KR20030061030A - Method and Apparatus for Producing High-density Polyidimide (HPI) Film - Google Patents

Abstract

The present invention relates to a method for producing a high density polyimide (HPI) film and a production facility thereof. This manufacturing apparatus includes a raw material supply device, a vacuum steel, an energy supply device, a coated laminate, and a calcined solidified polymer. With the above devices, the production equipment is combined and H ⁺ in the imide bond is extracted to form unsaturated C = N imino group by using monomer or polymer or ion containing imidine bond (CONH) as energy, and in vacuum The extracted H ⁺ polymerizes the unsolidified HPI film through the Ridchal co-polymerization of π electrons, and heat or light is applied to realign the solidified HPI film. According to the method disclosed in the present invention, HPI, which is not easily processed into a film originally, can be produced very easily as a high density polyimide in the form of a film on a coated laminate.

Description

Method for manufacturing high density polyimide (HPI) film and production equipment thereof {Method and Apparatus for Producing High-density Polyidimide (HPI) Film}

The present invention relates to a method for producing a high density polyimide (HPI) film and its production equipment. This manufacturing apparatus includes a raw material supply means, a vacuum steel, an energy supply, a coated laminate and a fired solidified polymer. With the above devices, the production equipment is combined and H ⁺ in the imide bond is extracted to form unsaturated C = N imino group by using monomer or polymer or ion containing imidine bond (CONH) as energy, and in vacuum The extracted H ⁺ polymerizes the unsolidified HPI film through the Ridchal co-polymerization of π electrons, and heat or light is applied to realign the solidified HPI film. According to the method disclosed in the present invention, HPI, which is not easily processed into a film originally, can be produced very easily as a high density polyimide in the form of a film on a coated laminate.

The present invention relates to a method for producing a polymer HPI film and a production equipment thereof, and more particularly, to a method for producing a polyimide film and a production equipment thereof by plasma polymerization in a low pressure environment.

In general, conventional films are formed in a coating manner, in which a film is produced after heating the raw material or dissolving the solvent, coating it on the coated laminate surface and cooling, or after the solvent is volatilized. Unlike conventional general film coating methods, conventional HPI films are manufactured in a chemical thermosetting process, and thus the raw materials must be simultaneously subjected to a polymerization reaction process and a coating process for film formation. As a result, this process requires higher technical capabilities and tighter parameter control, and the equipment is expensive. There are also some disadvantages, such as the formation of byproduct water molecules (H ₂ O) when the HPI acid is converted to HPI during the polymerization process. The formation of water molecules here affects the flatness of the film, creates pinholes and causes nonuniformity of thickness.

A first object of the present invention is to provide a method for producing a high density polyimide film compound.

A second object of the present invention is to provide a production facility for forming a polyimide film.

A third object of the present invention is to provide a method for producing a polyimide film having high density and excellent adhesion without forming small pores.

1 is a flowchart of a method for producing a high density polyimide film disclosed in the present invention.

2 is a cross sectional view of a production facility for producing the high density polyimide film disclosed herein.

3 is a structural diagram of an activated hollow ion gun.

4A is a flow chart of producing a high density polyimide film on a copper clad laminate in accordance with the method and production equipment of the present invention.

FIG. 4B is a cross-sectional view showing the form of the product formed at various stages for producing a high density polyimide film on a copper clad laminate in accordance with the method and production equipment of the present invention. FIG.

5A is a flow chart of producing a high density polyimide film on a glass coated laminate in accordance with the method and production equipment of the present invention.

FIG. 5B is a cross-sectional view showing the form of the product formed at various stages for producing a high density polyimide film on a glass clad laminate in accordance with the method and production equipment of the present invention. FIG.

<Description of the symbols for the main parts of the drawings>

201 vacuum steel 202 gas extraction device

203 Energy Supply204 Gas Regulating Valve

205 Cover laminates 206 Fixtures

207 Heating Device 208 Ultraviolet Projection Device

301 Copper Cathode 302 Hollow Pipe in Electrode

303 Target Material 304 Magnetic Terminals

305 Regulator 306 Electrode Immobilization Block

307 Anode Copper Ring 308 Filament Electrode

In order to achieve the above object, the present invention first provides a vacuum steel as a reaction progression site; Fixing the coated laminate to the vacuum steel; Substances containing imidemide bonds, for example, polymer compounds or complexes or copolymers or monomers are controlled by controlling variables such as environmental temperature, gas flow rate, polyimide voltage and current, and stimulating them to decompose and recombine Using a device to form a low pressure environment to extract the separated gas ions, thereby forming an active material including an unsaturated polyimide structure in the form of a film on the surface of the coating laminate, It can be an ion or a radical and this active material repeatedly undergoes a covalent polymerization in a suitable environment to produce a larger polymer, in which the formation of HPI is advantageous because the residual gas after the reaction is rapidly extracted. Unsaturated imides can be immediately converted into polyimides. The resulting polyimide film has a relatively high density, is more uniform in film thickness, has no small pores, and has good adhesion on the coated laminate, because it is polymerized and formed directly on the surface of the solid coated laminate under low pressure. And also excellent in reproducibility of the reaction.), And then heating or projecting light to produce an HPI film and rearranging the structure with a high molecular weight high density polymer to solidify and calcinate the polyimide film. .

The device disclosed in the present invention is a polymerization reaction in which recombination and polymerization recombination is repeatedly performed in a vacuum steel providing a low pressure environment of at least 20 torr, preferably 1 torr or less, and the energy-containing material of imideim repeatedly. Supplying raw materials such as monomers, polymers, copolymers or composites of polyimides, to energy supplies (which can be heat, light, electron collisions, ion bombardment and radiation, etc.) to produce polymers. At least a raw material supply means for securing the coating laminate and a mechanism for fixing the coating laminate in place. The coated laminate may be made of inorganic materials such as glass, ceramics, nonferrous metals, organic polymer materials, and the like, and may be designed as a roll to roll coated laminate or a sheet by sheet coated loader according to production demand.

Such a device may further comprise ultraviolet projection means or heating means or both means for providing energy for promoting the firing and solidification of the polyimide.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention will now be described in detail using the preferred embodiments in conjunction with the accompanying drawings in order to facilitate understanding of the object, construction, innovative features and performance thereof.

Other objects, features and advantages of the invention will be apparent from the following detailed description of the non-limiting preferred embodiments. The following description is made with reference to the accompanying drawings.

Referring to FIG. 1, a method for producing a polyimide film according to a preferred embodiment of the present invention may first include providing 101 a coated laminate; Placing (102) this clad laminate in vacuum steel; Depressurizing the pressure of the vacuum steel and simultaneously heating the temperature of the vacuum steel, wherein the so-called low pressure is about 2 × 10 ⁻⁵ Torr and the temperature is about 160 ° C .; Thereafter, dissolving and activating the material having the structure containing the imidine into smaller molecules using energy supplied from the energy supply to generate a plasma (104); Then introducing 105 into the vacuum cavity to coat the film on the coated laminate 105; Finally, the pressure in the vacuum cavity is restored to the normal pressure, and the coating laminate is taken out and heated again to solidify the film to mature (106).

One embodiment of an apparatus for making a polyimide film disclosed herein having components as shown in FIG. 2 includes a vacuum steel 201 providing a low pressure environment and reaction sites; A gas extraction device 202 which provides a low pressure environment of 20 Torr or less or even 10 ^-5 Torr and connected to the vacuum steel 201 through a pipe; An energy supply 203 connected to the vacuum steel 201 through a pipe to supply energy to cause a material having an idimine structure to undergo a chain reaction of decomposition and recombination repeatedly to form a polymer; A gas control valve 204 connected to the energy supply 203 through a pipe to control a flow rate of an inlet gas such as hydrogen, nitrogen, and oxygen; A coating laminate which is disposed inside the vacuum steel 201 as a production site of the film and may be an inorganic material such as glass, ceramic, nonferrous metal, organic polymer material, or the like, and may be an integrated circuit or a printed circuit board. 205; An immobilization mechanism 206 is used to secure the clad laminate 205 in place. The apparatus may further comprise a heating device 207 disposed inside the vacuum steel 201 and heating or providing energy to the vacuum cavity 201 to promote the formation of the polyimide and the solidified plasticity. The apparatus may further include an ultraviolet projection device 208 disposed in the vacuum steel 201 and supplying energy to facilitate the formation and firing of the polyimide.

The energy supply 203 may be an activated hollow ion gun as shown in FIG. 3. This ion gun comprises a copper cathode 301 having a hollow pipe 302 inside the cathode 301 to facilitate gas entry; (The cathode 301 is inserted into an immobilization device for disposing a substance, and the immobilization device holds a substance containing an idimine structure as the target material 303, and the immobilization device is controlled by the regulating device 305.) Control and rotation of the target material 303 to control the rotation of the target material (303) can be fed upwards); An anode copper ring 307 that acts as an anode and forms steel; An electrode fixing block 306 for fixing the electrode; A magnetic electrode 304 disposed along the outer periphery of the copper anode 307 to provide a magnetic field; It may be made of non-ferrous metals such as platinum, palladium, nickel and chromium, etc. and includes a filament electrode 308 disposed at the other end of the vacuum steel.

Figure 4a shows another embodiment of a method for producing a polyimide film disclosed in the present invention, the method according to the present invention, comprising the steps of first providing a copper foil as a coating laminate (205); Pretreatment and washing; Placing the copper foil on the fixing device 206 in the vacuum steel 201; Then immediately heating the copper clad laminate 205 to about 168 ° C. and extracting gas to reduce the pressure to about 2 × 10 ⁻⁵ Torr; Introducing hydrogen into the activated hollow ion gun to bring the pressure to about 1.8 × 10 ⁻³ Torr; Turning on the electricity to cause ionization of the polyimide into small molecules to form a plasma; Evaporating and polymerizing the polyimide film deposited on the copper clad laminate to form the polyimide in the form of a gel. Variables to meet the environmental conditions are as follows: The pressure that can produce a high density polyimide film is a pressure of about 1 Torr to 4x10 ^-5 Torr, the most preferred pressure is about 5x10 ^-2 Torr to 2x10 ^-3 Torr And the next preferred pressure is about ¹ × 10 ⁻¹ Torr to about 8 × 10 ⁻⁴ Torr. The polyimide molecular weight is the most preferred best polymerization condition is about 3x10 ^-3 Torr, and the next preferred condition is about 2x10 ^-2 Torr. The temperature range of the coated laminate is from room temperature to about 300 ° C., and the most preferred range is from about 150 ° C. to 180 ° C .; The next preferred range is about 100 ° C to 220 ° C. The final product is then produced by steps such as pressing, firing, protective coating, and processing into rods. Firing is carried out with an ultraviolet lamp of about 300 nm to about 500 nm. The structure at each step of this structure, which is composed of several steps, is shown in FIG. 4B.

In another embodiment, the method for producing a polyimide film according to the present invention as shown in FIG. 5A first comprises providing an inorganic coated laminate such as a piece of glass; Pretreating and cleaning the glass; Placing the glass in a fixture and heating to about 186 ° C., reducing the pressure to about 2 × 10 ⁻⁵ Torr and adjusting the pressure to about 4.2 × 10 ⁻³ Torr using nitrogen or hydrogen; Operating a power source of the stun gun. Decomposition and recombination are repeatedly performed through heating, and polyimide (PI) films are formed using low pressure and electron collision of hydrogen ions. Preferred conditions here are as follows: The temperature of the coated laminate is from about 150 ° C to about 180 ° C, and the next preferred temperature is from about 120 ° C to 200 ° C. Most preferred is heating by a resistor that provides sufficient minimum energy to break down the molecules. If there is too much energy, the resulting polyimide film can be decomposed back into H ₂ O and CO ₂ . Most preferred is the power pulse discharge, the amount of small molecules current Idi of poly imide is 2x10 ^-2 Torr to 3x10 ^-3 Torr, and most preferably, then preferably 1x10 ^-1 Torr to 1x10 by the ion gun for use in a ^{- 3} torr. The polyimide produced under these conditions is in the form of a transparent gel. After removal, the product is calcined and solidified in a nitrogen gas at 180 ° C. to obtain a transparent polyimide film, and finally packaged as a final product. The structure at each step is shown in Figure 5b.

According to the method of the present invention, it is possible to apply to uneven aluminum plate and to form polyimide of uniform thickness on the surface thereof. It can also be used to produce a polyimide film with a uniform thickness on the aluminum-coated laminate of IC required to block α rays with a film having a thickness of 50 µm.

The production of HPI in the form of non-solidified gel should be carried out by heat or ultraviolet rays to manufacture, rearrange and form high molecular weight HPI, and to solidify around the periphery, and the conditions of heat or ultraviolet light used for firing for solidification are optional. It depends on the type of PA raw material being. It is an ideal structure for making high molecular weight solidified HPI films from non-solidified HPI films by Forontior molecular aifital, which determines whether to use heat or ultraviolet light or both for firing for solidification. do. In general, a vacuum glow discharge of 1 Torr or less has a sufficient distance to accelerate so that the electron energy can easily reach an energy level of 2 to 5 eV. The formation of radicals takes an average of about 3 to 4 eV of energy and the formation of ions takes about 9 to 12 eV of energy, so it can be easily repolymerized into a film of organic material under low pressure vacuum.

Referring to the following PA conversion or PI plasma polymerization may be a PA such as the following formula (1).

Here, m is the number of polymers, n is the number of acid salts, such as PA-6, when n is 6 is represented by the following formula (2).

Raw material PA is the common name for compounds with (-CONH-) bonds. When PA decomposes under low temperature plasma, tetrahedral PA compounds are generally used to retain nitrogen radicals and remove hydrogen to form unsaturated C = N bonds (the atoms on the double bonded molecule must be on the same plane). Choose. Organic materials are generally less reactive in a vacuum environment, are very active in hydrogen removal, and high yields can be obtained because the products after imidization are not active, and C = O radicals are C = O to CO. It cannot be easily radicalized because it requires more energy (83.6 Kcal / mol) to convert. Thus, polyimides produce polymers with soluble ionic bonds.

Thus, in the plasma chemistry applied, low-temperature plasma can provide good selectivity of the reaction, high reaction production rate, rapid precipitation rate, and the deposited film exhibits excellent physical and chemical properties, and good adhesion to the coating laminate. It shows uniformity. In the case of general polymerization, monomers must possess special organic mechanisms of action such as double bonds, etc., but plasma polymerization can achieve high molecular weight polymerization with the following properties. Its features are: (1) no need for catalysts, (2) high material selectivity, (3) high density, (4) ultra-defect-free ultra-thin films, (5) withstanding high thermal temperatures, and (6) Thickness uniformity, etc.

As mentioned above, although this invention was demonstrated through the preferable embodiment exemplarily, this invention is not limited only to this embodiment. Rather, to cover various modifications and similar arrangements and procedures, the appended claims are to be accorded the broadest interpretation so as to encompass all such variations and arrangements and procedures.

Claims (18)

Providing a manufacturing apparatus comprising at least a cladding layer fixing mechanism, a vacuum steel, a raw material supply means, an energy supply; Using a material containing an imide bond as an initial raw material, applying a plasma under low pressure to provide energy to decompose the material to form molecules; Then hydrogen extraction to generate an activated species (ion bond or radical); And then polymerizing again to form a non-solidified high density polyimide film on the coated laminate. 2. The high density polyimide film of claim 1, further comprising a solidifying firing apparatus for performing a solidifying firing step to fire and solidify the non-solidified high density polyimide film to form a solidified HPI film. Method of preparation. The method of claim 1, wherein the initial raw material is a copolymer or a composite compound having at least two kinds of polyimides or preliminary monomers or polyimides thereof as raw materials under a low pressure vacuum environment, and is a low-temperature by heat, electrons, light and radiation ions. Through plasma repolymerization, containing other complexes or copolymers of high density polyimide compounds Reaction to produce a high density polyimide compound, characterized in that the production method of high density polyimide film. The method for producing a high density polyimide film according to claim 1, wherein the coating laminate is made of a nonferrous metal. The method for producing a high density polyimide film according to claim 1, wherein the coating laminate is made of glass. The method for producing a high density polyimide film according to claim 1, wherein the coated laminate has a surface made of organic macromolecules. The method for producing a high density polyimide film according to claim 1, wherein the coating laminate is made of an inorganic material. The manufacturing method of the high density polyimide film of Claim 1 whose coating laminated body is an integrated circuit. The manufacturing method of the high density polyimide film of Claim 1 whose coating laminated body is a printed circuit board. The method of claim 1 wherein the low pressure environment is a pressure in the range of about 20 Torr to about 10 ^-5 Torr. The method of producing a high density polyimide film according to claim 1, wherein the providing of the energy level is performed by heating, light projection, radiation projection, electron collision, ion bombardment, or a combination thereof. The method for producing a high density polyimide film according to claim 2, wherein the solidifying step is performed by heating. The method for producing a high density polyimide film according to claim 2, wherein the solidifying step is performed by projection of an ultraviolet illuminating device. 2. The high density polyimide of claim 1, wherein the material containing the imide bond comprises polyimide, a copolymer of polyimide, a complex compound of polyimide, or a monomer containing an imide bond. Method for producing a film. Vacuum steel providing a low pressure environment of 20 Torr or less as a reaction vessel; Raw material supply means for supplying a raw material containing a substance having an imide bond; An energy supply disposed in the vacuum steel to provide energy for decomposition, repetitive decomposition and recombination of raw materials; And a coating laminate fixing mechanism arranged in the vacuum steel to fix the coating laminate in place. 16. The production apparatus for high density polyimide film of claim 15, further comprising an ultraviolet projection device disposed in the vacuum steel or disposed outside the vacuum steel to provide energy for the solidification reaction. 16. The production apparatus for high density polyimide film of claim 15, further comprising a heating device disposed in the vacuum steel or disposed outside the vacuum steel to provide energy for the solidification reaction. 16. The production apparatus for high density polyimide film of claim 15, further comprising an ultraviolet projection device and a heating device disposed in the vacuum steel or disposed outside the vacuum steel to provide energy for the solidification reaction.