WO1984004102A1 - Fluorine-containing polyamic acids and polyimides - Google Patents

Fluorine-containing polyamic acids and polyimides Download PDF

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Publication number
WO1984004102A1
WO1984004102A1 PCT/JP1984/000182 JP8400182W WO8404102A1 WO 1984004102 A1 WO1984004102 A1 WO 1984004102A1 JP 8400182 W JP8400182 W JP 8400182W WO 8404102 A1 WO8404102 A1 WO 8404102A1
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WO
WIPO (PCT)
Prior art keywords
polyimide
following
bis
general formula
moisture absorption
Prior art date
Application number
PCT/JP1984/000182
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English (en)
French (fr)
Japanese (ja)
Inventor
Shunichi Numata
Koji Fujisaki
Noriyuki Kinjo
Original Assignee
Hitachi Ltd
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Hitachi Ltd, Hitachi Chemical Co Ltd filed Critical Hitachi Ltd
Publication of WO1984004102A1 publication Critical patent/WO1984004102A1/ja

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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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound

Definitions

  • the present invention relates to a fluorine-containing boriamidic acid, a polyimide obtained by curing the same, an insulating film for a multilayer wiring of a semiconductor containing the polyimide, a thin line shield film, a flexible printed circuit board, and the like.
  • an insulating film for various types of electronitas Useful as an insulating film for various types of electronitas.
  • imid-based polymers are used in flexible printed circuit boards.
  • ordinary polyamides have a high moisture absorption, which causes various troubles. For example, increase in leakage current and corrosion of wiring materials (especially in the case of aluminum-aluminum) are problems.
  • the polymer that has absorbed moisture has a problem in that it is swelled when heated rapidly in any of the processes such as gold wire bonding and solder reflow.
  • the present inventors have studied the heat resistance and the moisture absorption of polymers having various chemical structures, and as a result, it has been found that polymers having low moisture absorption generally have poor heat resistance.
  • the polyimide having a repeating unit of (A) Compared with the polyimide having a repeating unit of (A), the polyimide having a repeating unit of the following formula () has a moisture absorption rate reduced to about 1 Z3, but in terms of thermal decomposition temperature, 40 C is also low.
  • the polyimide having a repeating unit of the following formula (C) has a moisture absorption rate reduced to about 1 as compared with the polyimide of the formula (A), but the thermal decomposition About 100 ° C is low in terms of temperature.
  • the object of the present invention is to provide a novel polyimide and a raw material of polyimide, which are low in hygroscopicity and excellent in heat resistance, and are particularly useful for various insulating films in electronics.
  • the first invention of the present invention relates to a polyamic acid], which is represented by the following general formula I:
  • a ri and Ar 2 are aromatic-containing groups, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, C f is a fluorinated alkyl S directly bonded to ⁇ ⁇ , and represents m ⁇ l )).
  • the second invention of the present invention relates to polyimide, which is represented by the following general formula I:
  • the polyimide according to the present invention is a material having excellent moisture resistance and heat resistance, and is useful as a “stunning material, a functional forest material, and the like.
  • At least one of the following zeamines is
  • C f is a fluoroalkyl group having 1 to 4 carbon atoms
  • n,, and r are integers 0 to 4 and are n + P + q + r ⁇ l
  • N f , p ', q', are 0 to 4.
  • the polyimide (formula I) of the present invention can be obtained by heating the above-mentioned polyamide acid to dehydrate it by ring closure to imidize it.
  • heat resistance there are heat resistance from the viewpoint of thermal decomposition temperature and heat resistance from the viewpoint of glass transition point (T g).
  • T g glass transition point
  • the present inventors have generally suggested that the introduction of a fluorinated alkyl group decreases the Tg.
  • the fluorinated alkyl group is directly bonded to an aromatic ring, particularly a benzene nucleus, and forms a side chain.
  • the rate of moisture absorption also decreased, and that the decrease in Tg was extremely small.
  • the polyimide of the present invention or a polyamic acid as a precursor thereof can be obtained by introducing a fluorinated alkyl group into the aromatic of diamin and reacting them.
  • Examples of the diamine which is one of the raw materials of the present invention and in which a fluorinated alkyl group is directly bonded to an aromatic ring include the following.
  • Giamino Benzotrifluoride bis (trifluoromethyl) phenylene Giamin, jiminotetra (trifinolome) Benzene, Jiamino (Pentafuru) Benzene, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, 2,2'-bis (trifluoromethyl) ) ⁇ 4,4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) 1-4,4'-diaminodiphenyl, 3-—; 3 ', 5 , 5 '-Tetrakis (trifluoromethylenole)-, 4, jiaminodiphenyl, 3, 3'-Bis (trifluoromethyl) 1-4, 4 '-diamino benzophenone , Bis (aminofenoquine) di (trifluoromethyl) benzene, bis (amin
  • the boriamidic acid of the present invention is obtained by mixing a diamine represented by the following general formula and tetracarboxylic anhydride with a chemical equivalent or a compounding amount in the vicinity of the chemical equivalent (particularly with respect to 1 mol of sulfonic acid anhydride). It is most rational to produce the diamine by reacting it in a solvent (with a blending amount of 0.1 to 1.1 mol).
  • the solvent used in the CO reaction is N-methyl-, which is used in the synthesis of polyamic acid as is well known.
  • Examples of the skeleton in which the fluorinated alkyl group of the present invention is directly bonded to an aromatic ring include the following structural units.
  • OMPI The following are examples of aromatic diamines that may be used in combination with the above-mentioned diamines.
  • R 2 and R 4 are divalent organic groups, ⁇ and R 3 are monovalent organic groups, and P and q are 1! Represent a large integer. You may use jointly.
  • diamines and acid anhydrides shown in [ ⁇ ] and [IV] should be the main raw materials. If they are clear, diamine [DI] will be 70 ° h or more of the total diamine components, and the acid anhydride [IV] will be 5 0 of total anhydride
  • the polyamide of the present invention includes N-methyl-12-pyrrolidone (hereinafter abbreviated as NMP), dimethylformamide, dimethinoreacetamide, and snoleholane chloride. It is synthesized in solvents such as zole, xylenol, and halogenated phenol.
  • NMP N-methyl-12-pyrrolidone
  • dimethylformamide dimethinoreacetamide
  • snoleholane chloride snoleholane chloride. It is synthesized in solvents such as zole, xylenol, and halogenated phenol.
  • the polyamide amide according to the present invention is compatible with REAT for these solvents. Also, it has a feature that the solubility is excellent. Therefore, low-cost solvents such as dichlorobenzene: / ⁇ aceton ⁇ methinoleethynoleketone and diacetone alcohol can also be mixed and used.
  • the polyamide acid synthesized as described above was used as a varnish having a concentration of about 30% (weight and resin content) in the manufacture of a polyimide film, for example, in a semiconductor chip. (ICLSI, etc.) and used as a varnish as it is.
  • amide, sulfamoyl or sulfamoyl groups are further introduced into diamin to form a rigid ladder structure after curing.
  • nadic acid derivative or ethyl group 3 ⁇ 4 Inserting an unsaturated group and heat-crosslinking 10 ⁇ Introducing a hydroxyl group or hydroxyl group into the polymer and adding a curing agent Crosslinking is useful.
  • a tricarboxylic acid derivative may be used in combination.
  • the mixture was heated to about 160 C, and the remaining water and toluene were distilled off.
  • DAPP 2., 2—Bis [4 1 (4 1 Ryo Minou Enokishi) Fuenore] Fuso
  • DAPPP 2,2—Bis [4-1 (4-Amino Fenix) Feninore] Russia Nono 0 down
  • DCPFP 2,2-bis [4- (3,4-dicarboxyloxy) pheninole] hexafnoreo
  • DFAPFP 2,2-bis ⁇ 4— [21- (trifluoromethyl) -14-amino-phenoxy] phen 2 • hexaph norelov.
  • the varnish was spread thinly on a glass plate and heated at 100 for 1 hour to form a film.
  • the film was peeled from the glass plate, sandwiched between metal frames, and heated at 200 ° C for 1 hour and at 400 ° C for 1 hour.
  • the heat resistance of this film was evaluated in air.
  • the time for weight loss was 6 minutes at 500 C, 20 minutes at 475 C, 70 minutes at 45, and 125 minutes at 425 C.
  • the temperature that requires 100 minutes to reduce 3% (defined as the thermal decomposition temperature) is 40 U.
  • Tg 400 ° C.
  • the above-mentioned polyimide has a Tg of 60 C lower and a moisture absorption of about 3 times.
  • Example 2 A polyamic acid varnish was synthesized in the same mixing ratio as in Example 1 to obtain a polyimide film. Next, the thermal decomposition temperature and the moisture absorption Tg were measured in the same manner as in Example 1. As a result, they were 43 0 t and 1.1 ⁇ 180 C, respectively.
  • the T g of this polyimide was lower than that of the polyimide (11 polyimides).
  • a varnish was synthesized to obtain a polyimide film.
  • the pyrolysis temperature and the moisture absorption Tg were measured in the same manner as in Example 1.
  • T g decreases and the moisture absorption rate is small
  • a varnish was synthesized to obtain a polyimide film.
  • Comparative Example 2 Polyamide varnish was synthesized in the following mixing ratio in the same manner as in Example 1 to obtain a polyimide film.
  • the thermal decomposition temperature, the moisture absorption rate, and the Tg were measured in the same manner as in Example 1. As a result, they were 470 ° C, 3.0%, and 370 ° C, respectively.
  • Polyamide acid paste was synthesized in the following mixing ratio in the same manner as in Example 1 to obtain a polyimide film. ⁇
  • a boriamidic acid varnish was synthesized in the following mixing ratio in the same manner as in Example 1 to obtain a polyimide film.
  • T g also increased by about 50 C.
  • Example 4 A polyamic acid varnish was synthesized in the following mixing ratio in the same manner as in Example 1 to obtain a polyimide finolem.
  • a boriamid varnish was synthesized in the following mixing ratio in the same manner as in Example 1, and finally a polyimide film was obtained.
  • a polyamic acid diacid was synthesized in the following mixing ratio in the same manner as in Example 1, and a polyimide film was obtained.
  • Example 2 the pyrolysis temperature, the moisture absorption rate, and the Tg were measured, and as a result, 4300 t, 0.40,
  • a polyamide acid varnish was synthesized in the following mixing ratio in the same manner as in Example 1, and a polyimide film was obtained.
  • Example 2 the thermal decomposition temperature, the moisture absorption and the T g were measured as in Example 1. As a result, they were respectively 43 0 t :, 0.6%, and 220 C. Compared to Example 5, the moisture absorption was 1.5 times and g was slightly lower.
  • the polyamic acid was used in the same manner as in Example 1.
  • a varnish was synthesized. However, trimellitic anhydride was used.
  • T g was measured. As a result, respectively, 4 0 ⁇ , 0.7? &,
  • a varnish was synthesized to obtain a polyimide film. Then
  • the pyrolysis temperature, moisture absorption and Tg were measured in the same manner as in Example 1 (the results were 450 t: 1.8%, 370 C, respectively).
  • a modified polyamic acid varnish was synthesized in the following mixing ratio in the same manner as in Example 1 to obtain a polyimide film, (o TFAPB23.82 g
  • a polyamide acid varnish was synthesized in the following mixing ratio in the same manner as in Example 1 to obtain a polyimide film.
  • Example 1 fo TFAPB ?? 23.48 go DDE 3.99 g ⁇ o BPDA 3.69 go Trimellitic anhydride 3.83 g or NMP 255 g Then, as in Example 1, the thermal decomposition temperature, moisture absorption, T g was measured. As a result, they were 425 C, 0.78, and 315 C, respectively.
  • Polyamide varnish was synthesized in the following mixing ratio in the same manner as in Example 1, and a polyimide film was further obtained.
  • a polyamic acid varnish was synthesized in the following mixing ratio in the same manner as in Example 1 to obtain a polyimide film.
  • a boriamidic acid varnish was synthesized in the following mixing ratio in the same manner as in Example 1, and a polyimide film was further obtained.
  • the thermal decomposition temperature, the moisture absorption and the T g were measured in the same manner as in Example 1. As a result, they were 420 r :, 0.6%, and 320 C, respectively.
  • a boriamidic acid varnish was synthesized in the following mixing ratio in the same manner as in Example 1, and a polyimide film was further obtained.
  • the thermal decomposition temperature, the moisture absorption and the Tg were measured in the same manner as in Example 1, and as a result, they were 440 °: 0.35% and 430C, respectively.
  • a novel polyamic acid and polyimide are provided, and the moisture- and heat-resistant material containing the polyimide is different from conventional ones in heat resistance. Remarkable 3 ⁇ 4 effect in that both moisture and heat resistance are excellent And to provide new materials in the electronics materials field.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Wire Bonding (AREA)
  • Laminated Bodies (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
PCT/JP1984/000182 1983-04-11 1984-04-11 Fluorine-containing polyamic acids and polyimides WO1984004102A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6208083A JPS59189122A (ja) 1983-04-11 1983-04-11 含フッ素ポリアミド酸及びポリイミドの製造方法

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JP (1) JPS59189122A (enrdf_load_stackoverflow)
DE (2) DE3490169C2 (enrdf_load_stackoverflow)
WO (1) WO1984004102A1 (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4781439A (en) * 1986-01-22 1988-11-01 Hitachi, Ltd. Liquid crystal polyimide alignment free of scattering domains
DE4141489A1 (de) * 1990-12-17 1992-06-25 Occidental Chem Co Fluorhaltige polyimide
EP0452725A3 (en) * 1990-03-30 1992-10-28 Sagami Chemical Research Center Fluorine containing diaminobenzene derivatives and its use
JP2020111561A (ja) * 2019-01-16 2020-07-27 セイカ株式会社 ４つの芳香環を有するジアミノ又はジニトロベンゼン化合物、およびその製造方法、並びにポリイミド

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR910000832A (ko) * 1988-06-28 1991-01-30 랄프 챨스 메더스트 인터레벨 유전체 및 기질 피복물용의 저유전상수 및 저수분흡수율을 갖는 폴리이미드 및 코폴리이미드
US4876329A (en) * 1988-06-28 1989-10-24 Amoco Corporation Polyimide polymers and copolymers using 3,5-diaminobenzotrifluoride
JP2657700B2 (ja) * 1988-08-08 1997-09-24 日本電信電話株式会社 含フッ素ポリイミド光学材料
JPH0253827A (ja) * 1988-08-17 1990-02-22 Kanegafuchi Chem Ind Co Ltd ポリイミド共重合体
CA2021753A1 (en) * 1989-08-17 1991-02-18 Jeffrey S. Stults Bis-m-benzotrifluoride compounds
JP2851019B2 (ja) * 1990-09-28 1999-01-27 日本電信電話株式会社 全フッ素化ポリイミド，全フッ素化ポリアミド酸およびそれらの製造方法
CA2052368C (en) * 1990-09-28 1998-09-15 Shinji Ando Perfluorinated polyimide, perfluorinated poly(amic acid), starting compounds therefor, and methods for preparing them
KR20010087502A (ko) 2000-03-07 2001-09-21 윤종용 광학용 폴리이미드 단량체, 폴리이미드 화합물 및 그 제조방법
JP4962046B2 (ja) * 2007-03-01 2012-06-27 東レ株式会社 ポリイミドフィルムおよびその製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57180633A (en) * 1981-04-30 1982-11-06 Hitachi Ltd Curable polyimide resin composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1077243A (en) * 1965-05-18 1967-07-26 Monsanto Chemicals Polyimides
JPS58180531A (ja) * 1982-04-19 1983-10-22 Hitachi Ltd 含フツ素ポリイミド、アミド酸並びにそれらの製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57180633A (en) * 1981-04-30 1982-11-06 Hitachi Ltd Curable polyimide resin composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4781439A (en) * 1986-01-22 1988-11-01 Hitachi, Ltd. Liquid crystal polyimide alignment free of scattering domains
USRE34885E (en) * 1986-01-22 1995-03-28 Hitachi, Ltd. Liquid crystal polyimide alignment free of scattering domains
EP0452725A3 (en) * 1990-03-30 1992-10-28 Sagami Chemical Research Center Fluorine containing diaminobenzene derivatives and its use
EP0635533A1 (en) * 1990-03-30 1995-01-25 Sagami Chemical Research Center Polyimide-based liquid crystal aligning agent
DE4141489A1 (de) * 1990-12-17 1992-06-25 Occidental Chem Co Fluorhaltige polyimide
JP2020111561A (ja) * 2019-01-16 2020-07-27 セイカ株式会社 ４つの芳香環を有するジアミノ又はジニトロベンゼン化合物、およびその製造方法、並びにポリイミド

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JPH0214365B2 (enrdf_load_stackoverflow) 1990-04-06
DE3490169T (de) 1985-05-15
JPS59189122A (ja) 1984-10-26
DE3490169C2 (enrdf_load_stackoverflow) 1989-07-20

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