CN101600296B - Polyimide copper clad lamination containing thioether structure and preparation method thereof - Google Patents
Polyimide copper clad lamination containing thioether structure and preparation method thereof Download PDFInfo
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- CN101600296B CN101600296B CN2009100407233A CN200910040723A CN101600296B CN 101600296 B CN101600296 B CN 101600296B CN 2009100407233 A CN2009100407233 A CN 2009100407233A CN 200910040723 A CN200910040723 A CN 200910040723A CN 101600296 B CN101600296 B CN 101600296B
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- thioether structure
- polyimide
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Abstract
The invention discloses a polyimide copper clad lamination containing thioether structure and a preparation method thereof; the preparation method comprises the following steps: mixing diamine with thioether structure with other diamines and various dianhydrides for reacting to obtain polyamide acid, coating the obtained polyamide acid directly on the surface of copper foils and obtaining polyimide copper clad lamination containing thioether structure at a high temperature by thermal imidization reaction. The polymer of polyimide laminate containing thioether structure prepared by the invention has big polymer molecular weight, good mechanical property, high thermal stability, excellent film-forming ability, low thermal expansion coefficient and good adhesive property to copper and the material can be used to prepare single-layered or multiple-layered free-adhesives copper clad lamination.
Description
Technical field
The present invention relates to a kind of polyimide copper clad lamination containing thioether structure and preparation method thereof.
Technical background
In recent years, the expansion of the application requirements of assembling along with three-dimensional (solid or 3D) and pliability and the development of hyperfine pitch high density technology, electronic product continues to change development to " light, thin, short, little ", thereby further promote flexible copper-clad panel material and improvement of Manufacturing Technology thereof, flexible printed-circuit board (Flexible Printed Circuit Board is called for short FPCB) has presented it in copper-clad plate and the irreplaceable status of encapsulation industry.It can free bend, coiling, folding, can require to arrange arbitrarily according to space layout, and move arbitrarily and flexible at three dimensions, thereby reach integrated that the components and parts assembling is connected with lead.Utilize FPCB can dwindle the volume of electronic product greatly, adapt to the needs that electronic product develops to high density, miniaturization, highly reliable direction.
At present in the flexible printed circuit base material of producing, the modal adhesive that is to use is with the bonding compound glue type three-layer process product (being commonly called as three ply board) that has of polyimide film and Copper Foil.Yet, differ bigger with the thermal coefficient of expansion of base material because the existence of glue-line causes three ply board stool poor heat stability; The thickness of several layers of adhesive directly influences the thermal diffusivity of circuit, and these have all reduced the flexural property and the flex life of flexible electric circuit board widely.Therefore, in recent years, the focus of research mainly concentrated on the development of (claiming two laminates) of gum-free two-layer method flexibility coat copper plate.Its main production methods mainly contains following several: the first adopts vacuum sputtering technology or evaporation sedimentation, and copper is deposited to (as Chinese patent CN01109402/CN1579754A) on the dielectric film; It two is to form copper conductive layer (as Chinese patent CN95106677) on the polyimide film surface by chemical deposition and electric plating method; It three is to adopt the bismaleimides end-sealed type Thermocurable polyimide of modification directly to be coated on the Copper Foil, adopts chemical imidizate method and hot-imide method to prepare two stratotype non-gel flexibles simultaneously and covers Copper Foil (as Chinese patent CN101148509A); It four is that the polyamic acid solution as polyimide precursor directly is coated on the metal copper foil, carries out gradient increased temperature dehydration imidizate then and prepares coated polyimide Copper Foil (as Chinese patent CN00137383/CN1410471A).The 4th kind of method has low, the advantage of simple technology of production cost, yet, because present employed polyimides system, the adhesive property of itself and Copper Foil is relatively poor, be difficult to satisfy high performance requirement, therefore, need improve, obtain to have the new type polyimide system of excellent adhesive property, relatively low thermel expansion coefficient with Copper Foil to traditional polyimides system.
Summary of the invention
At the problems referred to above, the objective of the invention is to angle from Molecular Structure Design, be improved by the interaction of in the molecular chain structure of polyimides, introducing sulfide based structural itself and copper foil surface, thus the polyimide copper clad lamination containing thioether structure that provides a kind of adhesive property to improve greatly.
Another object of the present invention is to provide a kind of preparation method of polyimide copper clad lamination containing thioether structure.
The object of the present invention is achieved like this: a kind of polyimide copper clad lamination containing thioether structure is characterized in that: comprise one deck Copper Foil at least and directly be overlying on polyimide with thioether structure layer on the Copper Foil.
The general structure of described polyimide with thioether structure layer material is:
In the formula, the ratio of X and Y is (100～0.01): (0～99.99);
Ar
1For having in the following structural formula group one or more:
R wherein
1Be selected from the following radicals one or more:
-CO-,-O-,-SO
2-,-CH
2-,-C (CH
3)
2-and-C (CF
3)
2-;
Ar
2For having in the following structural formula group one or more:
R wherein
2Independently be selected from the following radicals one or more respectively:
-CO-、-O-、-SO
2-、-CH
2-、-C(CH
3)
2-、-C(CF
3)
2-、-NHCO-。
The preparation method of above-mentioned polyimide copper clad lamination containing thioether structure is as follows: by the diamine monomer that contains sulfide based structural, other structure diamines and various dianhydride monomer, hybrid reaction in solvent obtains polyamic acid; Institute is obtained polyamic acid directly be coated on copper foil surface, at high temperature obtain polyimide copper clad lamination containing thioether structure by hot imide reaction.
The present invention is by introducing sulfide based structural in the polymer molecule chain structure, utilize the lone pair electrons on the sulphur atom to make itself and metal that good compatibility be arranged, simultaneously because sulphur atom is bigger than oxygen atom, the feasible polyimides that contains sulfide based structural, its structural rigidity contains the big of phenylate structure than traditional, thereby make this base polymer have good dimensional stability, high thermal stability, excellent film forming and low thermal coefficient of expansion, and have good adhesive property with metallic copper, the single or multiple lift non-gel flexible coating foil for preparing has important application value.
Embodiment
A kind of polyimide copper clad lamination containing thioether structure of the present invention comprises one deck Copper Foil at least and directly is overlying on polyimide with thioether structure layer on the Copper Foil.
Selected monomer is when preparing described polyimide with thioether structure layer material: 4, and the 4`-diaminodiphenyl sulfide is as containing sulfide based structural diamine monomer, one or more other aromatic diamine monomer, one or more dianhydride monomers.The general structure of various monomers is as follows respectively:
4,4`-diaminodiphenyl sulfide monomer:
Dianhydride monomer:
Ar
1For having in the following structural formula group one or more:
R wherein
1Be selected from the following radicals one or more:
-CO-,-O-,-SO
2-,-CH
2-,-C (CH
3)
2-and-C (CF
3)
2-
Other diamine monomers:
H
2N-Ar
2-NH
2
Ar
2For having in the following structural formula group one or more:
R wherein
2Independently be selected from the following radicals one or more respectively:
-CO-、-O-、-SO
2-、-CH
2-、-C(CH
3)
2-、-C(CF
3)
2-、-NHCO-
Polyimide with thioether structure layer material of the present invention by the diamine monomer that contains sulfide based structural, one or more other structure diamines and one or more dianhydride monomers, gets by the two-step method copolymerization.This method comprises the hybrid reaction in solvent with aromatic series tetracarboxylic dianhydride and diamines, obtains polyamic acid; Institute is obtained polyamic acid directly be coated in copper foil surface, polyamic acid at high temperature obtains the polyimide with thioether structure layer by hot imide reaction.Polymers obtained general structure is shown below:
In the formula, the ratio of X and Y is (100～0.01): (0～99.99).
The concrete preparation method of polyimide copper clad lamination containing thioether structure of the present invention is as described below:
In the three-neck flask that electromagnetic agitation, thermometer and inert gas shielding device are housed, add earlier a certain amount ofly 4,4`-diaminodiphenyl sulfide, one or more other two amine blends require to add a certain amount of solvent according to solid content, with two amine solvents.Drop into the mixture of one or more dianhydrides then, the amount of substance that the assurance dianhydride is total and the mol ratio of diamines are 0.995: 1 in batches, and each joining day more than 10 minutes, guarantees that it fully reacts at interval.Behind reinforced the finishing, pick up counting, at room temperature stir some hrs, adopt senior rheology expanding system following response process, to reaction system viscosity reach stable after, stop to stir, obtain containing the sulfide based structural polyamic acid solution.
Above-mentioned gained is contained the sulfide based structural polyamic acid solution be coated in clean copper foil surface equably, place the high-temperature vacuum baking oven then,, in 250 ℃～400 ℃ temperature range, progressively carry out hot imide reaction by the mode of gradient increased temperature.Concrete intensification condition is as follows: heated up 1～1.4 hour to 130 ℃ ± 10 ℃ by room temperature (RT), be incubated 0.1～0.2 hour; Heat up 0.2～0.4 hour to 190 ℃ ± 10 ℃ then, be incubated 0.1～0.2 hour; Heat up 0.2～0.4 hour to 240 ℃ ± 10 ℃ then, be incubated 0.1～0.2 hour, heat up 0.2～0.4 hour to 320 ℃ ± 10 ℃ at last, be incubated 0.2～0.4 hour.Reaction obtains polyimide copper clad lamination containing thioether structure after finishing.
Below the present invention is described further by specific embodiment, but the present invention is not limited to this specific examples.
Embodiment 1
In the 100mL three-neck flask that electromagnetic agitation, thermometer and inert gas shielding device are housed, add 2.180g (10.0mmol) 4, the 4`-diaminodiphenyl sulfide adds 27mL N, and dinethylformamide is with two amine solvents.Drop into 3.2039g (9.95mmol) 3 then in batches, 3`, 4, the 4-benzophenone tetracarboxylic dianhydride, each joining day more than 10 minutes, guarantees that it fully reacts at interval.Behind reinforced the finishing, pick up counting, at room temperature stirring reaction is 4.5 hours, stops to stir, and obtains corresponding polyamic acid solution.
This amic acid solution evenly is coated on the clean Copper Foil, place the high-temperature vacuum baking oven then, gradient increased temperature carries out hot imide reaction, the intensification condition is: RT (intensification 1.2h) → 130 ℃ (insulation 0.15h, ℃ intensification 0.3h) → 190 (insulation 0.15h, intensification 0.3h) → 240 ℃ (insulation 0.15h, intensification 0.3h) → 320 ℃ (insulation 0.3h).Reaction obtains the polyimide copper clad lamination single sided board after finishing.This polymer has good thermal stability, and its initial decomposition temperature is greater than 480 ℃ in the nitrogen atmosphere; It is 296.0 ℃ that DMA measures its glass transition temperature, and the peel strength of itself and Copper Foil is 0.627kgf/cm, and the number of flexings of copper-clad plate is 77 (0.5kgf; 0.38R).
Embodiment 2
Described polyamic acid solution among the embodiment 1 evenly is coated in Copper Foil respectively, control certain wet-film thickness, then that the coat side of two Copper Foils that scribble coating is superimposed, be positioned in the high-temperature vacuum baking oven, carry out hot imide reaction according to embodiment 1 described gradient increased temperature condition.Reaction obtains the polyimide copper clad lamination double sided board after finishing.
Embodiment 3
Use 3.0mmol 4,4`-diaminodiphenyl sulfide and 7.0mmol 4, the hybrid diamine of 4`-diaminodiphenyl ether replace 4 of 10.0mmol among the embodiment 1, the 4`-diaminodiphenyl sulfide, and the reaction time is 5 hours, other implementation methods are with embodiment 1.The initial decomposition temperature of resulting polymers under nitrogen atmosphere is greater than 480 ℃; It is 295.3 ℃ that DMA measures its glass transition temperature, with the peel strength of Copper Foil be 1.037kgf/cm, the number of flexings of copper-clad plate is 117 (0.5kgf; 0.38R).
Embodiment 4
Use 5.0mmol 4,4`-diaminodiphenyl sulfide and 5.0mmol 4, the hybrid diamine of 4`--diaminobenzene anilid replace 4 of 10.0mmol among the embodiment 1, the 4`-diaminodiphenyl sulfide, and other implementation methods are with embodiment 1.The initial decomposition temperature of resulting polymers under nitrogen atmosphere is greater than 490 ℃, and it is 350.6 ℃ that DMA measures its glass transition temperature.
Embodiment 5
In the 100mL three-neck flask that electromagnetic agitation, thermometer and inert gas shielding device are housed, add 2.180g (10.0mmol) 4, the 4`-diaminodiphenyl sulfide adds 25.5mL N, and dinethylformamide is with two amine solvents.Drop into 2.9253g (9.95mmol) 3 then in batches, 3`, 4, the 4-BPDA, each joining day more than 10 minutes, guarantees that it fully reacts at interval.Behind reinforced the finishing, pick up counting, at room temperature stirring reaction is 3 hours, stops to stir, and obtains containing the biphenyl type polyamic acid solution of sulfide based structural.
This amic acid solution evenly is coated on the clean Copper Foil, place the high-temperature vacuum baking oven then, gradient increased temperature carries out hot imide reaction, the intensification condition is: RT (intensification 1.2h) → 130 ℃ (insulation 0.15h, ℃ intensification 0.3h) → 190 (insulation 0.15h, intensification 0.3h) → 240 ℃ (insulation 0.15h, intensification 0.3h) → 320 ℃ (insulation 0.3h).After finishing, reaction obtains containing the biphenyl polyimide copper-clad plate of sulfide based structural.This polymer has good thermal stability, and its initial decomposition temperature is greater than 528.8 ℃ in the nitrogen atmosphere; It is 291.5 ℃ that DSC measures its glass transition temperature; It is 17.9ppm/ ℃ that TMA measures its thermal coefficient of expansion.
Embodiment 6
Use 7.0mmol4,4`-diaminodiphenyl sulfide and 3.0mmol 4, the hybrid diamine of 4`-diaminodiphenyl ether replace 4 of 10.0mmol among the embodiment 4, the 4`-diaminodiphenyl sulfide, and the reaction time is 2 hours, other implementation methods are with embodiment 5.532.8 ℃ of the initial decomposition temperature of resulting polymers under nitrogen atmosphere; It is 303.8 ℃ that DSC measures its glass transition temperature; It is 14.87ppm/ ℃ that TMA measures its thermal coefficient of expansion.
Embodiment 7
In the 100mL three-neck flask that electromagnetic agitation, thermometer and inert gas shielding device are housed, add 2.1800g (10.0mmol) 4, the 4`-diaminodiphenyl sulfide adds 30mL N, and dinethylformamide is with two amine solvents.Drop into 2.1691g (9.95mmol) PMA acid anhydride then, each joining day more than 10 minutes, guarantees that it fully reacts at interval in batches.Behind reinforced the finishing, pick up counting, at room temperature stirring reaction is 5 hours, stops to stir, and obtains containing the sulfide based structural polyamic acid solution.
This amic acid solution evenly is coated on the clean Copper Foil, place the high-temperature vacuum baking oven then, gradient increased temperature carries out hot imide reaction, the intensification condition is: RT (intensification 1.2h) → 130 ℃ (insulation 0.15h, ℃ intensification 0.3h) → 190 (insulation 0.15h, intensification 0.3h) → 240 ℃ (insulation 0.15h, intensification 0.3h) → 320 ℃ (insulation 0.3h).After finishing, reaction obtains containing the equal benzene type polyimide copper clad lamination of sulfide based structural.This polymer has good thermal stability, and its initial decomposition temperature is greater than 560 ℃ in the nitrogen atmosphere; Glass transition temperature is 251.8 ℃.
Embodiment 8
Use 7.0mmol 4,4`-diaminodiphenyl sulfide and 3.0mmol 4,4`-diaminodiphenyl ether mixture replace 4 of 10.0mmol among the embodiment 6, the 4`-diaminodiphenyl sulfide, and other implementation methods are with embodiment 7.
Claims (9)
1. polyimide copper clad lamination containing thioether structure is characterized in that: comprise one deck Copper Foil at least and directly be overlying on polyimide with thioether structure layer on the Copper Foil, the general structure of this polyimide with thioether structure layer material is:
In the formula, the ratio of X and Y is (100～0.01): (0～99.99);
Ar
1Be in the following structural formula group one or more:
R wherein
1Be selected from the following radicals one or more:
-CO-,-O-,-SO
2-,-CH
2-,-C (CH
3)
2-and-C (CF
3)
2-;
Ar
2Be in the following structural formula group one or more:
R wherein
2Be selected from the following radicals one or more:
-CO-、-O-、-SO
2-、-CH
2-、-C(CH
3)
2-、-C(CF
3)
2-、-NHCO-。
2. polyimide copper clad lamination containing thioether structure according to claim 1 is characterized in that: described copper-clad plate is a single or multiple lift non-gel flexible coating foil.
3. the preparation method of polyimide copper clad lamination containing thioether structure according to claim 1 and 2, may further comprise the steps: 1. hybrid reaction in solvent aromatic series tetracarboxylic dianhydride monomer and diamine monomer, obtain polyamic acid, wherein diamine monomer comprise one or more and at least a for containing the diamine monomer of sulfide based structural; 2. institute is obtained polyamic acid and directly be coated on copper foil surface, at high temperature, obtain polyimide copper clad lamination containing thioether structure by hot imide reaction.
4. the preparation method of polyimide copper clad lamination containing thioether structure according to claim 3, it is characterized in that: described sulfide based structural diamine monomer is 4,4`-diaminodiphenyl sulfide monomer.
5. the preparation method of polyimide copper clad lamination containing thioether structure according to claim 3, it is characterized in that: the general structure of described aromatic series tetracarboxylic dianhydride monomer is:
Ar
1Be in the following structural formula group one or more:
R wherein
1Be selected from the following radicals one or more:
-CO-,-O-,-SO
2-,-CH
2-,-C (CH
3)
2-and-C (CF
3)
2-.
6. the preparation method of polyimide copper clad lamination containing thioether structure according to claim 3 is characterized in that: except that containing the sulfide based structural diamine monomer, also comprise one or more diamine monomers of following general structure in the described diamine monomer:
H
2N-Ar
2-NH
2
Ar
2Be in the following structural formula group one or more:
R wherein
2Independently be selected from the following radicals one or more respectively:
-CO-、-O-、-SO
2-、-CH
2-、-C(CH
3)
2-、-C(CF
3)
2-、-NHCO-。
7. the preparation method of polyimide copper clad lamination containing thioether structure according to claim 3, it is characterized in that: the amount of substance that described dianhydride monomer is total and the mol ratio of diamine monomer are 0.995: 1.
8. the preparation method of polyimide copper clad lamination containing thioether structure according to claim 3 is characterized in that: described step 2. in, the polyamic acid that obtains progressively carry out hot imide reaction by the mode of gradient increased temperature.
9. the preparation method of polyimide copper clad lamination containing thioether structure according to claim 7, it is characterized in that: described gradient increased temperature condition is: heated up 1～1.4 hour to 130 ℃ ± 10 ℃ by room temperature, be incubated 0.1～0.2 hour; Heat up 0.2～0.4 hour to 190 ℃ ± 10 ℃ then, be incubated 0.1～0.2 hour; Heat up 0.2～0.4 hour to 240 ℃ ± 10 ℃ then, be incubated 0.1～0.2 hour, heat up 0.2～0.4 hour to 320 ℃ ± 10 ℃ at last, be incubated 0.2～0.4 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115490853A (en) * | 2022-06-29 | 2022-12-20 | 江西有泽新材料科技有限公司 | High-performance polyimide flexible copper clad laminate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166853B (en) * | 2010-12-18 | 2013-09-18 | 广东生益科技股份有限公司 | Manufacturing method of two-layer single-sided flexible copper clad laminate |
| CN111842087A (en) * | 2020-07-21 | 2020-10-30 | 南通博联材料科技有限公司 | Method for preparing high-thickness polyimide film-coated metal product |
| CN115521456B (en) * | 2022-06-29 | 2023-07-21 | 江西有泽新材料科技有限公司 | Polyimide for glue-free flexible copper-clad plate and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115490853A (en) * | 2022-06-29 | 2022-12-20 | 江西有泽新材料科技有限公司 | High-performance polyimide flexible copper clad laminate and preparation method thereof |
| CN115490853B (en) * | 2022-06-29 | 2024-01-30 | 江西有泽新材料科技有限公司 | High-performance polyimide flexible copper-clad plate and preparation method thereof |
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