; After finally reducing the temperature to 150 DEG C with 1 DEG C/min speed, room temperature is down in cooling naturally.
2. the preparation method of a kind of dimensional stability non-gel flexible as claimed in claim 1 copper-clad plate, it is characterized in that, described rigidity diamine monomer is by 4,4'-diaminodiphenyl ether ODA and 1,4-diaminobenzene PDA mixes, wherein 4,4'-diaminodiphenyl ether ODA moles and rigidity diamines integral molar quantity are than being 0.8:1.
3. the preparation method of a kind of dimensional stability non-gel flexible as claimed in claim 1 copper-clad plate, it is characterized in that, rigidity diamines is 4,4'-diaminodiphenyl ether ODA and 1, two (3-amino-benzene oxygen) benzene 1 of 3-, 3-BAB mixes, and wherein 4,4'-diaminodiphenyl ether ODA moles are 0.7 ~ 0.8:1 with rigidity diamines integral molar quantity ratio.
4. the preparation method of a kind of dimensional stability non-gel flexible as claimed in claim 1 copper-clad plate, is characterized in that, copper thickness is 18 μm or 13 μm.
5. the preparation method of a kind of dimensional stability non-gel flexible as claimed in claim 1 copper-clad plate, it is characterized in that, in step b butyl titanate add quality account for add in step a rigidity diamines, add 8.7 ~ 22.4% of the quality summation of benzophenone tetracarboxylic dianhydride BTDA in bibenzene tetracarboxylic dianhydride BPDA, step c.
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| CN112062988A (en) * | 2020-08-06 | 2020-12-11 | 深圳丹邦科技股份有限公司 | White polyimide optical film and preparation method thereof |
| CN114679837A (en) * | 2020-12-24 | 2022-06-28 | 广东生益科技股份有限公司 | Black glue-free flexible copper-clad plate and preparation method and application thereof |
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| CN101157077A (en) * | 2007-09-18 | 2008-04-09 | 湖北省化学研究院 | A preparation method of gum-free flexible copper-coating plate |
| CN101340774A (en) * | 2008-08-01 | 2009-01-07 | 浙江大学 | Flexible glue-free copper coated plate and preparation thereof |
| CN102555348B (en) * | 2011-12-28 | 2014-08-13 | 广东生益科技股份有限公司 | Protective film used for producing non-adhesive double-sided flexible copper clad laminate and manufacturing method thereof |
| CN102673047A (en) * | 2012-05-28 | 2012-09-19 | 珠海亚泰电子科技有限公司 | Fabricating method of thermal conducting halogen-free binderless copper clad foil |
| CN102922819A (en) * | 2012-11-16 | 2013-02-13 | 江苏科技大学 | Preparation method of non-adhesive double-sided copper-clad foil with high smoothness |
| CN102941726B (en) * | 2012-11-19 | 2015-10-28 | 江苏科技大学 | The preparation method of the glue-free two-sided copper foil covered of a kind of ultrathin flexible |
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