CN1475518A - Method of forming polyimide film and its production equipment - Google Patents
Method of forming polyimide film and its production equipment Download PDFInfo
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- CN1475518A CN1475518A CNA021257531A CN02125753A CN1475518A CN 1475518 A CN1475518 A CN 1475518A CN A021257531 A CNA021257531 A CN A021257531A CN 02125753 A CN02125753 A CN 02125753A CN 1475518 A CN1475518 A CN 1475518A
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- polyimide film
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Abstract
An apparatus for preparing polyimide film is composed of raw material feeder, vacuum cavity, energy provider, base plate with mould, and solidifying unit. Its process includes using heat, electrons, light radioactive ray, or ions to act on the monomer, polymer, or copolymer containing amide bone for changing the amide bond into imine bond, cross-linking polymerization, optical or thermal addition and reforming. Its advantage is high density of polyimide film.
Description
Technical field
Relevant method and the production unit thereof that forms polyimide film of the present invention, particularly relevant a kind of in low pressure environment, with the method and the production unit thereof of electricity slurry polymerization formation polyimide film.
Background technology
The general film of tradition is with the coating method moulding, promptly is with raw material heating or with dissolution with solvents, is coated on then on the substrate surface, after cooling or promptly form a film after the solvent evaporates.Traditional polyimide film then is to make with chemical thermosetting method (Chemical thermosettingProcess), it is different from the mode of the general film coated of tradition, must simultaneously raw material be carried out polyreaction and coating film forming, therefore need higher technology and strict parameter control, and apparatus expensive.And still have some shortcomings to exist,, have water byproduct molecule H when being cyclized into polyimide by polyamic acid such as in the polymeric process
2The generation of O because the formation of water molecules can influence the planarization of film, causes pin hole and influences the even of thickness.
Summary of the invention
The method that the purpose of this invention is to provide a formation polyimide film, and the production unit of a formation polyimide film make polyimide film density height, the free of pinholes of formation and good adherence are arranged.
In order to reach above purpose, method of the present invention comprises as follows: at first, provide a vacuum cavity, with the place of carrying out as reaction.Then a substrate is fixed in this vacuum cavity.Afterwards, the material that will contain amido linkage, such as macromolecular compound or mixture or co-polymer or monomer, by parameters such as the temperature that controls environment, gas flow, electricity slurry voltage and electric currents, this material is excited and decompose combining again, and utilize an air extractor forming a low pressure environment, the hydrogen ion that dissociates out with extraction, so just can form a membranaceous active substance that contains the unsaturated polyimides structure on this substrate surface, this active substance can be an ion or a free radical.This active substance suitably can carry out crosslinking polymerization to form bigger polymkeric substance under the environment repeatedly.In this low pressure environment, the gas of reaction remnants can be drawn out of rapidly, forms so help imide.Therefore, this unsaturated acyl imines can change into polyimide immediately.The polyimide film of this generation is because the direct polymerization calmness forms in the solid substrate surface under low pressure environment, so have that higher density, thickness are even, free of pinholes, have the reproducibility of feature such as good adherence and reaction also preferable for substrate.Afterwards again with the heating or rayed with this polyimide film addition, be rearranged into the high molecular high-density and maturation solidified polyimide film.
Certainly the aforesaid one membranaceous active substance that contains the unsaturated polyimides structure can carry out crosslinking polymerization repeatedly to form in the bigger polymkeric substance under suitable environment, and chemical transformation does not take place, and only is that molecule number has increased.
This device of the present invention mainly comprises a vacuum cavity at least, so that a low pressure environment to be provided, can provide at least below the 20 holder ears, preferably can be below 1 holder ear; One energy supply, energy is provided so that contain the material of amido linkage dissociate repeatedly with bonded polyreaction again to form polymkeric substance.Energy is supplied with form can be heat, light, electronic impact, ion impact, radioactive rays etc.One raw material feed device is as the feedway of raw material monomer of polyamide or polymkeric substance or co-polymer or mixture raw material.One substrate smelting tool can be used to fixing base, and its substrate can be inorganic substance such as glass, pottery, non-ferrous metal or organic polymer material etc., can become Roll to Roll smelting tool or Sheet by Sheet smelting tool according to the production Demand Design.
This device also can comprise a UV curing apparatus or a heating unit, promotes the polyimide curing maturation so that energy to be provided, and also can use simultaneously.
Because the polyimide film that the present invention generates is that the direct polymerization calmness forms in the solid substrate surface under low pressure environment, so have that higher density, thickness are even, free of pinholes, have the reproducibility of feature such as good adherence and reaction also preferable for substrate.Following table is traditional polyimide film and the comparative data of traditional polyimide film of the present invention aspect density and density:
| Project | Density | Density |
| The tradition polyimide film | ??1.39g/mm 2 | ????0.054g/mm 2 |
| Polyimide film of the present invention | ??1.47g/mm 2 | ????0.1g/mm 2 |
Wherein, in the comparison of density, traditional polyimide film is selected the Uplex-R type of the ad eundem of Ube (UbeIndustries) production for use; And in the comparison at density, by the two is fitted mutually with the rolled copper foil of smooth flat and ganoid Kapton film, use traditional polyimide film and polyimide film of the present invention do to dial data respectively from the test gained of intensity, as can be seen from the above table data, the present invention has improved density, the density of polyimide film greatly.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for formation high-density polyimide film of the present invention;
Fig. 2 is the schematic cross-section of the production unit of the high-density polyimide film that forms of the present invention;
Fig. 3 is the structural map of a sensitization hollow ion gun;
Fig. 4 A is the method according to this invention and production unit, forms the schema of high-density polyimide film on a copper clad laminate;
Fig. 4 B is the method according to this invention and production unit, forms the product of high-density polyimide film in the shaped cross synoptic diagram in each stage on a copper clad laminate;
Fig. 5 A is the method according to this invention and production unit, forms the schema of high-density polyimide film on a glass substrate;
Fig. 5 B is the method according to this invention and production unit, forms the product of high-density polyimide film in the shaped cross synoptic diagram in each stage on a glass substrate; Drawing reference numeral:
201 vacuum cavities
202 air extractors
203 energy supplies
204 gases are adjusted valve
205 substrates
206 smelting tools
207 heating units
208 UV curing apparatus
301 copper negative potentials
Hollow pipeline in 302 electrodes
303 targets
304 magnetic poles
305 setting devices
306 electrode permanent seats
307 anodal copper rings
308 filaments
401 Copper Foils
402 uncured imide films
403 have solidified the imide film
404 pressings
405 slakings
406 finished products
407 imide films
501 inorganics substrates
502 imide films
503 slakings
504 not slakings
505 finished products
Specific implementation
Preferred embodiment of the present invention will go through as after.Embodiment uses a particular example of the present invention in order to describe, and is not in order to limit scope of the present invention.
Of the present invention one forms the embodiment of polyimide membrane method, and it comprises the following step: as shown in Figure 1, at first, provide a substrate 101, then this substrate is inserted in the vacuum cavity 102.With the decompression of this vacuum cavity and heat the temperature 103 of this vacuum cavity.Wherein so-called low-pressure ratio is as 2 * 10
-5The holder ear, temperature is then such as about 160 ℃.Then, will contain the material of amide structure, and provide energy to be dissociated into small molecules, and excite formation electricity slurry 104 via an energy supply.Afterwards, should import in this vacuum cavity and formation one film 105 on substrate by the electricity slurry.At last, vacuum cavity is returned back to normal pressure, take out substrate, carry out a heating steps again with film hardening maturation 106.
The embodiment of the device of formation polyimide film of the present invention comprises following each assembly: as shown in Figure 2, comprise a vacuum cavity 201, so that a low pressure environment and the place of carrying out as reaction to be provided.One air extractor 202 is linked to this vacuum cavity 201 via conduit, can provide below the 20 holder ears, even 10
-5The low pressure environment of holder ear.One energy supply 203 is connected in this vacuum cavity 201 via conduit, can provide energy so that contain the material of amide structure dissociate repeatedly with bonded chain reaction again to form polymkeric substance.One gas is adjusted valve 204, is connected to energy supply 203 via conduit, to control for example flow velocity of argon gas, nitrogen, oxygen etc. of inflow gas.One substrate 205 is positioned at this vacuum cavity 201, with the place that forms as film.Its material can be inorganic substance such as glass, pottery, non-ferrous metal etc., and perhaps organic polymer material etc. also can be a unicircuit, or a printed circuit board (PCB).One smelting tool 206 is used for fixing substrate 205.This device also can comprise a heating unit 207 in this vacuum cavity 201, heating this vacuum cavity 201, or provide formation that energy promotes polyimide with solidify ripe.This device more can comprise a UV curing apparatus 208 in this vacuum cavity 201, and is ripe with curing with the formation that provides energy to promote polyimide.
Above-mentioned energy supply 203 can be a sensitization hollow ion gun, as shown in Figure 3.It comprises a copper negative potential 301, enters to make things convenient for gas for hollow pipeline 302 in the negative potential 301.Negative potential 301 is embedded in one and places on the smelting tool of material, and the material that is equipped with the amide containing structure on this smelting tool is with as a target 303.This smelting tool can be by a setting device 305 controls, with 303 rotation and the chargings that can slowly make progress of control target.One anodal copper ring 307 conducts are anodal, and form a cavity.Electrode permanent seat 306 is in order to fixed electorde.Be with magnetic pole 304 so that magnetic field to be provided outside the anodal copper ring 307.One filament 308 is positioned at the cavity the other end, can be non-ferrous metal such as platinum, palladium, nickel, chromium and makes.
A kind of form of the embodiment of formation polyimide membrane method of the present invention, it comprises the following step: shown in Fig. 4 A, at first provide a Copper Foil 401 as substrate 205, carry out pre-treatment and cleaning again, place afterwards on the smelting tool 206 in the vacuum cavity 201, be warmed to about 168 ℃ with being about to copper clad laminate 205, and bleed and be decompressed to about 2 * 10
-5The holder ear.Then, argon gas is imported in the sensitization hollow ion gun, this moment, pressure was about 1.8 * 10
-3The holder ear.Then, activation electric power begins to hit from polymeric amide and becomes small molecules and form the electricity slurry, evaporates then to be attached on the copper clad laminate 205, carries out polymerization and forms gelationus polyimide film 403.The uncured imide film of 402 expressions, 403 represent solidified imide film.Above-mentioned environmental parameter is as follows: pressure asks ear to about 4 * 10 by about 1
-5The holder ear all can obtain the high-density polyimide film, and wherein Zui Jia pressure is about 5 * 10
-2The holder ear is to about 2 * 10
-3The holder ear, inferior good pressure is about 1 * 10
-1The holder ear is to about 8 * 10
-4The holder ear.Optimum polymerizating condition is that the micromolecular flow of polymeric amide is about 3 * 10
-3The holder ear inferiorly goodly is about 2 * 10
-2The holder ear.To about 300 ℃, wherein optimum range is about 150 ℃ to about 180 ℃ to the substrate temperature scope from normal temperature, and inferior good scope is about 100 ℃ to about 220 ℃.Can carry out pressing 404, slaking 405 then, add steps such as upper protective film, itemize processing to make finished product 406.407 represent polyimide film.Wherein slaking with about 300nm to the UV-lamp of about 500nm for it.Its at the structural representation in each step shown in Fig. 4 B.
Another form of the embodiment of formation polyimide membrane method of the present invention, it comprises the following step: shown in Fig. 5 A, at first provide an inorganics substrate 501, such as a glass.Then, this glass is carried out pre-treatment and cleaning, this glass is positioned over is heated to about 186 ℃ on the smelting tool again, pressure reduces to about 2 * 10
-5The holder ear adjusts to about 4.2 * 10 with nitrogen or argon gas with pressure again
-3The holder ear, active ions rifle power supply by heating, decomposes and combine repeatedly again, to hit from hydrogen ion, causes formation polyimide PI film 502 by low pressure and electronics.Wherein top condition is as follows, about 150 ℃ to about 180 ℃ of substrate temperature, about 120 ℃ to about 200 ℃ of inferior good temperature.Resistance-type heating is preferable with the minimum energy that the molecule that is enough to dissociate is provided, and becomes H if energy then may dissociate the polyimide film that has been shaped too greatly again
2O and CO
2It can impulsive discharge person be good that the ion gun power supply uses.The small molecules flow of polymeric amide is with 2 * 10
-2To 3 * 10
-3The holder ear is best, secondly is 1 * 10
-1Holder ear to 1 * 10
-3The holder ear is inferior good.By the formed polyimide film of above condition is transparent gelatinous substance, takes out the back and carry out the polyimide film that maturation curing 503 can get transparence in 180 ℃ of nitrogen gas stream gases.Be packaged into finished product 505 at last,, also can make finished product without overcuring 504 according to different requirements.Its at the structural representation in each step shown in Fig. 5 B.
Method of the present invention also can be applicable to rough aluminium sheet, and forms the polyimide film of equal thickness in its surface.In addition, also can be used to be formed on aluminium base internal memory IC and go up the required film that comes the 50 μ m thickness that protective barrier α-ray uses.
The uncured gelationus high-density polyimide HPI that the present invention forms, must high-density polyimide HPI addition, rearrangement, chow ring be formed high-molecular weight high-density polyimide HPI and solidify by heat or UV-light, wherein determine it with heat or use ultraviolet ray as maturation solidified condition according to selecting the PA raw material type.PA is the material that contains amide structure.It decides to use heat or ultraviolet or use UV-light or heat to do maturation simultaneously according to prostatitis molecule orbital theory and solidifies ideal mechanism, makes uncured high-density polyimide HPI film form high molecular solidified high-density polyimide HPI film.Generally the vacuum glow discharge below 1 holder ear has enough distances to quicken to make electronic energy, can reach the 2-5eV energy easily, and the generation of root can on average about 3-4eV, and ionic generate can about 9-12eV, so under low vacuum, be easy to can repolymerization become the film thing of organic substance.
Below change into the electricity slurry polymerization of polyimide PI with regard to PA, be described as follows: classify representative below the PA as
M refers to aggregate number, and that n refers to is its hydrochlorate number such as PA-6 n=6 this moment,
Raw material PA refers to the compound that general term has acid amides-CONH-key, when PA is subjected to dissociating of low temperature electricity slurry, PA tetrahedralization compound is normally selected the retained nitrogen base, sloughs hydrogen evolution unsaturated link(age) C=N (atom of the atom of two bondings on it must all at grade).Organic substance does not have reductive action very much in vacuum environment; on the contrary the extraction of hydrogen is comparatively active; therefore product torpescence after the inferior acidylate can get high productivity; and it is that C=O needs more energy (83.6Kcal/mole) when changing into C-O that C=O base is difficult for by free radical effect reason; therefore polyimide forms iolon; has solubility; so answer low temperature electricity slurry can react in the electricity consumption pulp good selectivity and high reaction productivity; enough fast speed of separating out, separating out film has outstanding physics; chemical property has good adherence and homogeneity for substrate.For polyreaction usually, monomer must have particular functional machines such as two keys, but can the polymer substance polymerization for the polymerization of electricity slurry, and its characteristics are as follows: 1, do not need catalyzer; 2, the selectivity height of material; 3, high-density; 4, can get zero defect as thin as a wafer; 5, high heat resisting temperature; 6, thickness is even etc.
The above is preferred embodiment of the present invention only, is not in order to limit scope of patent protection of the present invention; All other do not break away from the equivalence of being finished under the disclosed spirit and changes or modification, all should be included in the scope of patent protection of the present invention.
Claims (10)
1, a kind of method that forms polyimide film is characterized in that it comprises at least: a, be starting raw material by the material that contains amido linkage, provide energy to be dissociated into small molecules by an energy supply; B, under vacuum low-pressure, extract the hydrogen ion dissociate out out, the substrate surface in being placed on vacuum environment forms a membranaceous active substance that contains the unsaturated polyimides structure, this active substance crosslinking polymerization repeatedly forms bigger polymkeric substance.
2, the method for formation polyimide film according to claim 1 is characterized in that: also comprise step c behind step b, make this uncured polymeric film maturation be cured as solidified polyimide film.
3, the method for formation polyimide film according to claim 1 is characterized in that: in step a, the material that contains amido linkage comprises the monomer of polymeric amide, polymeric amide co-polymer, polyamide compound or amide containing key.
4, the method for formation polyimide film according to claim 1 is characterized in that: in step a, described energy supply is to carry out or multiple use simultaneously with a kind of of heating, rayed, radiation exposure, electronic impact or ion impact mode.
5, the method for formation polyimide film according to claim 1 is characterized in that: in step b, described low pressure is pressure range 20 holder ears to 10
-5The holder ear.
6, the method for formation polyimide film according to claim 2 is characterized in that: in step c, curing is to be cured by the heating or the method for UV-irradiation.
7, the method for formation polyimide film according to claim 1, it is characterized in that: in step b, the Facing material of substrate is non-ferrous metal or glass or organic polymer or inorganic, and perhaps substrate is a unicircuit, and perhaps substrate is a printed circuit board (PCB).
8, a kind of production unit that forms polyimide film is characterized in that it comprises:
Provide the 20 holder following low pressure of ear and as the vacuum cavity of reaction generator;
The raw material feed device of the raw material of the material that contains amido linkage is provided;
Be positioned at this vacuum cavity, energy be provided, be the dissociating of raw material, energy supply that crosslinking polymerization provides power;
The substrate smelting tool of fixing base places in this vacuum cavity.
9, the production unit of formation polyimide film according to claim 8 is characterized in that it comprises that also one makes uncured polyimide film maturation be cured as the maturation solidification equipment of solidified polyimide film.
10, the production unit of formation polyimide film according to claim 9, it is characterized in that: described maturation solidification equipment is that a UV curing apparatus or a heating unit or existing UV curing apparatus have heating unit again, is positioned within this vacuum cavity or places outside the vacuum cavity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02125753 CN1234753C (en) | 2002-08-16 | 2002-08-16 | Method of forming polyimide film and its production equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02125753 CN1234753C (en) | 2002-08-16 | 2002-08-16 | Method of forming polyimide film and its production equipment |
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| Publication Number | Publication Date |
|---|---|
| CN1475518A true CN1475518A (en) | 2004-02-18 |
| CN1234753C CN1234753C (en) | 2006-01-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02125753 Expired - Fee Related CN1234753C (en) | 2002-08-16 | 2002-08-16 | Method of forming polyimide film and its production equipment |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102729570A (en) * | 2012-06-15 | 2012-10-17 | 南京荣欣化工有限公司 | Production equipment of polyimide multilayer composite membrane containing inorganic nano-powder |
-
2002
- 2002-08-16 CN CN 02125753 patent/CN1234753C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102729570A (en) * | 2012-06-15 | 2012-10-17 | 南京荣欣化工有限公司 | Production equipment of polyimide multilayer composite membrane containing inorganic nano-powder |
| CN102729570B (en) * | 2012-06-15 | 2014-12-10 | 南京荣欣化工有限公司 | Production equipment of polyimide multilayer composite membrane containing inorganic nano-powder |
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| Publication number | Publication date |
|---|---|
| CN1234753C (en) | 2006-01-04 |
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Granted publication date: 20060104 Termination date: 20110816 |