WO2011016094A1 - Résine thermorésistante, sa composition, stratifié résine/métal et carte de circuit imprimé - Google Patents

Résine thermorésistante, sa composition, stratifié résine/métal et carte de circuit imprimé Download PDF

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Publication number
WO2011016094A1
WO2011016094A1 PCT/JP2009/003813 JP2009003813W WO2011016094A1 WO 2011016094 A1 WO2011016094 A1 WO 2011016094A1 JP 2009003813 W JP2009003813 W JP 2009003813W WO 2011016094 A1 WO2011016094 A1 WO 2011016094A1
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group
heat resistant
resistant resin
aminophenoxy
degrees
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PCT/JP2009/003813
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English (en)
Inventor
Katsunori Nishiura
Kazuyuki Fukuda
Masahiro Toriida
Toshihiko Takaki
Masanobu Ajioka
Chaobin He
Yang Xiao
Khine Yi Mya
Mohammad Abdul Wahab
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Mitsui Chemicals, Inc.
Agency For Science, Technology And Research
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Priority to PCT/JP2009/003813 priority Critical patent/WO2011016094A1/fr
Priority to TW098142929A priority patent/TW201105710A/zh
Publication of WO2011016094A1 publication Critical patent/WO2011016094A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
    • C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen

Definitions

  • the present invention relates to a novel polyimide resin, a polyimide resin composition, a polyimide/metal laminate and a circuit board material, which are suitably used for micro processing in manufacturing circuit boards and excellent in heat resistance and dimensional stability.
  • the present invention relates to a novel compound, which is suitably used as a crosslinking agent for organic polymers.
  • polyimide resins For example, a polyimide characterized by having a phosphazene skeleton is proposed. (See PTL 2 for example.) No crosslinking structure is formed in the polyimide for the phosphazene skeleton is incorporated in the main chain of the polyimide. Also, the effect of that invention is to improve the frame flame retardancy, and no clear statement is made concerning the elastic modulus at high temperature and the dimensional stability.
  • the purpose of the invention is to present a heat resistant polyimide resin, which is excellent in elastic modulus at high temperature and dimensional stability.
  • Another purpose of the invention is to prepare a polyimide/metal laminate having a layer comprising the heat resistant resin described above and thereby present a polyimide/metal laminate and a circuit board material suitable for a base material for COF.
  • the present invention relates to: (i) A heat resistant resin obtainable by crosslinking an organic polymer (I) having an imide bond and/or an amide bond in the main chain thereof with a compound (C) having at least three amino groups and a phosphazene skeleton and represented by the following formula (1), wherein m and n independently represents an integer provided that m + n is from3 to 25, R 3 , R 4 , R 5 and R 6 independently represents a phenyl group, an amino phenyl group or a substituted phenyl group having a structure represented by the formula (2), wherein R 7 represents an organic group selected from the group consisting of an alkyl group, fluoro group, chloro group, bromo group, nitro group, cyano group, hydroxyl group, phenoxy group and a substituted group connected via an amide, imide, esther or ether bond, formula (1) has at least three amino groups, and formula (2) has at least one R 7 .
  • (x) A process for producing the heat resistant resin as in (ix) or (v) above, comprising the steps of; (1) synthesizing a polyamic acid (Ia) from a tetracarboxylic dianhydride (A) and a diamine (B), (2) preparing a solution by adding the compound (C) to the polyamic acid (Ia), and (3) heating the solution to carry out imidation, in this order.
  • (xi) A compound represented by the following formula (3), wherein R 1 to R 6 are independently fluoro group, amino group or hydrogen atom, and at least three of R 1 to R 6 are amino groups and at least one of R 1 to R 6 is fluoro group.
  • a heat resistant polyimide resin which is excellent in elastic modulus at high temperature and dimensional stability can be obtained.
  • a polyimide/metal laminate having a layer comprising the heat resistant resin described above can cope with the high density mounting of chips, which has been accelerated recently, and effectively used as a polyimide/metal laminate for COF.
  • Fig. 1 is 1 H NMR chart of FACP (tris(4-fluorophenoxy)tris(4-aminophenoxy)cyclotriphosphazene).
  • Fig. 2 is 31 P NMR chart of FACP.
  • Fig. 3 is MALDI-TOF spectra of FACP.
  • the present invention is a heat resistant resin obtainable by crosslinking an organic polymer (I) having an imide bond and/or an amide bond in the main chain thereof with a compound (C) having at least three amino groups and a phosphazene skeleton and having a specific structure.
  • the polyimide resin composition of the present invention preferably comprises a polyimide derived from a tetracarboxylic dianhydride (A) a diamine compound (B) and/or a precursor thereof and a compound (C) having three or more amino groups and a phosphazene skeleton wherein the compositon of (C) is from 0.1 wt% to 80 wt% based on the total amount of (A) + (B) + (C).
  • A tetracarboxylic dianhydride
  • B diamine compound
  • C having three or more amino groups and a phosphazene skeleton wherein the compositon of (C) is from 0.1 wt% to 80 wt% based on the total amount of (A) + (B) + (C).
  • Organic Polymer (I) In the present invention, no particular limitation is imposed on the organic polymer (I) having an imide bond and/or an amide bond in the main chain thereof, except that the organic polymer should have at least one imide bond and/or amide bond in the main chain thereof.
  • the polymer preferably is a polyimide precursor, more preferably a polyimide precursor comprising a polyimide polymer and/or a polyamic acid polymer.
  • any polyimide precursor comprising a polyimide polymer and/or polyamic acid polymer synthesized using a known tetracarboxylic dianhydride (A) and a known diamine compound (B).
  • the polyimide precursor preferably comprises a polyimide polymer and/or a polyamic acid polymer synthesized using at least one tetracarboxylic dianhydride (A) and at least one diamine compound (B).
  • the diamine compouds (B) used as the starting material of the polyimide polymer and/or polyamic acid polymer in the present invention include, for example, 1,3-bis(3-aminophenoxy)benzene, 4,4-bis(3-aminophenoxy)biphenyl, 3,3'-diaminobenzophenone, 1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 1,3-bis(3-(3-aminophenoxy)phenoxy)benzene, 1,3-bis(3-(4-aminophenoxy)phenoxy)benzene, 5,7-diamino-1,1,4,6-tetramethyl indaine, 1,3-bis(4-(3-aminophenoxy)phenoxy)benzene, 1,3-bis(3-(2-aminophenoxy)phenoxy)benzene, 1,3-bis(4-(2-aminophenoxy)phenoxy)benzene, 1,3-
  • diamine compounds are 1,4-phenylenediamine, 4,4'-oxydianiline(4,4'-diaminodiphenyl ether) and 4,4-bis(3-aminophenoxy)biphenyl.
  • the tetracarboxylic dianhydrides (A) used as the starting material of the polyimide polymer and/or polyamic acid polymer are not particularly limited, and any known species can be used.
  • the examples of the tetracarboxylic dianhydrides (A) include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3'4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfide dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphen
  • tetracarboxylic dianhydrides or two or more thereof may be used.
  • Particularly preferable tetracarboxylic dianhydrides are pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.
  • the reaction molar ratio ((A)/(B)) of tetracarboxylic dianhydride (A) to diamine compound (B) is usually in the range of from 0.7 to 1.25, preferably not more than 1.05, more preferably not less than 0.8 and not more than 1.05. When the ratio is in the range defined above, a resin having high modulus of elasticity and excellent dimensional stability can be obtained.
  • the polyimide polymer or the polyamic acid polymer may contain any additional structural unit derived from any other component depending on the purpose of the embodiment.
  • the purity of the starting materials is preferably high, it is particularly preferable that the diamine does not contain any impurity having the molecular weight higher than that of the diamine itself and, for this purpose, the preparative method of removing impurities by conventional means, such as distillation, can be utilized.
  • a dicarboxylic anhydride can be added to terminate the polymer terminal.
  • the dicarboxylic anhydride to be used include phthalic anhydride, 2,3-benzophenonedicarboxylic anhydride, 3,4-benzophenonedicarboxylic anhydride, 2,3-dicarboxyphenylphenylether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfone anhydride, 3,4-dicarboxyphenylphenylsulfone anhydride, 2,3-dicarboxyphenylphenylsulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3
  • the dicarboxylic anhydride can usually be added at a molar ratio in the range of from 0.001 moles to 0.5 moles, preferably 0.005 moles to 0.25 moles, based on 100 moles of the total amount of the specific diamines described above as the main component, other amine compounds to be used together, the specific tetracarboxylic dianhydrides described above and other tetracarboxylic dianhydrides to be used together.
  • a monoamine can be added to terminate the polymer terminal.
  • the monoamine include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-aminophenol, m-aminophenol, p-aminophenol, o-anilidine, m-anilidine, p-anilidine, o-phenetidine, m-phenetidine, p-phenetidine, o-aminobenzaldehyde, m-aminobenzaldehyde
  • the monoamines can solely be used or used in combination of two or more species.
  • the monoamine can usually be used at a molar ratio in the range of from 0.001 moles to 0.5 moles, preferably 0.005 moles to 0.25 moles, based on 100 moles of the total amount of the specific diamine described above as the main component, other amine compound to be used together, the specific tetracarboxylic dianhydride described above and other tetracarboxylic dianhydride to be used together.
  • the polymerization of the organic polymer (I) (polyimide and/or precursor thereof) be carried out in an organic solvent.
  • the example of the solvent can be used include phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, N,N-dimethylformamide, N,N-dimethylacetoamide, N,N-diethylacetoamide, N,N-dimethylmethoxyacetoamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,
  • the examples of the solvents to coexist include p-xylene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene, chlorobenzene, bromobenzene and so on.
  • the reaction time of the polyamic acid which is a precursor of the polyimide, can roughly be from 1 hour to 48 hours, and is usually from 4 hours to 24 hours, although the time can vary depending on the species of the monomers to be used, the species of the solvent, the species of the organic base catalyst, the species and the amount of the solvent for azeotropic dehydration and the reaction temperature.
  • a guideline for the case of obtaining the polyimide by means of thermal imidization is to carry out the reaction until the most (usually 70 % to 90 % as not all of the distillate is recovered) of the theoretical amount of distillate water is obtained, which usually takes hours or tens of hours. In this case, it is common and useful to remove the water generated from the imidization using an azeotropic agent such as xylene or toluene.
  • reaction pressure Although no particular limitation is imposed on the reaction pressure, the atmospheric pressure is usually sufficiently suitable.
  • reaction atmosphere air, nitrogen, helium, neon or argon is usually used, and an inert gas such as nitrogen or argon is preferably used.
  • an organic basic catalyst is preferably used in the preparation of the polyimide of the present invention in an organic solvent.
  • the organic basic catalyst include, triethylamine, tributylamine, tripentylamine, N,N-dimethylaniline, pyridine, alpha-picoline, beta-picoline, gamma-picoline, 2,6-lutidine, quinoline, isoquinoline and so on.
  • the preferable is pyridine or picoline. No particular limitation is imposed on the amount of the catalyst to be used, provided that the polymerization reaction rate is substantially improved.
  • the heat resistant resin of the present invention is obtainable by crosslinking the above-described organic polymer (I) having an imide bond and/or an amide bond in the main chain thereof with the compound (C) having at least three amino groups and a phosphazene skeleton.
  • the examples include hexakis(4-aminophenoxy)cyclotriphosphazene, monomethoxypentakis(4-aminophenoxy)cyclotriphosphazene, dimethoxytetrakis(4-aminophenoxy)cyclotriphosphazene, trimethoxytris(4-aminophenoxy)cyclotriphosphazene, monophenoxypentakis(4-aminophenoxy)cyclotriphosphazene, diphenoxytetrakis(4-aminophenoxy)cyclotriphosphazene, tripheoxytris(4-aminophenoxy)cyclotriphosphazene, monoethoxypentakis(4-aminophenoxy)cyclotriphosphazene, diethoxytetrakis(4-aminophenoxy)cyclotriphosphazene, triethoxytris(4-aminophenoxy)cyclotriphosphazene, mono-n-propoxypentakis(
  • the compound (C) is usually added to a varnish comprising the tetracarboxylic dianhydride (A), the diamine (B) and the solvent described above, it can be added in any other step of the production.
  • the crosslinking can proceed either after the polymer (I) is generated form the tetracarboxylic dianhydride (A) and the diamine (B) or simultaneously with the generation of the polymer (I).
  • the compound (C) is preferably added 0.01 to 80 parts by weight based on total 100 parts by weight of the tetracarboxylic dianhydride (A), the diamine (B) and the compound (C).
  • Novel Compound (C') The inventors have also conceived that a novel compound (C') represented by the following formula (3), wherein R 1 to R 6 are independently fluoro group, amino group or hydrogen atom, and at least three of R 1 to R 6 are amino groups and at least one of R 1 to R 6 is fluoro group, is particularly suitable for crosslinking the polymer (I) .
  • compound (C') includes, 4-fluorophenoxypentakis(4-aminophenoxy)cyclotriphosphazene, bis(4-fluorophenoxy)tetrakis(4-aminophenoxy)cyclotriphosphazene and tris(4-fluorophenoxy)tris(4-aminophenoxy)cyclotriphosphazene.
  • three of R 1 to R 6 are preferably fluoro groups and three of R 1 to R 6 are preferably amino groups. Therefore, tris(4-fluorophenoxy) tris(4-aminophenoxy)cyclotriphosphazene is especially preferable.
  • Compound (C') can be synthesized, for example, by reacting phosphonitrilic chloride trimer with 4-nitrophenol and 4-fluorophenol and then reducing the product.
  • the method for synthesizing compound (C') will be explained in more detail in the examples.
  • the heat resistant resin composition of the invention is only required to contain a heat resistant resin obtainable by crosslinking the above-described organic polymer (I) having an imide bond and/or an amide bond in the main chain thereof with the compound (C) having at least three amino groups and a phosphazene skeleton, and may contain or does not contain any other component(s).
  • a bismaleimide compound can be added as another component to the polyimide compound of the invention, not more than 50 wt%, in order to adjust the glass transition temperature.
  • the bismaleimide compound include 4,4'-bis(4-phenyl)methane, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(3-(3-maleimidophenoxy)phenoxy)benzene, 1,3-bis(3-(3-(3-maleimidophenoxy)phenoxy)phenoxy)benzene, bis(4-(3-maleimidophenoxy)phenyl)methane, 1,1-bis(4-(3-maleimidophenoxy)phenyl)ethane, 1,2-bis(4-(3-maleimidophenoxy)phenyl)ethane, 2,2-bis(4-(3-maleimidophenoxy)phenyl)propane, 2,2-bis(4-(3-maleimidophenoxy)pheny
  • the thickness of the polyimide layer formed from the heat resistant resin composition of the invention is preferably not less than 1 micrometer and not more than 250 micrometers, more preferably not less than 4 micrometers and not more than 50 micrometers, and further preferably not less than 10 micrometers and not more than 40 micrometers, and it is desirable that the glass transition temperature thereof be not less than 300 degrees C or no glass transition temperature thereof be observed.
  • the linear coefficient of thermal expansion (CTE) of the layer in the temperature range of from 100 degrees C to 250 degrees C is preferably not less than 5 ppm/degrees C and not more than 30 ppm/degrees C, more preferably not less than 10 ppm/degrees C and not more than 20 ppm/degrees C.
  • the coefficient of hygroscopic expansion (CHE) of the layer at the relative humidity from 20 % to 60 % is preferably not less than 5 ppm/%RH and not more than 20 ppm/%RH, and more preferably not less than 5 ppm/%RH and not more than 15 ppm/%RH.
  • CHE hygroscopic expansion
  • the resin/metal laminate using the heat resistant resin of the present invention will be explained below.
  • the resin/metal laminate is a laminate, wherein a metal foil is (metal foils are) formed on a side or both sides of a heat resistant resin layer obtained by crosslinking a polyimide.
  • the heat resistant resin layer is formed with one or more layers. In case two or more layers exist, the composition of the layers can be the same or different.
  • copper and copper alloys copper and copper alloys, stainless steels and alloys thereof, nickel and nickel alloys, including 42 alloy, and aluminum and aluminum alloys can be exemplified.
  • the preferable are copper and copper alloys.
  • a foil wherein an anti-corrosion layer or a heat resistant layer can be formed, for example, by plating chromium, zinc or so on, is formed or a silane coupling agent is applied on a surface thereof can be used.
  • the preferable is a cupper alloy comprising copper and at least one component selected from the group consisting of nickel, zinc, iron, chromium, cobalt, molybdenum, tungsten, vanadium, beryllium, titanium, tin, manganese, aluminum, phosphorus and silicon.
  • the alloy is preferred in view of circuit processing.
  • the most preferable metal foils are copper foils formed by rolling or electro-plating.
  • the preferable thickness thereof is from 3 micrometers to 150 micrometers, more preferably from 3 micrometers to 35 micrometers, further preferably from 3 micrometers to 12 micrometers.
  • the metal foil can either be those without any surface treatment or those with roughening treatment on one or both side(s) thereof.
  • the preferable are low roughness foils and foils without roughening treatment.
  • Examples of market available foils can be used are F1-WS, F0-WS (manufactured by Furukawa Circuit Foil Co., Ltd., trade name), BHY, NK120 (manufactured by Japan Energy Corporation, trade name), SLP, USLP (manufactured by Nippon Denkai, Ltd., trade name), TQ-VLP, SQ-VLP, FQ-VLP (manufactured by Mitsui Mining & Smelting Co., Ltd., trade name), C7025, B-52 (manufactured by Dowa Olin Metal Corporation, trade name) and so on.
  • the ten-point mean roughness (Rz) at the side of the foil facing the heat resistant resin layer be less than 3 micrometers, preferably less than 2 micrometers, more preferably less than 1 micrometer, and those at the other side of the foil be less than 3 micro meters, preferably less than 2 micrometers, more preferably less than 1 micrometer.
  • the ten-point mean roughness (Rz) is measured according to the method defined in JIS B-0601, wherein the cut-off value is 0.25 mm, measurement length is 2.5 mm and the measurement is carried out along the width direction of the copper foil.
  • the surface of the metal foil facing the heat resistant resin layer have 0.05 mg/dm 2 to 1.0 mg/dm 2 , preferably 0.1 mg/dm 2 to 0.4 mg/dm 2 , of nickel, 0.5 mg/dm 2 or less, preferably 0 to 0.3 mg/dm 2 , more preferably 0 to 0.1 mg/dm 2 , of zinc, 0.2 mg/dm 2 or less, preferably 0 to 0.1 mg/dm 2 , of chromium, and 0.2 mg/dm 2 or less, preferably 0 to 0.1 mg/dm 2 , of silicon.
  • the surface not facing the heat resistant resin layer preferably be plated with nickel or zinc, or chromate treatment can preferably be applied thereon.
  • the silicon mentioned above is derived from a silane coupling agent applied to improve the adhesion to polyimide.
  • the silane coupling agent is dissolved in an alcohol or water, homogeneously applied to the uppermost layer of the treated surface of the metal foil, and then dried to form a layer at a temperature about from 50 degrees C to 150 degrees C.
  • the typical types of the agent include, but not limited to, vinylsilanes such as vinyltriethoxysilane, epoxysilanes such as and beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and aminosilanes such as gamma-aminopropyltrimethoxysilane.
  • the resin layer constitutes the resin/metal laminate of the invention can either be mono-layer comprising the heat resistant resin of the present invention or be multi-layers comprising polyimides having different compositions in order to improve the warpage, the dimensional stability or the heat resistance.
  • the method of manufacturing polyimide/metal laminates using the heat resistant resin of the invention will be explained below.
  • the method for manufacturing the heat resistant resin/metal laminate can be selected, as appropriate, from so called laminate method, wherein the heat resistant resin and the metal foil are laminated by heating and pressing, cast method, wherein a varnish of heat resistant resin precursor is applied on the metal foil and dried to form the laminate, and combination thereof.
  • laminate method is preferable for it takes shorter time for drying and thereby superior in productivity and saving costs.
  • Heat press method and continuous lamination method can be exemplified as the laminate method.
  • the laminate can be manufactured by stacking the metal foil(s) and heat resistant resin film(s) each cut to a dimension predetermined by the press machine and then heat pressing the stuck, for example.
  • the lamination can be carried out by inserting the materials between one roll and the other roll and then laminating them.
  • the rolls can be metal roll, rubber roll and so on.
  • steels and stainless steels can be used. It is preferable to use rolls treated to improve the surface hardness using hard chromium plating or by forming tungsten carbide layer.
  • a heat resistant rubber such as a silicone rubber or a fluoride rubber is preferably formed on the surface of a metal roll to form the rubber rolls.
  • the continuous lamination can also be carried out using the method so called "belt lamination".
  • the lamination temperature be in the range of from 200 degrees C to 400 degrees C.
  • conduction heating, radiant heating, such as far infrared heating, and Induction heating can be utilized.
  • Heat annealing is preferably utilized after the heat pressing and/or heat annealing.
  • Conventional heating furnaces, autoclaves and so on can be used as the heating equipment.
  • the atmosphere of heating can be air, inert gas such as nitrogen or argon and so on. Both of the method of heating the film continuously and the method of putting the film rolled on a core in a heating furnace are preferable are preferable as the heating method.
  • the preferable heating types are conduction heating, radiant heating and combination thereof.
  • the preferable heating temperature is from 200 degrees C to 600 degrees C.
  • the preferable heating time is from 0.05 minutes to 5000 minutes.
  • a solution containing a polyimide, which corresponds to the organic polymer (I), and/or a polyamic acid, which is a precursor thereof, and the compound (C) (hereinafter, collectively referred to as "varnish"), can be directly applied on the metal foil and dried.
  • the content of polyimide/polyamic acid in the varnish is preferably from 5 wt% to 70 wt%.
  • a viscosity of the varnish measured with type E viscometer at 25 degrees C is preferably 1 mPas to 100000 mPas.
  • any known apparatus such as a die coater, a comma coater, a roll coater, a gravure coater, a curtain coater or a spray coater can be utilized and selected as appropriate depending on the application thickness, varnish viscosity and so on.
  • the varnish can either be applied directly on the metal foil or be applied on a adhesive layer comprising a thermoplastic polyimide or so on for the purpose of improving the adhesion to the metal foil.
  • the thickness of the thermoplastic polyimide layer is preferably not less than 0.1 micrometers and not more than 10 micrometers, more preferably not less than 0.2 micrometers and not more than 5 micrometers.
  • the glass transition temperature (Tg) of the layer is preferably not less than 150 degrees C and not more than 350 degrees C, and more preferably not less than 150 degrees C and not more than 300 degrees C.
  • the CTE of the layer in the range of from 100 degrees C to 250 degrees C is preferably not less than 20 ppm/degrees C and not more than 70 ppm/degrees C.
  • a conventional heat drying oven can be used.
  • the atmosphere in the drying oven can be air, inert gases (nitrogen, argon or the like) and so on.
  • the drying temperature can appropriately selected depending on the boiling point of the solvent and the temperature range of from 60 degrees C to 600 degrees C is preferably selected.
  • the drying time can appropriately be selected depending on the thickness, concentration and type of the solvent and is desirably from 0.05 minutes to 500 minutes.
  • the thickness of the heat resistant resin layer is preferably not less than 1 micrometer and not more than 250 micrometers, more preferably not less than 5 micrometers and not more than 40 micrometers. It is preferable that the glass transition temperature (Tg) of the layer be not less than 300 degrees C or no glass transition temperature be observed.
  • the CTE of the layer in the range of from 100 degrees C to 250 degrees C is preferably not less than 5 ppm/degrees C and not more than 30 ppm/degrees C, more preferably not more than 20 ppm/degrees C.
  • the CHE of the layer at the relative humidity from 20 % to 60 % is preferably not less than 5 ppm/%RH and not more than 25 ppm/%RH, and more preferably not more than 20 ppm/%RH.
  • a protection film is preferably attached on a surface of the heat resistant resin layer of the resin/metal laminate of the invention in the production process or as a final product in view of conveyability and prevention of contamination with foreign objects or the like.
  • a protection film having weak adhesion is preferable. When the adhesion of the protection film is too weak, delamination may take place in the rolling process and thereby the effect of preventing wrinkles, folding, lines and so on is deteriorated. When the adhesion is too strong on the other hand, the protection fill is hard to remove and may thereby causes breaking of the tape, lines or wrinkles.
  • the adhesion to the polyimide layer is preferably in the range of from 0.1 g/cm to 50 g/cm.
  • the preferable thickness is from 10 micrometers to 100 micrometers.
  • the base film of the protection film can be a polyethylene film, a ethylene-vinyl acetate copolymer film or the like.
  • a multi-layer film obtained by multi-layer lamination of these resins for film can be utilized.
  • a resin having the adhesion mentioned above can be used as a single layer film.
  • the examples of the market available film include SUNYTECT (manufactured by Sun A Kaken Co. Ltd., trade name), MF1 (manufactured by Sanyokasei Co. Ltd., trade neme) and so on.
  • a film wherein an adhesive layer having weak adhesion is formed on the single layer or multi layer film mentioned above or a film made of a polyethersulfone, a polyetheretherketone, a polyimide, a polyester or the like, can also preferably be used.
  • the adhesive component acrylic adhesives, urethane adhesives, natural rubber adhesives, synthesized rubber adhesives, polyester adhesives, silicone adhesives and so on.
  • a polyester film laminated with an acrylic adhesive layer is preferable.
  • the elastic moduli of the resin is preferably as described below in view of obtaining the effect of the invention.
  • the Storage Elastic Modulus E' under Auto-Strain regulation at a frequency of 1 Hz in a temperature range close to the mounting temperature of Au-Au jointing or Au-Sn jointing is preferably not less than 0.5 GPa and not more than 3.0 GPa.
  • the temperature range close to the mounting temperature means not less than 250 degrees C and not more than 500 degrees C, more preferably not less than 300 degrees C and not more than 450 degrees C, further preferably not less than 350 degrees C and not more than 450 degrees C.
  • BPDA 3,3',4,4'-biphenyl tetracarboxylic dianhydride
  • PMDA pyromellitic anhydride
  • PDA 1,4-phenylene diamine
  • ODA 4,4'-oxydianiline(4,4'-diaminodiphenyl ether)
  • m-BP 4,4'-bis(3-aminophenoxy)biphenyl
  • NMP N-methyl-2-pyrrolidone
  • DMAc N,N-dimethyl acetamide
  • HACP hexakis(4-aminophenoxy)cyclotriphosphazene
  • BACP tripheoxytris(4-aminophenoxy)cyclotriphosphazene
  • FACP tris(4-fluorophenoxy) tris(4-aminophenoxy)cyclotriphosphazene
  • Viscoelasticity Measurement Measurement of Storage Elastic Modulus (E') at 450 degrees C
  • temperature dispersion measurement was conducted with RSA-II (manufactured by Rheometric Scientific Inc.) in a tensile deformation mode. The measurement was conducted in the temperature range of from 30 degrees C to 500 degrees C, at a heating rate of 3 degrees C/min, under Auto-Strain regulation at a strain of 0.02 % and at a frequency of 1 Hz.
  • a sample of 20 mm in length and 5 mm in width was used to determine the storage elastic modulus E' at 450 degrees C.
  • CTE linear coefficient of thermal expansion
  • Step 2 Synthesis of FACP by reduction method
  • the product FNCP (4.0 g, 4.54 mmol) was dissolved in a mixed solvent containing ethyl acetate (60 ml) and methanol (20 ml). A powder Pd (5 % in C, 0.98 g) was added into the mixture.
  • Synthesis of Polyamic Acid A - E (Synthesis Example 1: Synthesis of polyamic acid A) A vessel equipped with a stirrer and a nitrogen inlet tube was charged with 110 g of NMP as solvent and then with 13.3 g of PDA, and stirred at room temperature until the sample was dissolved. Thereafter, 25.75 g of BPDA and 8.2 g of PMDA were added thereto and stirred at room temperature for 1 hour, and then 237 g of NMP was added and stirred at 50 degrees C for 3 hours and at room temperature for 20 hours to give a polyamic acid varnish A.
  • Example 1 A 7-ml glass tube was charged with 0.046 g of HACP as C-component and 0.34 g of NMP and stirred until the sample was dissolved to give a HACP/NMP solution. Then 15 g of varnish A (polyamic acid A/NMP solution) was injected to a 100 ml reaction vessel and then the HACP/NMP solution was slowly added and stirred at room temperature for 10 minutes.
  • varnish A polyamic acid A/NMP solution
  • the resultant polyamic acid solution (polyamic acid content: 12 wt%) was applied on a glass plate using a Baker applicator to a dry film thickness of about 17 micrometers and dried using an inert oven under nitrogen atmosphere at 100 degrees C for 60 minutes, at 200 degrees C for 60 minutes, at 300 degrees C for 60 minutes, at 350 degrees C for 60 minutes and at 450 degrees C for 10 minutes.
  • the obtained polyimide/glass laminate was immersed in water at a temperature of 40 degrees C to remove the polyimide film from the glass.
  • the properties of the obtained polyimide film are shown in Table 1. As the crosslinking took place, the storage elastic modulus at high temperature was improved.
  • Examples 2 to 11 The reactions were carried out in the same manner as in Example 1 except that the compositions were changed to those shown in Table 1.
  • the solution reacted according to the composition shown in Table 1 was applied on a glass plate using a Baker applicator to a dry film thickness of about 17 micrometers and dried using an inert oven under nitrogen atmosphere at the same condition as in Example 1 to obtain a polyimide/glass laminate.
  • the film was prepared from the obtained polyimide/glass laminate in the same manner as in Example 1. The properties of the film are shown in Table 1. As the crosslinking took place, the storage elastic modulus at high temperature was improved.
  • Example 12 to 14 The reactions were carried out in the same manner as in Example 1 except that the compositions were changed to those shown in Table 1.
  • the obtained polyamic acid solution was applied on a copper foil using a Baker applicator to a dry film thickness of about 17 micrometers, dried using an inert oven under nitrogen atmosphere at from 50 degrees C to 180 degrees C at a heating rate of 3 degrees C/min, and then heat treated at from 280 degrees C to 380 degrees C using an IR reflow furnace to obtain a polyimide/metal laminate.
  • the copper foil in the resulting laminate was treated for several minutes by spraying a ferric chloride solution (40 Baume) through a spray nozzle until the metallic foil was completely eliminated, and then the sample was washed with water and vacuum-dried at 60 degrees C thereby obtained a polyimide film.
  • the properties of the obtained film are shown in Table 1. As the crosslinking took place, the storage elastic modulus at high temperature was improved.
  • the present invention there can be obtained a polyimide/metal laminate having a polyimide layer excellent in modulus of elasticity at high temperatures, dimensional stability, and transparency.
  • problems such as sinking, wiring deviation, release and plating soaking do not occur even in chip mounting via Au-Au jointing or Au-Sn jointing.
  • the polyimide/metal laminate of the present invention can cope satisfactorily with high density mounting, which has been accelerated in recent years, and can be used effectively as a polyimide/metal laminate for COF used widely in tape automated bonding (TAB) tape processing line.
  • TAB tape automated bonding

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une résine thermorésistante obtenue par réticulation d’un polymère organique ayant une liaison imide et/ou une liaison amide dans sa chaîne principale avec un composé ayant au moins trois groupes amino et un squelette phosphazène et ayant une structure spécifique.
PCT/JP2009/003813 2009-08-07 2009-08-07 Résine thermorésistante, sa composition, stratifié résine/métal et carte de circuit imprimé WO2011016094A1 (fr)

Priority Applications (2)

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PCT/JP2009/003813 WO2011016094A1 (fr) 2009-08-07 2009-08-07 Résine thermorésistante, sa composition, stratifié résine/métal et carte de circuit imprimé
TW098142929A TW201105710A (en) 2009-08-07 2009-12-15 Heat resistant resin, composition thereof, resin/metal laminate and circuit board

Applications Claiming Priority (1)

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PCT/JP2009/003813 WO2011016094A1 (fr) 2009-08-07 2009-08-07 Résine thermorésistante, sa composition, stratifié résine/métal et carte de circuit imprimé

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CN103467525A (zh) * 2012-06-07 2013-12-25 北京理工大学 双氧水氧化法制备六(4-羧基-苯氧基)-环三磷腈的方法
CN109679097A (zh) * 2018-12-25 2019-04-26 内蒙合成化工研究所 一种基于环磷腈的高阻燃性聚酰亚胺气凝胶的制备方法
CN109679133A (zh) * 2018-12-10 2019-04-26 沈阳化工大学 一种阻燃型高性能聚酰亚胺气凝胶的制备方法

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JP2006077064A (ja) * 2004-09-08 2006-03-23 Kaneka Corp 新規ポリイミド、ポリイミド樹脂組成物、およびそれを用いた難燃性樹脂組成物、並びにポリアミド酸
JP2006124685A (ja) * 2004-09-29 2006-05-18 Ube Ind Ltd Ｃｏｆ用ポリイミドフィルムおよび積層体
JP2008247800A (ja) * 2007-03-30 2008-10-16 Fushimi Pharm Co Ltd 反応性基含有環状ホスファゼン化合物およびその製造方法
WO2008139720A1 (fr) * 2007-05-11 2008-11-20 Mitsui Chemicals, Inc. Composition de résine, film sec et fabrications de ceux-ci

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JPH0418450A (ja) * 1990-04-16 1992-01-22 Fujitsu Ltd 感光性耐熱樹脂組成物とそれを用いたパターン形成方法
JP2002265773A (ja) * 2001-03-15 2002-09-18 Canon Inc 熱可塑性樹脂組成物
JP2005047995A (ja) * 2003-07-30 2005-02-24 Kaneka Corp 難燃性を向上させた耐熱性樹脂組成物およびその利用
JP2006077064A (ja) * 2004-09-08 2006-03-23 Kaneka Corp 新規ポリイミド、ポリイミド樹脂組成物、およびそれを用いた難燃性樹脂組成物、並びにポリアミド酸
JP2006124685A (ja) * 2004-09-29 2006-05-18 Ube Ind Ltd Ｃｏｆ用ポリイミドフィルムおよび積層体
JP2008247800A (ja) * 2007-03-30 2008-10-16 Fushimi Pharm Co Ltd 反応性基含有環状ホスファゼン化合物およびその製造方法
WO2008139720A1 (fr) * 2007-05-11 2008-11-20 Mitsui Chemicals, Inc. Composition de résine, film sec et fabrications de ceux-ci

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103467525A (zh) * 2012-06-07 2013-12-25 北京理工大学 双氧水氧化法制备六(4-羧基-苯氧基)-环三磷腈的方法
CN103467525B (zh) * 2012-06-07 2016-06-22 北京理工大学 双氧水氧化法制备六(4-羧基-苯氧基)-环三磷腈的方法
CN109679133A (zh) * 2018-12-10 2019-04-26 沈阳化工大学 一种阻燃型高性能聚酰亚胺气凝胶的制备方法
CN109679097A (zh) * 2018-12-25 2019-04-26 内蒙合成化工研究所 一种基于环磷腈的高阻燃性聚酰亚胺气凝胶的制备方法

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