Classifications

• • 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)

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• 1983
  • 1983-04-11 JP JP6208083A patent/JPS59189122A/ja active Granted
• 1984
  • 1984-04-11 DE DE19843490169 patent/DE3490169T/de active Pending
  • 1984-04-11 WO PCT/JP1984/000182 patent/WO1984004102A1/ja not_active Ceased
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