Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—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
  • 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

Definitions

• a polyimide (PI) resin is a high heat-resistant resin prepared by solution polymerization of an aromatic acid dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, and then imidization by ring dehydration at high temperature.
• Polyimide resins are widely used in electrical / electronic materials, space / aviation and telecommunications because of their excellent mechanical and thermal dimensional stability and chemical stability. In particular, since polyimide resins have high insulation performance, they are widely used in printed circuit boards and the like as components and members requiring reliability.
• the polyimide resin used in them has a high dielectric constant, particularly as an electrical characteristic for high frequency. Anger is required.
• Korean Patent No. 0859275 disperses a dispersible compound in a polyimide resin precursor solution and then forms a film using the dispersion, and extracts the dispersible compound from the film. It is disclosed to prepare a porous polyimide resin by removing and porousizing the same.
• the porous polyimide resin prepared by the above method has a limit in implementing a thin polyimide film because it has pores of a micro unit size.
• the present invention to achieve the above object, Polyimide resin; And primary particles having an average particle diameter of 300 nm or less, and secondary particles having an average particle diameter of 10 mm or less and an average porosity specific gravity of 1.2 g / ml or less, having primary pores of which the primary particles are concaved and having an average diameter of 300 nm or less. It provides a polyimide film comprising a.
• the present invention also provides a polyimide precursor, an imidization conversion liquid, and primary particles having an average particle diameter of 300 nm or less, and the primary particles having pores with an average diameter of 300 nm or less, having an average particle diameter of 10 or less and an average apparent specific gravity of 1.2.
• a method for producing the polyimide film comprising imidating and then mixing fluorine-based particles composed of secondary particles of g / ml or less.
• Figure 1 shows a SEM picture of the fluorine-based primary particles applied for the implementation of the present invention.
• Figure 2 shows a SEM photograph of the secondary particles formed by coarse fluorine-based primary particles applied for the implementation of the present invention.
• Figure 3 shows a cross-sectional SEM photograph of a polyimide film (prepared in Example 1) prepared by applying the secondary particles formed by forming the fluorine-based primary particles for the implementation of the present invention.
• the polyimide film of the present invention is a polyimide resin; And primary particles having an average particle diameter of 300 nm or less, and secondary particles having an average particle diameter of 10 / m or less and an average specific gravity of 1.2 g / ml or less, having primary pores of which the primary particles are concaved and having an average diameter of 300 nm or less. Particles, characterized in that the fluorine-based particles are preferably uniformly dispersed in the polyimide resin.
• the polyimide film of the present invention has a polyimide precursor, an imidization conversion liquid, and primary particles having an average particle diameter of 300 nm or less, and the primary particles having pores with an average diameter of 300 nm or less, having an average particle diameter of 10 or less and an average. It is prepared by mixing the fluorine-based particles composed of secondary particles having a specific gravity of 1.2 g / ml or less and then performing an imidization process.
• the method for producing the fluorine-based particles used in the present invention is not particularly limited as long as it can be produced by implementing the above-mentioned parameters.
• the primary particles constituting the fluorine-based particles may have an average particle diameter of 50 to 300 nm
• the secondary particles have an average particle diameter of 3 to 10 and pores of an average diameter of 50 to 300 mm 3 and 0.4 to 1.2 It may have an average apparent specific gravity of g / ml.
• the fluorine-based particles added to implement the dielectric constant of the polyimide is
• Fluorine resins having a melting point of 200 ° C. or higher are preferred, and specific examples thereof include polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA) and It may be at least one selected from the group consisting of fluorinated ethylene propylene (FEP).
• PTFE polytetrafluoroethylene
• PFA perfluoroalkoxy
• FEP fluorinated ethylene propylene
• the polyimide film of the present invention may include the fluorine-based particles in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, based on the total weight of the film.
• the fluorine-based particles having the above characteristics are included in the above content range, the dielectric constant characteristics of the polyimide film to be implemented may be exhibited by preventing the degradation of the fluorine-based particles due to the high temperature of the polyimide film manufacturing process. By adding a large amount of particles, the mechanical strength of the polyimide film can be maintained.
• the polyimide precursor used in the present invention can be used as long as it can be a polyimide resin by imidization, preferably a polyamic acid obtained by copolymerizing an acid dianhydride component and a diamine component in a conventional manner. .
• the acid dianhydride component and the diamine component may be appropriately selected from those commonly used.
• biphenylcarboxylic dianhydride or derivatives thereof, pyromellitic dianhydride or derivatives thereof, and the like may be used as the acid dianhydride component, and phenylenediamine or a derivative thereof, diaminophenyl ether or the like may be used as the diamine component. Its derivatives and the like can be used.
• the imidization conversion liquid used in the present invention may be used as long as it is a material commonly used to cause chemical curing, and may be three mixed solutions such as a dehydrating agent, a catalyst, and a polar organic solvent. More specifically, the imidization conversion liquid may be a dehydrating agent such as acetic dianhydride; Tertiary amine catalysts such as pyridine, betapicolin and isoquinoline; And a polar organic solvent such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), and dimethylacetamide (DMAc).
• NMP N-methylpyrrolidone
• DMF dimethylformamide
• DMAc dimethylacetamide
• the imidization conversion solution may be used in an amount of 30 to 70 parts by weight based on 100 parts by weight of the polyimide precursor, but may vary depending on the type of polyimide precursor and the thickness of the polyimide film to be produced.
• the polyimide film of the present invention may be prepared by conventional methods known in the art as follows.
• the acid dianhydride component and the diamine component are copolymerized in an organic solvent to obtain a polyamic acid solution.
• the organic solvent is generally an aprotic polar solvent, such as ⁇ , ⁇ '-dimethylformamide, ⁇ , ⁇ ' —dimethylacetamide, N-methyl-blood as the amide solvent. Redon, or a combination thereof may be used.
• a filler may be added to the polyamic acid solution in order to improve various properties such as the slidability, thermal conductivity, conductivity, and corona resistance of the polyimide film.
• layering agents include, but are not limited to, silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like.
• an imidization conversion solution containing a dehydrating agent, a catalyst, and a polar organic solvent was added and mixed firstly, and primary particles having an average particle diameter of 300 nm or less and the primary particles were condensed and averaged.
• the fluorine-based particles composed of secondary particles having a pore diameter of 300 nm or less and an average particle diameter of 10 // m or less and an average apparent specific gravity of 1.2 g / ml or less are added and then mixed.
• the timing of adding the imidization conversion liquid and the fluorine particles may proceed simultaneously without time difference, and may be added in a dispersion liquid dispersed in a polar organic solvent when the bloso particles are added.
• This mixed solution is applied to a support (eg, glass plate, aluminum foil, circulating stainless belt, stainless drum, etc.), and then imidized to obtain a desired polyimide film.
• the desired polyimide film can be obtained by chemically partially imidating the polyamic acid coating layer formed on the support by primary heat treatment and then completely imidating it by secondary heat treatment.
• Primary heat treatment for chemical partial imidization may be performed at 100 to 200 ° C. for 5 to 15 minutes
• secondary heat treatment for complete imidization may be performed at 250 to 850 ° C. for 5 to 15 minutes. .
• the polyamic acid film subjected to the first heat treatment of the chemical partial imidization state may be separated from the support and subjected to the second heat treatment, and the residual force in the film generated in the film forming process may be removed by heat treatment under a constant tension during the second heat treatment.
• the polyimide film according to the present invention prepared as described above is 2.3 to 1 ⁇ z
• the polyimide film of the present invention containing fluorine-based particles uniformly in the film is relatively compared to the polyimide film produced by applying the fluorine monomer
• the low coefficient of linear expansion can be realized, and the fluorine-based particles do not directly protrude on the surface of the film to realize high adhesion of the film, which can be applied to FPCB materials such as copper foil laminates and reinforcement plates.
• the polyimide film of the present invention uniformly includes fluorine-based particles having pores of a specific size in the film, thereby exhibiting electrical characteristics of the single fluorine particles, and at the same time embodying a porous form due to the pores to express a lower dielectric constant. It can be used in the manufacture of electrical and electronic devices and components, such as a printed circuit board that requires a low dielectric constant.
• fluorine-based particles having pores and capable of achieving the required average specific specific gravity fluorine-based particles in the product are prevented from sinking due to the application of fluorine particles having high specific gravity. It is advantageous in that the particles can be uniformly distributed and there is no need to add a separate dispersant to improve dispersibility.
• the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples. Production Example 1 Preparation of Polyamic Acid Solution
• DMF dimethylformamide
• ODA diaminophenyl ether
• PMDA pyromellitic dianhydride
• Example 1 fluorine particle application polyimide film production 100 g of the polyamic acid polymerization solution obtained in Preparation Example 1 was mixed with 45 g of the imidization conversion solution obtained in Preparation Example 2, and then applied to a stainless plate, dried for 3 minutes by hot air in a 120 ° C. oven, and then the film was removed from the stainless plate. Fixed with.
• Example 2 fluorine particle application polyimide film manufacture
• a polyimide film having an average thickness of 25 was obtained in the same manner as in Example 1, except that 45 g of the imidization conversion solution obtained in Production Example 3 was used instead of the imidization conversion solution obtained in Production Example 2.
• Comparative Examples 1 and 2 Manufacture of Polyimide Films Applying Fluorine Particles with Different Particle Sizes and Mole Density
• a polyimide film having an average thickness of 25 / was obtained in the same manner as in Example 1 except that 45 g of the imidization conversion solution obtained in Production Example 4 or 5 was used instead of the imidization conversion solution obtained in Production Example 2. Comparative Examples 3 and 4: Manufacture of Polyimide Film without Fluorine Particles
• a polyimide film having an average thickness of 25 was obtained in the same manner as in Example 1, except that 45 g of the imidization conversion solution obtained in Production Example 6 or 7 was used instead of the imidization conversion solution obtained in Production Example 2. Corona treatment of the film
• Corona treatment was performed on the polyimide films prepared in Examples 1 to 2 and Comparative Examples 1 to 4 using a corona discharge treatment apparatus (model names AGI: 060M, 063M, manufactured by Kasuga Denki Co., Ltd.) at the 4 kW output. Carried out.
• Test Example 1 Determination of Average Particle Size and Average Diameter of Pore
• the average particle diameter and average diameter of pores of the primary particles of the fluorine-based particles used for the present invention can be obtained from a scanning electron microscope FE-SEM (JEOL (zeol)). Using the model JSM-6700F), images of 200 primary particles and pores were randomly selected from the SEM image, and their size was measured to calculate an average. The measured values are shown in Table 1 below, and SEM pictures of the fluorine-based primary particles are shown in FIG. 1.
• Test Example 2 Measurement of Average Particle Size of Secondary Particles
• the average particle diameter of the secondary particles of the fluorine-based particles used for the present invention was measured using a laser diffraction particle size analyzer (Laser Difactact Particle Size Analyzer, SHIMADZU, Model SALD-2201). The measured values are shown in Table 1 below, and SEM images of secondary particles formed by condensation of fluorine-based primary particles are shown in FIG. 2.
• Test Example 3 Measurement of average apparent specific gravity of secondary particles
• the average apparent specific gravity of the secondary particles of the fluorine-based particles used for the present invention was measured using a volume densi ty meter and a density cup (Dens i ty cup, YASUDA, model 536, 558). The measured values are shown in Table 1 below.
• Test Example 4 Measurement of permittivity and dielectric loss tangent
• the polyimide film prepared in Examples 1 to 2 and Comparative Examples 1 to 4 was cut to a width of 5 mm X length 16 mm and TA thermal analysis apparatus (Thermal mechani cal apparatus)
• the coefficient of thermal expansion (CTE) was measured using a Q400. Samples were heated at a rate of 10 ° C./min from 30 ° C. to 420 ° C., and coefficients of thermal expansion were obtained within the range of 50 ° C. to 200 ° C.
• the measured coefficient of thermal expansion (linear expansion coefficient) is shown in Table 1 below.
• Test Example 6 Adhesion Measurement
• Bonding sheet (lmi l, Epoxy type, Hanwha L & C product) was placed between the polyimide film prepared in Examples 1 to 2 and Comparative Examples 1 to 4 and copper foil (2 / 3oz, Iljin Materials).
• the protective film was placed and heated to 180 ° C., and then thermally compressed at a pressure of 3 Mpa for 30 minutes. Then, the pressure was released to further cure in an oven at 200 ° C. for 30 minutes to obtain a flexible substrate. After the obtained flexible substrate was cut to a width of 5 mm and cut, the adhesive force was measured by a 90 ° wheel test of the IPC TM 659 2.4.9D method. The measured adhesive values are shown in Table 1 below.
• the polyimide films of Examples 1 and 2 of the present invention can express a low dielectric constant compared to the polyimide films of Comparative Examples 1 to 4 while showing excellent physical properties. Therefore, the polyimide film of the present invention It can be usefully used for the production of electrical and electronic devices and components such as printed circuit boards requiring low dielectric constant.

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• Organic Chemistry (AREA)
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• 2013
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