CN107108926A - Utilize the preparation method and the polyimide film of low-k of the polyimide film for having leachy particle - Google Patents
Utilize the preparation method and the polyimide film of low-k of the polyimide film for having leachy particle Download PDFInfo
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- CN107108926A CN107108926A CN201680004928.4A CN201680004928A CN107108926A CN 107108926 A CN107108926 A CN 107108926A CN 201680004928 A CN201680004928 A CN 201680004928A CN 107108926 A CN107108926 A CN 107108926A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/65—Electrical insulator
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
It the present invention relates to the use of the method for having leachy particle to prepare polyimide film, and the polyimide film of the low-k prepared according to the above method, according to the polyimide film of the present invention by including the particle of following feature, i.e. average grain diameter is less than 10 μm, relative to the particle of stomata of the particle density with less than 95% particle density of the intrinsic material of above-mentioned particle, that the dielectric constant less than conventional polyimide film can be shown, therefore it can be effectively used for needing electrical equipment/electronic equipment and the manufacture of part of the printed circuit board (PCB) of low-k etc..
Description
Technical field
The present invention relates to the use of the method for having leachy particle to prepare polyimide film, and according to the above method come
The polyimide film of the low-k of preparation.
Background technology
Generally, polyimides (PI, Polyimide) resin refers to, by polymerizable aromatic race dianhydride and aromatic diamine, or
Person's aromatic diisocyanate is prepared after polyamic acid derivative, under the high temperature conditions after closed loop dehydration, is led to
Cross and carry out the next prepared fire resistant resin of imidizate processing.
Polyimide resin is as insoluble, insoluble superelevation heat-resistant resin, with heatproof oxidation performance, heat-resistant quality, resistance to
The excellent characteristic of radiativity, low-temperature characteristics and resistance to chemical reagents etc., so as to be widely used in automotive material, aeronautical material, spaceship
The heat-resisting tip materials of material etc. and insulating coating agent, dielectric film, semiconductor, Thin Film Transistor-LCD (TFT-LCD,
Thin film transistor-liquid crystal display) electrode protective membrane etc. electronic material field.
Recently, by accumulating the bulk information corresponding to advanced information society, carry out high speed processing and pass on this at a high speed
In the electronic equipment of a little information, to hereinto used polyimide resin, it is also desirable to high performance, it is especially desirable to as right
Should in the electrical characteristics of high frequency low-k and it is low lure electricity just connecing.
In order to realize the low-k of polyimide resin, and in such as Japanese Laid-Open Patent Publication 2000-44719
It is disclosed in number to have following content, i.e. hydrophilic polymer is scattered in the polyimide resin that dissolves in organic solvent
After in precursor, these hydrophilic polymers are removed by using plastic working or solvent extraction, to carry out porous processing, are entered
And obtain porous polyimide resin.However, like this, the situation of porous processing is being carried out by removing hydrophilic polymer
Under, it is preferable that the shape of the fine shape isolating construction of the hydrophilic polymer in polyimide resin precursor is scattered in is kept
In the case of original state, hole is formed, if but direct removed using plastic working or solvent extraction carries out acyl after hydrophilic polymer
Imidization is handled, then porosity is less than ideal value because causing the flat of hole or blocking, is situated between so as to lead to not fully reduction
The problem of electric constant.
In Korean Patent No. 1299652 it is disclosed about preparing soft alloy plywood when using fluorine particle knot
Structure, still, this method be to fluorine particle it is monomolecular be applicable for, and there is above-mentioned fluorine particle and be difficult scattered lack
Point.
Thus, the present inventor embodies the electrical characteristics that air has by having leachy particle, not only embody than with
The low dielectric constant of the dielectric constant of past polyimide film, and develop to improve in preparation section and above-mentioned there is stomata
Particle dispersion phenomenon and deposited phenomenon polyimide film preparation method, so as to complete the present invention.
The content of the invention
Technical problem
Therefore, it is an object of the present invention to provide prepared using having leachy particle the method for polyimide film with
And the polyimide film of the low-k prepared according to the above method.
Technical scheme
To achieve these goals, the present invention provides the preparation method of polyimide film, and its feature is, including：
Step 1), prepare polyimide precursor；
Step 2), mix above-mentioned polyimide precursor and change liquid to prepare comprising the imidizate for having leachy particle
Gel mould；And,
Step 3), imidizate processing is carried out by being heat-treated to above-mentioned gel mould,
The average grain diameter of the above-mentioned leachy particle of tool is less than 10 μm, intrinsic relative to the leachy particle of above-mentioned tool
The particle density (particle density) of material, with less than 95% particle density.
In order to realize above-mentioned another object, the present invention, which is provided, includes the polyimide film of following content, i.e. as including tool
The polyimide film of leachy particle, the average grain diameter of the above-mentioned leachy particle of tool is less than 10 μm, relative to above-mentioned tool
The particle density of the intrinsic material of leachy particle, with less than 95% particle density.
Beneficial effect
According to the present invention, to prepare the minimum polyimide film of dielectric constant by using having leachy particle,
Therefore available for internal insulator, padded coaming and circuit board of electronic equipment etc. etc..
Brief description of the drawings
Fig. 1 is SEM (SEM, the scanning for the section for showing the polyimide film of the present invention
Electron microscope) picture.
Fig. 2 is to show to show on the surface of the polyimide film of the present invention to be dispersed with sweeping for the state for having leachy particle
Retouch the picture of electron microscope.Fig. 3 is to show that display expands a part of Dispersion on surface in polyimide film of the invention and had
Has the picture of the SEM of the particle state of the state of leachy particle.
Embodiment
The present invention provides the preparation method of polyimide film, and its feature is, including：Step 1), it is sub- for preparing polyamides
Amine precursor；Step 2), mix above-mentioned polyimide precursor and change liquid to prepare comprising the imidizate for having leachy particle
Gel mould；And, step 3), imidizate processing is carried out by being heat-treated to above-mentioned gel mould, it is above-mentioned that there is stomata
Particle average grain diameter be less than 10 μm, relative to the particle density of the intrinsic material of the leachy particle of above-mentioned tool, have
Less than 95% particle density.
The step of preparation method of the polyimide film of the present invention includes preparing polyimide precursor.
For used polyimide precursor in the present invention, prepared when disclosure satisfy that using imidizate processing
During the condition of polyimide resin, any material can be used.For example, can be under conditions of organic solvent, by using
Usual way comes combined polymerization acid dianhydride component and diamine component, to obtain polyamic acid.
Above-mentioned acid dianhydride component and above-mentioned diamine component can be appropriately respectively selected from the things for being commonly used for preparing polyamic acid
In matter.
Can be as above-mentioned acid dianhydride component, for example biphenyl tetracarboxylic dianhydride or derivatives thereof, pyromellitic acid anhydride
(PMDA, Pyromellitic dianhydride), 3,3 ' 4,4 '-benzophenone tetracarboxylic anhydride and p- phenylenes-bis- inclined benzene three
Acid dianhydride etc., but the present invention is not limited to this.
Can be as above-mentioned diamine component, for example p-phenylenediamine (pPDA, p-Phenylenediamine), diaminobenzene
Base ether, o-phenylenediamine, m-phenylene diamine (MPD), 4,4- diamino-diphenyls ether (ODA, oxydianiline), 3,4- diamino-diphenyls
Ether, 2,4- diamino-diphenyl ethers, but the present invention is not limited to this.
Acid dianhydride component and diamine component can be with 1：0.9 to 1：1.1 mol ratio is mixed.
Can be as above-mentioned organic solvent, such as N, N '-dimethyl formamide (DMF, dimethylformamide),
N, N '-dimethyl acetamide (DMAc, Dimethylacetamide) and N- methyl-pyrrolidons (NMP,
Dimethylacetamide) etc., but the present invention is not limited to this.
The preparation method of the polyimide film of the present invention, including mix above-mentioned polyimide precursor and leachy comprising having
The imidizate of particle changes the step of liquid is to prepare gel mould.
First, in above-mentioned polyimide precursor, i.e., imidizate conversion liquid is equably mixed in polyamic acid, hereinto
Disperse evenly and mix after the leachy particle of tool, prepare imidizate resin.
In the case of used material, above-mentioned imidizate conversion is being can be employed as generally for chemosetting is produced
Liquid is used.Above-mentioned imidizate conversion liquid can be selected from by such as dehydrating agent, catalyst, polar organic solvent and its mixture
In the group of composition, it is preferable that can be the mixed solution of dehydrating agent, catalyst and polar organic solvent.
More specifically, above-mentioned imidizate conversion liquid can be the mixed solvent for including following composition, above-mentioned mixed solvent
Comprising：Such as acetic anhydride dehydrating agent；Three-level in the group being made up of pyridine, beta-picoline, isoquinolin and its mixture
The catalyst of amine etc.；And comprising selected from by 1-METHYLPYRROLIDONE, dimethylformamide, dimethyl acetamide and its mixing
Polar organic solvent in the group of thing composition.
Above-mentioned imidizate changes liquid on the basis of the polyimide precursor of 100 parts by weight, and 30 parts by weight can be used to 70
Parts by weight, preferably can be used 40 parts by weight to 55 parts by weight, can be according to the species and prepared polyamides of polyimide precursor
The thickness of imines film etc. is different.
The average grain diameter of the above-mentioned leachy particle of tool is less than 10 μm, it is preferable that can be 1 μm to 10 μm, 1 μm to 7 μ
M or 2 μm to 5 μm.
Also, the above-mentioned leachy particle of tool, can relative to the particle density of the intrinsic material for the particle for not including stomata
With less than 95% particle density, it is preferable that can have 30% to 95% particle density, it is highly preferred that can have
50% to 90% particle density.
In the present invention, " particle density " refers to the bulk density of particle, refers to the density of particle in itself, " particle is solid
Have material " refer to the material that stomata is not present in particle.
On the basis of the gross weight of film, the leachy grain of above-mentioned tool of 2 percentage by weights to 30 percentage by weights can be included
Son, it is preferable that the leachy particle of above-mentioned tool of 5 percentage by weights to 20 percentage by weights can be included, for example, 5 weights can be included
Percentage is measured to the leachy particle of above-mentioned tool of 10 percentage by weights.When the content of the leachy particle of above-mentioned tool is 30 weight
When below percentage, the mechanical properties of polyimide film will not be reduced, when the content of the leachy particle of above-mentioned tool is 2 weight hundred
When dividing than the above, the low-k effect of polyimide film can be embodied.
The above-mentioned leachy particle of tool, as the particle with micropore, can be selected from by silica, aluminum oxide, dioxy
Change the hollow type particle or mesoporous type (mesoporous) particle in the group of titanium, zeolite and its mixture composition, it is preferable that can be with
For hollow type silica.
Can put into the leachy particle of above-mentioned tool itself, and be preferably in imidizate resin more uniformly
The state disperseed and mixed, therefore can also be thrown with being scattered in the scattered liquid status or colloidal state of polar organic solvent
Enter.
Then, imidizate conversion liquid is equably mixed in polyamic acid, and is hereinto uniformly dispersed and mixes above-mentioned
Have after leachy particle, imidizate resin can be prepared to gel mould.
Specifically, above-mentioned imidizate resin is coated on supporter (for example, stainless steel plate, glass plate, aluminium foil, circulation are not
Become rusty steel band or stainless steel cask etc.) after, by carrying out first time heat treatment and drying, to prepare chemically to come a part of
By the gel mould of carry out imidizate processing.
Can at a temperature of 100 DEG C to 200 DEG C, carried out using the time of 5 minutes to 15 minutes it is above-mentioned chemically
Carry out a part of above-mentioned first time heat treatment process by carry out imidizate processing.
Included carrying out by being heat-treated above-mentioned gel mould according to the preparation method of the polyimide film of the present invention
The step of imidizate is handled.
A chemically part made above is by the gel mould of carry out imidizate processing in order to carry out complete acyl
Imidization is handled, and after being initially separated from supporter, is carried out second and be heat-treated.
It can be carried out at a temperature of 250 DEG C to 850 DEG C using 5 minutes to 25 minutes above-mentioned complete for carrying out
Second of heat treatment process of imidizate processing.It is preferably to be carried out under certain tension force when carrying out second of heat treatment
Heat treatment, so that the residual stress inside the film produced in film-forming process can be removed.
According to an embodiment of the present invention, the present invention provides the preparation method of polyimide film, and its feature is, wraps
Include：The step of preparing the polyamic acid as polyimide precursor；Mix above-mentioned polyamic acid and be uniformly dispersed with gas
The imidizate of the particle in hole changes the step of liquid is to prepare imidizate resin；Above-mentioned imidizate resin is coated on support
After body, the step of carrying out first time heat treatment and dry to prepare gel mould；And second of heat is carried out to above-mentioned gel mould
The step of processing is to prepare polyimide film, the average grain diameter of the above-mentioned leachy particle of tool is less than 10 μm, relative to above-mentioned
Has the particle density of the intrinsic material of leachy particle, with less than 95% particle density.
On the other hand, present invention offer includes the polyimide film of following content, i.e. have leachy particle as including
Polyimide film, the average grain diameter of the above-mentioned leachy particle of tool is less than 10 μm, relative to the leachy particle of above-mentioned tool
Intrinsic material particle density, with less than 95% particle density.
Specifically, the polyimide film comprising the leachy particle of above-mentioned tool can be from including polyamic acid and with stomata
Particle imidizate conversion liquid synthesis polyamide-imide resin in obtain, and can be that above-mentioned tool is leachy
The average grain diameter of particle is less than 10 μm, relative to the particle density of the intrinsic material of the leachy particle of above-mentioned tool, is had
The polyimide film of less than 95% particle density.
5 μm to 200 μm of thin state is presented in the thickness of the polyimide film of the present invention.
Also, the polyimide film dielectric constant at 1 GHz of the present invention is less than 3.0, it is preferable that dielectric constant is in
In the low state of 2.0 to 2.9 scopes, and lure electricity just connecing less than 0.002, preferably lure electricity being just connected on 0.0005 to 0.001 model
Enclose, thus, can be effectively used for internal insulator, padded coaming and circuit board of electronic equipment etc. etc..
Embodiment
Hereinafter, using following examples, the present invention will be described in more detail.But, following examples are only used for illustrating
The present invention, the scope of the present invention is not limited to this.
【Preparation example】
Preparation example 1：The preparation of polyamic acid solution
After 0.5L reactors add 320g dimethylformamide (DMF, Dimethylformamide), temperature is set
20 DEG C are scheduled on, is dissolved, connect after the diamino-phenyl ether (ODA, diaminophenyl ether) for then putting into 27.59g
Be divided into units of 20.03g twice input pyromellitic acid anhydride (PMDA, Pyromellitic dianhydride) it is laggard
Row dissolving.Terminate after dissolving, after hereinto putting into 3.97g p-phenylenediamine and reacting 30 minutes, determined solution as sample
Molecular weight.After reaction terminates, the temperature of reactor is increased to after 30 DEG C, 1.00g p-phenylenediamine is put into, by diamines/acid
The mol ratio of dianhydride is adjusted to 1：1.After raw material has been put into, at a temperature of 40 DEG C, after fully reacting 2 hours, obtain poly-
Acid amides acid solution.
Preparation example 2：The preparation (1) of liquid is changed added with the imidizate for having leachy particle
As for imidizate change liquid solidification catalyst 2.8g beta-picoline (144 DEG C of boiling point),
The mixed solution of acetic anhydride as the 21.2g of dehydrating agent and the 13.4g as polar organic solvent dimethylformamide
In, the dispersion liquid for adding 13.4g hollow silica (Hollow silica) (contains 6% hollow silica (South Korea
White mountain steel VHSN-1000, the average grain diameter of particle are 3 μm, the average pore of particle is 200nm) dimethyl of solid constituent
Formamide mixed liquor) after be stirred, so as to obtain the imidizate conversion liquid of the 50.8g leachy particle of addition tool.
Preparation example 3：The preparation (2) of liquid is changed added with the imidizate for having leachy particle
As the solidification for changing liquid for imidizate, with the 2.8g of catalyst beta-picoline, (boiling point is 144
DEG C), as dehydrating agent 21.2g acetic anhydride and as polar organic solvent 0.9g dimethylformamide mixing
In solution, the dispersion liquid for adding 26.7g hollow silica (contains 6% hollow silica (the white mountain steel of South Korea
VHSN-1000, the average grain diameter of particle are 6 μm, the average pore of particle is 200nm) dimethylformamide of solid constituent mixes
Close liquid) after be stirred so that obtain 51.6g added with the imidizate conversion liquid for having leachy particle.
Preparation example 4：Imidizate added with imperforate silicon dioxide granule changes the preparation (1) of liquid
As the solidification for changing liquid for imidizate, with the 2.8g of catalyst beta-picoline, (boiling point is 144
DEG C), as dehydrating agent 21.2g acetic anhydride and as polar organic solvent 13.4g dimethylformamide mixing
In solution, the dispersion liquid for adding 13.3g spherical silicon dioxide (contains 6% spherical silicon dioxide (Japanese catalyst KEP-
250th, the average grain diameter of particle be 3 μm, pore-free) solid constituent dimethylformamide mixed liquor) after be stirred, so as to obtain
Obtained the 50.8g conversion liquid of the imidizate added with spherical silicon dioxide particle.
Preparation example 5：Imidizate added with imperforate silicon dioxide granule changes the preparation (2) of liquid
As the solidification for changing liquid for imidizate, with the 2.8g of catalyst beta-picoline, (boiling point is 144
DEG C), as dehydrating agent 21.2g acetic anhydride and as polar organic solvent 0.9g dimethylformamide mixing
In solution, add 26.7g spherical silicon dioxide dispersion liquid (containing 6% spherical silicon dioxide (Japanese catalyst KEP-250,
The average grain diameter of particle be 3 μm, pore-free) solid constituent dimethylformamide mixed liquor) after be stirred, so as to obtain
The imidizate conversion liquid of 51.6g addition spherical silicon dioxide particle.
Preparation example 6：Imidizate added with imperforate fluorine particle changes the preparation of liquid
Isoquinolin (boiling point is 242 DEG C), work in the 2.8g as the solidification catalyst that liquid is changed for imidizate
Acetic anhydride for the 21.2g of dehydrating agent and as polar organic solvent 0.9g dimethylformamide mixed solution in,
Add the dispersion liquid (Daikin (DAIKIN) of 26.7g polytetrafluoroethylene (PTFE) (PTFE, Polytetrafluoroethylene)
Products, the dimethylformamide mixed liquor of the solid constituent containing 6% fluorine particle (average grain diameter is 22 μm, pore-free))
After be stirred so that obtain 51.6g addition fluorine particle imidizate conversion liquid.
Preparation example 7：The imidizate for being not added with particle changes the preparation of liquid
It is mixed and stirred for the beta-picoline (boiling point of the 3.3g as the solidification catalyst that liquid is changed for imidizate
For 144 DEG C), as dehydrating agent 21.5g acetic anhydride and the dimethylformamide of 25.2g as polar organic solvent
Afterwards, 50g imidizate conversion liquid is obtained.
【Embodiment】
Embodiment 1：It is applicable the preparation (1) for the polyimide film for having leachy particle
In the 100g obtained from preparation example 1 polyamic acid polymeric solution, it is blended in what is obtained in preparation example 2
After 50.8g imidizate conversion liquid, stainless steel plate is coated on, and in the baking oven of 120 DEG C of temperature, utilizes 3 points of heated-air drying
Zhong Hou, is prepared for gel mould.
After the gel mould prepared by method so is removed from stainless steel plate, fixed, then existed with frame pin
At a temperature of 450 DEG C, the framework that gel mould is fixed is carried out to go membrane removal after the heat treatment of 7 minutes, so as to obtain average thickness
For 25 μm of polyimide film.
Figure 1 illustrates the SEM of the section of the polyimide film prepared by method so
Picture.
Embodiment 2：It is applicable the preparation (2) for the polyimide film for having leachy particle
Use the 51.6g's obtained from preparation example 3 except the imidizate conversion liquid for replacing obtaining from preparation example 2
Beyond imidizate conversion liquid, perform process same as Example 1 to obtain the polyimide film that average thickness is 25 μm.
Comparative example 1：It is applicable the preparation (1) of the polyimide film of imperforate particle
Use the 50.8g's obtained from preparation example 4 except the imidizate conversion liquid for replacing obtaining from preparation example 2
Beyond imidizate conversion liquid, perform process same as Example 1 to obtain the polyimide film that average thickness is 25 μm.
Comparative example 2：It is applicable the preparation (2) of the polyimide film of imperforate particle
Use the 51.6g's obtained from preparation example 5 except the imidizate conversion liquid for replacing obtaining from preparation example 2
Beyond imidizate conversion liquid, perform process same as Example 1 to obtain the polyimide film that average thickness is 25 μm.
Comparative example 3：It is applicable the preparation of the polyimide film of imperforate fluorine particle
Use the 51.6g's obtained from preparation example 6 except the imidizate conversion liquid for replacing obtaining from preparation example 2
Beyond imidizate conversion liquid, perform process same as Example 1 to obtain the polyimide film that average thickness is 25 μm.
Comparative example 4：It is not added with the preparation of the polyimide film of particle
Use the 50.0g's obtained from preparation example 7 except the imidizate conversion liquid for replacing obtaining from preparation example 2
Beyond imidizate conversion liquid, perform process same as Example 1 to obtain the polyimide film that average thickness is 25 μm.
Test example 1：The measure of density ratio
In the present invention, it is based respectively on specification (KSM 6020:2010) determine what is added when preparing polyimide film
The particle density of the intrinsic material (B) of particle (A) and its particle.Hollow two used in embodiment 1 and embodiment 2 now
The native silicon dioxide of the intrinsic material of silica and the spherical silicon dioxide used in comparative example 1 and comparative example 2 is profit
With the catalyst (model name from Japan's purchase：EP-250) it is measured.
Then, the particle that the intrinsic material calculated according to following calculating formulas 1 relative to particle has leachy particle is close
Ratio (%) is spent, its result is shown in the following table 1.
[calculating formula 1]
Test example 2：Has the measure of the average grain diameter of leachy particle
Using laser diffraction particle size analyzer (Laser Diffraction Particle Size Analyzer,
SHIMADZU companies, model name is SALD-2201) determine being averaged for the leachy particle of tool used in the present invention
Particle diameter, and the average size for having leachy particle is shown in such as table 1 below.
Test example 3：The measure of the particle content of film
The polyamides prepared in embodiment 1, embodiment 2 and comparative example 1 into comparative example 4 is determined using ash content (ASH) method
The particle content of imines film.Grey point-score is carried out by following method, i.e. be put into crucible after film, at 900 DEG C
At a temperature of after burning 3 hours, the residual quantity that remains in crucible is determined, to determine containing ratio.Show and surveyed in such as table 1 below
Fixed particle content (percentage by weight).
Test example 4：About having the confirmation of the distribution in the average film of leachy particle
Utilize field emission scanning electron microscope (FE-SEM, field emission scanning electron
Microscope) (Jeol Ltd. (JEOL), model name is JSM-6700F) has according to the present invention to observe
Embodiment 1 polyimide film in stomata particle distribution, and be shown in the picture of SEM.
Figure 1 illustrates the picture of the SEM of the section of the polyimide film of embodiments of the invention 1.
Also, there is the state for having leachy particle figure 2 illustrates the Dispersion on surface in above-mentioned film, and in figure 3
Show that the above-mentioned Dispersion on surface in above-mentioned film for expanding a part has and has the state of leachy particle to show particle state
Picture.
As shown in Fig. 2 being distributed in confirming the leachy uniform particle of tool of the polyimide film for the present invention
Whole film, so as to understand to show good dispersity.
Test example 5：Dielectric constant and the measure for luring electricity just connecing
Determined using the SPDR analyzers of Agilent (Keysight) company in embodiment 1, embodiment 2 and comparative example 1
The dielectric constant at 1 GHz of the polyimide film prepared into comparative example 4 and electricity is lured just to connect.Show and determined in table 1
Dielectric constant and lure electric positive ad valorem.
[table 1]
As shown in Table 1 above, comprising the embodiment 1 for having leachy hollow silica particle and the polyamides of embodiment 2
Imines film shows less than 3 low-k.
Also, according to the polyimide film of embodiment 1 and embodiment 2 in situation about being compared with following situation
Under, i.e. it is being more than 95% situation with density ratio, or is including the situation of fluorine particle, or in comparative example 1 into comparative example 4
Do not include particle situation compare in the case of, also show that low dielectric constant and lure electricity just to connect, so as to understand tool
There are outstanding electrical characteristics.Therefore, it can be effectively used for needing electrical equipment/electronic equipment of the printed circuit board (PCB) of low-k etc.
And the manufacture of part.
Claims (6)
1. a kind of preparation method of polyimide film, it is characterised in that including：
Step 1), prepare polyimide precursor；
Step 2), mix the polyimide precursor and change liquid to prepare gel comprising the imidizate for having leachy particle
Film；And
Step 3), imidizate processing is carried out by being heat-treated to the gel mould,
The average grain diameter of the leachy particle of tool is less than 10 μm, relative to the intrinsic material of the leachy particle of tool
Particle density, with less than 95% particle density.
2. the preparation method of polyimide film according to claim 1, it is characterised in that the leachy particle of tool
Average grain diameter is 1 μm to 10 μm, relative to the particle density of the intrinsic material of the leachy particle of the tool, with 30% to
95% particle density.
3. the preparation method of polyimide film according to claim 1, it is characterised in that on the basis of the gross weight of film,
The leachy particle of the tool comprising 2 percentage by weights to 30 percentage by weights.
4. the preparation method of polyimide film according to claim 1, it is characterised in that the leachy particle of tool is
Hollow type particle or mesoporous type grain in the group being made up of silica, aluminum oxide, titanium dioxide, zeolite and its mixture
Son.
5. a kind of polyimide film, comprising having leachy particle, the polyimide film is characterised by,
The average grain diameter of the leachy particle of tool is less than 10 μm, relative to the intrinsic material of the leachy particle of tool
Particle density, with less than 95% particle density.
6. polyimide film according to claim 5, it is characterised in that the dielectric of the polyimide film at 1 GHz is normal
Number is less than 3.0.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150010092A KR101728100B1 (en) | 2015-01-21 | 2015-01-21 | Method for preparation of polyimide film using porous particles and polyimide film having low permittivity |
| KR10-2015-0010092 | 2015-01-21 | ||
| PCT/KR2016/000131 WO2016117856A1 (en) | 2015-01-21 | 2016-01-07 | Method for preparing polyimide film using porous particles, and low dielectric constant polyimide film |
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| Publication Number | Publication Date |
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| CN107108926A true CN107108926A (en) | 2017-08-29 |
| CN107108926B CN107108926B (en) | 2021-05-07 |
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| CN201680004928.4A Active CN107108926B (en) | 2015-01-21 | 2016-01-07 | Method for producing polyimide film using porous particles and low dielectric constant polyimide film |
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| Country | Link |
|---|---|
| JP (1) | JP6865687B2 (en) |
| KR (1) | KR101728100B1 (en) |
| CN (1) | CN107108926B (en) |
| TW (1) | TWI593726B (en) |
| WO (1) | WO2016117856A1 (en) |
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| WO2022242547A1 (en) * | 2021-05-17 | 2022-11-24 | 上海瑞暨新材料科技有限公司 | Polyimide porous membrane and preparation method therefor |
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| WO2018044085A1 (en) * | 2016-09-01 | 2018-03-08 | 에스케이씨코오롱피아이 주식회사 | High heat radiation graphene-polyimide composite film having insulation ability, and manufacturing method therefor |
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| WO2021261607A1 (en) | 2020-06-23 | 2021-12-30 | 엘지전자 주식회사 | Polyimide and preparation method thereof |
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Also Published As
| Publication number | Publication date |
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| TW201634540A (en) | 2016-10-01 |
| JP6865687B2 (en) | 2021-04-28 |
| JP2018502964A (en) | 2018-02-01 |
| WO2016117856A1 (en) | 2016-07-28 |
| CN107108926B (en) | 2021-05-07 |
| TWI593726B (en) | 2017-08-01 |
| KR101728100B1 (en) | 2017-04-18 |
| KR20160090153A (en) | 2016-07-29 |
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